Fouling Science and Technology 1st Ed @ProcessEng

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Fouling Science and Technology

NATO ASI Series
Advanced Science Institutes Series
A Series presenting the results af activities sponsored by the NA TO Science Committee,

which aims at the dissemination af advanced scientific and technological knowledge,
with a view to strengthening links between scientific communities.
The Series is published by an international board of publishers in conjunction with

the NATO Scientific Affairs Division
A Life Sciences Plenum Publishing Corporation

B Physics London and New York
C Mathematical Kluwer Academic Publishers

and Physical Sciences Dordrecht, Boston and London
D Behavioural and Social Sciences
E Applied Sciences
F Computer and Systems Sciences Springer-Verlag

G Ecological Sciences Berlin, Heidelberg, New York, London,
H Cell Biology Paris and Tokyo
@ProcessEng
Series E: Applied Sciences - VoL 145

Fouling Science and
Technology
edited by
L. F. Melo
University of Minho,
Braga, Portugal
T. R. Bott
University of Birmingham,
Birmingham, UK
and
c. A. Bernardo
University of Minho,
Braga, Portugal
..
@ProcessEng
Kluwer Academic Publishers

Dordrecht / Boston / London
Published in cooperation with NATO Scientific Affairs Division

Proceedings of the NATO Advanced Study Institute on
Advances in Fouling Science and Technology,
Alvor, Algarve, Portugal
May 18-30, 1987
Library of Congress Cataloging in Publication Data

NATO Advaneed Study Instltute an Advanees In Foullng Science and
Teehnology (1987 Alvor, Portugal)
Foullng selence and teehnology / [edlted by) L.F. Melo, T.R. Bott,
e.A. Bernardo.
p. cm. -- (NATO ASI serles. Series E, Applled selences ; no.
145. )
·Publlshed In eooperatlon wlth NATO Seientifie Affalrs Division.·
Ine l udes Index.
1. Heat exeha~gers--Foul Ing. 2. Foul Ing. l. Melo, L. F. (Luis

F.), 1948- Il. Bo·tt, T. R. (Theodore Reginald), 1927-
III. Bernarde, e. A. (Carlos A.). 1946- IV. North Atlantlc
Treaty Organlzatlon. Seientifie Affalrs Division. V. TItle.
VI. Series.
TJ263.N39 1987
621.402'5--dc19 88-15079
eIP
ISBN-13: 978-94-010-7766-8 e-ISBN-13: 978-94-009-2813-8

001: 10.1007/978-94-009-2813-8
Published by Kluwer Academic Publishers,

P. O. Box 17, 3300 AA Dordrecht, The Netherlands.
Kluwer Academic Publishers incorporates the publishing programmes of

D. Reidel, Martinus Nijhoff, Dr W. Junk, and MTP Press.
Sold and distributed in the U.S.A. and Canada

by Kluwer Academic Publishers,
101 Philip Drive, Norwell, MA 02061, U.S.A.
In all other countries, sold and distributed

by Kluwer Academic Publishers Group,
P.O. Box 322, 3300 AH Dordrecht, The Netherlands.
All Rights Reserved

© 1988 by Kluwer Academic Publishers.
@ProcessEng
Softcover reprint of the hardcover 1st edition 1988

No part of the material protected by this copyright notice may be reproduced or utilized
in any form or by any means, electronic or mechanical, inciuding photocopying, recording
or by any information storage and retrieval system, without writlen permission from the
copyright owner.
Proceedings of the
NATO Advanced Study Institute
"Advances in Fouling Science and Technology"
held in Hotel D. Joao II, Alvor, Algarve

Portugal
from the l8th to the 30th May 1987
Organizing Committee:
Luis F. Melo (Director)

University of Minho, Braga, Portugal
Carlos A. Bernardo (Associate Director)
Theodore Reginald Bott
University of Birmingham, United Kingdom
Joao de Deus ~inheiro
Jens Rostrup-Nielsen
Haldor-Topsoe, Denmark
@ProcessEng
FOREWORD
The fouling of heat exchangers, reactors and catalysts remains one of
the most urgent problems facing the process industries. Over the past ten
years there has been limited research and investigation into the underlying
mechanisms which give rise to this problem.
For convenience, particularly in heat exchanger technology, the
mechanisms involved have been subdivided into different subject areas. It
is often the situation that individuals or groups of workers have concentra-
ted efforts in one or two of these specialist areas and there is a need to
integrate the ideas across the whole spectrum of the subject. In addition,
topics such as adhesion and surface phenomena have not been properly taken
into account up till now in the assessment of the fouling processes. For this
reason it was considered essential that the recognised experts from around
the world, who are actively concerned with research, development and design
in the fieId, should meet and exchange ideas and experience. Such a meeting
was held at Alvor, Portugal, in May 1987, sponsored by the NATO Advanced
St~dy Institutes Programme.
In order to obtain a common basis for the work of the Advanced Study
Institute, the whole technological field was reviewed right from the basic
concepts to the frontiers of present knowledge. Each invited contributor was
asked to make an overall presentation covering his or her area of expertise.
The texts of the lectures and the discussion reports of the meeting are
collected together in 12 chapters in this volume, representing an up to date
statement of the technological position with regard to industrial fouling. The
subject matter is developed from the fundamentals through the basic mechanisms
of surface contamination to industrial applications. Reviews on the so-called
types of fouling (particulate, biological, solidification, corrosion and
chemical reaction) and on adhesion science are presented. Fouling in food
processing, although essentiaIly reaction fouling, is kept separated in view
of its significance as a subject in its own right. In the chapter dealing
with chemical reaction fouling an overview of the field is presented,
together with reviews and papers covering specific topics, including fouling
of catalysts and hot metallic surfaces. Case studies in a number of important
industrial proces ses (water treatment, furnaces, homogeneous chemical
reaction and catalysis) are discussed. The final chapter contains short re-
ports of the discussion that took place as a direct result of the interest
generated during the lectures.
The editors would like to express their thanks to all the speakers and
participants for their active collaboration which has made this book pos-
sible. In addition, the support of the Scientific Affairs Division of NATO,
through the A.S.I. Programme, together with the support of the Universities
of Minho and Birmingham, Junta Nacional de Investiga~ao Cientifica e Tecno-
logica, Instituto Nacional de Investiga~ao Cientifica, Calouste Gulkenkian
Foundation and the Portuguese Ministry of Education is gratefully
acknowledged.
@ProcessEng
L.F. Melo
T.R. Bott
C.A. Bernardo
CONTENTS
FOREWORD vi
CHAPTER 1. FUNDAMENT ALS AND ECONOMICS
. General Fouling Problems

T.R. Bott 3
. General Thermal Fouling Models

N. Epstein 15
The Economics of Fouling

A.M. Pritchard 3 1
CHAPTER 2. MONITORING EQUIPMENT
Liquid Fouling Monitoring Equipment

J.M. Chenoweth 49
Gas-Side Fouling Monitoring Equipment

A. Tsados 6 7
Monitoring Fouling using a Novel Technique

P.G. Cousineau, G.P. Fulford and P.M. Simmons 77
CHAPTER 3. ADHESION
Adhesi.on and Removal of Particles - I

J. Visser 87
Adhesion and Removal of Particles - II

J. Visser 1 O5
Aspects of Cell Adhesion

R.S. Harbron and C.A. Kent 125
CHAPTER 4. P AR TICULATE FOULING

Particulate Fouling of Heat Transfer Surfaces:

Mechanisms and Models
N. Epstein l 43
Stochastic Model for the Induction Step on

Particulate Fouling
N. Vatistas 16 5
@ProcessEng
Fouling by Aqueous Suspensions of Kaolin and

Magnetite: Hydrodynamic and Surfaee Phenomena
Effects
L. Melo and J.D. Pinheiro 17 3
ix
x
• Gas Side Fouling

T.R. Bott 191
CHAPTER 5. BIOLOGICAL FOULING
• Biological Fouling: Basic Science and Models

C.A. Kent 2 O7
• Effect of Design and Operating Variables on
Biofouling
M.M.V.P.S. Pinheiro, L.F. Melo, T.R. Bott and
J.D. Pinheiro 223
• Surface Bound Biocides - A Novel Possibility

to Prevent Biofouling
K.J. Huttinger 233
• Experimental Investigation of Marine Biofouling

and Corrosion for Tropical Seawater
C.B. Panchal 24 l
CHAPTER 6. CRYSTALLISATION FOULING
• Crystallisation Fouling - Basic Science and

Models
T.R. Bott 251
• Deposition of Hardness Salts
A.M. Pritchard 261
• Crystallisation of Organic Materials
T.R. Bott 275
• Fouling of Cryogenic Liquids
H. Muller-Steinhagen 281
CHAPTER 7. CHEMICAL RE ACTION FOULING
• Basic Science and Models of Reaction F ouling

B.D. Crittenden 293
• Chemical Reaction Fouling of Heat Exchangers

B.D. Crittenden 3 l 5
• Fouling from Light Hydrocarbons on Metal

Surfaces
L. Sousa Lobo 333
• Fouling of Catalysts: Industrial Examples

@ProcessEng
J .R. Rostrup-Nielsen 35 l
• The Fouling of Catalysts by Deposition of

Filamentous Carbon
C.A. Bernardo 369
xi
Droplets and Filaments: on the Fouling of

Metal Surfaces by Carbonaceous Material from
Hydrocarbon Gases above 850K
A.I. LaCava 39 l
Carbon Limits in Steam Reforming

J .R. Rostrup-Nielsen 4 O5
Carbon Deposition in Steam-Cracking
J.L. Figueiredo and M.L.G.M. Pinto 425
CHAPTER 8. DESIGN AND OPERAnON OF HEAT EXCHANGERS
Basic Relationships for Heat Exchangers and

Impact of Fouling on Design
S. Kakac and A.K. Agrawal 437
. Selection of Heat Exchangers

J.M. Chenoweth 463
. General Design of Heat Exchangers for

Fouling Conditions
J.M. Chenoweth 477
Basic Concepts in Heat Exchanger Network

ModeIling
P. Fryer 495
The Fouling of Heat Exchanger Networks

P. Fryer 5 l l
Compensating tor Fouling in Heat Exchanger

Networks
E. Kotjabasakis and B. Linnhoff 529
CHAPTER 9. FOOD PROCESSING FOULING
Fouling by Milk and Dairy Product and Cleaning

of Heat Exchange Surfaces
M. Lalande and F. Rene 557
. On-Line Measurement of Fouling and Cleaning of

Industrial UHT Exchangers
G. Corrieu, M. Lalande and F. Ferret 57 5
CHAPTER 10. FOULING IN INDUSTRIAL WATER SYSTEMS
Effectiveness of Biocides
A. Marshall and T .R. Bott 59 l
@ProcessEng
. Case Study-Clean-up of a Coke Oven Cooling

System
A. MarshaIl, G.E. Ibbotson and T.R. Bott 6 Ol
Corrision Fouling: Liquid Side

E.F .C. Somerscales 62 l
xii
Avoiding Fouling and Corrosion in Water Cooled

Heat Exchangers: The Expert System Approach
A.E. Faltzin, H. Garcia and A.I. LaCava 637
Fouling of Geothermal Energy Systems

S.H. Chan 649
. Geothermal Water Scaling in Heat Exchangers

S. DIkii, M. Toksoy and A.C. Giirses 669
CHAPTER Il. FOULlNG IN FURNACES
High Temperature Fouling: The Nature of Deposits

J. Howarth and T.R. Bott 679
High Temperature Gas-Side Fouling Case Study

A. Tsados and T.R. Bott 7 Ol
CHAPTER 12. DISCUSSIONS
Cooling Water Fouling - Summary of Discussion

P. Watkinson 7 I 5
Debate: Food Processing Fouling

M. Lalande 7 I 9
. Cleaning of Fouled Surfaces: A Discussion

A.M. Pritchard and P.J. Fryer 721
Chemical Reaction Fouling Debate

5. Crittenden and I. Downey 727
Debate on Gas-Side Fouling

J.D. Isdale 731
INDEX 735
@ProcessEng
@ProcessEng
Chapter 1
Fundamentals and Economics
GENERAL FOULING PROBLEMS
T.R. BOTT
Department of Chemical Engineering, University of Birmingham, P.O. Box 363,

Edgbaston, Birmingham B1S 2TT
l. INTRODUCTION
The so called oil crisis ab out twelve to fif teen years ago initiated
large ly by the economic pressures of OPEC, has stimulated an interest in
Energy Management. Although conservation of energyas been an aspect of
industrial technology for many years, recently there has been an
intensification of activity to attempt to reduce the energy requirements in
response to the high prices demanded for energy, particularly oil. The
current relatively low price of oil at the time of writing, is unlikely to
remain for long and it may be anticipated that once the current world
economic recession is overcome, itself brought about at least in part by
the high oil prices, the cost of energy will again reach high levels.
Heat recovery is an important aspect of energy management and efficient
heat recovery will be dependent upon the operation of efficient heat
exchangers. Unless heat transfer is efficient in terms of the physical
size of associated heat exchangers for a particular operation, then the
good intentions in respect of energy management may be severely hampered.
The major restrietion to good heat exchanger operation is the problem of
fouling of the transfer surface.
Fouling of heat transfer surfaces has been a problem since the
beginning of the Industrial Revolution. For this reason it is surprising
that little work had been carried out in the area, till the stimulus of the
oil crLSLS, even though a call for more data had been made some years
earlier (l)
2. PROBLEM OF FOULING
Fouling may be defined as the accumulation of dirt, scale, corrosion
produets or other material on the surfaces of the heat exchanger. The
presence of this dirt layer ean have two major effects:-
l. The presence of the dirt layer presents a further resistance to
heat transfer in addition to those present due to the inherent design of

the exchanger. In general the thermal conductivity of a dirt layer is ve ry
much lower than metals, and often its resistance is greater than either of
the "film" resistances on either side of the metal wall.
2. The reduction of the flow area due to the presence of the deposit,
coupled with the usually rough surfaee presented by the foulant, increases
the pres sure drop through the heat exchanger.
@ProcessEng
Both these consequences ean represent additional energy requirements.

The loss of heat transfer efficiency usually means that somewhere else in
the system additional energy is required to make up the short fall. For
instance in a refinery pipe still where say acrude oil is being raised to
a high temperature prior to preliminary distillation, crude oil preheaters
are employed to recover heat from a hot produet steam. _ The purpose of the
preheaters is to raise the oil temperature before entry into the pipe
3
L. F. Melo el al. (eds.), Fouling Science and Technology, 3-14.

4
still. In general pipe stills are direct fired furnaces, possibly using a
heavy fuel oil produced in the refining process. As time passes the
preheaters (and possibly the tube still itself) will become fouled, with
attendant loss of heat transfer efficiency. Since there is a temperature
requirement for the crude oil inlet to the pipe still, the short fall in
energy will have to be made up by additional fuel consumption in the pipe
still, if production is to be maintained. Furthermore, the restrictions of
heat transfer in the preheaters probably means that the product temperature
leaving the preheaters will be too high and this temperature will have to
be reduced to the design value for subsequent processing or storage. In
general this temperature reduction will be achieved by the use of a cooler
using cooling water. In effect the high grade heat available in the fuel
oil, is being transferred to the co Id utility and this is something which
runs counter to the basic philosophy of energy management!
The increased pres sure drop through a heat exchanger represents an
increase in the pumping energy requirement to maintain the flow. Assuming
the pump responsibIe for the flow is capable of the increased load, and in
the limit it may not be so, it will require additional energy, which is
often electricity; a high grade secondary energy.
Although the two consequences of reduced heat transfer efficiency and
large r pumping costs are the obvious result of fouling, there are other
effects which may not always be attributed to fouling and they usually fall
into two categories; namely corrosion and additional maintenance.
The presence of the deposit layer in the heat exchanger can in some
instances protect the metal surface from the effects of corrosion, but
more often than not the effect is to enhance corrosion. For instance if
the corrosion resistance of a metal relies on the presence of an oxide
film, the accumulation of dirt may prevent access of oxide forming
reagents. In the presence of a film of micro-organisms on a metal surface
in say a cooling water system, oxygen may be prevented from reaching the
surface so that protective metal oxide formation is inhibited. Furthermore
within a small "pool" of water beneath the biological slime, an
electrolytic cell may be established which accelerates the corrosion.
In high temperature heat transfer for example, where heat is being
removed from combustion products, the combustion of a material with a high
chlorine content can lead to corrosion problems in the heat exchanger.
Usually the "ash" deposit which accumulates on the transfer surfaces is
high in active chlorine constituents which can give rise to rapid
corrosion.
The need for additional maintenance as aresult of fouling may be
manifest in different ways. In general any extensive fouling will mean
that the heat exchanger will have to be cleaned on a regular basis to
res tore lost efficiency. The frequency of cleaning will of course depend
upon the severity of the fouling problem and may range between l week and l
year or longer. Frequent cleaning involving repeated dismantling and
reassembly, will inevitably result in damage to the heat exchanger to a
lesser or greater degree, which could shorten the useful life of the
equipment. Furthermore, the repeated removal of the heat exchanger from
service could result in lost production, or additional energy requirements,
@ProcessEng
to make up for the lost heat recovery. Under some conditions, the
incorporation of a "standby" exchanger may be prudent, so that production
is not affected during the cleaning operation.
Because of the back pressure problem consequent upon the presence of
the deposit, leaks may develop at joints and flanges upstream of the main
body of the exchanger. The increased pressure requirement will throw an
additional load on the associated pump which as aresult, will require more
5
frequent attention.
It is clear that fouling of heat exchangers costs money, and in some
examples the cost is extremely high in terms of additional energy costs,
and maintenance charges. An improved understanding of the problem of
fouling should provide the opportunity to reduce these costs at the same
time conserving energy and making the produet of the process more
competitive.
3. FOULING MECHANISMS
The fouling proces s is generaIly a transient condition at least in what
might be termed the early stages of laying down a deposit. If the
resistance to heat transfer is plotted against time, different curves may
be produced depending on the conditions. Fig.l summarises the ideal curves
that are possible.
FIGURE l Idealised fouling curves
A and C are asymptotic which represent many fouling problems. The rate
of fouling for whatever reason, gradually falls with time, so that
eventuaIly a steady state is reached when there is no net increase of
deposit on the surface, and an asymptotic fouling resistance (R f =) is
obtained. In practical industrial situations, the "plateau" may be reached
in a matter of minutes or it may take weeks or months to occur. The
general equation describing the behaviour takes the form
(l)
where Rf is the fouling resistance at time t
Curve C is further complicated by the faet a per iod of time has to

elapse before fouling commences. Such a phenomenon is not uncommon, and it
is usually attributed to the time required to "condition" the surface. The
period before deposit appears is often referred to as the "induetion" or
"initiation" period.
@ProcessEng
Curves B and D on Fig.l represent situations where the mass of deposit

gradually increases with time; a straight line relationship of the form
( 2)
where a is the slope of the line.

Curve D displays an "induetion" period similar to Curve C.
6
Although fouling of the form represented by curves B and D is possible,

and indeed it is not unusual for heat exchanger tubes to become completely
blocked which would suggest that the fouling proces s is of this form, they
may only describe the early part of an asymptotic curve.
The curves represented on Fig.l are ideal and in industrial situations,
the ideality may not be achieved. A closer representation of asymptotic
fouling might be as shown on Fig.2 where the idealised Curve A from Fig.l
is modified.
Cl>
"
"O
Cl>
U
c
E
III
.iij
~
...
Cl>
in
c
e
i:i
Cl>
rL-------------------~T~im-e----------
FIGURE 2 An idealised "practical" fouling curve
The "saw tooth" effect is the result of partial removal of some deposit
due to "spailing" or "sloughing" to be followed for a short time by a rapid
build up of deposit. The "average" curve can be seen to represent the ideal
curve A on Fig.l. Similar effects of partial removal and deposition may be
experienced with the other types of fouling curve.
The underlying mechanism by which a surface becomes fouled may be
readily appreciated. The foulant or foulant precursor, approaches the solid
surface from the bulk fluid across the boundary layer. The principles of
mass transfer will apply to the transport of the foulant forming species
towards the surface, and in general will involve eddy diffusion, and nearer
the wall the transport will depend on molecular diffusion. Depending upon
the nature of the material involved, it will be subject to the fluid
conditions associated with flow across the surfaces.
All important are the factors influencing the adhesion to the surface
and in general all aspects of interface and colloidal science are involved,
to a greater or lesser extent. The adhesion will be influenced by such

properties as, the wettability of the surface, the short range forces, and
electro-chemical forces in the proximity of the surface. Adhesion may be
strong or weak, depending upon the nature of the surface and the foulant
layer; for example the quality of adhesion of bacteria is likely to be
quite different from that of a corrosive layer. Once at the surface, the
material may be subject to removal forces, or other factors which
@ProcessEng
consolidate the deposit or weaken it.

In general the shear forces at the interface between the fluid and
deposited foulant layer, are considered to be responsibie for removal.
However in more recent discussions in the literature (2) instability in the
boundary region is thought to contribute more to the removal mechanism. It
is not unreasonable to believe that the intensive localised activity
7
associated with the so called "turbulent bursts" could result in removal

from the deposit, provided the particles constituting the deposit were not
rigidly fixed. However there is some recent evidence (3) which suggests
that even for loose descrete particles, the turbulent bursts are hardly
capable of lif ting the particles from the surface. Clearly there is a need
for much more study of mechanisms of removal.
The nature of the deposit may change over a per iod of time, so that not
only its appearance, but its strength, is affected. There are many reasons
for this phenomenon, and particular examples will have particular causes.
For example, the re arrangement of crystals may result in a strengthening of
the deposit. On the other hand the incorporation of an occasional foreign
particle into a deposit of crystals, could set up a centre of weakness; as
the deposit thickens (i.e. with time) the number of points of weakness will
increase. As a foulant deposit thickens the temperature distribution
across it will change, so that for instance, any chemical reac~ions
involved may be affected giving rise to different chemical species. These
effects are more likely in situations where large temperature differences
occur, for example in boiler plant. For deformable deposits, say bacterial
growth, it is likely that at a certain critical thickness (i.e. af ter a
period of time), the deposit is affected more by the fluid flow than
previously, when the deposit thickness was lower. The flexibility
established may give rise to failure of the biomass with consequent
shedding of some, or all, of the biofilm.
In order to facilitate discussion and to provide a basis for systematic
study, the fouling of surfaces has been classified into six groups.
1. Crystallisation or Precipitation fouling: due to the deposition or
the formation of crystals from solution on the surface.
2. Particulate fouling: the accumulation of solid particles from the
fluid stream on the surface.
3. Biological fouling: the deposition and growth of micro-organisms
(or macro-organisms) originating in the proces s steam on the surface.
4. Chemical Reaction fouling: where the deposit is the result of one
or more chemical reactions between reactants contained in the flowing
fluid.
5. Corrosion fouling: the effects of corrosion on the heat exchanger
surface itself.
6. Freezing or Solidification fouling: fouling due to the freezing of
the proces s fluid itself on the surface.
It is perhaps unfortunate this classification has been made since it is
extremely unlikely, except in a few special situations, that industrial
heat exchanger fouling will be entirely due to one mechanism. Most
industrial problems will involve several mechanisms such as combinations of
particulate, biological and corrosion in cooling water systems, or

particulate, chemical reaction, and corrosion in combustion systems.
4. THE MITIGATION OF FOULING

Two opportunities present themselves for the mitigation of the problem
of fouling. The first calls for improved design which fully takes into
account the effects of fouling. The second is that once a heat exchanger
@ProcessEng
has been instalied and operating, to take steps in operation to limit or if

possible, eliminate the fouling problem. Both these initiatives require a
thorough knowledge of the fouling potential.
Effective design may be extremely difficult since the magni tude of the
fouling risk may not be appreciated, simply because the true composition of
the proces s stream may not be known. In many examples of fouling it is
trace materials which are responsibie for the accumulations on the surface
8
of heat exchangers, and these materials may not be evident from previous
experience or from pilot plant trials. Furthermore if the problem af
fouling is not "thought through" at the design stage, an elegant design af
heat exchanger may from the heat transfer point of view, fail rapidly!
Even a rudimentary understanding of the effects of certain variables may
help to reduce the risks.
During operation, if the problem is severe enough, chemical additives
may be used in an attempt to mitigate the fouling problem. In some
situations even though the quantities are small, this may not be a feasible
proposition because of the contamination or environmental effects. Again
such action demands a thorough understanding of the origin of the fouling
and the mechanisms involved in order that the treatment may be effective.
4.1 Fouling and design
The basic equation used in the design of heat exchangers involving
convective heat transfer is
Q UMT (3)
where Q is the rate af heat transfer

A is the heat transfer sur face only
!J.T is the negative driving force
U is the overall heat transfer coefficient
The overall heat transfer coefficient for design is usually obtained

from an equation of the form
l (4)
li
where hl and h 2 are the "film" heat transfer coefficients on the two sides
of the heat exchanger
.( is the thickness of the wall (usually metal) of thermal
conductivity k separating the two process streams l and 2
.( represents themresistance of the metal to heat transfer
k
m
Rfl + Rf2 are the resistances due to fouling on either side of the
heat exchanger
The effect of the introduction of the fouling resistances into the

design process represents an added area over and above that required fOl
the equivalent heat transfer under clean (non-fouled) conditions. Ir
general this increase in area is of the order of 20 or 30% but in samE
instances of severe or perhaps unknown fouling potential, the allowance fOl
fouling might be as high as 100%. This additional area requirement car

represent substantial increases in capital cost, particularly where hige
value materials of construction are necessary to avoid corrosion Ol
contamination of the product.
Furthermore Equation 2 represents a steady state condition, whereas it
was demonstrated earlier that the laying down of a deposit is a transient
condition. When it begins to operate, the heat exchanger does not suddenlJ
@ProcessEng
achieve the condition represented by Equation 2!

In many designs the aim would be to use fouling resistances whicl
represent the plateau values shown an the exponential curves on Fig.l, Ol
if "straight line" fouling is anticipated, to use sufficiently high value:
to avoid frequent cleaning.
The seriousness of this situation is not always appreciated. If largl
9
fou1ing resistances have been used in a particu1ar design because heavy

fou1ing is anticipated, when the exchanger begins to operate it may be
"over efficient" i.e. transferring more heat than is required by the
proces s specification. Under these conditions the operator may adjust the
heat exchanger flows, probab1y by the operation of a bypass on one of the
streams, which in turn wi11 affect ve10cities in the exchanger. The
combination of temperature and ve10city adjustments may serve to acce1erate
the fou1ing process, so that the fou1ing resistances used in the design are
reached ear1ier than anticipated, or even exceeded!
Improved understanding of the fou1ing proces s cou1d he1p to improve the
design for fou1ing and if suitab1e dynamic models of fou1ing were
available, Equation 2 cou1d be refined.
Apart from the therma1 design of heat exchangers, other aspects need to
be considered at the design stage in order to mitigate the fou1ing problem.
4.1.1 Basic design The basic heat exchanger design must be as simple
as possib1e so that it may be eas ily cleaned and maintained; this aspect is
part of the initial heat exchanger choice.
Se1f c1eaning of heat exchangers is an important feature worthy of
consideration for certain app1ications. The circu1ation of sponge rubber
abrasive ba11s (The Tapprogge System) has been successful in coo1ing water
systems subject to sca1ing problems. The use of a sand f1uidised bed to
scour surfaces in water systems, with specia1 reference to sca1ing from
geotherma1 waters, has a1so been attempted. The scraped surfaee heat
exchanger is a specia1 form of the se1f c1eaning heat exchanger.
Low residence times in equipment before the proces s stream reaches the
heat exchanger ean be a he1p in avoiding fou1ing conditions. Long
residence times may give an opportunity for physica1 processes (such as
agglomeration), or chemica1 reactions to occur which in turn, acce1erate
the fou1ing process.
4.1.2 Materia1 of construetion The choice of the materia1 of
construetion for the heat exchanger is important. Judicious choice wi11
avoid the possibi1ity of corrosion fou1ing. It may a1so be possib1e to
ensure that the surfaee does not encourage chemica1 reaction or deposition
by its own surfaee conditions (e.g. composition or surfaee charge).
The surfaee roughness of the materia1 of construetion cou1d be
important in the promotion of fou1ing; rough surfaces in general, appear to
favour deposit growth. On the other hand, smooth surfaces are known to be
1ess hospitab1e to dirt 1ayers. Coating surfaces with a film of polymer or
a glass 1ayer, ean be effective in reducing fou1ing problems even though
the film itse1f constitutes a resistance to heat transfer. High polish and
p1ating may produce the same resu1ts. Much current research is being
directed to obtaining quantitative data on these aspects.
By carefu1 choice of process plant design ahead of the heat exchanger,

fou1ing conditions may be avoided. Proper choice of the materia1 of
construetion in associated plant wi11 reduce the avai1abi1ity of particles
of corrosion produet (e.g. Fe 2 0 3 ) which cou1d be a nuisance in heat
exchangers. In the same way the avoidance of conditions enab1ing chemica1
reactions to proceed, which may be a source of particu1ate or crysta11ine
fou1ing or polymer formation on the surface, cou1d be he1pfu1.
4.1.3 Plant layout It has a1ready been demonstrated that the complete
@ProcessEng
elimination of fou1ing in heat exchangers is not 1ike1y to be possib1e, and

that c1eaning and maintenance wi11 be an unfortunate result. It will be
necessary therefore, where choice exists, such as in the design of
comp1ete1y new plant, to ensure that the design does not hinder cleaning or
maintenance.
The first important feature is "accessibility"; it is important both
IO
from a maintenance and cleaning point of view to have space around the heat
exchanger. Such conditions are most important where some form of drilling
out of say, the tubes in a shell and tube heat exchanger are concerned.
A second feature is the location of the equipment on a factory site.
Fouling rates could be accelerated in air blown coolers if the air
contained a relatively high concentration of dust particles or corrosive
fumes. Even moving exchangers short distances could have considerable
impact on the reduction of a potential fouling problem.
4.1.4 On-line cleaning At the design stage of a process plant it is

valuable to consider "on-line" cleaning since the adoption of the system
may demand specific design considerations.
If chemical cleaning is anticipated (or the use of antifoulants for
that matter) it will be appropriate to consider the installation of
suitable cleaning equipment. It would be useful to consider this at the
design stage, rather than to leave it till later (to see what happens)
since it would provide a much better overall design. Some further
techniques are described in Section 4 which could be considered at the
design stage.
The Tapprogge System which employs the circulation of sponge rubber
balls through a heat exchanger system is better incorporated in the design
rather than as a retrofit technique. The method is particularly suitable
for cooling water systems, where large quantities of water are used (say a
power station) on a "once through system" and biologicaljparticulate
deposition is likely to be a problem, and temperatures are not high. The
cost savings can be extremely high. Although there is an additional
capital cost associated with the equipment, the "pay back" time could be
well below l year, which makes the system attractive. Clearly if the
system is incorporated in the design the cost penalty is likely to be
reduced.
It has been claimed that magnetic devices have reduced the problem of
fouling particularly wherever inorganic scaling from water systems is
concerned. The use of turbulence inducers has also been claimed to be
effective against certain deposits, particularly where temperature is
important.
A great deal of development work needs to be done with both the systems
before they can be used with any confidence.
4.2 Fouling and plant operation

The expectation that fouling will occur in a heat exchanger has
implications for the operation of equipment.
If a heat exchanger has been designed with the potential fouling
process in mind, the limitations on the variables made in the design must
be respected during operation. Changes in flow conditions and temperature

from those called for in the specification could have significant effects
of the extent of the fouling. At the same time it has to be recognised
that this may not be always possible, where plant control to achieve the
desired product may dictate otherwise.
4.2.2 The use of additives ~ antifoulants) There is an increasing
use of additives, usually termed antifoulants to control the incidence of
@ProcessEng
fouling in heat exchangers. Many are proprietary and little is known about
their composition and the basis for their action. These compounds often
provide a combination of differing functions depending upon the nature of
the problem and the contributory factors. Where dissolved salts are likely
to be a nuisance, precipitation before entry to the exchanger may be
possible. The use of corrosion inhibitors and biocides may also
Il
provide relief. Where micro-organisms are concerned, avoidance of

situations which allow the solution to become aerated or to contain
bacterial nutrients, will do much to reduce the incidence of fouling. In
severe conditions of particulate fouling, it might be necessary to include
some form of filtration or settling proces s prior to the heat exchange
system.
4.3 Heat exchanger cleaning
Each situation will require special attention and often unique
solutions will be required; it is therefore impossible to give detailed
information for specific problems; however, the following summarises the
general situation.
4.3.1 Ghemical cleaning The technique has probably been practised for
many years for the removal of deposits from metal surfaces in process
plant. Present techniques are based on experience gained from pickling
steel and boiler cleaning using "fill and soak" methods. Typical deposits
which may be removed by chemical cleaning may involve organic or inorganic
material, derived as described earlier, and may range from fats to viscous
material, and rust to phosphates.
The choice of chemical treatment will depend upon the nature of the
deposit, its quality and chemical composition, i.e. whether it was hard or
soft or needs an organic solvent or mineral acid to dissolve it. Some
deposits will not respond at all to chemical treatment, and would need an
alternative method of removal.
4.3.2 Mechanical cleaning Techniques using mechanical means of
removing deposits are often used where chemical cleaning does not offer the
ability to deal with the problem; either because the deposit c anno t be
chernically affected or on grounds of accessibility.
Water jets and high pressure water lances, may be used for the removal
of external deposits. The effectiveness depends very much on access and
care is needed in application, to prevent damage to plant and injury to
personnel. Brushing techniques may be applied to external surfaces where
access is possible and the deposit is not difficult to dislodge.
Drilling and rodding of tubes is often used for tenacious deposits
inside the tubes. Good access is required, and care is again required to
prevent damage to the equipment.
Blast cleaning is the best method of preparing steel surfaces in
preparation for the application of coatings. Suitable abrasive material is
propelled at high velocity by a blast of air to impinge on the surface to
be cleaned.
"Soot blowing" is a technique which was developed for boiler plant and
the combustion space/flue gas heat exchangers in fired equipment. It is,
in simple terms, the removal of particles by the use of air or steam
blasts i.e. higher velocity than is present in the gas stream during normal
operation. Water washing has also been used to remove carbonaceous
deposits from boiler plant.
The use of sonic vibrations has been tried with some success in certain
applications. In some situations, thermal shock may be used to remove
deposits but this might cause damage to the heat exchanger unless carried
out with great care.
@ProcessEng
s. SOME EXAMPLES OF FOULING

The following are some typical industrial fouling problems which
exemplify the difficulties which may have to be faced in plant operation.
S.l Ghemical and refining operations
It has been reported (4) that a shell and tube for oil heater, fouled
extremely rapidly. Fig.3 shows that over a per iod of around 3 months the
12
overall heat transfer coefficient decreased by something like 40%.

Gleaning and installation of turbulence promotors not only enhanced the
heat transfer but reduced the fouling problem. It is anticipated that this
was an example of reaction fouling, the effectiveness of the turbulence
promotor in reducing the fouling, was probably due to the lowering of
the temperature at the heat exchanger surface.
In a steam cracking plant, the liquid organic feed vapouriser was
placed in the flue gases from the cracking furnace. Such a design would
seem to be admirable from an energy conservation point of view. However
the tubes of the vapouriser rapidly fouled up to such an extent that the
Enhanced performance
40 .e------__e__.
lL 30
Ol
~nal
<II
"O performance
.::!:. 20
e-e
::J
ro
~ 10
c>
~ O~~ __~~_L~ __ ~~~-L~_ _~_ _~
o 2345678910
Months of service
FIGURE 3 The effect of turbulators on the performance of a heat exchanger
plant had to be shut down every three weeks for cleaning. The blockage was
caused by the cracking of the organic liquid in the vapouriser tubes giving
rise to heavy carbonaceous deposits, and some corrosion.
The remedy was to operate a separate vapouriser using steam as the
heating medium so that the temperature on the metal heat-transfer surfaces
was very much lower in the system as designed i.e. below the temperature at
which cracking occurs. Under the new conditions the vapouriser was free of
problems for well over twelve months.
Van Nostrand et al (5) report on a typical refinery crude preheater
chain in which the heat transferred fell by about 42% over a twelve month
period. The fall in heat transferred was reduced to about 18% in a twelve
month per iod by the use of antifoulants.
The feed preheater to an alcohol/water distillation column attached to
a solvent recovery plant became inoperable af ter one week. The problem was
due to the accumulation of suspended resinous materials present in the feed
solution. The particles originated from an impregnation proces s which used

resin/alcohol solutions to impregnate paper and fabric. The impregnated
material was subsequently dried in a continuous, air blown dryer. Alcohol
was recovered from the air stream in bubble cap absorbers, but the resinous
material accumulated on the plates where it had time to polymerise.
Ghanging the internals of the absorbers, where the residence time was
greatly reduced, resulted in a much cleaner feed preheater to the
@ProcessEng
distillation column.
5.2 Gooling water systems
The problems in cooling water systems arise from biological fouling
accompanied by scale formation, particle deposition and corrosion. The
problem of fouling is extremely important in large power stations
particularly where "once through" cooling water is passed through the
13
condensers. The steam side pressure in the condenser, i.e. from the
turbine, is all important from the point of view of efficient power
generation. The lower the condenser pres sure the greater the work obtained
from a given steam pressure. Poor heat transfer in the condenser results
in a higher condenser pressure, with adverse effects on turbine efficiency.
In a particular power station, the condenser pressure was consistently
well above the target pressure due to fouling on the cooling water side of
the condenser. The fitting of a Tapprogge system restored the condenser
target pressure to that required, and over a twelve month test per iod it
was maintained at a steady value with a reduction in operating costs.
In other cooling water systems the use of chemical additives including
biocides, has produced satisfactory operation.
5.3 Combustion systems
A wide variety of fuels are used in industry ranging from light
"clean" gases to heavy "dirty" fuel oils. The fouling due to combustion of
these fuels is extremely wide ranging and can cover loose deposits of
carbon particles, hard deposits of mineral matter, and corrosion products.
Blauenstein (6) outlines an extensive trial on a 300 MW tangentially-
fired boiler burning a res i dual oil analysing 3.4 to 3.5% sulphur, 80-
100 ppm vanadium, 25-40 ppm sodium and 3.47% asphalt. Low excess air of
0.55-0.7% O2 was used but the operator had to wash the air heater eve ry
three weeks because of pres sure drop across the heater increased by around
100%. (i.e. from about 75-165 mm water gauge).
In the trial dispersed magnesia was injected into the combustion space
which reduced the fouling problem. The data obtained showed a 60%
reduction in the total particulate emissions. A further benefit was a 50%
reduction in metallic corrosion as indicated by higher pH ash and confirmed
by iron determinations on the ash. There was also a significant
improvement in boiler heat transfer.
5.4 Food industry
Many of the heat transfer operations in the food industry are
associated with boiling, sterilising and "cooking". In general the
operations involve temperatures which are obtained by the use of steam, but
as in all industries, there are exceptions.
A heat exchange system which has many characteristics of heat
exchangers in the chemical and oil industries, involves deep fat frying
having many of the fouling mechanisms described earlier. Often the fryer
temperature is maintained by passin& the hot oil through a heat exchanger
placed in a fired heater. On the flue gas side there could be problems of
particulate deposition and possibly corrosion, on the heat transfer
surfaces in contact with the flue gases. The quality of the fuel and the
maintenance of good combustion conditions will be factors in the fouling
process. On the hot oil side of the exchanger, particles of say carbonised
food from the fryer may become attached to the surface together, possibly,
with the products of cracking or "cooking on". In this example the fouling
process is seen to be extremely complex. At the same time there are no
problems of biofouling under normaloperating conditions, because of the
high temperatures involved.
Much processing, particularly sterilisation, is vulnerable to fouling
in the heat exchangers. The nature of the deposit is extremely complex,
@ProcessEng
and depends very much on the temperature of operation, residence time in

the exchanger, and the quality of the milk supply. Milk from two different
sources which apparently are alike in characteristics, can give rise to
very different fouling problems. The breed of cattIe, the pas ture quality
and the soil upon which it grows, all contribute indirectly to the fouling
problem.
14
The problem of fouling in the food industry is particu1arly troub1esome

for, apart from the additional costs due to heat transfer reduction, there
is the extreme1y important need to maintain the qua1ity of the product.
Production of fou1ing, can give rise to problems of texture, taste and
sometimes aroma of food whch in today's competitive wor1d, need to be of
top qua1ity to satisfy the demands of consumers.
6. CONCLUDING REMARKS
The incidence of fouling in heat exchangers can represent excessive
costs in terms of capita1 invested, and in the maintenance of equipment.
A1though some investigational work has been undertaken in the various areas
of fou1ing, a thorough understanding of the mechanisms involved has not
yet been achieved. The situation is not surprising in the light of the
comp1ex interaction between the many variables invo1ved in the proces s of
fou1ing. However, certain guide lines are available, which although they
may not e1iminate the problem comp1ete1y, wi11 go some way to mitigating
the difficu1ties.
Much of the deve10pment work in relation to fouling has been conducted
with petroleum and chemica1 processing, coo1ing water systems and
combustion applications in mind. Progress has been made but there remains
a great deal to be done if the problem of fou1ing is to be reso1ved.
REFERENCES
1. Bott, T.R., Chem.Engr., C.E. 126, June 1969.

2. Epstein, N., in Somerscales, E.F.C. and Knudsen, J.G_., Eds. "Fou1ingof
Heat Transfer Equipment" , Hemisphere Pub1ishing Corp., Washington,
1981.
3. Yung, B.P.K., Ph.D. Thesis, Univers ity of Birmingham, 1986.
4.
5. Van Nostrand, W.L. in Somersca1es, E.F.C. and Knudsen, J.G., Eds.
"Fou1ing of Heat Transfer Equipment", Hemisphere Publishing Corp.,
Washington, 1981.
6. Blauenstein, E. in R.W. Bryers Ed., nAsh Deposits and Corrosion due to
Deposition in Combustion Gases", Hemisphere Publishing Corp. ,
Washington, 1977.
@ProcessEng
GENERAL THERMAL FOULING MODELS
NORMAN EPSTEIN
Department of Chemica1 Engineering
University of British Columbia
Vancouver, B.C., Canada V6T 1WS
1. INTRODUCTION
If we describe the progress of a therma1 fou1ing process by a plot of
therma1 fou1ing resistance, Rf , against time, t, then the three upper
curves of Figure 1 represent the most common and primitive, though not the
on1y, eonfigurations observed in praetice. These are designated linear,
fa11ing rate (non-asymptotie) and (failing rate) asymptotic, respeetive1y.
A de1ay period, t D, is often, but not a1ways and not eonsistent1y,
observed before any appreciab1e fou1ing is recorded af ter starting an
experiment or a proeess with an apparent1y e1ean heat transfer surface.
The de1ay period is frequently mueh 1ess reproducib!e than the subsequent
fou1ing curve. The clean1iness of the initial heat transfer surface ean
be a crucial factor. Thus the presence of a measurable delay period in
Figure 2 for the up per heater but none for the spare heater is probab1y
re la ted to the faet that the former was reported by the operator to be in
a e1eaner condition than the latter at time zero [1].
The importance of asymptotie as opposed to simple (non-asymptotic)
fal1ing rate behaviour is that it raises the possibi1ity of indefinite
operation, without e1eaning, at the asymptotic condition [2]. It shou1d
be noted that, un1ess the fou1ing proeess has been earried on for a
suffieient1y 1cng period of time, one cannot be sure whether or not
apparent1y linear behaviour is real1y the start of what would eventuaily
turn into a falling rate mode, nor whether a fal1ing rate eurve is rea11y
the beginning of u1timately asymptotic behaviour. This is espeeia1ly true
when, as is often the case especia1ly for industria1 operation, there is
scatter in the data eo1leeted. An examp1e is the aforementioned Figure 2
in which are plotted Rf (determined as U- 1 - ~l) vs. t for two in-plant
Kraft pulp liquor heaters used in conjunetion with a Kamyr eontinuous
digester [1]. The spare heater clearly shows falling rate behaviour, but
could easily be on the way to an asymptotie mode had it not been shut down
for cleaning. Similarly the up per heater, af ter a SO-hour delay period,
shows apparent linear behaviour, but this toa might be turning to fal1ing
rate and eventua1ly even to asymptotic behaviour.
The bottom curve of Figure 1 exemplifies a not infrequently observed
"sawtooth" eonfiguration [3,4] in which a net rising curve is periodieally
interrupted by preeipitous falls in the fouling resistanee. The immediate
short range rises wil1 usually fol1ow one of either linear, falling rate
or asymptotic fouling modes, while the net longer-range rise wi11 a1so
@ProcessEng
describe one of these shapes, though not necessarily the same one as for
the short-range behaviour. The periods between fa1ls are not neeessarily
constant, while the precipitousness of the falls is attenuated when the
fouling is monitored globally instead of locally.
15
L. F. Melo et al. (eds.), Fouling Science and Technology, 15-30.

16
Let us now formulate In simple terms the more entrenched models for
linear, falling rate and asymptotic fouling, respectively. To illustrate
the effect of fluid velocity and of surface temperature on the fouling
process, the opposite extremes of mass-transfer control and surface-
reaction (or surface attachment) control will be considered in each case,
as will laminar and turbulent flow parallel to the heat transfer sur face
in cases where fluid flow assumptions are explicitly involved. The models
do not encompass the delay period but come into play once that period is
completed.
2. LINEAR FOULING
If we assume, af ter Kern and Seaton [5] and many subsequent
investigators, that the net fouling flux, ~, is the difference between a
gross deposition flux, ~d' and a removal flux, ~r' then a linear fouling
curve will result from a constant difference between ~d and ~r. This
situation will most usually occur under conditions where deposition
proceeds at a constant rate and deposit-removal is negligible, so that
dRf/dt (=~/Pfkf) is directly proportional to ~d.
For crystallization fouling, when there is stoichiometric equality in
solution of crystallizing cat ions and anions, we can write [6]
~d (l)
-.l + l
For most sparingly water-soluble salts, n ~ 2 [7]. Assuming a constant

value of cb and of fluid velocity, ~d will remain constant only if the
saturation concentration, c sat ' of the crystallizing species at the
liquid-solid interface temperature Ts remains constant, which can only be
effected if a constant heat flux is applied at the fouling surface.
Equation (1) with c sat =° applies also to chemical reaction fouling if
one neglects back-diffusion of the deposit [8]:
(2)
1
kr n-l
C s
and to colloidal particle deposition [9]. for which electrokinetic theory

indicates additionally that n = 1 [10]:
(3)
@ProcessEng
17
Equation (3) applies also to first order chemical reaction fouling. For
in situ corrosion fouling [11] one must add an additional term to the
denominator of Equation (2) to account for oxygen diffusion through the
corrosion deposit, and further modify this equation to account for the
fact that the corrosion chemical reaction occurs at the wall rather than
at the fluid-deposit interface:
~d (4)
1 + +
However, in this case, unless the term yf/D f is negligible relative to the
sum of the other two terms in the denominator of Equation (4), a constant
value of ~d and hence of dRf/dt (assuming ~r= O) is precluded, since
dRf=dyf/k f •
When fluid mechanics and hence mass transfer controls, Equation (1)
reduces to
~d (5)
(e.g. for crystal growth at sufficiently low fluid velocities), while

Equations (2) and (3) reduce to
(6)
The effect of temperature on ~d then manifests itself primarily through

its influence on diffusivity of the key component (e.g. the precursor
reactant or the particles), and hence on km' and is therefore relatively
small compared to its effect under the opposite extreme of
surface-reaction control. Assuming hydrodynamically fully developed
laminar flow in a tube [12], km and hence ~d vary as (v)1/3 for the common
case of a developing concentration boundary layer and become independent
of v for the tarer case of a fully developed concentration boundary layer.
For fully developed turbulent flow, on the other hand, km and he~ce ~d are
directly proportional to v raised to a power between 0.8 (smooth surface,
dissolved key component) and unit y (fully rough flow, microparticulate key
component).
When sur face attachment controls, cb~cs and Equation (1) reduces to
(7)
(e.g. for crystal growth at sufficiently high fluid velocities), while

@ProcessEng
Equation (2) reduces to
~d (8)
18
and Equation (3) to
(9)
The effect of increasing surface temperature is then to increase kr and

hence ~d since an Arrhenius-type equation relates the sur face integration,
reaction or attachment rate constant to the surface temperature Ts :
(10)
The large values of activation energy, E, which can occur especiaily for
chemical reaction fouling, give rise to a very large effect of Ts • In the
case of microparticulate fouling, however, this surface temperature effect
may be counteracted and hence confounded by thermophoresis of fine
particles from a hot surface to a colder fluid, especiaily if the latter
is a gas. In contrast to Ts ' fluid velocity now has no effect on ~d.
It should be mentioned at this point that, especiaily in the case of
particulate deposition, an alternative more empirical approach to
attachment used by some investigators is to modify a relationship such as
Equation (6) for a particle diffusion regime by a sticking probability S,
so that
(11)
where S = 1 for mass-transfer control and S < 1 when surface attachment is

important but not fully controiling, while i ~ 1. It has been argued [1]
that
-E/RT s -E/RT s
S e e (12)
~s
@ProcessEng
19
where j can vary from l for laminar flow to 2 for fully rough turbulent
flow. Combination of Equations (11) and (12) giv~s
4>d ex (13)
where y = j - i . Since generaIly j > i, therefore y > l and 4>d decreases

as v increases, in contrast to the increase of 4>d with v when stickability
is perfect.
3. FALLING RATE FOULING

A steadily decreasing difference between deposition flux and removal
flux, in which the difference approaches zero only as Rf approaches
infinit y, results in a non-asymptotic falling rate fouling curve. This
situation commonly occurs where deposit-removal is negligible, as in
scaling by single uncontaminated salts [13] or in monodispersed colloidal
particle deposition from an isothermal laminar flow field [14], and where
the deposition flux is subjected to an auto-retardation mechanism. Some
auto-retardation mechanisms which have either been observed or postulated
include
1. A decreasing oxygen diffusion rate in corrosion fouling as
the deposit thickens (i.e. increase of yf/D f in Equation 4).
2. The effect of deposit blockage in increasing the scouring
velocity and thereby suppressing attachment (i.e. reducing S)
via Equation (13).
3. A progressive change in surface charge due to deposition of
oppositely charged colloidal particles [15].
4. An ever-weakening wall catalysis of chemical reaction fouling
as the deposit buiIds up on the wall.
s. A decrease of deposit-fluid interface temperature, Ts ' with
time.
The last of these auto-retardation mechanisms is the basis for the model
of Hasson [16] and Reitzer [17] for inverse solubility scaling, derived as
follows.
For crystal growth, without removal, of an inverse solubility salt
from a solution saturated with respect to thi s salt at a concentration cb
and temperature Tb to a superheated surface at a temperature T s (>T b ) and
concentration c sat (>cb)' where c sat is the solubility of the salt at T s '
@ProcessEng
20
(14)
in which the lumped coefficient K and the lumped exponent n' [18] can be
related to ~, kr and n via Equation (1). Assuming linearity between salt
solubility and temperature over the range of concentration involved,
(15)
« (q)n' (16)
for a constant surface coefficient of heat transfer. In general,
~T
q U~T (17)
Where ~T, the overall temperature difference between the hot and cold side
of the heat exchanger, remains constant with time, as in the case of an
evaporator, combination of Equations (16) and (17) leads to
(18)
Integration of Equation (18) from t=O, Rf=O to any (t,R f ) results in
(R o+R f )n'+l - Ro n'+l (19)
which yields a non-asymptotic falling rate curve of Rf vs. t. Equation

(19) can be written alternativelyas
1 1 K't (20)
Un'+l
For mass-transfer control, K=km and n'=l, while for surface-reaction

control, K=k r and n'=n~2 for most sparingly soluble salts [7]. The
applicability of n'=l and n'=2 to scaling of inverse solubility salts in
low velocity non-stirred evaporators and high velocity well agitated
@ProcessEng
boiling systems, respectively, has been demonstrated previously [9].

21
It is of interest to note that Equation (20) with n'=l was originally

derived by McCabe and Robinson [19], who argued that for scaling of
evaporators,
q Ul'.T l'. T (21)
Assuming constant l'.T as before, and again integrating Equation (21) from
the initial condition t=O, Rf=O, the result is
R2 (constant)t (22)
o
which is equivalent to Equation (20) with n'=l.

The firs t of the auto-retardation mechanisms listed above applies to
in situ corrosion fouling, for which, on the assumption that the wall
corrosion rate is ve ry rapid compared to the oxygen transfer rate to the
wall, Equation (4) reduces to
<Ild (23)
as noted by Galloway [20]. But <Ild « dRf/dt assuming no deposit removal,

km constant for fixed operating conditions and vf « Rf , whence Equation
(23) reduces to
a
(24)
Integrating Equation (24) from the initial condition t=O, Rf=O, results in
(25)
which is similar in form to Equation (22) and again yields a non-

asymptotic falling rate fouling curve.
@ProcessEng
22
4. ASYMPTOTIC FOULING
A steadi1y decreasing difference between deposition flux and removal
flux, in*which the difference approaches zero as Rf approaches a finite
va1ue, Rf , resu1ts in an asymptotic fa11ing rate curve of Rf vs. t.
Removal of the deposit may or may not begin right af ter deposition has
started. That it do es so is an assumption implicit in the removal model
origina11y proposed by Kern and Seaton [S], according to which ~d
increases linearly with deposit thickness Yf and hence with mf' the
deposit mass per unit surface area:
bm f (26)
That removabi1ity increases linearly with deposit thickness has been

subsequent1y rationa1ized via a theory of deposit-shattering by therma1
stresses [21]. a1though the continuous co-existence of removal with
deposition (especia11y particu1ate deposition) is more readily
rationa1ized in turbulent [22] than in laminar flow [9], the fou1ing flux
at any time t according to this assumption is then given by
(27)
or
(28)
where (dRf/dt)t=O = ~d/Pfkf = constant. Integrating Equation (28) from

the initial condition t=O, Rf=O to any (t, Rf ) resu1ts in the c1assica1
Kern-Seaton [S] equation:
-tIt
Rf R*f (1 - e c) (29)
where t c l/b time constant and

R*f tc(dRf/dt)t=O ex t c • ~d (30)
Equation (29) is plotted in Figure 3. According to Kern and Seaton [S],

the time constant t c is inverse1y proportional to the shear stress ~s on
the heat transfer surface, whi1e according to Taborek et al. [3], it is
a1so direct1y proportional to the deposit strength ~:
@ProcessEng
23
l a _4>_ (31)
b 't s
Several interpretations can then be given tc' the first three of which are
shown in Figure 3, and the next two by Equation (31):
l) It is the time it woukd take to arrive at the asymptotic
fouling resistance, Rf , if the fouling proceeded linearly at
the inital deposition rate.
2) It is the actual time required to achieve 63.2% of the
asymptotic fouling resistance.
3) It is one-third the actual time required to achieve 9S% of
the asymptotic fouling resistance. It is generally
recommended that t for an experimental run be at l~ast equal
to 3t c in order to determine areliable value of Rf [23].
4) It is the average residence time of an element of fouling
deposit on the heat transfer surface.
S) It is a quantity which gets smaller as the fluid shear stress
at the sur face increases and gets larger as the deposit
strength increases. Many investigators have found an inverse
variation of t c with 't s ' while Morse and Knudsen [23] have
reported a direct variation of t c with crystalline deposit
purity and therefore presumably with deposit strength.
6) If we assume that the removal of deposits is caused by
turbulent bursts at the heat transfer surface (a mechanism,
of course, only available in turbulent flow) as proposed by
Cleaver and Yates [22,24], then assuming a removal efficiency
of 100%,
Average time between bursts (32)

Fraction of sur face covered
by bursts at any instant
where ~ ~ O.OOS or less. An efficiency of 100% signifies

that each turbulent burst would remove all the deposit which
it covered, an event that is likely only for the most weakly
adhering of deposits. Most fouling deposits would have
varying degrees both of coherence and of adherence to the heat
transfer surface, so that the removal efficiency E could be
orders of magni tude below 100%. In general, then,
(33)
Many investigators, when they h~ve found asymptotic fouling, have

attempted to correlate both t c and Rf with fluid velocity and surface
@ProcessEng
temperature. Note that from both Equations (31) and (33),

24
o: _<V_ (34)
'ts
and therefore from Equation (30),
(35)
where the expressions for ~d developed under LINEAR FOULING apply here as
well. If we assume no dependence of deposit strength <V on fluid velocity,
then the velocity dependence of 'ts is always greater than that of <V~d'
irrespective of regime (laminar vs. turbulent, m~ss-transfer control vs.
surface-reaction control), so that both t c and Rf fall with increasing
velocity - aresult which has been found by many investigators [1,25,26J.
There is, howver, some weak evidence [3,27J that <V may be affected by
fluid velocity, the greater the velocity the greater the strength of the
surviving deposit. Thus Pinheiro [28J has suggested that
(36)
where o: can vary between O and 2. Re also adopted Equation (13) for ~d'
in which he a1l~wed y to vary between O and 1. Assuming that 'ts varied
directlyas (v) , i.*. fully rough turbulent flow, Pinheiro worked out how
both b (=l/t c ) and Rf (and hence also ~d by Equation 30) varied with v
from Equation (36) for <Vand Equation (3) for ~d' assuming the latter
col1apsed to Equation (6) for mass-transfer control and to Equation (13)
for surface-reaction control, i.e.
(37)
_1_+ (v)y
km -E/RT s
k'e
By treating various combinations of 0:=0, 1 and 2 with y=O for

mass-transfer control and with y=O and 1 for s~rface-reaction control, he
genera ted many possible variations of ~d and Rf with v; so that almost

any result in the literature could thus be fitted. Unfortunately, little
re1iab1e information or insight is available on how to determine the
crucial empirical exponents o: and y in advance for any given fouling
process, so that the usefulness of Pinheiro's versati1e "generalized"
model is presently limited.
@ProcessEng
25
The variation of R; with Ts is eonfounded by the presence of ~ in the

numerator of Equation (35), sinee there is recent evidenee that te and
henee ~ for some seales deerease as Ts inereases [29] for a fixed fluid
veloeity v, bulk composition eb and bulk temperature Tb' whieh is
eonsistent with the hypothesis of deposit-weakening by thermal stresses
prop~sed by Loo and Bridgwater [21]. Thus an Arrhenius or any other plot
of Rf against Ts would be a eomposite of the expeeted inerease of ~d as
Ts inereases with the eorresponding deerease of~. To separate these
opposing effeets, it is desirable that ~d or (dRf/dt)t=O be isolated and
plotted against T s ' Sinee from Equation (30),
' dRf \
( (38)
~t=O
* e , or preferably a measured value of (dRf/dt)t=O [26,30],
a plot of Rf/t
should be plotted in the Arrhenius form against l/T s to reveal how the
gross deposition flux varies ~ith T s ' assuming eb is constant. The
extremes of mass-transfer and surfaee-reaetion control then conform to the
predietions under LINEAR FOULING.
It should be noted that Equation (29) ean alternately be derived on
the basis of a gross deposition rate whieh deereases linearly with
inereasing Rf and a constant (ineluding zero)removal rate. Auto-
retardation meehanisms sueh as those mentioned in the previous seetion
eould eoneeivably give rise to sueh behaviour. There are also situations
where it is appropriate [31] to combine a non-linearly falling deposition
rate sueh as that given by Equation (14) or (18) with a Kern-Seaton
removal term, Equation (26).
5. SAWTOOTH FOULING
The oeeurrenee of this fouling mode under conditions of steady flow,
fluid temperature and eoneentration implies periodie shedding of deposit
due to periodie weakening of the deposit to avalue of ~ below some
eritieal value. Sueh weakening eould be eaused by ehanges in erystal
strueture, ehemieal degradation, developing thermal stresses or slow
poisoning of miero-organisms in a biofilm. The eritieal value of ~ would
be sue h that the smaller of the adhesive or eohesive force of the deposit
is just exeeeded by the hydrodynarnie forces (e.g. ~s or turbulent bursts)
tending to disrupt the deposit.
The preeeding models ean be used to represent both the short-range
rises and the overall rise in the sawtooth eurve. The persistenee of an
underlying deposit while the rest of the deposit is periodieally shed
eould be eaused by the eo-existenee of two different types of fouling and
their respeetively different deposits, e.g. biofilm formation, weakening
and periodie removal over an underlying developing eorrosion deposit [32].
Periodie removal eou1d also be eaused by aeeidental disturbances
(hydrodynarnie or thermal) of partieulate deposits partially bound to a
@ProcessEng
metal wall, e.g. byerevice eorrosion produets [33], where the cessation
of ereviee eorrosion as the tube wall beeomes uniformly eovered with
deposit, rather than eontinuous deposit removal, eould aeeount for the
observed short-range asymptotie fouling mode.
26
NOTATION
A Arrhenius coefficient, m3n-2.kgl-n.s-l
a constant in Equation (24), W- 2 .m 4 .K 2 .s- l
B constant in Equation (24), W- l .m 2 .K
b removal constant, s-l
cb bulk concentration of key component (foulant or precursor), kg.m- 3
concentration of key component adjacent to surface, kg.m- 3
saturation concen!~ation of crystallizing species at surface

temperature, kg.m
concentration of key component, e.g. O2 , adjacent to wall, kg.m- 3
effective 2if!ysivity of'key component, e.g. O2 , through fouling

deposit, m .s
E activation energy, J.mol- l
e base of natural logarithms (=2.718)
i exponent on v in Equation (11)
j exponent on v in Equation (12)
K overall crystal growth rate constant, m3n '-2. kg l-n' .s-l
constant in Equation (18), W- l - n ' .m 2+ 2n ' .K l + n ' .s-l
K' constant in Equation (20) = (n'+l)K l , W- l - n ' .m 2+ 2n ' .Kl + n ' .s-l
kf thermal conductivity of fouling deposit, W.m-l.K- l
convective mass transfer coefficient, m.s- l
attachment or surface-reaction rate constant, m3n-2.kgl-n.s-l

k' constant in Equation (37), mY.s-Y
mass of deposit per unit surface area, kg.m- 2
n order of surface reaction
n' order of overall crystal growth proces s

@ProcessEng
q heat flux, W.m- 2

27
R universal gas constant = 8.314 J.mo1- 1 .K-1
Rf t~irm~l resistance of fou1ing deposit for unit surface area,

W .m.K .
R*
f asymptotic va1ue of Rf , W-1 .m.K
2
Ro
-1
1 / Uo' W .m.K
2
S sticking probability
Tb bulk fluid temperature, K
Ts surface, i.e. fluid-deposit interface, temperature, K
~T hot fluid temperature - co1d fluid temperature, K
t time af ter end of delay period, s
tc time constant (= l/b), s

tn de1ay time, s
U overall heat transfer coefficient, W.m- 2 .K- 1
Uo overall heat transfer coefficient at time zero, W.m- 2 .K- 1
v average or bulk fluid velocity, m.s- 1
v * friction velocity = (~s/p)1/2, m.s- 1
thickness of fou1ing deposit, m
exponent in Equation (36)
fraction of surface covered by turbulent bursts at any instant
y exponent in Equation (13) = j-i
fractional removal efficiency by turbulent bursts
fluid viscosity, kg.m- 1 .s- 1

p fluid density, kg.m- 3
density of fouling deposit, kg.m -3
~s fluid shear stress at surface, N.m- 2

@ProcessEng
net fouling flux, kg.m- 2 .s- 1

28
~d gross deposition flux or stoichiometrically equivalent precursor

flux, kg.m- 2 .s- l
deposit removal flux, kg.m- 2 .s- l
deposit strength factor or bond resistance
REFERENCES
1. Watkinson AF and Epstein N: Particulate Fouling of Heat Exchangers.

Proc. 4th Intern. Heat Transf. Conf., Vol. 1, Paper HE 1.6, Elsevier,
1970.
2. Kern DQ: Heat Exchanger Design for Fouling Service. Chem. Eng. Prog.,
Vol. 62, No. 7, pp. 51-56, 1966.
3. Taborek J, Aoki T, Ritter RB, Palen JW and Knudsen JG: Fouling - the
Major Unresolved Problem in Heat Transfer. Chem. Eng. Prog., Vol. 68,
No. 2, pp. 59-67 and No. 7, pp. 69-78, 1972.
4. Wahl EF: Scale Deposition. Chapter 5 of Geothermal Energy Utiliza-
tion, Wiley, New York, 1977.
5. Kern DQ and Seaton RE: A Theoreticai Analysis of Thermal Surfaee
Fouling. Brit. Chem. Eng., Vol. 4, No. 5, pp. 258-262, 1959.
6. Epstein N: Thinking about Heat Transfer Fouling: A 5 x 5 Matrix.
Heat Transf. Eng., Vol. 4, No. 1, 1983.
7. Konak AR: A New Model for Surfaee Reaction-controlled Growth of
Crystals from Solution. Chem. Eng. Sci., Vol. 31, pp. 147-151, 1976.
8. Crittenden B and Kolaczkowski S: Mass Transfer and Chemical Kinetics
in Hydrocarbon Fouling, in Fouling - Science or Art?, pp. 169-187,
Inst. of Corrosion Sci. & Tech. Conf., University of Surrey, U.K.,
1979.
9. Epstein N: Fouling in Heat Exchangers and Fouling: Technical Aspects,
in Fouling of Heat Transfer Equipment, Somerscales EFC & Knudsen JG,
eds., pp. 701-734 and 31-53, Hemisphere, Washington, D.C., 1981.
10. Ruckenstein E and Prieve DC: The Rate of Deposition of Brownian
Particles under the Action of London and Double-Layer Forces.
J. Chem. Soc. Faraday II, Vol. 69, pp. 1522-1536, 1973.
ll. Somerscales EFC: Corrosion Fouling, in Fouling in Heat Transfer
Equipment, 20th ASME/AIChE Heat Transfer Conference, HTD-Vol. 17,
pp. 17-27, ASME, New York, 1981.
12. Epstein N: Fouling Models: Laminar Flow, in Low Reynolds Number Flow
Heat Exchangers, Kakac S, Shah RK & Bergles AE, eds., pp. 973-979,
Hemisphere, Washington, D.C., 1981.
13. Hasson D: Precipitation Fouling, in Fouling of Heat Transfer

Equipment, Somerscales EFC & Knudsen JG, eds., pp. 527-568,
14. Bowen BD and Epstein N: Fine Particle Deposition in Smooth Parallel-
Plate Channeis. J. Col1oid Interface Sci., Vol. 72, pp. 81-97, 1979.
15. Bowen BD: Fine Particle Deposition in Smooth Channeis. Ph.D. Thesis,
Univers it y of British Columbia, Vancouver, B.C., Canada, 1979.
@ProcessEng
16. Hasson D: Rate of Decrease of Heat Transfer Due to Scale Deposition.

DECHEMA-Monogr., Vol. 47, pp. 233-252, 1962.
17. Reitzer, EJ: Rate of Scale Formation in Tubular Heat Exchangers. Ind.
Eng. Chem. Proc. Des. Dev., Vol. 3, pp. 345-348, 1964.
29
18. Mullin JW: Crystallization, 2nd ed. Butterworths, London, 1972.

19. McCabe WL and Robinson CS: Evaporator Scale Formation. Ind. Eng.
Chem., Vol. 16, pp. 478-479, 1924.
20. Galloway TR: Heat Transfer Fouling Through Growth of Calcereous Film
Film Deposits. J. Heat Mass Transf., Vol. 16, pp. 443-460, 1973.
21. Loo CE and Bridgwater J: Theory of Thermal Stresses and Desposit
Removal, in Progress in the Prevention of Fouling in Industrial Plant,
pp. 137-153, Inst. of Corrosion Sci. & Tech. Conf., Nottingham
University, U.K., 1981.
22. Cleaver JW and Yates B: The Effect of Re-entrainment on Particle
Deposition. Chem. Eng. Sci., Vol. 31, pp. 147-151, 1976.
23. Morse RW and Knudsen JG: Effect of Alkalinity on the Scaling of
Simulated Cooling Tower Water. Can. J. Chem. Eng., Vol. 55, pp. 272-
278, 1977.
24. Cleaver JW and Yates B: Mechanism of Detachment of Colloidal Particles
from a Flat Substrate in a Turbulent Flow. J. Col1oid Interface Sei.,
Vol. 44, pp. 464-474, 1973.
25. Gudmundsson JS: Particulate Fouling, in Fou1ing of Heat Transfer
Equipment, Somerseales EFC & Knudsen JG, eds., pp. 357-387,
Hemisphere, Washington, D.'C., 1981.
26. Newson IH, Bott TR and Hussain Cl: Studies of Magnetite Deposition
from a F10wing Suspension. Chem. Eng. Communications, Vol. 20,
pp. 335-353, 1983.
27. Gudmundsson JS: Fouling of Surfaces. Ph.D. Thesis, University of
Birmingham, U.K., 1977.
28. Pinheiro J de DRS: Fouling of Heat Transfer Surfaces, in Heat
Exchangers - Thermal Hydraulic Fundamentals and Design, Kakae S.,
Bergles AE & Mayinger F, eds., pp. 1013-1035, McGraw-Hill, New York,
1981.
29. Dunqi X and Knudsen JG: Functional Correlation of Surfaee Temperature
and Flow Veloeity on Fouling of Cooling-Tower Water. Heat Transf.
Eng., Vol. 7, pp. 63-71, 1986.
30. Muller-Steinhagen H, Reif F, Epstein N, Watkinson AP: Particulate
Fouling During Boiling and Non-Boiling Heat Transfer. Proc. 7th
Intern. Heat Transf. Conf., Vol. 5, Hemisphere, 1986.
31. Watkinson AP and Martinez O: Scaling of Heat Exchanger Tubes by
Calcium Carbonate. ASME J. Heat Transf., Vol. 97, pp. 504-508, 1975.
32. Ritter RB and Suitor JW: Fou1ing Research of Copper and Its Alloys,
presented at Battelie OTEC Biofouling and Corrosion Symposium,
Seattle, Wash., USA, 1977.
33. Hopkins RM and Epstein N: Fouling of Stainless Steel Tubes by a
Flowing Suspension of Ferric Oxide in Water. Proc. 5th Intern. Heat
Transf. Conf., Vol. 5, pp. 180-184, Tokyo, 1974.

@ProcessEng
30
Figure 1. Charaeteristie thermal

fouling eurves.
Asymptotie falling rate is
distinguishable from non-
asymptotie falling rate by the faet
that as t + 00, Rf + R~ in the
former and Rf + 00 in the latter.
·006
·004
Figure 2. Kraft liquor

fouling [1].
(BTU/hr.ft 2 .oF)-1 x 0.1762
= (W/m 2 .K)-1
oo 50 100 '50
Time hours
Figure 3. Plot of
Equation (29),
af ter Kern and
Seaton [5].
0.63 Ri
@ProcessEng
THE ECOOOMICS OF FDULING
A.M. PRI'ICHARD
HTFS Fouling Project, Harwell Laboratory UKAEA, Oxfordshire OXll ORA, U.K.
l. INTRODUCTION
Fouling was for long considered by many to be an 'aet of God'. The
simple theological implications of this view are that fouling is (a)
beneficial, and (b) unavoidable, while the legal implications suggest that
since no mortal ean be held responsible, no damages ean be sought as a
result of losses attributable to fouling. No apology is therefore required
for introducing the devil at this stage. Fouling, treated as an unwanted
deposition of materials on surfaces, is not beneficial, and al though it
may not be completely avoidable, both it and its effects can be reduced.
Estimating the costs of fouling is difficult for two reasons. 'l'he first
is purely human. Fouling has usually been allowed for in design of plant,
and there seems little point in measuring it if the plant cannot be
altered. There is therefore little published information (and, experience
would suggest, even less unpublished data) with which any measurements
could be compared if they were made : a vicious cirele. The second is more
a question of definition : burning more fuel to make up for a loss of heat
transfer is unquestionably a cost directly related to fouling, but anti-
fouling measures to reduce this loss also cost money. These two costs have
of course to be set against each other.
The formation of fouling deposits ean have a number of effects : it can
reduce heat transfer, impede fluid flow, impair safe operation of
equipment, assist or initiate corrosion, and lead to contamination of
fluids with which the deposits come in contact. In many industries it is
the effect on heat transfer that is the most important, and this will be
given most attention below. In most situations the effects of fouling are
proportional in some way to the amount of deposit formed, but in at least
one industry, the food processing industry, ~ fouling has to be regarded
as a potential source of biologi cal contamination, and therefore removed
at regular intervals.
In 1978 estimates were made of how much money fouling was costing the
United Kingdom economy (35,41). The costs were classified under four main
headings : Capital Expenditure, Fuel Costs, Maintenance Costs and Loss of
Production. These four will be used again below, with the addition of two
further categories : Safety and Unfulfilled Opportunities. Since this

paper does not accompany a request to industry or government for further
funding for research into fouling and its mitigation, the costs incurred
will be illustrated by specific examples, and no consistent attempt made
to calculate the total bill for fouling appropriate to any one country. It
is hoped that the examples and principles will be sufficient for reader s
to do this for themselves.
@ProcessEng
2. CAPITAL EXPENDITURE ATTRIBUTABLE TO FOULING

2.1. General
The largest item under this heading is almost certainly the increased
cost of heat exchangers due to fouling. This cost can be subdivided into a
number of components : necessary costs arising from the provision of extra
31
L. F. Melo et al. (eds), Fouling Science and Technology, 31-45.

32
heat transfer surface to allow for fouling, those due to the provlslon of
excessive extra heat transfer surface, and the costs of the extra civil
engineering work associated with the installation of the larger heat
exchangers. However, a substantial amount has to be allowed for the
provision of plant items connected with antifouling measures such as
sootblowers, water treatment plant such as clarifiers, filters, settIers
etc. Penner et al.(33) estimated that the capital cost in 1981 of gas
cleanup systems was about 10 per cent of the capital cost of $lOOO/KW(e)
for a coal-fired power station. The percentage of the cost might rise to
as much as 45% for a station designed to meet 1985 standards.
2.2. Provision of Extra Heat Transfer Surface

Heat exchangers are usually designed for a fixed dut y that can be
described in terms of the overall heat transfer coefficient U and the
surface area A :
l R,.
+-
UA A
It is immediately obvious from this relation that fouling resistances Rf

have in general to be allowed for by providing more surface area A, unless
the values of the convective heat transfer coefficients h on the clean
surfaces can be improved by using higher velocities. The designer of a
heat exchanger has therefore to decide what values of Rf to use before he
can decide what surface area to use. The increased cost of the heat
exchanger due to fouling thus arises from two causes :
a)the extra surface area to compensate for the fouling that
actually happens in practice, and
b)the extra surface area that is provided by the designer as an
insurance against any Rf value that he may have been able to
find being toa low.
A detailed discussion of the effects of fouling on condenser design for
power plants, including heat exchanger size, flow velocity (and thus
pumping power) and pres sure and temperature drop was presented by Curlett
and Impagliazzo in 1981 (14), who concluded that increases of 50% could be
expected in the capital cos t of a $lOM condenser for a hypothetical 600MW
coal-fired power plant depending on the fouling resistance chosen.
Crittenden and Khater (13) have given a more general analysis of the
selection of fouling resistances, taking into account the costs of plant
cleaning and loss of revenue during shut-down, with particular reference
to the petroleum and petrochemical industries.

It is worth commenting at this point on possibIe practical effects of
providing excess heat transfer surface area. The clean heat exchanger will
of course provide much greater heat transfer than is required, and a
common reaction of plant operators is to reduce the heat transferred by
reducing the flow velocity. This is often one of the most effective ways
of increasing fouling : shear forces on deposits are reduced, increased
@ProcessEng
surface ~emperatures can lead to more chemical reaction fouling and

deposition of salts with reverse solubility curves, while on the other
side of the tube lower temperatures can lead to crystallisation or
solidification fouling. In one case it was thought that more heat could be
recovered from coke oven gases if a fourth pass was added to the existing
three pass heat exchanger. Unfortunately it had been forgotten that coal
33
tar sets solid at about 250 C, and the result of adding the extra pass was
that no heat at all could be recovered, since the exchanger blocked. This
general problem is also discussed by Franklin and Cocks (15).
A simple estimate of the extra capital cost of fouling can thus be made
if the fouling resistances used in design are known. It was estimated that
the value of process plant built in the United Kingdom in 1968 was f475M
(1968 values), of which 56% was hardware. Some 6.5% of this hardware
consisted of heat exchangers, and with each exchanger having 30% excess
surfaee area to allow for fouling, this gave a direct cos t of some f5M
(20). A similar estimate for 1977 suggested a cost of some f20M due to
fouling out of a total cost of flOOM for heat exchangers in the United
Kingdom (35,41). A similar value of 30-40% excess was found in a survey of
heat exchanger manufacturers in the United States in 1982, leading to an
extra cost of $320M (16). A further $320M was added to this figure as the
cost of specialty materials such as titanium, stainless steel or graphite
in heat exchangers through which corrosive fluids were passed. However,
these costs are properly related to corrosion, and not to fouling. The
value of 30% excess are a clearly depends upon the process streams, and
also upon the quality of control and maintenance provided. Where this is
poor i t may be prudent to allow for a larger excess, to avoid the much
greater costs that arise if plant has to be taken out of service to
rectify fouling problems.
Quite apart from the extra surfacearea that must be provided to allow
for fouling in the normal situations where some fouling is inevitable,
there is the question of the extra surfaee area that is provided in case
the fouling resistance chosen is in faet too low. As indicated above, all
too often this extra surfaee area appears to be justified because
operating parameters have to be changed to reduce the heat transfer in the
clean exchanger ,leading to increased fouling. Cases are known in which
the excess area has been up to an order of magni tude larger than was
subsequently found to be necessary, and this suggests that overall perhaps
half of the extra surfaee area currently being built into heat exchangers
may be unnecessary.
2.3. The Cost of Installation

Provision of more heat transfer surfaee resul ts in larger and heavier
heat exchangers. To the cost of the heat exchanger itself must therefore
be added the cos t of the civil engineering work required, involving the
provision of extra space, stronger foundations, and increased transport
and installation charges. On readily accessible sites this may do little
more than double the cost of the exchanger i tse lf, but in remote si tes
(e.g. on offshore oil platforms) a factor of ten may be nearer the truth.
2.4. capital Costs of Antifouling Equipment

These include a range of items :
a) systems installed on heat exchangers such as those that
distribute and recirculate abrasive rubber balls or brushes
through the tubes of shell-and-tube heat exchangers during
operation to keep the tubes ide clean,
@ProcessEng
b) the extra cost of providing non-fouling heat exchangers such as

scraped surfaee device s or fluidised bed heat exchangers,
c) pretreatment plants that reduce the fouling propensity of
fluids, such as water clarifiers, filters, settlers, ion
exchange beds etc.,
34
d) cleaning-in-place equipment such as that installed for food-

processing plant,
e) dosing pumps and tanks etc. for antifouling chemicals.
While each of these individually may be relatively small (it was
estimated that ES-10M of the ElSM spent in the United Kingdom in 1977
(3S,41) was probably attributable to reduction in fouling), the total is
much more significant. The division between capital and running costs
varies with the system i ball or brush cleaning systems are expensive to
instalI, but relatively cheap to run, wereas the reverse is true for
chemical dosing systems. In one case, the provision of anti-biofouling
equipment for a proposed 300MW(e) Ocean Thermal Energy Conversion plant,
the capital costs reported in 1977 ranged from $1-2M to $lOM depending
upon the choice of chemical treatment or balls/brushes (38).
One of the major techniques for =ntrolling biofouling in cooling waters
is dosing with chlorine gas or hypochlorite solution. This is widely used
in the power industry, it was estimated tæt the total capitalised cost of
chlorination facilities in the U.S.A., calculated on a fixed charge rate
of 20% related to the value of chlorine consumed, was $267M (22). The
corresponding f igure for the Uni ted Kingdom i s l ike l y to be an order of
magnitude smaller, but still significant.
3. FUEL COSTS
3.1. Genera l
This item is often presented as "Energy Costs". However sinæ the cost
of energy is different according to whether i t is heat generated by the
primary combustion of coal, oil or gas in boilers and furnaces, or
a secondary form such as electricity, it is more informative if the cost
is related back through the form of energy that is used to the cost of the
fuel used to produce it.
In a large number of cases heat exchangers are used to remove heat from
a process stream without any attempt being made to recover it. Provided
that fouling does not introduce extra pumping costs, it will not increase
costs if the exchanger becomes fouled. Costs are however incurred when
fouling leads to extra fuel being burnt in a furnace or a boiler, or when
more secondary energy such as electricity or proæss steam has to be used
to over=me its effects. A third and major area in which fouling leads to
the lass of energy is in the working fluid circuits in processes by which
secondary energy is produced, principal ly in turbines, condensers and heat
recovery wheels in electric power plants.
3.2. Increased cost of primary energy

In one of the most detailed assessments made to date Van Nostrand, Leach
and Haluska calculated the fouling related expenses attributable to extra

fuel burnt, last output and maintenance and cleaning in various refinery
units in the U.S.A. (Table l), giving a total cost due to extra fuel burnt
of $427.7M per year, based on a process fuel cost of $2.80/ MBTU (43). The
largest part of this was due to fouling in hydrotreaters, visbreakers and
reformers, where coking occurs. Extension of these calculations to the
non-communist world suggested a cost of over $l,SOOM per year, though of
@ProcessEng
course the individual costs will depend upon the local cost of process
fuel. The calculation for the U.S.A. is reasonably consistent with the
later (1984) estimate of $700-3S00M fuel burnt to overcome fouling
problems, though this estimate included natura l gas and coal as well as
petroleum products (16).
35
TABLE l (reference 43)
FOULING REIATED cosrs IN UNI'IED STA'IES REFINERIES ($mi11 ion/year)
eapacity Energy Throughput Maintenance Total

Kbbl/SD & Cleaning
Crude Distillation 18,000 183.6 671.4 6.3 861.3

Hydrotreating 7,500 89.2 85.0 4.2 l78.4
Visbreaking 220 37.3 9.2 2.6 49.1
Reforming 3,800 162.6 106.4 2.3 27l.3
Total 427.7 872.0 15.4 1,360.1
The figures quo ted above are concerned with liquid-side fouling. The
cost of gas-side fouling in the U.S. petroleum industry is quoted by
Marner and Suitor (28) as $92m/year. This compares with a figure of
$121M/year for the U.S. cement industry and a total annual estimated
figure of $900M/year.
The loss of heat transfer due to scale formation on boilers has been
calculated (17) to lead to losses of output of 2-7% for a scale thickness
of 0.8mm, the loss depending upon the morphology and composition of the
scale. Significant fuel savings could be made if some or all of the
dissolved salts were removed from the feedwater beforehand, thus allowing
a higher concentration factor without scaling, and a smaller loss of heat
through the reduced rate of blowdown. A figure of 0.8-1.0% of fuel costs
for 2% blowdown has been suggested (7), together with costs of water
treatment ranging from 15% of the raw water cost for sodium zeolite
ion exchange treatrnent to 100-400% for complete demineralisation.
Air for boi lers is increasingly being preheated by exhaust gases to save
fuel. One of the most frequently used regenerators is the Ljungstrom type,
consisting of matrices of corrugated plates. In coal-fired boi lers these
become fouled by fly-ash. This has two effects : firstly, it reduces the
amount of heat that can be recovered, and secondly it impedes the flow of
air to the boiler. This latter effect both reduoes the thermal output of
the boiler and thus the electrical output, which may require the use of
less efficient power plant to make up the deficit, and also affects the
cornbustion prooess itself. Fossil-fired boi lers are usually operated with
the lowest possibIe percentage of excess air beyond that required for
complete combustion of the fuel. This minimises the amount of heat lost in
the cornbustion and nitrogen gases discharged through the stack. However,
if inadequate air is available for cornbustion in coal-fired boilers some
of the iron in the ash is only oxidised to the ferrous state rather than
the normQl ferric state, _producing an ash with a lower mel ting point that
tends to foul the boiler tubes much more severely, thus further reducing
the efficiency of the boiler. Chojnowski and Chew quoted a cos t of fl.5M
(1970 prioes) for losses at two 2000 MW(e) power stations where fouling of
@ProcessEng
the heaters led to inadequate amounts of cornbustion air and slagging (lO),
and in extreme cases the boi lers had to be taken out of service for the
air heaters to be cleaned by chemical means. They showed that fouling
could be reduoed by careful attention to the design of the corrugated heat
transfer surfaces. A loss of flO-20M per year has been estimated for
power-stations in the UK in 1979 due to this type of fouling(35,4l).
36
Fouling and slagging on boiler tubes in coal-fired power stations

depends to a very large extent on the type of coal being burnt, since this
determines the composition of the ash, and therefore i ts mel ting point.
A range of $lM-8M/year was. quoted in 1984 as the cost of fouling and
slagging for a 500 MW(e) power station, depending upon the type of co al
burnt (33). No complete solutions to the problems are usually possible,
and the success rate is often very site specific, but improvements in
sootblowing and reductions in heat re lease rates are two of the most
successful approaches.
A somewhat different aspeet is the lass of latent heat of water vapour
and acid combustion produets from fossil-fuelled boilers. These produets
are normally discharged to the atmosphere at temperatures above their dew-
points to avoid the severe corrosion of duets that =curs if the acids are
allowed to condense. Dewpoints in UK coal-fired power plant are in the
range 100-140 o C (6), and it has been calculated that if the exit gas
temperature from the final heat recovery plant could be reduced by 20 0 C
for all UK power stations burning coal, 0.7M tonne out of a total of 80M
tonnes could be saved each year, worth E30M (19). It has also been
calculated that adoption of domestic gas boi lers in which the choice of
materials permitted condensation to occur in flues could raise thermal
efficiency from 85 to 95%, and with a consumption of 6000M therms of gas
per year at EO.37/therm in the UK, annual savings of 600M therms or E200M
should be p:Jssible (6).
The need to reduce emissions from coal-burning power plants is likely to
become more urgent in the future for environmental reasons ; this could
account for as much as 35% of operating costs in the future (33).
3.3. Losses due to fouling in working fluid circuits

These are relatively well-documented for steam circuits used for
eleetricity generation, where very small amounts of fouling of turbines
and condensers can lead to very large losses in power output from large
stations through lowered turbine efficiency and increased backpressure as
aresult of reduced cooling efficiency by the condenser.
Losses of $6M were estimated to have been suffered by the United Kingdom
Central Electricity Generating Board as aresult of fouling by calcium
phosphate of condenser tubes in 14,000 MW(e) of coal-fired plant cooled by
river water during 1975 (32). Other calculations suggested that a loss of
l millibar back pressure arising from an increase in the steamside
temperature of 0.5 0 C due to tubeside fouling of condensers in all CEGB
stations led to an annual fuel penalty in 1980 of E1M/year (l). A more
recent report (4) estimated that the loss of l inch of mercury vacuum
(equivalent to 33.4 millibars) due to condenser fouling was equivalent to
an extra annual fuel bill of $450,000 for a 600 MW(e) coal-fired plant,
which is similar in magni tude to the CEGB data and confirmed by Chow,
Maulbetusch and Mussalli (11). These costs and the real ity of the problem
are illustrated by the annua l estimated cost of chlorine to the CEGB to
control this fouling : for 20,000 MW(e) installed plant some 48 tonnes of
chlorine a day were estimated to be used over a per iod of 200 days each
year. At El30/tonne this came in 1980 to €l.25M/year (9).
@ProcessEng
Examples of the costs of turbine fouling have been given by O'Neal (30)
for the Long Island Lighting Company with three 115 MW(e) 1650psig units,
four 185 MW(e) 2050 psig units and three 380 MW(e) 2900 psig units, each
with reheat at 1000o/1000Op (538 o/538 oC). By paying increased attention to
water chemistry and thus reducing deposition in the turbines the fouling
rate was reduced from 2% to 0.5% between overhauls (undertaken at
37
approximately 5-year intervals) leading to annual savings of $60,000 per

115 MW(e) unit, $170,000 on each of two 185 MW(e) units and $240,000 each
on the two others, and $500,000 per 380 MW(e) unit. Thus annual savings of
$2.5M (1975 values) were achieved for an expenditure of only $100,000.
3.4. Increased use of secondary energy

The major mechanism by which fouling leads to increased consumption of
secondary energy is in the increased loads on electric motors driving
pumps and fans. Formation of deposits on surfaces usually leads to a
roughening, either because of the naturaIly irregular surfaee of solid
deposits, or because of flow-induced roughening of gelatinous ones, such
as biofilms. Pump motors and cooling tower fans are usually sized to give
adequate performance in fouled systems, and therefore are larger and
consume more power than would be required in a clean system. The problem
is compounded by a tendency to run pumps and fans at a constant rate
irrespective of the dut Y actually required. Terrell reported that for
seven large well-controlled cooling towers the annua l cos t of the
electricity used ranged from 5 to 40 times the cost of the water (40).
This suggests that by balancing the cost of water and chemicals to control
the fouling and thus the power requirement for a gi ven cooling dut Y, at
least half of the costs could be recovered.
Examples of increased pumping cosrs due to fouling are hard to come by,
but Terrell stated that in a 250 m recirculating system with a 10-inch
(254 mm) main, a 10% decrease in diameter would double the pres sure drop
and thus the pumping power required (40). Formation of deposits in the
main could be expected to have similar effects, both by reducing the
cross-section and increasing the surfaee roughness.
Operation of chilIer and refrigeration equipment under fouling
conditions appears to have received relatively littIe attention, even
though in a large building the air-conditioning plant may have a power
demand greater than the heat input. It has been suggested that fouling in
refrigeration chilIer condenser tubes can increase energy consumption by
as much as 25% ; a deposit thickness of only 0.5 mm would be sufficient to
waste 15% of the energy required to produce chilled water. In a survey of
75 chillers, many were found to be operating at 10-30% above the design
performance ratings of 0.75-0.85 kW/ton (25). Another case, in which the
cleanliness factor decreased from 93% to 63% in 75 days' operation with an
established cooling water tower treatment programme, led to a 20% increase
in compressor power requirements af ter 6 months' operation (34). Power
savings of 15-33% have been recorded in four different locations in the
U.S.A. as aresult of using automatie brush cleaning systems (25).
4.MAINTENANCE COSTS
4.1. General
Maintenance costs ean be divided into two main classes : the costs of
removing fouling deposits during planned or unplanned maintenance, and the
costs of chemicals or other opera ting costs of antifouling devices. They
do not include the additional costs that may arise as aresult of an
unplanned shutdown, and no allowance will be made for any costs arising as
@ProcessEng
the result of corrosion associated with fouling.
4.2. Fouling deposit removal

I t was estimated in 1980 that about 15 per cent of the maintenance costs
of proces s plant in the United Kingdom could be attributed to boilers and
heat exchangers, with probably half of this HOM due to fouling (35,41).
38
The annual sales in 1982 of companies supplying heat exchanger online and
offline cleaning equipment, chemicals and cleaning services in the U.S.A.
were quoted as $2,000M (16). Marner and Suitor estimated $2,100M as the
cost of maintenance due to gas-side fouling alone, of which some $1,700M
was attributed to the cost of stearn used in sootblowers (28).
The cost of cleaning an exchanger obviously depends upon the type of
deposit and the size of exchanger. Solvent cleaning of a heat exchanger
was quoted in 1977 as $1200, of which $1000 was accounted for by the
chernicals, compared to $2070 for a chemical clean ($170 for chemicals) and
high-pres sure jetting (5). The major cost in chemical cleaning is usually
attributable to the chernicals themselves ; some typical values are quoted
in reference (36).
In a very different area, removal of marine fouling is becoming a major
cost on oil platforms in the North Sea. The fouling has three main
effects. The least important of these is probably the increased weight of
the fouled platform, though this might have an effect on stability. Much
more significant are the increased forces during storms on fouled
structural mernbers ; this is particularly noticeable with same seaweeds
that grow long fronds. The third problem is the need to remove fouling to
inspect the structural members beneath. At present all this cleaning has
to be carried out by divers, and it has been estimated that in the UK
sector of the North Sea the diving costs associated with cleaning will
reach €20M- 30M per year in 1990 (26).
4.3. Costs of antifouling measures

The major part of this is the cost of water treatment chemicals, a
market that was probably worth in excess of fl20M in the United Kingdom in
1984. Since water is provided as a service commodity that may be used for
a variety of purposes , some of the treatment may have been unnecessary,
since fouling would not have been a problem even with untreated water.
However, the main uses of chemicals, for pH control and softening,
flocculation/clarification, and disinfection can all be considered as
processes that have the effect of reducing different types of fouling
(scaling, particulate fouling and biofouling respectively) to a greater or
les ser extent . If chernicals used in effluent treatment are excluded, the
total cost can probably be assumed to be about flOOM/year in the U.K.
The cost of chlorine and hypochlorite for treating cooling water used by
the power genera ting industry in the U.S.A. were stated to be $27M/year
for the 58.7% of the total of 460,000 MW(e) installed generating capacity
that used chlorination for biofouling control in 1983 (22). Considerable
details were also given of the relative costs per MW per year of gaseous
chlor ine and hypochlorite for riverine, estuarine and marine cooling
systems, and for controIling different organisms.

A major market outside the U.K. is the supply of antiscalants for
desalination plants, mainly multi-stage flash evaporators. In 1968
the cost of scale control was estimated to be $32.4 per million
U.S.gallons of water produced with top o~erating temperatures of 250 0 F
(45). Costs of f5, f30 and f36 per 1000 m for po13Phosphate, polymer and
acid treatment chemicals respectively in a 12000 m /day multi-stage flash
@ProcessEng
distillation unit were quo ted in 1979 (46). Where no acid dosing is
undertaken the wain scales formed are calcium carbonate and magnesium
hydroxide, but when acid is used calcium sulphate may be formed. In severe
cases it may be necessary to rernove it mechanically with pneumatic tools.
The scale can also be removed chemically ; it cost f2500 and f1300
respectively in 1978 for the arnounts of EDTA and sodium glycollate needed
39
to dissolve l tonne of calcium sulphate.

Substantial use is made of antifoulant chemicals in oil refineries, and
Van Nostrand et al. suggested in 1981 antifoulant costs of $155,000/year
for a crude unit processing 100,000 barrels/SD, and $40,000/year on a
hydrotreater processing 25,000 barrels/SD. These costs were more than
justified by the savings in fuel, throughput and cleaning, which were
$755,000, $1,680,000 and $20,000 respectively for the crude unit, and
$223,000, $150,000 and $7,000 respectively for the hydrotreater, giving
net annua l savings of $2,300,000 and $340,000 for the two units (43).
It has been demonstrated that fouling problems in fossil-fuelled boilers
are amenable to treatment by additives, mainly magnesium compounds, that
lead to the formation of ash that melts at toa high a temperature to cause
slagging or corrosion. However, the cost of the additives has usually been
considered toa high to be economically viable for use with coal or oil. In
one exception it was claimed that expenditure of $0.6M on MgO additive to
correct problems associated with the combustion of 20 million barrels of
residual fuel oil led to a gros s benefit of $3.9M in 1976. The major
savings were estimated as $2M from greater cycle efficiency and $1.23M
from sale of the vanadium recovered (9% of U.S. needs in that year), with
smaller benefits from reduced high-temperature wastage, low-temperature
corrosion and acid smut elimination (31). This example does not appear to
have been copied widely.
5. COST OF PRODUCTION LOST DUE TO FOULING

This is often considered to be the main cost of fouling, arising from
unwanted plant shut-downs or possibly contamination of the product as a
result of fouling. However, it must be remembered that the lost production
is only of value if it can be sold, so that this cost is initially less
important during a downturn in economic activity. If no recovery in sales
occurs, it is sometimes decided to close less efficient plants and
rationalise production to increase the utilisation and thus the efficiency
of operation of the remaining plant and reduce maintenance costs. Avoiding
shutdowns due to fouling or other causes then becomes important again.
It is difficult to obtain reliable data of the losses due to this cause.
It has been suggested that an upper limit could be estimated by assuming
that the loss of production due to fouling over the life of a heat
exchanger should be less than the cost of providing redundant exchangers.
Assuming the average life of a heat exchanger to be 10 years, with a real
discount rate of 5%, the loss of production due to heat exchanger fouling
should be than 13% of the cost of annual heat exchanger sales, giving a
figure of less than $200M (16). However, the lack of reliable information
on heat exchanger fouling suggests that there will not be adequate data in
most cases to justify installation of redundant heat exchangers.

A survey of 27 ammonia plants in the U.S.A. in 1973 showed that a waste
heat boiler failure could be expected every 3 years, leading to 5 days'
loss of output (18). It does not seem unreasonable to expect that these
failures were mainly associated with deposit formation, giving an annual
loss of flOO,OOO in 1973. Longer shut-downs were not uncommon.
More reliable data are available for the power generation industry.
@ProcessEng
Collier stated that the loss of electricity generation attributable to

steam generator unreliability in pressurised water reactors (mainly caused
by corrosion associated with deposit formation) averaged 10-11 days/year.
The mean duration of an outage for repairs was 20 days, and for a 1000
MW(e) plant this incurred an economic loss of f4M (12). A figure of
$250,000/day has been quoted for the outage of a 1200 MW(e) plant (2), and
40
DM1M/day for a 1300 MW(e) plant (37). Condenser reliability problems are
also often eaused by eorrosion whieh is assoeiated with fouling, and they
were reported to eost the U.S. power industry $600M/year in 1983 for
replaeement power alone (22).
Van Nostrand et al. estimated an annual eost of $872M due to loss of
throughput eaused by fouling in United States refineries, the largest part
of this arising in erude distillation units (see Table l, above) (43).
However, the present exces s of refining capaeity worldwide suggests that
this is too high. The eost of lost throughput in the U.S. cement industry
due to gas-side fouling was estimated to be $108M/year in 1982 (27).
Very large costs ean be incurred if scaling or other fouling leads to
the need to stop production from oilwells for a 'work over' i figures of
several hundred thousand pounds have been quoted for the workover of a
platform well, and as much as f2M for a satellite well (21). Similar costs
can of course be involved if fouling of heat exchangers, separators etc.
on the platform itself causes oil production to be interrupted.
6. SAFEl'Y
Fouling is not normally associated with safety problems, and this is
probably one reason why i t has not reeeived as mueh attention as
eorrosion. This was not always so, and many thousands of boi ler explosions
occurred during the last eentury and the first years of this one, leading
ultimately to pressure vessel eodes sueh as ASME III and BS 5500 for
boi ler construction (12). Many of the explosions were eaused by waterside
scaling of the boiler, reducing the heat transfer coeffieient and thus
allowing the metal to become overheated, increasing the creep rate and
leading to craeking or creep rupture. Boiling beneath scale deposits can
also allow salts in the boiler water to concentrate and form corrosive
solutions that lead to failure of tubes through on-load corrosion. Sueh
events are rare r nowadays, but still need to be guarded against by eareful
control of water chemistry (3).
Scaling of safety val ves so that they are unable to close properly when
needed is a problem under some cireumstances in oilwells, and probably
also elsewhere. The infrequent use of these val ves makes it diffieult to
collect reliable data on the importance of the problem.
Deposits of combustible materials ean oeeur on air preheaters that
recover heat from the exhaust gases of fossil-fuelled boiler during poor
firing conditions during start-up. If these deposits are allowed to build
up they may later ignite spontaneously, possibly leading to a metal fire
that ean severely damage or completely destroy the heat exchanger (42).
A very different type of safety problem has been highlighted by the
inereasing use of offshore oil platforms in the Gulf of Mexico, the North
Sea and elsewhere. These platforms often are not linked to the shore by
pipeline, and are provided with oil storage tanks that also play an
important structural role. The oil that is pumpe d in and out of them
usually eontains some water (usually seawater), and this provides an
environment in which sulphate-reducing bacteria (SRB's) ean grow. Quite
signifieant concentrations of hydrogen sulphide can build up in the
enclosed spaces, and a number of deaths of maintenance staff have occurred
@ProcessEng
af ter entering the tanks, despite being provided with breathing sets.
SRB's are also implicated in the souring of oilwells. The formation of
biofilms or other deposits in which these organisms live is not normally
considered to be a major problem in reducing fluid flow, but the hydrogen
sulphide that they produce is very corrosive, so that mild steel equipment
has to be replaced with more expensive corrosion-resistant materials.
41
The most expensive fouling-related safety problem at the moment is

probably the transport of radioactive species out of the cores of nuclear
reactors. In most cases the amount of material involved is toa small to
affect fluid flow or heat transfer, but the very high penetrating power of
gamma rays from atoms such as cobalt, which is produced by irradiation in
the reactor core of small amounts of cobalt released by corrosion of the
stainless steel pipes and hard-facing surfaces in valves, means that
microgramme quantities can cause significant problems. The much greater,
though still low, solubility of cobalt in high-temperature water compared
to high-pres sure carbon dioxide or helium means that activity transport is
in general a much more serious problem in water-cooled reactors than in
gas-cooled ones.
Very expensive measures have been taken to minimise the exposure of
opera ting staff to ionising radiations. Costs of $1000-$5000 per man-rem
(a measure of the dose received by operating staff) have been quoted, and
i t is claimed that decontamination operations to remove or reduce the
radioactivity in parts of plants to which operators have access saved
10,000 man-rem in the U.S.A. in 1984 alone, i.e.$10M-50M. The cost of
these operations was estimated to be some $500 per man-rem, showing a high
cost-effectiveness for decontamination procedures (39). Reducing the
radiation level also reduces the number of pecple and the time for routine
maintenance, thus producing savings in down-time.
7. THE COST OF IDST OPPORrUNITIES

Most engineers are conservative, and unwilling to install plant for
which there is no operating experience. The relative lack of information
on fouling thus means that there are strong incentives to stick with a
process or piece of equipment in which the fouling behaviour is known to
some extent. For heat exchangers this usually means using shell-and-tube
types, for which most fouling data has been gathered. Significant
improvements in performance can be obtained by using enhanced tube
surfaces or different types of heat exchangers such as plate or plate-fin
types (48). The enhanced heat transfer coefficients can be used to reduce
the size and cos t of the heat exchanger : in boiling service with tube-
side water flow it has been estimated that size reductions of up to 55-67%
should be possible if enhanced tubing is used instead of plain tubes in
shell and tube heat exchangers (47). Alternatively the improved heat
transfer performance can be used to reduce the approach temperature
difference and the mean temperature difference. This can yield increased
thermodynamic efficiency for the process or cycle, and may be particularly
valuable in improving the efficiency of compressors, possibly leading to
the elimination of one or more stages. In offshore applications the small
size of units of the plate-fin type has an additional advantage in

reducing the space and platform weight required.
Even for shell-and-tube heat exchangers new developments such as the
used of electropolished stainless steel tubes in place of the usual
pickled surface have been slow to be adopted. These tubes are claimed to
be less susceptible to fouling, and easier to clean. Savings of 30% using
these tubes have been suggested, attributable to reductions in the amount
@ProcessEng
of water used for cleaning, the need for high-pres sure cleaning, and
pumping costs (29).
A most encouraging recent development is the fluidised bed heat
exchanger. This is avertical shell-and tube heat exchanger in which the
fouling fluid is passed upwards through the tubes, maintaining in
suspension inert particles of suitable materials. These not only help to
42
increase the tubeside heat transfer coefficient, but also provide an

abrasive action that keeps the walls clean. Heat can be transferred to a
number of different streams on the shell side. In the Multi-Stage
Flash/Fluidised Bed Evaporator (MSF/FBE) these can be the different
stages. It has been claimed that a MSF/FBE unit shows significant economic
advantages over a conventional horizontal flash evaporator used for
desalination. A number of other units have been placed in service where
fouling was severe, and have operated successfully (24). The fluidised bed
heat exchanger currently has the disadvantage that it has to be mounted
vertically, and it is not possibIe to retrofit the system to an existing
heat exchanger. Orr more recent examples i t has been possibIe to vary the
dut Y of the heat exchanger, and the slow rate of adoption of these units
appears to be due to conservatism rather than any technical shortcomings.
As noted above, coal- and waste-fuelled boilers suffer considerably from
fouling and the emission of pollutants in combustion gases. The
development of atmospheric and pressurised fluidised-bed combustors
removes the need for scotblowers, and should lead to greatly reduced rates
of slagging, as well as offering lower maintenance costs and low emission
rates for pollutants. Although development is well under way, the
advantages are not sufficient to justify the replacement of existing
boi lers, and large size units have still to be designed.
Significant reductions in cooling water temperatures can be obtained by
using high-surface area packings for cooling towers. These promise greater
efficiencies for steam turbines by lowering the back-pressure, and for
compressors such as those used in refrigeration and air-conditioning
equipment. It has been suggested that for every degree F colder the water
returns from the cooling tower within the operating range of the
compressor, a saving of 3.3% in energy used by the compressor can be made
for the same results (8). There would thus appear to be excellent reasons
for using these newer packings that use film cooling rather than drop let
evaporation. However, their introduction is likely to be limi ted by the
present lack of fouling information. Such surfaces are susceptible to
biofouling, which in turn is very efficient at trapping particulate
material from the water or cooling air. Deposit weights of up to ten times
the packing weight have been reported, bringing with them the risk of
mechanical collapse of the thin plastic material from which the units are
made. The advantages to be gained are so large that it is likely that
designs will be optimised to give the best heat transfer performance,
while still retaining enough strength to support a modest amount of
fouling and being reasonably easy to clean.
Where the likelihood of scaling increases with temperature, the adoption
of mechanical vapour recompression may significantly reduce the problem.
The effect of thi s process is to reduce the temperature of the walls on

which the scaling takes place. It has been claimed that the most
economical design of mechanical vapour recompression crystalliser is also
the least likely to foul (23).
8. CONCLUSIONS
The evidence presented above is a very incomplete story. However, it
@ProcessEng
should be sufficient to show that the cost of fouling is measured in

thousands of millions of pounds or dollars for the world's largest
economies. Substantial reductions in the capital costs associated with
fouling depend on the provision of greatly improved information about
fouling of existing plant, and the production of information about fouling
of newer and cheaper plant. Large savings in fuel costs as aresult of
43
improved control of fouling are likely to be limited to a few industries

such as power generation that are large consumers of fuel, though this
situation may change as energy conservation and process integration become
more widespread. The costs of maintenance due to fouling seem likely to
increase as the quality of materials such as fuels and ores for processing
declines. Increasing environmental restraints will have the same effect,
sinoe equipment for reducing emissions to the environment is likely to be
at least as susceptible to fouling as existing process equipment. In the
particular case of fouling by cooling water the imposition of restraints
has already led to the adoption ef less efficient treatment chemicals that
are less tolerant of system upsets.
Increasing awareness of fouling, and understanding of how it can be
control led and reduced should lead to fewer losses of production, though
newer intensified proces ses may themselves be more susoeptible to upset by
fouling. Safety costs seem likely to rise fairly quickly in the nuclear
industry, firstly because of pres sure for lower radiation doses, and
secondly because the spread and amount of radioactivity within nuclear
systems increases as they become older.
SYMBOLS
= overall heat-transfer coefficient based on tube area A
= convective heat transfer coefficients in the clean state
thermal resistance of fouling layer
surface area
thermal resistance of wall
REFERENCES
L Ainsworth, S.!., 'Chlorine/hypochlorite requirements within the
Central Electricity Generating Board'. Paper presented at
International Conference on Local Generation and use of Chlor ine and
Hypochlorite, London, October 1980.
2. Anon., 'Titanium tubes cut costs even in average water', Electrical
World Vol.183(4), pp.44-46, 1975.
3. Anon., 'Scale : the luxury you cannot afford', Vigilance Vo1.3(1l)
pp.135-137, 1979.
4. Aschoff, A.F., Chiesa, R.J., Jacobs, M.H. et al., 'Oechlorination
technology manual'. EPRI Report CS-3748, Palo Alto, U.S.A., 1984.
5. Axsom, J.F., 'Exchanger cleaning method cuts costs, ups throughput',
Oil Gas.J. Vol.75 (24), pp.71-72, 1977.
6. Bernie, J.A., 'Oewpoint corrosion - costs and potential savings', in
book 'Oewpoint Corrosion', ed. Holmes, O.R., Ellis Horwood,

Chichester, UK, pp.1l-16, 1985.
7. Betz Ltd., 'Water treatment for boilers', Processing, Jul/Aug 1980.
8. Burger, R., 'The neglected money maker, cooling towers', paper
presented at 1984 National Heat Transfer Conference, Buffalo, U.S.A.
9. Case, B. and Heaton, W.E., 'Cooling water electrolysis at coastal
power stations'. Par;er presented at International Conference on Local
@ProcessEng
Generation and use of Chlorine and Hypochlorite, London, October 1980.

10. Chojnowski, B. and Chew, P.E., 'Getting the best out of rotary air
heaters'. CEGB Research no.7, May, pp.14-21, 1978.
11. Chow, W., Maulbetusch, J.S. and Mussalli, Y.G., 'Biofouling through
targeted chlorination', Power Engineering, October, pp.38-41, 1984.
12. Collier, J.G., 'Re li ab i lity problems of heat transfer equipment'. Heat
44
Transfer Engineering Vo1.4 (3-4), pp.51-62, 1983.

13. Crittenden, B.D. and Khater, E.H., 'Economic Fouling Resistance
Selection'. In 'Fouling of Heat Transfer Equipment' eds. Somerscales
E.F.C. and Knudsen J.G., pp.645-652, Hemisphere, New York, 1981.
14. Curlett, P.L. and Impagliazzo, A.M., 'The impact of condenser tube
fouling on powerplant design and economics'. Paper presented at 20th
National Heat Transfer Conference, Milwaukee, August 1981.
15. Franklin, W.C. and Cocks, R.E., 'Determine the resistance that
controls heat exchanger cost'. Chemical Engineering Vol.87 (15),
pp.93-94, 1980.
16. Garrett-Price, B.A., Smith, S.A., Watts, R.L. and Knudsen, J.G.,
'Industrial fouling : Problem characterisaticn, economic assessment,
and review of prevention, mitigation and accommodation techniques'.
Review prepared for U.S.Department of Energy, 1984.
17. Hendrix, W.A. and Hoyos, G.H., 'Conserving boiler energy', Chemical
Engineering, Vo1.86(28), pp.77-78, 1979.
18. Hinckley, P., 'How to avoid problems of waste-heat boilers', Chemical
Engineering Vo1.82(l8), pp.94-98, 1975.
19. Holmes, D.R., in book 'Corrosion Resistant Materials for Coal
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20. Hudson, D., 'Fouling of shell and tube heat exchangers'. Paper 4,
Joint LCh.E./LMech.E. Symposium on Heat Exchangers, Manchester,
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21. Hughes, C.T., 'Scale : the problems and solutions', paper presented at
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22. Kasper, J.L., Chow, W., Graham, J. and Mussalli, Y.G., 'Use and cos t
of chlorination systems'. Power Engineering, pp.54-57, October 1983.
23. King, R.J., 'Mechanical vapour recompression crystallisers', Chemical
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24. Klaren, D.G., 'The fluid bed heat exchanger : principles and modes of
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Fouling Prevention Research Digest, Vo1.5(l), pp.iii-xvii, 1983.
25. Leitner, G., 'Controlling chiller tube fouling', ASHRAE J. Vo1.22(2),
pp.40-43, 1980.
26. Marine Technology Support Unit, 'Report of the Marine Fouling Working
Party for the Director of Petroleum Engineering Division', Offshore
Technology Paper OTP4, U.K. Department of Energy 1980.
27. Marner, W.J., 'An assessment of gas-side fouling in cement plants'.
Publication 82-83, Jet Propulsion Laboratory, California Institute of
Technology, 1982.
28. Marner, W.J. and Suitor, J.W., 'A survey of gas-side fouling in
industrial heat-transfer equipment', Publication 83-74, Jet Propulsion

Laboratory, California Institute of Technology, 1983.
29. Nordin, S. and Westergren, L., 'Practical experiences of prevention of
scaling by means of high-finish surfaces in evaporator tubes',
Proceedings of the International Workshop on Fundamentals and
Applications of Sur face Phenomena Associated with Fouling and Cleaning
in Food Processing, pp.356-364, Lund Univers ity , Sweden, 1981.
@ProcessEng
30. O'Neal, A.J., 'The dollar value of protecting steam turbines against
fouling', Combustion, Vo1.47(5), pp.20-23, November 1975.
31. O'Neal, A.J., 'The nature and cost of residual fuel oil problems and
the profits realised from proper corrective action', Combustion,
Vo1.49(6), pp.37-45, 1977.
32. Parry, D.J., Hawthorn, D. and Rantell, A., 'Fouling of power station
45
condensers within the midlands region of the C.E.G.B.', in 'Fouling of

Heat Transfer Equipment' eds. Somerscales E.F.C. and Knudsen J.G.,
pp.569-586, Hemisphere, New York, 1981.
33. Penner, S.S., Alpert, S.B., Beer, J.M., Bozzuto, C.R., Glassman, L,
Knust, R.B., Markert, Jr., W., Oppenheim, A.K., Smoot, L.D.,
Sommerlad, R.E., Wagoner, C.L., Wender, 1., Wolowowdiuk, W. and
Yeager, K.E. (1984), 'Developing Coal-combustion technologies',
Prog.Energy Combust. ScL Vol.lO, pp.87-144, 1984.
34. Petritsch, J., 'Case history of on-line condenser tube cleaning',
Heating/Piping/Air Condi tioning Vol.57 (l ), pp.15 5 -15 8, 1985.
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Prevention Research Digest Vol.l (1-4), iv-vi, 1979.
36. Roebuck, A.H. and Bennett, Jr., C.A., 'Heat-transfer payback is a key
to chemical-cleaning choice', Oil Gas J. Vo1.75(37), pp.93-96, 1977.
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cooling water system for improvement of heat exchanger efficiency',
paper presented at International Meeting on Industrial Heat Exchangers
and Heat Recovery, Liege, Belgium, November 1979.
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developments with chemical decontamination reagents', Water Chemistry
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presented at seminar 'Fouling and cleaning of heat exchangers',
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47. Webb, R.L., 'Performance, cost effectiveness, and water-side fouling
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@ProcessEng
@ProcessEng
Chapter 2
Monitoring Equipment
LIQUID FOULING MONITORING EQUIPMENT
JAMES M. CHENOWETH
Heat Transfer Research, Ine.

Alhambra, California 91802 USA
1. INTRODUCTION
Monitoring fouling ean provide useful information to permit the effective operation
of heat exchangers. Different techniques are used to detect fouling by observing the
buildup of a fouling layer, the accompanying deterioration in the thermal
performance, and the increase in the overall pressure drop. Some monitors determine
the relative performance of particular heat exchangers to signal the time for cleaning.
Other monitors are used to evaluate the effectiveness of various treatment programs
to control corrosion and minimize fouling. All have the objective of understanding
more about the fouling characteristics of plant streams that are known to foul heat
exchangers.
Most liquid fouling monitors have evolved from one or another type of research
unit used to study fouling behavior. Adaptations to plant fouling monitors have been
made by plant operators for their specific requirements. In addition, fouling monitors
ean be purchased or leased from manufacturers. By far, the largest number are
available on loan from organizations that offer fluid treatment produets or heat
exchanger cleaning systems. Some, monitors are quite simple and require minimum
instrumentation. Others are quite sophisticated and provide direct evaluation of a
number of relevant parameters. In some plants the monitor is an integral part of the
control systems that supplies treatment chemicals andi or regulates the on-line
cleaning.
2. RESEARCH UNITS TO MEASURE FOULING

Research units measure fouling in a number of different ways. Knudsen [l] lists in
Table l the more common test section geometries, methods for heating or cooling, and
techniques for monitoring the fouling deposit. For those units that indirectly measure
the thermal resistance of the fouling layer, temperatures, flow rates, and heat flux are
measured so that the "fouling resistance" or the "fouling factor" ean be calculated.
Table l
Techniques Used in Fouling Measurements ( Knudsen [l] )
Test Section Inside of Tube, Annulus, Sphere, Outside of U-tube,

Geometries Metallie Strip, Plate, Wire, Wire Coil, Shell Side of Shell-
and-Tube Heat Exchanger , Helix
Methods of Heating Sensible Fluid Heating, Condensing Vapor, Electrical

or Cooling Resistance Heating of Test Section, Indirect Electrical
@ProcessEng
Heating, Thermo-Electric Heating or Cooling
Methods for Visually , Direct Weighing, Microscopically,

Monitoring Deposit Pressure Drop, Thermally, Radioactively, Chemically,
Electrolytically
Reproduced by permission af Hemisphere Publishing Company,@1981
49
so
Since the extent of fouling varies with time, a series of measurements is usually made
at frequent intervals for an extended period of time. There is no known way to
compress the time required for fouling measurements to provide meaningful results.
Knudsen [1] reviewed a number of research units and categorized them according
to the geometry of the test sections and the way that heating or cooling of the test
fluid was provided. The most common geometries are test sections with the test fluid
either flowing inside a tube or inside an annulus. Heating is more common than
eooling and there are many advantages to doing it eleetrically either direetly or
indirectly. Electrieally heated devices have the advantage that the local heat flux can
be determined, permitting the determination of the local heat transfer coeffieients and
fouling resistanee. The use of indirect electrieal heating is preferred, sinee it does not
restrict the type of material of the heat transfer surfaee. Although direct eleetrieal
resistance heating is convenient, the materials of the test section are limit ed to those
with high eleetrical resistivities and the wall thiekness must be very uniform or else
the heat flux will vary over the surfaee.
Constant wall temperature deviees make use of the boiling or eondensing vapor to
transfer heat. As fouling proeeeds, the wall temperature remains eonstant and the
heat flux deereases. Even though the wall temperature may be known, the loeal heat
flux eannot be determined and hence only average fouling resistance for the test
section can be determined. Since the boiling and condensing coefficients vary with
time, there is considerable uncertainty in the measured fouling resistances.
There are some significant liquid-liquid devices where the test fluid is the one that
is fouling. The heating or cooling fluid should flow at a high mass rate to minimize its
temperature change and must be nonfouling in nature. These devices are limited to
low heat fluxes and are particularly attractive for studying heat transfer surfaces of
complex geometries.
Some units perm it direct visual inspection of the fouling buildup during a test run
while others require that the test section be disassembled before the fouling can be
examined or sampled. In addition, some fouling measuring devices determine the
increase in pressure drop with time. Although most research fouling measuring
devices operate with heat being transferred, a few operate isothermally. They do not
determine the fouling resistance, but rather provide information about the fouling
buildup either by a pressure drop increase or by visual observation.
A series of these different research units will be discussed under the general
categories of their test section geometries.
2.1 Annular Test Section. One of the most attractive geometries for a test section is
annular with the heat source in the central core so the heat transfer surface is its outer
wall, the test fluid flowing in the annular core, and the out er cylinder of a transparent
material to permit visual observation of the fouling growth. Such a measuring device
is described by Fischer, et al [2] and illustrated in Fig.!. Thermocouples are used to
measure the temperature of the wall of the heater rod which can be made from a
variety of different materiais. Heat is generated at a measured rate in an electrical
resistance heater that is located at a position so that fully turbulent flow of the test
fluid has been established.
The advantages of this test section configuration are that it can be small in size,
can give accurate results, the test section is removable for deposit inspection, and the
metal from which the heater wall is made can be varied. This type of unit can show
@ProcessEng
changes in fouling quickly, and the results can be immediately available fron an on-
line computer data acquisition and evaluation program. The limit at ions of this type
of test unit are those associated with thermocouple calibration, sensitivity to
fluctuations in the operating conditions, and the fact that it requires electrical power
(a possibie problem when testing hazardous fluids). This type of device is limited to
heating studies.
51
40 cm
Ou'.r Glau
Tub.
r-- 10cm -1
4 flgw
Figure 1 Annular Test Seetion Geometry with Indireet Eleetrieal Heating
Annular test seetions provide a well known geometry to ea1culate the loeal fouling
resistanee from heat flux, flow rate, and temperature measurements. Figure 2 shows a
typieal eross section of an annular test seetion that has been fouled. Notiee the
thermoeouple loeated in the heater wall. The objeetive is to ea1culate the fouling
resistanee from temperature measured by the thermoeouple. The thermal resistanees
ean be represented by an equivalent series of eleetrieal resistanees, R w' R f , and Rtf as
illustrated in Fig. 3. Temperatures are then represented by voltages. The
thermoeouple temperature, T te' the bulk temperature, T b' and the heat input are
measured. Knowing the heat transfer surfaee area the total thermal resistanee, R tot '
ean be ealculated.
(I)
(Q/A)
To ea1culate the fouling resistanee, R w and Rtf must be known. The R w eomes from
the heater rod ealibration, while Rtf is ealculated from known heat transfer
eorrelations and is a funetion of the reeiproeal of the test fluid velocity raised to a
power.
CIaø
Tube • Bulk TemperatuR, Tb
Foulin, Swface-:----....
~ ., Surfa.e Temperatu .., T.

/x ~ ~
'~ThennOCOUPI' TemperatuR, T te
Tube
?W)/. .~
WaIJ
Thennocouple
@ProcessEng
Figure 2 Cross Seetion of Annular Figure 3 Equivalent Thermal Cireuit

Test Seetion
52
2.2 Single Cylindrical Tube Test Seetion. Various forms of the eylindrieal tube test
seetion use different means for heating or eooling the test fluid flowing through the
tube. Direct eleetrieal heating, in direct eleetrieal heating, or thermoeleetrie heating
and eooling ean be used. Condensing vapors or boiling liquids to provide uniform
temperature or sensible liquid flow heating or eooling ean be used. The wall of the
test seetion ean be either thin or thiek, and the loeation of the thermoeouples varied
depending upon the method for determining fouling. Several different types of units
using single tube test sections are shown in Figs. 4 through 6. The tubes ean be made
of different metals; either eooling or heating fouling studies ean be made; and the
observed fouling ean be related direct ly to the tube side of a heat exchanger. The
limitations are the relatively large heat transfer surfaee area required and the inability
to visually observe the fouling buildup while the tests are in progress.
2.3 Transient Temperature Measurement Test Seetion. This type of test seetion uses
a different measurement teehnique to determine fouling. There is a large eopper block
that is elamped tightly around the single tube test seetion. This ean be indireetly
heated eleetrically and has thermoeouples imbedded in it at precisely known radial
loeations. Periodieally this block is heated to a uniform temperature and the power
turned off. The temperatures at the thermoeouples deerease with time as the bloek is
Reproduced by permission of Hemisphere Publishing Company,«>1981 Reproduc.ed by permisston of Hemisphere Publishing Company,~1981
Figure 4 Thin-W alled Cylindrieal Test Figure 5 Thiek-W alle d Cylindrieal Test
Seetion with Eleetrieal Heating Seetion with Electrieal Heating
[l) [1)
Steam
Instrumentation Outa- Jacket

Port
@ProcessEng
' - - Condensate
Condensate to Drain to Rotameter
Figure 6 Cylindrieal Test Seetion with Condensing Vapor Heating

53
~cu Reference Block
!
6 ft g~ 103
w
-'
li:
!I
eJ
i!'
102 ':---'-..--'--'--,'---'----:-'-:----'-cL:--,'----'
O 48 96 144 192 240
TIME -SEC
Reproduted by permission of Hemisphere Publishin& Company,@1981
Reproduced by permission of Hemisphere Publishinz: Com~ny,«:>1981
Figure 7 Test Section Using Temperature Figure 8 Transient Technique

Transient Technique [1) Temperature Decay [1)
being cooled by the flowing test fluid. These plots can then be used to determine the
fouling. Typically the fouling has taken place under isothermal conditions. This type
of monitor has been used extensively for biofouling studies where the temperature of
the heat transfer surface is normally very dose to that of the test fluid. A sketch of a
biofouling test unit by Fetkovich et al [3] is shown in Fig. 7 with the accompanying
typical temperature decay curve obtained shown in Fig. 8.
2.4 Multiple Cylindrical Tube Test Section. Multiple tube test sections are used so
that one of the significant parameters can be varied while maintaining the other
variables constant. Tubes of different materials in the same test heat exchanger are
used to study differences in corrosion and the development of fouling. Different
velocity or surface temperature in parallel tubes during a test can be used to evaluate
the influence of these parameters. Although requiring separate test fluid supplies,
some test units permit the evaluation of fluid treatment programs. A typical two-tube
test heat exchanger is shown in Fig. 9. The main characteristics of this type of test
section are: the buildup of fouling is not visible during tests; it only provides average
fouling results; and some units require disassembly before fouling determination can
be made.
Dr
@ProcessEng
=: CL----:::::-5 :
{}
Figure 9 Two-Tube Test Heat Exchanger

54
2.5 Shellside Heat Exchanger Test Section. All of the test sections discussed thus far
have had the test fluid flowing either inside ofa tube or in an annulus. These provide
the simplest geometries to analyze and control. However, many of the serious fouling
problems exist on the shell side of heat exchangers. Fiseher et al [2] describe the
HTRI shellside fou!ing research unit used to investigate the fouling characteristics of
treated cooling water. The unit uses steam-heated hot water as the sensible heating
fluid, and the fouling resistances are determined by overall measurements.
The unit has two 7-in. diameter shell-and-tube test heat exchangers, each with
over 100 tubes. One exchanger is 19 in. Ion g and the other is 37 in. long. Both have
the same number of crosspasses with baffle cuts to match the baffle spacing. In
addition to the two shell-and-tube heat exchangers, there was a plate heat exchanger
tested in parallel. Figure 10 is a schematic diagram for this packaged unit that ean be
transported by truck between test sites.
Nitrog en -t>lc:r-'---l
Condensate
200 psig --DI<r--+'

Steam
CTW
" - - - - - - - - - - - - - _ CTW
Figure 10 Flow Diagram for a Shellside Fou!ing Research Unit
2.6 Coiled Wire Test Section. The test section contains a small, electrically heated
coil mounted perpendicular to the flow of the test fluid as shown in Fig. 11.
Electricity is used to resistance heat the
wire coil and the voltage is measured to Flow
II
determine the temperature. The main o II

advantages of this type of test unit are that S.dlon 'A' ·'A'
it is small, gives quick results, and is simple
to operate. Its !imitations are: it ean only be
used for heating-fouling studies; the
accuracy of the heat transfer calculations to
determine the fouling ia questionable; and
@ProcessEng
the application of the data to actual heat

exchangers is difficult. However, Fetissoff et
al [4] have found that the initial fouling rate
and the initiation time until fouling begins
compare favorably with data observed from
a more sophisticated annular test section
Reproduttd by ptnniSSM)fl of Hemisphere Publishin, Company.(g1981
apparatus.
Figure 11 Electric Coil Test Section [1)
55
MIL K IN
Figure 12 Cross Seetion of Heated Radial Flow Test Seetion
2.7 Test Seetion to Study Wall Shear Effeets. Fryer et al [5] describe a fouling test
unit that causes the test fluid entering at the center to flow radially with ever
deereasing velocity. By examining the position where the fouling deposit develops, it is
possibie to ealculate the equivalent shear stress. Figure 12 shows the cross-section of
this heated test seetion.
2.8 Test Seetions without Heat Transfer. There are several different test sections that
measure the presence of fouling by manifestation other than thermal resistanee. These
units typieally operate in a nonheat transfer mode. There is no heated or eooled
surface. These units are often used to study biological fouling or the effeets of
eorrosion. Visual inspeetion of samples and eomparative data are the usual results.
The inerease in the pressure drop of a constant fluid flow through a eireular test
section is one teehnique that is used. As the fouling layer buiids up, there is a deerease
in the available flow area and often a roughening of the surface. Carefully measuring
the ehange in pressure drop gives an indireet indication of fouling. This teehnique is
very effeetive in determining the buildup of biofilms beyond the viseous sublayer of the
test fluid next to the wall. This ean be observed mueh earlier than anyehange in the
thermal resistanee.
Another phenomenon that is used to indieate the presence of microbiological slime
is the potentiodynamic polarization effeet. This alters the eathodie reaction of a series
@ProcessEng
of probes in an isothermal monitor to indieate the severity of this type of fouling.
3. PARAMETERSMEASURED
Depending upon the objectives of the monitor operation, different parameters are
measured. If visual inspeetion provides adequate information, then only those
parameters eharaeterizing the test fluid and its flow rate need be determined. On the
other hand, if the thermal resistanee of fouling is to be obtained, many additional
parameters must be measured.
56
There are at least three different measurement approaches used to monitor heat
transfer fouling.
• Maintain a uniform heating medium temperature and constant test fluid
velocity and inlet tempererature. Any change in the test fluid out let
temperature is an indication of the fouling.
• Maintain the test fluid inlet and outlet temperatures and flow rate constant by
adjusting the heating medium temperature. Any required increase in heating
medium temperature is an indication of fouling.
• Maintain the test fluid inlet and outlet temperatures and flow rate constant by
adjusting the heating medium temperature. Any required increase in the
heating medium temperature is an indication of fouling.
3.1 Instrumentation Reguirements. The degree of sophistication of the instruments for

fouling monitors varies with the need for accurate data, the amount of manual control,
and the requirements for automat ic data acquisition. The obvious parameters to be
measured during the progress of tests are flow rates, temperatures, pressure drops,
conductivity, pH, corrosion rate, and fluid characterization. Measurement of the
thickness of fouling layers is als o desirable. Analysis of the fouling layer subsequent to
visual observation is usually accomplished in a laboratory equipped with specialized
instrumentation. Automatic control of test con dit ions de pen ds upon feedback from
sensors that measure critical parameters. Test units are increasingly equipped with
small computers that act as data loggers, results calculators, and at times overall test
controllers.
Thermometers, thermocouples, resistance thermometers, and thermistors are used
on different test units to meas ure temperatures. These must be carefully installed to be
sure where the temperatures are being measured. Calibration is obvious if the
measured temperatures are to be trusted.
3.2 Calibration. To be able to calculate fouling resistance it is necessary to determine

the temperature at the heat transfer surface from a temperature measured in the tube
wall. Normally , neither the exact distance nor the thermal conductivity of the
intervening metal is known. However, Wilson [6] developed a graphical means to
calibrate a heater rod to obtain the wall resistance term, R., which is equivalent to the
ratio of the thermal conductivity to the distance. This technique is widely used to
calibrate the test sections of fouling measuring devices.
To be able to make a Wilson plot, it is necessary to first experimentally determine
the overall heat transfer coefficients, U, for a series of different velocities when the test
section is clean and unfouled. Then, plot values of l/U versus l/v". Curve fit the data
which wilt fall along a straight line which has an intercept equal to the value of R. =
ydkf. A typical Wilson plot is shown in Fig. 13. Notice that it is not necessary to
know either the distance from the thermocouple to the surface or the metal thermal
conductivity to determine R.; however, knowing one permits the calculation of the
other. The equation for the overall clean heat transfer coefficient can be shown to have
the folIowing straight-line form
@ProcessEng
It should be observed that higher velocity

u
measurements are more accurate than lower
velocity ones. Errors in calibration are
higher for materials of higher thermal
conductivity or for heaters with the
thermocouples nearer the wall surface. ---
Figure 13
l/V"
Typical Wilson Plot
57
3.3 Thermal Resistance Calculations. The simplest relationships required to

determine the fouling resistance make comparisons between the overall heat transfer
coefficients when the test section is dean and when it is fouled. The folIowing are those
relationships:
(Q! A)
D--- (3)
MTD
where D overall heat transfer coefficient

Q heat transfer rate
A heat transfer surfaee area
MTD effective mean temperature difference
(4)
where fouling resistance
overall heat transfer coefficeint for fouled test section
overall heat transfer coefficient for dean test section
It is necessary to adjust D o for the actual flow conditions and temperatures occurring
at the time that D f was measured. The values of (Do)meas were measured when the
test section was dean for varying flows. The values of (Uo)calc can be calculated from
known methods such as given in HEDH [7] for temperature and flow conditions at the
time U f was measured. A correction factor K can be determined
(5)
Thus, it is possibie to determine the value of the thermal resistance R f by
1 1
Rf =------ (6)
Uf K (Uo)calc
It is interesting to note that as a fouling
layer initially starts to build it causes the
surface to roughen with the effect that the
local heat transfer coefficien t inc reases.
Thus, the calculated fouling resistance may o
appear to become negative. As the fouling
layer thickens, the effect of the lower
thermal conductivity overtakes the

improved local heat transfer coefficient due
to roughening and the fouling resistance o --- Time
becomes positive. Crittenden and Khather
[8] pointed out this phenomenon as shown in Figure 14 Apparent Negative Fouling
Fig. 14. Resistance
@ProcessEng
3.4 Deposit Analysis. In addition to determining the thermal resistance and the
pres sure drop increase caused by fouling, it is usual to analyze the deposits to
determine their source and to seek methods of prevention. The major tests conducted
are atomic absorption spectra to identify the major element al constituents, x-ray
diffraction to determine the probable compounds, loss-on-ignition (LOI) tests to
measure the mass loss of organic materials and water of hydration, and total carbon
58
(TC) tests to determine the organic content of the deposit from hydrocarbons and/or
biological material. When studying biological fouling, it is customary to make colony
counts. If the test fluids are hydrocarbons, the coke fraction and the extent of
inorganics are determined from LOI tests. Solvent extraction tests are conducted using
pentane to identify resins and free oil and using toluene to identify asphaltenes.
3.5 Pressure Drop. It is well known that fouling als o causes an increase in the pressure
drop. In some instances the consequences of increased pressure drop are more critical
to a plant's operation than the deterioration of the thermal performance.
Instrumentation used to measure the pres s ure drop must be adequate to detect small
changes. Test units should be calibrated when clean for various test section flow rates
unless the geometry is such that pressure drops can be predicted accurately by well-
established equations.
3.6 Other Parameters. There are a nu mb er of measurements that can be made to

characterize the test fluid and assist in locating the causes of fouling. These include the
test fluid chemical composition, the presence of impurities, catalysts, treatment
additives, or suspended solids. In closed cooling water systems, the character and
extent of makeup can be important in the interpretation of measured results.
4. LIQUID FOULING MONITOR DEVICES

There are a number of ways in which fouling monitors can be used. Among the
obvious are their use to study the behavior of a particular heat exchanger, to predict
the fouling behavior of a cooling system, to evaluate the effect on fouling of anticipated
changes to an operating system, to determine the effects of a proposed treatment
program prior to installation and set dosage leveis, to determine when cleaning
operations should be undertaken, and to evaluate the effectiveness of the cleaning
process.
Fouling monitors can be as sophisticated as fouling research units, but they differ in
that their objective is somewhat different. Fouling monitors must be controllable so
that they simulate the actual conditions in an operating plant. They are usually
installed directly in series or parallel with plant equipment. They do not have the same
degree of control over uniform fluid control throughout the duration of a test and, in
fact, can be extremely valuable when there is some sort of plant upset. The parameters
measured and the techniques used to study fouling parallel those used in research test
units.
4.1 Experimental Fouling Monitors. A number of specialized fouling monitors have

been developed for a one-time investigation of a particular problem in an operating
plant. These are often special test exchangers that can be controlled to simulate
conditions in troubled exchangers. In addition, controlled changes in the operating
condi tions, filtration processes , treatmen t chernicals addition, or materials of

construction are typical. These fouling monitors are usually supplied with the test fluid
from a slip-stream of the suspected process stream. Precise measurement of fouling
resistances is desirable, but probably not as usual as comparison of the relative effects
of parameter variation.
4.2 Commercial Fouling Monitors. Moore p,nd Rays [9] prepared a survey of
@ProcessEng
commercial fouling monitors that could be used for cooling water systems. Since the
majority of liquid fouling monitors in the field are used in this service, the folIowing
summary of these is given:
• Betz Laboratories - Monital 79 - is a fouling monitor that uses an indirectly
heated tube test section. It can be used for corrosion, biofouling, and total
fouling studies. Local fouling resistance can be determined; however, pres sure
drop is not measured. See Fig. 15.
59
r;:==-=;;:;::;, TEIT ASSEMILY r;::==::::::::::::::;-t
L:===~~ :~~ ~~===:J

TUT BLOCIC W1TH WATfltsuPPl,Y
GlASSCYLlIiIOERAIID
ACIYUCltul!lO
R~produced by permission of Bett Laboratories, Inc.(91919

Figure 15 Betz Monitrol 79 Fouling Figure 16 Betz Dual Tube Test Heat
Monitor Exchanger
• Betz Laboratories - Test Heat Exchanger - uses a smal! steam-heated multiple-
tube heat exchanger as the test section. It can be used for corrosion,
biofouling, and scaling fouling studies. Average fouling resistance is measured.
Results from tests using tubes of different metals or test fluids can be
compared. Pressure drop is not measured. Figure 16 is a picture of a two-tube
test heat exchanger.
• Bridger Scientific - DATS 1200 - uses an indirectly-heated single tube test

section surrounded by a block of metal in which thermocouples are mounted at
different radial distances. The unit als o measures pres s ure drop and has on-
board control and data acquisition equipment to perrnit real time data
calculation. It can be used for biofouling and scaJing studies. Local and
average fouling resistances can be measured. The unit is pictured in Fig. 17.
H {Af) OlHPtfT
----,..,-.-.--A'--···~--·-···Courtesy of Bridger Scientifie, Ine, Sandwich, MA
Figure 17 Bridger Scientific DATS 1200 System

• Calgon Corporation - CORROSION DEPOSIT TEST UNIT - uses a test

section composed of a series of samples subjected to the same test fluid.
Average fouling is determined after a test run is completed. The effect of
corrosion is indicated by the amount of sample weight loss for the test run.
• Drew Industrial Division - P-U-L-S-E® Mobile Analyzer - uses an indirectly-

heated annular test section. The unit is mounted in a climate-controlled
@ProcessEng
mobile van that can be moved to the plant site. On board are the
measurement, control, data logging, and computer equipment to make
sophisticated evaluations of corrosion, biofouling, scale, and local fouling
resistance. In addition, fluid conductivity and pH are logged; however,
pressure drop is not measured. The Drew Van is shown at a plant location in
Fig. 18.
60
Reproduced by permission of Drew Industrial Division, Reproduced by lHrmission of Drtw Industrial Division,
Ashland Chemical Co., Div. Ashland Oil. Ine. Ashland Che,.'ical Co., Div. Ashland Oil, Ine.
Figure 18 Drew P-U-L-S-E® Mobile Figure 19 Drew P-U-L-S-E® Fixed

Van Fouling Analyzer Fouling Analyzer
• Drew Industrial Division - P-U-L-S-E®Fixed Analyzer - is a version of the P-U-

L-S-E®Mobile Analyzer that ean be installed for ongoing monitoring at a plant
site. It has essentiaIly the same features, but it is not installed in the mobile
van. This unit is illustrated in Fig. 19.
• Great Lakes Chemieals - BIO FILM MONITOR - uses an isothermal test

section to measure the variation of pressure drop to deteet the development of
biological fouling. This unit is not intended to measure thermal fouling.
• Mogul Corporation - DEPOSIT MONITOR - uses an indireet eleetrially-

heated annular test seetion. The unit has a special eorrosion probe and
provisions for sample eoupons. Both loeal and aver age fouling resistanees ean
be ealculated. This unit is not in ten de d for biofouling studies.
• Naleo Chemieal Companies - MONITOR DMI-M - uses an indirect

eleetrieally-heated tube whieh ean be used to obtain total and aver age fouling
resistanees. This monitor has provisions for eorrosion measurements and
sample eoupons.
• Naleo Chemieal Companies - DEPOSIT MONITOR DM2T - uses an in direct

eleetrieally-heated annular test section to obtain both loeal and and total
fouling resistanees. It is not suited to biofouling studies. Corrosion is
measured by weight los s of samples.
• Petrolite Corporation - FOULING MONITOR - uses an indireet eleetrieally-

heated annular test seetion to obtain total, average, and loeal fouling
resistanees. Heat input and flows are controlled manually. It is not well suited
@ProcessEng
to biofouling studies. Corrosion is measured by a special pair probe, and

provisions are made to measure test fluid pH and eonductivity.
To supplement these deseriptions, Table 2 has been prepared to summarize addition al

features of these monitors. Included are the addresses of the suppliers, the physieal
size and weight of the units, and their availability. The list of monitors presented is
representative, but not meant to be exhaustive. There eertainly are additional liquid
monitors commercially available.
61
Table 2
Commercial Fouling Monitors
Vendor Unit A vailability, Size, and Weight
Betz Laboratories Monital 79 Loan

Somerton Road 1.5 x 1.5 x 2 ft
Trevose, P A 19047 40 Ibs
Test Heat Loan

Exchanger 3 x l-ft dia
30 Ibs
Bridger Scientific DATS 1200 Lease or purchase

805 N. 7th Street 2 x 7 x 8 ft
Suite 240 120 Ibs
Bozeman, MO 59717
Drew Industrial Division P-U-L-S-E® Loan

Ashland Chemical Co Mobile Installed in mobile van
One Drew Place
Boonton, NJ 07005 P-U-L-S-E® Special Arrangements
Fixed 3x5x7ft
600 Ibs
Great Lakes Chemicals Bio Film Sale

P.O. Box 1878 1x4x7ft
El Dorado, AR 71730 50 Ibs
Calgon Corporation Corrosion Loan or lease

Calgon Center, P.O. Box 1346 Deposit 1.5 x 1.5 x 2.5 ft
Pittsburgh, P A 15230 40 Ibs
Mogul Corporation Deposit Loan

7145 Pine Street 3 x 2.8 x 0.75 ft
Chagrin Falls, OH 44022 50 Ibs
National Association of Test Heat Built to specifications

Corrosion Engineers Exchanger 5 x 5 x 5 ft
Technical Activities Dept. 100 Ibs typical
P.O. Box 218340

Houston, TX 77218
N alco Chemical Company DM1-M Sale

1801 Diehl Road 2 x 1 x 1.5 ft
N aperville, IL 60 Ibs
@ProcessEng
N alco Chemical Company DM2T Loan

2901 Butterfield Rd. 2 x 1 x 2.5 ft
Oak Brook, IL 60521 70 Ibs
Petrolite Corporation Fouling Loan with treatment program

369 Marshall A ve. Monitor 1x2x4ft
St. Louis, MO 63119 80 Ibs
62
The choice as to which of the available monitors to consider depends upon a

number of very practical considerations. What, where, when, and how long are the
monitor activities expected to continue? How much data are required and how
accurate do they need to be? Can the data be intermittent or need they be taken
continuously? Will the monitor be used to retlect the operation of a particular plant
heat exehanger? Are the data obtained from the monitor easy to correlate to plant
experienee? Will they be used to predict anticipated performance? How much plant
personnel attention will be required? What are the operational and maintenanee
requirements of the monitor? As ean be seen from the above questions, it is important
that the intended use of a fouling monitor be clear before selecting the appropriate
fouling monitor.
5. INSTRUMENTATION OF PLANT HEAT EXCHANGERS

Although not uniquely fouling monitors, an increasing number of heat exchangers
are being instrumented to provide individual performance data from which fouling
information ean be obtained. The exchangers in question are most often those that
have experienced severe fouling problems. However, one large refinery on the west
coast of the United States has instituted an on-line surveillance of all its heat
exchangers. The trend of performance for each is traced through its apparent fouling
resistance. This monitoring is used to determine the appropriate time for cleaning
and maintenance. The data ean provide diagnostics for troubleshooting and needed
performance data for unit replacement and plant expansion.
In the usual proeess plant, the instrumentation is not adequate to perrnit local
measurements for a specific heat exchanger. Some data ean be obtained by inference
from other measurements. Therefore, much of the data from plant heat exchangers is
found to be inaecurate and ineonsistent. It may be difficult to trace variations in
conditions that initiated a particular fouling trend.
For these, and many more reasons, it is increasingly attractive to install small-
sized fouling monitors that operate using slip-streams in operating plants. These ean
indicate the rate of fouling buildup and the effect on the performance of plant heat
exchangers. They ean als o be operated to simulate different operating conditions to
determine the consequences. Changes in the treatment program ean be tested on a
small seale so that when applied to the whole plant the effects will be understood.
Several different examples of instrumentation of plant heat exchangers will illustrate
typical applieations.
5.1 Seawater Heat Exchangers. Lira et al [10] describe tests where seawater on the
tube side was causing serious biological fouling. Copper-based tubes had been
replaced by titanium tubes which were found to biologicaIly foul more rapidly. While
the eopper-based tubes emit toxic agents, the titanium tubes do not. Chlorination
had been the means for preventing the buildup, but there were environmental
consequenees. Thus, there was a search for another means to prevent this fouling. A
new teehnique was proposed that involved passing a small eleetric current through a
titanium wire at the center line of each tube. This would provide anodic proteetion
and re due e biological fouling. Three small double-pipe heat exchangers as shown in
Fig. 20 were constructed to be tested in parallel. The results of the initial
investigation were encouraging as fouling was significantly redueed. A full-scale
installation has now been made in a power plant con dens er to verify the results of the
@ProcessEng
monitor tests and to demonstrate the effectiveness of the technique.

63
WBE
3.81 cm OD
3.56 cm ID
ENCLOSURE~-:A~~;;;t)
WBE SIllE
SHELL SIllE
2.64 m.
Figure 20 Experimental Shell-and-Tube Heat Exehanger
5.2 Surfaee Condensers. Sato et al [11] deseribed tests to validate the effeetiveness of
ad ding a proteetive film on in situ tubes of a large surfaee condenser in Japan. To test
the approach they built the small test heat exehanger shown in Fig. 21 to compare the
performance of a fouled tube removed from the plant surfaee condenser with that of a
clean tube. After reworking the surfaee condenser , they then installed in seleeted
tubes instrument probes as shown in Fig. 22 to measure local velocities and
temperatures. The results of the tests using this specialized monitor instrumentation
were indications that the procedure would extend the usefullife of the existing tubing,
prevent eorrosion, and minimize the effects of fouling.
M.nom ••.,
Cooling water Pitot tube
(4 mm 0.0. 3S0mm L)
r;======''!==~==~=;] Standard
~1t==--fl(C_'-" ~
Pt ,.liltancl
th.rmoml'lr
Til. tube
(foul.d tube)
(3.2 mm 0.0.. 1002) IT'htrmomt.ar I
cover
Figure 21 Steam Heated Two-Tube Heat Figure 22 Probe for Tube Local Flow
Exehanger Fouling Monitor Rate and Temperature
6. CONCLUSIONS
Fouling monitors eome in a variety of configurations. They range from simple
devices that provide qualitative information from visual inspection to highly
sophisticated research-quality instruments that provide detailed data concerning the

many charaeteristics of fouling. Most fouling monitors have had their origin in one or
another of the research fouling measuring devices. They have been refined and
adapted to meet the specific needs of industry. Organizations providing various
treatment products for the control of corrosion and fouling have been instrumental in
promoting the use of these devices in support of their sales and services. Large users
of heat exchangers have been interested in installing monitors to assist in plant
@ProcessEng
operation performance improvement. The incentive is to reduce operating,

maintenanee, and cleaning eosts. The impaet of fouling measuring deviees is only
beginning to be felt as the competitive nature of the process and power industries
beomes increasingly intense. A suceessful fouling monitor program ean result in
substantial energy savings and provide the necessary feedback for improving the
design of future heat exchangers.
64
Acknowledgment
The author is grateful to the HTRI Management and Technical Committee for
permission to publish this paper. It should be noted that it does not contain HTRI
proprietary information nor does it necessarily represent HTRI recommendations.
Rather, it is intended to provide a helpful interpretation of published literature in the
light of HTRI experience in the same area.
References
l. Knudsen, J. G., "Apparatus and Techniques for Measuring of Fouling of Heat

Transfer Surfaces," Fouling of Heat Transfer Equipment, pp. 57-81,
Hemisphere, Washington, 1981.
2. Fischer, P., Suitor, J. W., and Ritter, R. B., "Fouling Measurement
Techniques," Chem. Engr. Prog., Vol. 71, No. 7, pp. 66-72 (1975).
3. Fetkovich, J. G., Grannemann, G. N., Mahalingham, L. M., and Meier, D. L.,
"A System for Measuring the Effect of Fouling on Heat Transfer Under
Simulated OTEC Conditions," Proc. 4th Conf. on Ocean Thermal Energy
Conversion, pp. VII-15-23, New Orleans, 1977.
4. Fetissoff, P. E., Watkinson, A. P. and Epstein, N., "Comparison of Two Heat
Transfer Fouling Probes," Proc. 7th lntl. Heat Trans. Conf., Vol. 6, pp. 391-396.
Munich, 1982.
5. Fryer, P. J., Pritchard, A. M., Slater, N. K. H., and Laws, J. F., "A New Device
for Studying the Effects of Surface Shear Stress on Fouling in the Presence of
Heat Transfer ," ASME HTD- Vol. 35, pp.33-42, N alt. Heat Transfer Conf.,
Niagara Falls (1984).
6. Wilson, E. E., "A Basis for Rational Design of Heat Transfer Apparatus," Trans.
ASME, Vo1.37, pp. 47-82 (1915).
7. Bell, K. J. (ed.), "Thermal and Hydraulic Design of Heat Exchangers," Heat
Exchanger Design Handbook, Vol. 3, Hemisphere, Washington, 1983.
8. Crittenden, B. D. and Khather, E. M. H., "Fouling from Vaporizing Kerosene,"
Fouling in Heat Exchange Equipment, J. W. Suitor and A. M. Pritchard, eds.,
ASME HTD-Vol. 35, pp. 57-64 (1984).
9. Moore, W. E. and Hays, G. F., "Guidelines for Selection and Use of On-Line
Fouling Monitors," Paper TP-85-2, Cooling Tower lnstitute, CTI Annual
Meeting, 1985.
10. Lira, R., Poteat, L. E., Camerota, L, and Sengupta, S., "Marine Biofouling
Control with Anodically Polarized Protection in Shell and Tube Heat
Exchangers," Effects of Fouling and Corrosion on Heat Transfer, ASME HTD-
Vol. 50, pp. 25-32, Miami Beach (1985).
Il. Sato, S., Nosetani, T., Hotta, Y., lkushima, Y., and Yamashita, S.,
"lmprovement of Surface Condenser Performance by ln-Situ Artificial Protective
Film Coating," Effects of Fouling and Corrosion on Heat Transfer, ASME HTD-
Vol. 50, pp. 17-24, Miami Beach (1985).
COPYRIGHT ACKNOWLEDGMENT
Figure 15 is reproduced by permission of Betz Laboratories, Inc.
@ProcessEng
Copyright 1980, from Betz Handbook of Industrial Water Conditioning, 8th

Edition, 1980.
Figure 16 is reprodueed by permission of Betz Laboratories, Ine.
Copyright 1979.
Figure 17 is reprodueed by permission of Bridger Seientifie, Ine.,
65
Sandwich, MA, USA.

Figures 18 and 19 are reprinted with permission by courtesy of Drew In-
dustrial Division, Ashland Chemical Company, Div. Ashland Oil, Ine., USA.
Figures 4, 5, 7, 8 and 11 are reproduced by permission of Hemisphere
Publishing Corporation, N.Y., USA.
@ProcessEng
GAS-SIDE FOULING MONITORING EQUIPMENT
A. TSADOS
CHEMICAL ENGINEERING DEPARTMENT, UNIVERSITY OF BIRMINGHAM, P.O. BOX 363,

EDGBASTON, BIRMINGHAM, BIS 2TT, U.K.
1. INTRODUCTION
Gas-side fouling is a subject which has received increasing attention
in recent years. The variety of fuels used by industry has added to the
problems of gas-side fouling which were generaily limited to oil and coal
firing systems. In situations involving combustion produets, heat is
transferred from the gases to the proces s fluid and depending on the
contamination of the gas steam, the insulating layer of material which
accumulates on the heat transfer surfaces, reduces the flow of heat.
A wide variety of devices has been used to obtain fouling data from
gas streams. These device s range from simple circular discs to full-size
heat exchangers. Most of the fouling probes are in the form of single
cylinders, which are capable of maintaining a surfaee temperature by
passing air or water through the inner section of the probes.
2. CLASSIFICATION OF F?YyING PROBES

Marner and Henslee recently reviewed the devices used to characte-
rise the fouling tendency of a gas stream. They identified five different
types of probes:
a) Heat flux meters. These follow the changes in heat flux, thus
monitoring deposition on surfaces.
b) Mass accumulation probes, which ean also measure corrosion rate.
c) Opitical devices these are limited to laboratory control led
conditions.
d) Deposition probes, which are used for qualitative analysis of the
deposit.
e) Acid deposition probes. These measure the acid dew-point and acid
deposition rate, and are available commercially.
In the present study, the mass accumulation and deposition probes will
be considered, with brief reference to the other types. Additional
experimental techniques and methods to characterise the combustion gas and

the foulant will also be described.
3. FOULING PROBE REQUIREMENTS

Inthe design of a fouling probe, which has to be used on different
sites under varying conditions the foliowing characteristics are
desirable:
@ProcessEng
a) The probe should be of robust construetion, to tolerate arduous

operating conditions.
b) It must be of sufficient length to reach the required test
location.
c) Its weight should be kept to a m1n1mum for ease of handling.
d) The required services should be kept to a minimum for practical
reasons.
67
L. F. Melo et al. (eds.), Fouling Science and Technology. 67-:76.

68
e) The sur face temperature should be controllable over a range of

temperature.
f) The collecting surface should be large enough to ensure adequate
amounts of deposit to permit (i) accurate weighing and (ii)
chemical analysis.
g) The target surface texture should be reproducible.
h) Testing of different materials under similar conditions at the
same time would be an advantage.
i) Automatic data acquisition enables long term exposure of the probe
to be employed.
In order for a fouling probe to be able to monitor fouling resistances
during a test, certain gas properties should be evaluated as a function of
time. These properties are the gas velocity and gas temperature near the
target area.
4. MASS ACCUMULATION PROBES

The most useful information extracted from the employment of mass
accumulation probes, is the measurement of the deposit mass collected on
the probe. The mass deposition rate can then be expressed as a function
of surfac t2y emp erature.
Brown investigated the deposition of sodium sulphate from
combustion gases. A pilot-scale furnace was used where flue gases were
produced by burning kerosene stoichiometrically. The probe was air cooled
and the deposit collecting surface was in the form of cylindrical
stainless steel sections. The diameter of the test sections was 25 mm
with thermocouples inserted in holes drilled into the inside wall to
monitor surface temperature. The weight difference before and af ter
exposure was taken as the total deposit. No corrosion was observed on the
surface of the specimens during the runs. The advantage of this probe was
its ability to test a number of specimens at different temperatures. The
surface temperature could be controlled in the range 400 o C, in tests
lasting up to 10 hours. Brown used this probe to study the effect of
additives in the fuel at different excess air levels to (less than 1 per
cent to 25 per cent). He found that the rate of vapour deposition of
sodium sulphate was independent of the quantity of excess air used in the
combustion process. This would suggest that sodium sulphate could be
formed by a series of reactions involving S02 instead of S03' Vapour
diffusio?3yas assumed to be the main deposition mechanism.
Hein made a study of deposit formation from flue gases produced
from combustion of coals, in thermal power stations. The experimental rig
consisted of a roof-fired, steam-cooled, cylindrical combustion chamber of
1.2m diameter. The maximum throughput was 500 kgfhr of coal. Parameters
which could be varied included the coal particle size distribution, excess
air level and temperature of combustion air. Using a fouling probe Hein
was able to produce empirical correlations relating the deposition rate
with the above mentioned parameters. The probe included two sections; an
air cooled section and an uncooled ceramic tube. The whole assembly was
introduced into the combustion chamber through a water-cooled jacket. The
air cooled section was controlled at temperatures comparable to those
@ProcessEng
found at tube walls in boilers, while the uncooled section simulated an

aiready fouled surface. Methods for analysing the ash, fly ash and
deposit were wet chemical ana lys is , X-ray fluorescence and X-ray
diffraction. (4)
A novel probe design was used by Rogalski to follow the progress of
deposition in a gas turbine exhaust. The inovating feature of this probe
69
was the ability to follow the total hotside resistance with time. The
results he reported showed some degree of scatter, but the underlining
trend ean be clearly seen, even during a five hour test. This probe was
in effect, a stainless steel heat pipe. The heat from the fouled end was
transferred to the finned condenser ends which were air cooled. The
surfaee temperature of the probe at the exposed end could be regulated by
adjusting the air flowrate. The flowrate of the coolant together with its
inlet and exit temperatures were monitored thus providing a value for the
thermal resistance. Measurements of the exhaust velocity and of the
particulate concentration in the gas stream were also made. Foliowing the
withdrawal of the probe from the exhaust stream, the thickness of the
deposit was measured with an opitical comparator. This allowed values of
thermal conductivities to be obtained, although these values are not
representative of the foulant layer thermal conductivity during a test.
Further analysis of the deposit included X-ray fluoresenee tests for
elemental composition. Tests of up to 114 hours were conducted with gas
temperatures in the range 272 0 to 495 0 C and probe surfaee temperatures of
o o
63 to 380 C. (15)
Jackson and Duffin designed a probe for studying deposition from
flue gases. Their test furnace was a vertical tube unit where the main
input of energy was electrical. This had the advantage of more precise
temperature control over a wide range. The compounds to be studied were
introduced into the burner air supply as atomised aqueous solutions.
Benzene was burnt to provide the hot gases. The target section was held
in position between the two sections of the carrier tube with the help of
tensioning units. The outside diameter of the test section was 1 cm and
the length 5 cm. The surfaee temperature was varied between 300 and
900 0 C, and the cooling air supply was controlled by a solenoid valve. The
method of collecting the deposit was to dismantie the probe af ter a test
and wash the fouled target area with distilled water. The washings were
then analysed for sodt~, potassium t91 chloride.
Jackson and Raask and Jackson constructed a probe for use in the
high temperature regions of boilers. This probe was 4m in length and 25 mm
in diameter, with five thermocouples welded in position just below the
surface, at 0.6 m intervals along the probe. Air was used to cool the
target area and was discharged into the boiler environment. Four
different samples, obtained at different surfaee temperatures could be
analysed foliowing each test. The samples were analysed using flame
photometry (sodium), atomic absorption (vanadium and magnesium), and
gravimetric analysis ~~ulphate). 9
Sondreal et al ( and Tufre and Beckering( ) described a laboratory
furnace burning pulverised coal. The combustion chamber was a
cylindrical vessel 76 cm in diameter by 2.4m high 6 insulated on the inside

surface. Flue gas leaving the furnace at 1093 C passed into a 25 cm
square duet which was refractory lined. Three probe banks, each
consisting of three probes, were control led at metal temperatures of 538,
538 and 427°C. All probes were cylindrical 4.2. cm outside diameter type
304 stainless steel pipes and were cooled by compressed air. The gas
velocity over the probes was 7.6 m/sec. Analysis of the deposits was
@ProcessEng
performed by X-ray diffraction and electron microprobe scanning

techniques. The latter method is very useful in identifying elements in
different layers of the deposits. Sondreal et al developed fouling rate
equations involving th{18~mposition of the fuel.
Lee and Spengler used internally cooled cylindrical probes of
2.5 cm diameter and 5.0m long, to evaluate the deposition rate and corro-
70
sion effects in a gas turbine simulator exhaust. Various additives were

tested including silicon and magnesium. The probe was instrumentated with
12 thermocouples placed in wells drilled in the inside surface of the
probe wall. The deposits formed on the probes were characterised by
scanning electron microscope, by electron beam microanalyser and two X-ray
diffraction technique~ll
Bishop and Samms ) designed two pilot scale furnaces to study the
initial stages of deposition from burning high alkali coals. Both fur-
naces had a circular combustion chamber which was refractory lined and had
a water-cooled outer shell. The probes, which simulated superheater
conditions, were built from 25 mm cylindrical sections, 50 mm in diameter
and were air cooled. Bishop and Samms were the only workers to instrument
their probe so as to measure the temperature variation circumferentially
and axially. Eight thermocouples used to monitor the temperature distribu-
tion, were positioned in grooves on t~I surface of the supporting tubes.
It was not apparent from their paper ) the method of positioning the
thermocouples on the surface of the probe. The surface texture is an
important factor, when the initial stages of deposition are examined.
Although their probe could provide useful information, it is not practical
for use in industrial environments due to the complicated instrumentation.
An interesting feature of their deposit analysis was the collection of
deposit separately from the forward and re ar stagnation position and from
the sides, coupled with separate analysis for the deposit in contact with
the probe surface.
The National Engineering Laborat~~~ (N.E.L.) in Glasgow, U.K., has
developed a mass accumulation probe L to be used in industrial exhaust
streams (Fig. l). The sample collection pieces are in the form of a
r A Oownstream Hal! Sample
-e- @- :;:,~mm;t;m::n~ RES-

I
Sel:tion A-A
,
L A
/
\
Sample Holder
X
Position at Gas
TemperatuA
Th.rmoc:0up4e
Upstream Hall Sample

Flow ol Exhaust Gases
Fig. l. National Engineering Laboratory Fouling Probe Measuring Section

@ProcessEng
with its Associated Cooling System.
simple cylindrical shell bisected axially. The two sample pieces are
clamped together over the end part of the probe, which can be cooled by a
circulating fluid (air or water). The cylindrical shells are 50 mm long
and 25 mm in diameter. The support pipe is 38 mm in diameter and is
71
inserted into the exhaust stream along aspecially designed valve. The
purpose of the valve is twofold: First it minimises air infiltration which
could disturb powdery deposit formed on the sample pieees, and second, it
provides an enclosure where the probe surfaee temperature reaches the
required level before being introduced into the exhaust. A secondary role
of the valve is to provide support for the probe and associated equipment.
The advantages offered by the removable semi-cylindrical test sections
of the N.E.L. probe are:
a) The total amount of the accumulated material ean be quickly and
eas ily assessed by direct weighing of the test sections before and
af ter the test. This also includes the effects of corrosion at
higher temperatures.
b) The amount of deposit collected at the forward and rear positions
of the probe ean be determined, thus providing an insight into the
mechanisms of deposition.
c) The design offers the possibility of quick changes of the
substrate material, therefore maxim1s1ng the number of tests
possibie within a normal 8 hour working period.
d) Removal of the deposit material together with the substrate make
subsequent chemical analysis of the deposit and corrosion if
present, much easier.
e) Examination of the effects of different substrate materiaion the
overall fouling and corrosion problem ean be undertaken.
The temperature of the sample collection pieces is measured by inser-
ting thermocouples in 0.5 mm bore wells drilled axially into the metal.
The temperature of the coolant is measured by thermocouples at the
entrance and exit of the test section below the sample pieees, and its
flowrate is measured at the inlet to the support pipe. A pilot tube is
also positioned near the fouling surfaee for the determination of the
exhaust gas velocity. Dew point measurements and particle size analysis
are performed simultaneously. Chemical analysis of the deposits is
carried out by scanning electron microscopy and atomic absorption
spectroscopy.
5. DEPOSITION PROBES
Chaikivshy and siegmund(13) examined the fouling and corrosion in oil
fired boilers, when operated at high temperatures and at low excess air
leveis. Probes, in the form of 347 stainless steel cylindrical tubes were
exposed to the exhaust gases, for periods up to 100 hours. Removal of
deposits from the surfaee of the test probes was carried out by both hand
scraping and electrolytic descaling. The total amount of material
collected on the probe was the result of both fly ash deposition an
corrosion produets. (14)

A constant temperature corrosion probe was developed by Kear The
main feature of this probe was its ability to maintain the surfaee at a
constant temperature determined by the choice of probe coolant. Extraction
of the heat from the probecoolant was achieved by two condensers; a
primary one situated inside the probe and an outside secondary condenser.
The test section was 0.5 m long and 50 mm in diameter, located on to the
main probe with the help of a central rod passing through the probe.
@ProcessEng
Corrosion effects were evaluated by foliowing the weight loss of the test
piece. One disadvantage of using a relatively heavy test section, as in
this probe, was the need for long duration tests.
A l~tmilar probe to that developed by Kear, was used by Attig and
Sedar( in their assessment of low temperature corrosion in oil fired
72
boilers. Goldberg et al(6) used an air cooled probe which presented a flat
surface to the flowing gases. Because of its location, very near to the
combustion space, additional water cooling on the outside of the main
probe was employed to permit better control of temperature. Surface
temperature was measured by thermocouples attached to the inside of the
test section. (17)
Durie, Milne and Smith investigated the deposition of salts from
hydrocarbon flames, containing sodium and sulphur species with the help of
an air cooled probe. lts temperature was controlled at 450 0 C by means of
a solenoid valve. The target section was 10 cm long and 2 cm in diameter.
Because of the test section being supported from both ends, the use of
this probe is restricted to laboratory conditions. (18)
Another deposition probe was used by Mannyet al to obtain infor-
mation on waterwall corrosion from coal combustion. EssentiaIly their
probe was a pipe, where cooling air could be delivered via a central pipe
and returned through the annulus. Ring-shaped test sections at the end of
the probe were exposed to the gases in power stations. This probe, which
could also determine mass accumulation rates, had two novel features:
a) Two or three test sections - each 30 mm long could be attached to
the probe, thus providing the opportunity to test for different
materiaIs, and offering the advantage of multiple sets of data
from one test. The thermocouple positions in these sections allow
surface temperature monitoring.
b) The air coolant pipe position was adjustable, so that the surface
temperature of the test section could be adjusted.
When the above probe is used for corrosion evaluation, metal loss of
the test sections can be provi1i9J?20~sion rates.
Vaughan, Krause and Boyd reported on the use of a probe to
investigate fireside corrosion in refuse incineration plants. The probe
was air cooled with the section extended through the boi ler wall being
water-cooled. The characteristic feature of this probe was the gradual
reduction of the cooling pipe diameter, which permitted control of the
surface temperature of the test section at varying leveIs. Another
advantage was its ability to carry 34 test specimens during the test. The
specimens, having a diameter of 25.4 mm, were held together with lap
joints, the end specimen being attached to the cooling pipe. Methods for
analysing the deposit included emission spectrography and wet chemical
techniques complemented by electron microprobe analysis and X-ray
diffraction.
6. HEAT FLUX PROBES

Mass accumulation or deposition probes are not capable of monitoring
the deposit thickness in situ. One method of folIowing the bui Id-up of
deposit is the use of heat flux probes. These probes must conform to the
circular shape in order t2lJollect a representative thickness of ash.
Neal and Northover describe three differe~2 types of heat flux
devices, capable of measuring fluxes up to 600 KWm . These device s have
been used in C.E.G.B. boi lers producing very similar results. Two of
these devices, the flux tube and the Dometer have to be attached on to the
@ProcessEng
heat receiving surface. Good thermal contact has to be established bet-

ween the meter and the surface. The third device called the flux probe,
is a portable, self-contained instrument which can be easily inserted into
a boiler through a 10 mm hole. The flux probe which is essentiaIly a heat
pipe, can measure local values of incident heat flux from flames but is
unsuitable for long term monitoring of heat flux.
73
Chambers, Wynnyeky and Rhodes(23), used eommercially available dise

type meters to monitor ash fouling in boiler tubes. One meter was kept
elean by eonstantly blowing air over it to prevent deposition. Thus,
eomparison of the heat flux as measured by the clean and fouled devices
gave an indication of the amount of ash on the boiler surfaces. This
method will not produce accurate results in industrial situations where
large flame temperature fluetuations occur.
A heat flux probe (Fig. 2) was used in an experimental rig at
TlIERHoc:ourlE HOlES 1.5"'" IH DIAMETER
INSUlfITlON BEnn:EH SEGMENTS
~o mm
S{UIO'" A-A'
-------
________ "EAT FLUX HEASURIHG SEellON.
SPI\CE PlUtO WITU IN5ULIITfNG

.' HMERtAl.
Fig. 2. University of Birmingham Heat Flux Probe.
Birmingham University(26) to monitor the deposit build-up during tests.

The measuring section of the probe eonsisted of a cylindrical block 50 mm
long and 30 mm in diameter. The wall thickness was 13 mm. Water was used
to cool the probe. The heat flux measuring section of the probe was
divided into eight equal segments separated from each other with insula-
ting material. Chromel alumel thermocouples were used to monitor the
temperatures at the pobe surface and near the coolant flow. To approximate
one-dimensional heat flow the two ends of the measuring section were
insulated with fibreglass. In order to prevent the same surfaee texture
to the gases at the start of a test, the outside surface of the probe was
polished using the same method eaeh time. The total hotside resistanee is
followed as an indication of deposit build-up.
7. ACID DEPOSITION PROBES

Fouling and corrosion at low temperatures presents one of the most
difficult problems when maximum boi ler efficiency is to be achieved. The
practiee is to operate ab ove the aeid eondensation levels and use
corrosion resistant mt~~)ials.
Alexander et al used an air eooled probe to measure aeid
deposition in oil-fired boilers. The probe was 2.5 m long and 25 mm in
@ProcessEng
diameter. The cooling air was discharged directly into the flue gases and
the temperature along the wall of the probe varied between 80 0 and l70 0 C.
At surface temperatures below 94 0 C, the probe surface was damp, with a
small amount of dust. The sample per iod was 30 minutes. Chemical
analysis of the deposit collected below 94 0 C showed that it eonsisted
mainly of iron, chromium and nickel sulphates.
74
The British Coal Utilization Research Association (BCURA) (25)

developed a dew-point meter which ean measure the dewpoint temperature,
the maximum rate of condensation and the temperature of its accurence.
The two latter quantities are abetter indication of corrosion potential.
The BCURA dewpoint meter consists of a glas s thimble set at the exposed
end of the probe. The surfaee temperature of the glass thimble is
measured using a Platinum-Rhodium thermocouple. The junction of the
thermocouple is fused into the glass and forms one electrode of a condue-
tion cello The glas s thimble is cooled by a stream of air the rate of
which is increased until a conductivity film of liquid starts to form.
8. DISCUSSION
Gas-side fouling measuring device s have been used in a number of
industrial and laboratory applications. Five types of these devices have
been identified with the mass accumulation probe being more frequently
used. This type of probe offers the advantage of obtaining quantitative
data on deposition rates. The most commonly used geometry is the cylinder
as it represents the most widely used heat transfer surfaee and results
obtained with this geometry ean be eas ily translated to real situations.
Most of the probes are cooled either by air or water, in order to maintain
the surfaee temperature within a certain range. Many probes are equipped
with an Rutomatic data aquisition system enabling long exposures in ex-
haust gases possible. A number of probes have been designed to carry many
test sections, so that simultaneous tests at different surfaee tempera-
tures ean take place. These probes ean be very useful when an evaluation
of corrosion resistance of various materials in a particular combustion
stream has to be made.
Measurement of on-line fouling resistance is a difficult task and only
approximate values ean be evaluated. Very few probes are equipped to
obtain fouling resistances. Assuming that a fouling layer of thickness Yf
(and af thermal resistance Rf) is formed, the heat flux q is given by:
In order to monitor the fouling resistance, all the other quantities in

the above equation must be known as a function of time. The heat transfer
rate Q, ean be measured by using the folIowing relation:
where W is the coolant flowrate, c is the specific heat of the coolant

and TI and T 2 represents the inlet aRd outlet coolant temperatures. Most
probes are designed with short test sections. As a consequence, the
temperature drop along the probe will be very small and accurate
determinations of the heat transfer rate are not possible. The convective
@ProcessEng
heat transfer coefficient ean not be determined accurately either, as it

is a function of the gas velocity, the fluid properties and the geometry
of the probe. As the deposit buiIds up, the geometry of the probe, the
surfaee roughness and hence the fluid flow properties will change. The
value of the clean surfaee area will also change. Heat flux probes
provide accurate values of the total hotside resistance as deposit buiIds
7S
up. The fouling resistanee ean be calculated at the same time by

considering the heat flux values at clean eonditions. For maximum
accuracy, allowances have to be made for the changing surface temperature
of the deposit and the changing flow distribution of the gas over the
deposit. Both the ab ove mentioned variables affeet the convective and
radiative heat transfer coefficients.
In addition to using fouling probes in eombustion environments, a
eomplete evaluation of the fouling potential involves gas and deposit
analyses associated where possibIe with particle size analysis. This
information will provide the mechanisms involved in the deposition pro-
cess.
REFERENCES
1. Marner, W.J. , Henslee, S.P., "A survey of gas-side fouling measuring

deviees" , JPL Publication 84-11, EG & G Idaho, Inc. Idaho Falls,
Idaho.
2. Brown, T.D., "The deposition of sodium sulphate from eombustion
gases", J. Inst. Energy, Vol. 39, 1966, pp. 378-384.
3. Hein, K., "Charaeteristics of Rheinisch Brown Coals with respeet to
their eombustion and fouling behaviour in thermal power stations", J.
of Eng. for Power, Dct. 1977, pp. 679-683.
4. Rogalski, R. D., "Fouling effects of turbine exhaust gases on heat
exchanger tubes for heat recovery systems", David W. Taylor Naval Ship
Research and Development Centre, Tech. Rep. No. 790647, 1979.
5. Jackson, P.J., Duffin, H.D., from "The Mechanisms of corrosion by fuel
impurities", pp. 427-442, London Butterworths, 1963.
6. Jackson, P.J., Raask, E., "A probe for studying the deposition of
solid material from the flue gas at high temperatures", J. of the
Inst. of Fuel, July 1961, pp. 275-280.
7. Jackson, P.J., "Deposition of inorganic material in oil-fired
boilers", from "Ash deposits and corrosion due to impurities in
combustion gases", R.W. Bryers (Ed.), Hemisphere Publishing
Corporation.
8. Sondreal, E. A., Gronhov, C. H., Tuf te , P . H., Beckering , W., "Ash
fouling studies for low-rank western, U.S. eoals", from "Ash deposits
and eorrosion due to impurities in eombustion gases", R.W. Bryers
(Ed.) Hemisphere Publishing Corporation.
9. Tuf te , P. H., Beckering , W., "A proposed mechanism for ash fouling
burning northern plane lignite", J. of Eng. for Power, July 1975, pp.
407-412.
10. Lee, S.Y., Sengler, C.J., "Characterization of corrosion and deposit
in the laboratory gas turbine simulator burning heavy fuels with

additives", from "Ash deposits and corrosion due to impurities in
combustion gases", R.W. Bryers (Ed.).
11. Bishop , R. Y., Samms, J .A. C., from "The mechanism of corrosion by fuel
impurities" , pp. 155-172, London: Butterworths, 1963.
12. Isdale, J.D., et al. 1st U.K. Nat. Corp. on Heat Transfer, Vol. l,
415, 1984.
@ProcessEng
13. Chaikivsky, M., Siegmund, C. W., "Low excess air combustion of heavy
high temperature deposits and corrosion", J. of Eng. for Power, Dct.
1965, pp. 379-388.
14. Kear, R.W., "A constant temperature corrosion probe", J. of the Inst.
of Fuel. June 1959, pp. 267-273.
76
15. Attig, R.C., Sedor, P., "A pilot-plant investigation of factors

affecting low-temperature corrosion in oil fired boilers", J. of Eng.
for Power, April 1965, pp. 197-204.
16. Goldberg, S.A., Gullagher, J.J., Orning, A.A., "A laboratory study of
high temperature corrosion fires ide surfaces of coal fi.red steam
generators". J. of Eng. for Power, April 1968, pp. 193-198.
17. Durie, R.A., Milne, J.W., Smith, M.Y., "The deposition of salts from
hydrocarbon flames containing sodium and sulphur species", Combustion
and Flame, 30, 1979, pp. 221-230.
18. Manny, E.H., Bartok, W., Crawford, A.R., Hall, R.E., Vatsky, J.,
"Studies of waterwall corrosion with staged combustion of coal" , from
"Ash deposits and corrosion due to impurities in combustion gases",
R.W. Bryers (Ed.), pp. 387-401.
19. Vaughan, D.A., Krause, H.H., Boyd, W.K., "Chloride corrosion and its
inhibition in refuse firing" from "Ash deposits and corrosion due to
impurities in combustion gases", R.W. Bryers (Ed.).
20. Miller, P.D., Krause, H.H., "Factors lnfluencing the Corrosion of
boiler steels in municpal incinerators", Corrosion-NACE, Vol. 27, No.
l, January 1971, pp. 31-45.
21. Neal, S.B.H.C., Northover, E.W., "The measurement of radiant heat flux
in large boiler furnaces, I. Problems of ash deposition relating to
heat flux" lnt. J. Heat Mass Transfer, Vol. 23, 1980, pp. 1015-1021.
22. Neal, S. B. H. C., Northover, E. W., Preece, "Development of heat flux
measuring instrument", lnt. J. Heat Mass Transfer, Vol. 23 , 1980, pp.
1023-1031.
23. Chambers, A.K., Wynnycky, J .R., Rhodes, E., "A furnace wall ash
monitoring system for coal fired boilers", J. of Eng. for Power, Vol.
103, 1981, pp. 532-538.
24. Alexander, P.A., Fielder, R.S., Jackson, P.J., Raask, E., "An air
cooled probe for measuring acid deposition in boiler flue gases", J.
of the lnstitute of Fuel, Vol. 33, 1960, pp. 31-37.
25. Flind, D., "The lnvestigation of dewpoint and related condensation
phenomena in flue gases", J. lnst. Fuel, 21, 1948, pp. 248-253.
26. Tsados, A., Thesis on Gas-side Fouling, University of Birmingham,
1987.
@ProcessEng
MONITORING FOULING USING A NOVEL TECHNIQUE
P.G. COUSINEAU
Aughinish Alumina Ltd., Askeaton, Co. Limerick, Ireland
G.D. FULFORD, P.M. SIMMONS

Alcan International Ltd., Kingston R&D Centre, Kingston, Ontario
K7L 424, Canada.
l. INTRODUCTION
The efficient recuperation of heat between process streams is critical

to the economic operation of Bayer proces s plant s for the production of
alumina from bauxite. Unfortunately, the fouling of heat exchanger
surfaces by sodium aluminosilicate scales arising from the nature of the
process liquors is a major problem. A thorough understanding of the
fouling kinetics and behaviour is required in order to adequately design
the shell and tube heat exchangers used in this service.
A laboratory technique has been developed to follow this type of

fouling under controlled conditions, the details of which were presented in
[l]. Here the results obtained will be compared with accept ed calculations
in order to examine the validity of the method. The process variables
important in this service and an empirical modelof the fouling proces s
will be discussed, and some possibie further applications of this technique
will be given.
2. METHOD
The technique developed involves the measurement of the real average

metal tube wall temperature for the determination of the film heat transfer
coefficients, especiaily the inside film coefficient, which is influenced
by the fouling layer in the configuration studied. To do this, the average
tube temperature is determined by measuring the electrical resistance over
a length of tube, and using a calibration of electrical resistance vs.
temperature to determine the average tube temperature Tavg • Knowing the
overall heat flux Q over a tube length L from measurements of the mass flow
rate of fluid and its gain in temperature, the average inside wall tempera-
ture Twi can then be determined from the relationship:
(l)
The basic assumption made in deriving (l) is that the heat flux in the
longitudinal direction along the tube wall is negligibie compared with the
@ProcessEng
heat flux in the radial direction.
Since only an average inside wall temperature is obtained, the effect

is that the longitudinal wall temperature profile is reduced to a constant
average temperature over the tube length. This does not truly represent
the situation in most shell and tube exchangers, as illustrated in FIGURE l
77
L. F. MelD el al. (eds.), Fouling Science and Technology, 77-84.
78
for the case of inside fouling. The temperature profile across the fouling
layer is calculated assuming that the average fouling layer thickness Yf
and thermal conductivity of the scale k f are known using the relationship:
Q • In (2 )
The values obtained can be used to calculate an inside film coefficient

allowing for fouling averaged over the length of the surface or to
calculate an average fouling resistance, as required.
In some cases, however, local film heat transfer coefficients (or

fouling resistances) are desirable. These can be determined by dividing
the total tube length into sectors, and measuring the electrical resistance
of each sector and the mean fluid temperature leaving the sector, as out-
lined in [1]. A series of film coefficients averaged over the lengths of
each sector will be obtained, from which a reasonable curve showing the
true variation of the film coefficient with length can be constructed. The
approximation to the true longitudinal distribution will improve as the
number of sectors is increased, but unless a micro-ohmmeter of very high
sensitivity is available for measuring the electrical resistances of the
tube sectors, the accuracy of the tube wall temperature measurement will
suffer if the sectors are made too short, and a compromise must be sought.
Aresult using thi s approach is illustrated in FIGURE 2, where a curve has
been fitted through the sector midpoints (marked "x" on Figure), which
gives an improved representation of the longitudinal wall temperature. or
surface temperature profile along the tube.
In the discussion above, it is assumed that the thickness of the

fouling layer and its thermal conductivity are known. In practice, the
thickness of the fouling layer is not known, except at the end of a fouling
rate test when the tube can be removed and sectioned. In practice, there-
OUTSIOE I
----~---
FLUID I
ITwo
I
- - - - 1 Tavg
J OUTSIOE I
_Fl.!,~ _
1
r---!. 1
I-:.. ____J
1
1- _____ t~----~T.Vg
ITwo
t
ACTUAL
I Twl
I
r-----i
Twl
TUBE
I
I
I
I Tfls
I
I
t TUBE I
I
I
TIIs
w w I I
a: T f Is CALCULATED a: I
~ ---- ~ ---- I
I
'"ffi I I ~ I
!i SCALE I I ~ SCALE 1 I
i!' I I ill~ I I
I
I
I
----I I
INSIDE I
I IMSIOE I 1 I I
FLUID I FLUID I Sectlan 1 ! Sectlon 21 $action 3\ Sec110n 4!
INLET OUTLET INLET OUTLET
@ProcessEng
FIGURE 1. Expected wall temperature FIGURE 2. Improved wall

profiles for concentric tube exchanger temperature profile
with inside fouling compared with obtained by sectioning the
measured Tavg and calculated Tfis • tube.
79
fore, T fis is not known in advanee, but it is clear that the longitudinal
profile Twi ean be found, and by using the value of Twi and the fluid bulk
temperature, the sum of the contributions of the inside film eoeffieient
and inside fouling resistanee ean be found as a funetion of the operating
parameters.
3. VALIDATION
The teehnique outlined above is thought to be a reasonably aeeurate

way of foliowing the effeet of various parameters on the fouling inside a
tube earrying a fouling fluid. It is simple, eeonomie, and leads to
reprodueible results. FIGURE 3 shows results obtained for water, sodium
hydroxide solutions, and sodium hydroxide/sodium aluminate solutions
without fouling. The results are seen to be in good agreement with the
usual Sieder-Tate type of equation [2):
Nu = 0.027 o Re O• 8 o Pr l / 3 o (~/~ )0.14 (3)

w
Sinee the Prandtl number Pr va~ed only sli~htly in thi s work, the results
have been plotted as (Nuopr- l 3o(~/~w)-0.1 ) vs. Re to show the effeet of
the Reynolds number.
From FIGURE 3 it is seen that there is quite good agreement between

the measured values and the predietions of the Sieder-Tate equation for the
non-fouling liquids. The small variation in slope noted is almost
eertainly due to the relatively small range of Reynolds numbers eovered by
the present tests and uneertainties with respeet to the physieal properties
of the eaustie-aluminate (Bayer) solutions.
A large advantage of the teehnique is the eeonomy of eonstruetion of

the apparatus. The apparatus uses an ordinary low-eost heater tube in a
eoneentrie jacket, and ean be easily disassembled af ter a run and rebuilt
and reealibrated with a new tube in less than half a day [1). As aresult,
a new tube ean be used for eaeh fouling test, if required, avoiding
questions of how eompletely the fouling layer is removed between tests, and
the used tube ean be seetioned as required to physieally inspeet the
undisturbed fouling layer, measure its thiekness, etc.
FIGURE 4 shows that the teehnique gives reprodueible results when

applied to sodium hydroxide/sodium aluminate solutions eontaining dissolved
siliea, whieh leads to the formation of sodium aluminosilieate seales. The
final asymptotie inside film eoeffieient is the same for three runs under
similar conditions whether new tubes or cleaned tubes are used. An

initiation period of -20 hours is found for the two new tubes, but not for
the ehemieally cleaned, re-used tube. Af ter the initiation period, a sharp
jump in the film eoeffieient is observed, thought to be due to the first
deposition of solids on the wall leading to greatly inereased turbulence
and henee to improved heat transfer at the wall. Subsequently, inereased
coverage of the wall with a growing fouling layer leads to the usual
@ProcessEng
deerease in the inside film eoefficient (Le., inside film plus fouling
layer).
80
500.---------~---------.
'1" 25 ---<9 NEW TUBE l

O ... _.., NEW ~UBE 2
SIEDER-TATE EGN....... " X ---.. CLEANED TUBE
100
"s ,/'
E"~
Q
G N
01Jl ,.,••• ,{ \ E
CG ·e EXPTL. ~
ølll LINE ....-1
f' Z
6 W
~X)
Q
• WATER ~10
W
tf'L " NAOH SOLN. O
Cl... U
i--
.. BAY ER UQUOR W 5 Re=11800
O Pr=5'6
li)
b
1103 104 lOS °O'~~4~O~~8~O~~120~~~~O~
REYNOLDS NUMBER, Re TIME, h.
FIGURE 3. Comparison of FIGURE 4. Inside heat transfer

experimental heat transfer data (fouling layer plus film)
for non-fouling solutions using coefficient for sodium
present technique with Sieder- hydroxide/sodium aluminate
Tate equation. solutions containing dissolved
silica (fouling conditions).
4. EXPERlMENTAL PROGRAMME
In the Bayer proces s plants the increased operating costs for energy
arising as aresult of the fouling of the surfaces of the recuperative heat
exchangers gives cause for concern. Abetter understanding of fouling by
sodium aluminosilicate scales should help to reduce the problem. The
classical approach to such types of fouling is through the Kern-Seaton
approach [3]. in which the rate of deposition of scale ~d and the rate of
removal of scale ~r onto and from the fouled surface are determined
separate ly and then combined to give the overall fouling rate:
(4 )
Although this approach should give the information needed for the adequate
design and optimum operation of the heat exchangers, a very large effort
would be required to thoroughly describe the parameters ~d and ~r in the
complex, real system of fouling in multicomponent Bayer liquors.
@ProcessEng
Our approach was therefore to study the overall fouling phenomenon

rather than studying the individual steps as can be done in simpier
systems. Testwork and experience showed that the foliowing parameters are
81
important in the fouling of heat exchange surfaces: the reaction kinetics

for the formation and deposition of the sodium aluminosilicate solid from
solution; the flow velocity; the condition of the tube surface; and the
tube geometry. The effects of these parameters on scaling rates have been
studied experimentally.
4.1 Reaction Kinetics
The kinetics of the formation of solid sodium aluminosilicate from

typical Bayer plant liquors have been studied previously [4, 5). The
results can be fitted by a rate equation which is second order in the
silica supersaturation of the liquor:
(5)
The kinetic constant k is a function of temperature and the sodium hydrox-

ide and alumina concentrations in the liquor (4); in the zone of conditions
of interest, the reaction rate approximately doubles for each 8 to 10°C
rise in liquor temperature. The silica solubility CSiO is also a function
of the sodium hydroxide and alumina concentrations, but 2 is large ly indepen-
dent of temperature in the range of conditions of interest. FIGURE 5 shows
some typical curves for desilication rates of liquors when a large sodium
aluminosilicate surface area is present.
Tests carried out at constant tube-side velocities but different

values of the silica supersaturation (C SiO _ CSiO ) have confirmed that
the fouling rate decreases markedly and the ~symptotfC value of the inside
film coefficient (including the fouling resistance) increases as the silica
supersaturation is decreased.
4.2 Flow Velocity
It was expected from previous studies that the flow velocity should
have a considerable effect on the fouling rate. Our experimental results
have confirmed this, as shown in FIGURE 6. Here the asymptotic (limiting)
inside film heat transfer coefficients reached af ter prolonged operation
(one to three weeks) for given jacket and feed temperatures and silica
supersaturation are plotted against the tubes ide liquor velocity. The
thicknesses of the fouling layers at the tube exit measured by sectioning
the tubes af ter the tests are also shown.
The results are interpreted to indicate that the scale deposition rate
~d should be approximately constant under these conditions, but that the
removal rate ~r increases with increasing liquor velocity, leading to
thinner equilibrium fouling layer thicknesses and larger inside film
coefficients (including the fouling resistance) at the larger velocities.
@ProcessEng
4.3 Tube Surface Condition
FIGURE 4 shows that there is a relatively large increase in the inside

film heat transfer coefficient when the deposition of the fouling layer
first begins in a clean, smooth tube. This is thought to be due to a
roughness effect, which increases the degree of turbulence in the flow zone
82
E50 rrO
05 ~ ..--
120g/L NoOH A
V)
~
60g/L AIP3 V)
~40
::.::
N
U
~
I
1- 300
~
LL
~ W
...J O
CL U
<.9 200 w
-:\160-~---------- z Q
:J 5 V)
:::>
« Solubility
~
~0'1 f21 -.J
...J
Vi
...J
:5
O
§
O w
O 20 40 60 80 100
00 1 2 30
TIME,min. TUBESIDE VELOC.,m/s
FIGURE S. Rates of silica FIGURE 6. Effect of flow velocity on

deposition at different asymptotic inside film heat
temperatures for typical transfer coefficient and fouling
Bayer liquors with large layer thickness at constant liquid
sur face area of inlet and jacket temperatures and
deposition. liquid composition.
near the wall and improves the inside heat transfer conditions until more
complete coverage of the wall by a fouling layer of increasing thickness
occurs. A similar effect has been observed in [6].
FIGURE 7 gives an impression of the extreme degree of roughness which

arises in the present system at a velocity of approximately l m/s at the
point when coverage of the heating surface is almost complete.
To date, we have not succeeded in achieving the balance of conditions

to permit enough roughness to form to increase the inside film coefficient
but not so much deposition as to lead to further growth of the fouling
layer, which would be of practical interest if the balance is not too

delicate to maintain under realoperating conditions.
4.4 Tube Geometry
Under similar operating conditions (inlet and outlet liquor tempera-

tures, jacket temperature, flow velocity, and liquor composition), the
@ProcessEng
asymptotic (equilibrium) inside film coefficient (including the fouling

83
SOpm
1---1
FIGURE 7. Photomicrograph of heat transfer surfaee fouled by sodium

aluminosilicate deposit at tubes ide velocity of -l m/s.
resistance) measured in small laboratory tube (-l cm diam.) has been found
to be considerably large r than the value found in plant-scale equipment
(tubes of -4 cm diam.). This is considered to be due to the faet that at a
constant flow rate corresponding to the specified velocity in the clean
cube, the velocity will increase as the fouling layer blocks a fraction of
the tube cross-section until the increased velocity leads to a removal rate
~r large enough to balance the deposition rate ~d' For tubes of different
sizes, the equili brium fouling layer thickness (and hence the fouling
resistance to heat transfer) should therefore increase with increasing tube
diameter.
The implications of this hypothesis remain to be checked in a speeial

set of experiments to determine if indeed smaller tubes wil1 have higher
values of the asymptotie inside eoeffieient (ineluding fouling) for a given
elean-tube liquor veloeity.
5. CONCLUSIONS
The teehnique used here, based on direct tube wall temperature

measurement by aresistance method, ean be applied in many situations. It
has great flexibility as a laboratory tool: ealibration is simple and
rapid, and tube replaeement is rapid and inexpensive. Fouling proces ses on
both sides of the tube ean be followed independently of eaeh other. It
eould als o be applied to foliowing fouling in high temperature systems,
sueh as in boilers and furnaee tubes. Data ean be obtained more easily for
building models of real processes oeeurring in industrial heat exehangers.
Data eo11eetion is straightforward, and ean be easily interfaeed with
microcomputers.
NOMENCLATURE
A: surfaee area (m 2 ); Nu: Nusselt number;
C,COO eoncentration, solubility (goL- I ); Pr: Prandtl number;

@ProcessEng
k: Q: heat transferred (W);
L: tube length (m); r: tube radius (m);

84
Re: Reynolds nJmber; y: fouling layer thickness (m) ;
t: time (s); Il: liquid viscosity (Pa.s);
T: temperature CC); $: flux of fouling material (kg. s-l)
Subscripts
avg: average; r: removal
d: deposition; s: surface
f: fouling layer; t: tube;
i: inside; w: wall.
o: outside;
REFERENCES
1. Cousineau, P.G., and Fulford, G.D.: "Measuring the inside film heat
transfer coefficient of a concentric tube heat exchanger in a scaling
environment: a novel method", Paper at 36th Can. Soc. Chem. Engrs
Meeting, Sarnia, Ontario, Canada, October 1986 (to be published in
Can. J. Chem. Engng.).
2. Kern, D. Q.: Proces s Heat Transfer, McGraw-Hill Book Company, New

York, 1950.
3. Kern, D.Q., and Seaton, R.E., Br. Chem. Eng., 1959, !:, No. S, 258-
262.
4. Oku, T., and Yamada, K., "The dissolution rate of quartz and the rate
of desilication in the Bayer process" , pp. 31-45 in "Light Metals
1971", (T.G. Edgeworth, ed.), A.I.M.E., New York, 1971.
5. Cousineau, P.G., and Fulford, G.D., "Aspects of the desilication of

Bayer liquors", pp. 11-17 in "Light Metals 1987", (R.D. Zabreznik,
ed.), A.I.M.E., Warrendale, Pa., 1987.
6. M. Bohnet: Chemie-Ingenieur-Technik, 1985, ~, No. l, 24-36.

@ProcessEng
@ProcessEng
Adhesion
Chapter 3
ADHESION AND REMOVAL OF PARTICLES I
J. VISSER
UNILEVER RESEARCH LABORATORIUM VLAARDINGEN

Olivier van Noortlaan 120, 3133 AT Vlaardingen, the Netherlands
l. INTRODUCTION
In general, fouling is a proces s of gradual deposition of particulate
material onto solid surfaces, predominantly from a fluid phase. However,
in certain specific cases, airborne dust may also constitute problems, for
example when it adheres to motorcars, to objects near railway tracks or
when generated by sooting burners, chimneys or exhaust pipes.
Fouling problems arise when gravitational forces are negligible, e.g.
when the dimensions of the particulate material, at least in one
direction, are equal or smaller than l ~m. As a consequence, fouling is in
fact a proces s that can be described in terms of colloid chemistry. Since
in almost any conceivable ~ase, the nature of solid surfaces will be
different from those of the contaminating materials, initial fouling can
be described by a proces s of heterocoagulation. Once the first layer has
been deposited, a second layer can be formed, either by homocoagulation
when identical particles deposit onto already deposited ones, or by a
second heterocoagulation process, when "other" particles are attracted by
and bound to the initially deposited material.
From a basic understanding point of view, it is, therefore, important
to review the principles of colloid chemistry both with regard to homo- as
well as to heterocoagulation. In 'real' systems such as milk, not only
particulate material, e.g. insoluble calcium phosphate is formed during
heating. Proteins, fat and a broad range of ions are also present and each
of these materials may give rise to specific fouling problems, in
particular in cases where calcium phosphate has been formed by heating.
In order to put the problem of fouling in a more general context, apart
from the basic principles of colloid chemistry, also effects related to
fouling by dairy fluids will be treated in the following survey to
illustrate the interrelationship between the various effects.
On the basis of the background knowledge given, predictions will be
made as to possible measures to reduce or minimize fouling. In part II,

the removal of already deposted material will be treated.
2. COLLOID CHEMISTRY AND FOULING

2.1 Model systems
Analysis of 'fouled' systems reveals a broad range of contaminating
materials of particulate origin. Typical examples are soot or carbon black
@ProcessEng
particles, iron oxide, clay platelets, bacteria and fat crystals. In

addition, fluid soil such as grease may be present in which the above-
mentioned particles are embedded. The surfaces onto which these particles
87
L. F. Melo et al. (eds.), Fouling Science and Technology, 87-UJ4.

88
adhere are far from ideal: micro-roughnesses, crevices and cracks may
either limit the contact between the adherents or, as the other extreme,
may even trap the particle (Fig. la and lb).
Q~ Q a b
t
c
,H
Fig. l
t
d
* 2p
e
Particles and surfaces: a,b real systems; c,d,e idealized models
For a basic understanding of the factors involved in fouling, it is

essential to confine oneself to two ideal configurations, the interaction
between a perfect sphere of radius R and a flat surface (Fig. lc) and the
interaction between two perfectly flat parallel plates (Fig. ld), both at
a separation distance H. The 'real' situation may be idealized by the
representation given in Fig. le: a sphere of radius R in contact with a
flat sur face via an extended contact area of radius p.
2.2 Colloid chemistry and fouling

As already indicated in the introduction, the dimension of particles
involved in fouled systems are colloidal, i.e. l pm or smaller. Larger
particles will not adhere to a sur face because gravitational and fluid-
dynamic forces are sufficiently strong to remove any contaminating
particle, e.g. when tilting a surface with deposited pigment particles.
The changing geometry of windswept sand dunes is another example.
The principal interaction forces between colloidal particles are the
van der Waals forces of attraction and for irnrnersed systems in water, the
electrostatic double-layer forces of repulsion (l). In addition, adsorbed
polyrners may lead to steric hindrance effects (2) whereas certain ions may
lead to bridging (3). The balance between all possible interactions
determines whether a system will foul or not. Essential is that in
liquids, Brownian diffusion will bring the colloid particle into contact
with the surface in question. Adhesion only arises if the flow of the
liquid in which the particles are dispersed, is not able to provide a

force strong enough to overcome the attractive force.
2.3 Van der Waals forces

On the basis of the deviations from the ideal-gas law at high
pressures, van der Waals concluded that molecules attract each other (4)
and London was the first to quantify this statement when the theo ry of
@ProcessEng
quanturn mechanics was developed (5). Hamaker then applied London's ideas
to calculate the interaction between solid bodies, simply by using the
principle of the additivity of molecular interactions even between the
molecules of two interacting bodies (6). As aresult, he obtained for the
interaction force FA between a sphere and a flat plate (Fig. lc)
[l]
89
and for the interaction force between two flat plates per unit of surfaee
are a (Fig. Id)
I
_A_ _
[2]
6 11' H3
I
where A is a material constant, named the Hamaker coefficient af ter its
originator. For any material and combination of materiaIs, A' ean be
calculated from the molecular properties of the materials involved (3).
More recently, Lifshitz and co-workers (7) were able to calculate the
van der Waals interaction between macroscopie bodies avoiding Hamaker's
assumption of the additivity of molecular interactions. The equations
obtained were identical except that A'could now be linked to measurable
bulk material properties, e.g. the optical characteristics from visible
light to the far-ultraviolet. Some results based on their method of
calculation are given in Tables l and 2.
TABLE 1 Lifshitz-van der Waals constants (in eV) of various materiaIs and
their combinantions in vacuum and in water (8)
Material Vacuum Water

1 An Al31
Au 14.3 9.85
Ag n.7 7.76
Gu 8.03 4.68
Diamond 8.60 3.95

MgO 3.03 0.47
PS (polystyrene) 1. 91 0.11
H20 1.43
TABLE 2 Negative Lifshitz-van der Yaals constants (in eV)
Materials
l 3 2 A132
Si A1203 H20 - 0.78

Ge edS PS 1.17
Au PS H20 0.68
From the data presented it ean be concluded that the more electron-
dense the material, the larger is A~ Immersion in a third medium (H20)

results in areduetion of the van der Waals attraction. This reduction is
higher, the weaker the van der Waals interaction in vacuum. For
combinations of two different materials l and 2 in vacuum, Al2 ean be
obtained in good approximation via equation
[ 3]
@ProcessEng
For some specific combinations of 3 materials according to the Hamaker

expression:
(JAli - JA33) eJ A22 - JA33) [4]

90
A132 can become negative, in casu when
An < A33 < A22

or
An > A33 > A22
Combinations of materials fu1fi11ing these criteria were als o found to

give negative A132 va1ues when ca1cu1ated on the basis of the Lifshitz
theory. The possibi1ity of van der Waa1s repulsion in the case of three-
component systems, is now (more) sound1y based scientifica11y. Despite the
fact more and more optical data are becoming available, ca1cu1ations based
on the Lifshitz theo ry are still very tedious. A very simple method to
obtain information on the van der Waa1s contribution to the interaction of
co110ida1 systems including proteins has been introduced by van Oss et al.
(9) by linking All and the surface tension ~LW of materiall, using
equation
[S]
~LW can be ca1cu1ated from a simple contact angle measurement of a droplet

of a given non-polar fluid deposited onto the sur face in question.
For co110ida1 particles, surface characterization can be done by

positioning the droplet on a deposit of particles on a micropore filter.
Ana1ysis of a large number of materials showed that d ~ 1.3SÅ (10),
a1lowing an accurate estimate of A of any material of interest by a simple
contact angle measurement.
For polar liquids like water, a1so other contributions to the interaction
are operative. Therefore, the situation is more complex. Theories are
being worked out to account for these mainly short-range effects.
The reason why Hamaker's original approach to ca1culate A from

molecular properties was incorrect, is his assumption that molecular
forces are additive. This is not so because the interactions betwecn
molecu1es at larger separations are screened by molecules at a closer
distance. As a consequence, layers of adsorbed materials in particular can
markedly inf1uence the interaction between two macroscopic bodies. On the
basis of the Lifshitz theory, Langbein (11) has shown that, as soon as the
thickness of the surface 1ayer dl, d2 becomes 1arger than the separation
distance H of two interacting bodies 1 and 2, their interaction is
determined by the properties of the 1ayer and not by the material
underneath (Fig. 2).
@ProcessEng
Fig. 2 Influence of a thin layer on the interaction between two solid

bodies
91
This has great consequences in practice and the result may be used to
prevent or reduce fouling.
2.4 Electrostatic double-laver forces

All solid materials in an aqueous environment attain a surface charge
due to preferential adsorption of ions present in the solution or due to
dissociation of surface groups. This charge becomes manifest for example
when an electric field is imposed on a colloidal dispersion: by a
displacement of positively-charged particles to the anode and that of
negatively-charged particles to the kathode. When this displacement is
measured under control led conditions, it is possibIe to obtain the so-
called zeta potential of the colloidal particle under investigation. The
surface charge of the particle is balanced by a counter-charge of ions of
opposite sign in order to make the system electrostatically neutral. Here,
a so-called double layer is established. Independently, Qeryagin and
1andau (12), and yerwey and Qverbeek (l) developed a theory, which was
later named af ter these 4 scientists, the DLVO-theory. It describes the
interactions taking place when two of these double layers interpenetrate
in the case of two identical colloidal particles approaching each other.
On the basis of this theory, Hogg et al. (13) calculated the corresponding
force of repulsion when two particles of different radii approach each
other under the conditions that the potential ~ or the charge a of the
particles remains constant. The resulting equations for the force of
interaction of a sphere and a plate are:
F~ (sphere-plate) ER 2 2 K, exp ( -K,R)

R 2 (~O1 + ~O2) l - exp (- 2K,H)
2 ~Ol ~O2
x [ 2 2
- exp (- KR)] [6]
~Ol + ~O2
and
Fa (sphere-plate) = ER 2 2 K,exp (- K,H)
R 2 (~Ol + ~O2) l - exp (- 2K,H)
x
[ 2 ~Ol ~O2
2 2
~Ol + ~O2
+ exp (- KR)] [7]
where ~O is the surface potential (to a first approximation it is possibIe

to equate ~O and the experimentally-obtained zeta potential), E is the
dielectric constant of the medium and K, the reciprocal double-layer
thickness 6 defined by:
2
K, [8]
where k is the Boltzmann constant, T the absolute temperature, zi the

valency of ion i, niO its bulk concentration/ml and e the electronic
charge.
For 'real' systems, it is likely that neither of the two conditions is
applicable and that an in-between situation is more realistic.
@ProcessEng
However, equations [6] and [7] permit computation of the magnitude of the
forces involved in the proces s of fouling. Combination with equation [l]
will give the total force balance.
In terms of the DLVO-theory, however, it is customary to describe the
balance between van der Waals attraction (A) and double-layer repulsion
(R), in the form of an energy (V)-distance (H) diagram as illustrated in
Fig. 3.
92
Vmax ---
Fig. 3 Energy-distance curves
As aresult of differences in V-H dependency, the sum curve shows a

maximum (Vmax ) at short separation distances and a minimum (Vmin) at
relatively large H. As long as the thermal energy of the colloidal
particles in question (a few kT) is smaller than Vmax (the energy barrier
between the two interacting species), no interaction will take place and
fouling will not occur (similar curves are obtained for the sphere-plate
geometry). In real ity, the situation is more complex because other
interactions are also possible. Nevertheless, from simple zeta potential
and contact-angle measurements it is possibie to predict the potential
fouling behaviour for a given system as outlined above.
2.5 Other charge-related interaction forces

In the DLVO theory it has tacitly been assumed that both surfaces of
two interacting colloidal particles have the same charge and sign. The
corresponding double-layer force is, therefore, always repulsive.
Situations do exist, however, where surfaces are oppositely charged. In
that case, also electrostatic attraction forces in addition to van der
Waals forces are operative, which will further enhance adhesion. The
effect has been demonstrated in particular for clay particles where the
edges of the platelet structure may have a positive charge under
conditions where the platelet surface is negatively charged. Hence,

negatively-charged gold particles were found to adhere to the edges of
kaolin whereas positively-charged AgI particles were only found on the
kaolin surface (15). Another charge-induced interaction can take place
when two negatively-charged surfaces are linked by positively-charged ions
such as calcium (Fig. 4).
@ProcessEng
93
+ + + + +
Ca Ca Ca Ca Ca Ca H
+ + + +
Fig. 4 Calcium bridging
This mechanism can be generalized by the situation that 1 bivalent ion

such as Ca++ is replaced by 2 monovalent ions. The magnitude of the
adhesive force is then related to H and H, in its turn, to the degree of
hydration of the cation in question.
2.6 Surface hydration and steric hindrance

In addition to double-layer repulsion preventing the close approach and
subsequently the adhesion between colloidal particles, two other barriers
against flocculation exist: surface hydration and polymer adsorption.
In both cases, interpenetration of the adsorbed layers prevents
collision and hence adhesion; in the case of adsorbed polymers, steric
hindrance is the driving force. The situation becomes more complex when
only half the system is covered with a polymer layer. As aresult, the
adsorbed polymer mayaIso bind to the still naked surface and polymer-
bridging (16) leads to aggregation or to adhesion, that is, to enhanced
fouling. The complexity of the matter makes force calculations as
indicated in sections 2.3 and 2.4 impossible although the effect of
polymers cannot be ignored. A typical illustration of a system stabilized
by sur face hydration is milk, where the casein micelles are covered with a
surface layer of strongly-hydrated K;-casein, even making the system boil-
resistant. Once the surface layer has been removed by enzymatic means as
during cheese making, coagulation takes place and a (cheese) curd is
formed. The residual surface charge was not sufficient to prevent
collision.
2.7 Non-immersed systems

So far, only systems immersed in a fluid (mainly water) were
considered. In real it y, fouling also takes place in gaseous environments
as in the case of airborne dust. In addition to the always present van der
Waals forces of attraction, factors contributing to the adhesion of sub-
micron particles in air are:
a) electrostatic forces caused by differences in work function if two
different materials are in contact;

b) triboelectric forces operating over large separation distances and
c) liquid bridging in humid environments for systems in contact.
Prevention of fouling is very difficult because no real barriers against
adhesion exist. The only remedy is to use filters to 'clean' air.
2.8 Influence of the contact zone

@ProcessEng
So far, the interaction between two idealized systems, the sphere/plate

and the plate/plate configuration, was considered (Figs. Ic and Id). In
practice, the situation will be a combination of the two, as illustrated
schematically in Fig. le.
94
The contact area wi11 substantia11y contribute to the van der Waa1s
interaction when
[9)
An extended contact are a wi11 form either as aresult of elas tic or

plastic deformation of the softer of the two adherents 9r due to the
presence of an irregu1ar partic1e moving a10ng an irre gul ar surface trying
to find its most favourab1e position, which is in a surface indentation
best fitting its own configuration (Fig. 1b).
In this case, the van der Waa1s force of adhesion wi11 be at a maximum.
Surface and partic1e morpho10gy are, therefore, crucia1 in fou1ing. When
surface asperities (Fig. la) are much smaller than the dimensions of the
particle, the effective separation distance H over the contact zone wi11
become so large that the van der Waa1s force becomes neg1igib1e.
Elastic deformation wi11 not contribute to adhesion, because upon
separation of the adherents, this deformation wi11 be eliminated in
contrast to plastic deformation, which is permanent. Plastic deformation
is often time-dependent and manifests itself by an increase in adhesion
with time.
3. PROTEIN CHEMISTRY AND FOULING

3.1 Dairy f1uids
Mi1k and whey are co110ida1 systems processed on such a large sca1e
that fou1ing of processing equipment such as p1ate heat-exchangers, quark
centrifuges and ultrafiltration membranes is seen as one of the major
problems in the dairy industry, in particu1ar in the case of high-
temperature processing. The occurence of 'mi1kstone' is a we11-known
phenomenon and its presence resu1ts in a substantial 10ss off heat
transfer. As far as mi1k is concerned, its co110ida1 components, the
case in mice11es and the fat globules, are sufficient1y stabi1ized by
doub1e-1ayer forces and hydration 1ayers so that fouling problems are
main1y related to its solub1e components, the whey proteins, solub1e
casein and calcium phosphate. A sound understanding of its solution phase
with respect to temperature is necessary to understand the process of
fou1ing not on1y in this case, but this is a1so true of any system posing
fouling problems.
3.2 Mi1k composition

The composition of skimmi1k is given in Tab1e 3.
TABLE 3 Composition (%) and pH of skimmilk (yearly variation factory bulk
mi1k)
Component range
Fat - 0.1
Lactose 4.52-4.85
Casein, total 2.53-3.04
aS1 casein 0.78-1.38
ø casein 0.61-1.18
~ casein 0.16-0.42
Whey proteins, total
@ProcessEng
0.35-0.57
Ø-Le 0.32-0.67
a-LA 0.06-0.52
NPN 0.02-0.05
Urea (% X 10 2 ) 1.5 -4.6
Calcium, total 0.09-0.12
Phosphorus, total 0.06-0.11
Citrate 0.15-0.19
For cheese whey, these data will be similar except that the caseins are
removed as curd. ,,,hile releasing GriF, the saluble breakdown produet of K-
casein upor renneting.
The only heat-labile components are the whey proteins and calcium
I>'hen milk is heated, ,8-lactoglobulin Ul-LG), tr'e major whey protein,

reaets with casein. Tha type of interaction is strongly pH-dependent
(Fi!'.. :) and (,) and a func tion of the calcium level.
,- c'c et total W~'E-'J proteIn)

·100,- rlalurai pH
range of mil k
a - - - - - - a ~. ~. .. •
"'---
~~--L! ~., .:
"-~-f>
~ +: ~
y(
i
D~
~<_.:- !
, g~
~*I
:~
~~ li~~
20~-
i
OLi__~__________~LI__L -____~__~I~__________~~I
6.4 66 6.8 1.0
pH
Fis. J Casein-miselle-whey protein interaction on heating skimmilk as a

function of pH (90°C, 30 min). Distribution of denatured whey
proteins:O,., micellar phase o , . , serum; 11, Å, total. Total
",hev pro,-ein content: open symbols 0.60%; solid symbols 0.65%
'-H, addition of .5 mmol CaCl2; • .... Å, addition of .5 mmal ED'I'A
@ProcessEng
.().l""'l B
Fig. 6. Electron micrograph of heated Ø-lactoglobulin and casein

micelIes. A, pH 6,5; B, pH 7.0
96
At a low pH (6.5), P-LG is bound to the casein micelles but at a higher

pH (7.0), individual particles are formed. At the same time, the levelof
serum casein increases (Fig. 7) whereby a preference for K-casein is
found, which is in line with its known interaction with p-LG (17).
Serumlcasein
(mgl100ml) +citrate
10-;9-41
300
J
13-54-~
o dg o
o7<aL
200
100 18-72-10
6.4 6.7 7.0

pH
Fig. 7 Effect of heating on the amount and composition of serum casein
Amount of serum case in in skim milk as a function of pH and its
relative composition (as,l-p-K)
o~ room temperature (29-48-18, independent of pH)
o ~ room temperature af ter heating at 90·C for 30 min
These data are given here to illustrate the pH and calcium dependency
of the protein reactivity in milk: even a small shift in pH may have a
dramatic effect. In this case, this effect may be related to asharp
transition in p-LG behaviour at pH 6.8. Below this pH, the free SH-group
of Ø-LG is exposed upon heating and it is then able to form intermolecular
s-s bonds with itself and with K-casein. Above pH 6.8, a limited heat
denaturation takes place and only re arrangement of intramolecular s-s
bonds is possible. It is clear that these solution effects on a molecular
level will also be reflected in the fouling behaviour of milk and whey, in
particular in the latter case at low pH when no case in micelles are
available for reaction.
3.4 Salt effects

Model studies (18) showed that heating the imitation milk salt buffer
prepared according to Jenness and Koops (19) makes it turbid. The higher
the pH of the buffer, the lower the temperature at which turbidity is
observed.
TprK.lOC
50
'0
@ProcessEng
JO
20,!'.J-'!-,.,;--,f..''---;'''.'--,''7'---';''.•.----.!'9
pH
Fig. 8 Precipitation temperature of amorphous calcium phosphate (T prec .)

of milk salt solution as a function of pH (unaltered Jenness-Koops
buffer)
97
Prolonged heating times and temperatures close to 100·C, make the

process irreversible and a precipitate is formed which could be identified
as hydroxy apatite. Heating milk also results in a 20% decrease in soluble
phosphate. It is clear that during heating milk or whey, a new colloidal
phase of calcium phosphate particles is formed - a potential fouling
material often referred to as milkstone.
4. DEPOSITION AND FLOW

4.1 Rotating disc and cylinder
In order to understand the mechanisms involved in particle fouling, it
is essential to study the factors controiling the depostion of colloidal
particles onto surfaces either by excluding any effect related to flow or
by controiling the flow conditions in a standard way. One of the simplest
and most straightforward tools for studying deposition under controlled
flow conditions, is the rotating disc method developed by Kitchener and
co-workers (20, 21). The rate of deposition of particles from a colloidal
dispersion onto the surface of a disc rotating in that dispersion, is
controlled by mass transfer through the dispersion up to the surface of
the disc. Particles sufficiently close to the disc surface will either
adhere to it or be repelled, depending on the balance between the forces
of attraction and repulsion. Hull (21) has shown that if there is no force
barrier, the rate of deposition is controlled by diffusion and convection
up to the surface. For the rotating disc, this transport can be calculated
by the theory of Levich. The maximum flux j of particles up to the surface
per unit of surface are a is given by Fick's lowas:
J
. = dn = ~ (C
dt 6 solution
csur face ) = ~ C
6 solution
[10]
where D is the diffusion coefficient of the particle. For spherical

particles of radius R, D is given by the Stokes-Einstein equation:
D = kT/6 ~ ~ R [11]
where ~ is the viscosity of the solution. The Nernst equivalent thickness

of the diffusion layer (6) is, according to Levich given by:
[12]
Here, v is the kinematic viscosity of the solution, and w the rate of

rotation of the disc (in radians/s).
For a rotating disc, 6 has a constant value across the entire disc
surface, implying that regardless of the distance from the axis of
rotation, the conditions for transport of matter to any point on the

surface of the disc are the same. Hence, the maximum deposition rate can
be calculated from:
j = 0.621 Co D2/3 v -~ w~ [13]
This expression was verified experimentally by Hull for particles and a

@ProcessEng
disc of opposite charge in order to exclude any barrier against

attachment.
In reality, flow conditions as those found for a rotating disc seldom
occur and the high fluxes observed are very unlikely. However, equation
[13] clearly shows that Co' the particle concentration, its diffusion
coefficient D and the viscosity of the solution are the principal
parameters determining deposition in cases where no barrier against
98
adhesion exists. It is clear that the rotating disc is an ideal tool to

study and predict the conditions under which particle deposition may
occur.
A uniform deposition of colloidal particles on the outer surface of a
rotating cylinder was also observed. Since, for this case, the
hydrodynamics, are not yet sol ved, calculation of the corresponding
equation for the flux of depositing particles is not possible. Experiments
using this technique confirm, however, that the basic parameters
controiling fouling are the same as in the case of the rotating disc.
4.2 Forces actin~ on depositin~ and deposited particles

The hydrodynamic modelof Levich for the flow to a rotating disc is
only valid for laminar flow conditions, that is, when (22)
2
Re = ~ < 5 • 10 4
v
where X is the distance from the centre of the disc. Under these
conditions, the flow in the vicinity of the surface to which particles
adhere can be represented by the so-called laminar boundery layer
(Fig. 9).
Xl,
~.:r-._._.
I V
6 X
Fig. 9 Flow in the vicinity of an adhering particle
Adhesion will only take place when the force FF exerted on the particle by
flow is not able to overcome the force of attraction FA. From model
removal experiments described in part II it was concluded that when
[14]
detachment of spherical particles from a flat surface occurs by liquid
flow.
In the other words, if the flow conditions of a system are such that the
forces of attraction are weaker than the flow forces, no fouling will take
place. This situation is favoured by turbulent flow conditions if also
components of the flow in a direction perpendicular to the flow lines

along the surface (Fig. 9) are present, thereby keeping suspended
particles in motion continuously.
5. MEASURES TO REDUCE DEPOSITION

In the absence of repulsive forces and flow, colloidal particles will
@ProcessEng
attract each other in air and in a liquid environment via van der Waals
forces. Any collision will lead to bonding. Fouling will take place when
particles stick to surfaces. In the case of a liquid phase, a three-
component system will be involved since it is very unlikely that the
particles implicated in deposition are of the same nature as the
contaminating surface. For such a system (cf. section 2.), conditions
exist whereby van der Waals forces may become negative; in other words,
99
the interacting bodies will repel each other. However, thE"se conditions
may be difficult to achieve, so that a detailed analysis of the components
involved in the fouling process may provide indications how to minimize
the van der Waals attraction, the principal driving force of fouling. The
almost always present repulsive forces and the forces due to the flow of
the system, will then be sufficient to prevent deposition. For their van
der Waals contribution to the overall interaction, particles and surfaces
can be characterized by contact angle measurements and liquids by directly
measuring the surface tension. By inserting the data obtained in equations
[5] and [4], estimation of A132 is possible. When the fouling system is
fixed, the only possibility to reduce the van der Waals attraction is to
modify the surface susceptible to fouling, e.g. by using another material
or by coating the surface in question with a thin layer either by
adsorption of a rigid monolayer of a polymer or a surfactant or by a real
coating.
A typical illustration of reducing bacterial adhesion by altering the
surface tension, the van der Waals attraction, of a surface (tooth enamel)
is given by Busscher (23). In addition to the van der Waals interaction,
also other specific interaction forces are acting in the case of proteins,
as indicated by van Oss (9). Here also, contact angle measurements can be
carried out to estimate their additional contribution to the interaction
and establish ways to overcome or reduce it.
For a gaseous environment, the situation is different. Van der Waals
forces are here always attractive and particles of colloidal dimensions
will always adhere when brought into contact with a surface. The only way
to minimize fouling is to keep particles such as airborne dust
, suspended' .
5.2 Electrostatic double-layer forces and pH

All particles and surfaces in contact with a liquid are negative ly or
positively charge d , due to preferential adsorption of ions or by
dissociation of surface groups. The effect is most pronounced in water
where an extended double-layer can be formed. Interpenetration of double
layers of like sign will lead to repulsion. An estimate of the magni tude
of the corresponding repulsive force can be calculated from equations [6]
and [7], using zeta potential data of the materials involved. Zeta
potential data of colloidal particles can easily be obtained by micro-
electrophoresis. For surfaces, these data can be obtained either by
grinding the material into particles of colloidal dimensions or by
streaming-potential measurements. Typical examples are given in Fig. 10
for polystyrene and cellophane particles. The latter were obtained by
grinding frozen wetted cellophane with a pestle in a mortar.
zeta
potential (mV)
-80
A
-60
-40 B
@ProcessEng
-20
_20
Fig. 10 Zeta potential of polystyrene (A) and cellophane (B) particles as

a function of pH and ionic strength (25°C; 1:1 electrolyte; 10- 2
mol dm- 3 )
100
These data show that the higher the pH of the system, the higher the I
potential will be; hence the higher the force of repulsion. Fouling
problems mainlyarise near or at the isoelectric point, in particular if
the two interacting systems have an opposite charge. A smal l shift in pH
may then marked ly reduce fouling, for instance when attraction is revers ed
into repulsion. This situation only arises if the two systems differ in
isoelectric point at intermediate pH-values. Characterization of
components involved in fouling on the basis of their isoelectric point and
the actual pH of the solution is, therefore, essential to predict and
control fouling.
For systems like polymers, which hardly ever attain a negative charge
(even at high pH's), it may be advisable to introduce surface groups
either by oxidation or other chemical means or by adsorption of, for
example, surfactant molecules to augment the charge. For proteins, the
situation is more complex because these molecules have negative and
positive charge s at the same time. At the isoelectric point, their numbers
are equal and only the overall charge is zero. For caseins, this results
in precipitation (at pH 4.5) but for undenatured whey proteins this is not
the case; they remain in solution.
Depending on the type of groups exposed to the solution phase at a
given pH, aggregat ion or fouling will occur. It is clear that a smal l
shift in pH mayaiso have here a large effect on sticking or non-
sticking.
5.3 Steric hindrance and solvation

Certain polymers are added to colloidal systems in order to make them
more stable by a mechanism referred to as steric stabilization. Often,
these polymers have also charged groups which strongly bind water, thereby
also creating a hydration barrier against flocculation.
A specific example of such a system is the case in micelles in skimmilk.
The (bio)-polymer in question is a protein named ~-casein; its bound sugar
residue is known to enhance the stability of these micelles as does the
overall negative charge at the pH of milk (6.7).
Fouling problems only arise if milk is heated and the whey proteins become
reactive by exposure of -SH groups. In addition, insoluble calcium
phosphate particles are formed, which mayaiso deposit. Since both
processes are pH-dependent, as indicated in Figs. 6 and 8, a smal l shift
in pH may overcome the fouling problems. On the other hand, colloidal
systems stabilized by polymers may undergo polymer bridging with the
uncoated surface of the process equipment. In this case, it is advisable
to use the same polymer for precoating the surface. Applying hydrat ion
layers onto hydrophobic surfaces of processing equipment such as
ultrafiltration membranes, mayaiso be effective in minimizing deposit

formation in the same way as it does in stabilizing colloidal particles.
5.4 Ion bridging

Ion bridging may occur when two negatively-charged surfaces are closely
contacted, whereby positively-charged ions are acting as bridging agents,
neutralizing the overall charge (Fig. 4). Bivalent ions such as calcium
@ProcessEng
are particularly thought to be responsibie for such an effect. Problems

encountered with systems rich in calcium ions should, therefore, be
investigated regarding the use of calcium binders, such as polyphosphates,
for their capacity to reduce the levelof calcium bridging as a possibie
source of the fouling observed. At the sam time, a small shift in pH may
add to the overall effect of reducing fouling through the enhancement of
double-layer repulsion. The latter effect may be more important since the
101
occurrence of calcium bridging is probably confined to some specific

systems.
5.5 Heat induced fouling

Plate heat-exchangers are often severly fouled by the systems to be
heated. Apart from dead spaces, leaking seals or cracks where fouling may
be induced the composition of the heated fluid is crucial in terms of
fouling potential. Slight temperature adjustments may already reduce
fouling dramatically. For example in the case of dairy fluids, heating may
induce calcium phosphate precipitation (Fig. 8) causing fouling due to the
insoluble precipitate (as hydroxy apatite) formed. To solve this problem,
lowering of the pH and/o r addition of calcium binders may be considered.
This approach may also be applicable to the solution of the problem that
the calcium phosphate deposit may attract other components, in particular
caseins, since these proteins are known to bind to hydroxy apatite via
their phosphoserines (24).
When undenatured whey proteins are present, heat will induce their
denaturation whereby initially -SH groups are exposed. These very reactive
groups may cause binding of these proteins to the heated surface. Possible
ways to overcome this problem are to add an SH-blocking agent, to allow
the whey proteins to react with case in or with itself-both reactions are
strongly pH-dependent (Figs. 5 and 6) or to heat below their heat
denaturation temperature, that is below 72°C.
Again, pH-adjustment may provide a solution to this problem. Air may
also induce fouling because once a deposit has dried, the contact between
the adherent and the sur face may become so close due to removal of
interstitial water that molecular bonding may occur and even burning.
Exclusion of dissolved air or gas is, therefore, crucial to prolonged
processing of dairy and other fluids involving heating.
5.6 Surface structure and contaminations

In the case of ideally smooth surfaces, any potential deposit will
contact the flow near the surface and particles will be entrained as long
as the fluid velocity is sufficiently high to overcome the adhesive force
(see Fig. 9).
For non-ideal systems, as normal ly encountered in practice, the
situation is different. Particles may be get trapped in crevices (Fig. lb)
and non-spherical particles may move along the surface to find the most
favourable position, that is one providing the largest intimate contact
are a (Figs. ld and e). Exclusion of crevices and surface cracks on the one
hand and increasing the surface roughness on a micro-scale (Fig. la) to
minimize the number of contact points with a deposit on the other, may
help minimize fouling. However, the presence of reactive sites on

asperities should be avoided. The same applies to any predeposited dirt
such as rust particles from unclean rinsing water. Both may act as kernals
for secondary deposition.
In other words, surface finish and the precleaning conditions should be
given major attention before processing operations are started.
@ProcessEng
5.7 Flow conditions

As long as particles are entrained by the processing fluid (see under
4.2), fouling will not occur if the drag force is stronger than the
adhesive force. Any dead space can, therefore, be a potential are a for
fouling. So a close analysis of flow patterns in processing equipment is
als o essential to prevent fouling.
102
6. SUMMARY
l. Major factors responsibIe for fouling:
- van der Waals forces
These forces are always present and are the major cause of fouling.
Only in some specific cases are they repulsive.
- Electrostatic forces
Systems of oppositely-charged partners, in particular when surface-
reactive sites are present as at the edges of clay platelets, attract
each other. Their effect is only occasionally encountered in
practice.
- Gontact area
The large r the contact area between adherents, the stronger the
attractive force and the stronger the adhesion. This will be the case
for non-spherical particles and surfaces with roughnesses of the same
order as the dimensions of the particles.
- Surface reactions
Exposure of reactive groups of proteins and the formation of
insoluble complexes such as calcium phosphate upon heating, may lead
to substantial fouling problems.
These factors are particularly encountered in practice if the flow

conditions are non-homogeneous or stagnant, dissolved air or gas is
present, surfaces are hydrophobic or when the processing fluid is
unstable, i.e. settIes at rest.
2. Principal ways to prevent fouling:
- Greation of conditions where van der Waals forces become repulsive

either by a proper choice of the liquid or by surface coating.
- Greation of strong repulsive forces through charging, e.g. by raising

or, in certain cases, lowering the pH.
- Binding of calcium ions to reduce ion bonding.
- Suppression of surface reactions during heating by changing the pH,

raising or lowering the temperature and rinsing with clean fluids.
To create flow conditions excluding dead space s or stagnant regions

but where high drag forces are operative e.g. by high flow
velocities, preferably turbulent.
3. Data required to predict fouling:

@ProcessEng
Overall composition and properties of the processing fluid, in

particular particle size, particle morphology, particle contact
angle, particle zeta potential, protein reactivity, formation of
complexes, insoluble salts and crystals at various pH's,
\03
temperatures and salt levels
- Processing equipment: flow pattern, materials used, zeta potential,

contact angle and surface roughness.
Composition and properties of deposits in relation to those of the

processing liquid, e.g. Ca, P, Fe, ash, fat, protein content and
composition.
The conclusion is justified that the rotating disc is an ideal tool for
model fouling studies.
LIST OF SYMBOLS
A' - Hamaker coefficient (erg)**

C - concentration
D - diffusion coefficient
FA - force of attraction
FF - drag force
H - separation distance
PA - force of adhesion/unit of surface are a
R - radius
T - temperature (OK)
V - interaction energy
X - distance from centre of disc
d - separation distance
dl,2 - thickness of an adsorbed layer
e - electronic charge
j flux
k - Boltzmann C0nstant
V x - velocity at a distance x from a surface
~ - surface tension
o - boundary layer thickness
o - double-layer thickness
- dielectric constant
I - zeta potential (mV)
K - reciprocal double-layer thickness o
a - particle charge
p - radius of contact area
~ - viscosity
v - kinematic viscosity
w - rate of rotation (radians/s)
** A' was used to avoid confusion with the symbol (A) denoting heat
transfer areas
REFERENCES
1. Verweij E.J.W., Overbeek J.Th.G., Theory of Stability of Lyophobic

@ProcessEng
Colloids, 1948, Elsevier, Amsterdam.

2. Scheutjens J.M.H.M., Fleer E.J.; Some Implications of recent Polymer
Adsorption Theory in The Effects of Polymers on Dispersion Properties,
Tadros Th.F. (ed), Academic Press, London, 1982, 145.
104
3. Visser J.; Adhesion of co11oida1 Particles in Matijevic E (ed).

Surface and Co11oid Science ~ 1975, p. 3, John Wi1ey & Sons, Inc. NY.
4. van der Waa1s J.D.; Over de continuiteit van den gas- en v1oeistof-
toestand, Thesis, Leiden, 1873.
5. London F.; Zur Theorie und Systematik der Mo1eku1arkrafte, Z. Phys.,
63, 245, 1930.
6. Hamaker H.C.; The London-van der Waa1s Attraction between spherica1
Particles, Physica (Utrecht), ~, 1058, 1937.
7. Lifshitz E.M.; The Theory of mo1ecu1ar attractive Forces between
Solids, Sov. Phys., l, 73, 1956.
8. Visser J.; On Hamaker constants: A comparison between Hamaker
constants and Lifshitz- van der Waa1s Constants, Adv. Co11oid
Interface Sci. l, 1972, 331.
9. van Oss G.J., Good R.J., Chaudhury M.K.; Corre1ation between Lifshitz-
Hamaker Constants and Surface Tension of Liquids and Solids,
Separation Sci. Techno1. (in press).
10. van Oss G.J., Good R.J.; The 'Equi1ibrium Distance' between two Bodies
immersed in a Liquid, Co11oid and Surfaces, ~, 373, 1984.
11. Langbein D.; Van der Waa1s Attraction between macroscopic Bodies, J.
Adhes., l, 237, 1969.
12. Deryagin B.V., Landau L.O.; Theory of the Stabi1ity of strong1y
charged 1yophobic Sols and of the Adhesion of strong1y charged
Particles in Solns of E1ectro1ytes, Acta Phys. Chim USSR, 14, 633,
1941.
13. Hogg R., Hea1y T.W., Fuerstenau D.W.; Mutua1 Coagu1ation of co11oida1
Dispersions, Trans. Faraday Soc., 62, 1638, 1966.
14. Wiese G.R., Hea1y T.W.; Effect of Partic1e Size on Co11oid Stability,
Trans Faraday Soc., 66,490, 1970.
15. Thiessen P.A.; Wechse1seitige Adsorption von Kolloiden, Z.
E1ektrochem., 48, 675, 1942.
16. F1eer G.J.; Polymer Adsorption and its Effect on co11oid Stability,
Thesis, Wageningen, 1971.
17. Smits P., van Brouwershaven J.H.; Heat-induced Association of ø-
1actog1obu1in and Casein Mice11es, J. Dairy Res 47, 313, 1980.
18. Visser J., Minihan A., Smits P., Tjan S.B., Heertje I.; Effects of pH
and Temperature on the mi1k salt system, Neth. Mi1k Dairy J. 40 351,
1986.
19. Jenness R., Koops J.; Preparation and Properties of a Salt Solution
which simulates Mi1k Ultrafiltrate, Neth. Mi1k Dairy J. 16, 153,
1962.
20. Marshall J.K., Kitchener J.A.; The Deposition of co11oida1 Particles
on Smooth Solids, J. Co11. Interf. Sci, 22 342, 1966.
21. Hu11 M., Kitchener J.A.; Interaction of spherica1 co11oida1 Particles

with planar Surfaces, Trans. Faraday Soc, 65 3093, 1969.
22. Sch1ichting H., Grenzschicht Theorie, Ver1ag G Braun, Kar1sruhe 1958.
23. Busscher H; Surface free energy and the Adhesion of oral Bacteria,
Thesis, Groningen, 1985.
24. Donnelly W.J.; Chromatography of Mi1k Proteins on Hydroxyapatite, J.
Dairy Res. 44, 621, 1977.
@ProcessEng
ADHESION AND REMOVAL OF PARTICLES II
J. VISSER
UNILEVER RESEARCH LABORATORIUM VLAARDINGEN

Olivier van Noortlaan 120, 3133 AT Vlaardingen, the Netherlands
l. INTRODUCTION
Cleaning fouled surfaces is mostlya proces s whereby 'particulate
material' is removed from a solid surface, predominantly by liquid flow.
Cleaning problems may arise if the flow of the liquid cannot reach the
fouled surface, e.g. when particles are trapped in crevices, or when
adhesion forces between the contaminating material and the support are
very strong. In the latter case, acids and/or alkalis are mostly used in
combination with a detergent to 'detach' the deposit. In some specific
cases, also enzymes are used to break down or diges t the material
deposited, in particular proteinaceous components. In most cases, the
mechanism of removal can be described in terms of colloid chemistry and
fluid dynamics because in fouled systems, predominantly submicron or
colloidal particles are involved as shown in part I and because the
cleaning operations are mainly based on the flow of liquid solutions along
the fouled surface. In this review, both aspects are described in detail,
including the van der Waals forces of attraction and the electrostatic
double-layer forces of repulsion as well as the flow of a fluid in a
laminar boundary layer. The equations given in part I are used to describe
the colloid chemistry aspects. On the basis of the results obtained from
model experiments, conditions will be given to optimise the removal of
'particulate' dirt.
2. COLLOID CHEMISTRY AND ADHESION

As shown in Part I, the van der Waals forces of attraction, FA, between
a sphere of radius R and a flat plate at a separation distance H, can be
described by the equation:
I
F A·R
=-- [l]
A 6 H2
I
where A is the Hamaker coefficient of the interacting bodies. For a three-
component system (the van der Waals interaction between two different
materials l and 2 in a third medium 3):
I
A = A132 = (;-Ali - ;-Aj3) (;-A22 - ;-Aj3) [2]
@ProcessEng
where Aii is the individual Hamaker coefficient of material i. If medium 3

is vacuo:
I
A = Al2 [3]
105

106
A132 can become negative when
All < A33 < A22 or [4]

An > A33 > A22
The force of interaction PA between two semi-infinite flat plates per unit
of surface area equals:
__A_
,
[5]
6 'Ir H3
The van der Waals force of attraction between a 'real' particle and a
substrate can be estimated by means of equations [l] and [5].
2.2 Electrostatic double-layer interaction

In contrast to the principal driving force of the adhesion of
particulate material to a substrate -the always present van der Waals
forces- the electrostatic double-layer forces are only operative if a
double-layer around the adherents can be established. This requires
charging of the two interacting materials -which is only possible in
water- by preferential adsorption of ions, or by dissociation of surface
groups, such as carboxylic groups.
The basic equations for double-layer repulsion (Part I) in the case of
sphere-plate geometry under the condition that, upon approach, the charge
o, or the potential ~ remains constant are:
.L...R (~2 + 2 It exp (-ItH)

FR No (sphere-plate) 2 Ol ~02) l - exp (-2 ItH) x
x[ 2 ~Ol ~02
2 2
~Ol + ~02
-/+ exp (-ItH) l [ 6]
where It, the reciprocal of the double-Iayer thickness 0, is defined by:

2
4 'lre
[7]
€ kT
2.3 Other interaction forces
2.3.1 Electrostatic forces in vacuo (l)
When two solids in vacuo are separated by a smal l gap, electrons from
the material with the lower work function are transferred to the material
with the higher one. Equilibrium is attained if the two work functions
have reached the same value. The potential difference, ~U, arising from
this levelling may lead to values of up to 0.5 V. The corresponding
adhesive pressure, Pel, can be found from the conventional capacitor

equation. For flat plates:
€ (~U)2
o _G_
Pel [8]
2
2 H2
€
o
@ProcessEng
and for a sphere and a flat plate:
R (~U)2
Fel 'Ir € [9]
o H
107
where €o is the permittivity of vacuum and G the surface charge density.

Electrostatic forces mayaIso arise from a coulombic interaction: when a
charged particle is brought into contact with an uncharged surface, the
charged particle induces an equal charge of opposite sign at an equal
distance from the surface in the material under that surface. This so-
called image charge leads to an attractive force Fe of
[10]
where Q is the charge of the particle and l the distance between the
charge centres. When electrostatic forces of this kind -generated
specifically as in electrical air filters or by triboelectricity- are
dominating, the interaction between a sphere of radius R and a flat plate
will be proportional to R2 since Q is proportional to R2.
2.3.2 Electrostatic attraction of oppositely-charged surfaces

Although the electrostatic attraction forces described above may give
rise to 'fouling' and to strong adhesive forces in vacuo, these
contributions will be negligibIe in water. Here, an electrostatic force of
another nature may be operative, e.g. the interaction between negatively-
charged particles and a positively-charged surface. As indicated in
part I, this interaction was demonstrated for negatively-charged gold
particles exclusively adhering to the positively-charged edges of clay
platelets. In general, this effect will be observed for materials with
different isoelectric points due to a different ratio between positively-
and negatively-charged surface groups. At high pH's, a sufficient number
of negatively-charged surface groups will be present and, as aresult,
attraction will be reversed into repulsion. The corresponding repulsive
force can be calculated in the way as described in section 2.2.
2.3.3 Ion bonding

The presence of ions between adherents may influence the adhesion by a
bridging mechanism. When two negatively-charged surfaces are brought into
contact, interstitial positively-charged ions may form a bridge so that
the overall charge of the system will be zero. However, this bridging may
lead to an additional attraction force and it will become more likely that
the overall force of attraction will be determined by the 'spacing'
between the two surfaces. Swelling studies of clay particles by Norrish
(2) showed that the magni tude of this spacing can be correlated with the
hydration energy of the interlayer cation. The results indicate that
calcium ions behave in the same way as the other cations. In other words,
there is no reason to speak of a specific calcium bridging effect,

although these ions may indeed increase adhesion by their ability to lower
the surface charge of the adherents and thereby the electrostatic double-
layer repulsion.
2.3.4 Humidity
The presence of a liquid film between a sphere and a flat plate
@ProcessEng
(Fig. l) due to capillary condensation of environmental humid air, results

in an extra contribution FLF to adhesion, given by:
FLF = 4 ~ • ~ • R [Il]
108
where ~ is the surface tension of the liquid. This contribution is

generaIly small compared to the overall force of adhesion.
Fig. l Capillary conden~ation of a liquid (water) between a sphere and a

flat plate in humid air
Its 'neutralizing' effect on the electrostatic force contributions to

adhesion may, however, result in a reduction in adhesion.
2.3.5 Thin layers

Thin layers will markedly affect the adhesion of particles to a surface
by their ability to 'screen' the overall van der Waals force of adhesion.
When the thickness of the layer is larger than the distance between the
adherents (see Part I), the adhesion is only determined by the properties
of the layer. Characterization of the actual surface is, therefore,
essential for predicting the performance of a given cleaning solution. The
effect of thin layers on adhesion becomes more complex if the particles
are 'embedded' in a layer of a high-viscosity liquid such as grease. In
this case, the particles will try and penetrate the layer until a pseudo-
equilibrium has been reached between the forces tending to 'sink' the
particles and the resistance of the viscous layer.
For a thick layer, the particles to be removed may be released together
with the 'liquid', and the force required to remove the particles will be
a function of the properties of the layer, rather that of its thickness.
2.3.6 Temperature and time effects

Both temperature and time may increase the contact area between
adherents, the more so if one of the components can undergo plastic
deformation. By increasing the contact area, the van der Waals force of
adhesion increases. When the radius of the contact are a
p> jRH [12)

the adhesion is dominated by the contribution across the contact area. A
consequence of the effect of time is that adhesicn increases with ageing,
so the older the deposit, the more difficult it is to remove.
For proteins, elevated ternperatures may lead to unfolding and thereby to
exposure of specific surface groups, which may result in an increase in

the number of attachment points. The more binding sites, the more
difficult it will be to detach the protein molecules.
3. REMOVAL AND FLOW

3.1 Introduction
Once a surface has been fouled, two separate mechanisms are applied for
@ProcessEng
removing the contaminating material.

These meachanisms are:
- liquid flow e.g. by passing a liquid (predominantly water) along the

surface at a high velocity;
chernistry, by incorporating in the liquid components such as a

detergent, alkali, enzymes etc. to reduce the force of adhesion.
\09
In addition, elevated temperatures are used when liquid/fatty so il is

present. These meachanisms will be treated separately primarily because
the interpretation of chemical effects on removal is only possible if the
removal conditions have been standardized. The sphere/plate model has been
chosen to facilitate this interpretation.
3.2 Control led flow conditions between rotating cylinders

3.2.1 General
Particle deposition studies described in part I show that the flow to a
rotating disc is ideally suited as long as the flow conditions are
laminar. For the removal of deposited particles, however, a turbulent flow
is required in view of the high adhesion forces involved.
Under these conditions, the flow to the rotating disc is no longer
uniform and turbulence can only be induced by extremely high rotational
velocities at a substantial distance from the centre of the disc. To
overcome the problem of non-uniformity in flow, a concentric cylinder
geometry was chosen. Here, the hydrodynamic forces were found to be
identical at any point of the outer surface of the inner cylinder to which
model particles were attached.
3.2.2 The role of the wall shear stress r

Experiments under well-controlled conditions using spherical carbon
black particles adhering to a cellophane surface showed that their removal
is only determined by wall shear stress, independently of the way the flow
was generated (Fig. 2) (3).
Removal (.,.)
I::. rotating outer cylinder

'il rotating innercylinder
40
60
80
200 400 600 'rIdyne
Fig. 2 Removal of carbon black particles from cellophane as a function of

wall shear stress (r)
From measurements with the rotating inner cylinder at various gap widths
it was found that the removal is proportional to r 2/3 (Fig. 3) (3).

Removal(%)
O
"o o Gap-widlh= 0.05=
, A .. =0.10cm
20
v"""-c
:: ------------~
o = 0.20 cm
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80 ~
~
1000L--L.-4.':.0-",-.L80-:"---'-...J120-...J...--'160
1"2/3
Fig. 3 Removal carbon black ~articles from cellophane as a function of
wall shear stress r 2/
110
3.2.3 Hydrodynamic force and r

For turbulent flow it is assumed that in the vicinity of a surface, the
flow is still laminar in a region of thickness 6
6 _ __
v_
[13]
- Jr/p
In this so-called laminar sublayer (Fig. 4), the hydrodynamic force, FH,
excerted on aspherical particle adhering to a flat surface can be
expressed as (l):
[14]
where r ~ 0.23 pv~ w3 / 2 : [15]
w is the angular velocity, Ri the diameter of the inner cylinder and Ro

the diameter of the outer cylinder.
I I
I I
I I
I ~I
Fig. 4 Velocity profile at the surface of the inner cylinder
By plotting the percentage of removal as a function of r 2 / 3 (Fig. 3), the

wall shear stress r at 50% removal can be calculated. By assuming that
this value is representative of the force of adhesion of a particle with
radius R and equal to the aver age value R, it is possibie to quantify the
removal data in terms of adhesive forces, provided the relationship
between the hydrodynamic force, FH, and the force of adhesion, FA, is
known, (Fig. 4).
3.2.3 Relationship between hydrodynamic and adhesive force

Since no direct relationship exists between the force of adhesion FA

and the force FH applied by flow, an indirect method was used to establish
this relationship. To this end, the adhesion of carbon black particles to
cellophane was measured by a centrifugal method whereby FA was measured
directly. The results were compared with those obtained from a removal
experiment using the concentric cylinder method. The results plotted in
Fig.Sindicate that
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[16]
This calibration experiment permits the force of adhesion of colloidal

particles to be calculated directly from a removal study, using the flow
between concentric cylinders and equations [14] [15] and [16].
111
Removal '"Io)
100
80
60
_ _ _ _0
40
.,fo-0----O
20 rl:1.
O 2 3 4
Force (10- 6 dyne)
Fig. 5 Comparison of percentage of removal of oxidized carbon black

particles from a cellophane substrate in 4.1.10- 3 M sodium decane
sulphonate af ter application of a tangential force (o) or a normal
force (11)
These results show that the principal factor in the removal of particulate
material by liquid flow is the shear stress at the wall.
3.3 Flow induced by a rotating disc

As indicated ab ove , removal of colloidal particles by liquid flow is
determined by the wall shear stress r. For a rotating disc, the wall shear
stress as a function of the Reynolds number Re (3)
2
Re ~ X w [17)
v
is given by Fig. 6 where X is the distance from of a point on the surface
to the centre of the disc, w the angul ar velocity and v the kinematic
viscosity.
log' l, pw2X 2)
-1 2
4 6 7
log Rel
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Fig. 6 Wall shear stress r as a function of Reynolds number for liquid

flow to a rotating disc
Removal experiments with (and without) an anti-drag agent (Polyox) to

suppress turbulence in the turbulent flow region, confirm the relationship
between removal and r for the flow to a rotating disc (Fig. 7; curve 2).
112
°4L-------~5~------~6L---
log Re
Fig. 7 Removal of carbon black particles from the surface of a PMMA disc
as a function of Reynolds numbers with (e) and without an anti-
drag agent (o)
When turbulence is not suppressed in the transition region between laminar

and turbulent flow, a sharp increase in removal is observed, demonstrating
the additional contribution of turbulence to particle removal.
Quantification of the results is, in this case, less straightforward and
would require a second calibration experiment.
3.4 Laminar boundery layer theory and the mechanism of removal

So far, it has been assumed that even in the case of turbulent flow,
there is a laminar boundary layer. For the interpretation of the removal
data in terms of forces of adhesion, a calibration experiment was
performed because there is, to our knowledge, no theory for the removal
mechanism of submicron particles from a solid wall by liquid flow.
Hubbe (4) was the first to make a detailed analysis of the detachment
of particles from a flat surface exposed to flow, taking into
consideration the Cleaver and Yates (5) model in which a lif ting force is
assumed due to stagnation-point flow in the viscous sublayer of turbulent
shear. Depending on the size and shape of the particles and the direction
of the dominant hydrodynamic force (normal or parallel to the wall) , a
particle mayeither slide, roll or be lif ted away from its initial
deposition site during removal.
Hubbe's analysis shows that the component of the hydrodynamic force
acting parallel to the wall, is larger than the normal forces considered
by Cleaver and others. In other words, the above analysis based on an

assumed laminar boundary layer is still acceptable. The actual detachment
mechanism is difficult to establish. It will strongly depend on the
geometry of the system. Simple rolling will only occur in the case of a
perfect sphere adhering to an ideally flat surface. Here, the force
required to move a particle will be much smaller than the adhesive force
as centrifugal experiments showed where a force was applied perpendicular
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and parallel to a surface (6).

For real systems, an extended contact area will rather require a kind
of pivotal movement followed by a lif ting process. This is in line with
the observation that in removal experiments with a rotating cylinder,
particles were never found in a position adjacent to their original
location, thereby excluding a rolling mechanism as the principal cause of
removal. Hubbe further pointed to three time-dependent proces ses leading
113
to detachment of a particle e.g. viscous flow, Brownian motion (when the

adhesive energy falls below 3/2 kT) and fluctuations in the hydrodynamic
forces acting on the particles.
When the adhesion of carbon black particles was substantially reduced,
(Brownian) movement of adhering particles could indeed be established by
observation under a microscope using darkfield illumination. So far, the
rate of detachment observed could not be explained by either of the time
effects proposed.
3.5 Passage of an air/water interface

Carbon black particles strongly adhering to a gold sur face , which
requires very high rotational speeds in a rotating cylinder set-up to
generate removal, were found to be detached simply by slowly passing the
system through an air/water interface. Leenaars (7) recently demonstrated
the same phenomenon both theoretically and by experiment. The results were
found to be particle radius-independent. The most important parameters
were the wetting properties of the particles and the substrate as well as
the kinetics of the process. When the phase boundary passed at a speed of
several cm s-l, no removal took place whereas at a speed of 3 ~m s-l, 70-
90% of the particles was found to be detached.
4. CHEMISTRY AND REMOVAL

4.1 Introduction
Apart from liquid flow, specific cleaning solutions are used to enhance
the removal of deposits from fouled surfaces. These solutions mainly
include alkali, detergents, calcium binders and in some specific cases,
enzymes. Acids are used to dissolve components such as calcium carbonate.
Elevated temperatures are often applied in addition to a chemical compound
to enhance removal of liquid soil (grease, fat etc.) to ensure hygenic
conditions. The different theories and mechanisms presented above were
tested in model experiments using controlled flow conditions.
4.2 Immersion
Simple immersion will reduce the adhesion of particles to a surface by
lowering the van der Waals attraction, as outlined in part I. By a proper
choice of the liquid, adhesion may be reduced to a minimum and, in certain
cases, even be reversed into repulsion. The latter effect is applied in
dry-cleaning.
Proper analysis of the overall system using contact angle measurements
will indicate the conditions required to minimize the van der Waals
attraction. The experiments reported by Neumann et al. (8) in which the
passage of a liquid/air interface was used, are a typical example.
Depending on the surface tension involved, particles were either engulfed

or repelIed by passage of a solidification front. For water, the situation
is more complex because for this liquid, not only van der Waals forces are
operative but other interactions are involved as well, except for
hydrophobic systems. These other interactions, surface hydration for
instance, may cause an additional reduction in adhesion through an
increase in separation distance between the adherents. The time dependency
@ProcessEng
of this effect show up in a reduction in adhesion by a factor of two when

presoaking in water for 30 min before actually starting a removal
measurement. The role of the separation distance with respect to adhesion
has been clearly demonstrated for carbon black particles deposited onto
cellophane by means of a range of different mono- and divalent cations,
(Fig. 8).
114
Removal (.,.) • Cs+

D Na+
O
20 ~• vLt
A Ca++
~~~~20
50 --------------------- i~---~
60 I I I
I I I
i i
i
I
Lt :Na,Ca++ : Cs+
40 80 120 160 200
Fig. 8 Removal of carbon black particles from cellophane in water at room

temperature as a function of wall shear stress r 2/ 3 for different
ions of deposition
The cation with the highest hydration energy (lithium) gives the lowest
force of adhesion. The results are in agreement with those of thc clay-
swelling studies of Norrish (Table l) (2).
TABLE l Effect of the hydrat ion energy of cations on the interlayer
spacing of montmorillonite
Hydration enerfy/unlt of charge Interlayer

(Kcal x g 10n- ) spacing (run)
Li+ 136 1.3

H30 + 130 1.3
Na+ 114 1.0
Ca++ 102 1.0
Cs+ 80 0.5
The adhesive forces for Na+ and Ca++ are identical, indicating there is no
specific calcium bridging meachnism.
Calculation of the separation distance H on the basis of the
extrapolated forces of adh3sion FA corresponding to 50% removal (Fig. 8)
shows (Table 2) that similar data are obtained as found for the interlayer
spacings of clay particles.
TABLE 2 Force of adheslon of carbon black particles to cellophane as a
functlon of ion of deposition
FA (x 10- 6 dynes) Ion H (run)
6.2 u+ 1.4
8.1 H30+ 1.3
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8.1 Na+ 1.3

8.1 Ca++ 1.3
13.1 Cs+ 1.1
4.3 pH and ionic strength

The adhesion of carbon black and polystyrene particles to cellophane is
115
strongly pH (and ionic strength)-dependent as shown by model removal

studies, using the flow between concentric cylinders (Figs. 9 and 10).
Removal (.,.) 124

~ I
'I I
/0 ~,':
100 f~ j 20
80 l \ /1
60
\.0..,'I ,\
,; \
I
I
40 "0/ \ ~ 8
rI\...~ /8" J1
20 "o'
,
0, ,o .....
.............. i 4
o ........... 0-...'
O ~_-L_-L._-'-_--'-_~I O
O 2 4 6 8 10
pH
Fig. 9 Carbon black particles: percentage of removal from and force of

adhesion to a cellophane substrate (n - 4700 rev/min; 23°C)
FH (10- 6 dyne)
80
\
70 \,
60 '\ "o
'\l> \
"~\
50
40
30
20
~ CIJb~~o
10
~~Q D......
O 2 4 6 8 10 12
pH
Fig. 10 Hydrodynamic force (FH) corresponding to 50% removal of

polystyrene from cellophane as a function of pH (25°C; 1:1
electrolyte). 0 - 100 mOle/m 3 ; ~ - 10 mOle/m 3 ; D - l mole/m 3
A maximurn adhesion is found at the isoelectric point of the adherents

@ProcessEng
where double-layer repulsion forces can be neglected. Evaluating of the

data for polystyrene particles at the indicated ionic strength on the
basis of the zeta potential results of the adherents, and comparison of
the results with those obtained from the theoretically-derived equation
for constant charge and constant potential (equations 6 and 7) show, as
expected, that the theoretically-derived equations represent two extremes
with the 'real' situation lying in-between (Fig. 11).
116
FR(arbitrary units)
o lO 2.0 3.0
KH
Fig. 11 Electrostatic force of repulsion (FR) as a function of ~H. o FR
(constant charge); D = FR (constant potential); ~ = FR
(experimental)
Rather suprisingly, the adhesion of polystyrene to cellophane is

determined exclusively by the zeta potential of the substrate
(cellophane). This finding is supported by the results of the carbon black
particle on polyethylene experiments reported below. Overall, the
conclusion may be drawn that the pH plays a dominating role in reducing
the adhesion between a colloidal particle and a substrate. The lower the
ionic strength, the larger the effect. This is still noticeable at
pH = 12, avalue quite common for many industrial cleaning solutions.
4.4 The ro le of calcium binders

(Poly)phosphates are often included in cleaning systems because of
their calcium-binding properties, high pH and good buffering capacity. A
typical example is sodium triphosphate (STP). Its functionality was tested
in a series of experiments in distilled and hard water (15°DH) with
respect to the removal of carbon black particles from cellophane under
standard hydrodynamic conditions (flow between rotating cylinders).
Removal (0/0)
100
OOOJ:L--o-
80 _ _~ ~IJ-
o 150 0 H / " -
60 /
40 /
20!:-::::"
O 2 3
STP (g/l)
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Fig. 12 Influence of the concentration of STP on the percentage of

removal of carbon black particles from cellophane at 3500 rev/min
in O and l5°DH
117
FH (dynesxlO-6)
30 c
20
10
o o
'(OH
\
o-o
c~
O.OH
iJ=_:-----O
o 2 3
STP (g/l)
Fig. 13 Influence of the STP concentration on the force of adhesion of
carbon black particles to cellophane in O and lsoDH
The results presented in Figs. 12 and 13 and in Table 3 show that, when
the water hardness is increased to lsoDH, the adhesive force FA increases
4-fold to avalue similar to that of the same system at the isoelectric
point of one of the components or to that of a solution containing a high
levelof NaGl, the double-layer repulsion is completely suppressed and the
adhpsion is only governed by van der Waals forces.
TABLE 3 Influence of STP on the adhesion of carbon black partieles to
eellophane in water of O and 15·DH
Cone. STP ·DR pH F(dynes x 10. 6 )

(g/l)
O 5.3 8.0
15 6 31
O 3.3 32
0.2 O 9.4 1.3
0.8 O 9.6 1.2
0.8 15 7.8 8.0
2.0 15 9.4 1.4
2.0 O 9.7 1.0

O 10 2.1
Addition of STP strongly reduces adhesion. At a concentration where all

calcium ions are sequestered, the difference between adhesion in the
presence or absence of calcium ions disappears almost completely (Fig.
13), demonstrating the calcium-binding role of STP. Although the effect of
STP on removal (Fig. 14) suggests a pure pH effect, a comparison of
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removal data at identical pH-values shows, however, that the reduction in

adhesion in a solution containing STP is higher than one containing only
NaOH.
118
SD
5 L - I_ _ L.....--_---l'L-_---:"
O 2 3
STP(gl1)
Fig. 14 Course of pH of a solution of STP in water of 0° and l5°DH as a

function of the STP concentration
This points to a special effect, which is probably related to a specific

absorption onto the adherents, as follows from the relatively high zeta
potential of carbon black particles in STP. The role of the substrate is
equally important since the adhesion of carbon black particles to
polyethylene is unaffected by STP.
This result further substantiates the above findings that the adhesion
is mainly determined by the properties of the substrate.
4.5 The role of surfactants

In order to distinguish between the effect of charge and hydrocarbon
chain-length, a series of nonionics was selected to test their adhesion-
reducing capacity at low and high pHs and in the presence/absence of
calcium ions. The data presented in Table 4 show that the length of the
EO-chain does not influence the reduction in adhesion of a series of
nonyl-phenol-based nonionics.
TABLE 4 Influence of nonlonlcs on the adheslon of carbon black partlcles
to cellophane at pH S.7 and pH 10 ln dlstl11ed vater and ln vater
of lS'OH)
Nonlonlc pH - 10 pH - 5.7
O' IS' O· 15'
nonylpheonl 6 EO 1.0 4.0 11 21

nonylphenol 9 1.2
nonylpheno1 IS 1.1
nonylphenol 20 1.3 4.0 13 18
2.9 23 12 31
hexanol 2S EO 6.1 39 2S 18
dodecanol 25 EO 4.2 8 13 9.9
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The binding of these nonionics to the adherents via their EO-groups is

apparently the only important meachanim. At pH - 10, calcium seems to
promote this binding because at this pH, the reduction in adhesion is
strongest. The influence of the hydrocarbon chain-length was tested by
comparing the effect of hexanol and dodecanol-based nonionicswith an
identical number of EO-groups (25). The results presented in Table 4 show
119
that, compared to the surfactant-free system, hexanol 25 EO promotes

adhesion probably via a 'polymer'-bridging mechanism related to its
relatively short chain-length, which is comparable to the separation
distance between the adherents. Dodecanol 25 EO with a hydrocarbon chain-
length twice as long, did, however, not affect adhesion except when
calcium ions were present, which suggests a calcium-promoted adsorption
via the EO-group, which is in line with the results for the nonylphenol-
based nonionics. At low pH's, dodecanol 25 EO is more effective than the
nonylphenols, which can be attributed to its longer hydrocarbon chain-
length.
The effects are still difficult to interpret considering the influence
of the adsorbed nonionic molecules on the electrostatic double-layer of
the adherents.
Both adsorption and chain-length seem to determine surfactant
functionality.
4.6 Protein removal

A clear picture of the binding of a protein to an interface has been
presented by Shimizu et al. (9). Using a proteolytic digestion method,
these authors showed the location of 9 (non-digested) regions 'buried' in
the oil phase of an oil-in-water system, using 0sl-casein as an
emulsifier. These regions were not found to be related to hydrophobicity
only but also to other factors.
In other words, proteins are apparently adsorbed to an interface via
specific binding sites. These sites are less prone to enzyme attack than
other parts of the protein. Residual bound peptides may, therefore,
constitute a problem in cleaning fouled systems containing proteins, even
if the wash solution contains enzymes. Displacement of these peptides by
smaller surface-active molecules in a second cleaning cycle seems to be a
logical consequence, considering the theory recent ly developed by de
Feijter (10) on this subject.
4.7 Temperature
Cleaning at elevated temperatures is not only applied for hygienic
reasons (e.g. cleaning of processing equipment) but also to promote the
removal of liquid 'soil' . The principal mechanism here is the so-called
rolling-up mechanism. Surfactants lower surface tension and emulsify oil
initially by contracting the adsorbed film into droplets. Deformation of
these droplets by hydrodynamic forces into a cylindrical shape will then
cause droplet break-up as aresult of the Gibbs-Maragoni effect due to a
(temporary) lowering of the surface tension. In this way, the bound oil
film is brok~n into small emulsion droplets, which are then removed with
the cleaning solution. The mechanism only applies to liquid soil; hence
the elevated temperature required to melt all crystalline fat t y material.

In the removal of particulate dirt, the presence of fat may assist in
its removal by this rolling-up mechanism, resulting in entrainment of the
solid particles. In the absence of liquid soil, there are no specific
reasons to enhance removal by raising the temperature. However, a change
in viscosity or an increase in adsorption of surface-active molecules,
thereby altering, amongst others, the double-layer repulsion forces, may
@ProcessEng
be effective. Model removal studies using carbon black particles adhering

to a gold surface - to prevent plasticizing of a polymer surface with
temperature - ind~ed showed the absence of any temperature effect for
systems containing DOBS or SDS. On the other hand, a pronounced
temperature effect was found for a solution containing STP (Fig. 15) with
a maximum in removal at 50·C.
120
100 Removal (0'0)
80
60
40
20
Fig. 15 Percentage of removal as a function of temperature T in STP (o),

SDS (~) and DDBS (O), gold substrate (Ti = 400 g cm- l sec- 2 )
There is no straightforward explanation for this phenomenon, although

adsorption and zeta potential studies indicated that in the low-
temperature region, an increase in adsorption takes place if the
temperature is raised. Desorption at temperatures above 50°C could explain
the reduction in removal at higher temperatures. This temperature effect
points to an optimum temperature for any 'cleaning' composition, not
necessarily the highest temperature attainable.
5. SUMMARY
l. Basic chemical factors promoting the removal of particulate

contaminants:
The dominating factor in promoting the removal of particulate

material is a high pH in order to maximize the electrostatic double-
layer repulsion. This effect is the higher, the lower the ionic
strength.
- If non-aqueous fluids can be used, a specific choice of the liquid

in regard to surface tension may reduce, the van der Waals attraction
to such an extent that spontaneous removal becomes possibIe either by
Brownian motion or directly if the attraction is revers ed into van
der Waals repulsion.
- When hard water is used, addition of a calcium sequestrant will

substantially reduce the adhesion by promoting electrostatic double-
layer repulsion
- Both the surfactant chain-length and an increase in adsorption will

promote the removal of particulate dirt by surfactants. The ED chain-
length of a nonionic has, however, no influence on removal; the ED
groups are only involved in adsorption. Promotion of nonionic
@ProcessEng
adsorption by these groups and addition of calcium ions, indeed

results in an enhanced removal.
Temperature predominantly affects the removal of liquid so il via a

rolling-up mechanism. For particulate soil, removal is only promoted
if the adsorption increases with increasing temperature. STP was
found to show maximum removal at 50°C.
121
- There are indications that the adsorption properties of the surface

to which soil particles adhere, determine its removal. For example,
the removal of carbon black particles from cellophane is strongly
promoted by STP whereas the same particles adhering to polyethylene
are not affected by STP, despite its strong influence on the zeta
potential of the carbon black.
2. Basic hydrodynamic factors promoting removal of particulate

contaminants:
- The wall shear stress exerted by fluid flow on particles adhering to

a surface, is the determing parameter for their removal. Turbulent
flow conditions promote removal as aresult of their influence on the
wall shear stress.
- The mechanism by which particles are removed, from a surface by

liquid flow is, to our knowledge, not yet known. Only in the case of
an ideal system -a perfect sphere adhering to a flat surface- will
removal be initiated by simply rolling of the particle along the
surface. For real systems, the extended contact area will determine
the removal mechanism. Detachment by a lif ting mechanism is unlikely
so that a mechanism by which the particles are removed via a pivoting
motion seems to be the most realistic.
The flow between rotating cylinders is ideally suitable to study the

factors determining particle adhesion and removal and to aim insight
into the corresponding mechanisms.
3. Data required to predict optimal removal conditions:
Surface characterization measurements:
• contact angle data
• zeta potential data
• adsorption properties (surfactants, ions)
• surface roughness
Characterization of deposits:
• composition: particulate material, proteins, ions (calcium,

phosphate, iron) , oil, etc.
• protein type, isoelectric point, degree of unfolding, hydrophobicity
• particulate material: zeta potential, morphology size.
LIST OF SYMBOLS
@ProcessEng
I
A, All, A12, A123 - Hamaker coefficient (erg)
FA - van der Waals force of attraction
Fel - electrostatic double-layer force of repulsion
FC - Coulombic force of attraction
FLF - Contribution of a liquid film to the force of
adhesion
122
FH - hydrodynamic force
H - separation distance
PA - van der Waals force of attraction per unit area
Pel - electrostatic double-layer pressure of repulsion
Q - charge of particle
R - radius particle
Ri - radius inner cylinder
Ro - radius outer cylinder
Re 1,2 - Reynolds number
T - absolute temperature
X - distance from the centre of a disc
t,U - differences in work function
e - electronic charge
k - Boltzmann constant
l - distance of charge centres
nio - concentration of ion i (in bulk)
zi - charge of ion i
r - surfaee tension of a liquid

6 - double-layer thickness
6 - thickness of the laminar layer
- dieleetric constant
EO - permittivity of vacuum
K, - reciprocal of the double-layer thickness
V - kinematic viscosity
P - fluid density
P - radius of contact area
a - surfaee charge density
r - wall shear stress
w - angular ve10city
..po i surfaee potential of material i
7. REFERENCES
l. Visser J; Adhesion of colloidal Particles in E. Matijevic (Ed) Surfaee

and Colloid Science, VoL 8, p 3, Wiley Interscience, New York, 1976.
2. Norrish K; The swelling of Montmori11onite, Disc. Faraday Soc., 18
120, 1954.
3. Visser J.; The Adhesion of colloidal Particles to a p1anar Surfaee
in aqueous Solutions, Thesis, CNAA, London, 1973.
4. Hubbe M.A.; Detachment of colloida1 Hydrous oxide Spheres from flat
Solids exposed to Flow .2. Mechanism of Release, Colloids and Surfaces

16, 249, 1985.
5. Cleaver J.W., Yates B.; Mechanism of Detachment of co11oidal Particles
from a flat Substrate in a turbulent Flow, J. Co11oid Interface Sci.,
44 464, 1973.
6. Po1ke R.; Adhesion at elevated Temperatures, Proc. Conf. Phys.
Adhesion (R. Polke, P. Hohn, Ed) Kar1sruhe 1969, p 89.
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7. Leenaars A.F.M.; A new Approach to the Removal of co1loida1 Particles

from solid (silicon) Substrates, to be pusblished in Particles on
Surfaces, Detection, Adhesion and Removal (K.L. Mittal, Ed).
8. van Oss C.J., Neumann A.W., Omenyi S.N.; Repulsive van der Waals
Interactions; their Ro1e in various Separation Methods, Absolom D.R.,
Sep. and Purif. Methods, 2, 245, 1978.
123
9. Shimizu M., Ametani A., Kaminoguwa S., Yamauchi K.; The Topography of
as1-Casein adsorbed to an oil/water Interface: an analytica1 Approach
using Proteolysis, B.B.A, 869, 1986, 259.
10. de Feijter J.A., Benjamins J.; Adsorption Displacement of Proteins by
Surfactants in oil-in-water Emulsions, Col1oids and Surfaces, (in
press).
u
Part of this work was commissioned by the Development & Application Centre
of Lever Industrial, Maarssen, Holland.
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ASPECTS OF CELL ADRESION
R.S.HARBRON and C.A.KENT
DEPARTMENTS OF PLANT BIOLOGY and CREMICAL ENGINEERING

TRE UNIVERSITY OF BIRMINGHAM, PO BOX 363, BIRMINGHAM BIS 2TT, ENGLAND
l. INTRODUCTION
Almost any surface, whether living or inert, when brought into contact
with a fluid will become fouled. Renee, the effects of surfaee fouling are
extremely widespread, with fouling occurring, for example, on heat transfer
surfaces, the hulls of ships and marine structures, medicai prostheses,
plant surfaces, animal tissues, filtration, membranes etc. The type, or
combination of types, of fouling that occur on a particular surfaee varies.
For example, in the case of heat transfer surfaces, the type of fouling ean
be divided into six main categories (l): viz: particulate or sedimentation
fouling, precipitation fouling or scaling, corrosion fouling, reaction
fouling, freezing or solidification fouling and biological fouling
(biofouling). We shall concentrate on the phenomenon of biofouling.
In essence, biofouling is the fouling of surfaces by the deposition or
growth of organisms or materials of biological origin. These may ine lude
micro-organisms and their produets, or higher organisms, such as water
weeds, sea weed and barnacles. The former situation is generaily referred
to as microbial fouling and the latter as macrobial fouling.
This paper describes the physico-chemical factors affecting microbial
adhesion (in particular for bacterial adhesion), microbial aspects of
adhesion and selected studies of adhesion as an early event in microbial
fouling) .
2. PRYSICO-CREMICAL ASPECTS OF MICROBIAL ADRESION

Before considering the physico-chemical aspects of microbial adhesion
to surfaces, it is convenient to mention the means by which micro-organisms
are transported from the bulk fluid to the region of the surface. The
mechanisms of transportation of bacteria from bulk liquid to the vicinity
of the surfaee have been sumrnarised by Marshall (2).
For particles of size 0.01 to 0.1 /lm, transportation to the surfaee ean
be adequately described in terms of diffusion. Rowever, for particles of
bacterial size, which range in length from about 0.2 /lm, to several
micrometers, the mechanisms of transportation include sedimentation,
chemotaxis, Brownian motion, cell surfaee hydrophobicity and fluid dynamic
forces. If the system is undergoing turbulent flow, then particle
transport is likely to occur by fluid dynamic forces. It is in quiescent
or low shear systems that the other transport processes assurne greater
significance. A detailed discussion of rhe accurnulation of microbial films
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is also given by Kent in this volume

Once in the vicinity ot the surtace, the adhesion of micro-organisms
ean be explained in terms of colloid chemistry. It should be borne in
mind, however, that bacteria are living colloids (3,4) and not inert
colloidal particles and as such are capable of metabolism, growth, and
possibly independent motion. In considering the adhesion of micro-
125
L. F. Melo et al. {eds.}, Fouling Science and Technology, 125-140.

126
organisms to surfaces, therefore, account must be taken of the

physiological aspects of micro-organisms existing both in the fluid and at
the surface.
The adhesion of micro-organisms to surfaces ean conveniently be
considered in terms of reversible adhesion and irreversible adhesion (2).
The former is the instantaneous attraction by long-range forces holding
micro-organisms near a surface, whereby the micro-organisms still exhibit
Brownian motion and ean eas ily be removed from the surfaee under conditions
of shear (5-10) and the latter is a time dependent firm adhesion whereby
the micro-organisms no longer exhibit Brownian motion and cannot be removed
by washing (6).
2.1 Long-range forces
There are basically three types of long-range interactions between
surfaces: van der Waals, electrostatic and steric forces. The case in
which only van der Waals and electrostatic forces are operative is
described by the classical DLVO theory. However, in the case where steric
interactions are involved, the situation becomes much more complex
and controversial (11-14).
2.1.1 DLVO theory. Though there are many potential problems in the
application of DLVO theory to biological systems [see, for example, Lips
and Jessup (15), Pethica (16), Tadros (17)] the DLVO theory helps to
explain the observed behaviour of micro-organisms, such as bacteria, when
they arrive in the vicinity of a macrosurface. The DLVO theory, developed
independently by Derjaguin and Landau (18) and Verwey and Overbeek (19),
relates the stability of colloidal dispersions to the total potential
energy of interaction between two partieles. It is assumed that the total
interaction energy, VT' is given by the sum of two terms: a term, VA , due
to the dispersion forces (i.e. London-van der Waals forces) and a term, VE'
due to the overlap of the electrical double layers associated with tlie
charged surfaces, i.e.
(l)
2.1.2 Dispersion forces. When two molecu1es approach one another they
experience attractive dispersion forces, the energy of which (for non-polar
molecules) at moderate separation is inversely proportional to the sixth
power of their separation. However, when two particles approach one
another the attractive energy is given by the sum of all possibie
interactions between pairs of mo1ecu1es on the different particles (20).
Consequent1y, this constitutes a long-range interaction, the energy of
which, for aspherical particle approaching a macroscopie surface, is
approximately given by: (2)
VA - Aul2r
"6
~ )
y~y + 2r P )'
p
(2)
where ~is the net Hamaker constant for the system, r is the radius of the
particle and y is the distance of the centre of the ~article from the flat
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surface.
when y expression (2) simplifies to
V - (3)
A
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In general,. for aqueous systems the net Hamaker constant is positive

and hence the interaction energy is attractive. However, circumstances ean
arise under which the interaction energy is repulsive. An excellent
account of van der Waals forces is given by Israelachvili (22).
2.1.3 Electrostatic forces. Most solids when immersed in an aqueous
environment acquire a surfaee charge. This generally occurs either by ion
adsorption or by the ionisation of surfaee groups. Under normal conditions
most surfaces assume a negative charge. However, this will be dependent on
the composition of the aqueous phase. For example, most bacterial surfaces
comprise acidic groups (e.g. carboxyl or phosphate) and basic groups (e.g.
amine) and at conditions of low pH the bacteria could carry a net positive
charge.
A charged solid surfaee in contact with an aqueous medium will attract
oppositely charged ions (the counter-ions) from the medium and at the same
time repel like charged ions (the co-ions) away from the surface. This,
together with the opposing effects of thermal motion distributes the ions
in a Poisson-Boltzmann distribution throughout the aqueous phase and leads
to an imbalance of positive and negative ions in the region of the charged
surface. It is this region, in which there is an unequal balance of
positive and negative ions, that is generally referred to as the diffuse
electrical double layer. A schematic representation of the electrical
double layer associated with a planar surfaee and aspherical particle is
shown in Fig.l.
o 8 0 8
.0
•
<:) :
øP
_ +
-00 ..
•
FIGURE l. Distribution of ions around a charged particle and a charged

planar surfaee - the electrical double layer. --- represents an estimate of
the effective double layer thickness (= l/K).
The potential energy of the electrical double layer interaction of a

particle of radius r with an infinite planar substrate separated by a
distance y has been eva~uated by Hogg, Healy and Fuernstenau (23) and Wiese
and Healy (24). The expressions are only valid for small surfaee
potentials (l~l < 25 mV):
V/
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(y)
(4a)
128
o
VE (y) =
(4b)
where VE~ and vEO are the electrostatic interactions at constant surface
potential and constant surface charge, respectively. ~l and ~2 are,
respectively, the surface potentials of the planar surface and sphere at
infinite separation. e is the dielectric constant of the medium and e is
the permittivity of free space. K is the reciprocal Debye-Huckel scre~ning
parameter and is given by
222
K2NAz ce
eeoKBT (5)
where NA .is Avogadro's number, z is the counter-ion valence, c is the

concentrat10n of electrolyte, e is the electron charge, KB is Boltzmann's
constant and T is the Absolute temperature. In the case of bacterial
adhesion, the constant potential model is probably the most realistic (25)
although in practice the interaction curves differ significantly only at
smal l values of y.
The total energy of interaction for a charged particle approaching an
infinite planar substrate of the same sign of charge (which is usually the
case) is shown schematically in Fig.2. Notably, at low electrolyte
concentrations there is a
v \
\
,, v v
,, \
,
\
'" '" \
,
\
\
\
,,
\
\
\
y y " y
I
I
I
I
I
a , I
c
I
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FIGURE 2. Interaction free energy (V) - distance (y) profiles for a

charged particle approaching a macrosurfaee of the same sign at (a) low,
(b) intermediate and (c) high electrolyte concentration.
large free energy barrier whereas, at high concentrations the barrier has
been removed. In the intermediate concentration range, the energy barrier
is significantly reduced, though the exact form of the interaction profile
129
critically depends upon the properties of the attractive and repulsive

forces involved. The most important parameters governing these forces are
r , ~l'~? and K. In general, however, at intermediate electrolyte
cEncenEraEions, according to DLVO theory, particles will experience
attractive forces at small and large distances of separation from the
surface and repulsive forces at intermediate distances.
2.1.4. Steric forces. Biological systems often contain macromolecules
of one kind and another (e.g~ glycoproteins, proteoglycans or their
products) and adsorption of these macromolecules almost certainly occurs
before any appreciable adhesion of micro-organisms takes place. These
macromolecules, which may be neutral polymers or polyelectrolytes can have
a significant effect on particle interactions (11-14, 26-28) and hence, can
play a major role in the attachment of micro-organisms to surfaces. The
resulting adsorbed layer of macromolecules is often referred to as the
conditioning film; but although the effect of a conditioning film on
bacterial adhesion has been extensively studied in the case of the pellicle
formation on tooth surfaces (2), littie is known about the effects on
adhesion of micro-organisms and their subsequent colonisation of such
surfaces. The interactions between polymer modified surfaces are
considered below from a colloid-chemical point of view.
Let us consider a simplified case of a polymer-coated sphere
approaching a polymer-coated planar surface. In the first instance,
polymers adsorbed at the interface will modify the attraetive and the
electrostatie repulsive forces. For example, the net Hamaker constant for
the system will need to include contributions from the adsorbed layers.
Also, the potentials given in equations (4a) and (4b) now correspond to the
peripheries of the adsorbed layers and the distance of separation y, will
need to be replaced by y-26, where 6 is the thiekness of the adsorbed
layer. In addition to these modifications, as two polymer coated surfaces
approach one another, provided that the polymers are strongly attached to
the surfaces, that they are at full coverage and that they are in a good
solvent environment [i.e. the Flory-Huggins parameter is less than 0.5
(29], a strong repulsion will be experienced when y is equal to 26. A
typical ener gy-distance interaction profile for an uncharged system is
shown sehematically in Fig.3. In this diagram, V represents the steric
potential energy of interaction. The form of theSinteraction is complex
(11-14, 26-28) but essentiaily comprises contributions from three additive
terms:
a) an elas tic term, which arises from the loss of configurational
entropy of the polymer chains.
b) a mixing term, whieh arises from the loeal segment/solvent
interaction and the change in polymer segment concentration in the
interaction region between the particles.

c) a bridging or adsorption term which is of importance at low
coverages when, polymer segments are free to become adsorbed on the
opposing surface. A much more complex situation occurs when the surfaces
are charged or, as is commonly the case, when the sur face layers are
polyelectrolyte in nature. Under these circumstances the relative
importance of the steric and the electrostatic factors are hard to predict
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(30-32).
In terms of colloid stability, polyelectrolyte can be used to produce
very robust dispersions. For example, whereas charge-stabilised
dispersions typi~~lly aggregate at monovalent electrolyte concentrations
around 0.1 mol dm ,polyelectrolyte-stabilised dispersions may require the
addition of several moles of electrolyte before aggregat ion occurs. It
should be mentioned, however, that under certain circumstances
130
polyelectrolyte-stabilised dispersions may be destabilised by the addition

of low levels of electrolyte owing to a complex phase-separation phenomenon
(33) .
r-~-======y
, , ,'-
,,
I
I
I
: VA
I
.. .
28
FIGURE 3. Interaction free energy (V) - distance (y) profile for a

sterically stabilised system.
2.2. Short-range forces.

In essence, the long-range forces determine whether or not the micro-
organisms are able to get close enough to the surface to interact.
However, once close to the macrosurface the micro-organisms can interact
via short-range forces. For example, bacteria in the vicinity of a
macrosurface are believed to bind strongly to the surface through fine
polymeric components external to the cell envelope (2,5,6). These
polymeric components typically comprise extracellular polymers, pili,
fimbriae and flagelia. The types of component present clearly depend upon
the organism in question and its physiological state. The microbial
aspects of adhesion are discussed in alater section.
The forces operating at small distances of separation (typically less
than 0.4 nm) can be loosely classified into three types (17,22). These are
outlined below.
a) Chemical bonds. This category includes, for example,
electrostatic, covalent and hydrogen bonds.
b) Dipole interactions. This category includes dipole-dipole
(Keesom), dipole-induced dipole (Debye) and ion-dipole interactions.
c) Solvation forces. This category includes hydration forces and
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hydrophobic bonding. The former occur in aqueous systems whenever water

molecules bind to surfaces containing hydrophilic groups [ see, for
example, Israelachvili (22)]. The strength of the interaction depends on
the energy needed to disrupt the ordered water structure and ultimately
dehydrate the two surfaces as they approach one another (34). Hydration
forces can lead to oscillations in the force-distance profile of two
approaching surfaces (35). The latter (hydrophobic) interaction is an
131
attractive solvation interaction that occurs between hydrophobic surfaces

and groups in water. The attraction arises because the orientation of
water molecules close to hydrophobic surfaces is entropically unfavourable
- the ejection of entropically unfavoured water into the bulk as the
surfaces approach one another leads to a reduction in the total free
energy.
2.3 Surface-free energy approach to microbial adhesion
The surface-free energy theory is often used as an alternative to the
colloid-chemical approach to long-range interactions. Briefly, in this
theory the contact processes of micro-organisms and surfaces are considered
in terms of surface-free energies, approximations for the free energy being
obtained from the determination of critical surfaee tension (36). In
general minimal bacterial adhesion in aqueous media has been claimed to
occu:lon substrata with critical surfaee tensions in the range 20-30
mN m (37). For a fuller description of the surfaee energy approach, the
reader is referred to Marshall (2).
Although often treated as separate entities, the connections between
the surfaee energy and colloid-chemical approaches are not always fully
appreciated. For a detailed discussion, from a thermodynamic basis, of the
relationships between the two approaches, see Pethica (16).
3. MICROBIOLOGICAL ASPECTS
Treating microorganisms as "living colloids" and using classical
theories of colloid chemistry to explain their adhesion to surfaces is
likely to run into difficulties, unless some refinement is made of such a
treatment: for example, some microorganisms are motile: that is, they are
able themselves to move against a fluid flow, a concentration gradient, or
along a solid-liquid interface. Furthermore, and perhaps more important
than this, are surfaee charge effects. Microorganisms, including most
bacteria, tend to possess nett negative ionogenic surfaces (38). Most
surfaces found in aquatic systems also carry a nett negative charge.
Therefore, on the basis of colloid theory, the interaction of, say, a
bacterial cell with a surfaee is likely to be one of nett repulsion: the
cell will be unable to make direct contact with the surfaee because of the
high repulsion energy barrier that comes into play when the cell comes
close to the surface. The shorter-range forces, such as hydrogen and ionic
bonds (of the order of 0-2 to 0.3 nm long) , necessary for firm attachment,
will not be able to overcorne the potential energy barrier at around l nm
from the surface. Thus, the cell would be expected to get no closer than
the "secondary minimum" distance, of around 5 to 10 nm from the surface.
At this position, the DLVO theory does predict that reversible adhesion ean
take place (39). However, this doesnot explain why many bacteria will
firmly attach to surfaces within hours of the immersion of these surfaces

into natural waters (38). For this, a further explanation is necessary.
This is, at leas t in part, forthcoming, and, backed up by observations of
the existence with rnany microorganisms of:
(a) Specialised Attachment Structures.
(b) Extracellular Polymers.
3.1. Specialised Attachment Structures
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According to the DLVO theory, for a particle (or spherical surface)

interacting with a flat (or plane) surface, as the radius of the particle
decreases the repulsive energy barrier decreases (39,40). Thus, if a cell
could reduce its effective radius of interaction with the surfaee
sufficient ly , this could allow it to overcome the potential energy barrier
and thereby attach to the surfaee at the "primary energy minimum" (41).
132
Here, attachment would be much stronger and more permanent than at the
"secondary minimum".
Now, many cells, both microbial and higher, produce extracellular
filamentous appendages. These may, therefore, play a role in the
attachment process, seeing as their radius of interaction with the surface
is far lower than that of the cell itself. A number of such structures
exists (see Fig.4).
~
PILI, FIM BRIAE
POLAR FLAc:.ELLUM ~_ ESC.HEllrCHl:A COL!.
e.~. P5EUDOMONAS spr· PSEuDOMONA5 Spf'.
SPHAI:R.OTI LIAS spp·
5TALK (s) AND

HOLD FAST (h)
PROSTHEC.AE
e_~_ CAU.LOBAC.TER. s,.p-
e'5- PftOSTH Eeo JI1ICRO BI U. M
srr-
FIGURE 4. Specialised Attachment Structures.
3.1.1. FlagelIa, when present, are responsibIe for the motility of

bacteria. These are very fine threads of the protein flagellin with a
helicaI structure extending out from the cytoplasm through the cell wall.
FlagelIa may have a diameter between 0.01 to 0.02 ~m, and a length of up to
10 ~m. Many types of bacteria have flagelIa, including the common aquatic
organisms of the genus Pseudomonas and species of Sphaerotilus(42).
Whereas the energy imparted to the cell by flagelIate action is very
unlikely to be enough to propel an organism through the potential energy
barrier to the "primary minimum"(6) it is possible that the flagellum
itself may form an adhesive bond with the substratum surface (40). As yet
though, there is no conclusive evidence to show that this is so. Much more
likely to play a ro le in attachment are:

3.1.2. Pili or Fimbriae. These are found on many Gram-Negative
bacteria, including Escherichia coli and Pseudomonas species. They are
fine, filamentous appendages, also of protein, 4 to 35 nm wide and up to
several micrometers long. They are usually straight, and are not involved
in motility. Their only known general function is to make a cell adhesive:
Bacteria with pili can adhere strongly to other bacterial cells, mammalian
cells, soil particles, etc.(40,42), although they are not always involved
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in the attachment proces s even if they are present (39). Piliated cells
may contain several hundred pili per cell,or as few as l to 5 per cell (42).
3.1.3. Prosthecae or Stalks form a third group of attachment structures.
These occur in several types of organism, including such gram-Negative
bacteria as species of Caulobacter and Hyphomicrobium. They may occur at
one or more sites on the surface of the cell, and are filiform or blunt
133
extensions of the cell wall and membrane, commonly 0.2 #m thick. At the
end of a prostheca or stalk is usually found an adhesive disc, or "hold-
fast". This enables the organism to stick firmly to other organisms or to
surfaces (40,42,43). The stalk and "hold-fast" structure is one quite
often used by diatoms to attach to a surface (39).
Thus, there exists a variety of protruding structures by which numbers
of species of microorganisms are able to come into closer contact with a
surface and attach firmly to it. However, many, perhaps most, aquatic
microorganisms possess no obvious attachment structure, yet are able to
adhere firmly to surfaces. This is thought to be due to the second major
means of attachment employed by microorganisms:
3.2.Extracellular Polymers
Extracellular polymeric materials are secreted by many bacteria, as
well as algae and diatoms. Widely different molecules exist, ranging from
simple homopolysaccharides assembled from identical monomeric units to more
complex heteropolysaccharides and muco-lipoproteinaceous polymers (40).
Often, the type of bacterial polysaccharide is unique to the species of
bacterium (44). Many different monomers have been identified as going to
make up microbial extracellular polymers, including: neutral sugars (e.g.
D-glucose, D-galactose, D-mannose, L-fucose, L-rhamnose), amina sugars
(e.g. N-acetyl-D-glucosamine and N-acetyl-D-galactosamine), and uronic
acids (e.g.D-glucuronic and D-galacturonic acids). Pentose sugars such as
D-ribose and D-xylose are found frequently in polymers from yeasts and
algae, although not very often from bacteria. In addition, numerous
extracellular polysaccharides contain combined phosphate, acetate, formate,
or pyruvate, thus providing acidic groups for further interactions.
Although polysaccharides appear to be major components in the extracellular
polymer ic structures produced, at least by bacteria, other polymeric
material (glycoproteins, proteins, nucleic acids) has also been found to be
present, and may well contribute significantly to the overall adhesive
process that these polymers are known to be involv~d in (4,45).
The production of extracellular polymers (also referred to as slime)
can lead to a variety of structures: clearly-defined gel-like capsules are
formed around the cells of certain bacteria. Gliding bacteria, such as
Cytophaga, deposit on the surface a slime that enables them to attach to
that surface, yet which induces a low enough horizontal drag to allow the
bacterium to slide over it to fresh sur face , leaving a trail of slime
behind (38). A similar deposit is produced by types of diatom, through the
raphe canal: a single or double slit in the silica cell wall which allows
direct communication between the cytoplasmic membrane and the environment
of the surface (39). Polymeric material secreted into the raphe canal is
thus likely to aid both attachment and movement of the dia tom over the
surface. Yet other organisms produce a les s well-defined polymeric

structure, which takes the form of diffuse fibrillar strands of soluble
slime that extend into the surrounding medium.
3.2.1. Interactions. A polymer attached to a cell can be assumed to
have part of its length extending into the bulk of the solution around it.
When a surface is near, the interaction of these extending lengths with
vacant bonding sites on that surface will subsequently lead to the
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attachment of the organism to the surface. Such a proces s is known as

polymer bridging. Although this phenomenon is well-documented, the
mechanism of the interaction between the bridging polymer and the sur face
remains vague. Possible mechanisms for polymer bridging include hydrogen
bonding, ion exchange by the polymer with adsorbed ions of the same charge
(acting as a polyelectrolyte) , and interactions with oppositely charged
ions on or near the surface (39,40,41).
134
The extent to which microbial attachment to surfaces in aquatic systems

involves highly specific interactions between complementary molecular
configurations on the cell and on the solid surface is unknown. Specific
binding of extracellular polymers of microorganisms to the surfaces of both
plant and animal cells is quite widespread, and is a feature of
pathogenicity. Simple proteins, called "lectins" have also been implicated
in mediating specific adbesion of bacterial cell polymer to organic
molecules on the substratum surface (46). However, there is some doubt as
to whether specific adhesion proces ses are likely to be important in
biofouling (38). The bacteria that are mainly responsibie for primary, or
initial, biofilm formation are capable of adhering to surfaces with a wide
range of properties (38) and so attachment at this stage is likely to be
non-specific. Whether specific adhesion increases in importance as the
biofilm develops is a matter for investigation, although the diverse
structure of mature biofilms would still suggest the dominance of non-
specific attachment. Perhaps, however, some distinction needs to be drawn
between adhesive (cell-surface) and cohesive (cell-cell) adhesion
processes.
3.2.2. Effects of Ions We have aiready discussed how the DLVO theory
predicts how electrolyte concentration and counter-ion valence have an
important influence on the energy of interaction between a charge d particle
and a surface. Thus, it is not surprising that inorganic ions have been
observed to affect microbial attachment to surfaces. Cat ions , particularly
divalent ones, have been especiaily implicated, which is not unexpected
since most aquatic surfaces and microorganisms have a nett negative charge,
making cations prime candidates as counter-ions. Thus, the reversible
adhesion stage of attachment is influenced by cation concentration, with
glas s (6,47).
2
high levels promoting an increase in the attazhment O Achromobacter R8 to
Claims have been made that Ca + or Mg I are necessary for
the efficient adhesion of aquatic bacteria (6,48), with the suggestion that
these ions are important in maintaining the structure 0f the extracellular
polymeric matrix. Various mechanisms of stabilisation have been
postulated, including the involvement of the divalent cation in bridge
formation between the negatively-charged surfaces of the substratum and the
cell(48), and the precipitation by the cation of polymer in the space
between the cell and the substratum (49). The effects of other cations are
perhaps more problematical and may well depe~i on the3~icrobial species as
well as the environment. For example, Al and La have reduced the
attachment of a marine pseudomonad to polystyrene (50), possibly by
affecting the adhesive properties of the acidic attachment polysaccharide.
A greater than 50% reduction in the attachment of Pseu20mona~flu~rescins
t02~tai~iess s2~el w/n reg~~tere~+ in t~e pr}1~ence 0~3tb ... , Fe +, Cu , Cd ... ,
Hg ,Zn , Mn ,Al ,Co ,Zr ,Ag, Sn ,or T1 (51). However, other

cations can increase attachment, by reversing the charge on bacteria in an
acid medium (52). Care must be taken in interpreting these results, since
the effects of the ions on cell physiology and viability may in cases be
more important than their effects on the extracellular polymer.
3.2.3 Extracellular polymer formation is, indeed, highly dependent not
only on the physico-chemical conditions surrounding an organism but also on
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its physiological state and the nutrient status of its medium. The most
common phases of growth for significant polymer production by bacterial
cells is during the late exponential and stationary phases . . A high carbon-
to-nitrogen ratio in the medium, and, indeed, the limitation of nitrogen,
phosphorus, or sulphur source in the presence of exces s carbohydrates, will
usually lead to increased synthesis of polymer. Sometimes vast amounts of
extracellular polymer may be produced, compared with the volume of the
135
cells synthesising it (40). Therefore, the nature and levels of potential

nutrients within a system containing water may well affect the type and
concentration of extracellular polymer synthesised, which will in turn
exert a major effect on the adhesive properties of the cells present, and
thereby the rate and extent of fouling likely to occur.
Now, an important aspect of microbial adhesion proces ses concerns the
question as to whether attachment via polymer bridging and other proces ses
is spontaneous when a cell comes close to a surface - essentiaily a
function of the compatibility of the polymer or structure and the
substratum sur face - or whether it is time-dependent, requiring
physiological activity - that is, synthesis, at a later stage, of
extracellular polymer.
We have aiready outlined one view, that microbial adhesion is composed
of a two-stage process: an initial, reversible, stage, in.which long-range
forces hold the cells near the surface, but shear forces can easily remove
the cells. This occurs almost immediately the cells and surface "corne into
contact". Then, later, there is a second, "irreversible" stage of much
firmer attachment. This is time-dependent and is characterised by the
synthesis of extracellular polymer that binds the cells to the sur face
(2,47). Some observations of initial stages of biofilm formation suggest
that the production rate of polymer can increase as biofouling progresses
(53). However, not all organisms appear to behave this way. Some bacteria
can bind rapidly and permanently to surfaces via polymer aiready present on
their surfaces (i.e. the cells). This is followed by synthesis of
additional, very fibrous polymer to further "anchor" the cells ·(48).
Furthermore, certain marine algae and diotoms will only attach to surfaces
"irreversibly", with polymer being produced extracellularly, within 30
minutes of attachment (54). The picture is therefore complex, showing a
high degree of diversity of means and rates of attachment of microbial
cells to surfaces: and, for that matter, of cells to cells.
4. ADHESION IN FLOWING SYSTEMS.

Most of the observations outlined above have been made on systems
exposed to littie or no fluid motion, and therefore shear stress. However,
in most systems there is significant fluid flow, especiaily in industrial
~rocesses, where, for example, cooling water velocities in excess of 1 m s
are common. Although an increasing amount of information is being
gathered on the development of biofilms within flowing systems, relatively
littie appears to be available on the early events within these systems,
andon both adhesive and cohesive strengths. Knowing about these are as is
relevant if surfaces are to be designed, or shear-related operation or
cleaning procedures are to be considered, so as to minimise biofouling.
It has been repor~2d (55) that biofilms can withstand shear forces
exceeding 1 to 1.5 N m , corresponding to the low side of those commonly
existing in water-carrying heat exchangers (56). Moreover, biofilms
developed under higher-velocity/shear conditions may adhere to surfaces
more firmly than those forrned at lower velocities (55).
With regard to early stages of biofouling - that is, before the
formation of a monolayer of cells upon an exposed surface - it would appear
@ProcessEng
that both shear forces/flow velocity and nutrient status of the surrounding
medium exert important influences on the nett rates of attachment, and that
adhesive strength may often be time.-dependent.
For example, defined-flow studies have been made both in the laboratory
and "in the fie Id" using Radial-Flow Growth Chambers (RFGC). This device
was developed for the study of biological films by Fowler and McKay (57),
and modified for pre-film adhesion studies under turbulent-flow conditions
136
by Kent and co-workers (58). It consists of two narrowly-spaced parallel

discs, one with a central inlet pipe. Fluid may then flow radial ly
outwards between the discs, giving a radial decrease of linear fluid
velocity, hence surface shear stress, from the centre outwards, at constant
flow. Thus, cells deposited (or previously attache d) at different radial
positions will be subjected to different surface shear stresses.
For laminar flow (Re r < 2000), the surface shear stress is given
approximately (57) by:
1"
3Qn Il
S
(6)
2
11" r x
For turbulent flow (Re> 2000), the foliowing empirical correlation may
be used (59) away from thervicinity of the inlet pipe:
1" 0.0395p V 2 Re -0.25 (7)

S r
Both laboratory work, using Pseudomonas fluorescens and other single-
species systems, and "field-work", using coarse-filtered river water,
showed a similar pattern (52,56,58): in general, rates of cell deposit
formation fell rapidly with increasing surface shear stress up to
"criticai" value of shear stress beyond which rates remained low but
significant. Indeed, Pseudomonas fluorescens cells were observ~2 to attacr
in regions exposed to surface shear stress in excess of 100_~ m (51,58).
Typically, "criticai surface shear stresses" of 6 to 8 N m were recordec
for Pseudomonas fluorescens af ter 48h contact with a stainless steel test
plate, whereas the figure ~~r river water organisms af ter a simi1al
contact time was 2 to 3 Nm (56). However, af ter a week, both th~
amounts of deposit from the river water and the_zcritical surface sheal
stress" had increased - the latter to 6 to 7 N m . Thus, the deposit!
appeared to grow "stickier" with time, possibly reflecting the productiOl
of more and more extracellular polymer over this period. Furthermore, whe!
the river water was supp1emented with glucose, not only did the rate oj
deposit formation significantly increa~Z' but so did the va1ue of "criti:+
surface shear stress": from 2 to 3 N m ,with no glucose, to 6 to 7 N m
with only 0.14 mg glucose supplement/kg, and 48h contact (56).
These results, although preliminary, do suggest that adhesion can b,
very tenacious, and that fluid shear forces alone may not be completel:
effective in preventing microbial fouling of surfaces. Furthermore, il
would seem as though early control is desirable, for adhesive strength ma:
well increase with time. Also, where possible, contamination of water wit1
even trace amounts of potential nutrients should be avoided.
5. CONCLUSIONS.
The adhesion of microbial cells to surfaces is an essential stage il
biofouling. Many aspects of microbial adhesion may be described b·
@ProcessEng
reference to theories of colloid chemistry, especiaily the DLVO theory

involving both long - and short - range forces. However, suc1
consideration needs modification, not only to regard microorganisms a:
"living colloids" capable of metabolism, growth, and possibly independen
motion, but also to account for the specialised attachment structures an,
extracellular polymers produced by many species. The picture that emerge:
is a highly complex one that is further complicated by the dynamic, varied
137
and adaptable nature of microbial cells. Therefore, much more needs to be

known about microbial adhesion to surfaces before this range of phenomena
can be fully characterised, let alone systematically controlled.
ACKNOWLEDGEMENT
R.S.Harbron acknowledges with thanks the provision of a Research
Fellowship by the Science and Engineering Research Council.
SYMBOLS
AH Hamaker constant (J) -3

c Concentration of electrolyte (mol dm )
e Electron charge (C)
KB Boltzmann's constant (JK- l )
NA Avogadro's number (-)
(m 35 -1)
Qfl Fluid volumetric flow-rate
r Radial distance from plate centre (m)
r Radius of spherical particle (m)
RR Local Reynolds number, at r(=QflP/wr~)
T r Absolute temperature
(-)
(K)_l
v Mean linear velocity of fluid, at r.(-Qfl/2wrx) (ms )
van der Waals potential energy of interaction (J)
~ Electrostatic potential energy of interation
vE Steric potential energy of interaction
(J)
(J)
VS Total potential energy of interaction (J)
T
VEo Electrostatic potential energy of interation (J)
at constant surface charge
V 1/1 Electrostatic potential energy of interaction at (J)
E
constant surface potential
x· Distance between plates (m)
y Distance of centre of particle from flat surface (m)
z Counter-ion valence (-)
li Thickness of adsorbed polymer layer (m)
Dielectric constant (-)
Permittivity of free space (J- 1 C2m- l )
Reciprocal Debye-Huckel parameter (m-l~2
Fluid viscosity (Nsm _j
Fluid density (kg_, )
Shear stress at the surface, at r (Nm )
Surface potential of planar surface (V)
Surface potential of spherical surface (V)
@ProcessEng
138
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@ProcessEng
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29. F10ry PJ: Principles of Polymer Chemistry, Corne11 Press, Ithica,
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30. Hesse1ink FTh: On the theory of po1ye1ectro1yte adsorption: J.Co11oid
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31. Corner T: The co11oid stabi1ity of po1ye1ectro1yte stabi1ised
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(G.W.Poeh1ein, R.H.Ottewi11 and J.W.Goodwin eds.), NATO ASI Series,
Martinus Nijoff, The Hague, Vol. II, pp.600-618, 1983.
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interaction of co11oid particles: Modern Trends of Co11oid Science in
Chemistry and Bio1ogy, Int.Symp.Co11oid and Surface Sci., (H-F. Eicke
ed.), pp.55-73, 1985.
33. Inegami A and Imai N: Precipitation of po1ye1ectro1ytes by sa1ts:
J.Po1ym.Sci., 56, 133-152, 1962.
34. van 01phen H: An Introduciton to Clay Co11oid Chernistry,
2nd.ed.,chp.10, Wi1ey, New York, 1977.
35. Christenson HK and Horn RG: Direct measurement of force between solid
surfaces in a polar 1iquid: Chem.Phys.Lett., 98,45-48, 1983.

36. van Oss CJ, Gi11man CF and Neumann AW: Phagocytic engulfment and ce11
adhesiveness: Micro-organisms and Infectious Diseases, (H.D.Isenberg
ed.), Marcell Dekker, New York, Vo1.2, 1975.
37. Baier RE: Inf1uence of the initial surface conditions of materials on
bioadhesion: Proceedings, 3rd Int.Congr.on Marine Corrosion Fou1ing,
(R.F.Acker, B.F.Brown, J.R.DePa1ma and W.P.lverson eds.), Northwestern
University Press, Evans ton , Vol. III, pp.633-639, 1973.
@ProcessEng
38. Marshall KC: Bacteria1 Behaviour at Solid Surfaces - a Pre1ude to

Microbia1 Fou1ing: Fou1ing of Heat Transfer Equipment (EFC Somersca1es
and J.G.Knudsen eds.), Washington: Hemisphere, 1981.
39. Charack1is WG and Cooksey KE: Biofilms and Microbia1 Fou1ing. Advs.in
App1d.Microbio1, 29, 93-138, 1983.
140
40. Kent CA and Duddridge JE: Microbia1 Fou1ing of Heat Transfer Surfacel
in Coo1ing Water Systems. AERE Report R 10065. United Kingdom Atomi<
Energy Authority, 1981.
41. Rogers HJ: in Adhesion of Microorganisms to Surfaces (DC E11wood.
J.Me11ing, and P.Rutter eds.), London: Academic Press, 29-56, 1979.
42. Stanier RY, Adelberg EA, and Ingraham JL: General Microbio1ogy.
London: MacMillan Press, 4th edition reprinted, 1983.
43. Paer1 HW: Microbio1 Eco1., ~, 73-83, 1975.
44. Wi1kinson JF: Bact.Rev.,22, 46-73, 1958.
45. E11wood DC, Me11ing J and Rutter P (eds.): Adhesion of Microorganisml
to surfaces. London: Academic Press, 1979.
46. Costerton JW, Geesey GG and Cheng KJ: Scientific American, 238, 86-95
1978.
47. Marshall KC, Stout R and Mitchell R: Can.J.Microbio1.,17, 1413-1416
1971.
48. Fletcher M and F100dgate GD: J.Gen.Microbio1.,74(2), 325-334, 1973.
49. Rutter PR: in Ce11 Adhesion and Moti1ity (ASG Curtis and JD Pitt:
eds.), London: Cambridge Univers ity Press, 103-135, 1980.
50. Fletcher M: in Adhesion of Microorganisms to Surfaces (DC E11wood
J.Me11ing and P.Rutter eds.), London: Academic Press, 87-108, 1979.
51. Duddridge JE, Kent CA and Laws JF: Bacteria1 Adhesion to Metalli,
Surfaces. I.Corrosion Sci.Techno1/I.Chem.E. Conference on Preventio,
of Fou1ing in Industria1 Plant, Nottingham University, 1-3 April
1981.
52. Daniels SL: Dev.lnd.Microbio1., 13, 211-253, 1972.
53. Bryers JD and Charack1is WG: Kinetics of Initial Biofilm Formatio
within a Turbulent Flow System: Fou1ing of Heat Transfer Equipmen
(EFC Somersca1es and JG Knudsen eds.), Washington: Hemisphere, 1981.
54. Jones EBG: Personal Communication, Portsmouth Po1ytechnic, UK, 1979.
55. Zvyagintsev DG: Microbio1ogy (USSR), 28, 104-108, 1958.
56. How I, Duddridge JE, Kent CA and Pritchard AM: The Effects of Shea
Stress on Biofou1ing Deposit Formation and Removal. H.T.F.S. Researc
Symposium, Warwick University, 14-17 Sept., 1982.
AERE Report R-10583. United Kingdom Atomic Energy Authority, 1982.
57. Fow1er HW and McKay AJ: in Microbia1 Adhesion to surfaces (RC
Berke1ey, JM Lynch, J.Me11ing, PR Rutter and B.Vincent eds)., London
Academic Press, 1980.
58. Duddridge JE, Kent CA and Laws JF: Effect of Sur face Shear Stress o
the Attachment of Pseudomonas fluorescens to Stain1ess Stee1 unde
Defined Flow Conditions: Biotechno1.Bioeng.,24, 153-164, 1982.
59. Moller PS: Trans.ASME, J.Basic Eng., 155-162, March 1966.
@ProcessEng
@ProcessEng
Chapter 4
Particulate Fouling
PARTICULATE FOULING OF HEAT TRANSFER SURFACES: MECHANISMS AND MODELS
NORMAN EPSTEIN
Department of Chemieal Engineering
Vaneouver, B.C., Canada V6T IWS
l. INTRODUCTION
In the present eontext partieulate fouling is defined as the
aeeumulation of solid partieles suspended in a fluid onto a heat transfer
surfaee. Some of the meehanisms whieh oeeur are similar to those whieh
govern the fouling of membranes or filters. Unlike filtration surfaees,
however, heat transfer surfaees are more often parallel than perpendieular
to the flow. Furthermore, the presenee of temperature gradients near a
heat transfer surfaee ean perturb the isothermal fouling meehanisms as
well as introduee additional partiele transport meehanisms, thereby
drastieally modifying the rate and extent of fouling.
It will be assumed in what follows that, onee a possibie initiation,
delay or surfaee eonditioning per iod has passed, during whieh no fouling
is reeorded, at least thermally, the proeesses whieh govern the rate and
extent of fouling are transport of partieles to the heat transfer surfaee,
attaehment of partieles at the surfaee and re-entrainment of partieles
from the surfaee. The transport and attaehment together eonstitute the
gross deposition proeess, so that the net fouling flux is given by
(l)
The heat transfer maerosurfaee will be assumed to be parallel to the

mainstream flow, and primary but not exelusive attention will be given to
turbulent rat her than laminar flow. The initial foeus will be on
isothermal transport, on whieh far more work has been done than on fouling
in the presenee of temperature gradients.
2. ISOTHERMAL PARTICLE TRANSPORT

Exeluding for the moment gravitational settling, whieh applies mainly
to relatively large partieles on horizontal surfaees, it is eustomary to
write for transport of partieles from the mainstream to the deposition
surfaee [l],
(2)
where es = e w when the wall is elean. Assuming that all partieles whieh
ar rive at the surfaee adhere to it, e = O and the transport eoeffieient
k t beeomes identieal to the depositio~ eoeffieient (or "deposition
@ProcessEng
veloeity") kd • Most hydrodynamie theories of partiele deposition [2] are

formulated on this assumption of perfeet stiekability; they are therefore
really theories of partiele transport. Starting with submieron partieles,
143
L, F, Melo et al, (eds.), Fouling Science and Technology, 143-164.

144
the fo110wing three transport mechanisms progressive1y predominate in

turbulent flow as the partic1e size increases [3].
2.1. Diffusion
In the diffusion regime, suspended co110ida1 particles move with the
fluid and are carried to the wa11 by the Brownian motion of the fluid
mo1ecu1es - through the viscous (pseudo-laminar) sub1ayer in the case of a
turbulent flow. The submicron particles can then be treated 1ike large
mo1ecu1es, so that k t becomes equiva1ent to the conventiona1 mass transfer
coefficient, km' which can be obtained from the relevant empirical
correlations or theoretical equations for forced convection mass transfer
in the literature. To use these relationships requires knowledge of the
Brownian diffusivity, which for a dilute suspension of spheres is given by
the Stokes-Einstein [4] equation,
KBT
(3)
3'Jt~dp
so that for O.S-~m spheres in water, for example, Sc = ~/pDB ~ 10 6 •

Provided we are not dea1ing with excessive mass fluxes of the particles
towards the deposition surface, any relationship for the forced convection
heat transfer coefficient in laminar or turbulent flow can be converted to
a relationship for the forced convection mass transfer coefficient by
substituting Sh for Nu and Se for Pr (or St m, Pe m and GZ m for St H, PeH and
Gz H, respeetive1y).
If a momentum-mass transfer ana10gy for turbulent flow is used at the
high values of Sc (i.e., 10w molecular or mo1eeu1e-driven diffusivity)
characteristic of Brownian particles (as opposed to monomeric molecules),
it must be one whieh a1lows for the fact that in the viscous sublayer the
eddy diffusivity does not vanish, except at the wa1l, and is typical1y of
the same order of magni tude as the Brownian diffusivity. Using the
Reichardt analogy [5], which meets this criterion, Metzner and Friend [6]
derived for turbulent flow of binary solutions of high Schmidt number
that
f/2 (4)
v 1.20 + 11.8 /rTr(Sc-l)Sc- 1 / 3
For Sc in the order of 10 6 , Equation (4) simplifies to
0.0847 (5)
Sc 2 / 3
Using an entirely different approach, based on a computation of the

stagnation backflow toward the wa11 which compensates for the turbulent
bursts away from the wa11, Cleaver and Yates [7] independent1y derived for
the diffusion regime that
@ProcessEng
0.084 (6)
v* v/rTr Sc 2 / 3
which is in remarkable agreement with Equation (5).
145
It should be noted that if one adopts the classical Blasius [S]

equation for smooth pipe flow,
f = 0.0791 (7 )
ReO. 25
then substitution of Equation (7) in to Equation (6) and re-arrangement

results in
Sh (S)
which is only marginally different than the empirical equation for solute
mass transfer of Berger and Hau [9],
Sh = 0.0165 ReO.S6Scl/3 (9)
advocated for particle mass transfer recent ly by Hussain et al. [10] as

"established" and "comprehensive". Equation (9) underpredicts most of the
highly scattered initial deposition data of Hussain et al. [10] for
magnetite from aqueous suspension onto an aluminum tube, whtle the
predictions of Equation (S) are actually better. Combination of Equations
(3) and (6) indicates that for diffusion control led deposition,
(10)
2.2. Inertia
In the inertia regime, the particles are sufficiently large that
turbulent eddies give some of them a transverse 'free flight' velocity
which is not completely dissipated in the viscous sublayer. These
particles then possess sufficient momentum to reach the wall.
A large number of investigators, starting with Friediander and
Johnstone [11], have taken on the task of predicting the results of this
free flight excursion or inertial coasting in a turbulent fieid, and their
theo ries have been recently summarized in a comprehensive review paper by
Papavergos and Hedley [2]. Table 1 from that paper is reproduced at the
back of the present document (with reference numbers and symbols from the
original paper). Papavergos and Hedley divide the theories into two
groups, those based on classical concepts of turbulence and eddy diffusion
(the firs t seven in Table l) and those based on stochastic (probabilistic)
approaches such as random walk [12] or turbulent 'bursts' [7] (the last
four in Table l). It is common to represent the results as a plot of a
non-dimensionalized transport coefficient, k~ = kt/v*, against a non-

dimensionalized particle relaxation time, t;, which has its origin as
follows.
Consider aspherical particle of diameter d p and mass mp in free
flight at an initial velocity Vo which is decelerated to velocity zero by
means of a Stokes drag exerted by the surrounding fluid of viscosity ~.
Then by a force balance at any instant,
@ProcessEng
(11 )
3 p /6 and dt = dS/v ; hence Equation (11) simplifies to

~dp p p
146
ds = (12)
Integrating from initial condition s=O, v p Vo to final condition s = sp'

v p = O, the result is
sp = (13)
where sp is known as the Stokes particle stopping distance. The

corresponding particle relaxation time is given by
(14)
which is a parameter that is independent of Vo and is commonly non-

dimensionalized as
2
t + ppd p
(15)
P lBj.Å v
Figure l shows a typical plot of k t + vs. t +, theoreticaI or
experimental. The transition from diffusional fo inertial control occurs
at t p+ ~ 0.1-0.2, i.e. d p in the order of 1-2 j.Åm depending on v*, p , p
and j.Å. A vast amount of experimental data for particle deposition From
gases (usually air) onto deliberately sticky walls follow the general
trends shown by Figure l, but with a good deal of spread on the data,
which is accentuated for horizontal duets at t + > 0.2 when floor
deposition is distinguished from ceiling deposrtion, presumably because of
gravity effects [2]. It should be noted, however, that both from
considerations of ordinary dimensional analysis and by virtue of the
complicated physics underlying the phenomena summarized by Figure l, it is
unlikely that the large number of variables involved ean be uniquely
represented by only two dimensionless groups. For example, while the
slope of -1/3 for the diffusion regime in Figure l correctly represents
the variation of k with d given by Equation (10), it misrepresents the
direct prop~rtionaiity of ~t with v* given by the same equation, according
to which k t should be drawn as ~ horizontal line as was done by
Papavergos and Hedley [2] for t < 0.2. The data spread even for this
less complicated regime is suffrcient to justify either slope. For the
inertia regime it is likely that a significant ro le is played by the
dimensionless groups pp/p, reflected in the turbulent burst theory of
Cleaver and Yates [7], and the duet Reynolds number, Re~ in fact there is
strong experimental evidence for the latter for Re > 10 [2].
Papavergos and Hedley ~2] recommend, as a rough empirical
generalization for 0.2 < t p < 20,
kt+ = 0.00035 (t p+)2 (16)

@ProcessEng
147
according to which
(17)
2.3. Impaction
In this regime, which starts at t p+ = 10-20 (d p ~ 10-20 ~m), the
particle velocity towards the wall approaches the friction velocity v* and
the particle stopping distance becomes of the same order as the pipe
diameter. The response of such large particles to turbulent fluctuations
becomes limited and k t + therefore levels off. As the particles get still
larger+ they get even more sluggish in their response to turbul+nt eddies
and k t actually starts to fall and approach a dependence on t p similar
to that of the diffusion regime. Thus k t is at first independent of d p
and subsequently falls gradually as d p increases. An approximation
recommended for this regime is [2)
k + 0.18 (18)
t
according to which
(19)
2.4. Surface roughness
The aforementioned theories and results are mainly for smooth
surfaces. There is ample experimental evidence to indicate that the
effect of surface roughness, even microroughness, is to enhance the
transport of particles to the surface [2,13), especiaily for particles
smaller than about 5 ~m [14). The enhancement occurs because of the
decrease in viscous sublayer thickness and corresponding increase in
turbulence level due to the roughness elements [3,14), because of the
smaller stopping distance required for the particles to arrive at the
out er asperities of the roughness elements, and because of the additional
mechanism of particle interception by those elements along flow lines
parallel to the macrosurface [15,16). Recent experimental results [13)
for transport of aerosol particles to a sand-roughened wall indicate that
the enhancement is increased as the roughness, particle size and turbulent
intensity increase. Davies [16) has argued that the inverse dependence of
k t + on Sc in the diffusion regime changes from an exponent of 2/3 for
smooth surfaces to 1/2 for very rough surfaces, and that in the inertia
regime,
k + = et +(l+t +)p/p (20)

t p P P
where the constant e varies from 0.05 for very smooth surfaces (e.g.
polished brass) to 100 for very rough surfaces (e.g. filter paper).
Equation (20), unlike (16), shows the slope change from 1 to 2 depicted in
Figure 1 as t + increases within that regime.
Most ini~ially smooth walls would tend to roughen as particle
deposition occurred, so that roughness would then have to be taken into
account. In the absence of appreciable blockage by the deposit in a duct
@ProcessEng
undergoing fouling, the increasing equivalent sand roughness can be

monitored by a continuous pres sure drop measurement. On the other hand,
deposition of fine particles onto initially rough surfaces can conceivably
148
result in filling the roughness cavities and thereby smoothing the surface
[17]. Auto-retardation of the particle transport process then occurs [3].
2.5. Gravitational settling

For particles at t T ) 1, gravity comes into play. For sufficiently
large and/or heavy partjcles in non-vertical, especiaily horizontal,
channe Is , gravity may control the deposition process, in which case
(21)
In the absence of appreciable re-entrainment, we then have what is known

as sedimentation fouling, which can often be prevented by pre-filtration
of the offending particles.
2.6. Neglected hydrodynamic forces

Many investigators [2,18-21] have pointed to the possibie importance
of the particle lift force analyzed by Saffman [22] in influencing
particle behaviour close to the wall in turbulent flow. This so-called
Magnus Effect is the force experienced by a rotating object in a shear
flow. When the particle motion parallel to the wall is faster than that
of the fluid, as would be the case for downflow in a vertical duct
assuming pp)p, then this force is directed towards the wall, while for the
correspondlng upflow it would be directed away from the wall. Deposition
is therefore enhanced by downflow and inhibited by upflow.
Another neglected force near the wall, which has received less
attention than the lift force, is the fluid drainage or viscous
interaction force analyzed by Brenner [23]. As a particle approaches a
wall there is an increased viscous resistance to its motion because the
friction between the fluid and the two approaching surfaces progressively
increases the force required to push the fluid out of the particle's path
[19,23]. The net effect of this force is to inhibit deposition.
Lister [19] and subsequently Bea1 [20] have pointed out that both the
lift force and the drainage force are relatively sma11 in a gas but
considerably greater in a 1iquid, so that the large number of reported
deposition experiments on aerosol particles from flowing air, as compared
to the relatively sparse data on particle deposition from liquids, provide
littie information on the possibie importance of these forces. When one
combines the previous transport mechanisms with a sticking probability to
rationalize particle attachment to the walls, as discussed later, then it
is likely that the above forces are automatically accounted for by this
empirical dodge.
3. NON-ISOTHERMAL PARTICLE TRANSPORT

In the presence of heat transfer and therefore temperature gradients
within a fluid, properties of the fluid such as viscosity and density
change throughout the flow field and hence the calculation of transport
rates based on isothermal conditions must be modified accordingly. Such
modification is accentuated at lower duct Reynolds numbers due to the
possibie influence of natural, in addition to forced, convection at these
@ProcessEng
Reynolds numbers. These effects are amply discussed in the standard

literature on heat and mass transfer. Two additional mechanisms which
come into play under non-isothermal conditions will be discussed briefly
below.
149
3.1. Thermophoresis
This is the phenomenon whereby a 'thermal force' moves fine particles
down a temperature gradient. Rence cold walls attract and hot walls repel
colloidal particles. There is now a large theoreticai and experimental
literature on thermophoretic transport and no attempt is made to cover it
here; only one of several approaches to the subject is discussed.
The thermophoretic velocity vth of micrometer-size particles has been
shown to be representable by [24]
vth = - cx2- 'IT (22)

T
where, for continuum flow, the coefficient a is given by
a = c' (23)
and the constant c' is 1.8 for gases and 0.26 for liquids. Clearly, since
the kinematic viscosity v of a gas is typically at leas t an order of
magni tude greater than v of a nonviscous liquid at the same temperature
(especiaily at high temperatures), and since conversely the thermal
conductivity k for a gas is much smaller than k for a liquid so that at a
given heat flux q (= -kVT), -'IT is again much larger for gases than for
liquids, it follows from Equation (22) that vth for gases is considerably
greater than vth for 1iquids. Neverthe1ess, even for liquids,
thermophoresis cannot be negleeted in the presence of large heat fluxes.
By assuming that the entire temperature difference between the bulk stream
and the wa1l is confined to a thin laminar film near the wall, Whitmore
and Meisen [24] used Equation (22) to deve10p the foliowing expression for
the fractional particle removal efficiency, eth' by thermophoresis from a
suspension in turbulent flow through a duet with cold sticky walls (i.e.
no particle rebound or re-entrainment):
T aPr
e th = 1 - (~) (24)
Tin
If the fractional removals of particles onto a cold wall by transport
mechanisms other than thermophoresis, e.g., Brownian diffusion, inertia,
gravity, etc., are denoted by ed' ei' eg' etc., it ean be shown [24] that,
provided there is no interaction between remova'. mechanisms, the overall
fractional removal e is given by
(25)
The measurable decrease of particle transport from a gas to a heat ed as

compared to an unheated wall has been shown to occur for particle
diameters as high as 11 ~m [25]. The potency of thermophoresis in
modifying fine particle transport to hot surfaces has recently been
demonstrated in our own 1aboratories [26,27], amongst several others.
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150
3.2. Thermoelectric effect

A surface subjected to a heat flux will induce a "thermoelectric" EMF
in the adjacent coolant stream if that stream has a sufficient
concentration of charge carriers [19]. The EMF in turn will induce
electrophoretic transport of charged particles in accordance with the
relation
<l>n = e'ucq/k (26)

According to Lister [19]. Equation (26) has provided a basis for some
reasonable predictions of particle deposition in various high temperature
waters.
4. ATTACHMENT
While theoretically at least fluid mechanics can explain and predict
how a particle gets to a wall, it cannot determine whether or not the
particle adheres to the wall. Only a consideration of surface forces can
do so.
4.1. Sticking probability

The problem of attachment can be formulated statistically in terms of
S, the probability that a particle which gets to the wall sticks to it, or
alternatively the fraction of particles reaching the wall which stay there
(before any re-entrainment).
One approach to S is to put c s = O in Equation (2), which thus
temporarily assumes perfect stickability, and then write
(27)
Thus
S
~ = (kd)actual (27a)
kt (k d ) S=1
It has been proposed [28,1], af ter Parkins [29], that
S ex:
adhesive bond between particle and surface
shear stress on particle at surface
-E/RT S
e
-E/RT S
e (28)
(v*/v*min )2
where v~in is the saltation friction velocity and the denominator of
Equation (28) is taken as unit y when v* < v~in. Then when E = ø or Ts O
@ProcessEng
or v* = ø, S = O; and when E = O or Ts = ø, S = 1 provided that

v* " v~in.
151
Amongst those who have investigated the hydrodynamics of particle

transport in turbulent flow, Beal [30] alone has incorporated a sticking
probability, which we shall call P to distinguish it from S above, into
his deposition model,
l (29)
l 1
+
For perfect stickability (P=l=S),
(kd )S=l = ---1---~1~-1-- (30)

+
~
Combining Equations (27a), (29) and (30),
kmS
p = ----~~~~-- (31)
~ + v o (l-S)
Thus Beal's P is different from, but can be related to, the S defined by
Equation (27). Beal [20] attempted to evaluate S via Equation (27a),
using data in the literature on particle deposition from both air and
water to determine (kd)actual" and computing (kd )S=l from Equation (30)
under comparable conditions. He then determined P by means of Equation
(31) and corre1ated the results with a dimensionless stopping distance.
His resu1ts where P was less than unit y can be summarized approximate1y as
p ~ (vd )-6 (32)

p
Beal's va1ues of Vo are, however, considered to be unrea1istic [2],
which cou1d be one reason for the fact that some of his calculated values
for both S and P turned out to exceed unity. They a1so throw doubt on his
empirical results for P. He did not report his values of S, but by
algebra ic re-arrangement of Equation (31),
S (33)
Since P appears in both the numerator and denominator of Equation (33),

and since for the mixed regime data looked at by Beal [20] both terms in
the denominator of either Equation (29) or Equation (33) were important
{note that Beal [30], unlike Cleaver and Yates [7] and other
investigators, treated diffusion (eddy + Brownian) and inertia as series
rather than parallel resistances}, it can be seen that the very high
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152
dependence of P on both d and v shown by Equation (32) would be

attenuated for S, in keep~ng with Equation (28). On the other hand, any
dependence of S on Ts shown by Equation (28) would be accentuated for P
according to Equation (31).
The combustion of fossil fuels, especiaily coal, gives rise to
considerable gas-side fou1ing problems. At the high temperatures
prevailing near boi ler tubes, molten compounds of Na, K, S and V from the
ash deposit on and react with (corrode) the walls [31]. Rosner and
Nagarajan [32] have recent ly addressed the complicated problem of
determining a sticking fraction for fly ash from combustion gases, where
the 'glue' is provided by the deposition of condensed alkali sulphates.
4.2. Surface forces

Measured deposition coefficients for hydrosols from water, as opposed
to aerosols from air, are usually one or two orders of magni tude smaller
than what would be predicted for S=l, i.e., by pure transport [3]. A more
fundamental approach to the particle attachment process in an ionic liquid
medium, especiaily when the transport is in the diffusional regime, is to
consider the actual surfaee forces between a colloidal particle and a wall
[33]. The two most important of these are
l. London-Van der Waals forces, which arise from the interaction
of fluetuating dipole moments generated by the motion of
electrons around the nuclei of neutral atoms in close proximity
to each other. In a single phase fluid, the resulting forces
between particles and between a particle and a surfaee are
always attractive. For d p ~ 100 ~m, Van der Waals forces
dominate over the effect of gravity [34].
2. Electrical double layer interaction forces, which arise from
the electrical charges commonly acquired by particles or
surfaces immersed in an electrolyte, and the compensating
diffuse layer of counter-ions in the liquid adjacent to these
surfaces. If the particles and wall have unlike charges, these
forces are attractive; if they have like charges, the forces
are repulsive.
The electrical double layer sur face (zeta) potentials can be changed
from positive to negative by increasing the pH, so that at pH values
between the points of zero charge for particles and wall, respectively,
attachment is greateot [35]. The diffuse layer of counter-ions is
compressed by addition of a neutral electrolyte, thus increasing the
possibility of Van der Waals adhesion even with like surface charges.
Matijevic, Kallay [36] and co-workers, in a series of papers, have
correlated deposition (ineluding attachment) and removal (i.e. particle
detachment) with pH, ionic strength and flow rate for both spherical
«-Fe203 and rod-like ~-FeOOH colloidal particles from aqueous solutions.
Figure 2 is a plot of interaction energy vs. separation distance for
the case of zeta potentials of like signs, in the presence of the
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153
ubiquitous London-Van der Waals forces. It is seen that the summation of

the interaction energies results in a large energy barrier which must be
overcome before a particle can actually get to the wall. This barrier is
analogous to the activation energy barrier for a chemical reaction at the
deposition surface; Ruckenstein and Prieve [37] and others have shown
that the attachment process can then be represented by
(34 )
in which kr is related to surface temperature via

-E/RT s
kr = Ae (35)
Combination of Equations (2) and (34) with kt=k m leads to
l (36)
Equation (36) has been proved out quantitatively for laminar flow, but
only when the particles and the wall have opposite charges, in which case
a good approximation is that mass transfer controis, i.e. (l/kr) « (l/km)
[36,38]. For the case where the particles and the wall have like charges,
values of kr estimated from first principles, though they show the correet
qualitative trends, are quantitively orders of magnitude smaller than what
is measured experimentally [38]. This deficiency ean be attributed
primarily to the failure as yet of electrokinetie theo ry to appropriately
take aeeount of heterogeneities in charge distribution and microseopic
geometry of real surfaces.
Since kr is related to surface temperature Ts by an equation of the
Arrhenius type, Equation (35), it follows that at time zero, when the wall
is clean, $d should increase with Tw' Watkinson and Epstein [39] have
indeed shown sueh behaviour for gas oil fouling, but for more
unambiguously particulate fouling, what data exist show variously
positive, negative and negligibie wall temperature effects [3]. The non-
isothermal transport effects, particularly thermophoresis, diseussed ab ove
could account for sueh apparently contradictory data.
5. RE-ENTRAINMENT
The re-entrainment process for particulate fouling is in principle no
different than the removal proces s for any other type of fouling.
Foliowing Kern and Seaton [40] and Taborek et al. [41],
B(v*)2 mf
$r ex (37)
<J;
where the deposit strength factor, <J;, can either be taken as independent
of v, or, as in the case of Taborek et al. [41] for particulate fouling in
the presence of sealing,
@ProcessEng
(38)
with i > O. Gudmundsson [3], based on his results for net wax deposition
154
from hydrocarbons, suggested i = l. Combining Equations (l) and (37), and

integrating the result from the initial condition t = O, mf = O on the
assumption the ~d remains constant, yields an equation of the Kern-Seaton
[40] or Cleaver-Yates [42] form:
*
mf = mf (l-e
-t!t
c) (39)
where the time constant,
(40)
and the asymptotic deposit mass (per unit sur face) ,
(41)
An interpretation of t c in terms of the turbulent burst re-entrainment

mechanism of Cleaver and Yates [42] has aiready been given in the earlier
paper [43].
Rodliffe and Means [34] have reported that particles large r than
about 10 ~m are very subject to re-entrainment by water coolant flows,
while particles smaller than about l ~m are typically stable against
re-suspension.
6. EFFECT OF FLUID VELOCITY

In general, for deposition in turbulent flow,
(vlm) j (42)
For trans port-control led deposition, ~=1 for the diffusion regime by
Equation (5) and j=3 for the lower t (i.e. lower d ) part of the inertia
regime by Equation (20). For deposi~ion in which bo~h transport and
attachment are important, combination of Equations (27) and (28), assuming
v* > (v*)min' leads to
(43)
which is equivalent to Equation (42) wijh j = -1 and +1 where diffusion

(k t « v*) and lower d p inertia (k t « v* ) respectively, control the

transport part of the deposition process. Finally, for adhesion-
-controlled deposition [52), cb ~ C s and kr is independent of v*, so that
from Equation (34), j=O in Equation (~2).
Table 2 shows how both t c and mf would be expected to vary with v
for each of the above regimes combined with i=O and i=l in Equation (38),
assuming f = constant (fully rough flow), so that the index on v is
@ProcessEng
identical to that on v*. The exponents a and b in Table 2 are defined as

155
follows:
(44)
and
(45)
From Equations (38) and (40), it is apparent that a = i-2, and from
Equations (41) and (42) that b = j+a = j+i-2.
Table 3 lists values of j and bobtained experimentally by different
investigators of particulate fouling from liquid media. The corresponding
values of a may be estimated as b-j, but it has been found [26,47] that
such estimates are not always the ones obtained by fitting all the data of
a run to Equation (39), since this procedure may not provide the best fit
to the initial data points, which are the ones that should be used to most
accurately determine ~d and hence j. It can be noted that the
experimental results for j and b all fall within the limits predicted by
the models, and at least two sets of data agree with both j and b with two
of the models. There is nevertheless insufficient consistency to warrant
generalization without a detailed case by case consideration of each
investigation and the full range of conditions associated with that
investigation.
7. BOILING CONDITIONS
A deposition-release model, similar to that of Equations (l) and
(39), but without any velocity terms in the expressions for ~d and ~r' has
been found to be applicable for boiling conditions [48]. Additionally, ~d
has commonly been found to be proportional to the square of the heat flux,
especiaily under well-stirred conditions. Both normal and inverse
solubility salts tend to concentrate at the vapour-liquid-solid (triple)
interface [49], along with colloidal particles. Gasparini et al. [50]
have focussed on the electrical double layer effect to qualitatively
predict and even control metal-oxide fouling from steam-water flows in
power stations. Fouling under boiling conditions, however, is generaily
beyond the scope of the present paper, and requires separate attention.
NOTATION
A Arrhenius coefficient, mIs
a exponent on v in Equation (44)

4
B constant in Equation (37), sIm
b exponent on v in Equation (45)
C constant in Equation (20)

@ProcessEng
c particle concentration, no.1m 3

156
bulk concentration of partieles, kg/m 3
heat capacity of fluid at constant pressure, J/kg.K
concentration of particles adjacent to surface, kg/m 3
concentration of particles adjacent to wall, kg/m 3
et constant in Equation (23)
D molecular diffusivity of solute in solvent, m2 /s
Brownian diffusivity of partieles, m2 /s
d duet equivalent diameter, m
particle diameter, m
activation energy, J/mol
e base of natural logarithms (= 2.718)
e' thermoelectric emf, volt/K
f Fanning frietion factor = 2~s/p(v)2
heat transfer Graetz number
mass transfer Graetz number
h convective heat transfer coefficient, W/m 2 .K
i exponent on v in Equation (38)
j exponent on v in Equation (42)
KB Boltzmann constant = 1.38xlO- 23 J/K
k thermal conductivity of fluid, W/m.K
kd deposition coefficient, m/s

km mass transfer coefficient, m/s
kp thermal conductivity of particle, W/m.K
kr attachment rate constant, m/s
kt transport coefficient, m/s

@ProcessEng
k + non-dimensionalized transport coefficient

t
157
L duct length, m
mass of fouling deposit per unit surface area, kg/m 2
asymptotic value of mf ' kg/m 2
particle mass, kg
Nusselt number = hd/k
p Beal sticking probability
heat transfer Peclet number RePr
mass transfer Peclet number ReSc
Pr Prandtl number = cp~/k
q heat flux, W/m 2
R universal gas constant = 8.314 J/mol.K
Re duct Reynolds number = dv/v
s Parkins sticking probability
s distance, m
Stokes particle stopping distance, m
Schmidt number = v/D for solute = V/DB for particles
Sh Sherwood number = kmd/D B
heat transfer Stanton number
mass transfer Stanton number
T fluid temperature, K
VT gradient of temperature, K/m

Tb bulk fluid temperature, K
Tin bulk fluid inlet temperature, K
Tout bulk fluid outlet temperature, K
Ts surface, i.e. fluid-deposit interface. temperature, K

@ProcessEng
Tw wall temperature, K
t time, s
158
time constant, s
partiele relaxation time, s
non-dimensiona~ized partiele relaxation time = t p (v*)2/ v
u eleetrophoretie mobility of partieles, m2 /volt.s
v bulk fluid veloeity, m/s
v* friet ion veloeity = ~ = vlfrr, m/s
saltation frietion veloeity, m/s
initial value of v p ; average partiele veloeity normal to the

wall, m/s
vp veloeity of partiele in free flight, m/s
vt terminal settling veloeity of partieles, m/s
vth thermophoretie veloeity, m/s
W mass flow rate of fluid, kg/s
a thermophoretie veloeity eoeffieient
E total fraetional removal of particles from fluid by wall
Ed fraetional removal of particles by Brownian diffusion to wall
Eg fraetional removal of particles by gravity to wall
Ei fraetional removal of particles by inertia to wall
Eth fraetional removal of particles by thermophoresis to eold wall
~ fluid viseosity, kg/m.s
fluid kinematie viseosity
fluid density, kg/m 3

Pp partiele density, kg/m 3
~s fluid shear stress at surface, Pa
~d partiele deposition flux, kg/m 2 .s

@ProcessEng
~n partiele flux, no./m 2 .s

159
~r particle re-entrainment flux, kg/m 2 .s
~ deposit strength factor
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40. Kern DQ and Seaton RE: A Theoreticai Ana1ysis of Thermal Surfaee
Fouling. Brit. Chem. Eng., Vol. 4, No. 5, pp. 258-262, 1969.
41. Taborek J, Aoki T, Ritter RB, Palen JW and Knudsen JG: Fouling - The
Major Unresolved Problem in Heat Transfer. Chem. Eng. Prog., Vol. 68,
No. 2, pp. 59-67 and No. 7, pp. 69-78, 1972.
42. Cleaver JW and Yates B: The Effect of Re-entrainment on Particle
Deposition. Chem. Eng. Sci., Vol. 31, pp. 147-151, 1976.
43. Epstein N: General Thermal Fouling Models. NATO ASI on Advances in
Fouling Science and Technology, Alvor, Portugal, May 1987.
44. Hopkins RM and Epstein N: Fouling of Stainless Steel Tubes by a
Flowing Suspension of Ferric Oxide in Water. Proc. 5th Intern. Heat
Transf. Conf., Vol. 5, pp. 180-184, Tokyo, 1974.
45. Thomas D: Experimental Investigation of the Deposition of Suspended
Magnetite from the Fluid Flow in Steam Generating Boiler Tubes. Ph.D.
Thesis, Technica1 University of Munich, 1973.
46. Burrill KA: The Deposition of Magnetite Particles from High Ve10city
Water on to Isothermal Tubes. AECL Report No. 5308, 1977.
47. Newson IH, Bott TR and Hussain Cl: Studies of Magnetite Deposition
from a Flowing Suspension. Chem. Eng. Communic., Vol. 20,
pp. 335-353, 1983.
48. Charlesworth DH: The Deposition of Corrosion Produets in Boiling
Water Systems. Chem. Eng. Prog. Symp. Series, Vol. 66, No. 104,
pp. 21-30, 1970.
49. Macbeth RV: Fouling in Boiling Water Systems. Chapter 15 of Two-
Phase Flow and Heat Transfer, Butterworth D & Hewitt GF, eds., Oxford
Univ. Press, 1977.
50. Gasparini R, DelIa Rocca C and Ioannilli E: A New Approach to the
Study and Prevention of Deposits in Modern Power Stations.
Combustion, Vol. 41, No. 5, pp. 12-18, 1969; Mechanism of Protective
Film Formation on Cu-Alloy Condenser Tubes with FeS04 Treatment.
Corrosion Sci., Vol. IO, pp. 157-163, 1970.
51. Prieve DC and Ruckenstein E: Effect of London Forces upon the Rate of
Deposition of Brownian Partieles. AIChE J., Vol. 20, pp. 1178-1187,
1974.
52. Hasson D, Marmur A and Tor Y: Fouling of a Cylindrical Obstac1e
Placed in an Air Stream. Proc. 6th Intern. Heat Transf. Conf.,
Vol. 6, pp. 301-306, Hemisphere, 1982.
@ProcessEng
162
Table 1. Summary af Major Theories an Turbulent Particle Transp0rt [2]
Type ol' Range øf

InvestigalOr thclHctical modI.'! ;'ipplic.ltion Additional features Remarks and conclusi0ns
Friediander and Pal'lide dill'usiollo Whcn: piHliclc inertia UP1 = 0.911· = II;. Theory makes questiomlble
Johnstone 7 projeclion Io thI! wall, is. the main deposition Lp., = l:III,r' assumptions, which tend IO limit ils
adopling the com:ept mcchanislll Muhilayered wall cancep' application in cases other than
of storring distance those were panicle inertia is the
dominant mechanism
Owen J2 Partiele diffusion- Wheec gravity efli:cts t:~1.f a:: t pu ' Lengthy e.xpressions for tht:: partide
projeclion to Ihc wall, intlucncc partiele M ultilayen:d wall concept dl!position ratc on the noor. roof
incorporuting Ihl! deposition and side walls an: dt::rivl!d. without
dfecl af gravilY the support ol' reliablt: I!xpenmcntaJ
evidenee
Davies" Inertial and diffusive lntended lo Cover II p .l:= t m.,· Theory underpredicIs deposition
(eddy and molecular) all cases, ie Multilayered wall concept. rates and is complex Io use in
mc:chanisms eOllsidc:red, 0.001 ';d,'; 100/lm Empirical equation for routine design. but provid.cs more
while retaining the in the absence of em.r to apply across the physical insight inlo the occurnng
eonec:pt of stopping extraneous forces enlire boundary layer phenomena than the previous theo ries
distance
BeaiiS Similar Io Davies'. Cases involving Free Hight velocity is In spile 01' thc: unrealistic rrec
with the addition of a panicles ranging from laken to be onc half of ftight velocitic:s assumed, tht:
steady state panicle molecular size to the axial tluid velocity prediclions tend to tit rhe
accumulation J1t:ar tht: 100 fim in d p experimenral data more
wall satisfactorily than tht! previous
theories
Similar to Davies', Empirical relalionships The empirical The theory wOls tested. over a narrow
adopting empirical limit application of rdationships adopled are range of experimental conditions.
expressions for t: p .1 theory to within the physically incorrect and therefore lacks generality. The
to fit experimenlal specitied range empiric:!1 relalionships undennine
resulLs the theory
Liu and lIori H Similar Io Davies'. Intended for a wide t: P.T = Dø + e'M + e'. Despite (ht! t..:(uesrinnable J.ssumptions
Nc:w relalionship for range ol' conditions, e' "" (u;)!t p ol' thc: theory. better tit \"'ith tht:
Ep.t imroduceJ. bUI reliable only available expenmc:ntal dat J. was
wilhin .2 < t; < 20 obtained than the prt!vious thc:ones
of FriedIamier and. Johnstone. and
Davies
Wasan Slmllar IO Uea!'s. Cases IOvol\'lng em .• = ep,r; two layered The ex pressIOns at partlclt:
el aPU9 e",.r expn:ssed. as a particles ol' wall region: deposilion rates are based llO mass
el.lntinuous funclion dp«IOOJIOl O~yt.:::;:19.75 and momentum analogie ... and.
yt~19.75 t m., = t<l.c' laler \I,.·ork re . . eakd
thai these analogies Jre nnt . . alil.!
HUlchinson Probabilistic Iheory- lntc:nd.ed to cover all The theory is more realistie than
el al::U randlHn \~alk concepl eliSeS. wirh no J:li~i~ior~ ~~~~~e all Ihc pre . . ious thel.>ries Jod
extran~ous forces rckvant turbulence satisfactorily prediclS de position
present paramelers rates of partides of J, ~ It) ~tm
CJeaver and Probabilislic Ihc:ory, All cases not involving QU:'lsi-steady two- Provides physical insight iOlO the
Yates H ineluding Ihe exlraneous forces dimensional flow piet ure mechanics of dt!posltion. without
occurrc:nce of 'bursts' ncar thc boundary wall taking in Io account p;trudt:
near the bl.>undary wall bcha .... iour in tht! turbulent .:ore.
Satisfactory agrcement ~twt::en
predietions and available
expcrimental data
R«ks and Similar IO Hutchinson All cases invol\'ing Diffusion appears to stop The theor)' is very dilficult 10
Skynne<Wo el al's in pnnciplc: partieles outside the at an arbitrar)' 'dilTusion vcrify experimentally and thereforc
molecular range edge' near the wall ils validil)' remains uneeetain
Papavergos and Combined HUlchinson Cases in\"olving all Two slages for partiele Theory ex.amines particle b(haviour
Hediey" et al's wilh Oc:aver partiele sizes, and deposition: from the turbulent eore to the wall
and Yates' theones free from (a) m'lcro-meehanism until its final deposition.
extraneous effocts (b) micro-mechanism satisfactory agreement with
.. _ _ _ _ _ _ _ ~ ____ .~ _ _ _ _ _ _ _ _ _e__'xpe'-rimental data
First published by The Institution af Chemical Engineers in Chemical

Engineering Research & Design, pp. 275-295~ Sept.1984.
@ProcessEng
163
Tab1e 2. Predictions of Ve10city Effects on

Deposition-Re1ease Parameters
Control of Deposition i j a b I
Diffusion + adhesion O -1 -2 -3
1 -1 -1 -2
Adhesion O O -2 -2
1 O -1 -1
Inertia + adhesion O +1 -2 -1
1 +1 -1 O
Diffusion (S=l) O +1 -2 -1
l +1 -1 O
Inertia (S=l) O +3 -2 +1
l +3 -1 +2
Tab1e 3. Experimenta1 Ve10city Effects on

Deposition-Re1ease Parameters
Investigators System Tube j b I

Watkinson & Epstein [39] coke/gas oil stain1ess -1.07 -2
Watkinson & Epstein [28] sand/water stain1ess 0.92 -1.2
Hopkins & Epstein [44] hematite/water stain1ess 0.3 -0.9
Thomas [45,47] magnetite/water* stain1ess 1 +0.5
Burril1 [46,47] magnetite/water* Zircal1oy-4 ~2
Newson et al. [47] magnetite/water* a1uminum 0.73 -0.66
*Isotherma1 experiments; the other studies were performed under

sensible heating conditions.
@ProcessEng
164
slope =1-- 2
slope = -1/3
......
II
.x
Diffusional lnertial Impaction

kt =km
- 0.1 -10
+ t {v·)2 e d {v·)2
2
t p = ~= ~'v
Figure l. Particle transport regimes.
\
\
\ Total Interoction Energy
~ Repulsive Double-Loyer Energy
\
EnergYI ~ \
O~~--~------~--------~--------
" .......
- Separation h
.,..
/
""Attractive London Energy
@ProcessEng
/
I
Figure 2. Particle-surface interaction energy bar rier when
particle and surface have like charges, from Prieve and
Ruckenstein [511; hmax = distance from wall of primary
maximum; hmin = distance from wall of secondary minimum.
STOCHASTIC MODEL FOR THE INDUCTION STEP ON PART I CULAT E FOULING
N. VATISTAS
Dipartimento di Ingegneria Chimica, Chimica Industriale e Scienza dei

Materiali
Via Diotisalvi, 2 56100 Pisa - Italy.
l. INTRODUCTION
The fouling phenomenon is often preceded by the induction step, that
can be more or less long, according to the system under consideration. In
this step it is the type of the material and the smoothness of the fouling
surface that are important contributory factors.
For particulate fouling, the particles must reach the wall from the
bulk flow, this constitutes the transport stage. The next step is the
sticking of the particles to the wall, which depends on the particle/wall
interaction for the system. During the sticking stage the particle is
unstable and can be detached by perturbations reaching the particle from
the fluid.
The development of theories and relationships for the particle
depositon stage follows the progress made in understanding the structure of
turbulence, but only empirical relationships based on the experimental data
have been used in this work.
For the sticking stage of the particles on the wall knowledge of the
structure of turbulence in the boundary sublayer suggests the possibIe
supposition that the proces s is not instantaneous, but this was not
possible. In fact according to the classical theories of turbulence, the
shear stress in the wall region is constant for any regime of fluid and so
instantaneous sticking has to be assumed.
The new theories of turbulence suggest that the shear stress in the
wall region is not constant but varies periodically: from short-lived high
values to long-lasting low values, because of presence of bursts in the
sublayer boundary. The location of bursts varies in a stochastic manne r ,
and the high and low values of the shear stress are also stochastic in the
wall region.
2. STRUCTURE OF THE FLOW IN THE BOUNDARY SUBLAYER

Descriptions of the structure of the flow within the sublayer of
turbulent flow have become available (l, 4). Several authors have
suggested that the near-wall region is inhabited by densely packed pairs of
counter rotating vortices lying in the streamwise direction. They are
quite long in axial extent but with a small diameter.
Periodically these vortices interact with the outer portions of the
flow through a sequence of four events: gradual outflow, liftup, sudden
oscillation and breakup. The sequence of three events from liftup to
@ProcessEng
breakup is called bursting.

The mean period between bursts is approximately:
(l)
v
*2
165

166
The probability distribution of tb is log normal and estimates of its

variation are given (2).
Virtuaily all the net produetion of turbulent energy near the wall
occurs during bursts. The burs ting proces s occurs in two dynamic stages, a
sudden burst followed by a quick relaxation to a relative quiescent, but
still turbulent state. The duration of the second stage is long compared
te; the first.
;. PARTICLE TRANSPORT
The transport of particles from a turbulent flow stream to the
~djacent surfaee is due to Brownian diffusion for very small partieles, to
inertial effects for large particles and to Brownian diffusion - inertial
,ffects for medium sized particles .
For the transport of partieles, empirical relationships are used on
th· experimental data of various investigators (5), which were found to be
ve,y useful in design and are as follows:
~iffusive mechanism
*2
-2/3 * v 2
0.089cb sc v at --d <3.6 (2a)
,} P
Diffusive - inertial mechanism
2 *5 *2
0 v 4 P v
-6
W 10 cb ~
2
--d
\)4 P
at 3.6< -.-J2..
p 2
d2
p
<360 (2b)
P \)
Inertial mechanism
W .18cb v * at >360 (2c)
The transport flux to the wall W is a function of the number of

particles deposited np' during the time between bursts tb/unit area of
wall.
*2
p d3 v
W .52~n 5.2 x 10 -3 p d
3 --n (3)
t p P P \) p
b
Substitution in equations (2a) - (2c) from (3) yields for the various
mechanisms :
Diffusive mechanism
*2
cb l \) p v 2
@ProcessEng
n at -.-J2.. - - d <3.6 (4a)

p 13 sc2/3 -p-d3 v* p \)2 P
p p
Diffusive - inertial mechanism *2
n = 1.9 x 10- 4 c PI'._ v*3dp at 3.6< ~~ d 2 <360
p b p2 \)3 p \)2 P
(4b)
167
Inertial mechanism
l \J p *2
~ _v
__ d2
n at >360 (4c)
2 D
p
Pp
d3
P v* P \J ~
4. THE KINETICS OF STICKING

The classic theory of turbulence assumes that the shear stress in the
wall region does not change, so that an instantaneous process for the
sticking to take place is required. At the same time a critical wall shear
stress is the controIling parameter for the re-entrainment of the deposited
particles.
The recent theories of the structure of the flow in the wall region
suggest that a high value of shear stress in the wall region exists only
periodically due to the effect of the bursts, so it is possibIe to assume
non-instantaneous kinetics for the sticking stage.
Assuming uniform diameter, any particle deposited on the wall sticks
according to the folIowing surface reaction:
(5)
The kinetic constant of sticking k depends on the particular system

particle - wall and the temperature effegt follows the Arrhenius law.
The temperature can have in many cases, a more complex effect on the
sticking stage with the change in the type of sticking and therefore the
type of sur face phenomenon involved.
The stability of the deposited particle depends on the are a of the
contacting surface between the particle and wall and on the value of the
adhesive forces/unit area. It is ve ry difficult to know the kinetics and
the quality of the adhesion for any particular system, therefore use of the
stabilization time which includes both factors, is to be preferred.
Any particle deposited on the wall can be re-entrained by the bursts
if the time in contact with the wall is shorter than the stabilization
time. The stabilization time can be very long, not only because the
kinetics involved are very slow but also because the adhesive force is very
weak.
The induction stage is followed by the growth stage of particulate
fouling. In this step the stabilization time depends on the particles, on
the quantity of deposited particles, on the growth rate, etc. for the
folIowing reasons:
a) Af ter the initial deposition the adhesion is between particles

which depends on the nature of the particles rather than on particles and
wall.
b) The rate of growth affects the quality of the deposit which in
turn affects the physical properties of the deposit, such as thermal
conductivity.
c) The thickness of the deposit affects the temperature difference
@ProcessEng
which in turn affects the temperature distribution and consequently the

surface temperature. A change in temperature affects the kinetics and
quality of adhesion of particles. Furthermore a change in the surface
temperature can affect local velocities (changes in viscosity) which can
modify the rate of growth.
In this work only the induction stage has been studied. During this
step the stabilization time is a constant depending on the wall - particle
168
system. The same model will be extended for the growth stage in the case
of particulate fouling of a heat transfer surface.
S. RE-ENTRAINMENT OF PARTICLES
The re-entrainment of the particles is due to the effect of the bursts
that periodically occur in the fluid in the region of the wall. Such a
mechanism has been suggested by Cleaver and Yates (S), who assumed however,
an instantaneous sticking step and a critical value for the wall friction
velocity.
During the time between bursts t a part of unit wall area p is
subject to bursts, which is the produc~ of the number of bursts/unit area
and the specific area of bursts. It is supposed that p has a constant
value for any system that does not depend on the wall friction velocity.
Suppose that the wall is originally without particles and that the
particles arriving on the wall become stable if they have a per iod on the
wall, longer than the stabilization time sSb.
For the induction stage it is assumed that the particles preferably
arrive to the empty positions on the wall.
The number of particles n deposited on unit area of wall during time
tb are subject to perturbationR from the bursts and may be removed. The
number of particles resting on unit area of wall af ter the time ~ is:
(l - p) n
p
Similarly af ter the time 2tb is:
(l-p)n + (1_p)2n
p p
By inference af ter the generic time qt b < st b the number of particles
on the wall:
n = (l-p)n + (1_p)2 n + ... + (l-p)qn (6)

p p p
The relationship that gives the number of deposited particles on tl
unit area wall for a generic time rt b > stb is:
2
n = n (l-p) + n (l-p)
p p
+ ... + n p (l_p)s + n p (r-s) (l_p)s (7)
The last term of the relationship gives the number of stable particles
deposited, that increases linearly with the time. The other terms give the
number of particles that are unstable.
The value of p must be quite small and so (7) may be written in a more
convenient approximate form:
n N= n
pL
~-exp
- - -(-ps)
p
- - - + (l-p) s (r-s) J (8)
It is supposed that the induction stage is complete if on unit area of

@ProcessEng
wall the number of particles deposited is given by:
l
(9)
169
Combining the relationships (8) and (9) results in the foliowing

expression:
r~s+
(1_p)S
[1
d~ n
1-ex:(-ps) l ( 10)
Combining Equaiton (10) anå Equations (4a - 4c) gives data on an
estimate of the time necessary for the induction stage for the various re-
gimes of deposition.
6. RESULTS AND CONCLUSIONS

Some results of the model are plotted in Figures 1 - 4 to show the
effect of the various factors on the induction time. (pp = 2500 Kg.m- 3 p =
1000 Kg.m- 3 \! = .25 x 10- 6 m2 sec- 1 , Cb=l Kg.m- 3 ).
The effect of the friction velocity on the induction time in general
changes sharply but the change depends on the value of the stabilization
time. The induction time depends strongly on the stabilization time under
all the conditions, for small or large values of the fraction p and the
diameter of the particles.
It is possible to see the effect of the fraction on the induction
time by the comparison of Figures 1 and 2, as also Figures 3 and 4: the de-
crease of the value of p decreases also the part of the surface subject to
bursts and so decreases the re-entrainment of the particles, and the
induc t ion time.
A comparison of Figures 1 and 3 and also Figures 3 and 4, shows that
the increase in particle dimensions decreases the induction time, because
fewer particles are necessary to cover the wall surface.
In conclusion this model considers in a explicit way of defining the
stricking stage and so makes it possible to separate the mechanism of
sticking relative to the wall-particle system from the fluid dynamics.
ACKNOWLEDGEMENTS
Financial support from CMR-Progetto Finalizzato Energetica 2, is
gratefully appreciated.
NOTATION
Ap Contact area b 2tween wall Gas - law constant
and particle m Schmidt number
Bulk concentra~~on of Stabilisation time
particles kg.m Temperature oK
d Particle diameter m Friction velocity m.~ec-1
E~ Activation energy Mass flow rate Kg.m- sec- 1
k Reaction rate const. s-l

o
n Particles deposited Greek Symbols
p
during tb/unit area
p Part of unit are a subject v Kinetic viscosity nf ~-31
to bursts during tb p Density of fluid kg.m
Pp Density of Particles Kg.m- 3
@ProcessEng
REFERENCES
l. Bermam, N.S. The effect of sample probe on sublayer per iod in turbu-
lent boundary layers, Chem. Eng. Comm. 5, 337, 1980.
2. Nakagawa, H., Nezu, I. Bursting phenomenon near the wall in open-
channel flows and its simple mathematical model, Memoirs, Fac. Eng.,
Kyoto Un., 40, 213, 1978.
170
3. Brown, G.L., Thomas, A.S.W. Large structure in a turbulent boundary

layer, Phys. Fluids, 20(10), S243. 1977
4. Cantwell, B.J. Organized motion in turbulent flow, Ann. Rev. Fluid
Mech. 13, 457, 1981.
5. Cleaver, J.W., Yates, B. The effect of re-entrainment on particle
deposition, Chem. Eng. Sc., 31, 147, 1976.
20
...;
..c:: ~l sec
15 ______ 5 II
Cl>
, 15 .
I
E I _._._._.30 ..
f= I
I
I
- __ 60 ..
-'"
I:: I
co I
u I
I
dp=l/km
I
"C
I p ~1/200
I:: ,
I
.1 .2 .3
Frietion Velocity v· m/sec
FIGURE l. Plot of induction time

vs v* for p = 0.005
20 ,I
I
stb 1 sec I
I
I
..c::
15 5 I
I
I
15 .. I
I
30 . I,
Cl> I
E
10
t= ' ___ 60 . I II
- dp l/km ,/
I:: I
co
i
5 I
P 1/29ØO
u
'"
"C (
i
I:: I
I
,/
---_..-;
.1 .2 .3
Frietion Velocity v'" m/sec
@ProcessEng
FIGURE 2. Plot of induction time

vs v* for p = 0.0005
171
20 .. ! II
..:
..c::
Il
Ii
I
i
I
I
!
I
i i
,
I
I
I
I
I ~1 sec
15 I i I
I
I _____ 5 ..
I i i i I
15 -
I
GO
i Ii : ..
I
E
i= la ! iI
I i
I
,
I - ---30 "
-d;~lSJ
j I
c i 1
o i I I
1
u !
5 \! I , ,
1
P =.1/200
""c:'" "
i f
,- I
,
\)
I
I
i ,
I
.05 .1 .15 .2 .25 .3

Frietion Velocitv ~ m/see
vs v*
20
i
~ !~ 1 see
15
;-----5 .
Cl> !H.H 15 -
E
t= IO .!----30 -
c:
o
/---.60
i
-
dp =1001t.m
u 5
'"
"'" / p=1!2000 /
-= -./ -,,#
.15 .2 .25 .3
Friction Velocity v· m/stC
vs v*
@ProcessEng
FOULING BY AQUEOUS SUSPENSIONS OF KAOLIN AND MAGNETITE: RYDRODYNAMIC AND
SURFACE PRENOMENA EFFECTS.
L. MELO and J.D. PINREIRO

University of Minho - C.Q.P.A./INIC, 4700 Braga, Portugal
1. INTRODUCTION
When a suspension flows in contact with solid surfaces, the particles
it carries can be transported to the walls and, through a process of adhesion
form a more or less stable deposit. The basic phenomena of particulate
fouling include these two processes, together with the simultaneous removal
of the deposited particles. Knowledge of the mechanismsinvolved and also of
their mutual interference is essential to the qualitative as well as quanti-
tative characterization of different fouling situations.
The work reported in this text was based on experiments with kaolin-
-water suspensions, magnetite particles being also present in some cases.
Two major kinds of tests were performed: a) "Fouling tests", where the build-
-up of the deposit was continuously monitored through the measurement of 10-
cal heat transfer coefficients in an annular heat exchanger; b) "cohesion
tests", for the assessment of the "mechanical resistance" of the deposit,
which were carried out in an apparatus with two concentric cylinders, the
outer one being able to rotate at different velocities.
The paper also presents simple concepts and calculations that exemplify
two different approaches which are believed to be useful in fouling studies:
one is a more phenomenological (or "overall") approach based mainly on the
interpretation of the so-called "fouling-factor curves"; the other relies
upon a more detailed (or "microscopic") analysis of the individual proces ses
involved in the formation of the deposits (the adhesion process was used as
an example in this study). The two approaches agree in the interpretation of
several features of the experimental results. Although both approaches need
to be substantially developed (particularly in mathematical terms), they
seem to have a potential for practical applications in the prediction of
fouling tendencies.
2. EQUIPMENT AND EXPERIMENTAL METRODS

2.1. Annular heat exchanger

This test section is 2 meter long and is composed by an inner copper
tube, easily removable, and an external perspex tube (diameters: 25mm and
36mm respectively). Thermocouples are located on the internal wall of the
inner tube, as well as in the fluid at positions A,B,C,D and E (Figure 1).
The pres sure drop is measured with a differential manometer, allowing the
calculation of friction factors to be made. The heat flux, provided by an
@ProcessEng
electrical resistance placed inside the copper tube, is determined from

continuous recording of voltage and current intensity. Local thermal resis-
tances of the deposits (fouling resistances) at the different positions can
be then calculated as described elsewhere (1). The annular heat exchanger is
inserted in a closed loop circuit containing a stirred cooling tank (250
liters) and PVC tubes of 25mm diameter (Figure 2).
Several fouling tests were run with the kaolin suspension flowing at
173

174
Thermocouples
on the wall
!
~20em.
l i.t.l~~
i::"'~ '"
Copper tube
. 4Sem 7S.Sem .
~~~~~~~~~~~~lt~'~.5~e~m~L:~~~~:
~ 14Sem. Thermocouples
in the water
FIGURE 1 - Annular heat exhanger
Reynolds numbers (based on the equivalent diameter of the annulus) between

2300 and 11000, using a constant heat flux of about 3000 W/m 2 , pH=7.S, bulk
water temperature = 12 0 C and kaolin concentration = 2.2 Kg/m 3 . The final
thickness of the deposit was measured with a micrometer-based device.
Tests with a magnetite suspension and with a mixed kaolin-magnetite
suspension were also carried out (only at Re = 6900).
2.2. Rotating cylinder apparatus
This equipment is composed by a removable inner copper tube (which in
the present study was made of samples of the fouled copper tube obtained in
the heat exchanger tests) and a 36 mm diameter perspex outer tube, 8 cm long
(Figure 3). The latter is connected to an alternating current motor with
,J
.----- !..~
ep \
l
I
./
~ r--
Test section
Valve
jl
CO
f- RotQmeter II I
@ProcessEng
Retrigerator Tank Data log

system
l-Q
FIGURE 2 - Fouling test rig
175
Inner
Cylinder
(copper)
Rotating
Cylinder
/ (perspex)
Figure 3. - Rotating cylinder apparatus
control led input voltage. The velocities of rotation of this cylinder were
measured with a stroboscope.
The fouled samples (2 cm long) were dried, weighed and placed inside the
apparatus af ter filling it with water at pH 7.5. Af ter about one hour, the
outer tube was rotated at a low velocity for 3 minutes, the fouled inner cy-
linder was removed, dried and weighed. This technique was rep ea ted several
times using higher and higher rotating speeds.
2.3. Particles
A laser flow granulometer and a scanning electron microscope were used
to characterize the geometric features of the kaolin and magnetite particles.
The kaolin particles are roughly similar to discs of 16 microns diameter
and 1 micron thickness (average values), corresponding to an equivalent
diameter of 7 microns (the diameter of the sphere with a volume equal to that
of the particle) . The particles in the deposit seem to adhere to each other
bu their large r faces. Their surfaces, however, are very irregular which
makes the contact area much smaller than if they were smooth flat plates.The
density of kaolin is 2600 Kg/m3 .
The shape of the magnetite particles, although irregular, is more
similar to the shape of a sphere or of a cube, and their average diameter is
21 microns. The density of magnetite is 5200 Kg/m3 •
@ProcessEng
The electrokinetic ("zeta") potential of the kaolin and magnetite par-

ticles at several pH values was obtained from electrophoresis measurements
using a "zetameter" apparatus (Figure 4). At pH 7.5, the zeta potential is
about - 0.05 V for kaolin and -0.04 V for magnetite, both bearing negative
176
Zeta 40,.....-----------,
Potential o MAGNETlTE
(mv)
20
x KAOLIN
-20 ro
-40 ro
-60~------------------J
pH
Figure 4. Zeta potentials of kaolin and mangetite
surface charges.
3. FOULING TESTS AND THEIR INTERPRETATION

3.1. Fouling Models
The data from the "fouling tests" were studied in two stages. First,the
basic modelof Kern and Seaton (2) was fitted to the experimental fouling
curves in order to obtain values of the deposition flux (Ød) and of the
asymptotic fouling resistance (Rf). Then, the processes controiling the
deposition flux were identified and characterized on the basis of a more
detailed model such as the one of Pinheiro (3,4).
Assuming that fouling occurs as aresult of the competition between a
deposition flux (Ød, constant with time) and a removal flux (Ør ' increasing
with time), Kern and Seaton derived the asymptotic fouling equation:
Rf = Rtco [l-exp (-IH) l (1)
where:
(2)
and:
s Ør IRt (3)
Parameter Sis supposed to be directly proportional to the wall shear
stress (i.e., to the square of the average fluid velocity) , and its recipro-
cal (liS) can be regarded as a measure of the cohesion of the deposit in a
given hydrodynamic environment.
The modelof Pinheiro brings together the ideas expressed by Taborek et
al (5), Watkinson and Epstein (6) and Crittenden and Kolackzkowski (7)about
the deposition and removal terms of Kern and Seaton's equation. In the case
of particulate fouling, deposition is considered to be the result of two
proces ses occurring in series - the transport of particles to the deposition
surface and their interaction at this surface (adhesion):
Cb
(4)
Ød = ~f Kf [ (1/K t ) + (1 IK) l
@ProcessEng
ef and Kf are the density and the thermal conductivity of the deposit: Cb
is the bulk suspension_ concentration. Kt , the mass transfer coefficient,
is dependent on Jf. v for turbulent diffusion. The adhesion coefficient,
Ka , will tend to decrease as the velocity increases and Pinheiro suggested
that it should be proportional to (v)-b. f is the friction factor, v the
average fluid velocity and b an empirical parameter that changes with the
type of mechanism that controls the deposition process.
177
For lower fluid veloeities, the mass transfer rate ean be mueh slower
than the adhesion rate (Kt« Ka ), implying that the former will be the
eontrolling step. Then:
(5)
l? f kf
where ø t is the transport flux and b _ O .
If Kt» Ka , the deposition rate will be governed by the adhesion flux
(Ø a ) that deereases as the veloeity inereases:
(6)
with b>O, approaehing 1.

The fluid veloeity is eonsidered to affeet the removal flux in two
ways: and inerease in v produees a higher shear stress but, at the same time,
tends to ereate more eompaet deposits. Thus, Ør will be not only proportional
to f.v% but will also vary inversely with 'la, 1! being an empirieal parameter
related to the eohesion of the deposit.
Equation 3 ean be written as:
Ør ~ K3 f (v)2-a Rf (7)
Pinheiro suggested also that the greater the fraetion oeeupied by the "loose"
layers in the deposit, the greater will be Ør. A "hard" deposit will then
have a high 1/13 ("meehanieal resistanee" or "eohesion") and a low fraetion
os "loose" material.
3.2. Results and Diseussion
3.2.1. Tests with pure kaolin suspensions. The "fouling tests" produeed
eurves of Rf versus t (time) for different Reynolds numbers. Values of Rf~'
Ød and 13 were obtained from the fitting of Equation 1 to these data (Figures
5 to 7). It had previously been observed (8) that for the lower range of
Reynolds numbers, positions A, B and C are in an entranee zone eharaeterized
by a developing laminar layer where the deposits are mueh thieker, as shown
~n Figure 5.
It appears that partiele transport will be the proeess eontrolling
20r-------------------~
16
~
.... B
x:
N
12
E
~
8
2
8~
a:
"
@ProcessEng
OL...----L__.....J._ _---'-_ _....J-_ _....L-.........J
O 2000 4000 6000 8000 10000

Re
Figure 5. Asymptotie thermal resistance

178
deposition for Re less than about 4000 (Ød = øt). The mass transfer mechanisn
is expected to be turbulent diffusion, because the dimensionless relaxation
time, given by:
(v*)2. D D2
,p P
(8)
18 \lU
is much smaller than 0.1, for the kaolin particles in this range of Reynolds
numbers (t; <0.015). In faet, for 2300<Re<3850, the average dependence of
ø t (~Ød) on Re, obtained from Figure 6 is (9):
Ød- Re O • 73 (9)
quite similar to the dependence usually found when turbulent diffusion
mechanisms are present. It should be stressed that the increase in R~with
Re is due to the increase not only in Ød but also in the relative cohesion
of the deposit, as shown in Figure 7. For this case, parameter a of Pinhei-
ro's model was found to have avalue of 2.4 (1), indicating that-the increasE
in the "mechanical strength" of the deposit is higher than the increase in
the fluid shear stress.
For Re> 4000, a change of control seems to occur, as shown by the
gradually decreasing values of Ød' Here, adhesion is the slower process,
therefore determining the rate of deposition (Ød =Ø a ) , with b =1 (1).
Changes of control were also observed by other authors in particulate
and precipitation studies (6, 10, 11).
3.2.2. Tests with magnetite partieles. A pure magnetite suspension and a
mixed kaolin-magnetite suspension were used in two fouling tests with Re
= 6900 and pH = 7.5. The magnetite concentration was 0.3 Kg/m3 in both
tests and the kaolin concentration was kept at 2.2 Kg/m3 . Table 1 compares
the data from these two runs with those obtained using only kaolin at the
same Reynolds number and pH. The deposition flux (Ød) was reduced in the
presence of magnetite, and the deposit cohesion (l/S) was increaEed. The
faet that tp+~ 0.1 for the magnetite particles suggests that the transport
proces s will probably be determined by an inertial mechanism (12), resulting
in higher values of the transport flux. In faet, if a particle transport
model such as that of C. N. Davies (13, 14) is used to estimate the mass
transfer flux (J t ) for the pure kaolin and the pure magnetite suspensions,
substantially greater values are obtained in the second case:
Jt (pure kaolin) 7.7 .10-8 Kg/m 2 s
J t (pure magnetite) = 5.4 .10- 6 Kg/m 2 s
2,0 r - - - - - - - - - - - - - - - ,
1,6 ,
III
3: " ,
.... '+..
x: 1,2
N ' ... ...... D
E
... 0,8
"'+...
2
-æ
@ProcessEng
0,4
OL-~_~_~_~_~__J
O 2000 4000 6000 8000 10000

R~
Figure 6. Deposition flux
179
1,5 . - - - - - - - - - - - - - ,
1,0
ID
'"
'o
IQ.
...... 0,5
~
~
E------
D -
OL_~l _ _~l_L_~__~__~
O 2000 4000 6000 8000 10000
Re
Figure 7. "Resistance to removal" of the kaolin deposits
Obviously, if mass transfer were the governing step, the experimental

deposition flux would show higher values for the magnetite deposits, which
was not the case. This leads to the assumption that adhesion was also the
controIling process during magnetite deposition at Re = 6900. Therefore, the
conclusion from Table 1 is that the adhesion process is "more difficult" (or
"slower") in the formation of pure magnetite deposits than in the formation
of pure kaolin deposits.
Note that in spite of the higher total concentration of particles in the
kaolin/magnetite experiments, the fouling rate is again lower than in the
pure kaolin tests. The values of Rf for t = 10 days confirm the slowness of
the fouling proces s when there are magnetite particles in suspension.
4. BASIC STUDY OF TRE ADRESION FORCES IN TRE DEPOSITS

4.1. Theory and Equations
In the case of particulate deposition, the physical forces of adhesion
(mainly van der Waals and electrostatic forces) seem to play the more
important role since it is supposed that no chemical reactions or phase
changes are involved in the buid-up of these deposits. While van der Waals
forces are almost always attractive, the electrostatic double-layer forces
originate repulsion effects when the surface charges of the particles are
of the same sign (as is the case in this study). Equations for the calcula-
tion of these forces are presented below in orde r to show the potential
Table 1. - Results with suspensions containing magnetite(fully developed

flow region)
9
Re Suspended Ri'" 104 Yf Ød ·10 ( 1I S) .10-6 Rf for
Particles (m 2 K/w) (microns) (m 2K/J) (seconds) t =lOdays
Kaolin(2.2Kg/m 3 ) 5.0 81 1. 19 0.42 4.4 .10- 4

@ProcessEng
Magnetite(0.3KgI
1m3 ) 3.9 76 0.79 0.42 3.2 .10- 4
6900
Kaolin(2.2Kg/m3 )
+Magnetite(0.3KgI
1m3 ) 5.0 69 0.75 0.66 3.6 .10- 4
180
usefulness of a more detail ed interpretation of the adhesion process. A

deeper theoreticaI understanding of the phenomenon is available in this
book and elsewhere (15,16,17,18).
4.1.1. van der Waals Forces. In the case of two different spherical
particles of radii R1 and RZ, these attractive forces can be estimated by:
A' Rl RZ
(10)
6(Rl+RZ) HZ
where H is the separation distance between the two particles and A' is the
Hamaker constant. For two particles of the same material ~ in vacuum, the
Hamaker constant is given by (16, 18):
3
( 11)
4
Nl is the number of molecules per unit volume, Il is the ionization potential
of the material and a 1 is the polarizability of the material given by (19):
3 njZ - 1
al = ( lZ)
41TN 1 n1 2 + Z
nl being the refractive index of the material.
For two particles of different substances (1 and Z) immersed in a third
medium (substance 3), the Hamaker constant will be:
Al 3 Z = (fA11 - fA33) . (fA22 - VA33) ( 13 )
If substances 1 and Z are the same, the last expression results in
(14)
4.1.Z. Electrostatic Double-Layer Forces. Phenomena Buch as the
dissociation of surface groups and the adsorption of ions from the liquid
phase tend to create charges on the surfaces of the particles. In orde r to
maintain the overall system electrically neutral, oppositely charged solutioI
ions concentrate near the solid surfaces. Each particle will then have its
own electrostatic double-layer that may interact with similar double-layers
of other particles.
For two different particles, and Z, immersed in a liquid, the double-
-layer force is (ZO):
E R1RZ(1y01Z+'rOZZ) .exp(-H/o) {ZIfOl 'rOZ }
FR=- Z (R 1+RZ)' o. [l-exp(-ZH/o)] Y012+yOZz - exp(-H/o) (15)
E is the dielectric constant of the liquid. 'Y 01 and 'YOZ can be considered to
be similar to the zeta potentials of particles 1 and Z, and ois the thick-
ness of the double layer. This equation is reasonably valid for values of
~ 01 and YOZ less than 50-EO mV (ZO)and for double-layer thicknesses that ar(
small compared to the particle size(R~10.8) .The thickness of the double-
layer (8) is given by:
1 ,4 e Z (zi Z nio) (16)
-02 E KB T .
e = 1.6 .10- 19 Coulomb ~s the charge of the electron, KB ~s the Boltzmann
@ProcessEng
constant (1.3805 .10- Z3 J/K), zi is the valency of ion i and nia is the
number of ions i per unit volume of the liquid. In the case of water, E =
=717.10- 1Z (Coulomb)Z/Nm Z and zi=l or -1.
4.1.3. Force of Adhesion and Potential Energy of Interaction.The resultant
adhesion force (F T) is the sum of the two forces described above:
( 17)
181
although a few other eontributions to the overall bond effect could be

considered (21, 22, 23). The potential energy of interaetion (V T) and the
force of adhesion are related by:
FT --~
dH (18)
Figure 8 shows the typical shape of the Potential Energy of Interaction
versus Distance curve for the case of two solids with surfaee charges of the
same sign (15) (Bohr repulsions at very short distances are also eonsidered
in this schematic representation).
The distance at which adhesion occurs has an outstanding effect on the
intensity and stability of the interactions between the two bodies. For
instance, particles depositing in a secondary minimum ean be more eas ily
removed than those stabilized in a primary minimum.
The existence of an energy barrier makes adhesion more difficult and
ean explain why in some situations this process controls the deposition rate.
In faet, as Rajagopalan and Kim (24) noted in the cases where an energy
barrier exists, an increase in the fluid velocity originates a decrease in
the concentration of the particles at the secondary minimum, due to; i) the
relatively weak adhesion force that makes removal more efficient; ii) the
difficulty of the particles to overcome the energy barrier. The result is
that the deposition flux will decrease with higher velocities, meaning that
it is control led by the adhesion process.
The shape of the curve of Figure 8 depends on various factors, such as
Potencial Energy
of Interaction
Energy
Repulsion
-l~----~~---j~--~~~::::::~~::==~separation
Atract ion distance
@ProcessEng
Primary minimum
Figure 8 - Potential energy of interaction

182
the ionic strength of the solution, the surface charge potential (pH effects
included) or the value of the Hamaker constant (21, 22, 25). In particular,
a greater Hamaker constant tends to decrease the height of the energy
barrier and to flatten the secondary minimum (21,22).
4.1.4. Hydrodynamic force in the rotating apparatus. In a concentric
cylinder apparatus with a rotating outertube the relationship between the
wall shear stress (rw ) and the angular velocity (w) can be obtained from
the foliowing correlation developed by Wendt (17, 26):
T w = 0.5 e .w 2 % 2 0.0013 [0.04 +(Ri/R o ) 10] (19)
where e is the density of the liquid and Ri and Ro are the inner and outer
radii of the annulus, respectively.
Assuming that the partices deposited on the inner surface of the
annulus are located in a laminar sub-Iayer, the hydrodynamic force (FH)
exerted by the fluid on them can be estimated by:
CD v 2 \' Ap
(20)
2
where Ap is the projected area of the particle (perpendicular to the
direction of flow), v is the local fluid velocity and CD is the drag coef-
ficient (=24/Re p in the Stokes regime). Rep is the particle Reynolds number
based on the particle equivalent diameter (D p ) and on the local fluid
velocity at a distance equal to the half-thickness of the particle. The
expression of the universal velocity profile in the laminar sublayer is:
v = y (T W /ll) (21)
If Y = Yc ' the half-thickness of the particle (i.e., the distance of the
adhesion surface to the center of the particle), Equation 20 will give:
TW
(22)
Dp
The work of Visser (16, 17, 18) showed that the numerical values of the
adhesion and hydrodynamic forces are identical, that is:
(23)
which enables the experimental determination of the adhesion force by
carrying out tests in this type of rotating apparatus.
4.2. Results and Discussion
4.2.1. Kaolin deposits. a) The two-Iayer structure of the deposits. Figure
9 presents the results found in the rotating cylinder apparatus using
samples of copper tubes fouled by kaolin-water suspensions. These deposits
were obtained in the developed flow region of the annular heat exchanger at
the Reynolds numbers, (Re)h.e., indicated in the Figure.

As expected, the mass of deposit removed from the sample tube increased
with the velocity of rotation, that is, with the hydrodynamic force exerted
by the water. However, all the curves show a clear transition point that
separates an eas ily removable portion of thedeposit from a very cohesive
layer. The results confirm the existence of layers with different adhesion
characteristics within the same deposit, the outer ones being rather "loose"
and the inner ones much more "rigid" or "hard".
@ProcessEng
Note that the mass percentage of "hard" inner layer goes from 50% to
70% and that this layer is practically not removable even at high
velocities. The increase in the mass percentage of hard layer from Re=2300
to Re=4140 is substantial and may explain the increase in Rf~with the
Reynolds number at the lower velocity range; it constitutes also an argument
to support the assumptions included in the removal term of Pinheiro's model.
183
60
(Reke.:' Z300
.- •
-i
o
Ul
> ~ (Re)....~ 'CJØO
O
~
Ul
a:
40
/. . •
t:
!Il
ta•l ......,"
O
!l.
Ul
o 20
u..
O
o
o
•
O~--~----~----~----~--~
O BO 120 160 200
rot/sec
Figure 9. - Mechanical resistance of the kaolin deposits
In the case under study, Equation 19 can be written as:

TW= 5.5 .10- 4 nr 2 (24)
where nr is the number of rotations per second (r.p.s.).
The shear stress in the annular heat exchanger, (TW )h.e.' can be
estimated by:
(25)
2
where f is the Fanning friction factor (obtained from pres sure drop measure-
ments). For equal values of the two shear stresses (Equations 24 and 25),
the folIowing values of the velocity of rotation are obtained: 29 rps for
Re = 2300; 52 rps for Re = 4140; 78 rps for Re = 6900, showing that the
hydrodynamic force acting in the annular heat exchanger could not remove
the inner layer of the kaolin deposits, but was able to affect the outer
"loose" layer quite easily.
The fact that particles can deposit in the primary m~n~mum or in the
secondary minimum offers some explanation for the existence of a "hard" and
a "loose" layer in the same deposit. If the particles in the outer layers
remain on the deposit for a sufficient time, they can be gradually "pressed"
against the inner layers as the deposit grows, thereby increasing their
probability of reaching the stable primary minimum. Other authors (27)
suggest that in some cases the adhesion between solid surfaces may increase
with time due to the slow reorientation of electrical charge s at the
surfaces. This could happen in the inner layers of a deposit since they are
not being affected by the hydrodynamic removal forces.
@ProcessEng
b) Approximate calculation of the adhesion forces. The Van der Waals

force can be roughly estimated as a function of the separation distance
considering the folIowing kaolin properties: molecular weight = 242;
refractive index = 1.56; density = 2600 Kg/m3 ; N1 = 6.47 .10 27 molecules/m 3
and Il = 9.58 .10- 19 Joules per molecule (the ionization potential of
aluminium). The value obtained for the Hamaker constant of kaolin was:
184
A11 ~ 4.20 .10- 20 J

The polarizability of water is (19):
a3 ~ 1.44 .10- 30 m3
giving:
A33 ~ 3.76 .10- 20 J
Thus, when two kaolin particles interact in water:
A131 ~ 1.21 .10- 2 2 J
Precise values of the separation distance between the kaolin particles in
water are not known. According to Grim (28) and Norrish (29), an almost-
-crystalline water layer is formed between clay particles, its thickness
varying from a few angstroms to hundreds of angstroms, depending on the
swelling properties of these minerals. In the case of kaolinite, swelling
is much less pronounced than in other clay minerals such as montmorillonite.
Thus, it is not unreasonable to assume a particle separation distance of the
order of 10 Angstroms for kaolinite, this being a common value of the thick-
ness of the crystalline water interlayer when swelling is not significant
(29) .
Although the kaolin particles are similar to discs, their surfaces are
far from being smooth and the contact between two neighbouring particles is
probably established at one or two points. Assuming that there is only one
point of contact, the sphere-sphere approach can be roughly used replacing
the diameter of the sphere by the thickness of the kaolin particles (1~ m).
Considering that each particle in the deposit is surrounded by eight other
particles,Equation 10 gives, for H ~ 10 Å :
FA ~ 4.0.10- 11 N
The electrostatic double-layer force can be estimated using the value
of the zeta potential at pH 7.5 obtained from Figure 4. The thickness of
the double-layer is (Equation 16):
6 = 1. 54 .10- 7 m
considering that the only ions in the liquid are H+ and OH-o Then (Eq.15):
F R =-1.2.1O- 11 N
and the resultant adhesion force will be:
F T = 2.8.10- 1 1 N
On the other hand, the hydrodynamic force exerted on the kaolin deposit
in the rotating cylinder tests can be calculated from Equation 22, taking
into account that for the kaolin particles Ap = 16 .10- 12 m2 , Yc = 0.5.10- 6
m and Dp = 7.3 .10- 6 m, giving:
FH = 7.26 .10- 15 n r 2
The equality between FT and FH implies that:

n r = 62 rps
which seems to be a very reasonable value when compared with the results
shown in Figure 9.
4.2.2. Deposits with magnetite. The kaolin-magnetite deposit obtained in
the annular heat exchanger with Re ~ 6900 showed a stronger "mechanical
@ProcessEng
resistance" than the pure kaolin deposit formed at the same operating
conditions (cf. Figures 9 and 10): the "hard" inner layer of the mixed
deposit represents 80% of the total mass of the deposit, against about 50-
60% for the pure kaolin situation. From the results of Table 1, it appears
that the rate of adhesion in the mixed deposit is lower than in the pure
kaolin deposits, although at the same time the adhesion forces are stronger.
185
60~----------------------------~
o
~
D
~ 40
lJ.J
ex::
t:
(j)
D
Cl.
lJ.J
O
20
• D •
.-.
U-
D
OL---~----~----~----~--~
O 40 60 120 160 200
rot/se,
Figure 10. - Mechanical resistance of the kaolin-magnetite deposit
a) Approximate calculation of the adhesion forces. It is highly probable

that a significant part of the interactions in these deposits will occur
between kaolin particles, due to the greater concentration of this material
in the suspension. Nevertheless, there is a clear indication that the
presence of magnetite affects the overall system, and even a rough estimate
of the adhesion forces between the two types of particles may lead to a
better understanding of the synergic effects aIready detected.
Magnetite has the folIowing properties: molecular weight = 232;
refractive index = 2.42; density = 5200 Kg/m 3 ; N2 = 1.35 .10 28 molecules/m3 ;
12 (ionization potential of the iron) = 7.19 .10-19 J/molecul~ The Hamaker
constant of magnetite will be :
A22 = 11.5 .10- 20 J
while for kaolin plus magnetite particles immersed ~n water this parameter
has the folIowing value:
A132 0.28 .10- 20 J (26)
The Van der Waals force ~s then given by:
2.23 .10- 28
FA =
H2
In the case of surfaces with dissimilar zeta potentiaIs, the 10wer one
(that of magnetite, 0.04 V) appears to determine the intensity of the
repulsive forces (16).
There are however no indications about the probable distance of inter-
action (H) between the particles of magnetite and of kaolin, but the order
of magnitude of the overall adhesion force (FA) can be seen in Table 2, as-
@ProcessEng
suming that each magnetite particle is surrounded by five kaolin particles.

The theoreticaI values given by Equation 26 and in Table 2 are much greater
than those obtained for the pure kaolin deposit, showing a qualitative
agreement with the experimental results presented in Figures 9 and 10.
b) Interpretation of the results. At first sight, the higher cohesive forces
in the mixed deposit seem to be in contradiction with its lower rate of
adhesion (or the increased difficulty of adhesion). This could b-e---
tentatively explained by the fact that the Hamaker constant is 23 times
186
Table 2. - Adhesion forces between kaolin and magnetite particles
Interaction Overall
distance, H Adhesion Force, FT
(Å) (N)
10 1. 11 x 10- 9
20 2.7 x 10-10
50 3.6 x 10-11
greater for the mixed deposit than for the pure kaolin layers, leading to a
more flattened secondary minimum and to a smaller energy barrier (see point
4.1.3.). Therefore, the probability of a stable adhesion at this secondary
minimum is rather low on account of the weak bond forces present, which woulc
explain the small percentage (20%) of the "loose" layer in the kaolin-magne-
tite deposits. However, those particles that succeed in overcoming the
relatively small energy barrier will stabilize at the primary minimum where
the adhesion force is supposed to be stronger (Table 2) than for the pure
kaolin deposits. In short, the behaviour of the mixed deposits could be
described by the existence of a certain "induction" or "delay" per iod before
a stable adhesion is obtained but once this is achieved the result is a more
compact and rigid fouling film.
It must be emphasized that the interpretation given above is no more
than an attempt to show the potential applications of the studies of the
physical-chemistry of surfaces on the analysis of actual fouling situations,
at least from a qualitative point of view. The approach presented in this
text is a ve ry simplified one, since many other factors may affect the
adhesion phenomena in the kaolin-magnetite deposits, such as: the different
shapes of the two types of particles, the amphoteric nature of aluminium,
the possibIe creation of opposite charges on the edges of kaolin particles,
etc.
5. FINAL REMARKS
From a practical standpoint, the work carried out so far with kaolin
and kaolin-magnetite suspensions in water showed that it is possible, at
least in simple situations such as pure particulate fouling, to make some
kind of useful predictions about the characteristics of the deposit build-
-up (the properties of the foulant fluid must be known, of course). For
instance, the greater strength of the pure magnetite as well as of the
kaolin-magnetite deposit could be foreseen knowing the zeta potentials of
both materials and evaluating the Hamaker constants of each system.
TheoreticaI predictions of the rate of fouling are still not feasible

in most cases, but the use of general fouling models containing two or
three empirical parameters can be of some hel p if simulation experiments
are conducted with carefully chosen operating conditions (taking also into
account the geometry of the equipment), in order to evaluate those parameter
The identification of the proces ses controIling the fouling rate is
important because it shows the mechanisms upon which the calculations
@ProcessEng
should be based. For instance, when diffusion mass transfer is the controI-
ling process, the prediction of fouling tendencies is facilitated by the
existence of reliable mathematical tools describing that transfer phenomenon
The analysis of the curve of the potential energy of interaction may
also be an important source for the detection of the type of process
controIling inorganic deposition; further investigation is needed in order
187
to apply the surface forces approach to the interpretation and prediction

of actual fouling cases.
ACKNOWLEDGEMENTS
The financial support of JNICT, Portugal, through Project No. 212.80 .
. 36 is gratefully acknowledged. The authors wish to thank also Dr. Luisa
Leitao (University of Coimbra, Portugal) for the experimental determination
of the zeta potential curves and Dr. J. Visser for his helpful comments on
the subject of this paper.
LIST OF SYMBOLS
A' - Hamaker constant (generic case), J
A.· - Hamaker constant for the system i-j, J
ApD _ particle area perpendicular to the flow, m2
a,b - empirical parameters in Pinheiro's model
Cb - bulk suspension concentration, Kg/m3
CD - drag coefficient
Dp - equivalent particle diameter, m
f - friction factor
FA - van der Waals force, N
FH hydrodynamic force in the rotating apparatus, N
FR - electrostatic double-layer force, N
FT - overall adhesion force, N
H - separation (interaction) distance, m
Ii ionization potential of substance i, J/molecule
Jt - mass transfer flux, Kg/m 2 s
K1,K2,K3 proportional it y constants
Ka - adhesion coefficient, m/s
KB - Boltzmann constant, J/K
Kf - thermal conductivity fo the deposit, W/mK
Kt - transport coefficient, m/s
Ni - number of molecules of substance i per unit volume, m- 3
ni - refractive index of substance i
nio - number of ions i per unit volume of solution, m- 3
nr - number of rotations per second, s-1
R1' R2 - radii of particles 1 and 2, m
Ro, Ri - inner and outer radii of the rotating apparatus, m
Re - Reynolds number
Rf - thermal resistance of the deposit, m2K/W
R~ - asymptotic thermal resistance of the deposit, m2K/W
T - fluid temperature, K
t - time, s
t p+ particle dimensionless relaxation time
v - local fluid velocity, m/s
v average fluid velocity, m/s
v* - friction velocity, m/s
VT - overall potential energy of interaction, J
Y - distance normal to the deposition surface, m
@ProcessEng
Yc - half-thickness of the particle, m

Yf - thickness of the deposit, m
zi - valency of ion i
ai polarizability of substance i, m3
S - parameter related to the cohesiveness of the deposit, s-1
E - dielectric constant, (Coulomb)2/Nm 2
o - thickness of the electrostatic double-layer, m
188
Ød deposition flux, in termal units, m2K/J

Ør - removal flux, in thermal units, m2K/J
øt particle transport flux, in thermal units, m2K/J
~oi - zeta potential of substance i, V
~ - fluid density, Kg/m3
~f - density of the deposit 3 Kg/m 3
~p - particle density, Kg/m
~ - dynamic viscosity, Ns/m 2
v - kinematic viscosity, m2 /s
Tw - wall shear stress on the inner tube of the rotating apparatus, N/m 2
(Tw)h.e. - wall shear stress in the annular heat exchanger, N/m 2
w - angular velocity of the rotating apparatus, s-1
REFERENCES
1 . Melo,L.F. and J.D. Pinheiro, "Particulate fouling: controIling processes
and deposit strucutre", 8th Intern. Heat Transfer Conf., Vol. 6, Paper
HX-16,2781-2786, S. Francisco, USA, 1986.
2 Kern, D. and R. Seaton, "A theoreticaI analysis of thermal surface
fouEng", Brit. Chem. Engin., 4(5), 258-262, 1959.
3 Pinheiro, J.D., "Fouling of heat transfer surfaces", in "Heat exchangers
Thermal-Hydraulic Fundamentals and Design", Ed. byKaka\;, Bergles and
May inger , 1013-1033, McGraw-Hill, 1981.
4 . Pinheiro, J.D., "Fouling of heat exchangers - discussion of a model",
Intern. Semin. Advanc. in Heat Exchangers, Intern. Center of Heat and
Mass Transfer, Dubrovnik, Yoguslavia, 1981.
5 . Taborek, J., Aoki, T., Ritter, R.B.Palen, J.W. and J.G. Knudsen,"Fouling
the major unresolved problem in heat transfer", Chem. Eng. Progr., 68(2)
59-67, 1972.
6 Watkinson, A.P. and N. Epstein, "Gas oU fouling in a sensible heat ex-
changer",-'Chem. Eng. Progr. Sump. Ser., 65(92), 84-90, 1969.
7 Crittenden, B. and S.T. Kolackzkowski, "Energy savings through accurate
prediction of heat transfer fouling resistance", in "Energy for industry'
Ed. by O'Callaghan, 257-260, Pergamon, Oxford, 1979.
8 Melo, L. and J.D. Pinheiro, "Hydrodynamic effects on particulate
fouling", I. Chem. Engrs. Symp. Ser., No. 86. Vol.1, 381-390, 1984.
9 Melo, L. and J.D. Pinheiro, "Particle transport in fouling caused by
kaolin-water suspensions on copper tubes", to be published in Can. J.
Chem. Eng., Vol. 65, Det:. 1987.
10. Watkinson, A.P., Louis, L. and R. Brent, "Scaling of heat exchanger tu-
bes", Can. J. Chem. Eng., 52, 558-562, 1974.
11. Watkinson, A.P. and O. Martinez, "Scaling of heat exchanger tubes by
calcium carbonate", J. Heat Transfer, 504-508, 1975.

12. Wood, N.B., "A simple method for the calculation of turbulent deposition
to smooth and rough surfaces", J. Aerosol ScL, 12(3),275-290,1981.
13. Davies, C.N., "Deposition of aerosols from turbulent flow through pipes"
Proc. Roy. Soc. London, Ser. A, 289, 235-246, 1966.
14. Davies, C.N., "Brownian deposition of aerosol particles from turbulent
flow through pipes", Proc. Roy. Soc. London, Ser. A., 290, 557-562,1966.
@ProcessEng
15. Shaw, D.J., "Introd. to Colloid and Surface Chernistry", Butterworths,

London, 1980.
16. Visser, J., "The adhesion of colloidal particles to a planar surface in
aqueous solutions", Ph.D. Thesis, London, 1973.
17. Visser, J., "The adhesion of colloidal polystyrene particles to
cellophane as a function of pH and ionic strength", J. Coll. InterLSci.
~(3), 664-667, 1976.
189
18. Visser, J., "Adhesion and removal of particles - I and II", in "Fouling
Science and Technology", Ed. by Melo, Bott and Bernardo, Kluwer Academic
Publishers, 1988.
19. Barrow, G.M., "Physicai Chemistry", 2nd Ed., McGraw-Hill, 1966.
20. Hogg, R., Healy, T.W. and D.W. Fuerstenau, "Mutual coagulation of col-
loidal dispersions", Transf. Faraday Soc., 62, 1638-1651,1966.
21. Ruckenstein, E. and D.G. Kalthod, "Role of hydrodynamics and physical
interactions in the absorption and desorption of hydrosols or globular
proteins", in "Fundam. and Appl, of Surf. Phenom. Assoc. with Fouling
and Cleaning in Food Processing", 115-147, Univ. Lund, Sweden, 1981.
22. Ruckenstein, E. and D. Prieve, "Absorption and desorption of particles
and their chromatographic separation", AICHE J., 22 (2), 276-283, 1976.
23. Schubert, H., "Particle adhesion to solid surfaceS", in "Fundam. and
Appl. of Surf. Phenom. Assoc. with Fouling and Cleaning in Food Proces-
sing", 57-75, Univ. Lund, Sweden, 1981.
24. Rajagopalan, R. and J.S. Kim, "Adsorption of brownian particles in the
presence of potential barriers: effect of different modes of double-
-layer interaction", J. Coll. Interf. Sci., 83(2), 428-448,1981.
25. Prieve, D. and E. Ruckenstein, "Double-layerLnteraction between
dissimilar ionizable surfaces and its effect on the rate of deposition",
J. Coll. Interf. Sci., 63(2), 317-329, 1978.
26. Wendt, F., "Turbulent Stromungen zwischen zwei rotierenden konaxialen
Zylindern", ing.-Arch., 4, 577-595, 1933.
27. Van den Tempel, M., "Interaction forces between condensed bodies in
contact", Adv. Coll. Interf. Sci., 3, 137-159,
28. Grim, R.E., "Clay Mineralogy", 2nd Ed., McGraw-Hill, 1968.
29. Norrish, K., "The swelling of montmorillonite", Disc. Faraday Soc., 18,
120-134, 1954.
@ProcessEng
GAS SIDE FOULING
T.R. BOTT
Department of Chemical Engineering, University of Birmingham, PO Box 363,

Edgbaston, Birmingham BiS 2TT, England.
l. INTRODUCTION
The problem of gas side deposition is apparent in a wide range of
industries, where particles are carried in a gas stream. The problem can
be manifest in dryers, gas lines, reactors, and combustion spaces, as well
as heat exchangers involved in gas processing. The examples indicate that
the temperature range over which deposition may be encountered is extremely
wide, covering temperatures from ambient to well over 1400 K.
The particulate matter involved can also cover a wide range of
materials including mineral matter, organic particles and natural products
like wood particles. Inorganic substances together with possibly carbon
particles, are common foulants in combustion systems burning traditional
fuels like oil and coal. Similar deposits may also be found in newer
combustion systems like waste derived fuels such as domestic refuse or
motor car tyres. The deposition of particles of organic material may be a
problem in air swept dryers, for example in the continuous drying of
impregnated paper or fabric for the manufacture of laminated plastics. In
this example the particles are generally in the form of liquid drops, but
if they are exposed in the air stream for any length of time they could
arrive at the "target" surface in the form of solid particles. In two
phase flow systems, usually involving droplets and a gas phase, droplet
deposition in heat transfer operations is of considerable importance,
particularly in relation to the problem of "burn out" in boilers and
vaporisers. In extraction systems such as may be found in a wood saw mill,
the particles carried forward will be wood dust. Size reduction plant will
also experience the problem of particulate deposition.
Particle size and shape will also vary considerably depending upon the
orLgLn of the particle and the kind of system involved. Particle sizes
from submicron to a few mm in diameter could be experienced, even in one
particular system.
As far as the fouling of heat exchanger systems by particulate matter
is concerned there are probably two areas which may be considered to be

dominant; fouling from combustion gases, eg. boilers or pipe stills, and
dust deposition in air cooled heat exchangers. Deposition in other heat
transfer systems such as dryers, although important, are general ly more
specific but nevertheless the principles of particulate deposition are
applicable.
The fouling of a heat exchanger sur face due to particulate matter
@ProcessEng
involves the same basic mechanisms as other fouling problems, namely:

l. Transport of particles to the surface.
2. Adhesion of particles (or agglomerates) to the surface.
3. Removal of particles from the surface.
However, the detail of these mechanisms will vary depending upon the
overall fouling proces s involved, and for solid particles suspended in a
191
L. F.Meloet al. (eds.), FoulingScience and Technology, 191-203.

192
gas stream the fluid dynamics and the particle/gas interaction will be
dominant in the deposition process.
In high temperature systems particularly, it is also possibie for
material to be transported to the surface by vapour diffusion rather than
in particulate form, so that at the surface some sort of condensation takes
place. In some examples vapour diffusion could lead to corrosion of the
heat transfer surface, which will add further to the growth of the deposit
on the surface.
2. PARTICLE DEPOSITION
Particle deposition from flowing streams has been studied extensively
over a long period, much of the work involving deposition of aerosols. In
other work the systems have been well defined, which may be regarded as
somewhat ideal, but which nevertheless does give some indication of the
effects of certain v~3iables3 The particle diameter range covered is at
leas t in the range 10 to 10 #m (l). Some of the early work ignored the
presence of the boundary layer in the fluid near the target surface, yet as
with many transfer processes, the presence of the boundary region will have
a major influence not only on deposition, but on the removal of particles.
2.1 Transportation of particles towards the surface

The transport of particles towards a solid surface such as a heat
exchanger surface can be visualised as involving two stages; transport
through the bulk gas stream to the boundary region followed by transport
across the boundary layer to the wall. The major mechanisms in the former
process will be:
Brownian motion resulting from concentration

Eddy diffusion gradients
Thermal diffusion resulting from temperature gradients
Gravitational influences depending upon density differences, could

also be a fouling mechanism in certain examples, particularly where gas
velocities are low.
Once in the region of the boundary layer, the smaller particles
particularly, may be influenced by electrostatic forces.
Transport of particles across the boundary region will have
corresponding mechanisms to those for transport through the bulk gas, and
include:-
Particle diffusion
Initial impaction
Thermal diffusion (Thermophoresis)
2.2 Particle diffusion

Small diameter particles below about 0.1 #m are subject to the
diffusional proces ses which are generaily associated with mass transfer
operations, resulting from a concentration gradient which acts as a driving
force. For this reason the general equations for mass transfer may be
applied, and consideration given to the passage of particles across the
boundary layer.
@ProcessEng
In turbulent flow the rate of mass transfer to unit are a may be

expressed.
N = (DB + e) dc (l)
dy
where DB and E are the coefficients of molecular diffusion and eddy

193
diffusion respectively.
Particle diffusivity may be determined from
(2)
where KB is the Boltzmann constant
TI the absolute temperature

and F a resistance term related to Stokes' law
Thermal diffusion is an important consideration in the transport of small

diameter particles under the influence of a temperature gradient or,
driving force. Bemrose (l) states that it applies to particles up to 10 ~m
diameter but is only significant for particles below 2 or 3 ~m diameter.
The movement arises from the difference in agitation of particles at
different levels in temperature. In a temperature gradient a particle at
a particular point will have on one side, particles at a slightly higher
temperature and at the other, at a slightly lower temperature. The
increased agitation of the hotter particles puts a "pressure" on the one
side of the particle, whereas the "pressure" due to the cooler particles is
lower. The overall result is a tendency for the particle to move towards
the cool er regions. This effect will of course, be more pronounced where
cool surfaces are exposed to high temperature, particle laden atmospheres,
such as might be encountered in a coal fired boiler.
Application of theoreticaI principles to particles suspended in a
stagnant gas are straightforward, but mathematical analysis of the
situation when the particle burden is moving, is difficult. For this
reason it is only over the past twenty years that systematic study has been
undertaken. Owen (2) devised a relationship which related gas velocity to
the other variables in the system.
0.09
(3)
v*
where ~I is the terminal velocity of the particle

is the frictional velocity
vb is the gas velocity (air in Owens' theory) at the edge of
the boundary layer (ie. approximately the bulk veloeity)
Ts and Tb are the absolute temperatures of the eold surfaee and the
bulk gas respectively
As the deposition proeess continues the deposit on the cool surface

will aet as an insulator, whieh in turn will ensure that surface exposed to
the gas stream gradually increases in temperature. With the passage of
time, as the deposit thickens, the temperature difference causing the
thermophoretic effect will reduce so that the rate of deposition due to
@ProcessEng
this pheonomenon, will deerease and ultimately become almost zero.

2.3 Particle movement across the boundary region
Thermophoresis and particle diffusion will be important meehanisms by
whieh particles can cross the boundary region. .The effects of
thermophoresis are likely to be higher in the region compared to in the
bulk, due to the steeper temperature gradients. However the other
meehanism which was mentioned in the introduetion to this Section, namely
194
inertial impaction is equally important. The deposition process occurs

because of the inability of particles (above about 0.5 ~m diameter) to
follow exactly, changes in the gas stream direction. Although this
phenomenon would be apparent where gas streams changed direction eg. around
bends, it will also occur as aresult of the rapid changes in direction
which accompanies turbulent motion. It is these latter effects which are
responsible for much of the particle deposition from gas streams, and
because turbulence is difficult to model mathematically, it is difficult to
analyse theoretically the inertial impaction process. The analysis has
usually centred on a so-called "collection efficiency", which may be
defined as the ratio of particles collected by an obstacle (say a cylinder)
in a gas stream, to the number of particles contained in a cross-section of
the gas equal to the frontal are a of the obstacle presented to the gas
stream (3). A number of attempts have been made to determine the magni tude
of the collection efficiency. These assessments often include the so-
called inertial parameter
mv
k D
s
where m is the particle mass
v is the gas velocity
D is the linear dimension of the collector
k is the Stokes' Law resistance coefficient
s
Following the initial work of Sell (3), Albrecht (4) concluded that a
critical value of the inertial parameter exists, below which no deposition
by inertial impaction occurs. Taylor (5) demonstrated that particles would
not reach the surface if the group
l
9'
. p
-pp was <8l (4)
where
p and Pp are the densities of the gas and particle respectively
r and r are the radius of the particle and the cylindrical
c
target respectively
Re represents the Reynolds number f'or flow based on the
c
collector diameter (2r c )
The critical particle radius r crit which make the group

Re l (5)
c
8'
could be defined by
r cæiE- 0.75 Ær
-c
(6)
@ProcessEng
Ppv
where ~ is the gas viscosity
and v is the gas velocity
Particles with a radius below r it follow the streamlines round the

object (cylinder in the studies of Ta§Ior (5».
195
The analysis holds for particles of uniform size but in practical

examples a range of particle size will be encountered.
Under these circumstances if Stokes' Law may be applied to the
particles in the system, the overall collection efficiency can be estimated
by summing the individual efficiencies determined for individual particle
sizes under constant physical conditions.
2.4 The "stopping distance"
An alternative approach to the foregoing analysis was established in a
classical paper by Freidlander and Johnstone (6), in which they defined,
what they called, the "stopping distance". The concept has been used by
many subsequent workers in the analysis of problems related to particle
deposition. In the original work of Freidlander and Johns tone they
examined the deposition of 0.8 to 2.63 ~m iron and aluminium particles and
30 ~m lycopodium spores from air onto the inside surfaces of glass and
brass tubes from 5.4 to 25 mm diameter. It was assumed, not unreasonably,
that particles of the size studied, would follow the streamlines of the gas
in the gas core, ie. the particles would behave as gas particles in the
turbulent regime. In the boundary layer however, gas molecules are able to
diffuse to the surface whereas the solid particles, although subject to
diffusion mechanisms, could also reach the surface due to inertia effects.
The basis of the analysis of Freidlander and Johnstone was that the
solid particles would be carried in the turbulent and diffusion eddies from
the gas core to within one "stopping distance" of the wall. The so-called
"stopping distance" was that distance (~) which a particle with a given
initial velocity (v ) would travel through a stagnant gas. Clearly this
"stopping distance" ~ill involve
l. The momentum of the particle, which in turn will not only be
dependent upon the particle velocity but also its size (diameter) and its
density.
2. The frictional drag on the particles exemplified by the viscosity
of the gas through which the particle is travelling.
~ = Tv (7)
o
T is the so-called particle relaxation time
For Stokes' flow the particle relaxation time is given by
d 2
T ~
(8)
Gudmundson and Bott (7) reviewed the literature and found that if the
dimensionless relaxation time T* was defined as
where v* is the "friction" velocity and" the kinematic viscosity, it was

@ProcessEng
possible to identify the regime of particle travel and the transport

mechanism. The following Table may be constructed, which separates
inertia and impaction, grouped together in earlier analysis, through the
magni tude of the particle relaxation time.
196
TAB LE l. Particle relaxation times and transport mechanisms
Regime Transport mechanism
Diffusion <0.1 Brownian motion

Inertia 0.1> <10 Turbulent eddies
Impaction 10> <100 Momentum
The importance of inertial impaction and particle diffusion in

relation to particle size was published by Beal (8). It shows that the
minimum mass transfer coefficient occurs at a particle size of l ~m for low
velocities (- 0.3 m/s), but that at higher velocities (- 10 m/s) the
minimum occurs at a particle diameter of around 0.2 ~m. The Figure also
shows how the mass transfer is substantially increased in all regions
between 0.3 m/s and the upper velocity.
A major contribution to the theory of deposition was made by
Hutchinson et al (9) in which a model was devised allowing for differences
between particle and eddy diffusivities. Unlike the Freidlander and
Johnstone model (6) Hutchinson et al considered that particles could move
randomly in all directions due to the fluid turbulence. Such an assumption
meant that those particles ariving in the region of the boundary layer,
could move to the wall and become captured or could move back into the
turbulent core. The theory was tested against published data for particles
in the size range 0.8 - 125 ~m and Reynol~~ numbers fro~35000 - 300,000 and
a gas/particle density ratio of 1.6 x 10 to 1.5 x 10 . The agreement
was satisfactory for tubes of circular cross-section and with length to
diameter ratios between 5 and 200. The diameters were in the range 9.5
63 mm.
About the same time Beal (8, 10) developed a model for predicting the
deposition of particles carried in turbulent flow onto a channe l or pipe
wall. The method confirmed the effects of Brownian motion, turbulent
diffusion and inertial effects with applications to particles ranging from
molecular size to about 100 ~m in diameter.
In 1983 Bemrose and Bott (11) provided a list of important
contributions to the technology of gas side fouling. This information is
reproduced as Table 2, and represents a starting point for further reading.
Reference to liquid systems in addition to gas side fouling is made, since
in some respects they are related; the principle difference being the
viscosity of the fluid.
3. VAPOUR DIFFUSION
Hedley et al (36) and Samms and Watt (37) suggest that vapour
diffusion can be an important mechanism for the fouling of surfaces in
combustion systems. The transport of material towards the cooler surfaces
will depend on the vapourisation of residual combustion products usually
associated with fuel ash components. In general, the theory of mass
@ProcessEng
transfer involving molecular and eddy diffusion will be applicable to these

components, but some marked differences will apply. As the material moves
from the hot region to the cooler areas, its characteristics will change,
general ly as described by Brown (38). Fig. l shows diagramatically how the
nature of the foulant might change across a combustion gas space.
In the hottest part of the system assuming that the temperature is
sufficiently high, the diffusing material will exist as a gas. As the
197
material moves through a cooler region condensation will occur with the
possibility of droplet formation and coalescence. As the droplets continue
to move into a lower temperature region, solidification will occur, so that
the deposition proces s becomes more particulate in character. As the co Id
surface is approached the deposition becomes entirely particulate, provided
the co Id surface is at a sufficiently low temperature, as would be
available on the clean heat transfer surfaces in say, a boiler.
The location of the different zones, involving vapour, droplet and
solid particle will be under constant change due to the changing
temperature distribution as deposit thickness increases, as described in
Section 2.4. This will mean that the vapour, and droplet zones will get
nearer to the cold surface as time passes. In the limit, if vapour
diffusion were the sole mechanism for deposition, the deposit mass versus
time curve would become asymptotic because the deposit surface temperature
would be above the dew point of the diffusing species.
4. ADHESION AND REMOVAL

The discussion so far has centred on the approach of particles to a
surface from the bulk gas stream, but it provides no explanation of how the
particles adhere to the surface. The process of deposition which relies on
the fluid mechanics of the system, is general ly non-dimensional, at least
in the bulk fluid so that the forces involved could also act to transport
the particles from the surface. In the boundary region the randomness is
restricted, but instabilities within the boundary region could carry any
particles back into the stream before they come into contact with the
surface. The adhesion forces at the particlejsurface interface will
counteract the tendency for re-entrainment to occur. The physical picture
is complex, and will involve a number of contributory factors, but a simple
classification has been suggested (37). The adhesion can be separated into
two groups, depending upon whether or not there is a material bridge
between the particle and the surface. The bridging material can be either
of the same material as the particle, or a different substance.
Fur thermore the bond material could either be liquid or solid. Bonding
without a material bridge can result from electrostatic or van der Waals
forces.
It is important to stress that as the deposition proces s continues the
interfacial forces must change, as the original surface becomes
contaminated with the deposit. Factors which were important during
initiation of the fouling process, may become of minor importance during
the building up of substantial deposits.
The usual mechanism cited as being responsibIe for removal is the one
aIready referred to earlier in this Section - ie. the effect of random
disturbances in the boundary layer, often referred to as "turbulent

bursts". Cleaver and Yates (28) are often quoted as the originators of the
removal concept, and showed that wall shear stress was a controIling
parameter. There is some limited recent evidence (39) admittedly with a
particle suspension in water, that evenwith smal l particles « 2~m),
unless the particle is "rolling" along the surface a turbulent burst is
unlikely to account for a removal mechanism. The phenomenon is likely to
@ProcessEng
be further complicated if the surface is rough.
5. PRACTICAL ASPECTS OF DEPOSITION

The mathematical treatment and the discussion in the previous sections
has, of necessity concentrated on essentiaIly ideal systems. In practical
industrial situations such idealities are unlikely to be realised, although
the fundamental relationships are a useful guide to possibIe trends.
198
High Temperature
Vapour diffusion only

--- ---- - -- -------
Condensation~
liQuid droplet formation~
thermal diffusion of dropletsJ
c droplet coalescence~
-O
.+->
O
vapour diffusion .
"O l.-
O Q)
l.- 4-
"':J
en
c Solid particle forrnation~
C o
Cl l.-
+->
thermal diffusion of particles~
c:
o
._ en reduced vapour diffusion.
.j...I o
u E;
Q)
>"0
c c
o o Pa rt i c le
_9
u
tranS90rt to the surfaee onlY.
+->
o
Q)
:c
JJJWDeposit an metal
/~ surfaee
Low Temperature
FIGURE l. Deposition of particles from combustion gases

@ProcessEng
199
TABLE 2. Some theories of particle deposition
Geometry Particle size Fluid Theory Reference
Vertical, 0.B-3#m mono turbulent gas Stokes stopping 6

straight layer only distance
round tubes
Round tubes liquid Deposition and 12

removal
-l
Smooth sur- 10 #m turbulent air Eddy diffusivity 2
faces and inertial
coasting
Pipes up to SO#m turbulent aero- Eddy diffusivity 13

sols and inertial
coasting.
Vertical 0.6S-S#m turbulent a i::: Brownian motion 14

surfaces and impaction
(pipes)
Heat ex- various gas Thermophoresis lS

changer
Smooth cir- O.S-SO#m turbulent las Stopping distance 16

cular
tubes
Tubes 0.3-1. 3#m hot turbulent Thermophoresis and 17

gas Knudsen number
Vertical up to 30#m turbulent air Effective parti- lB, 19

pipe' cle eddy diffu-
sivity; re-
entrainment
Tubes l2.B-17.3#m liquid Mass transfer and 20

adhesion
Tubes (?) l-40#m turbulent gas Transverse lift 21

force
Channels or 10-2_ l02#m turbulent gas Combination of 10, B, 22

pipes Brownian diffu-
sion and inertia
@ProcessEng
Tubes .37S- 0.B-12S#m turbulent gas Different eddy 9

2.Sin. dia. and particle
diffusivity
(cont'd)
200
TABLE 2 (cont'd)
Geometry Particle size Fluid Theory Reference
Heat mainly liquid Deposition and 23, 24

changers removal
(incl.
finned
tubes)
Pipes at turbulent Diffusion, field 25

any inclina- fluid forces, sticking
tion probabilities
WaUs up to 30~m Turbulent bursts 26, 27, 28
Vertical 0.65-5~m turbulent air as for

annuli Ref. 14 29
-3 3
Gas flow- 10 -10 ~m turbulent gas Combined 30
ing paral-
lel to
surfaee
Flow past ? ? Shadow effect 31

a collector
Heat ex- various gas and liquid Review 32

changer
Extended gas and liquid Thermal resis- 33

surfaces, tances in
uniform series or parallel
deposit
Heat ex- magnetite water Deposition and 34

changer suspension, removal
tubes 2~m
Heat ex- magnetite water Demonstration of 35

changer suspension, Kern-Seaton model
tubes 2~m
@ProcessEng
201
In a low temperature idustrial system the fouling such as might be

experienced on the air side of an air blown heat exchanger, will be
essentiaIly particulate deposition. In any application of the theory some
idea of the particle size distribution will be required. Such data are
extremely difficult to obtain, largely because of the possibIe
agglomeration of particles in the air stream. Beal (22) studied the effect
of agglomeration on the rate of deposition making the folIowing
assumptions.
l. Steady state conditions
2. Collisions occurred only between particles of the same size
3. Particles remained attached to each other af ter colliding
For particles smaller than 0.01 ~m agglomeration rates exceed
deposition rates and for particles above 10 ~m in size the reverse is true.
In the particle size range 0.1 to 1.0 ~m the rates of deposition and
agglomeration were similar.
For complex geometries such as finned tubes across which dusty gases
are passing, any theory developed for plain surfaces must be severely
modified. Indeed it is highly likely that an adequate theory could not be
developed, and empLrLcLsm will be required. Particulate fouling and
friction factors were correlated by Bemrose and Bott (11) for tests in a
model air cool ed heat exchanger.
For systems in which high temperatures are involved, eg. furnaces, the
problem of mathematical treatment becomes even more difficult bearing in
mind the contributing mechanisms that occur, eg. particulate and vapour
diffusion in addition to thermophoresis. Furthermore the possibility of
chemical reaction taking place within the deposit may not be neglected,
particularly when the deposit is at a high temperature. At the same time
the condensation zone, associated with vapour diffusion, could eas ily occur
at the deposit surface or even within the deposit. The presence of this
liquid could assist the sticking of particles to the surface, and could on
subsequent cooling (as the deposit buiIds up) cement the particles together
in a hard mass, which might otherwise be a loose friable deposit. In
addition to these effects it is possibIe to obtain low melting point
deposits resulting from "fluxing" of different compounds. Again this could
contribute to a sticky surface and bonding of captured particles.
Corrosion of the heat exchanger surfaces is possibIe in the presence
of deposits, which may enhance the corrosion rate. The availability of
acidic compounds such as SO?' S03 and chlor ine compounds in combustion
gases, are often responsibIe for corrosion although complex chemical
reactions with mineral compounds and metal oxides are also possible.
Realistic models of gas side fouling would need to consider these
chemical aspects as well as the physical and fluid mechanics effects
discussed earlier.
CONCLUDING REMARKS
Gas side fouling is a complex phenomenon. It is possibIe by making a
number of simplifying assumptions, to model the mass transfer of particles
and vapours to a surface, but of necessity, these represent ideal
situations general ly far removed from practical problems. Nevertheless
@ProcessEng
these simplified approaches do indicate the general effects of certain

variables. But the idealised models presented so far, are extremely
limited and before reliable models suitable for design purposes, can be
formulated, a great deal more investigative work needs to be carried out.
Even then the models developed, will probably only be applicable to
specific well defined, situations, and different models will be required
for different conditions.
202
Well controlled tests using probes, as described earlier, are likelJ

to yield the most useful data not only for the evaluation of particular gal
side fouling problems, but for the eventual construction of usefu:
mathematical models.
ACKNOWLEDGMENT
The author would like to record his thanks to his friends anc
colleagues, Drs. Colin Bemrose and Andrew Tsados, for useful discussionl
and suggestions.
REFERENCES
l. Bemrose, C.R. Ph.D. Thesis, University of Birmingham 1984.
2. Owen, P.R. Int. J. Air Pollution 3, 8, 1960.
3. Sell, W. Ver Den Inf. Forschungsheft 347, 1931.
4. Albrecht, F. Physik 2, 32 48 1931.
5. Taylor, G.I. "Notes on possible equipment and technique for experiment
on icing of aircraft" Reports and Memoranda No. 2024 15th Jan 1940.
6. Freidlander, S.K. and Johnstone, H.F. Ind. Eng. Chem. 49 1151 1957.
7. Gudmunds en , J.S. and Bott, T.R. J. Aerosol Sci. 8 317 1977.
8. Bea1, S.K. Nuc1. Sci. Eng. 40 l, 1970.
9. Hutchinson, P., Hewitt, G.F. and Duckler, A.E. Chem. Eng. Sci. 26 41
1971.
10. Bea1, S.K. "Transport of particles in turbulent flow to channel or pip
walls" Westinghouse Electric. Corp. Report, Microfische No. WAPD-TM
765. 1968.
11. Bemrose, C.R. and Bott, T.R., in Bryers, R.W. (Ed.). "Foulingofhea
exchanger surfaces" Engineering Foundation New York 1983.
12. Kern, D.Q. and Seaton, R.E. Brit. Chem. Eng. 4 258 1959.
13. Davies, C.N. Proc .. Roy. Soc. Series A, 289 235 1965.
14. Wells, A.C. and Chamberlain, A.C. Brit. J. Appl. Phys. 18 1793 1967.
15. Hawes, R.I. and Garton, D.A. Chem. Process Eng. 48 143 1967.
16. Keen, T. and Strauss, W. Atmospheric Environment 3 55 1969.
17. Byers, R.L. and Calvert, S. Ind. Eng. Chem. Fundamentals 8 646 1969.
18. Sehmel, G.A. Aerosol Sci. 2 63 1971.
19. Sehmel, G.A. J. Geophys. Res. 75 1766 1970.
20. Watkinson, A.P. and Epstein, N. 4th Int. Heat Trans. Conf. Paris Vol.
(paper HE 1.6) 1970.
21. Rouhiainen, P.O. and Stachiewicz, J.W. J. Heat Transfer 92 169 1970.
22. Beal, S.K. J. Aerosol Sci. 3 113 1972.
23. Taborek, J. et al. Chem. Eng. Prog. 68 59 1972.
24. Taborek, J. et al. Chem. Eng. Prog. 68 69 1972.

25. Soo, S.L. and Tung, S.K. Powder Technol. 6 283 1972.
26. Cleaver, J.W. and Yates, B. J. Colloid and Interface Sci., 4446
1973.
27. Cleaver, J.W. and Yates, B. Chem. Eng. Sci. 30 983 1975.
28. Cleaver, J.W. and Yates, B. Chem. Eng. Sci. 31 147 1976.
29. Kitamoto, A. and Takashima, Y. Bull Tokyo Inst. Technol. No. 121 6
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1974.
30. Gardner, G.C. Inst. J. Multiphase Flow 2 213 1975.
31. Wang, C.S. et al. A.I. Chem. E.J. , 23 879 1977.
32. Epstein, N. Proc. 6th Int. Heat Transfer Conf. Toronto Vol. 6 235 1978
33. Epstein, N. and Sandhu, K. Proc. 6th Int. Heat Transfer Conf. Toront
Vol. 4 397 1978.
34. Newson, I.H. "Studies of particulate deposition from flowiIl
203
suspension". Gonf. Fouling Science or Art. University of Surrey,

Guildford, UK. 35 1979.
35. Newson, I.H. et al. 20th National Heat Transfer Gonf. Milwaukee,
Fouling of Heat Exchange Equipment ASME HTD Vol. 17 73 1981.
36. Hedley, A.B., et al. ASME paper No. 65 - WA/GD4.
37. Sammo, J.A.G. and Watt, J.D. B.G.U.R.A. 30 part 7 225 1966.
38. Brown, T.D. J. Inst. Energy 39 378 1966.
39. Yung, B.K.K. Ph.D., Thesis University of Birmingham 1986.
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@ProcessEng
Chapter 5
Biological Fouling
BIOLOGI CAL FOULING: BASIC SCIENCE AND MODELS
C.A. KENT
DEPARTMENT OF CHEMICAL ENGINEERING

UNlVERSITY OF BIRMINGHAM
PO BOX 363
EDGBASTON
BIRMINGHAM BIS 2TT
UNITED KINGDOM
l. INTRODUCTION
Before proceeding to the subject matter of the title it is necessary to
begin with some definitions and to define the scope of this paper.
First of all, what is biological fouling, or biofouling? It may be
considered as the deposition or growth on a surface of organisms on
materials of biological origin(2S). Such materia1 may inc1ude
microorganisms (e.g. bacteria, a1gae, diatoms, yeasts, mou1ds) and their
products, which go to make up microbia1 fou1ing. When deve10ped, this
wi11 usua11y take the form of a film, or 1ayer, over the fou1ed surface,
called a biofilm. In other cases, higher organisms, such as water weeds,
seaweed, and barnac1es form deposits known as macrobia1 fou1ing. If 1eft
10ng enough, both types of biofou1ing may occur together. It is a1so
very common for other types of fou1ant to be associated with biofou1ing,
especia11y inorganic particles such as sand or corrosion products.
The major are a of concern of this paper wi1l be microbia1, rather than
macrobial, fou1ing. Many of the principles are common to both, and it
may be argued(ll) that microbia1 fou1ing wi11 generally precede macrobia1
fou1ing. Therefore an understanding of microbia1 fouling is essentia1 to
the control of both types of biological fou1ing.
2. TRE OCCURRENCE OF BIOLOGICAL FOULING

Biofilms and other deposits of biological origin are ubiquitous in
nature, especiaily where there is f10wing water. At first sight, this
may appear strange, since the concentration of nutrients in the bulk
aqueous phase of both salt - and fresh-water environments is generally

very 10w. This provides poor conditions for growth and metabo1ism of
many heterotrophic microorganisms. However, there is a tendency for
both organic and inorganic species dissolved in the water to accumu1ate
at solid-1iquid phase boundaries, owing to the resu1ting reduced free
energy of the modified system(2S). Of the organic mo1ecu1es present as a
resu1t of past biologi cal breakdown, proteins wi11 accumu1ate at a
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solid-1iquid interface part1y because of the resultant reduction of

interactions between non-polar groups and water mo1ecu1es. This wi11
give rise to an altered activity at the solid surface(27), especia11y in
the case of enzyme proteins. Another important inf1uence may be due to
adsorption phenomena. It has a1so been reported that large mo1ecu1es may
be broken down to more easily metabo1ised species at the interface(26).
207

208
This concentration of potential nutrients at the surface of sands, silts,

gravels, rocks, and other submerged solids and structures may therefore
provide relatively nutrient-rich areas in an otherwise unpromising
environment. So, those organisms that are able to attach to surfaces and
use the accumulated nutrients will have a major advantage over those
only capable of living in free suspension. An added advantage is that,
not only do the surfaces act as "anchors" to prevent the organisms being
swept away from their food source(l7), but the water flow transports
nutrients constantly to these organisms, and likewise removes metabolic
products which could act as poisons(22). Therefore, most solid surfaces
in streams, rivers, and the sea will be covered by microbial deposits,
and many will also support growths of higher organisms.
For obvious reasons, biologi cal fouling is not confined to purely
natural systems. Indeed, biofilms and other biologi cal deposits are
widespread in man-made systems involving flowing water. These include
pipelines, heat exchangers, cooling towers (especially on the packing),
water deionisers, filter beds, and other packings used in wastewater
treatment. Heavy marine fouling of ships' hulls and other submerged
structures has been known ever since man took to the seas(32), and is
believed to require previous microbial film formation. Non-flowing
systems are also susceptible to biofouling: for example, in water-sealed
gas holders, calorimeters, and wet meters in the gas industry(31), and on
the outside of gas holders, cooling towers, and other plant. Biofouling
is found internally nearer home, too, in domestic central heating systems
and within the mou th.
In wastewater treatment, finally, biofilm formation is exploited to
industrial advantage: in the trickling filter and the rotating disc
contactor, the microorganisms attach to the packing material or discs and
form a reactive surface for the adsorption and breakdown of organic
materials.
Therefore, it may be expected that, almost everywhere where there is_
water, the potential for biofouling exists.
3. COMPOSITION AND PROPERTlES OF MICROBIAL BIOFILMS

3.1. Microbiological Aspects
Biofilms take the form of a gelatinous matrix or "slime" containing a
complex and heterogeneous microbial population composed of bacteria,
aquatic fungi, protozoa, and algae(2S). Various macroorganisms, such as
aquatic invertebrates, may feed on these films, and other higher
organisms, such as water weed, seaweed, and barnacles, may also be
associated.
The structure of microbial slimes most commonly encountered in
industrial systems may vary, on the macroscopic level, from flocculant or
filamentous growths to gelatinous films barely visible to the naked eye.

However, under the microscope, these biofilms readily appear as
heterogeneous associations of bacteria, algae, diatoms, fungi, and
protozoa embedded within a matrix of microbial extracellular products,
cell debris, and non-biological particles entrained from the bulk aqueous
phase.
During the initial stages, before the development of the mature
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biofilm, it is thought(28,29) that bacteria play the major part of

initiating attachment and early colonisation of the surface, or
substratum, modifying it to favour the development of the more complex
community. Within these biofilms are sites of pronounced metabolic
activity, which, in natural systems, play a key role in the cycling of
209
organic and inorganic materials by decomposing plant and animal residues.

Both industrial and non-industrial biofilms are communities of
organisms in a state of dynamic interaction (see Fig. 1). This leads
ultimately to the predominance of certain organisms, and a succession or
gradation of species in the mixed population. Several types of microbial
interaction can occur, including:
a) Commensalism: one organism benefits while the other is
unaffected.
b) Mutualism: Each organism benefits from the others.
c) Amensalism: One organism adversely changes the environment
for the others.
d) Parasitism: One organism steals from another.
e) Predation: One organism ingests another.
f) Neutralism: Lack of interaction.
Biofilms are thus complex systems, in which the number of organisms,
their species type, and the extent of microbial interaction will depend
upon the environment in which the biofilm developed, and will change as
the environment does. The concentration of available nutrients, oxygen,
light, temperature, pH, and flow conditions will combine to influence the
composition of a biofilm. Therefore, during its formation and
development, not only will there be a variety of active microorganisms,
but a shift in the dominant species with time is quite likely. Biofilms
are thus able to adapt to a very considerable degree to changes in the
environment, unlike most other types of fouling. However, on surfaces at
only modest temperatures - say at lOOoe, or even less - cells will lyse
and the biochemical molecules discharged may de grade to produce a
'cooked-on' deposit.
Biofilms found where light is absent contain bacteria as the
predominant type of microorganism. These bacteria in general are
heterotrophic, requiring pre-formed organic compounds as their sources of
carbon and energy. Some of these organisms will require oxygen for
growth and metabolism (aerobes). These are likely to predominate in the
more oxygenated areas of a biofilm, i.e. nearer the interface with the
continuous aqueous phase, provided the latter has been aerated. Other
bacteria (anaerobes) survive and grow in the absence of oxygen. These
may predominate in deoxygenated areas, particularly in thicker biofilms
nearer the substratum surface.
In systems where there are significant levels of light, algae will also
be important components of a biofilm. These photosynthetic organisms can
synthesise complex organic molecules (such as are needed for cell growth)
using light, water as a source of reducing power, and carbon dioxide as a
carbon source, along with inorganic nutrients (such as are common in
natural waters). Algae are thus likely to be found in a biofilm large ly
near the solid/liquid interface. However, algae from a biofilm deposited

in areas exposed to light can be entrained into flowing water and carried
into dark areas to be incorporated into biofilms there. Thus, in a
cooling-water cycle, algae may grow on the light-exposed surfaces of a
cooling tower packing, and then become entrained and carried off to
deposit within a biofilm on the (dark) surface of a heat exchanger
downstream.
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Electron microscopic studies (17,24) of mature bacterial films show

them to be composed of cells embedded within a loose gelatinous matrix of
extracellular material. This type of matrix consists of polymeric
material secreted by the bacteria, algae, and dia toms of a biofilm, and
is a commonly-observed structure, which produces the characteristic
210
"slimey" texture of most biofilms. The polymers are mostly

polysaccharide or glycoproteinaceous in nature. They possess an expanded
structure(8) and form aqueous gels at very low concentrations, with the
aid of calcium, magnesium, and iron(ll). These structures can entrap a
large volume of water per unit weight of polymer(33). The polymers from
each bacterial, and other, species are unique to that species. Some
bacterial capsular materials can contain up to 98% water(35). Therefore,
developed biofilms are likely to contain cells as only a small proportion
of their total volume: typically, l to 10% by volume as cells(12,16,24).
Thus, as shown in Fig.l, a developed biofilm will be a complex and
dynamic structure, which is likely to change with time. It is likely to
have various zones, in which different organisms will predominate. These
may include: algae and other photosynthetic organisms near a biofilm
surface exposed to light; aerobic organisms in an aerobic zone near the
surface; grading to anaerobic organisms in any anaerobic zone which may
form near the substratum surface. These zones are likely to contain, by
volume, largely microbial polymeric structures. The reactions going on
will vary with the type of zone, reflecting changes in metabolism, but
are likely to be interrelated, as products from one zone are used as
substrates within another zone.
3.2. Physico-Chemical Aspects

The chemical composition of biofilms developed in a variety of areas
has been measured by various workers. Table l gives examples of
measurements made on biofilms deposited within closed conduits displaying
high frictional losses:
TABLE l. Chemical composition of Biofilms in closed conduits(10)
Sample Water, %w/w Organics, %w/w Minerals,%w/w
l 87.0 2.5 10.5

2 95.4 3.25 1. 35
3 85.6 2.7 11. 7
4 90.0 1.9 8.1
5 95.0 2.4 2.6
Elemental analyses of dried biofilms obtained from both industrial

equipment and the laboratory are given in Table 2.
TABLE 2. Elemental composition of Industrial and Laboratory

Biofilms(11,12,25)
Source C,% dry wto N,% dry wto C/N
Power Plant Condenser Biofilm 6.4 - 13.8 0.5 - 3.0 2 - 27

Laboratory Biofilms 19.0 - 42.8 9.2 -10.0 2.1 - 4.3
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Laboratory Biofilm 37.5 2.3 16.3

Cooling Tower Biofilm 28.2 3.4 8.4
Escherichia coli cells 50.0 14.0 3.6
211
From these tables, it may be seen that naturally-oeeurring biofilms ean

retain a high eoneentration of mineral elements. This is probably due to
adsorption of inorganie ions and entrainment of partieles by the
polymerie exudates. The variability of the data is most likely a
refleetion of the different physieal and ehemieal eonditions under whieh
eaeh film was formed. But, whatever the eonditions for formation, almost
all the weight of a biofilm is generaIly water: e ommon ly 85 to 96%.
Therefore, it is to be expeeted that the d~~sity of a biofilm should be
approximately that of water = i.e. 1000 kg m (21).
Biofilms that develop within flowing~ater systems are likely initially
to have fairly smooth surfaees(3,4). However, the surfaees of well-
developed biofilms have been observed to be rippled(lO). Indeed, it is
elaimed(s) that biofilms are viseoelastie, and that this propert y eauses
temporary surfaee deformations. This behaviour takes the form of a
rippling motion, whieh eould explain the unusually high pressure drops
observed in slime-eoated water pipelines(12).
There is same evidenee to suggest that the strength of both biofilm-
surfaee and intrabiofilm bonding depends upon the eonditions under whieh
the biofilm was formed(9) and mayehange with the age of the deposit(23).
This should be covered in more detail in alater paper.
3.3 Frictional Resistance

In systems conveying flowing fluids, it is commonly the case that a
fouling deposit on the sur face s of the equipment will tend to roughen
that surface unless it was initially very rough. The fouled surface will
thus provide extra frictional drag on the fluid flowing over it, which
will produce energy losses within the fluid. These are usually
manifested as a pressure drop, and result in increased pumping costs or
decreased flow, if not checked. Two ways in which that pressure drop may
be estimated are via the Fanning friction factor, f, and via the
Equivalent Sand Roughness, k .
Biofilms are no exception i~ thi s behaviour. Experimental measurements
have been made(ll) of biofilm frictional resistance in terms of both a
modified Friction Factor, f' (equal to 4f).
d LlP (1)
f 2.0 L Pv2
and the Equivalent Sand Roughness, k es ' empirically related to the

Reynolds number by the Colebrook-White equation for all flow regimes:
( _l
d (10(0.87 - O.SOf' 2)
k 18.70 (2)
es 2 ( --1-
f' 2Re
The flow regime may be hydraulically smooth, transitional, or fully
rough, depending upon how k es compares with the size of the viscous sub-
layer, 8 , where:
lOd (f')-O.S
(3)
o (2 )
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Re
when k <8, the regime is hydraulically smooth.
14 ~> k >8 , the flow is in the transitional regime.
k l~g , the flow is in the fully rough regime(34).
es
212
Laboratory studies seem to suggest(ll) a similar dependance for

biofilms, of frictional resistance on Reynolds number, as with
commercially rough pipes. This resistance depends on biofilm thickness,
and does not increase above that for a hydraulically smooth pipe until a
critical biofilm thickness is reached, roughly equal to å (See Fig.3).
At this stage, it is thought that surfaee irregularities protrude through
the viscous sub-Iayer. However, biofilms with rippled surfaces have been
known in practice to produce much higher frictional 10sses(10).
Furth~rmore, biofilms formed in model condensers(30) carrying seawater ~~
2 ms have caused pres sure drop increases of between 0.9 and 4.5 kN m
per metre of tube within l to 2 weeks - much higher than the calculated
value.
3.4 Heat Transfer Properties

As with any other fouling deposit, biofouling presents an added
resistance to heat transfer within heat exchange equipment. This reduces
the overall heat transfer coefficient, thereby requiring a larger surfaee
area of equipment for a given dut y, as determined by:
Q (4)
where U will initially have a 'clean' value, U, which will be reduced

by fouling resistances Rfi and Rfo (inside an~ outside surfaces) to a
level, Uf:
l (5)
Uf
For a flat surface:
(6)
Rf
To complicate matters, since biofilm thickness, yf, will change with

time of contact with a fouling liquid, Rf will change, too. It may or
may not reach a plateau level. Work done in the laboratory(11,14) has
shown an initial decrease in heat transfer resistance before it increases
(see Fig.3), for systems exhibiting biofouling. This is thought to be
due to an initial roughening of the surface, as the biofilm begins to
form, which disturbs the thermal boundary layer and reduces convective
heat transfer resistance. At this stage, the conductive resistance of the

(very thin) biofilm is insignificant. However, as the biofilm becomes
thieker, its conductive resistance increases; and, owing to its high
water content, that resistance more than offsets any decrease in
convective resistance due to the biofilm surfaee topography.
Measurements made of Rf values show general agreement between systems
operating in the laboratory and those taking natura l waters, both fresh
@ProcessEng
and marine. For example(3) an appar~~t ~ilm_ihickness of 30C)Jm gave an

Rf value of approximately 1.8 x 10 m K W , with a roughly linear
relationship between Rf and wet film thickness.
As biofilms are largely water, it would be expected that their thermal
conductivities should be similar to that of water. Measurements on
213
o
1aboratory biofi1ms(14) at various glucose loadings at 2~lt~132 C showed
this: Average biofilm thermal conductivity was 0.65 Wm K , compared
with water at 0.61 to 0.62. A biofilm might therefore be regarded, for
heat transfer purposes, as a1most equiva1ent to a simi1ar thickness of
stagnant water.
4. OBSERVED EFFECTS OF BIOFOULING

In the light of the composition and properties of biofilms described
above, severa1 of the effects of biofou1ing are not surprising. The most
common effects may be divided into three areas:
1) Fluid Flow Effects

2) Heat Transfer Effects
3) Corrosion Effects
4.1 Fluid Flow Effects

Biofou1ing may inf1uence fluid flow behaviour in two main ways:
a) Biofilm formation within a pipe or flow passage may

significant1y reduce the effective flow diameter, thereby
causing restrictions in flow, e.g. A 1.5mm thick biofi1m on a
12.7mm diameter pipe wi11 reduce the flow area by 42%. Severe
growth may cause blockage or uneven flow distribution. A1ga1
growth on coo1ing tower packing, producing uneven flow
distribution and consequent insufficient water coo1ing, can
be a problem.
b) The uneven, viscoe1astic, biofilm surface causes pressure
drops within f10wing systems. This can resu1t in increased
pumping energy requirements or decreases in f1uid-carrying
capacity, e.g. a c10sed water-carrying conduit of stee1 was
observed(10) to have accumu1ated a 0.64mm thick biofilm and
thereby lost 55% of its water-carrying capacity over 3 years.
Simi1ar energy losses concerning ships and due to macrobia1
and microbia1 fou1ing have been known for years. A Wor1d War
2 Admira1ty ca1cu1ation(19) estimated that 6 months' cruising
in temperate waters at 20 knotts produced enough biofou1ing on
the hu11 of a batt1eship to increase its fue1 consumption at
that speed by 40%.
4.2 Heat Transfer Effects

These have large ly been covered in Section 3.4. Because of the
predominant effects of the added fou1ing resistance of the biofilm, the
overall effects of biofou1ing of heat transfer equipment is usua11y to
reduce the overall heat transfer coefficient of the exchanger, and

therefore its efficiency. Therefore either large r equipment is required
for a given dut y - to take account of fou1ing - or the heat transfer
rate achieved progressive1y fa11s more and more be10w the dut Y required.
Thus, for examp1e, in e1ectricity generation, fou1ing in the steam
condenser reduces condensation, causing 10ss of vacuum, 10wer turbine
efficiency, and therefore higher fue1 consumption to achieve a given
e1ectricity output. In Ocean Thermal Energy conversion, a 0.05mm thick
@ProcessEng
biofilm wou1d be expected to reduce heat transfer in the heat exchangers

by approximate1y one-third(20).
214
4.3 Corrosion Effects

Several types of organism that can occur in biofilms are capable of
creating conditions conducive to corrosion, especiaily of metallic
surfaces(18):
a) If the biofilm is thick enough, oxygen may become depleted at

the substratum surface, where differential oxygen cells may
occur, causing corrosion. Aerobic iron-oxidising bacteria of
the Gallionella and Sphaerotilus species have been known to
have been involved in this area.
b) Anaerobic sulphate-reducing Desulphovibrio bacteria are
thought to use hydrogen produced by the initial corrosion of,
for example, mild steel to reduce sulphate present to
sulphide. This removes the hydrogen which would otherwise
form a polarising layer, thus allowing further "chemical"
corrosion to proceed.
c) The aerobic, sulphur-oxidising bacterium Thiobacillus
thiooxidans can produce sulphuric acid in concentrations of
over 5% w/w. Organic acids are produced by many organisms as
part of their normal metabolism. Wood-rotting fungi produce
cellulolytic enzymes that will destroy wooden cooling tower
packings.
Therefore, biofouling may increase pumping costs, reduce heat exchanger

efficiency, and add to equipment replacement costs as aresult of
corrosion. It is thus a phenomenon that, in general, needs to be
controlled, and, if possible, eliminated. To do this systematically, or
even only to account for its development in designing processes and
equipment, knowledge of the proces ses involved in biofilm accumulation is
advantageous, even necessary. Models which predict biofilm development
under various operating conditions would also help in both equipment
design and operating strategy, including both type and frequency of
cleaning.
5. HOW BIOFILMS ACCUMULATE

The accumulation of biofilms is the nett result of physical transport,
physico-chemical interactions, and biological rate processes, which may
occur sequentially or simultaneously(2S). In flowing systems, biofilm
formation is thought to be determined by a combination of five types of
process(11,13,25), shown diagrammatically in Fig.2. Aspects of these
will be dealt with in more detail in later papers, but the processes are
outlined below:
5.1 Formation of an Organic conditioning Film"

If a surface is exposed to a natura l water containing low
concentrations of organic compounds, in nearly all cases, within minutes
that surface will have adsorbed on to it a monolayer or film of organic
molecules. These are commonly glycoproteins, proteoglycans,
polysaccharides, or their degradation products(13,25) - Laboratory
observations suggest that this deposit is unlikely to be more than O.l~m
@ProcessEng
thick(13), but this is enough to 'condition' the surface by significantly

altering many of its properties, such as wettability and surface
charge(l). This in turn means that the nature of this 'conditioning
film' is likely to influence the type and extent of the microbial
interactions with the surface which follow this molecular adsorption.
215
The surface that a contacting organism "sees" in the ear1y stages of

biofou1ing wi11 thus be not the 'clean' surface but that surface modified
by the 'conditioning film', since attachment of organisms (and other
particles) wi11 generally occur at a much 10wer rate than mo1ecu1ar
adsorption.
5.2 Transport to the Surface

When a c1ean sur face comes into contact with water containing
microorganisms and other material, organisms (and other particles
present) wi11 be transported from the bulk of the fluid to the surface in
contact with the fluid. This wi11 continue, so that, as the biofilm
bui1ds up, mass transport wi11 occur from the bulk to the biofilm
surface. Within flowing systems, microbia1 ce11s (generally with an
effective diameter of 0.5 to 10pm) can be transported by severa1
mechanisms, inc1uding(13): Diffusion (Brownian motion), Sedimentation
(gravity), Thermophoresis, Moti1ity (taxis), and Fluid Dynamic forces
(inertia, lift, drag, drainage, and downsweeps).
If water flow is turbulent, Eddy Diffusion wi11 disperse the ce11s
within the turbulent core region and propel them into the viscous (or
laminar) sub-1ayer. However, frictiona1 drag forces wi11 slow the ce11s
dawn before they approach the surface. Because microbia1 ce11s are sma11
and their density is simi1ar to that of water, inertia1 forces, lift
forces (which direct the partic1e towards the surface), and sedimentation
are generally very sma11. Brownian diffusion contributes 1itt1e to the
transport of particles of over 1 m in diameter in turbulent flow.
Drainage forces wi11 tend to repe1 microbia1 ce11s from a surface, as
wi11 thermo-phoresis if the sur face is hotter than the bulk fluid.
Those organisms capab1e of moti1ity cou1d well be he1ped by this abi1ity
within the viscous sub1ayer or under laminar flow conditions. However,
in turbulent flow, perhaps the most important mechanism directing the
ce11s to the surface within the viscous sub1ayer is that of downsweeps of
fluid from the turbulent core, which transport particles all the way to
the surface on penetrating the viscous sub1ayer(15). Neverthe1ess, many
organisms wi11 naturally form aggregates in suspension. For these,
sedimentation effects wi11 be more significant than for single ce11s,
especia11y at 10wer flow ve10cities.
Much of this exp1anation, however, is general, and attempts to quantify
microbia1 transport rates are rather tentative. At the moment,
information on ce11 'striking' rates at a surface is not available.
Therefore, any models which try to predict the ce11 mass transport rate
cannot be verified. One such model is that of Bea1(2), which is a model
for particles in general, but cou1d well be applicab1e to microbia1
suspensions, since the size range it covers (0.5 to 20)Am) encompasses
many microbia1 cells. It is derived from an equation analagous to Fick's

Law, and accounts for the effects of eddy diffusion within turbulent
flow:
(7)
which, on integration, gives:

@ProcessEng
(8)
216
wherev r , the radial ve10city of the particle, may be described(11) in

terms of vm' v sd ' vB' v fl : ve10city components for, respective1y,
moti1ity, sedimentation, Brownian motion, and fluid motion. These
components, and especia11y S, the 'sticking probabi1ity' of the
particles, may be very difficu1t to estimate. In general partic1e flux
shou1d increase with fluid ve10city and ce11 concentration.
Finally, it must a1so be remember that, at the same time as particu1ate
transport is occurring, dissolved components, which may function as
nutrients for the organisms, wi11 be transported to the surface.
Equations describing such transport shou1d be those generally used for
solute mass transfer, and wide1y available in the literature. The
problem here, however, wi11 be identifying just what is being
transported. Once that is solved, transport rates shou1d be ab1e to be
estimated.
5.3 Microbia1 Attachment at the Surface

Once an organism has been transported to the surface whether the
'conditioned' substratum surface or that of the biofilm - it may succeed
in attaching. If not, it wi11 eventuaily be carried away by detachment
forces. Processes of attachment will be covered in more detail in a
later paper. However, briefly, it is though that both physico - chemical
forces (such as electrostatic and van der Waals forces) and attachment
structures and extracel1ular polymers play significant parts in thi s
area. It has a1so been observed that many organisms will exhibit a two-
stage attachment(28): The first, a 'reversible' stage, where attachment
is rapid but the organisms are easily washed from the surface. This is
thought to be maintained large ly via physico-chemical forces. The second
stage is "irreversible', time-dependent and slower. The cells gradually
synthesise extracellular polymers which more firmly bond the organisms
to the surface - and also help to capture other organisms and particles.
5.4 Biofilm Development and Growth

Biofilms are living communities, so once cells have become attached to
the surface the film can develop not only via organism capture, but a1so
through the biochemical con version processes which use available
nutrients to produce more cells, extracellular polymer, and other
excreted products, which may, in turn, function as nutrients for other
organisms present. Nutrients reaching the surface of a biofilm must
diffuse into the film until assimilated by the organisms. Therefore,
nutrient concentration gradient s wi1l exist within the film, which may
resu1t in limitation or even exhaustion of the substance in question.
This could alter the balance within that area of biofilm, especiaily if
that nutrient is oxygen. In the initial stages of biofilm development,
nutrient or oxygen depletion is unlike1y to be significant. However, as

the film develops, both the added diffusional resistance of the film
structure and the increased demand from the large r microbial population,
will progressively reduce nutrient levels at the substratum surface,
until a 'critical thickness' of biofilm is reached for that nutrient,
when its concentration at the substratum surface is zero(ll). Therefore,
if biofilm develops beyond this stage, there will exist in it regions of
@ProcessEng
zero nutrient: such as anaerobic zones 'underneath' an aerobic structure.

The existence of such zones will be influenced by the nutrient type, the
biofilm structure and cell population, and the rate of nutrient supply to
the outside surface of the biofilm. All these factors interact, so the
nature of a biofilm is likely to change with time.
217
5.4.1. Biofilm Growth Models. Several rate expressions exist to describe

biofilm growth, either in terms of biomass production rate or nutrient
depletion rate, with rate constants that are functions of pH,
temperature, limiting nutrient concentration and type, terminal electron
acceptor, and organism concentration(7). These need to account for the
fundamental processes going on within the biofilm, i.e. cell growth and
multiplication, cell maintenance, product formation (extra-and
intracellular), death by viability loss, and death by cell lysis.
Thus in one treatment(ll), the stoichiometry of the "growth" process is
described in terms of concentrations and stoichiometric coefficients:
KI (Substrate) + K2 (Nutrient) + K~ (EIectron Acceptor)

; K4 (Biomass) + KS (Product) K6 (Netabolite) (9)
And "observed" substrate removal rate is given (-St) in terms of proces s

rates and stoichiometric ratios:
- St ; RI (Growth Rate) + R2 (Maintenance Rate) + R3 (Product (10)

Rate - R4 (Lysis Rate)
A Process Rate/Stoichiometry matrix was constructed. This highlights
the complexity of such a model, since many species of organism,
nutrients, and products will be involved, making many parameters very
difficult to measure and interrelate. It must also be borne in mind that
mass transfer may control these processes under many circumstances,
rather than intrinsic kinetics.
5.5. Biofilm Detachment

At the same time as cells and nutrients are transport ed to the surface
and accumulate within it, areas of biofilm may be detached and
reentrained into the bulk of the fluid, especiaIly in flowing systems.
Reentrainment of relatively small sections of the biofilm surface is a
fairly continuous process, and is caused by the scouring action of the
flowing fluid exerting shear forces on the surface(11,25). Increasing
fluid turbulence/velocity will increase surface shear stress and
therefore reentrainment rates. As the biofilm grows thicker, it will
therefore be exposed to higher levels of shear stress, so will suffer
increasingly from reentrainment. Sloughing, or removal of large masses
of biofilm, causing a rapid but temporary reduction in film
thickness(3,4) is thought to be a random process, attributed, at least in
part, to oxygen or other nutrient depletion within the biofilm. It is
more frequently witnessed with thicker, dense films, especiaIly in

laminar flow.
5.6. Factors Affecting Biofilm Development and Accumulation

Since biofilm accumulation occurs as anett result of the five types of
interacting process described ab ove , and since any of these (except the
formation of the "conditioning film") is likely to be rate-limiting at
@ProcessEng
s orne stage, it would be expected that a number of factors should

influence the rate and extent of biofouling. These include: substrate,
nutrient, oxygen, temperature, cell concentration and type, pH,
inorganic ions, and fluid flow velocity. Aspects of these will be
covered in later papers.
218
6. TRE TIME-COURSE OF BIOFILM DEVELOPMENT

Enough detail has already been given to show why biofouling develops
with time. A generalised progression with time is given in Fig. 3, which
illustrates both observations that biofilm eventually "plateaus" (no
sloughing) and those recording sinusoidal variations in mass or
thickness, due to sloughing. In both cases, sigmoidal curves are shown,
indicating induction, growth and ··plateau" phases similar in appearance
to the batch growth curve of an organism exhibiting Monod-type growth
kinetics.
6.1. Biofilm Accumulation Models

Relatively few mathematical models of biofoulant accumulation have been
published. Two have been developed by Bryers and Characklis(6,7), on the
basis of results from tubular loop recycle systems in the laboratory,
assuming complete mixing:
Model 1 is based upon the relationship commonly assumed for particulate
fouling(6):
(11)
giving rise to the following expression:

ThP f kNc N _ Cl «l - exp (Th/(Th-Th »»T(t)
dTH(t) ~~______~~___~~~m=a=x~~s__
dt ~ + cN C2 (l/Th)m (12)
Model 2 describes the kinetics of biofilm formation in the initial, or

induction, phase(7):
(13)
or, in integrated form:
(14)
Alternatively, both linear accumulation (observed in some runs) and an

exponential rise could be accommodated by a polynomial equation obtained
from a Taylor series expansion of the exponential term of equation(14):
2 4
XA = Ca + Cb t + Cc t + Cd t + (15 )
These models may well have to be modified for systems with different
flow patterns, and also tested on a variety of systems "in the field" to
assess how widely applicable they are.
7. CONCLUSION
@ProcessEng
Biofouling is a highly complex, adaptable, and dynamic phenomenon,

which is the nett result of physical transport, physico-chemical
interactions, and biological rate processes. Although many of these
219
processes and interactkmsare to a certain extent understood, much still

needs to be done before the interrelationships are sufficiently
characterised to enable predictions to be made of the rates and nature of
accumulation under the wide range of conditions likely to be found in
practice. Until such progress is made, control of biofouling is likely to
remain less than optimal, and consequent energy and efficiency losses and
equipment deterioration will continue to form part of our industrial "way
of life".
SYMBOLS
A Heat Transfer Area (m 2 )

-3
c Particle Number Concentration (Particles m_ 3 )
c Average c over tube cross-sectional area (Par!~cles m )
cay Nutrient Concentration
~ .... Constants in equation (15)
1st Proportionality constant in equation (12)
(kgm _~ -n
(kg m s )
f-)
Cl
2nd Proportionality constant in equation (12)(kg mm-2 s - )
~ Tube/pipe diameter (m~ _
DB Particle Molecular Diffusivity (m s l)
f Fanning Friction Factor (- )
f' Modified Friction Factor (-2 2 -l
J Particle flux (Particles m_ 2s_ 1 )
Jt Particle flux at surface (paEricles m s )
k tw Particle deposition coefficient (ms )
kD Equivalent sand roughness ()Jm2 1 -l
kes Foulant thermal conductivity (Wm K )
~ Maximum nutrient utilisation rate/unit weight 3
of organism
-l -l
(m 3kg_ l s )
Specific biofilm accumulation rate constant (m ~T )
Particle transfer coefficient (ms )
Saturation constant: c N when utilisation rate -3
is kN/2 (kg m )
Stoichiometric coefficients in equation(9) (-)
Tube/pipe length (m)_2
Pres sure drop along tube/pipe length (Nm )
Heat transfer rate (W)
Reynolds Number = dvp/)J (-~
Inside sur face fouling resistance (m 2s
Outside surface fouling resistance (m s
Stoichiometric ratios in equation(lO) (-)
"Sticking Probability" of particles (-)
"Observed" substrate removal rate (Moles s -l)
Time (s)
Biofilm thickness in equations (11), (12) (m)
Steady-State Biofilm thickness (m)
Log-Mean temperature difference over heat exchan_~r_fK21
Overall Heat Transfer Coefficient (Wm_2s_lK_l)
Fouled and "clean " values of U (Wm s K )
-l
Average fluid velocity (mS_l)
@ProcessEng
v
Particle radial velocity (ms 2 3
Dispersed biomass concentration (kg m_ 2 )
Attached biofilm mass per unit area (kg m_ 2 )
Initially-attached biofilm (kg m )
Distance from surface (m)
220
yf Biofilm thickness in equation (5)

å Thickness of viscous sub-layer
E: Eddy diffusion coefficient
~ Fluid dynamic viscosity
~DB Dispersed biomass growth rate
p Fluid density
Pf Biofilm density
'( (t) Shear Stress at biofilm surface
Ø~,Ør Rates of biofilm deposition and removal
REFERENCES
1. Baier RE: Adhesion in Biological Systems (Manly RS (ed». New York:

Academic Press, 15-48, 1970
2. Beal SK: Nucl. Sci. Engng., 40, 1-11, 1970
3. Bott TR: I.Cor.Sci.Technol.7f.Chem.E. Conference: Fouling-Science or
Art? Surrey University, Guildford, U.K., 117-144, 1979
4. Bott TR: Effl. Water Treatment J., 19(9), 453-461, 1979
5. Bott TR and Harty DWS: I.Chem.E. 6t~Ann.Res.Meeting, London, 1979
6. Bryers JD and Characklis WG: 97th. AN. A.W.W.A. Conference and
Exposition. Anaheim, Ca., U.S.A., 1977
7. Bryers JD and Characklis WG: Int. Conference on Fouling of Heat
Transfer Equipment. Rensselaer Polytechnic Institute, Troy, N.Y.,
U.S.A., 1979.
8. Cagle GD: Can. J. Microbiol., 21, 395-408, 1975
9. Characklis WG: M.S. Thesis, Univ. of To1edo, U.S.A., 1967
10. Characklis WG: Water Res., 7, 1249-1258, 1973
ll. Characklis WG: Int. Conference on Fouling of Heat Transfer Equip.
Troy, 1979
12. Characklis WG: Biofilm Development and Destruction. EPRI Report RP
902-1, Palo Alto, Ca., U.S.A., 1979
13. Characklis WG and Cooksey KE: Advs. in Appld. Microbiol., ~, 93-138,
1983
14. Characklis WG, Bryers JD, Trulear MG, Zelver N: Condenser Biofouling
Control Symposium, EPRI, Atlanta, Ga., U.S.A., 1979
15. Cleaver JW and Yates B: Chem.Eng.Sci., 30, 983-992, 1975
16. Costerton JW: Condenser Biofouling Control Symp., EPRI, Atlanta, 1979
17. Costerton JW, Geesey GG, Cheng KJ: Scientific American, 239, 86-95,
1978 -
18. Creedon B: I.Cor.Sci. Technol./I.Chem.E. Conference: Fouling-Science
or Art?, Surrey University, Guildford, U.K., 1979
19. Dick RJ: Paint Varn. Prodn., 60 (11), 35-40, 1970
20. Fava JA and Thomas DL: Ocean Engng., 5, 269-288, 1978
21. Fowler HW and McKay AJ: University College, Swansea: Personal

Comm'n., 1979
22. Harty DWS and Bott TR: Int.Conf. on Fouling of H.T. Equip., Troy,
1979
23. How I, Duddridge JE, Kent CA, Pritchard AM: Paper HTFS RS 419: HTFS
Research Symposium, Warwick, U.K., 1982
24. Jones HC, Roth IL, Sanders WN: J.Bact., 99, 316-325, 1969
@ProcessEng
25. Kent CA and Duddridge JE: Microbia1 Fouling of Heat Transfer Surfaces
in Cooling Water Systems: Harwell Report AERE-R 10065, Harwel1, U.K.,
1981
26. Kriss A and Markianovich Y: Mikrobiologiya, 28, 399, 1959
27. Marshall KC: Interfaces in Microbia1 Eco1ogy:-Cambridge, Mass., USA:
221
Harvard University Press, 1976

28. Marshall KC, Stout R, Mitchell R: Can.J.Microbiol., ~, 1413-1416,
1971
29. Marshall KC, Stout R, Mitchell R: J.Gen.Microbiol., 68, 337-348, 1971
30. Nosetani T, Sato S, Onda K, Kashiwada J, Kawaguchi K:-Int. Conf. on
Fouling of H.T. Equip., Troy, 1979
31. Pankhurst ES: Gas Eng. Management, 3-16, January, 1976
32. Plutarch: Miscellanies - Symposiacs, Book II, Question 7: Clough AH
and Goodwin WW (eds)
33. Rees DA: Polysaccharide Shapes. New York: Halstead Press, 1977
34. Schlichting H: Boundary Layer Theory. London: Pergamon Press, 1955
35. Wilkinson JF: Bact. Rev., ~, 46-73, 1958
@ProcessEng
222
o,
NUTRIENTS
+
10RGANIC & INORGANICI
co,
t t o,
AOUEOUS
---''--...-t........--I----"''''-~=::::::::;;;;::;b.~~.~~b"-t-- PHASE
PHOlOSYNTHETlC MICROORGANISMS
~co,
/
AEROBIC
ZONE
ORGANIC
PRODUCTS
~ORGANIC ACIOS
BIO-
FILM
&
ALCOHOLS
t
~ FERMENTATION
ANAEROBIC MICRDORGANISMS - - - - -....
}
ANAEROBIC
ZONE
&
METABOllSM
zzz////ZZZZ!!!!!! SUBSTRATUM
FIGURE l. Conceptual Diagram of a Developed Biofilm: Structure and

Metabolte Processes. (From ref.2S, with permission of UKAEA,
Harwell)
Ul
\J
-<
U.
O O(
O
o ... ... ~
III
O o
~
~
::j
~ O l-
O
-< - - - - ,I - P - -
-'
U. . O!::
l- I
~ V)
ca
O C:ELL ::S TrME
(J)
" OIl.C,ANXC. r: INDIACTroN c,: C.ROWTH
MoLECLl..LIi
P: PLATEAU
(/) CONOI:TIONIN<1
®rRANSPORT @ATTACHlT
@ProcessEng
æC.ROWTH @DETAcHMlT FIGURE 3. Generalised Progression of

Biofouling.
FIGURE 2. Biofouling
Proces ses
EFFECT OF DESIGN AND OPERATING VARIABLES ON BIOFOULING
(1,) (*) (*,~) (*)

PINHEIRO.M.M.V.P.S. ,MELO,L.F. ,BOTT,T.R. and PINHEIRO,J.D.
(*) University of Minho, C.Q.P.A./I.N.I.C., 4700 Braga, Portugal

(**) University of Birmingham, Chem.Eng.Departm., U.K.
INTRODUCTION
Biofouling, like other types of fouling, may cause serious problems in
heat transfer equipment. In general, the formation of deposits is dependent
on several physical and chemical variables, but in what respects bioufouling
other conditions have to be considered. These are related with the growth
and reproduction of microorganisms in the fluid and also in the films. In
this work reference is made speciaIly to the effects on bioufouling of:
- fluid velocity;
- surfaee characteristics;
- surfaee and fluid temperature;
- pH of the fluid;
- nutrient concentration;
- presence of inorganic suspended particles
1. EFFECT OF FLUID VELOCITY

Taking into account the sequence of proces ses that contribute to the
formation of biofilms(1), it is obvious that the fluid velocity is of funda-
mental influence to the phenomena, though its effects may be contradictory.
It ean be said that lower velocities tend to favour initial colonization of
surfaces due to the characteristics of the laminar layer that facilitates
the anchorage of microorganisms. But, on the other hand, this low velocity
layer constitutes an obstacle to the diffusion of nutrients and oxygen in-
dispensable to the metabolism of the attached cells. In this way, higher
velocities are considered more favourable to the renewal of nutrients near
the surfaces, allowing a faster growth of the microorganisms. Nevertheless,
high values of shear stress associated with higher velocities induce the re-
moval of deposits. So, in general, higher velocities tend to produce thinner
films than lower velocities. However, it was shown (2) that the influence of
higher velocities is not restricted to the erosive effect. In faet, when the
fluid velocity was increased from 0.03m/s to 0.3m/s, the uptake of oxygen in
the biofilm was 60% higher. These results lead to the conclusion that the
microbial activity in the film was increased, although it has lower thickness.
Summarizing, one may conclude that the true effect of increasing the
fluid velocity is the compaction of the film, otherwise Sanders (2) would
have found lower values for the oxygen uptake.
The compaction of biofilm under conditions of higher fluid velocities
was also studied by Bott (3). He obtained higher topographical variations in
@ProcessEng
the film surfaee under laminar regime than with turbulent flow.
Recent experimental results obtained with a culture of Pseudomonas
fluorescens (12), revealed higher film densities for higher velocities, as
shown in Table 1.
The structure of the deposit (also dependent on the fluid velocity)has
a relevant effect on the growth and reproduction of the attached microorga-
223

224
TABLE 1. Film densities for different fluid

velocities (Kg/m3 )
deposition
v = 0.43m/s v = O. 13m/ s
surf ae e
cooper 43.5 17.3
aluminium 38.6 13.0
brass 25.8 15.2
nisms. Experimental results obtained with suspended inorganic particles (4)

suggest that the structure of the deposits is not uniform along the thick-
ness of the films resulting in a more compact layer near the deposition sur-
face and a somewhat looser one near the solid-liquid interface. The relative
dimension of these layers is also an important factor in what concerns bio-
fouling, since microbial growth is favoured by the presence of high concen-
trations of nutrients. Thus, a more compact structure may be a limiting fac-
tor for diffusion of those nutrients throughout the deposit. In faet, for
moderate velocities, cell growth may be increased in presence of higher
fluid velocities, but for much higher velocities the "active" layer become
limited to the superficial layer of the deposit.
Experimental work on biofouling produced by Pseudomonas fluorescens(5)
has shown that there is a relationship between microbial growth and fluid
velocity. For this purpose, a biofouling model was developed (5) including
terms associated with the rate of transport (cells and nutrients), adhesion
and reproduction of microorganisms. The results presented in Fig.1 were ob-
tained by fitting this model to the experimental data.
2. EFFECT OF SURFACE CHARACTERISTICS

The surfaee characteristics are usualy related with the formation of
the first layers of biofilm.
In faet, the formation of the organic conditioning film that triggers
the adhesion of the first layers depends naturally on the surfaee characte-
ristics, namely on its critical surfaee tension.
c
. .60
.!
..'" .50
E .40
-"
.. .20
@ProcessEng
5000 7000 9000 11000 13000 15000

Re
FIG. 1. Deposition flux due to microbial growth (øg) as a function of

Reynolds Number
225
This propert y has been related to the number of the attaehed eells ~n the
first layer per unit area (6,7) as it ean be seen in Figure 2.
It appears that there is an interval (generaly referredin the range of
20-30 dyne/cm) for whieh the adhesion of mieroorganisms is les s favourable.
For these conditions, it was proved (7) that the adsorbed biofilm rectract
and rolls back from the surface, indicating low adhesion capacity.
However, most enginnering materials and coatings show high eapaeity for
adsorbing the first layers of the biofilm, presenting values of critieal sur-
face tension above the mentioned interval.
As regards the roughness of the deposition surface, it is accepted that
higher surfaee roughness favours the anchorage of microorganisms due to the
increase in the contact area. However, this effect is limited to the first
layers of deposit (8) and therefore to the induetion per iod of the overall
process. The final thickness of the deposits is not significantly affected
by this surfaee characteristics, but by the eharacteristics of the previous
fouling layers that cover the surface. Nevertheless,the period of time neees-
sary to attain the maximum thickness is enlarged, which is favourable to in-
dustrial operations.
Another surfaee charaeteristic that is often mentioned, related to the
formation of biological deposits, is the toxicity of some metallic ions (9).
However, the results published in the literature are not conelusive, since
they appear to depend on the dominant mierobial species and on the environ-
mental condition.
Aluminium surfaces are sometimes referred (20) as the less fouled subs-
tractum, due to the toxie effeet of A1 3+ ion acting on the polyssacharide
adhesive structure. Yet, Duddridge (9) concluded that brass (compared with
copper, aluminium or stainless steel: prevents microbial fouling due to the
leaehing of Zn 2 + ions - see Figure 3.
On the other hand, eopper is usually mentioned (10,11) as an effeetive
material inhibiting cellular metabolism. However, contradictory results do
not confirm this antimicrobial action (9,12). Table 2 reiers the-results
obtained when measuring the thickness and mass of deposits forrned af ter 48
hours exposure using copper, aluminium and bras s surfaces.(12)
,
Most
tj Engineering
v
I.... surf.aces
tj
.-c I
::J
I....
I Metallie oxides
v I
a.
I
V!
Gj
u I
'5
o
z
Critical surfaee tension

@ProcessEng
FIG. 2. Number of attaehed eells as a funetion of the eritieal surfaee

tension
226
10 Q.
- .---,
-
- - -
r-
r-
r-r-
"-
r-
5 n,-
O i1l
Pb2• Fe3 +Cu· Cd 2·Hg2·Zn2 ·Mn2 ·Cs· AI 3 ·Co?'·U· Z'" Ag Ni2'Edla C/Mg"CI- S,:'I,3.
Ion Type (SO~ . • 1 -',
FIG. 3. Influence of metallic ions on the attachment of cells (9).
It is thoughtthat the toxic effect of the metallic ions ceases af ter

several layers of biofilm are formed. In these case, this effect may be res-
ponsible for retarding the overall process without eliminating it completely
3. EFFECT OF FLUID AND SURFACE TEMPERATURE

Temperature constitutes a critical parameter in the development of bio-
fouling. In faet, it is often found an optimum temperature range for growth
of each specie of microorganism. The majority of microbial species present
in contaminated waters has its optimum growth temperature between 20 and
45 0 C, but there are others that can grow at lower (Psicrophilics) or higher
(Thermophilics) temperatures.
Bott and Pinheiro (3) evaluated the influence of temperature in the
formation of biofilms by varying it from 30 0 C to 35 0 C (Fig. 4). The increase
in biofilm thickness was about 70%, noting that the optimum temperature for
growth of the predominant bacteria (E.coli) is 37°C.
A similar result was obtained by Miller (13) utilizing a culture of
Pseudomonas fluorescens. In fact,a variation of only 5 0 C from the optimum
temperature for growth ot that microorganism resulted in a drastic decrease
in the biofilm thickness.
Studies carried out in industrial cooling water systems revealed a di-
TABLE 2. Mass and thickness of deposits on different surface

materials
surface m Y
material (mg) ( t" m)
@ProcessEng
copper 4.1 52
aluminium 3.9 47
brass 2.8 31
227
...
I /~
Oll
I
I
/ li ,
,
I
o '-~ -~_ ... "
"
• .. "
Timo (day.'
FIG. 4. Influence of temperature on biofouling
rect relation between the biofilm thickness and the ambient temperature du-
ring the year. Biological deposits increased during the summer months to
which corresponds higher mean temperatures.
Results reported by Novak (15) for river water show that only minor va-
riations in the biofilm thickness were noted when the temperatures varied
from 10 0 C to 45 0 C. However, in this case, other types of fouling may have
been present, masking the usual effect detected in biofouling.
The majority of studies reported in the literature is concerned with
thefluid temperatures, but not with the actual temperature developed at the
deposition surfaces. It is thought, though, that these temperatures have a
relevant effect on the process as illustrated by the results of Hattori (16)
and shown in Fig. 5. Kent (10) refers that these temperatures affect the pro-
duction ofexopolymers by the cells and, therefore, the mechanism of adhesion
to the surfaces.
Io" "-
ao 0""- o
(o
"'"
!
.'"
~
~ 4.
!
~tI
O\.
\
@ProcessEng
30 40 Sø
FIG. 5. Influence of the surface temperature on biofouling

228
The utilization of temperatures above or below the optimum values for

growth of the predominant microbial species is a potencial process for dimi_
nishing the intensity of biofouling.
4. EFFECT OF FLUID pH
The influence of fluid pH is related not only with the growth rate of
the microorganisms but also with the adhesion forces at the surfaces.
As to the growth rate, the majority of microorganisms in contaminated
waters has a preference for growth at a neutral pH (17). However, some spe-
cies may growth at pH as low as 4.0 or as high as 9.0 (10). Experimental
studies undertaken to relate the pH of the fluid with the microbial growth
on the surfaces (9,18), indicate that greater amounts of deposits are forrned
at pH coinciding with the best values for growth and reproduction of the mi-
croorganisms present in the film.
For instance, higher film densities were obtained for pH=7 than for
pH=9, when using a culture of Pseudomonas fluorescens (12) (Table 3). Note
that this microorganism shows a specific growth rate 53% higher for pH=7
than pH=9.
It is worth mentioning that the pH conditions in the solid-liquid in-
terface may be altered by the cellular metabolism which may procude acids
or alkalis.
The adhesion of macromolecules and microbial cells is also dependent on
the pH, since it can affect the distribution of electrical surface charge s
of materials in presence, and thus, their zeta potentiais. The adhesion be-
tween these materials is increased when the corresponding zeta potencials ha-
ve opposite signs.
Most usualy, the majority of bacteria have negative electrical surface
charges (19), thus presenting higher facility for the adhesion to solid sur-
faces with positive zeta potentiais.
Fletcher (20) found a higher number of adherent bacteria (Pseudomonad
marina) in platinium than in glass or mica surfaces when using the pH value
favourable to the growth of this microorganisms. In these circumstances, it
was found that the less fouled surfaces have negative zeta potentiais, while
the other tested surfaces have positive zeta potentials (21).
MacRae and Evans (22) studied the adhesionof bacteria to magnetite par-
ticles in aqueous suspensions. The adhesion was higher under conditions of
pH=3 and pH=6, for which the two substances (bacteria and magnetite) show
opposite surface charges.
It can be said that the coating of solid surfaces with materials that
increase the electronegativity, would reduce tha possibilities of adhesion
of the great majority of bacteria.
fABLE 3. Influence of fluid pH on bifouling density (Kg/m 3 )
deposition pH 7 pH 9
surface
@ProcessEng
copper 57.9 40.3

aluminium 61.0 41.8
brass 66.4 35.8
229
S. EFFECT OF NUTRIENT CONCENTRATION

It is general ly accepted that biofouling is directly related with the
concentration of nutrients and oxygen in the fluids. As the microorganisms
become attached their growth will depend on the diffusion of those elements
through the film. The limit for this diffusion depends on the thickness and
on the structure of the film. Kornegayand Andrews (23) report a limiting
value for film thickness of 70l'm through which the diffusion of oxygen is
possibIe , but other investigators refer different values (200 f'-m, 300 )Am)
(24) •
The low levels of nutrients in the deeper zones of films may result in
a decrease in the production of excreted polyssacharides thus rendering films
more vulnerables to shear forces. Yet, the suppression of nutrients in the
fluid causes a reduction in the heat transfer resistance of the preformed
films - Fig. 6. It seems that this reduction is due to the decrease in the
polyssacharides production by the cells, modifying the biofilm structure and
resulting in a reduction of the stagnant layer of water within that structu-
re.
6. PRESENCE OF INORGANIC SUSPENDED PARTICLES

Industrials fluids contain usually,a mixture of foulants and the asso-
ciation of different types of fouling is often found in industrial equipment.
Experimental studies have been made to investigate the influence of kao-
lin particles on biofouling (S,2S). The induction period seems to be enlar-
ged and it was found that a lower number of cells became attached to the sur-
face, this fact being attributed to the tendency of microbes to cover the
suspended inorganic particles (26), forming aggregates.
On the other hand, higher quantities (weights and thermal resistances)
of biofilm were obtained when the asymptotic values of fouling were reached.
This may be due to the new type of deposit structure or to the stimulation
of atached cells growth and metabolism in the presence of kaolin. The struc-
ture is certainly different since it contains entrapped kaolin~particles
~ 30
.....
:o::
. .
o
E 20
10 .. . .... -•..
••• ••••
•..................................
c: II Ii. •••
@ProcessEng
O
O 2 4 6 8 10 12
t (d)
FIG. 6. Effect of the suppression of nutrients on the thermal resistance

of biofilms
230
which have lower values of thermal conductivity. Besides, it was found (5)
that the growth and reproduction of cells in the film is increased due to
the presence of these inorganic particles. This stimulation is related to
the structure formed in the deposit that tends to be les s compact and there-
fore more favourable to the diffusion of nutrients. It can also constitute a
positive factor for microbial growth the possibility of inorganic particles
function as a source of nutrients when entrapped in the film. In fact, kao-
lin particles tend to became not only colonized by microbe but also coated
with organic molecules when in suspension.
7. IDENTIFICATION OF FOULING MECHANISMS THROUGH THE STUDY OF DESIGN AND

OPERATING VARIABLES
It is eas ily recognized that research on the effects of one or more va-
riables on biofilm formation can be of great assistance in the detection of
the mechanisms controIling a fouling process.
Figure 7. presents values of the deposition flux Ød, as a function of
the Reynolds Numbers, obtained when studying the velocity effect on fouling
caused by Pseudomonas fluorescens (12). The deposition flux decreases with
increasing velocities, indicating that adhesion may be governing the build-
-up of the deposits. In this case, however, for higher Reynolds Numbers the
clear flattening of the curve shows that there is probably another mechanism
affecting biofilm formation. This mechanism was thougk to be bacteria growth
Further studies with the same bacteria confirmed this assumption, since it
was found that the amount of biofilm was highly dependent on the best condi-
tions for growth and reproduction, namely the pH level (as mentioned in poin
4) .
60
~
J
;;:
N
--2
! 40
\
o
...
• 20
\0'-...0 "-0 _ _
o
4000 1000 12000 1aOOO
Re
@ProcessEng
FIG. 7. Deposition flux as a function of

Reynolds Numbers.
231
REFERENCES
1. Characklis, W.C. "Microbial fouling: A Process Analysis" in Int. Conf. on
Fouling of Heat Transfer Equipment, Rensselaer Polythecnic Institute,
Troy, ll.Y., 13-17 August, 251,1979.
2. Sanders, W.M., Ph.D. Thesis, John Hopkins University, Baltimore, U.S.A.
3. Bott, T,R" Pinheiro, M.M.V.P.S., "Biological fouling-velocity and tem-
perature effects", The Canadian Journal of Chemical Engineering, 55, 473,
Aug, 1977.
4. Melo, L.F., Pinheiro, J.D., "Particulate fouling: ControIling processes
and deposit structure" in 8 th Int. Heat Transfer Conf., Paper HX-16, S.
Francisco, USA, 1986.
5. Pinheiro, M.M.V.P.S., Ph. D. Thesis, Univ. Minho, Braga, Portugal, 1987.
6. Dexter, S.C. "Influence of substractum critical surface tension on bac-
terial adhesion - in situ studies", in Journal of Colloid and Interface
Science, vol 70, no. 2, June 15, 1979,
7. Meyer, A.E., Baier, R.E., King, R.W. "Fouling of non toxic coatings in
fresh, bracckish and sea water" in 36 th Canadian Chem. Eng. Conf., Sar-
nia, Canada, 1986.
8. Lund, D., Sandu, C., "State of art of fouling: heat transfer surfaces"
in "Fundamental s and Applications of Surface Phenomena Associated with
Fouling and Cleaning in Food Processing", Tylosand, Sweden, 27 April
1981.
9. Duddridge, J.E., Kent, C.A., Law, J.F. "Bacterial adhesion to metallic
surfaces" in Progress in the Prevention of Fouling, Nottingham Universi-
ty, 137, April 1981.
10. Kent, C.A. "biologial Fouling" Cont.Educ. Course, Univ. Birmingham, 23,
I. Chem. Eng. March 1981.
11. Knudsen, J.G. "Fouling of Heat Transfer Surfaces" in"Workshop on Modern
Developments in Marine Condensers", Monterry, California, March 1980.
12. Pinheiro, M.M.V.P.S., Melo, L.F.; Pinheiro, J.D. "Surface phenomena and
hydrodynamic effects on the deposition of Pseudomonas fluorescens" in
36 th Canadian Chemical Engeneering Conf., Sarina, Canada, 1986
13. Miller, P.C., Ph.D. Thesis, Univ. Birmingham, 1982.
14. Bott, T.R., Miller, P.C., Patel, T.D., "Biofouling in an industrial coo-
ling water system" in Process Bioch. Jan/Feb, 10, 1983.
15. Novak, L. "Control of the Rhine water fouling" in Fouling of Heat Trans-
fer Equipment; Eds: Somerscales and Knudsen, Hemisph. Publ. Corp., 397,
1981.
16. Hattori, R., Hattori, T., "Effect of a liquid-solid interface on the li-
fe of microorganisms", in Ecological review, vol 16, no 1, 63, 1981.
17. Bott, T .R., "Biological fouling of heat transfer surfaces" in Conf. "Fou-
@ProcessEng
l ing-Art or Sc ience?", 117, Uni v. Surrey, England, 1979.

18. Hussain, C.I., M. Sc. Thesis, Univers. Birmingham, 1978.
19. Harden, V.P., Harris, J.O., "The isoelectric point of bacterial cells"
in Journal Bacteriol. Vol. 65, 198, 1953.
232
20. Fletcher, M., Loeb, G.I., "Influence of substractum characteristics on

the attachment of a marine Pseudomonad to solid surfaces" in Applied En-
vironm. Microb., Vol. 37, nO 1, 67, Jan 1979.
21. Neihof, R.A., Loeb, G. L, "The surface charge of particulate matter in
sea wate.r" in Limnol. Oceanogr., vol 17, 7,1972.
22. Mac Rae, I.C., Evans, S., "Factors influencing the adsorption of bacte-
ria to magnetite in water and waste water" in Water Res., vol 17, no 3,
271, 1983.
23. Kornegay, B.H., Andrews, J.F.; Final Report, Fed Water Pollut. Contr.,
1967.
24. Schulze, K.L. Sem. Ind. Wastes, 29, 458, 1957.
25. Lowe, M.J., Duddridge, J.E., Pritchard, A.M., Bott, T.R., "Biological-
particulate fouling interactions: effects of suspended particles on bio-
film development" Symposium Series, no 86, 391, 1984.
26. Gerson, D.F., Zajic, J.E., "The biophysics of cellular adhesion" in Immo
bilized Microbial cells, Ed. K. Venkatsubramanian ACS Symp. Ser., 106,
29, 1979.
@ProcessEng
SURFACE BOUND BIOCIDES - A NOVEL POSSIBILITY TO PREVENT BIOFOULING
K.J. HOTTINGER
Institut fUr Chemische Technik, Universitat Karlsruhe, KaiserstraBe 12,
D-7500 Karlsruhe 1, W-Germany
1. INTRODUCTION
The various types of fouling are classified as biologi cal fouling, chemi-
cal reaction fouling, corrosion fouling, freezing fouling, particulate foul-
ing and precipitation fouling (l). Biological fouling or biofouling repre-
sents the attachment and metabolism of macroorganisms (macrobial fouling)
and/or microorganisms like algae, bacteria and fungi (microbial fouling) on
surfaces. It plays a major role in systems, in which the surfaces are in
contact with water or aqueous solutions. The hulls of ships, heat exchan-
ger s or water tanks are exposed to biofouling deposits. Ion exchange resins
or membranes are further examples, where biofouling poses severe problems.
Methods of mechanical, physical and chemical nature are used for control-
ling or preventing biofouling. The most common method is a chemical one,
namely chlorination, which is applied periodically or continuously.But this
oldest and very effective method, which is also applied in drinking water
supply, is not unproblematic, because chlorinated and probably cancerogenic
hydrocarbons can be formed. Chlorine may react with ammonia forming hazar-
dous chloramines. Therefore, other chemicals or biocides like ozone or qua-
ternaryammonium compourids were introduced.
Bioeides can be devided into two or three categories, namely oxidizing and
n?n-oxidizing chemicals and metal-organic compound s (Sn, Hg). Oxidizing che-
mlcals are chlorine or sodium hypochlorite, chlorine dioxide and ozone. Most
important non-oxidizing biocides are phenolic compounds,quaternary ammonium
compounds, amines and organosulfur compounds. Oxidizing biocides are low-
conventional
@ProcessEng
2 3
time, years
Figure 1 - Biocide (Cu 20) release rate comparison for various types of
antifouling paints
233

234
cos t and very effective products, whereas non-oxidizing biocides are more
expensive and often not effective against all types of microorganisms. Ad-
vantages and disadvantes of the various types of biocides have been summa-
rized by B.M. THOMAS et al (2). The same au thors developed chlor-dialkyl-
amino-s-triazine, which shows a remarkable synergistic effect with chlo-
rine.
Another variety to control or prevent biofouling are antifouling paints or
coatings (3). They may be classified into three categories, namely conven-
tional or soluble matrix paints, long life or insoluble matrix paints and
self-polishing or chemically bound biocides. The effect to these products
is based on a continuous release of the biocides (Cu/O, organotin-compounds)
A linear release or constant release rate is only aChieved with chemically
bound but hydrolysable biocides, so called self-polishing paints, as shown
in Fig. 1. Surface bound antimicrobial substances (biocides) differ from
self-polishing paints. They are directly, i.e. without any binder, bound
to the surfaces, which shall be protected against microbial fouling. The
covalent bond is stable against hydrolysis and the microorganisms (algae,
bacteria, fungi) are killed by contact (4). This new concept will be des-
cribed in the following.
2. THE ROLE OF ADSORPTION AND ADHESION IN MICROBIAL FOULING

The initial step in biofouling is the adsorption of microorganisms on a
surface. Adsorption or adhesion, which is the decisive factor in flow sy-
stems, are control led by selective interactions between the surface of the
substrate and the microorganisms. Most microorganisms bear a negative char-
ge. For illustration of these selective interactions Figs. 2 and 3 show re-
sults on the adsorption of Escherichia coli, which has an isoelectric point
between 2 and 3, on various polystyrene materials and ion exchangers of sarr
morphology (spheres of equal diameter) but different functional groups (5).
Fig. 2 reveals that adhesion to the pure, i.e. non-polar, polystyrene is
negligible, whereas strongest adhesion occurs on amino-methylated polysty-
rene. On the other hand, electrostatic repulsion hinders adhesion of Esche-
richia coli on the cation exchange resin (Fig. 3). As a consequence, non-
polar surfaces due to small dispersive interaction forces only cause weak
adhesion and the microorganisms can easily be removed.
o .8--!-------- - - - j -
_1'Ø'~
~ ~.
~-2 "'~~
-3 I~~.
...... '-..~ .....".~
'"
-4
:~
-50~----~~----~100~~--~1~·
TIME. MIN
@ProcessEng
Figure 2 - Logarithm of relative bacterial counts versus time; shake tests:

polystyrene (~) chlormethylated (6), hydroxymethylated (.) amini
methylated polystyrene (~), aminomethylated polystyrene at pH 71
235
o ''''~",. 8 - - - 0 - - - - - _ _ __
o Cl.::::::::.. Cl
:~8
~8~8
E -2 I~
I~
-4~-----~-----~---J
o so 100
TIME, MIN
Figure 3 - Logarithm of relative bacterial counts versus time; shake tests;

ion exchange resins, strongly acid (o), weakly basic (~), strong-
ly basic (e)
A probably more effective solution of the problem represent surface bound
biocides, which differ from known antifouling coatings or paints by a hy-
drolysis stable bond. In principe, all types of biocides may be used for
surface binding, provided that they are antimicrobial active in the bound
state (4).
3. ANTIMICROBIAL ACTIVITY OF SURFACE-BOUNO 610CIOES
The possibilities of binding biocides on inert surfaces are shown in
Fig. 4. Binding can be performed without or with a spacer or coupling
agent; biocides must have one reactive group, which may not be the anti-
microbial active group.
Screening tests, to determine whether a surface bound biocide is active or
not, were performed with cellulose as substratematerial. Table l gives some
results with pure organic and metal-organic antimicrobial active compounds
(4). For these studies, the agar plate test was used. It follows that only
phenol (hydroxyaniline) and tetrachlorobenzene (tetrachloroaniline) are not
active. These biocides obviouslyrequire incorporation into the protoplasma
of the microorganisms, which is not possible. The highest activity is achie-
ved with mercury- and tin organic compounds, which is equivalent to the ac-
tivity of these chemicals in the dissolved state.
®--c8 ~ Inert solid
lsp~ aellvallon l
ma t ter surfaee
ar coupling
agent
@-Co-e
~ solid matt~r surfaee
6
l
WI th reactlve groups
8~cK:1®=C D--@i~L~ ~~;ound

@ProcessEng
G--C
Spacer
J-®
B without
wlth spacer ar spacer ar
Figure 4 - Possibilities of covalent biocide binding on solid surfaces

236
Sample Ant imi crobi a l Activity

Remarks
Ce 11 u-
Spacer Bioeide Ch.vio-
lose A.niger E .co l i M.flavus
l aceum
A a l dehyde (A-Ce 11 . ) ++
I ami no~utyra l dehyde +
A
I hYdro~yani 1 i ne
A
I tetrach loran i l ine
A -" -
ami no~henylmercuryacetate ++ ++ ++
++ ++ ++ ++
-" - + + ++ pH4, pHIOI)
-- " -- ++
++
++ ++ ++ pH71)
Ex.5 daysl)
" ++ ++ ++
C diamino-
hexane d i butr,lt i ndi ch lori de ++ ++ ++
M
A diamino-
hexane tri bu~ylt i nch l or i de ++ ++ ++ ++
C -" - ++ ++ ++ ++
C -" - -- " - + pH4, pHIO
C -" - "- ++ ++ ++ ++ pH7
C "
A diamino-
-- -" - ++ ++ ++ ++ Ex .5 days
propane
C diamino-
-- ++ ++ ++ ++
hexane tri phenylt i nch l ori de ++ ++ ++ ++
++ no growth
inhibition of growth
no inhibition of growth
1)
pH4, pHIO : hydrolysis test with buffer solutions, 7 days
pH7 : hydrolysis test with HZO, 7 days
Ex, 5 days: extract i on with HZO, 5 days
Table 1 - Results of the agar plate tests

Some applications of the products with cellulose as substrate were success·
fully demonstrated. Fig. 5 shows the effect of surface-bound biocides agair
biodeterioration of paper &6). Paper strips ((a) untreated, (b)-(f) treatel
were exposed to soil at 30 C and 95% relative humidity.The untreated paper
is strongly deteriorated already af ter 3 days, whereas the same paper with
surface bound aminophenylmercuryacetate is only sligthly attacked even af ti
17 days.
Paper with bo und aminophenylmercuryacetate was used as filter for a germ
filtration of air. Fig. 6 shows results of the agar stamp test, whereby thi
used filter papers were stamped on agar and then incubated (7). No colonie~
are found on the stamp of the paper with bound biocide, which again under-
lines the effectivity of this product.
The most attractive application of surface-bound biocides is disinfection
of drinking water. For this purpose, special quaternary ammonium compounds
were bound on glass microbeads. Packages of such microbeads were success-
@ProcessEng
fully tested as deep-bed-filters for water disinfection. It was found that

complete disinfection (Escherichia coli) is already possible with a bed
height of 6 cm.
237
Figure 5 - Paper strips af ter expo- Figure 6 - Growth of air germs on fil-
sure to soil for various ter stamp areas. top: trea-
times. a: untreated, b: ted filter paper: bottom:
carboxycellulose, c: tri- untreated filter paper.
butyltinchloride impregna-
ted, d: tributyltinchloride bound, e: aminophenylmercuryacetate
impregnated, f: aminophenylmercuryacetate bound.
yH3
O,
Hj:-O-S,i -(CH2)3-CI +
,
O
CH3
yH 3
O R1
, '.,
H3C-O-~i -(CH2)3-~ -R3 Cl e
O
, R2
CH 3
R1.Ri -CH 3: R3: -C-oI121 up to -C1sH37

@ProcessEng
Figure 7 - Synthesis of quaternary ammonium compound s with silane coupling

agent
238
4. ADVANCED BIOCIDES FOR ANTIFOULING TREATMENTS

In the basic studies described above, the substraies ~ere carefully se-
lected in view of an absolutely hydro lys is-stable bond of the biocide. No
care was taken on the economics of binding. For technical applications, spe-
cial biocides were developed, which can economically be bound on the surfa-
ee of numerous materials. This was possible by applying silane coupling
agents (8, 9).
Biocides are formed by reaction of t -chloropropyltrimethoxysilane with
tertiary amines as shown in Fig. 7. The tertiary amines ean bear two methyl
gro ups (R , R ) and one long-chain aliphatic group (R ). But it is also
possible,lthaf RI and R2 are two long-chain aliphatic 3groups, for instance
C H and R is a methyl group. As the long-chain aliphatic group deter-
mt~e§5the wettabilty of the treated surface, the availability of different
quaternary ammonium compounds allows the preparation of the surface as de-
sired.
Application of the products is easy. Impregnation of the surfaces with
aqueous solutions of the biocides followed by thermal treatment at about
100 0 C in air is sufficient. By this treatment, the methoxy groups hydro-
lise and form a Si-O-Si-network, which is hydrolysis-stable up to 120 0 C.
Fig. 8 shows the binding on a glass surface. Besides the covalent bond with
silanol surface groups, electrostatic and composite bonds can additionally
be formed. The composite bonds lead to multilayers of the biocide, which
is favourable. This is specially the case with glass, in which an adsorp-
tive layer of water can exist between the surface and the biocide layer.
Quaternary ammonium compounds as bioeides ean have disadvantages. Due to
their positive charge, they attract negatively charged microorganisms.
They ean also be inactivated by several substances like serum or proteins
(10). Both properties are unfavourable. The problem may be overcome by de-
velopment of non-polar biocides for binding on surfaces. For example, use
ean be made of triorganotin compounds which are even more active than quar-
ternaryammonium compounds (11). A possible synthesis if these produets
using vinyltrimethoxysilane as coupling agent is shown in Fig. 9
@ProcessEng
Figure 8 - Binding of quats with silane coupling agent on a glass surface

239
~H3
O R
I
H3C-O-Si -CH =CH 2
I
+ H-Sn-R
I
•
O R
CH 3
~H3
O R
H3C-O-Si-CHT CH 2
I
-Sn-R
I
O R
CH3
Figure 9 - Synthesis of organotin compounds with silane coupling agent

5. CONCLUSION
Covalent chemical binding of bioeides on surfaces offers a novel tech-
nique with numerous applications. It is unprobable that the problem of
biofouling ean generally be solved by this technique. However, for some spe-
cial problems in this broad field, chemically bound bioeides could repre-
sent the preferred solution.
6. REFERENCES
l. Epstein, N.: in 'Fouling of Heat Transfer Equipment' (Somerscales and
Knudsen, Eds.), Hemisphere Publ. Corp., Washington, D.C. (1981) 31
2. Thomas, B.M. et al.: in 'Specialty Chemicals' Redhills, Surrey 3 (1983)
(a) 22-27
3. Sghibartz, C.M.: FATIPEC Congress, Weinheim (1984) 145
4. HUttinger, K.J., MUller, H. and Bomar, M.T.: J. Coll. Interf. Sc. 88
(1982) 274 --
5. HUttinger, K.J., Rudi, H. and Bomar, M.T.: Zentralblatt fUr Bakteriologie,
Mikrobiologie und Hygiene, Reihe B (1987) in press
6. HUttinger, K.J.: Material und Organismus 17 (1982) 285
7. HUttinger, K.J., and MUller, H.: Chem.-In~-Techn. 54 (1982) 58
8. HUttinger, K.J., and Zeller, D.: Chem.-Ing.-Techn. 59 (1987) in pres s
9. HUttinger, K.J.: Chemiker-Zeitung 111 (1987) in press
10. Wallhauser, K.H. and Schmidt, H.: 'Sterilisation, Desinfektion, Konser-
vierung', Chemietherapie, Thieme-Verlag, Stuttgart (1975)
ll. Bokranz, A. and Plum, H.: Fortschritte der Chem. Forschung ~ (1971) 365
@ProcessEng
EXPERIMENTAL INVESTIGATION OF MARINE BIOFOULING AND CORROSION
FOR TROPICAL SEAWATER*
C.B. PANCHAL
Argonne National Laboratory

Argonne, Illinois 60439 U.S.A.
1. INTRODUCTION
Biofouling and eorrosion for marine heat exehangers are being
investigated at the Natural Energy Laboratory of Hawaii under eontraet to
the U.S. Department of Energy. The objeetive of this experimental
investigation is to determine effeetive fouling-eontrol teehniques for
ocean thermal energy conversion (OTEC) heat exehangers, whieh must be kept
elean enough to maintain heat-transfer resistanee (R f ) values below 0.02
m2K/kW. Due to the laek of experimental data bases and predietion
methods, fouling-eontrol teehniques developed for eonventional heat
exehangers cannot easily be extended to OTEC applieations. In addition,
it is important for the sueeess of OTEC to develop low-eost heat exehan-
gers that will use less-expensive materials.
Therefore, a long-term experimental program was initiated during an
early stage of the projeet. Af ter conducting preliminary experiments in
the gulf of Mexico on a floating platform (1) and in Hawaii with a
submerged buoy (2), a permanent test faeility was built on the island of
Hawaii. Over several years of eontinuous testing, many series of experi-
ments were earried out to develop a teehnieal data base for biofouling and
eorrosion of eandidate materials. In this paper, the experimental inves-
tigation is summarized, and observed data are diseussed.
2. EXPERIMENTAL ANALYSIS
2.1 Test Faeility
The test faeility for the OTEC biofou1ing and eorrosion studies is
loeated at the Natura1 Energy Laboratory of Hawaii (NELH). The warm-water
intake is loeated 100 meters offshore in a water depth of 20 meters. The
warm water is pumpe d through a 30.S-em-diameter polyethylene pipe into a
1900-1iter elevated tank. Water from the elevated tank is distributed to
the experiments by a plastic booster pump. The cold water-eonduit is also
a 30. S-em-diameter polyethylene pipe about 1700 meters long, taking deep
cold water from a depth of about 670 meters. The cold-water intake pump
is submerged at a depth of 10 meters and is about 3S meters offshore; the
cold water is pumped under pressure to shore and then distributed to the
experiments. Water flows continuously through the test system. Water
interruptions are general ly limited to a few hours; however, during one
major storm that caused the breakup of the eold-water pipe, flow was
interrupted for several days. During flow interruptions, steps are taken
to preserve experimental eontinuity by maintaining some minimum flow, or
at least by keeping the surfaee wet. On all oecasions, continuity in the
@ProcessEng
fouling curve was observed, indicating that no major upset took place in
the fouling layer.
*Work supported by U.S. Department of Energy, Assistant Secretary for

Conservation and Renewable Energy, under Contract W-31-109-Eng-38.
241

© 1988 by Kluwer Academic Publishp, •.
242
The chernistries of the warm and cold water used for the present
experimental investigation are shown in Table l, averaged over ayear.
Parameters such as total organic carbon (TOC) show some seasonal vari-
ation. Warm-water temperatures varied from about 25°C in winter to about
29°C in summer. Cold-water temperatures during the test period ranged
from about 8.5°C to 10.5°C; these variations are mostly due to changes in
the cold-water flow rate in the 1700-meter pipe, which in turn varies the
heat gain from the surrounding warm water.
2.2 Experimental Test Loop

Eighteen (12 for warm water and 6 for cold water) parallel test
loops were installed at NELH. Each experiment consisted of a Carnegie
Mellon-Argonne National Laboratory heat-transfer monitor (HTM) installed
on a 2. 54-em-diameter metal tube, followed by a series of 15-cm-long
sample tubes, which were used for biofouling and corrosion analysis. For
a detailed discussion of construetion and operation of the HTM, refer to
Argonne report (3).
3. RESULTS AND DISCUSSION

3.1 Biofouling of Corrosion Protective Surfaces
Figure l shows free fouling of a titanium surfaee in warm water.
Only a portion of the total per iod is shown; the remaining data show a
similar fouling behavior. The water velocity was 1.86 m/s, and the test
section was cleaned with a soft nylon brush when the Rf value reached
about 0.09 m2 K/kW. During each brushing cyc1e, Rf was brought to about
zero in 2 to 5 cycles of brushing. Data analysis and the scanning elec-
tron microscope (SEM) show that the biofilm is not completely removed.
However, the small fraction of patchy film left on the surfaee enhances
the convecti ve heat-transfer coefficient. As aresult, the HTM measure-
ment shows negligibie fouling resistance although the surfaee has
scattered microorgani sms and a polymer layer. However, the resul ts show
that the res idual fi 1m does not grow wi th each cycle, even though no
chlorination was used for the oxidation and subsequent destruetion of the
film.
TABLE l Chemistry of Water Used at NELH
Surfaee Deep
Parameters Warm Water Cold Water
Salinity, parts per thousand 34.69 34.30

pH 8.19 7.54
Constituents, ~g-atom/l
phosphate 0.14 2.97
nitrate and nitrite 0.12 40.10
silicate 3.34 77.70
Total dissolved nitrogen (TDN)b 4.23 41.80
Total dissolved phosphorus (TDP)b 0.34 3.00
Total organic carbon (TOC)a 0.75 0.38
@ProcessEng
Dissolved oxygen (ppm) 7.80 1. 70
aUnits for TOC are mg!l.

bUnits for TDN and TDP are ~g-atom/l.
243
0.12,------------------------,
• Rf Volu. afte r 1 Cycle of Brulhlng
Wanual Brulhlng 6
0.10
5 ...
o.oa 52
~ x
~ 4 :l
~
o
0.06
3
~
o
'"E ....
.s:::
rI 0.04 '"~
~
0.02
0.00 o
600 700 800 900 1000

Test Period (Days)
FIGURE l. Free Fouling of Titanium Followed by Manual Brush Cleaning
In a separate series of tests, periodic chlorination as a

biofouling-control method was studied. The objective was to experimen-
tally determine the minimum use of chlorination required for maintaining
the Rf value below 0.02 m2 K/kW. Table 2 shows the chlorination schedule
that was followed in thi s series of experiment. The resul t s show that
70 ppb of residual chlorination (equivalent oxidant) a~plied for one hour
per day kept the fouling resistance below about 0.02 m K/kW. Subsequent-
ly, chlorination was reduced to 50 ppb, again applied for one hour per
day. There was a slow increase in the fouling resistance, especially
during the summer months when the rate of fouling is in general greater
than normal. This observation was confirmed with a separate series of
experiment s wi th an AL-6X alloy-s teel test section. The analys i s of
biofilm show that the ratio of total dry film weight to fouling resistance
Rf for chlorination experiments is higher than that for manual-brushing
experiments (4). A possibie explanation is the existence of patchy films
in chlorination experiments that might increase the wall roughness -- and
hence the enhancement of heat transfer.
In order to determine the effects ofaxial distribution of
chlorine, a series of tests was carried out in which two HTMs were
instalied one at the upstream end and one at the downstream end of the
flow loop separated by about 12 meters (Tests 6 and 7 in Table 2). The
results show that the initial chlorination rate of 50 ppb applied for one
hou r per day maintained low Rf value for both HTM locations. However,
during the summer months, biofouling observed at the downstream HTM could
not be maintained at a low level, al though no significant foul ing was
observed at the upstream HTM. The analysis of biofouling samples located
near both HTMs confirm the heat-transfer measurement • It can be argued
that due to entrance effects for the in-situ-generated hypochlorite ions,
their diffusion to the upstream HMT surface is greater than for the down-
stream HMT, where a fully developed concentration profile for hypochlorite
@ProcessEng
ions has been established. Water samples taken at both HTM locations
showed an insignificant consumption of oxidant. Later, the chlorination
level was increased to 70 ppb on the same application schedule. The Rf
value decreased but not significantly. When the chlorination level was
further increased to 100 ppb on the same application schedule, the fouling
resistance was maintained below 0.02 m2K/kW at both HTM locations.
244
TABLE 2. Chlorination Schedule for Biofouling Control Experiments
Test Test Residual Schedule Test

Section No. Oxidant (ppb) (h/day) Duration (days)
Titanium l 70 l 745
2 50 l 305
AL-6X Steel 3 35 l 155
4 70 2 75
5 70 l 284
Titanium 6 50 l 193
7 100 l 251
Chlorination was also evaluated for removing an established

biofouling film. A titanium test section was allowed to foul to an Rf
value of about 0.09 m2K/kW before a chlorination schedule was initiated.
The number of hours for which chlorination was required to remove the
established biofouling film and res tore the heat transfer coefficient
varied with the chlorination dosage and application schedule 0, 2, 4
hours per day or continuous). The fouling-resistance (R f ) curve shows a
sudden drop, and then becomes nearly linear unti1 a low value for Rf is
reached (5). The rate of removal of biofouling was nearly constant for a
given dosage level, irrespective of chlorination schedule. Chlorination
dosage, on the other hand, had a significant effect on the rate of removal
of biofilm; the removal rate for 70 ppb chlorination was about 2.5 times
that for 50 ppb chlorination.
Af ter about 1500 days of experimental measurements, no significant
biofouling resistance caused by deep cold water was observed. The sample
analysis showed littie buildup of biofilm. It is argued that the combined
effects of low concentration of microorganism, low TOC, low water tempera-
ture, low oxygen, and the change in pres sure from about 60 atm to l atm
are responsibie for the negligibie biofouling from deep cold water.
3.2 In-Situ Corrosion Fouling

Since aluminum alloys are leading candidates for OTEC heat exe han-
gers, several commercial alloys were tested to determine their corrosion
rate. Table 3 summarizes the test matrix. Except for Test l, biofouling
is control led by adaily dose of chlorin~tion. For Test l, the biofouling
was allowed to reach to about 0.09 Km /kW before the test sect ion was
brush-cleaned. All cold-water experiments were run without any cleaning,
as no biofouling was expected. A typical warm-water fouling curve shows a
rapid increase in the heat-transfer resistance before an asympototic value

is reached. (See Fig. 2 for warm-water corrosion fouling of Al-3003.)
Daily chlorination of 100 ppb for this test series kept biofouling to a
minimum value. The fouling curve for aluminum alloys in general follow
the curve for uniform wallioss due to corrosion. It has been observed
that if the chlorination level is not sufficient, unusual fouling behavior
ean occur in which fouling will increase rapidly and then drop. This ean
@ProcessEng
be explained on the basis of sloughing off of biofilm that may be unstable

on corrosion film.
245
TABLE 3. Test Matrix for Corrosion Experiments
Ch1orination
Test Dosage/Duration Test Duration
No. Test Section (ppb/hr) per day Materia1 Days
Warm Water Tests

l P1ain tube None Al-3003 b 1840
2 P1ain tube 100/1 Al-5052 1280
3 Rectangu1ar channe l 70/1 Al-3003 a 1290
4 Spirally f1uted tube 70/1 Al-6061 720
5 P1ain tube 100/1 Al-3003 760
Co1d Water Tests
6 P1ain tube None Al-3003 b 1670
7 P1ain tube None Al-5052 1190 c
8 Spirally fluted tube None Al-5086 190
9 Rectangu1ar channe l None Al-3003 a 1280
10 Plain tube None Al-3003 760
aDiffused zinc coating on Al-3003 surface

bAl-7072 c1adding on Al-3003 surface
cTest section was acid cleaned af ter 766 days and test restarted
0.1O-r---------------------~- 20
0.09 x FOULlNG FACTOR
O WALLLOSS
0.08
- 15
0.07
o
a= 0.06
o
~
......... O
~ 0.05 0° -10
C\l
:::!I O
0.04
r:.
~
0.03
- 5
0.02
0.01
~
X
0.00 o
O 100 200 300 400 500 600 700 800
TEST PERIOD, DAYS
@ProcessEng
FrGURE 2 Corrosion Fouling of Bare Al-3003 in Surface Warm Water

246
0.10
0.08 X AL - 3003
O AL-3003ZN
0.06 + AL - 5052
~
::.::
..........
::.:: 0.04
C\I
::::!!
ro..
o:: 0.02
0.00
-O.02+--...,.--.....,r----.,---""T"----r---,....---!
O 200 400 600 800 1000 1200 1400
TEST PERIOD, DAYS
FIGURE 3. Corrosion Fouling of Bare Al-3003 and Al-5052 Tubing, and
Diffused-Zine-Coated Al-3003 Reetangular Test Sections
Figure 3 shows fouling resistance from deep eold water. No sig-

nifieant biofouling is expected to be caused by deep water; therefore, the
observed fouling is mostly due to corrosion film and possibly the preeipi-
tation of inorganic eompounds. The analysis (4) showed that the organic
components of the film eonstitute less than about 3% of the total film
weight. Three aluminum alloys showed different fouling characteristics as
seen in Fig. 3. For unexplained reasons, the fouling resistanee for Al-
3003 remained negligible; it became negative indicating heat-transfer
enhancement due to inereased roughness. During the test period, the HTM
ealibration was redone; however, the previous trend continued. On the
other hand, the fouling resistanee inereased linearly for Al 5052. The
trend continued af ter aeid cleaning to remove the corrosion-fouling
film. The rectangular test seetion of Al-3003 showed an asympototie
fouling behavior. Clad Al-3003 (not shown in Fig. 3) showed fouling

behavior similar to the Al-300l rectangular test seetion. The exaet
mechanism for in-situ eorrosion fouling of aluminum alloys has not been
fully investigated. Therefore, it is not possible to quantitatively
determine the effects of oxygen, seawater ehemistry, temperature, and pH
on the rate. of corrosion fouling.
@ProcessEng
4. CONCLUSIONS
An experimental investigation of fouling in tropieal seawater was
carried out. Af ter an extended period of testing, several key conclusions
important to ocean-energy systems were reached. Moreover, the experimen-
tal data ean be used to gain an improved understanding of fouling mechan-
isms, and ean aid in the development of predictive methods.
247
REFERENCES
l. Sasscer DS, Torsteson TR, and Morgan TO: OTEC Biofou1ing, Corrosion,
and Materials Study from a Moored Platform at Punta Tuna, Puerto Rico,
Argonne National Laboratory Report, ANL/oTEC-BCM-023, August 1981.
2. Munchmeyer FC, Berger LR, and Liebert BE: Five OTEC Biofouling and
Corrosion Experiments at Keahole Point, 1976-1980, Argonne National
Laboratory Report, ANL/oTEC-BCM-026, November 1981.
3. Panchal CB et al.: OTEC Biofouling-Control and Corrosion-Protection

Study at the Seacoast Test Facility: 1981-1983, Argonne National
Laboratory Report, ANL/OTEC-TM-5, July 1985.
4. Berger LR, and Berger JA: Countermeasures to Microfouling in

Simulated Ocean Thermal Energy Conversion Heat Exchangers with Surface
and Deep Ocean Waters in Hawaii, Applied and Envi ronmenta1
Microbiology, Vol. 51, No. 6, June 1986.
5. Panchal CB, Larsen-Basse J, and Little B: Biofouling Control for

Marine Heat Exchangers using Intermittent Chlorination, Fouling in
Heat Exchange Equipment, ASME Publication HTD-Vol. 35, August 1985.
@ProcessEng
@ProcessEng
Chapter 6
Crystallisation Fouling
CRYSTALLISATION FOULING - BASIC SCIENCE AND MODELS
T.R. BOTT
Department of Chemical Engineering, University of Birmingham, PO Box 363,

Edgbaston, Birmingham B15 2TT, England.
l. INTRODUCTION
One of the common ways in which heat exchangers, or other pieces of
equipment for that matter, become fouled is through the process of
crystallisation. It usually involves aqueous solutions of soluble salts,
which are either being heated or cooled. For this reason cooling water
systems are often prone to crystal deposition, due to hardness salts, the
problem being more acute where the dissolved solids content is high.
Potential scale former~ are CaC0 3 , CaS0 4 , C~3(P04)2 and corrosion
products. In an open cool~ng system where water ~s evaporated to effect
cooling, concentration of salts will occur even though the lost water is
replaced since the make up water will contain salts. It is usual to employ
a bleed 'of concentrated cooling water in order to reduce the solids content
and maintain control; a careful balance between make up, bleed and
atmospheric loss is necessary. Fouling due to crystallisation can lead to
a hard tenacious deposit often referred to as a "scale", or a more porous
loosely adherent mass, described as a "softscale" or a "powdery deposit" or
a "sludge".
In general it can be said that fouling due to crystallisation from
cooling water will be accompanied by other mechanisms notably biofouling,
particle deposition and corrosion. In certain plant, sea water is used for
cooling purposes, and was common practice in the older systems of ship
propulsion where steam turbines were employed. The sea water with its high
levelof dissolved salt, could give rise to deposition in the condenser
tubes.
It has long been recognised that, notably for reasons of efficiency,
but more importantly for the sake of safe operation, boi ler feed water must
be free of dissolved solids, or at leas t treatment carried out so that
deposition does not occur on the boiler tubes.
The utilisation of energy derived from geothermal water sources may be

subject to crystallisation fouling. If the geothermal water is at a high
temperature under the appropriate pressure, flashing will release steam
which may be utilised directly for expansion through a turbine to obtain
drive energy. The residue water from the flash proces s still contains a
substantial amount of energy but in general, it will contain a high level
of dissolved salts. To extract some of this remaining energy means that
@ProcessEng
the problem of crystallisation will have to be faced in the heat recovery

system.
In the food industry, the occurrence of "milk stone" in exchangers
used for milk sterilisation is often attributed to a crystallisation
process, although it will be apparent, because of the complex chemical
nature of milk, other fouling mechanisms are likely to be present.
251

252
In processes where the production of crystals is part of the process,

for instance in the manufacture of solid salt from brine, or caustic soda
crystals from the aqueous solution, there is also likely to be a fouling
problem from crystallisation. In these proces ses the concentration of the
salt in solution is increased by evaporation in suitable heat transfer
equipment. The heat effect coupled with the removal of water can give rise
to some difficult fouling problems.
These few examples indicate how widespread the problem of
crystallisation fouling is likely to be in a large variety of different
industries.
In 1981 a very detailed review of crystallisation fouling was
published by Hassan (l) which covered many aspects of the subject and
probably represents the most comprehensive accumulation af published data
available at the present time. It contains 122 references.
The process af crystallisation consists essentially af two stages,
which generally occur at the same time, but for the purposes af
understanding the mechanism, they may be considered separately. The firs t
stage involves the creation af small particles, which are aften referred to
as nuclei. The second stage is the growth af the crystalline structure
around the nucleus. The number af nuclei present in a solution controls
the ultimate size af crystals formed.
2. FUNDAMENTALS OF GRYSTALLISATION
Deposition from solution is a camp lex phenomenan. For all soluble
salts there will be definite relationships between the saturated solubility
af the salt and temperature. In general the solubility will increase with
temperature but there are certain salts whose behaviour is different and
the temperature coefficient af solubility is negative and same times it is
zero.
Grystallisation ar precipitation fouling arises from the creation af
supersaturation potential. The usual process conditions which may lead to
supersaturation situations are:
l. A solution evaporated beyond the solubility limits af adissolved
salt.
2. A solution containing a dissolved salt af normal solubility is
cooled below its solubility limit temperature; or a solution containing a
dissolved salt of inverse solubility is heated ab ove the solubility
temperature.
Fig. l shows a typical saturation curve for a normal solubility salt -
say NaGl.
~
o
c: C~ ____~______,a
o
....es Ca - - - -
....c:
'-
GI
u
c:
o
u
@ProcessEng
Tempera ture
FIGURE l. Saturation concentration versus temperature for a typical salt
253
If the salt is dissolved in water at a temperature of T so that its

concentration is c , the solution will be homogeneous with Ro evidence of
crystals. On coolrng the concentration remaining constant, a point on the
saturation curve b will be reached. It will be expected that at this point
precipitation would occur, but in general this will not happen unless
nuclei are present. Usually a measure of supercooling will be required
before precipitation begins. On Fig. 1 point c is usually referred to as
the supersaturation point of the solution, and the supersaturation in terms
of temperature is bc and in terms of concentration, cd. Point c may be
re garde d as a kind of metastable point in the solution, the stability of
which may be affected by the presence of nuclei - either small crystallites
of the salt in solution or indeed foreign particulate material. The
implications for heat exchanger fouling where conditions near to saturation
are present, and in the heat exchanger the necessary temperature changes
take place around the saturation temperature, are apparent.
Fig. 2 presents a solubility curve for a salt whose solubility
decreases with temperature (usually called an inverse solubility salt to
be contrasted with a normal solubility salt).
o~
c
O
Temperature
FIGURE 2. Saturation concentration versus temperautre for an inverse
solubility salt
If the salt is dissolved in water at a temperature of T so that its

concentration is c , the solution will be homogeneous witha no crystals
present. As the te~perature of the solution is raised, the concentration

remaining constant a point on the saturation curve corresponding to point b
will be reached. As for the normal solubility salt being cooled, it is
unlikely that crystals will appear at this point and as the temperature is
raised still further, the solution will enter a metastable state.
Superheating will be required before crystals of salt appear. Point c on
Fig. 2 represents a saturation point and the supersaturation may be
@ProcessEng
measured in terms of temperature bc or concentration cd. As with normal

solubility salts, precipitation may be initiated by the presence of a
surface, contaminating partieles, or small crystallites.-
In some chemical species the stable crystal-form changes as the
temperature changes, for instance with hydrated salts, and the curve unlike
those on Figs. 1 and 2 is discontinuous. The temperature coefficient may
254
be positive over part of the range of temperature and negative over the
remainder.
A negative coefficient indicates a heat of reaction as the material
passes into solution, which is greater than the heat absorbed due to the
solution of the solid and the heat of dilution combined. Some salts like
ferrous sulphate show a number of discontinuities which are associated with
the changes in the stable form of the material. Crystallisation from
aqueous solution of ferrous sulphate at temperatures up to SOoC gives rise
to the formation of a hydrate with seven waters of crystallisation i.e.
FeS0 4 .7H ZO. At higher temperatures the salt contains 4 waters of
crystal11sation, or even anhydrous ferrous sulphate (i.e. FeS0 4 4H ZO or
FeS0 4 ). The crystalline form which will appear on a surface therefore,
depends very much on the temperature in the proximity of the surface or
more precisely the temperature of the solid salt itself. It is evident
that with salts of this character the crystal form may change from location
to location in a heat exchanger. This sort of behaviour has been noted in
heat exchangers and may account for some of the "layering" observed to
exist across deposits.
In a heat transfer process there is, of necessity, a temperature
gradient across the metal/solution interface, so that supersaturation
conditions may exist with respect to the heat transfer surface, without
necessarily having supersaturation with respect to the bulk solution
temperature.
2.1 Chemical eguilibria

Other principles of chemistry may be important in the production of
conditions within the solution which may lead to supersaturation. Because,
in general, fouling problems are produced by sparingly soluble salts, the
princip les involved will be those concerned with equilibria particularly at
saturation.
The saturation concentration of a sparingly soluble salt is determined
by the solubility product principle e.g.
++ --
[Ca ls [C0 3 l = Ks i.e. the concentration solubility product
If the concentration of any Ca++ is increased in a saturated solution then

the [C0 3 --1 must decrease to maintain a fixed solubility product.
In other words the common ion effect acts to repress the saturation
concentration of one of the ions forming the salt e.g. excess Ca++ reduces
the saturation concentration of C0 3 --
The distribution of ions is governed by solution equilibria relating to
an independent set of reactions in which the ions participate. Acid-base
equilibria are particular examples.
When the liquid is exposed to a gas phase e.g. air, the gas-liquid
equilibrium will determine the saturation concentration of the dissolved
molecular species.
The pH of the solution is also likely to affect the potential of the
solution for fouling, since pH generaIly affects the equilibrium between
the species of ions present, particularly under sparingly soluble
conditions.
@ProcessEng
2.2 Nucleation
Spontanous nucleation as the foregoing brief discussions suggests,
takes place with some difficulty; it requires an "upset" in the metastable
condition. "Seeding" of the solution may occur as aresult of random
variations in concentration or temperature on the molecular scale. It is
255
generaily accepted that smaller particles will have a greater solubility

than larger partieles, and as a result, a nucleus will grow only if it is
sufficiently large for the solution to be supersaturated with respect to
it.
The experimental study of nucleation is difficult because it is usually
impossible to separate the proces s of nucleation from the mechanism of
crystal growth. However it is possibie to make some generalised statements
about nucleation and growth:-
l. Large crystals will be formed as aresult of a slow rate of
cooling, because the spontaneous nucleation is reduced and the deposited
material is clustered around relatively few nuclei.
2. Small crystals are formed in relative profusion when rapid cooling
takes place because a relatively large number of nuclei are present.
In some materials spontaneous nucleation takes place when even a small
degree of supersaturation is present. In others very large supersaturation
temperatures are required before any deposition occurs.
Spontaneous or homogenous nucleation may probably only be associated
with clean conditions, in terms of the vessels in which the solution is
contained or the solution itself. Conditions associated with heat
exchangers could hard ly be described as "clean" in these terms. The
surfaee of a heat exchanger is likely to be contaminatedand rough, and the
solution itself is likely to contain suspended particles or other
impurities.
Primary heterogenous nucleation is based on the concept that
spontaneous nucleation is more readily achieved in the presence of trace
impurities. Under these conditions, it is assumed that the nucleus
requires less interfacial energy for its formation than without the
impurity due to contact with a wetted solid surface.
At much lower supersaturation leveis, so-called secondary heterogenous
nucleation occurs and is the major mechanism in the presence of crystals.
Secondary nucleation is extremely complex and covers a wide range of
situations. Collision breeding for instance, is believed to be widespread
whenever high fluid shear conditions exist, which favour crystal to crystal
or crystal to wall collisions. Regions of high fluid shear are very likely
to exist in heat exchanger systems. At low supersaturation leveis,
collision breeding may result in crystals (partieles), in suspension, so
that the mechanism of fouling at the wall, is rather that of particulate
deposition instead of crystallisation at the heat exchanger wall itself.
The final result, namely a reduction in heat transfer will be the same,
although the quality of the deposit layer could be substantially different.
The deposit formed could be a loose aggregate of partieles, whereas
crystals formed on the surfaee may present a strong structure.
Where supersaturation is high, primary heterogenous nucleation is
likely to occur on the wall of the heat exchanger leading to an adherent

crystal layer, that resists the effects of fluid shear.
Nucleation at the surfaee under boiling conditions may be different
from that experienced where there is no change of phase; conditions at the
surfaee will be different where vapour is being produced. Since the
surfaee of the metal wall in contact with the solution represents a lligher
temperature than the remaining bulk of the solution, it is at the surfaee
@ProcessEng
that boiling will occur. The presence of bubbles of vapour at the surfaee
will influence the crystallisation proces s , particularly as far as
nucleation is concerned. Palethorpe (2) demonstrated that crystals form
around the bubble envelope, in confirmation of the work of Partridge and
White (3). These authors published photographs showing that the evolution
of bubbles left a ring of CaS0 4 scale on the surfaee to mark the site of
256
the original bubbles. Partridge and White concluded that the local
temperature on the dry metal surface in contact with the vapour, together
with the concentration effect due to the growth of the bubble, created a
high supersaturation level at the triple point - vapour, solution and metal
interface.
Since the rate of generation of bubbles is a direct function of the
heat flux, the fouling rate due to crystallisation under boiling
conditions, will also depend upon heat flux.
2.3 Induction periods

There is usually a period of time which elapses between the achievement
of supersaturation and the appearance of the first crystals, which may be
referred to as the "induction" or the "initiation" period. The magni tude
of the induction per iod is governed by the degree of supersaturation, the
temperature level, mixing intens it y (or turbulence) and the presence of
impurities. The induction period is related to the kinetics of nucleation.
2.4 Crystal growth

The rate of crystal growth will be dependent both on temperature and
concentration of the solution at the deposition interface. These
conditions at the interface are unlikely to be the same as in the bulk
solution. This is particularly so in a heat exchanger where there are
likely to be temperature gradients to accomplish the necessary heat
transfer, and there is likely to be concentration gradients which give rise
to the necessary mass transfer effects.
Crystal structures grow both parallel and perpendicular to the surface
that is becoming fouled. As the process proceeds, smaller crystals, having
a higher solubility than larger ones will redissolve. Growth will occur at
certain preferred faces but since the rapidly growing faces intersect more
than slowly growing ones, the situation is reached where the rate of growth
is governed by the slowest growth rates.
In many instances, a soluble impurity will remain in the liquid phase,
so that it does not become incorporated in the crystal matrix on the
surface, or even in crystals in suspension, if these have been formed as
described earlier. Under these circumstances pure crystals are produced,
but the presence of the soluble impurity may affect the rate of nucleation
and the rate of crystal growth. The effect is usually one of retardation
and it may be visualised that the impurity is adsorbed onto the surface of
the growing crystal, thus preventing further growth at that particular
point. Alternatively it can be imagined that the presence of a large
molecules in solution, will have the effect of hindering the passage of the
crystallising species towards the heat exchanger surface or the surface of
the crystallites. These effects are the basis of some of boiler feed water
treatments to prevent the production of scale in boilers.
3. TRE MECHANISM OF CRYSTALLISATION FOULING

Once a supersaturated condition within the solution has been
established, a number of proces ses can take place. The important
components making up the complete fouling proces s are as follows:
l. Nucleation phenomena - at the surface and in solution as
@ProcessEng
generally described in Section 2.

2. Diffusional phenomena - transport of ionic species or molecules
and crystalline particles (from the bulk) to the wall, due to
mass transfer effects.
3. Deposition pheomena occurring on the solid-layer interface whose
overall result is wall crystallisation; reaction of transported
257
ionic species and possible adhesion of transported particles.

4. Removal phenomena occurring during the deposition stage.
5. Changes due to the passage of time. Either hardening due to
recrystallisation and crystal transformation or softening/weakening due to
lack of cohesion as the deposit grows, and the production of planes of
weakness.
Any attempt at creating a mathematical model to describe the
phenomenon of crystallisation fouling must take these factors into
account, but it will be appreciated that although the mass transfer may
lend itself to mathematical analysis the effects within the crystal matrix
will be difficult to describe in mathematical terms.
3.1 Mass transfer effects

The rate of mass transfer to the sur face is given by the product of a
mass transfer coefficient and the concentration driving force between the
bulk and the solid/liquid interface.
The rate of incorporation of the salt into the crystal lattice is
given by a function of the supersaturation of the solid/liquid interface.
The rate of crystallisation a (cb - Cs)n (l)
where cb and c are the bulk and saturation concentrations

s
respectively.
(cb - cs) is in fact the "supersaturation" discussed in Section 2.
n is constant for a particular system.
If n - l the deposition is mass transfer control led and
dm f
k t A (Cb - Gs ) (2)
dt
m is the mass of deposit

t is time
kt is the mass transfer coefficient
A is the surface area involved
3.2 Simple crystallisation models

In order to avoid the problems as mentioned ab ove , of describing
crystallisation in the crystal lattice once the species has arrived at the
surface by mass transfer, it is possible to "lump" these effects together
as a "chemical reaction" the rate being given by some product of the

concentration of the ions or crystallising species at the interface. This
is a simplified model which igores details of behaviour at the interface
where surface migration to growth edges is likely to be part of the
mechanism.
The temperature dependence of the rate constant has often given an
equation of the Arrhenius form, ie.
@ProcessEng
dmf.
-1s~(A,~) (3)
dt
258
where
-E
RT (4)
Al is a constant.
3.3 Non-boiling flow of scaling water

Probably the simplest example of crystallisation fouling is where
crystal formation is experienced under non-boiling conditions. The basic
Kern model (4) has influenced the development of models to describe the
phenomenon. A general form is:
dR f dm f
- ( i t-
( i t-
(5)
- dt
thermal conductivity of the foulant scale
deposit thickness
total deposit
A total deposition area
deposit density
fluid shear stress
is some sort of adhesion parameter, ie. the greater FA

the lower the removal rate
Integration yields:
_C~tD)
c
(6)
tD induction per iod
t
c ~ a time constant characterising,deposit tenacity and
dm f l
t (7)
c
dt
By using curve fitting techniques it is possible to obtain a value for

t and this gives a good indication of deposit tenacity. The value of t
dIminishes rapidly with the amount of impurities in the deposit layer ana
itself appears to reach an asymptotic value. Glearly there is a need to
@ProcessEng
develop these basic ideas further if a practical model suitable for the
design of heat exchangers is to be established.
A problem of practical importance in the light of the previous
discussion, is to relate the fouling resistance to supersaturation
potential, exchanger surface temperature and flow velocity. However this
is l ike ly to result in extremely complex relationships and difficult to
259
apply due to the inherent lack of specific data.

One modeliumps the ionic and particulate deposition into a single
term (1)
-E
dm f RT
s
(8)
dt
Ts is the surface temperature
Kl is a constant
S is the "sticking probability" - a function of velocity
n is an empirical parameter characterising water composition and

supersaturation potential
-E
RT
e s characterises the overall surface reaction leading to deposition
Few data exist with which to test the equations. However some results
(5) at approximately 1 m/s fluid velocity for GaG0 3 deposition give
-42,000
RT
s
e (9)
Other data (6) at approximately 1.5 m/s for GaG0 3 , Mg(OH)2 and Si0 2 in
solution give
-44,000
RT
R ~ = (2.5 x 10 12 ) e s (10)
t
The deposit consisted of Si0 2 /MgO in the ratio 1.5 with lit tIe GaG0 3 .
3.4 Boiling flow of scaling water

Because of the complex nature of crystallisation under boiling
conditions discussed in Section 2 there are few examples of reliable models
to describe the process. An early empirical model was presented by McGabe
and Robinson (7) in 1924, based on the amount of liquid evaporated.
It:may be safely assumed that this model would be specifically related
to the system from which the data were obtained, the geometry and the
conditions of temperature and velocity such as might be experienced in an
evaporator for salt solutions.
It is probably true to state that it is unlikely that any universal
model will be derived which may be applied to different systems. Reliance
will of necessity, be placed on empirical relationships, which will need to
be treated with caution because of the effects of even small changes in
@ProcessEng
operating conditions can produce.
3.5 Water control indices

Because of the complexities of scaling due to the deposition of
crystals, water chernists have devised indices which are designed to
indicate the fouling potential of a particular sample of water. The
260
earliest of these is the so-called Langelier Index (8) which relates the pH
of the water to the so-called saturation pH. The saturation pH (pH) is
the pH of the water which is just in "equilibrium" with solid CaC0 3 s
The Langelier Index is (pH - pH s ) (Il)
If the resulting index is positive the water has potential scaling

properties. On the other hand if the index obtained is negative the water
has corrosive properties.
Many water chemists and corrosion engineers prefer the more recent and
more sensitive Ryznar index (9) where the index is empirically
(2pH s - pH) (12)
If the index is above 7 the probl'em is one of corrosion. An index

below 6 suggests a tendency to scale formation.
The phenomenon of crystallisation fouling in heat exchangers is
complex depending not only on the conditions of temperature and velocity,
but also on the detailed chemical properties of the solution which is
causing the problem. For these reasons it is unlikely that universal
models will be obtained which will explain in a satisfactory way, the
fouling potential of the system. The engineer is thrown back onto
emp~r~c~sm for guidance in the allocation of fouling resistances in heat
exchanger design.
The discussion presented in this paper does illustrate the mechanisms
by which crystallisation on a surface can take ~lace. An understanding of
these mechanisms has been used in the development of suitable treatment
chemicals for the relief of fouling problems. Water indices have been
found helpful in the analysis of crystallisation fouling problems.
REFERENCES
l. Hasson, D., "Fouling of Heat Transfer Equipment" eds. Somerscales

E.F.C. and Knudsen, J.G. Hemisphere Pub. Corp. Washington 1981.
2. Palethorpe, S., Ph.D thesis University of Birmingham 1986.
3. Partridge, E.P. and White A.H., Ind. Eng. Chem. 21 834 1929.
4. Kern, D.Q. and Seaton R.E., Brit. Chem. Eng. 4 258 1959.
5. Knudsen J.G. and Story, M., Chem. Eng. Prog. Symp. Series 74 25 1978.
6. Knudes en , J.G., ASHRAE, J 37 March 1978.
7. McCabe, W.L. and Robinson, C.S. Ind. Eng. Chem. 16 478 1924.
8. Langelier, W.F., J. Am. Water Assn., 28, 1500, 1936.
9. Ryznar, J.W., J. Am. Water Assn., 36,472, 1944.
@ProcessEng
DEPOSITION OF HARDNESS SALTS
A.M. PRITCHARD
HTFS Fouling Project, Harwell Laboratory UKAEA, Oxfordshire OXll ORA, U.K.
l. INTRODUCTION
1.1.Hardness salts
Hardness salts are one of the most familiar forms of fouling. They are
salts of the alkaline earth metals magnesium, calcium, strontium and
barium, the first two of which are found in almost all natura l waters. The
most common is probably calcium carbonate CaC0 3 , but calcium sulphate
dihydrate (gypsum, CaS04.2H20) is deposited from some waters, and where
the silica content is hlgh MgSi0 3 and CaSi0 3 may be formed (e.g.ref.(l)).
Magnesium hydroxide (brucite, Mg(OH)2) can be formed in desalination
plants, as can anhydrous calcium sulphate (anhydrite) at high enough
temperatures. Where waters have been polluted with phosphates from sewage
or fertiliser run-off calcium phosphate may also form. Although uncommon
in surface waters, strontium and barium are often present in considerable
amounts in underground aquifers, and cause severe problems when they meet
sulphate-rich waters such as seawater and precipitate their sulphates.
1.2. Causes of deposition of hardness salts

There are a number of causes of deposition of hardness salts :
a) Changes in the composition of a water, e.g. removal of CO 2 from
seawater under vacuum in flash distillation plants increases the
pH so that Mg(OH)2 is precipitated :
[l]
b) Increases in temperature for salts such as gypsum that are les s

soluble in hot water than in cold.
c) Mixing of incompatible waters, e.g. seawater and barium-rich
brines :
BaS04 + 2 NaCl [2]
d) Evaporation at a triple interface, e.g. a water meniscus.

e) Corrosion. In water the mechanism is usually electrolytic. The
metal dissolves at the anode, releasing electrons which are
consumed at the cathode by the reduction of oxygen or the
production of hydrogen. Both these reactions increase the pH,

which increases the carbonate concentration. For iron in water :
anodic reaction Fe ~ Fe++ + 2 e [3]
cathodic reaction 02 + 2 e [4]

@ProcessEng
[5]
Where the cathodic and anodic sites are distributed evenly there
is relatively little effect, but where two different metals are
involved or where differential oxygen concentration cells are
set up the pH may increase locally and assist scaling. Advantage
261
L. F. Melo et al. (eds.), F ouling Science and Technology, 261-273.

262
is taken of this in cathodic protection of structures against

corrosion, e.g. in seawater, where a sacrificial anode of a
metal such as zinc or aluminium is attached to steel structures.
The consequent build-up of a carbonate/hydroxide scale on the
structure provides an electrical resistance and reduces the
electric current and potential required to prevent corrosion -
this shows that fouling can sometimes be beneficial.
1.3. Plant in which hardness salts are often found

1.3.1. Boilers. Calcium carbonate is one of the most common, but also
silicates, and phosphates as well from boi ler water treatment chemicals.
Phosphates sometimes form sludges, in which case they can be removed by
blow-down. Dispersants are often added to maintain them in suspension.
1.3.2. Cooling condensers. Calcium carbonate is canmonest, but calcium
phosphates, whose solubility decreases rapidly with increasing temperature
and pH, may also form from wastewaters with high phosphate loadings (2).
1.3.3. Desalination plants. Calcium carbonate and magnesium hydroxide
form in flash evaporators as aresult of the increase in pH that occurs as
CO 2 is stripped from the water. This can be counteracted by dosing with
sulphuric acid, but at the risk of increasing the likelihood of deposition
of calcium sulphate. Although less soluble than the hemih~rate, anhydrous
CaS04 does not form at a significant rate below about 120 C. Above this it
is a major problem.
1.3.4. Food processing eguipment. Milk and milky foods contain calcium
and phosphate, and on heating they may be released and combine to deposit
calcium phosphate.
1.3.5. Geothermal plants. Many geothermal waters have considerable
amounts of carbon dioxide dissolved in them under pressure, and if this
comes out of solution the pH rises, and calcium carbonate may be
deposited. Silica is another common constituent, and calcium and magnesium
silicates may be deposited as well as silica itself.
1.3.6. Oil production equipment. Substantial volumes of water are often
produced together with oil. This water may contain calcium salts and
carbon dioxide under pressure, leading to calcium carbonate deposits as
the pressure decreases. Strontium and barium may also be present in the
produced water, and if sulphate-rich water such as seawater is injected to
maintain pressure in the oil-bearing formation, these ions may be
precipitated as their sulphates.
1.3.7. Reverse osmosis plant. The concentrations of ions in the solution
being treated increase as aresult of the process, and the solubility of
sane hardness sal ts may be exceeded.
2. CONDITIONS FOR DEPOSITION TO OCCUR

2.1. The thermodynamic solubility product Ks .

No salt can deposit until its thermodynam~c solubility product Ksp is
exceeded. This is related to the Gibbs free energy change for the
precipitation reaction G = -RT logf"KSp , and this is known for many common
depositing species as a function ot t~perature. For CaC03
KSp (CaC0 3 ) = c Ca++ c C03 = '(Ca++ '! C03= [6]

@ProcessEng
where c and ~ are respectively the concentrations (in mole/kg of solution)

and thermodynamic activity coeffisients. These latter can be related to
the ionic strength I = 0.5Li mi zi ' where mi. is the molality of the 1. th
species and zi is its charge. For values of I less than 0.1 (3),
263
[ 7)
where A = 1.8246 x 10 6/(78.54 T(1-O.004579(T-25)+1.19 x 10-5(T-25)2))1.5.

When r>O.l the expression for Ksp becomes much more difficul t to
calculate. Thus for CaS04.2H20 (4)
10<110 (nca2+·rnso4=) = loglO(Kspa w2 ) + 8Sr O. 5/(1 + ~prO.5)

+ B'r - c'r 2 [ 8)
where a w is the thermodynamic activity of water, S is the Debye-Htlckel

limiting slope for a l-l electrolyte, multiplied by the sguare root of the
density of water, and Asp' B' and C' are constants that allow for the
variation of a w and '{ witrr ionic strength.
An alternative approach used by Pitzer (5) expresses the activity
coefficient in terms of functions f of the ionic strength and type of
electrolyte (e.g. 2:2 for MgS0 4 ) and specific ion interaction parameters B
and C :
ln~= 4f + m B MX + m2 CMX [ 9)
Using this approach good predictions of the solubility of gypsum have been
possible in solutions of NaCl up to 6 mol/kg (6).
2.2. Saturation indices

2.2.1. Definition. The saturation index (S.L) of a salt is defined as
the ratio between the activity product of its ions and the solubility
product at the appropriate temperature. Deterrnining whether deposition of
a sal t is thermodynamica11 y possible (i.e. i f S.I.> l) therefore requires
knowledge of the concentrations and activity coefficients of all the ions
present in solution. Al though the overall chemical composition of a water
is known from analysis, the distribution of ions between different species
such as H2C03 , HC0 3-, COJ = and ion pairs for carbonic acid-related species
requires the Solutlon of a series of simultaneous eguations corresponding
to the chemical equilibria in solution, for which the equilibrium
constants are known at the required temperature. Although electronic
computers now permit this to be done in a reasonable time, a number of
simplified saturation indices have been devised and are widely used.
2.2.2. Langelier rndex (7). This describes the tendency of a solution to
deposit calcium carbonate, and is defined by the equation
L.S.I. = pH - pHsat [10)
where pH is the measured pH and pHsat is the pH at which the water is just
saturated with respect to CaC0 3 • For values of L.S.L>O scaling can be

expected, while for L.S.L<O the water is likely to be corrosive. pH sat
can be derived from the equilibrium constant K for the precipitatlon
reaction
CaC03 solid + H+ ~--

--"o. °-
Ca 2+ + HC 3 [ 11)
@ProcessEng
K =~2+ . a HC0 3- / a H+ = Ksp / Ka2 [ 12)
where Ka2 is the second dissociation constant for carbonic acid, i.e. for
264
[13J
Whence
[14J
in which the pK's are known as a function af temperature, the

concentrations c from the water analysis, and the activity coefficients ~
can be calculated as indicated above.
2.2.3. Ryznar Index (8). This also gives a measure af the tendency to
deposit caco3 , and is defined by the relation
R.S.I. = 2 pHsat - pH [15)
where the symbols are as above. For values af R.S.I.< 6.0 scaling is
expected, and when R.S.I.> 6.0, corrosion.
2.2.4. Stiff and Davis Index (S.D.L). For calcium carbonate (9) this is
defined by :
S.D.I. = pH - pca - pAlk - K [16)
Here pCa is -loglOCCa' and K is a factor that allows for the effect af
ionic strength, val ues af which are given graphically in the original
pa~r for temperatures in the range 0-90 o C and iani c strengths up to 3.6
(9). pAlk = -loglO(Alk), Alk being the alkalinity, defined as the number
af moles af strong acid required to titrate Ilitre af solution to the
colour change af methyl orange (pH=4.3). It must not be confused with the
p-alkalinity, the number ar moles af strong acid required to titrate l
litre af solution to pH=8.3 (the colour change af phenolphthalein).
In a separate paper (10) the same authors defined the solubility af
calcium sulphate in terms af a product af four functions : ST' its
solubility in distilled water at temperature T ; F l , the common ion
factor, ar its solubility in the presence af excess calcium ar sulphate ;
F 2 , the sodium ion factor, ar its solubility in the presence af sodium
ion, and F 3 , the magnesium ion factor, ar its solubility in the presence
af magnesium ion. Values af ST as a function af temperature from O-lOOoC,
and af the other three factors as a function af concentration from 0-5000
milliequivalents/litre are given graphically in the original paper (lO).
3. MECHANISMS OF SCALING
3.1. Homogeneous nucleation followed by deposition
The Gibbs free energy for formation of an embryo solid nucleus in
suspension in a liquid containing no other solid particles can be written

as the sum of two terms, the first of which is the surface free energy
required to create the new solid/liquid interface, and the second the free
energy change associated with the loss of water of hydration from the ions
and the lattice energy released in forming the embryo :
[17)
@ProcessEng
where O'"AL is the surface free energy of the embryo, Vm is the molar volume
of the solid phase, and AG v = RT 10ge(S,I.) (ll). When 2 is smalll1G is
positive, sfnce the surface energy is proportional to r and the lattice
energy to r-, and therefore belowa certain critical radius rc' given by
265
[18]
the embryo will spontaneously tend to dissolve, whereas above r c it will

qrow. This also shows that the larger the saturation index, the smaller
the critical radius, and therefore the smaller the number of units
required to form a stable nucleus.
3.2. Heterogeneous nucleation
A similar approach can be used for nucleation on an existing solid
surface (e.g. dust in solution or the wall of a vessel). If a
hemispherical nucleus is assumed the free energy change is
[19]
and re = (2cr"AL + OAs - eLs) Vm/Il~, where ~S and eLs are the surface free
energies for the embryo/substrate and t~quid/ substrate interfaces
respectively. In general oLs > oAs' and so heterogeneous nucleation is
favoured over homogeneous.
3.3. Growth on existing nuclei
In the absence of scale inhibitors crystals grow by the addition of
further units to the surface. The surface of a growing crystal can be
considered as consisting of flat terraces across which growth steps mnve.
These steps are easily seen in the electron microscope. They are not
perfectly linear, and contain low energy kinks that are the preferred
sites for growth at low supersaturations (Figure l).
Figure l - Schematic representation of growing crystal surface, showing

terraces (T), steps (S) and low energy kink sites (K)
4. CONrROLLING HARDNESS DEPOSITION

4 .1Pretrea tment of wa ter
There are four main methods of removing hardness from water.
a) Ion exchange. This can involve exchange of the hardness cations

for sodium ions, e.g. in a zeolite :
2 Na.zeolite + Ca++ = Ca.zeolite + 2 Na+ [20]
the reaction being reversed by treatment with strong NaCl

solution. Alternatively organic materials may be used that carry
@ProcessEng
H+ or OH- groups that are replaced by cations and anions from

the water :
[21]
266
[22]
b) Lime softening. Addition of lime to water increases the pH and

thus the concentration of carbonate ions, precipitating most of
the calcium and magnesium in the water:
Ca(OH)2 + 2 HC03 CaC03 + 2 H20 + C03= [23]

Ca++ + CO =
3 Caco3 [24]
Ca(OH)2 + Mq++ = Mg(OH)2 + Ca++ [25]
c) Acid treatment. Acid is added to convert bicarbonate to carbonic

acid, which decomposes, releasing CO2. The water may become very
corrosive if too much acid is used. Sulphuric acid is often
used, and calcium sulphate may be precipitated if the
concentration is high enough.
d) Reverse osmosis. Pressure is applied to the water, which
diffuses through a semi-p::!rmeable membrane. The solution left
behind becomes more concentrated, and the solubility product of
salts present in it may be exceeded, fouling the membrane.
4.2. Scale inhibitors.

4.2.1. Mechanism of action. Scale inhibitors are chernicals which inhibit
the nucleation and growth of hardness scale crystals. The concentrations
that are needed, typically l-IO mg/litre, are far too low for any
significant complexing of the scale-forming components to oc=, though
this may happ::!n at higher concentrations. Scale produced in the presence
of inhibitors loses the characteristic sharp crystal facets, but its
lattice dimensions do not differ significantly from those of scale forrned
from untreated water. In some cases one crystalline form may be favoured
over another, e.g. vaterite over aragonite or calcite for calcium
carbonate in the presence of phosphonates (12). These observations are
consistent with a model in which the inhibitor molecule or ion adsorbs at
the lowest energy growth sites and prevents further addition of material.
If it is assumed that the nucleation embryos with radii less than r c are
very similar to small pieces of crystal, the inhibitors may pr even t
nucleation in the same way.
4.2.2. Types of inhibi tors_o There are three main types of inhibitor in
current use:
a) Polyphosphates. These are cheap, but hydrolyse quite quickly
above 60 uC, especially in acid, forming phosphates which in turn
may give deposits of calcium phosphate.
b) Phosphonates. These contain a phosphorus-carbon bond and are

much more stable to hydrolysis. Their calcium salts are not very
soluble and may be precipitated if tao high a concentration is
used. They can be metabolised by some organisms, and they are
oxidised by chlorine.
c) Organic polymers. A range of these is available, the most common
heing polyacrylates, polymethacrylates and polymaleates. They
@ProcessEng
are very stable, and their efficiency (and solubility) varies

with their molecular weight.
4.3. Testing scale inhibitors. There are three main methods currentl y in
267
use. All require solutions to be carefully filtered to remove possibIe

sources that would assist heterogeneous nucl eation.
4.3.1. Jar tests. Two solutions are chosen that produce, on mixing, the
solid scale material and the solution from which it forms in practice.
Scale inhibitor is added to one of these to give the required
concentration af ter mixing. The two solutions are mixed in a beaker,
incubated for a period and then the deposit is filtered off. If the
weights of scale formed with and without inhibitor are w· and wo
respectively, the efficiency of the inhibitor is 100 x (wo-wJ-/w o ' The
test is isothermal, and the mixing is poorly defined, so that the
proportion of homogeneous, heterogeneous nucleation and growth on the
nuclei may be variable. Only simple equipment is required for the test,
and with care satisfactory reproducibility can be achieved. A standard
procedure has been defined by the U.s. National Association of Corrosion
Engineers (13). However, measurements smuld always be carried out using
waters of the composition in which the inhibitors are to be used, since
their efficiency varies with the composition of the water (14).
4.3.2. Tube-blocking test (15). As in the jar test, two solutions are
cmsen and pumped independently into a mixing chamber and thence through a
stainless steel capillary across which the pres sure drop is continually
measured. As deposit forms on the surface of the capillary the pres sure
drop increases. The capillary is usually thermostatted so that heat
transfer takes place. There are no standard conditions for the test as
yet, though current work is likely to provide firmer guidance within the
next year. The proportion of material nucleated in suspension and on the
walls is ill-defined. The test is usually used to determine the
concentration of inhibitor required to prevent any increase in pressure
drop af ter prescaling wi thout any inhibitor. In principle the test and
equipment is simple, but fairly rigorous experimental technique is
required to give reproducibIe results, e.g. the capillary must be cleaned
before use each time, and distilled rather than demineralised water should
be used to make up solutions.
4.3.3. Seeded growth/constant composition test. In this test the deposit
is not produced by mixing solutions, but instead a known amount of well-
characterised seed crystals of the material is added to a supersaturated
solution containing the inhibitor at the required concentration, and the
change in composition due to crystal growth is measured (16). In the
constant composition version the changes are measured by a sensor (e.g. a
pH electrode) and more solution is automatically added to maintain the
concentrations, the volumes being recorded (17). This test clearly gives
no information about nucleation. Standard seed crystals are required, and
the stirring causes some secondary nucleation (bits of crystal break off
the seeds through mechanical interactions). Only low supersaturations can
be used, below the value at which homogeneous nucleation would occur

spontaneously. Good reproducibility has been achieved under laboratory
conditions.
5. HETEROGENEDUS NUCLEATION OF CALCIUM CARBONATE

5.1. Introduction
The jar test and the tube-blocking tests described above are not
@ProcessEng
sufficiently well controlled to distinguish between the processes of

nucleation and growth, since in neither is there adequate control of the
mixing process. The seeded growth test in principle can be used to study
the effects of inhibitors on the growth of scale on existing crystals,
provided no secondary nucleation occurs. However, in many items of
268
industrial plant such as in heat exchangers, the saturation index

increases fairly gradually as the temperatur e increases, and under these
conditions the first process to occur is heterogeneous nucleation. This
section describes a technique that has been used successfully at Harwell
for studying the heterogeneous nucleation of CaC03 on heated surfaces in
the laboratory, and the effects of water chemistry and scale inhibi tors on
the process (18).
5.2. Experimental
The experiments were carried out in a closed loop in which the partial
pres sure of carbon dioxide, and thus the pH of the solution, were
controlled by sparging with argon or carbon dioxide gas (Figure 2). The
Heal Ex chang er
Control
Valve
Test Gas Trap

Se-ction
Rotam~ter
Pump
Figure 2 - Closed loop for Caco3 nucleation experirnents
solution was circulated by a pump over a srnall 50mm x 25mm copper coupon
heated indirectly by electric cartridge heaters (Figure 3). The surface
temperature increased in the direct ion of flow as a therrnal boundary layer
buH t up, and was measured by thermocouples brazed into the surface. The
INLET OUTLET
l
Slainlns si l'et
sandwich
@ProcessEng
Figure 3 - Heated test section

269
coupons could be removed from their holder and used for glancing angle x-
ray diffraction studies of the deposit on the surface and examination in
the scanning electron microscope.
Analytical grade reagents and demineralised water were used for all
experiments. The calcium bicarbonate solution was prepared by suspending
the required amount of calcium carbonate powder in the water and sparging
wi th carbon dioxide unti l i t had all dis sol ved. It was then circulated
over the heated coupon and the pH increased by sparging with argon or
adding dilute alkali until crystals of calcium carbonate were observed to
form on the coupon. Af ter about 30 minutes at a constant pH no further
movement of the crystallisation front was observed, and from its position
the surface temperature was calculated. The S.I. was then calculated from
the pH, water composition and the surface temperature using a computer
program. Measurements could be made at different surface temperatures
using different scale inhibitors, at different concentrations and with
different added salts. Provided clean copper surfaces were used, good
reproducibility was achieved.
5.3. Results
Typical results for one inhibitor are presented in Figure 4, which shows
the attainable S.I. values for calcium carbonate in 6 millimolar calcium
bicarbonate solution containing different amounts of magnesium and
2.0
'.5 Water Chemlatry Cm mol 1"')
~
Ol
""Ol
..... :::
o
E E
3-
c c
o o
~ ~
!: !:
c c
'c"
(J '"
(J
c
o o
() ()
0.5 ~
o
.c .c
.<:: .<::
c c
o
Saturatlon Index S.1.
Figure 4 - Concentrations of inhibitor required to prevent CaC0 3

nucleation from calcium bicarbonate solutions containing different amounts
of Mg++ and S04= ions for different saturation indioes
sulphate ions. They show that the higher the inhibitor concentration, the
higher the S.I. that could be attained before nucleation took place on the
@ProcessEng
4
heated surfa e. The attainable S.I. was significantly decreased by as
little as 10- moles/litre of either magnesium or sulphate. At these low
conoentrations this is not an effect of ionic strength, but is more likely
to be the result of competitive adsorption with the inhibitor at the
embryo surface. Figure 4 shows that at the highest S.I. values vaterite
270
was the first type of calcium carbonate formed, with aragonite and calcite
forming at lower values as indicated. In all cases nucleation was observed
on the surface before it occurred in the bulk solution. If no inhibitor
was present, nucleation took place on a clean surfaee from pure calcium
bicarbonate solution with no added salts at a S.1.=l.l, whereas a S.1. of
3.0 was necessary before homogeneous nucleation was observed at the same
tEmperature .
5.4. Discussion
The observed resul ts can be f itted to a simple diffusion model. It is
assumed that nucleation requires the critical nucleus of radius r c to be
formed in a time tbefore one or more inhibitor molecules or ions reaches
the surface, otherwise the embryo redissociatesj The critical nuc1eus will
contain n formula units, where n c = 21fNAr /3V m and N is Avogadro's
number. If these n c units are forrned from a ~emispheric~ vol urne Vi of
solution of radius rh' then
[26]
where c· is the concentration of the most dilute component i of the

2
deposit lin this case carbona e ions). The minimum time required to form
tills embryo is given by t = rh /2Di , where Di is the diffusion coefficient
of component i. If this embryo is to be prevented from reaching a critical
size, one or more scale inhibitor molecules or ions must reach i t in a
time be5s than t, meaning that they must be within a hemisphere of radius
(2tDa ) . , where Da is the diffusion coefficient of the inhibitor species.
For this to happen the inhibitor concentration must be greater than ca'
where
3(Di/Da)1.5navmci/(2 r c 3NA) moles/dm 3 [27]

and
(2Cl"'AL + ifAS - eLS) Vm/(RT loge(S.1.)) [28]
Tills is a relationship between the attainable S.1., the concentration of

inhibitor ca and the number of inhibitor molecules n~ required to prevent
the embryo reaching the critical size, and can be evaluated if the surface
energies and diffusion coefficients are known or can be estimated.
FolIowing this process the dotted line shown in Figure 5 was obtained for
a series of experiments with a polymaleic acid inhibitor in pure calcium
bicarbonate solution. There is good agreement with experiment at S.1.=7,
but for S.1.>7 the concentration predicted is too high, and for S.1.<7 it
is too low.
This observation may be explicable in terms of the change in r with S.I.
When S.I. is small r c is relatively large, and one inhibitor motecule may
not be able to block enough surface area of the embryo to prevent it from
growing. If each ~bitor molecule is equivalent to a surface area ~ of
embryo, n a = 2'7t"r c /A, and ca is proportional to r c -l instead of r c - as
in equation [27] above. Using the data plotted in Figure 5, and assuming
that na=l exactly at S.1.=7, the solid line is obtained, which gives a
dependence of S.I. on ca that matches the experimental results very
@ProcessEng
closely.
Values of A obtained in this way give a measure of the molecular
efficiency of a scale inhibitor. F~2 a ~lymaleic acid of molecular weight
800, A was found to be 7400 x 10 O m ; for aminophosphonic aCidfjfjd ~
polyacrylic acid of m.w. 5000, the values were 1200 and 18000 x 10- m
271
One molecule
10- 6
...
~
~
u
"
.
~
.!
u
".
.Ci
~
10-7
2
2
.c
~
<;
~
o
..
.g
~
o
o
10-8
1 2 8 10 12 14 16 18 20
Saturation Index S.I.
Figure 5 - The concentration of inhibitor required to prevent nucleation

of CaC0 3 from calcium bicarbonate solution. The dotted and full lines
represent the predicted dependence on the diffusion model assurning only
one, and more than one, rnolecule of inhibitor is required to prevent the
nucleus reaching a critical size, respectively
respectively. This suggests that the small phosphonate molecule is able to

cover les s surface area than the larger polymers, though this may well
depend upon water chemistry, since the conformation of polymers is
affected by other species in solution. These molecular efficiencies can
easily be converted to the more conventional efficiencies per unit weight.
6. SUMMARY
Hardness salts are encountered in a wide range of environments and

industrial processes. The reasons why they deposit are fair ly well
understood, and a number of methods have been devised for avoiding the
problem. However, the variety and complexity of the environrnents make it
difficult to make accurate predictions of when scaling will occur, and
what salts will be deposited, from equilibrium thermodynamics, and a
number of approximate scaling indices have been devised to provide some
guidance. One of the most favoured methods of controlling scale deposition
is the addition of scaling inhibitors, which interfere with both scale
nucleation and growth processes. Most available testing methods for
@ProcessEng
inhibitor s do not distinguish between nucleation and growth processes, and

a technique is described that has been used successfully for measuring the
efficiency of inhibitors against nucleation of calcium carbonate scale on
a heated surface.
272
7. SYMBOLS
A surface area of embryo crystallite

constant in equation [8]
~~ alkalinity (equation [16])
a thermodynamic activity
specific ion interaction parameter (equation [9])
~ constant in equation [8]
c concentration
C~ specific ion interaction parameter (equation [9])
C constant in equation [8]
D diffusion coefficient
f =nstant in equation [9]
G Gibbs f ree energy
I ionic strength
Ksp thermodynamic solubility product
m molality
NA Avogadro 's number
p( ) -loglO( )
pH -loglO(c B+)
pHsat pH at WhlCh a water of given composition is saturated with
calcium carbonate
r radius
R gas constant
S.I. saturation index
t time
T temperature
V volume
w weight
z number of charge s on ion
thermodynamic activity coefficient
o surface free energy
SUBSæIPTS
a additive
A crystal
c critical
L mother liquor
m molar
S substrate for nucleation
w water
8. REFEREN:ES
1. Lee, S.H. and Knudsen, J.G., 'Scaling characteristics of cooling

tower water', ASHRAE Transactions Vo 1. 8 5 (l ), pp. 2 81 - 3 02 (1979).
2. Parry, D.J., Hawthorn, D. and Rantell, A., 'Fouling of power station
condensers within the Midlands Region of the CEGB', in 'Fouling of
Heat Transfer Equiprnent' eds. Somerscales, E.F.C. and Knudsen, J.G.,
@ProcessEng
pp.S69-S86, Hernisphere, New York, 1981.

3. Davies, C.W., 'Ion Association', Butterworths, London 1962.
4. Marshall, W.L. and Slusher, R., 'Therrnodynarnics of calcium sulphate
dihydrate in aqueous sodiurn chloride solutions', J.Phys.Chem.
Vol.70(12), pp.401S-4027 (1966).
273
5. Pitzer, K.S., 'Theory: ion interaction approach', in 'Activity

Coefficients in Electrolyte Solutions, Vol.l' ed. Pytkowicz, R.M.,
pp.157-208, CRC Press, Boca Raton, 1977.
6. Scrivner, N.C. and Staples, B.R., 'Equilibria in aqueous solutions:
industrial applications', in 'Chemical Engineering Thermodynamics',
ed. Nevm1a11, S.A., pp.349-362, Ann Arbor Science, 1983.
7. Langelier, W.F., 'The analyticaI control of anticorrosion water
treatment', J.Amer.Water Works Assoc., Vol.28, pp.1500-1521 (1939).
8. Ryznar, J.W., 'A new index for determining the amount of calcium
carbonate scale formed by water', J.Amer.Water Works Assoc., Vo1.36 ,
pp.472-486 (1944).
9. Stiff, H.A. and Davis, L.E., 'A method for predicting the tendency of
oi l field waters to deposi t calcium carbonate', Petroleum Trans.
AIME, Vol.195, pp.213-216 (1952).
10. Stiff, H.A. and Davis, L.E., 'A method for predicting the tendency of
oil field waters to deposit calcium sulfate', Petroleum Trans. AlME,
Vol.195, pp.25-28 (1952).
ll. Nielsen, A.E., 'Kinetics of Precipitation', Pergamon, Oxford, 1964.
12. Nancollas, G.H. and Sawada, K., 'Formation of scales of calcium
carbonate polymorphs : the influence of magnesium ion and
inhibitors', J.Petrol.Technol., Vol.34, pp.645-652 (1982).
13. 'Laboratory screening test to determine the ability of scale
inhibitors to prevent the precipitation of calcium sulfate and
calcium carbonate from solution', National Association of Corrosion
Engineers Test Method, Nl\CE Standard 'lM-03-74 (1974).
14. Vetter, O.J., 'An evaluation of scale inhibitors', J.Petrol.Technol.,
pp.997-1006 (1972).
15. Hughes, C.T. and Whi ttingham, K.P., 'The selection of scale
inhibitors for the Forties fieId' , Proc.European Petrol.Conf.,
pp.341-356, London 1982.
16. Davies, C.W. and Jones, A.L., 'The precipitation of silver chloride
from aqueous solutions. Part I', Discussions of Faraday Soc.no.5,
pp.l03-119 (1949).
17. Kazimierczak, T.F., Tomson, M.B. and Nancollas, G.H., 'Crystal growth
of calcium carbonate. A control led composition study',
J.Phys.Chem.vol.86(1), pp.l03-107 (1982).
18. Dawson, D.M. and Pritchard, A.M., 'Effects of inhibitor s on calcium
carbonate scale nucleation in heat transfer equipment', Fouling in
Heat Exchange Equipment, ASME publication HTD-Vol.35, pp.19-25, ASME,
New York 1984.
@ProcessEng
CRYSTALLISATION OF ORGANIC MATERlALS
T.R. BOTT
Department of Chemical Engineering, Univers it y of Birmingham, PO Box 363,

Edgbaston, Birmingham, B1S 2TT, England.
l. INTRODUCTION
The deposition of organic crystals onto a heat transfer surface is
usually associated with the "freezing" of the organic fluid itself, on
surfaces at a sufficiently low temperature. For this reason the proces s is
often called "freezing" or "solidification" fouling. Deposition from waxy
hydrocarbons onto cool ed surfaces is a problem which has existed in the oil
industry for many years and may be regarded as a typical example of
"freezing fouling". The transport of crude oil in pipelines in the North
Sea has produced some severe problems of this nature, partly due to the
relatively long distances involved and partly due to the relatively low
temperatures encountered, coupled with the composition of the crude oil.
Although in this particular example the crystals deposited on the surface
are not strictly of the identical character of the fluid stream as a whole,
they do represent organic material; the fluid stream itself being a mixture
of different substances. The deposits consist main ly of n-paraffins with
smaller amounts of branched and cyclic paraffins and aromatics.
The amount of material which may be regarded as the precursor of
paraffin deposition is usually present in the bulk hydrocarbon in the range
of 1-30% (l). The so-called "cloud point" temperature of waxy hydrocarbons
is a controlling factor in the deposition. The "cloud point" temperature
is determined by a standard empirical method, and is the temperature at
which crystals appear as the liquid is cooled under standard conditions
(2). Another relevant empirical property is the so-called "pour point"
temperature which will be lower than the cloud point temperature. Using a
standard empirical method the "pour point" temperature is defined as the
temperature at which liquid flow does not occur under prescribed conditions
(3). Surface active agents within the fluid can have an appreciable effect
on the formation of paraffin crystals, with a depression of the pour point.
In pipelines, paraffin wax deposition usually results in increased
pres sure loss during normal operation and severe problems of restarting
satisfactory operations af ter a shut down. During processing when waxy

hydrocarbons ar cooled in heat exchangers, there is a tendency for wax to
precipitate resulting in increased overall heat transfer resistance and
increased pressure loss.
Methods used in industry to reduce wax deposition or overcome the
disadvantages of the process, involve mechanical and chemical techniques.
Pipelines are frequently cleaned by "pigs" transported with the bulk flow,
@ProcessEng
with the object of scraping away deposits on the pipe wall. The problem
may be extremely difficult to overcome if adequate bulk flow to carry the
projectiles is not possible due to the presence of the wax layers. Long
pipe lines as found in the North Sea, are particularly prone in these
difficulties. Should the use of "pigs" prove unhelpful alternative, often
expensive, methods must be tried. If the blockage can be located it may
275

276
even be necessary to dismantie the pipeline, in situ underwater, with all

the hazards and costs involved.
Chemical additives designed to affect the crystal structure of any wax
deposited, thereby making it more vulnerable to remove mechanisms, may be
employed. Other chemical additives may modify the solidifaction
temperature so that, under the conditions of operation, there is a reduced
tendency to generate crystals of wax.
Recognition of the effects of operating variables such as flow rate
and temperature, may lead to improved designs, which are less susceptible
to fouling than designs where these variables are ill-considered. However,
approaches to improved design demand an understanding of the fundamentals
of solidification fouling and the mechanisms involved.
In common with other crystallisation processes the size and number of
crystals formed is a direct function of the rate of cooling. High rates of
cooling will tend to favour the formation of large quantities of crystals.
Under these conditions many centres of crystallisation occur giving rise to
a multitude of fine crystals on the other hand, slow rates of cooling will
give rise to fewer centres at which crystallisation occurs, leading to the
formation of large uniformly packed, clusters of crystals.
2. THE MECHANISM OF CRYSTALLISATION

The determining factor in the mechanism of crystal formation in
organic liquids is the temperature distribution within the physical system.
Somewhat in contrast to the mechanism of scale formation described
elsewhere, the process does not depend upon "supersaturation", at least in
the terms generaily applied to solutions of inorganic salts.
If a waxy hydrocarbon flowing across a metal sur face is being cooled,
and the metal/liquid interface is at the cloud point temperature, crystals
will form at the interface. However, if the metal temperature is below the
cloud point temperature, the cloud point temperature will be located some
distance into the bulk liquid; the actual distribution of temperature
depending on the thermal resistance in the boundary region near the
metal/liquid interface. Low liquid heat transfer coefficients will mean
that the cloud point temperature will exist near the interface but in the
liquid. Good heat transfer coefficients will ensure that the cloud point
temperature is more remote from the metal/liquid interface into the bulk
liquid. Under these circumstances crystals or crystalites are likely to be
produced in the liquid phase. Although freezing will still occur at the
metal sur face due to the prevailing low temperature, additional deposition
will occur due to the migration of crystals from the boundary region, or
bulk flow, to the metal surface. Under these conditions the fouling
proces s will be governed by the mechanisms associated with particulate
deposition.
As the deposit develops with time, the temperature distribution in the

region of the metal/liquid interface will change, due to the relatively
high thermal resistance of the crystal layer. In the limit the outer
region of the deposit, in contact with the liquid, will approximate to the
cloud point temperature. In the region of the metal surface the pour point
temperature may be approached, and the deposit assuming a more solid
character. Under these circumstances, the conditions remaining steady,
@ProcessEng
there would be littie further change in deposit thickness with time. The
rate of change of deposit thickness with time will be relatively high in
the early stages, but with the redistribution of temperature, the rate of
change of deposit thickness will gradually decrease. The overall process
of change will be asymptotic. In other words an asymptotic fouling
resistance will have been reached. Experimental work by Gudmundsson and
277
Bott (4) suggests that the time required to reach this equilibrium fouling
resistance is extremely short, although it will depend upon the temperature
difference between the hydrocarbon and the coolant and the flow rate. A
typical time to reach equilibrium deposition is of the order of 2 hours,
and could be considerably lower depending on conditions, ie. in contrast to
an inorganic scaling problem where the time to reach steady conditions
could be of the order of weeks.
The mathematical analysis of Siegel and Sarino (5) may be applied to
the simple mechanism described above. The method basically considers
temperature distribution, and provides an equation for the equilibrium of
the deposit.
(l)
where is the film heat coefficient on the "liquid side" of the

deposit.
is the bulk liquid temperature

is the cloud point (assumed to be the temperature of the deposit
(liquid interface temperature)
Assuming no fouling on the coolant side,

T
c
- T2
Q is also = co
(2)
y y l
f m
+ +-
kf k h2
m
where h 2 is the film heat transfer coefficient on the "coolant side"
y and k are the thickness and thermal conductivity respectively of the
m~tal walT separating the coolant from the freezing liquid.
T 2 is the bulk temperature of the coolant

Tc - T 2
(3)
y l
m +
kf k
m
(T c - T 2 )
ie. YfCO (4)
(TI - T2 ) k
m
For given conditions Equation 4 may be used to estimate the asymptotic

thickness of the deposit.
Due to the fact that the chemical species of the deposit and the
liquid are similar, unlike inorganic crystallisation from aqueous solution,
the liquid/crystal deposit surface will be iII defined. In the region of
this interface it would be anticipated that the deposit would be "mushy",
ie. eas ily deformable. Crystals interspersed with liquid could be
visualised as being the general form of the deposit. Depending upon the
@ProcessEng
magni tude of the temperature distribution the deposit would become more
robust as the metal surface is approached. Furthermore because of the
existence of "turbulent bursts" or instabilities in the flow in the
boundary region adjacent to the "solid" layer, incursions of "packets" of
liquid at temperatures above the cloud point will occur. The effect of
278
this will be to "melt" some of the crystals in the surface layers, to be

followed by further freezing as the intabilities die away. A variable
deposit thickness, particularly at a localised position will be the
outcome.
For these and other reasons the analysis is extremely limited,
manifest in the following:-
l. The thermal conductivity of the deposit is difficult to estimate
with accuracy, even if values for the solid and liquid are known which
itself is unlikely, since the character of the deposit will change between
the metal wall and the liquid, there may be no certainty which value is
applicable .
2. The film heat transfer coefficient h, is difficult to estimate for
the following reasons:-
a) the deposit/liquid interface is deformable and "rough" - both
unknown effects on the film heat transfer coefficient.
b) the "viscosity" of the liquid in the region of the deposit/liquid
interface will be determined by the crystalite content of the liquid, in
addition to the normal rheological properties of the liquid. The situation
will be a dynamic one depending on the turbulent burst activity.
3. No fouling has been allowed on the coolant side of the metal wall.
If the fouling here is known with any accuracy its effect can be allowed
for in Equation 4 by adding a further thermal resistance to the analysis.
However, the effect of the roughness of this dirt layer on the value of h 2
is unlikely to be known with any accuracy.
4. T is essentially an empirical measurement developed for
comparison purposes, its value depends on the standard method of
determination. The conditions at the deposit/liquid interface are unlikely
to be identical with those of the standard method, so that T c is
inappropriate as the temperature at which crystals appear.
Despite these limitations with certain judicious assumptions, the
simple model is useful for the estimation of the asymptotic fouling
resistance for given operating conditions. Such estimates will be of value
in the choice and sizing of equipment.
3. THE EFFECTS OF SOME VARIABLES

Although in the previous sections some discussion of the factors
influencing the deposition of organic material on cold surfaces was
necessary in order to develop the theme, a more detailed account of the
effects is useful. The review by Gudmundsson and Bott (4) is useful in
this respect.
3.1 Velocity
In laminar flow, the estimated deposition of paraffin wax from crude
oils on steel and plastic coated pipes, increases with flow rate (6), with
a maximum near to the transition from laminar to turbulent flow. As the

turbulence increased accompanying an increase in velocity, the deposit
thickness decreased. In general, this result supports the observation
relating to a number of fouling processes. The viscous drag of the flowing
liquid is likely to be responsible for the removal mechanism, by overcoming
the cohesive forces holding the deposit together. As instability in the
boundary layer increases with velocity, "temperature incursions" are likely
@ProcessEng
to have a further effect on deposit coherence. Such effects are in

contrast to the mass transfer effects on the deposit build-up facilitated
by a larger number of crystals or crystalites in suspension as the heat
transfer increases with velocity (ie. turbulence). The final equilibrium
thickness will be aresult of the interaction between these three effects.
279
Other workers (7, 8) have also demonstrated that deposit thickness is

lowest at the extremes of velocity with thicker deposits occurring at
intermediate values of velocity.
Deposit hardness also appears to be a function of velocity. Tronov
(8) concluded that the increase in deposit strength with velocity was due
to the fact that only the well organised crystals and crystal clusters,
were capable of stability and retention under the shear stresses developed
at the higher velocities. As with inorganic precipitates on heat exchanger
surfaces a regular crystal lattice structure is more able to withstand the
effects of the aplied removal forces.
3.2 Temperature
The size and number of crystals formed in the fouling process is very
much dependent on the temperature and particularly the rate of cooling.
The formation of large quantities of small crystals is favoured by a high
rate of cooling. On the other hand a relatively slow removal of heat will
encourage the growth of fewer but larger coherent crystals (4), capable of
good packing qualities on the surface, with good structural qualities.
The rate of cooling will be very much a function of temperature
difference across the exchanger, ie. large temperature differences will
give rise to rapid cooling and visa versa. At the same time the
temperature difference will influence the composition of the deposit if it
contains a number of different compounds as for instance, in paraffin wax
deposition. In this example, the various devial species will separate out
according to a melting point distribution (4).
As the temperature difference between the heat exchanger wall and the
liquid oil increases the deposit becomes looser since under the rapid
cooling conditions produced, both "high" and "low" melting point components
come out of solution together. The result is a porous weaker structure
with interstices containing still liquid oil.
3.3 Surface condition

Adhesion of solids to su~faces under heat transfer conditions is ve ry
much a function of the character of the surface in relation to the fluid
flowing across the surface. The crystalisation of organic material is no
exception.
Rough surfaces in general, could be expected to be favourable for
increased eposition, if nothing more than the increased area associated
with a rough surface in comparison with a smooth surface of similar
projected area.
The presence of certain absorbed compounds on the surface, prior to
contact with the organic liquid, can modify the adhesion qualities of the
depositing layer (9). Adsorption will depend upon the surface free energy
so that as this is reduced for the heat exchanger surface, a decrease in

deposit could be expected under the prevailing flow conditions. The
presence of adsorbed layers on the surface could have this effect and may
be the basis of a potential technique for mitigating the fouling problem.
The deposition of organic crystals onto heat exchanger surfaces is not
a particularly common industrial problem, when compared with other fouling
@ProcessEng
phenomena. However it is a problem particularly in the oil industry,

during the transport of waxy hydrocarbons through pipelines. Under these
circumstances the cooling heat transfer is not usually intentional, but is
aresult of transport over long distances in co Id environments. Given
these limitations there are probably only three methods to overcome the
280
problem apart from the use of projectiles mentioned earlier.

l. The use of additives to modifyand weaken the crystal structure,
or possibly to inhibit the surfaces.
2. Attempt to heat the pipeline.
3. The use of lagging to reduce heat losses.
The costs involved in all three applications are likely to be high and
make the techniques economically unacceptable. The use of additives also
has the problem of contamination, although of the three.possibilities this
is likely to be the most acceptable.
In processing operations where organic liquids are likely to give
crystallisation fouling, the obvious answer is to try to avoid the
conditions that produce it. lf cooling is desired, in whatever equipment in
most situations the product will still be required in liquid form. lf
solid product is required it is inconceivable that this would be attempted
using a heat exchanger followed by filtering where problems of fouling are
likely to occur in the exchanger. lf solid crystals of the product are
required, a conventional or speciaIly designed crystaliser would be
required, with perhaps some pre-cooling.
The guidelines to remove fouling provided by the operations in Section
2, offer the approach to be adopted. In general this will mean high
velocities and maintenance of heat exchanger surfaces at or just above the
cloud point of the solution, if the process fluid is a mixture, or the
freezing temperature if it is a pure compound. Such an approach will
demand special attention to the cooling medium temperature and for this
reason it may well be that the site cold utility will have too low a
temperature. Under these circumstances special cooling facilities may be
required, where temperatures can be carefully controlled. Inevitably this
will mean increased capital cost and this would have to be carefully
considered in relation to the cost of increased heat exchanger area to
allow for the fouling in the exchanger.
An alternative approach is to use some technique of "mel ting off" the
deposits on a regular basis. For instance if two exchangers are instalIed
in parallel, while one was performing the heat removal dutY using say, site
cooling water, the other could be heated with say low pressure steam, in
place of the cooling water. This technique would have the added advantage
that the presence of the steam could act as a sterilising medium to reduce
any biofouling produced by the cooling water.
5. REFERENCES
l. Jordan, R.M., J. Pet. Tech. 1605 1966.

2. ASTM D25 a-66 (and IP 219/67).
3. ASTM 97-67 (and IP 15/67)
4. B6tt, T.R. and Gudmundsson, J.S., J. Inst. Pet. IP 77-007 1977.
5. Siegel, R. and Sarino, J.M. 3rd lnt. Heat Transfer Conf. 4, 141 1966.
6. Jessen, F.W. and Harwell, JN, Pet Trans. AIME 213 80 1958.
7. Eaton, P.E. and Water, G.Y. Paper 76-CSME/CSChE-22 16th Nat. Heat
Transfer Conf. St. Louis 1976.
8. Tronov, V.P. Tatar Neft Nauch-lssled lnst. 13 207 1969.
9. Parks, C.F., Oil and Gas J., 58 87 1960.
@ProcessEng
FOULING OF CRYOGENIC LIQUIDS
H. MULLER-STEINHAGEN
Department of Chemical and Materials Engineering, The Univers ity of

Auckland, Auckland, New Zealand.
l. INTRODUCTION
Fouling resulting from the flow of cryogenic liquids (liquid H2 , He,
N
o2 ' Ar, etc.) is usually not considered a serious problem, since the purity
I the liquids involved is high. Nevertheless, it was sLated during a
panel session at the recent International Heat Transfer Conference in San
Francisco (l) that fouling during the evaportation of cryogenic liquids is
one of the major unsolved problems in the separation and production of
liquified gases. Reboilers associated with the respective distillation
columns have to be designed using heat transfer coefficients much lower
than the values previously determined in pool boiling studies.
In some low temperature processes, such as the cooling of
superconducting magnets with boiling helium or the cooling of cryocables
with liquid nitrogen, small temperature differences between the heating and
cooling side are essential. Heat transfer coefficients for boiling
cryogenic liquids are very high due to the activation of very small
nucleation sites. Therefore, even small deposits on the heat transfer
surface may lead to a considerable reduction in heat transfer. As the
critical heat flux for boiling cryogenic liquids is low, heat transfer
usually occurs close to the critical heat flux or critical temperature
difference. If the wall temperature is increased locally due to fouling,
this may lead to boiling cris is and burn out, with the possibility of
destroying expensive equipment.
Although fouling effects during evaporation of cryogenic liquids have
been observed by several investigators, these effects were usually not
considered worth following up or even publishing. In this paper, low
temperature fouling phenomena are described. Attempts are made to obtain
some understanding of the influence of system parameters such as heat flux,
flow quality and mass velocity on the deposition process.
2. LOW TEMPERATURE FOULING PHENOMENA

2.1 Hydrogen.
Measurements of pool boiling heat transfer to liquid hydrogen as
described by Bewilogua et al. (2) are shown on Figure l. The experiments
were performed with an electrically heated horizontal plate at a reduced
pressure p ~ 0.658. As the heat flux was increased, the difference
between wall temperature and saturation temperature increased. For lower
heat fluxes (data points l, 2 and 3), the wall temperature remained
@ProcessEng
constant once the heat flux was adjusted. For higher heat fluxes, however,
the wall temperature showed a transient increase via 4, 5 to 6 at a rate of
approximately 0.5 K/min. This temperature transient continued for more
than 10 minutes, during which time the heat transfer coefficient dropped by
about one order of magnitude. Bewilogua reports that a deposit was formed
on the initially shiny heat transfer sur face during this transient
281

282
increase. The deposit disappeared once the surface was heated to a

temperature exceeding 60 K (T = 30.5 K at p = 0.658).
If hydrogen with a high~r purity was u~ed, the temperature transient
was reduced. It comp1ete1y disappeared for purities above 99.9999%. The
variation of wa11 temperature as well as the visible thickness of the
deposit, decreased with decreasing system pressure; at 1 bar the effect was
bare ly noticeab1e. The authors assumed that the deposit may be oxygen or
nitrogen sub1imating at a temperature of 60 K. They a1so mentioned
observations during hydrogen measurements by Roubeau (3) and Graham (4)
which may be exp1ained by the formation of a deposit at the heat transfer
surface.
Denton (S) reports observations from a hydrogen purification process,
where CO 2 was continuous1y freezing out at temperatures between 90 K and
140 K.
2.2 Nitrogen.
Thome, Bland and deNewton (6, 7, 8) investigated pool boi1ing heat
transfer from a copper heat transfer sur face to nitrogen, argon and
mixtures of the two. They used nitrogen with a purity of 99.992% and argon
with a purity of 99.996%.
Due to the deposition of CO 2 on the heat transfer surface, no
reproducib1e measurements were poss~b1e during deNewton's experiments (8).
Therefore, Thome (6) in his subsequent investigations used a co1d trap to
purify the fluid used in his experiments. Neverthe1ess, he had to boi1 his
1iquids at the beginning of each experiment for severa1 hours at high heat
flux to obtain reproducib1e data. During this period, the heat transfer
coefficients decreased continuous1y. Figure 2 shows the resu1ts of Thome's
experiments with nitrogen. Despite the use of a co1d trap and pre-boi1ing,
the resu1ts of the various runs vary great1y. The differences cannot be
exp1ained by the slight differences in system pressure between the runs.
According to (9), increasing the pressure from 1 bar to 2.7 bar shou1d on1y
1ead to an increase in heat transfer coefficient by 50%.
Lyon (10) found, from his experiments with a horizonta1 copper p1ated
heat transfer surface, that the heat transfer coefficients were reduced
considerab1y af ter the heat transfer surface had been exposed temporarily
to the atmosphere. Af ter c1eaning the heat transfer surface, the original
heat transfer coefficients cou1d be reproduced. Lyon (10) attributes the
reduction in heat transfer to the formation of a thin copper carbonate
1ayer on the heat transfer surface. However, even with p1atinum p1ated
heat transfer surfaces, on1y minimum reproducibi1ity was achieved in 1ater
experiments (11). Again, these observations may be exp1ained by the
solidification and sublimation of CO 2 on the heat transfer surface.
2.3 Oxygen.
Figure 3 shows resu1ts of two experimenta1 runs for boi1ing oxygen at

10 bar (11). In both runs measurements were performed with increasing and
with decreasing heat flux. The measurements with increasing heat flux look
simi1ar to the resu1ts with hydrogen described by Bewi10gua (2) inasmuch as
the wa11 temperature seems to be independent of the heat flux for high
va1ues of heat flux.
It is common knowledge that heat transfer coefficients for nuc1eate
@ProcessEng
boi1ing, measured with increasing heat flux, are lower than the respective
va1ues measured with decreasing heat flux. This hysteresis effect is
attributed to the activation of bubb1e nuc1eation sites. Figure 3,
however, shows an inverse hysteresis behaviour with considerab1y lower heat
f1uxes for the measurements with decreasing heat flux. As the data were
283
first taken with increasing and then with decreasing heat flux, this result
may have been caused by deposits built up during heat transfer with
increasing heat flux. For nitrogen, no inverse hysteresis was observed.
The oxygen used in the investigation had a purity of 99.5 to 99.8%.
2.4 Argon
Figure 4 shows the results of Thome's experiments with argon. Again,
the large difference between the results of the two test series c anno t be
explained solely by the difference in system pressure.
As with oxygen, Lyon and Kosky (Il) observed an inverse hysteresis for
the measurements with argon (see Figure 5). They also mentioned that the
characteristics of the heat transfer sur face changed abruptly af ter an
excursion into film boiling.
From his measurements on flow boiling of argon in a horizontal pipe,
Bonn (12) obtained the results shown in Figure 6. It can be seen that the
measured heat transfer coefficients for the first run are clearly higher
than for the second run which was measured several days later. Additional
experiments showed that a continuous increase in wall temperature occurred
with time for fixed values of heat flux, flow quality, mass velocity and
system pressure. In a subsequent investigation (13), the transient
decrease in heat transfer could be attributed to the deposition of CO 2 onto
the heat transfer surface. This investigation will be described in more
detail in Section 3.
2.5 Other liguified gases

Poor reproducibility and inverse hysteresis were also reported for
pool boiling of methane and carbon tetrafluoride (Il), (see Figure 7). For
methane, the authors associate this result with the extreme difficulty of
removing impurities from methane.
Recently, pool boiling heat transfer was investigated for a variety of
liquified gases by Bier and co-workers (14). Stable measurements were
possible for boiling of nitrogen, whereas a transient decrease in heat
transfer coefficient was observed for argon and methane. Unfortunately,
the results of these observations have not been published.
3.
INLUENCE OF SYSTEM PARAMETERS ON FOULING RATES
From the above investigations it may be concluded that considerable
fouling may result from the boiling of cryogenic liquids. However,
systematic investigations on the influence of such parameters as foulant
concentration, flow velocity, flow quality, heat flux and system pres sure
have only been made using argon (13) and nitrogen (15). A detailed
description of the test equipment used for these investigations is given in
(12, 15).
3.1 Range of investigations

Fouling was investigated for the flowing argon and nitrogen within the
folIowing range:
heat flux q 100 - 100,000 w/m 2

pressure p l - 20 bar 2
@ProcessEng
flow velocity m 120 - 1,000 kg/m s

flow quality x O - l
3.2 Description of fouling proces s

The fouling resistance Rf was calculated from:
284
Rf = (Tw - Tw,O) / q
The fouling resistance for a flow of 99.996% pure argon as a function
of time and heat flux is shown on Figure 8. With increasing heat flux, the
transient increase in fouling resistance with time becomes more pronounced.
Linearizing the fouling curves for t=O, a relationship
was found. While the fouling resistance approached an asymptotic value for
lower heat fluxes, a boiling crisis, indicated by a very rapid increase in
wall temperature, occurred for higher heat fluxes. Heat fluxes shown in
this diagram are well within the region of nucleate boiling. For
measurements in the convective boiling region, no fouling was observed.
The initial values of heat transfer coefficient could be reproduced if the
test section was warmed up to about oOc.
The influence of the mass velocity on the fouling process is shown in
Figure 9. For the higher mass velocity, the transient increase of the wall
temperature is considerably lower than for the lower velocity. The boiling
cr~s~s, however, occurs for both experiments once the perimeter averaged
wall temperature exceeded avalue of approximately 152 K.
In subsequent experiments it was found that the deposition rates
increased considerably with increasing flow quality and system pressure.
If 99.999% pure argon was used instead of the 99.996 percent pure
fluid, a considerably reduction of fouling rates was observed. Figure 10
shows that conditions originally leading to a boiling cris is were modified
with only a minor temperature increase.
3.3 Influence of CO concentration

3.3.1 Argon. -r~e reduction of fouling with the use of higher purity
argon indicated that the foulant must arise from the impurities contained
in the bottled gas. An analysis of the 99.999% pure argon showed:
N2 2.0 - 2.5 vpm CO < 0.5 vpm

02 1.4 - 1.7 vpm CO 2 < 0.5 vpm
H2 0 1.5 - 1.6 vpm unsaturated
hydrocarbons < 0.5 vpm
Since the foulant must be in its solid state for the temperature of the
experiments (90 K - 140 K) and in its gaseous state at 273 K, N2 , 02 and
H2 0 can be eliminated as possibie foulants.
To investigate the effect of the CO 2 concentration in the fluid on the
transient temperature increase, 99.999% pure argon was used as test fluid.
The CO~ concentration was then increased in steps of 0.5 vpm. Figure Il
shows chat the initial fouling rates increased with increasing CO
concentration in the fluid. For concentrations of 3 vpm and higher, a hea~
flux of 80800 W/m immediately caused a boiling crisis.
Af ter passing argon containing 3 vpm CO 2 through the test sections for
1.5 h, the test sections were isolated and heated at the rate of 3.5 K/h in
order to test for the presence of deposited CO 2 . The gas in the test
section, in the remaining flow loop and in the gas cylinder was analysed
@ProcessEng
using infrared spectroscopy to detect CO 2 . While the CO 2 concentrations in

the gas cylinder and the flow loop were close to zero, a concentration of
nearly 250 vpm of CO 2 was found in the isolated test sections.
3.3.2 Nitrogen. No temperature transients have been found during pool
and flow boiling experiments with nitrogen. However, to investigate the
285
effect of dissolved G0 2 on heat transfer to boiling nitrogen, CO 2 was added

during nitrogen runs under conditions similar to those for the argon
experiments described above. Figure 12 shows that the difference between
wall and saturation temperature increases continuously with increasing G0 2
concentration in the nitrogen. However, temperature transients were only
found for concentrations ab ove 2 vpm.
4. MECHANISM OF DEPOSITION
In the previous section it was demonstrated that the transient
decrease in heat transfer was caused by the deposition of CO on the heat
transfer surface. To solidify at the heat transfer surface, ~he solubility
limit for CO 2 in the particular liquid must have been exceeded, at leas t
locally. However, equilibrium solubility values for solid CO 2 in liquid
argon and in liquid nitrogen (16) are far higher than the CO 2
concentrations used in the experiments. Even for a flow quality of 90%,
the CO 2 was about two orders of magni tude below the respective saturation
concentration. Therefore, supersaturation must have occurred in the
immediate environment of the growing vapour bubbles.
From the theory of boiling it is known that a thin liquid microlayer
exists between the heat transfer surface and the growing bubble. Heat is
conducted from the heat transfer surface through the microlayer, which is
evaporated into the bubble and continuously replaced from the bulk of the
fluid. Since nitrogen and argon have a boiling pressure considerably
higher than that of CO 2 , it must be assumed that these two liquids are
evaporated predominantly. Therefore, the concentration of CO 2 in the
microlayer increases continuously over a bubble growth per~od until
supersaturation and hence CO 2 precipitation occurs. The percentage of heat
transferred by microlayer evaporation increases with increasing wall
superheat and increasing system pressure. This may explain the influence
of these two parameters on the fouling rates, as described in Section 3.
5. CONCLUSION
Considerable fouling may occur during boiling of cryogenic liquids,
even if the liquids are of very high impurity. Gommon foulants are minor
impurities which would be solid at the boiling temperature of the carrier
liquid. Due to local supersaturation in the vicinity of the growing
bubbles, these constituents may solidify on the heat transfer surface.
Fouling rates observed generally increased with increasing wall superheat
and increasing system pressure.
Obviously, a close correlation exists between bubble dynamics,
microlayer evaporation and fouling rates which may be used to improve
prediction of fouling rates during nucleate boiling.
LIST OF SYMBOLS
concentration vpm 2
mass velocity kg/m 2 s
mass velocity of gas kg/m s
mass velocity of liquid kg/m2s
pressure bar
@ProcessEng
critical pressure bar

reduced pressure (=p/pc)
heat flux W~m2
fouling resistance mK~
time min, h
temperature K
286
saturation temperature K
wall temperature K
initial wall temperature K
flow quality ( - m /(m +m.)
heat transfer coeffici€nt W/m2K
REFERENCES
l. Streich, M., Research Needs in Low Temperature Proces s Heat Transfer.

8th lnt. Heat Transf. Conf., panel session 2,1986.
2. Bewilogua, L., Gorner. W., Knoner, R. et al. Heat Transfer in Liquid
Hydrogen. Cryogenics 14, No. 9, pp. 516-517, 1974.
3. Roubeau, P. Progress in Refrigeration Science and Technology Vol. l,
p.49, 1960.
4. Graham, R.W., Hendricks, R.C., Ehlers, R.C. Advances in Cryogenic
Engineering Vol. 10, p.342, 1964.
5. Denton, W.H., Shaw, B. et al. Purification of Hydrogen for
Distillation, Part II. Trans. lnst. Chem. Eng. 37, pp.277-288, 1959.
6. Thome, J.R. Nucleate Pool Boiling in Cryogenic Binary Mixtures. Ph.D.
thesis Oxford, 1978.
7. Bland, M.E. Bubble Nucleation in Cryogenic Fluids. Ph.D. thesis
Oxford, 1970.
8. deNewton, J.G. Bubble Nucleation and Heat Transfer in Cryogenic
Liquids. M.Sc. thesis Oxford, 1977.
9. Gorenflo, D. Warmeubergang bei Blasensieden, Filmsieden und
einphasiger freier Konvektion in einem gro pen Druckbereich. C.F.
Muller, Karlsruhe, 1977.
10. Lyon, D.N. Peak Nucleate Boiling Heat Fluxes and Nucleate Boiling Heat
Transfer Coefficients for Liquid Nitrogen, Liquid Oxygen and Their
Mixtures in Pool Boiling at Atmospheric Pressure. lnt. J. Heat Mass
Transfer, Vol. 7, pp. 1097-1116, 1964.
ll. Kosky, P.G. and Lyon, D.N. Pool Boiling Heat Transfer to Cryogenic
Liquids. AIChe Journal vol. 14, No.3, pp. 372-387, 1968.
12. Bonn, W. Warmeubergang und Druckverlust bei der Verdampfung von
Stickstoff und Argon im durchstromten horizontalen Rohr sowie
Betrachtungen uber die tangentiale Warmeleitung und die maximal
mogliche Flussigkeitsuberhitzung. Dissertation TU Karlsruhe, F.R.G.,
1980.
13. Muller-Steinhagen, H.M., Hechler, C. et al. 'Fouling' - Vorgange bei
der Verdampfung von Argon im waagerecht durchstromten Rohr. Warme- und
Stoffubertragung 17, pp. 47-53, 1982.
14. Bier, K. et al. Institut fur Technische Thermodynamik und Kaltetechnik
der Universitat Karlsruhe, F.R.G., unpublished data on pool boiling of
cryogenic liquids.
15. Muller-Steinhagen, H.M. Warmeubergang und Fouling beim Stromungssieden
von Argon und Stickstoff im horizontalen Rohr. Fortschr. -Ber. VDl-Z,
vol. 6, No. 143, 1984.
16. Landolt-Bornstein: Zahlenwerte und Funktionen, vol.4, sect. c2,
Springer Verlag 1980.
@ProcessEng
287
lO'
HYDROGEN
Pr=0,658 OXYGEN
10
W
w emt. 2
cm'
10'
10
Tw- Ts
lO'
lO
Figure l Transient increase of O 15 20
T - T
wall temperature during pool w s
boiling of hydrogen /2/
Figure 3 Inverse hysteresis for
pool boiling of oxygen /11/
q
\ol 1m 2
I I
q Argon
W/m 2
200000
200000 I
run 3 run 3
U ar p:l,2 bor- ~
150000
150000
1000004-----+- 100000 I
1/
5 O000 +---~_I_+-I+---I--__1___-_I.__. f
/ Vi: r
50000
run 1
1
......,
o
6 8 10 12 o 2 4 6 8 10 12
Tw - T5 ål I K
@ProcessEng
Figure 2 Poor reproducibility of Figure 4 Poor reproducibility of

nitrogen pool boiling measurements /6/ argon pool boiling measurements /6/
288
"'99,996%
. S'---~~r---,-~ m :120 kg/m's
q Pr :0,4
W/m 2 10'~-----,------fr~'-~--~-;
2 4---1--4-/ ex:.
w
10 5 +------I-,(-+-.l. m'K _O_-"1I--t
S +---+-/-----1-1 10·'+---------+---.-db~,_+_------- X
'" O,,
4 days later • 0,3
2 005
V 07
104+---~~~--~--4 00,9
S 10·+---------~----------~----------4_~
10' lo'
Figure 5 Inverse boiling hysteresis Figure 6 Variations of flow boiling

for pool boiling of argon /11/ data for argon /12/
10' 0.5,------------------1
eF,
q5 ARGON
w/cm
0,4 m; 120 kg/m's
2 p; 19.6bar
x: 0.7
10'
l
0,3
0,2
------
1 q. 50800 W/m'
2 q= 60900 W/m
o, l 3 q; 80800 W/m'
t;.
o
p" 16 bar
p= 36 bar 1boiling crisis 4 q= 97800 WI m'
0,0~0Jft!::.---..,-----1'T"0------:1':'5---~20
t, h
Figure 7 Poor reproducibility and Figure 8 Influence of heat flux on

inverse hysteresis for boiling fouling rates for flow boiling of argon
of carbon tetrafluoride /11/
@ProcessEng
289
180 , - - - . . . , - - - - - , - - - - - - , - - - _ r _ - - - - , - - - - - , 25..---~---_r_--~
Argon 99,996 %
åT NITROGEN
TW P, • 0,4 P, .0,4
K x • O,S m= 120 kg/m 2 s
160 1---~tboHing--~
cr~s~s,
kg/m 2s
I
.95600 20 f-(~ • 700~00~w~lm'-!.2-1__I---_l
k .0,6
Q N2
b 1 "pm C02
I
c 2 "pm C~
/
151------I----I'-d 3 vpm co,
! J eS vpm 002
T.
120 L-_ _...L.._ _--L_ _--.,-l_ _ _. L_ _...L_ _.....J
L----------' V f 6
1
vpm C02
O 100 200 300 400

t min
500 600
10 t-v----1:::::= F--.----I
1 1
~==~~==~::::-=
I I g
Figure 9 Influence of mass velocity
on the transient increase of wall temperature
O+----+---+---~
O 25 50 75
40 t min
x .0,7 ! ri> = 120 IkQ/m2S

P, = 0.4 q • 80000 W/m 2 boiling
cris is I Figure 12 Influence of CO 2
JO
~ Tw - Ts
~ concentration on the wall
K
20 9 99'0 L----- superheat for flow boiling

of nitrogen
~
~
__ A-,_9~~~ - - - - - - - -
10
o
o 100 200 JOD 400
t min
Figure 10 Reduction of fouling due to

circulation of argon with a higher purity
0,20..---------------------,
o
ARGON
X• 0.73
m'" 120 kgfmls
p ~ 19.6 bar
0.10
0.05 o
l'>
4 5
@ProcessEng
CO, P pm
Figure 11 Influence of CO 2 concentratlon on

initial fouling rates for flow boiling of argon
@ProcessEng
Chapter7
Chemical Reaction Fouling
BASIC SCIENCE AND MODELS OF REACTION FOULING
B.D. CRITTENDEN
SCHOOL OF CHEMICAL ENGINEERING

UNIVERSITY OF BAT H, BATH BA2 7AY
UNITED KINGDOM
1. INTRODUCTION
In principle, there are two categories of reaction fouling, viz,
corrosion fouling and chemical reaction fouling. However, in many process
environments in the oil, petrochemical, chemical, food and utility
industries, the two mechanisms are inextricably linked with each other and
with other mechanisms of fouling, such as particulate and crystallisation.
Whilst corrosion and chemical re action fouling have fundamental ly
different mechanisms, chere is much common ground in the development of
their heat transfer fouling models.
1.1 Corrosion fouling

With in situ corrosion fouling, reviewed by Somerscales 1 and Lister 2 ,
the heat transfer surfaee itself reacts to produce corrosion produets
which foul the surface. With ex situ fouling, reviewed by Lister 2 , the
corrosion produets are formed elsewhere and then deposited on heat transfer
surfaces either by precipitation or by particulate mechanisms, depending
on whether the corrosion produets are soluble or insoluble at the bulk
fluid conditions. Precipitation and particulate mechanisms are discussed
elsewhere in this book.
1.2 Chemical reaction fouling

With chemical reaction fouling, the deposits are formed as aresult of
chemical reactions within the process fluid. The heat exchange surfaee
material is not a reactant, but it may aet as a catalyst in complex
chemical mechanisms, such as cracking, coking, autoxidation and polymeri-
sation. Corrosion produets mayaiso aet as catalysts or simply form part
of the deposit. Reviews of chemical reaction fouling are given by
Froment 3 , Garrett-Price et al 4 and Crittenden et alS. Fouling in the food
processing industries is discussed elsewhere in this book.
2. MECHANISMS
In any reaction mechanism reactants, or foulant precursors, must be
transported by convective mechanisms from the fluid bulk to the reaction
zone. Likewise reaction pro duets including the foulant, if it is still
mobile, may be transferred back to the fluid bulk to take part in
further fouling processes elsewhere. In corrosion fouling, the re action
@ProcessEng
zone is the heat transfer surface. In fouling from hydro carbon streams,
material of increasing molecular weight and complexity exceeds its
solubility in the fluid and forms a deposit, which initially may not be
rigid, in a zone where the local conditions are favourable. The foulant
may have to be transported, perhaps in colloidal form, to be adsorbed on
or otherwise attached to the heat transfer surface. In both corrosion and
293
294
chemical reaction mechanisms, the possibility also exists for wholesale

removal of deposits by the turbulent action of the fluid. From this
overview of reaction fouling, surnrnarised in Figure l, it is clear that the
overall rate of reaction fouling may be dependent upon physical and/or
physico-chemical mechanisms, such as mass transfer and surfaee phenomena,
in addition to those parameters which strongly affect individual chemical
reaction rates, viz temperature, pressure, composition, catalysts etc.
Thus many parameters can affect, and, in turn, be affected by the deposi-
tion process, Figure 2.
2.1 Corrosion fouling

The basic electrochemical reaction of corrosion is the removal of a
metal atom from an anodic site to form an ion in solution, leaving behind
excess electrons on the metal:
eg Femetal ~ (l)
Simultaneously, electrons are consurned at nearby cathodic sites by a

balancing reaction, Figure 3, which for neutral and alkaline solutions is
usually the reduction of dissolved oxygen:
ie Oz + 2HZO + 4e --7 40H (2)
Metallie oxide, or hydroxide, deposits are formed thus:
Oz + 2HZO + !z M ~ !z M(OH)
z
(3)
The reduction of hydrogen ions to hydrogen as the balancing reaction only

becomes important in solutions of decreasing pH and predominates in
strongly acid environments:
ie 2t + 2e ~ 2H ~ HZ (4)
The presence of both anodic and cathodic sites on the corroding heat
transfer surfaee arises from:
(a) differences in temperature between different parts of the surfaee
(b) stress in the material of the corroding surfaee
(c) differences in the oxygen supply rate to different parts of the
surfaee
(d) different metals in the flow system which are connected elect-
rically outside the flow system etc
When a metal is irnrnersed in a solution of its ions and allowed to reach
equilibriurn, a potential difference, the electrode potential, develops

across the metal/solution interface. In a molar solution of metal ions at
298 K, it is the standard electrode potential. The potential of the
standard hydrogen electrode is arbitrarily chosen to be zero, Table l. Two
dissimilar metals in a conducting solution develop different potentials.
In this case, the potential difference provides the driving force for
galvanic corrosion. The more resistant metal corrodes less and is often
@ProcessEng
completely proteeted. The galvanic series, Table l, is a more useful

guide to the ranking of alloys and metals than the electrochemical series.
Other corrosion mechanisms found in process plant ine lude crevice, pitting,
intergranula~ stress, erosion and selective leaching.
295
shear
removal
heat flow
bulk
fluid t
flow •• +
t
w chemical
c reactant, recursor
oxygen flow
at
Cbf produet, foulant flow
Figure l Overview of re action fouling
r----l- - --~- - -- -1---1

composition bulk temp heat flux pressure
t t
I
t
l
I
I
I
r - - - - fluid
properties
~
I
I
heat transfer
coefficient
+ flow
regime I
I
mass transfer I
I-~-I~ coellicient ~-I
I
wall shear
I
I
stress
,
I
I
I
I
I
@ProcessEng
tube material surfaee tube fluid

rou~hne&s dia'1'eter velycity
,t.._ _ _ _ _t ______....__
Figure 2 Parameters affecting and affected by deposition

296
Table l Electrochemical and Galvanic Series
Electrochemical Series
Metal-metal Standard elect- Galvanic Series in Seawater

ion equili- rode potential
brium (unit at 25°C
activity) (volts)
Au-Au+ 3 + 1.498 Platinum

i pt-pt+ 2 + 1. 200
Gold
U
•.-1 Graphite
'Cl Pd-Pd+ 2 + 0.987 Titanium
G
ilro Silver
Ag-Ag+ + 0.799
u Chlorimet 3 (62 Ni, 18 Cr, 18 Mo)
{
Hg-H9 2 +2 + 0.788 Hastelloy C (62 Ni, 17 Cr, 15 Mo)
18-8 Mo s/steel (passive)
Cu-cu+ 2 + 0.337
18-8 s/steel (passive)
H2 -W 0.000
1 Chromium s/steel 11-30% Cr
(passive)
Pb-Pb+ 2 - 0,,126
~ Nickel
Inconel (passive) (80 Ni, 13 Cr,
Sn-Sn+ 2 - 0.136 7 Fe)
(passive)
Ni-Ni+ 2 - 0.250 Silver solder
Monel (70 Ni, 30 Cu)
Co-Co+ 2 - 0.277
Cupro-nickels (60-90 Cu, 40-10 Ni
Cd-Cd+ 2 - 0.403 Bronzes (Cu-Sn)
Fe-Fe+2
Copper
- 0.440
Brasses (Cu-Zn)
Cr-Cr+ 3 - 0.744 ChlOrimet 2 (66 Ni, 32 Mo, l Fe)
{
Hastelloy B (60 Ni, 30 Mo, 6 Fe,
zn-Zn+ 2 - 0.763
l Mn)
Inconel (active)
AI-Al+ 3 - 1.662 {
Nickel (active)
Mg-Mg+ 2 - 2.363 Tin
Lead
Na-Na+ - 2.714
Lead-tin solders
K-K+ - 2.925 18-8 Mo s/steel (active)
{
18-8 s/steel (active)
Ni-Resist (high Ni cast iron)
Chromium s/steel, 13% Cr (active:
{ cast iron
Steel or iron
Cadmium
Commercially pure aluminium (llOe

Zinc
Magnesium and magnesium alloys
2.1.1. Polarisation When a metal is in thermodynamic equilibrium with a

solution of its ions the rate of metal dis solution must equal the rate of
deposition from solution. To drive the net reaction in one direction, the
@ProcessEng
metal must be displaced from its equilibrium potential in a positive

(anodic) sense to promote the oxidation or dis solution reaction, and in a
negative (cathodic) sense to promote the reduction or deposition reaction.
The extent of the displacement of electrode potential from the equilibrium
297
value is called polarisation; when the rate is controlled by the electrode

reaction itself, activation polarisation.
In corrosion, the difference between the equilibrium potential for the
metal dissolution and for the (dissimilar) cathodic reaction on the same
metal provides the driving force for the spontaneous dis solution of the
metal. The metal must be equipotential. Thus the dis solution rate
increases as i t is polarised anodically by the cathode and the cathodic
rate, eg H2 evolution, increases as i t is polarised cathodically by the
anode, Figure 4, until the corrosion potential E corr is reached, at which
the total cathodic current is equal to the total anodic current I corr . The
whole of the driving force is then dissipated. In practice, a finite
potential difference is necessary to drive the corrosion current through
the solution. This is represented by the line I'corrRs, where Rs is the
solution resistance. E'corr is then the corrosion potential.
The rate of hydrogen evolution in acidic environments is activation
controlled. In some systems as the re action rate increases, it may become
limited by the diffusion of reactants or products. This is concentration
polarisation, and is often exhibited by the oxygen reduction reaction,
where, af ter a short period of activation polarisation., the rate becomes
limited by the rate of supply of oxygen across the diffusion boundary layer,
and a limiting current density is reached at 30 to 100 ~A cm- 2 , irrespective
of further reductions in electrode potential, Figure 5. This current often
controls the maximum corrosion rate in near-neutral aqueous solutions.
2.1.2. Passivation Most metals display an activation control led region

when polarised anodically. However, technological alloys and metals enter
a region in which a solid corrosion product, often an oxide, is the stable
phase rather than the dissolved ion. If this product is in contact with
the metal, has reasonable strength, adhesion and low ion-conductivity, the
metal dis solution rate is limited to the rate at which metal ions can pass
through the film, and may be a factor of 10 3 to 10 6 les s than the free
dissolution rate at the same potential. Passivity is exhibited by stainless
steels, nickel alloys, titanium etc. A typical polarisation diagram is
shown in Figure 6. Ep is the prima ry passivation potential, Icrit the
critical current density, Ip the passive current density which may be very
low (10- 8 to lO-IO A cm- 2 ). The increase in current at high values of
anodic polarisation is due to oxygen evolution on the oxide film.
(5)
Some alloys, especially those rich in chromium, can also show increased
currents at low polarisation due to further oxidation of the passive film
to a soluble species:
2-
2Cr04 + 10H+ + 6e (6)
Film formation and stability depend on interfacial conditions, the rate of

oxygen transport, temperature, concentration of metal ions and hydroxides,
and the solubility product of the film compound.
@ProcessEng
2.2 Chemical reaction fouling

The principal chemical mechanisms are cracking and cOking, autoxidation
and polymerisation.
2.2.1. Cracking and coking At high temperature, coke is formed via the
secondary reactions (synthesis) of the products of the primary reactions
298
cathode 2~ + 2e ~ H2
I
-r-
Fe ~ Fe 2 + + 2
I Ul
~
~
o
I -ri
~
fil
ri
fil
-ri
.jJ
I':r:~t
\
~
Q)
.jJ
o
\ P;
anode I corr
I'corr
current I
Figure 3 Corrosion cell showing Figure 4 Polarisation diagram

solid deposits for determination of
corrosion potential
evolution
40H
passivity
ri
fil
-ri 30-100
.jJ
~ -)lA/cm 2
Q)
.jJ
o
h
L-._-::;oo, - - - Ep
,active dis-
solution
current I current I
Figure 5 Oxygen reduction and Figure 6 Polarisation diagr

concentration for active/passive
polarisation metal
(cracking and dehydrogenation). At temperatures > 650 K the primary reac-

tions are fast in the gas phase 6 and the mechanisms are reasonably well
understood 6 •
Cracking:
,-/'HI-CH;r CH 3 + R2-CH = CH2
eg 2RI-CH2-CHZ-CH2-CHZ-R2 (7)
~RI-CH = CHZ + R2-CH2-CH3
Dehydrogenation:
@ProcessEng
(8)
The pyrolytic cracking of a c-c or a C-H bond can take place via radicaI (
ion formation:
299
radieal (homo ly tic decomposition) A:B --;) A· + B· (9)

ionie (heterolytic decomposition) A:B --7 A + B+ (10)
Heterolytie decomposition requires about three times as much energyas the
homo ly tic reaction meehanism. Thermal pyrolysis therefore proceeds via
free radical mechanisms, whereas catalytic cracking involves ion formation.
The secondary reactions first involve eyelisation of hydro carbon chains
to form aromatics and then involve eondensation of aromatics to form high
moleeular weight polycyclic aromatic systems 6 . Aromatisation occurs
preferentially at temperatures > 950 K, whilst chemical condensation of
aromatics in the liquid phase ean oecur at temperatures between 650 and
800 K. Cross-linking between polyeyclic systems ean occur below 650 K.
The chemical meehanisms of the synthesis reactions are not well understood
but both Diels-Alder and free-radical pyrocondensation mechanisms have
been proposed 6 .
Diene synthesis:
eg ( + O - CD - CD
"
-'""'
~
(U)
.
Pyrocondensation:
.
eg
CO+(O
" " ~ ~
- --+
(12)
Synthesis reactions are slow and therefore coke deposition in craeking

furnaces can be minimised by operation at low residence times. The
craeking/coking mechanism is summarised sehematically in Figure 7.
2.2.2. Autoxidation It is general ly accepted that deposition at low

temperatures, partieularly for hydrocarbons in the liquid phase, is due to
free-radieal autoxidation reaetions which are initiated by hyd~ogen
abstraction from the substrate molecule RH by a free-radical X:
ie R-H + X ~ R + XH (13)
Reaction of the substrate radieal with molecular oxygen and further hydrogen
abstraction results in a chain reaction involving peroxy radicals and
hydroperoxide moleeules:
ie R + 02 - - ) ROO (14)
ROO + RH ---'> ROOH + R (15)
possible termination steps are:

R + R~ R-R (16)
@ProcessEng
R + Roå ---7 ROOR (17)

ROO + ROO ---'> ROOR + 02 (18)
With a good supply of oxygen, re action (14) should be rapid with the result
300
primary pyrolytic
reactions (degradation of molecules)
secondary pyrolytic I
reactions (synthesis of I
high mole weight compounds) I
I
I
low MW low MW hydrogen
paraffins aromatics + gases [ hydrogen [
+ olefins + gases
/ i / j/ i/
feedstock
hydrocarbon
cyclic
ydrocarbon
aromatics heavy
r-------,
calcined
coke
+
Step l Step 2 Step 3 Step 4

dehydrogenation formation of I dealkylation calcining of
cracking cyclisationl aromatics I polycondens- semicoke
I I at ion to pcah
I I
I I
Figure 7 Schematic of hydrocarbon pyrolysis 6
saturated hydrocarbons
energy, time, inorganic acids
unsaturated hydrocarbon
+ H
energy, time, oxygen
organic acids
energy, time, metals
resins, asphaltenes
energy, time, hot metals

@ProcessEng
coke polymerisation
Figure 8 Successive degeneration of hydrocarbons to coke 7

301
that the concentration of substrate molecules will be low. Therefore it is

general ly considered that reaction (18) is the most important termin at ion
step. Once autoxidation has been initiated homolysis of the weak o-o bond
in the hydroperoxide forme d in reaction (15) leads to the formation of more
radicals which can initiate further hydrogen abstraction from the substrate
molecule:
ie ROOH ---7 RO + OH (19)
The reaction chain thus breeds, since via reactions (14), (15) and (19) one
free-radical generates three. Soluble salts such as those of cobalt,
manganese, iron, copper, chromium, lead and nickel catalyse the reaction
by increasing the rate of hydroperoxide homolysis and possibly by taking
part in the initiation reactions:
ie ROOH + Co Z+ ----? RO + OH + Co 3+ (20)
ROOH + Co 3+ ------7 ROO + t + Co 2 + (21)
+
RH + Co 3+ ----7 R + H + Co 2+ (22)
The position of the -OOH group in the hydroperoxide molecule is determined

by the strength of the bond ruptured and the stability of the radical
formed. Oxidation of the aroma tic nucleus and of primary C-H bonds in
paraffins is difficult, but becomes increasingly easier for secondary and
tertiary C-H bonds. A considerable increase in the rate of oxidation is
found when there is a double bond or an aromatic nucleus in the position
a to the group undergoing oxidation, eg for olefins and alkyl substituted
aromatic hydrocarbons. The autoxidation mechanism is summarised in the
schematic proposed by Eaton and Lux 7 in which asphaltenes are also seen to
play a key role in the formation of deposits, Figure 8.
2.2.3. Polymerisation A polymerisation reaction is the conversion of a

particular compound (monomer) to a large chemical multiple of itself. An
extremely large number of polymerisation reactions and mechanisms exist, an
overview being given by Kirk and Othmer 8 . Polymers may be produced by a
wide variety of processing techniques which include bulk, solution,
suspension, emulsion, precipitation methods etc. If a polymer becomes
insoluble in its monomer, or in a particular monomer-solvent combination,
it precipitates as it forms. Precipitation will occur at any location
where conditions are favourable; this may be in the bulk or on a surface.
Since polymerisation reactions are strongly exothermic, there is always a
likelihood of deposition on the surfaces of heat exchangers used to remove
the heat of reaction.

Polymerisation reactions are involved in the formation of deposits from
hydrocarbons. The reactions involve three basic steps:
(a) radical formation and chain initiation:
XH --} X + il (23)
R - CH CH 2 + X R CH - CH2X (24)
@ProcessEng
--}
(b) chain propagation:

1f R
R - CH + n (R-CH = CH2) --} R-crt CHZ-CHtCHZ-~H (25)
I
CH2X CH2
302
(c) chain termination:

R R
R-Cr~CH2-~H~CH2-~H + H ~ (26)
CH2 n
The rate of each step and length of the chains formed depend upon many
factors including the r.oncentration and activity of the reactants. Oxygen,
halides, sulphides, nitrogen compounds, certain metals or metallic compounds
are all known to be able to initiate polymer formation. The operating
temperature as well as the stability of the radicals determine the extent
of their involvement. At certain temperatures mercaptans and sulphides can
undergo reactions with the metal surface.
eg Fe + R-SH ~ FeSH + R (27)
Such corrosion reactions can yield hydro carbon radicals which in turn may
initiate polymerisation and autoxidation reactions.
3. PREDICTIVE MODELS
It is not possible to develop a single general model to account for all
forms of reaction fouling owing to the diversity of feedstocks, processing
environments and fouling mechanisms encountered in the process industries.
Nevertheless in outline most published models adopt the scenario shown in
Figure l, and include the following steps:
(l) diffusion/convection of reactants (foulant precursors) from
the fluid bulk to the reaction zone
(2) reaction of precursors to foulant
(3) diffusion/convection of reaction products and/or foulant back
to the fluid bulk
(4) removal of foulant from the surface by the shearing action of
the flowing fluid
Most models relate to fouling inside round tubes, but there is no reason in
principle why they could not be adapted to other geometries. In addition,
most models assume that the fouling rate of a whole exchanger or furnace
can be modelled in terms of a single set of parameters such as temperature,
flow rate, tube diameter ete, but again, in principle, there is no reason
why such models could not be applied locally at all points within the
equipment in the manner described by Fryer and Slater 9 for milk fouling,
and then average fouling resistances be computed.
3.1 Corrosion fouling models

Theoretical models generally assume that the corrosion rate is controllee
by the resistance due to the transport of oxygen to the corroding surface,

and is not controlled by the corrosion reaction itself. This assumption
implies that the reaction kinetics are fast and that the oxygen concent-
ration at the corroding surface is zero. The transport of oxygen involves
two steps:
(a) transport from fluid bulk to the fluid/deposit interface
(b) diffusion through the deposit to the metal sur face
@ProcessEng
Somerscales 1 has developed a model for the in situ corrosion fouling of

non-ferrous heat transfer surfaces exposed to flowing water, which initiall~
included the reaction step as well as the two oxygen transportation steps.
Having then made the assumption about fast kinetics, the deposition flux
~d was given by:
303
(28)
where Md' molar mass of deposit, oxygen, respectively

bulk concentration of oxygen
mass transfer coefficient for oxygen
diffusivity of oxygen in the deposit
valency of the metal (equation 3)
Equation (28) was made non-dimensional as:
zMox dy1 l
(29)
4M d dt+
where Y1 Yf/d (30)

D+ Df/DSh (31)
f
Sh ktd/D (32)
t+ tC b Df /P f d 2 (33)
and D diffusivity of oxygen in the bulk fluid
For very thin deposits, that is either for the initial stages of fouling or
for situations in which the deposit formation rate only slightly exceeds a
deposit removal rate:
+
Yf«
D+f (34)
For very thick deposits the diffusion of oxygen through the deposit becomes
the rate controIling step, and
+
yf » D; (35)
PossibIe deposit removal mechanisms are:

(a) dissolution - material leavinq in ionic form
(b) erosion - material leaving in particulate form
(c) spaIling - mate ria l leaving as large masses
Somerscales 1 compared his model with previous theoreticaI investigations of
in situ corrosion on non-ferrous metals. A summary is given in Table 2.
Not all the models include the effects of heat transfer. When heat flows
from a corroding surfaee to water the corrosion process may be altered as
follows1 O:
(a) the formation of soluble species at the metal/deposit interface

is encouraged, thereby weakening the attachment of corrosion
produets
(b) the solubility of oxygen in water decreases as the temperature
increases and consequently its transport may be inhibited by
the temperature gradient
3.2 Chemical reaction fouling models
Chemical reaction fouling models which relate specifically to fouling
@ProcessEng
from hydrocarbon streams are reviewed elsewhere S and are summarised

chronologically in Table 3. All models have been developed for heat trans-
fer applications but not all include deposit removal terms, reflecting the
observation that organic deposits are often tenacious.
Several models 16 ,21,23,24 are based on film theories of heat and mass
@ProcessEng
'"~
Table 2 l40dels of in situ aqueous corrosion
Deposition Removal Fluid velocity Heat transfer

Authors Application
term term effects effects
Dillon (1959) 11 dissolution

diffusion control y; »~ through temperature
at constant removal term included
rate
(1966) 12 mass transfer

Butler y~ « I{
control
- through 11 no
diffusion control y~ » n;
Mahato et al intermediate between
mass transfer and y+ Cv JJf:.f - through ~ no
(1968) 13 f -
diffusion control
Galloway (1973)14 intermediate between y+ '" JJf:.

f - through ~ no
mass transfer and f -
diffusion control
Khailov et al growth and removal probably not through model

yes
(1975)15 processes not y+ « ~
specified constant
separated f f
y+ » D+ dissolution
Somerscales general f f through D;
(1981) l and
y+ '" D+ erosion yes
f - f removal terms
+
Yf«
D+f spa11ing
-~ - ---- - ---- - - - - - -- ----- --
@ProcessEng
Table 3 Models of chemical reaction fouling
Authors Appl ication Depos i t i on Term Removal Term Remarks
Nelson (1934)16 ail refining Rate is directly dependent upon None ean s idered Fouling rate can be reduced by
thickness ef thennal boundary layer increasing fluid velocity
Alkins (1962) 17 Fired heaters in oil Constant monthly increase in coke None considered Two layer concept - porous
industry resistance for various refinery streams coke adj acent to f1 Ul d and
hard coke adjacent to wa 11
Nijsing (1964)'8 Organic coolant in Hydrodynamic boundary layer and diffusion Produet diffusion back (1) Solution with diffusion
nuclear reactors partial differential equations to the fluid bulk is an control fits plant data.
(l) instantaneous first arder reaction in i ntegra l part af the Foul i ng ra te predi cted to
zone close to wall differential equations increase with velocity
(2) very rapid crystallisation at hot (2) Extended to consider
surface colloidal transfer to the
hot surfaee
Watkinson and L;quid phase fouling Mass transfer and adhesion of suspended First arder (1) Correct prediction af
[pstein (1970)'9 from gas oi 1s particles Kern and Se",ton25 initial rate dependence
( l) s t i cl< i ng probabi 1i ty proparti ona 1 to shear remova l term an velocity
, exp (-E/RT) (2) Incorrect prediction af
(2) sticking probability inversely asymptotic resistance an
proportional to hydrodynamic forces veloci ty
an particle as it reaches wall
--
Jackman and Vapour phase pyrolysis Kinetics control - two reactions: None considered (l) Quasi-steady state
Ari s (1971 ),u (l) first order dissociation of A into assumption
products (2) Untested
(2) zero arder coke fonnation
Fernandez-Bauj i n Vapour phase pyrolysis Kinetics and/ar mass transfer control None cons; dered Solution with mass transfer
and Solomon with fi rst arder reaction control fits plant run-time
data. ie fou1ing rate increases
( 1976)21 with ve10city
Sundaram and Vapour phase pyrolysis Kinet;cs control None con s idered (l) Quasi -steady state
Froment (1979)22 of ethane (l) at surface temperature assumption
(2) first order in propylene concen- (2) Good agreement between
tration, a product af primary industrial and numerical ly
cracking reactians simulated data
i
Crittenden and Hydroca rbons i n Kinetics and/o r mass transfer control (1) Diffusion af foulant (l) Comp l ex - many parameters
Kol aczl<awsl<i genera l with first arder reaction back into fluid bulk (2) limited testing with oi1s 24
(later with other orders 5) (2) First arder (3) Tested wi,th styrene
(1979)"'" Kern and Seaton25 po lymeri sa t i on"l
shear remova l term (4) Extended 24 to two layer
---
concept proposed by Atkins 17 w
&:
306
transfer,Figure 9. Nelson suggested that the rate of eoking is direetly

dependent upon the volume of fluid in the film whieh is at a temperature
higher than that of the bulk fluid. Sueh a theory ean aeeount for the
wide ly held view that a fouling rate ean be redueed by inereasing the fluid
veloeity, thereby reducing the heat transfer film thickness. Reaction
kinetic effects have been introduced by Fernandez-Baujin and Solomon and
by Crittenden and Kolaczkowski. In both cases the mass flux of reactant,
or foulant precursor, to the reaction zone, J t , is given by:
(36)
where Cs = reactant concentration at the fluid/solid interface. Under

steady conditions this flux is balanced by the consumption of reactant in
the fouling reaction. Assuming simple first order kinetics, with a rate
constant, k:
(37)
The rate of fouling, which is proportional to J t , is obtained by eliminating

Cs from equations (36) and (37), ie
dRf
(38)
dt
The reaction velocity constant increases exponentially with absolute

temperature according to the Arrhenius expression, Figure 10. For the high
tube wall temperatures in steam cracking furnaees Fernandez-Baujin therefoD2
assumed that in equation (38) k » kt, and they expressed kt in terms of
the aver age fluid velocity and fluid physical properties by the Chilton and
Colburn analogy. Hence:
(39)
(d-2y ) 1.8
f
where K* a function of feedstock, cracking severity and selectivity,

dilution steam ratio eta
Very good agreement was claimed between actual furnace run lengths and
those predicted by using equation (39).
Crittenden and KOlaczkowski 23 ,24 assumed that the possibility also exists
for the removal of foulant, if still mobile, by a convective or diffusive
mechanism. The mass transfer and kinetics model was extended thus:
(40)
where J f flux of foulant back to the fluid bulk

(41)
@ProcessEng
mass transfer coefficient for foulant convection

concentration of foulant at deposit/fluid interface
The foulant concentration in the fluid bulk, Cbf ' was assumed to be zero,
and hence equation (40) became:
307
heat flow
mass
flow
1 slope E/R
Eg Nu Cl ReD. 8pr D. 4
å hd/k Cl VD.8dl.8w-O.8pr-O.4
å heat transfer film thickness
V viscosity l/T (absolute)
Re Reynolds number
Pr Prandtl number
h heat transfer coefficient
k fluid thermal conductivity Figure la Arrhenius plot
Figure 9 Heat transfer film
d
(42)
dt
Mass transfer coefficients were again expressed in terms of flow rate and
physical properties by application of the Chilton and Colburn analogy to
give an equation which showed a complex dependency of fouling rate on mass
flow rate. Whether the fouling rate increases or decreases with flow rate
depends on the relative balance between mass transfer and kinetic effects,
Table 4. The model has been tested on a chemical system comprising the
polymerisation of 1% styrene in kerosene. The order of reaction for this
system is 5/2 26 rather than l, assumed in equation (37), and in the
development of equation (42). The only adjustable parameter required in
the testing was the concentration of polystyrene at the deposit-liquid inter-
face, ieCsf in equation (42). However, it was found that, as expected,
this interfacial concentration was independent of mass flow rate, but
increased strongly with interfacial temperature .

Crittenden and Kolaczkowski 24 extended their model to include the
build-up of two layers on the tube wall in the manner described original ly
by Atkins 17 • The assumption made was that a mobile tarry layer would
thermally degrade with time to produce a hard coke, the thermal conducti-
vity of which was greater than the tarry layer. This model has not been
tested.
@ProcessEng
The removal or re lease of deposits by the shear action of the fluid, as

original ly proposed by Kern and Seaton, has been included in chemical
reaction fouling mOdels 19 ,23,24. The removal flux ~r was assumed to be
proportional to both the shear stress at the wall T and to the deposit
thickness, ie
308
Table 4 Scenarios of deposition and removal in

mass transfer and kinetics mode1 23
release/removal term effect of

deposition term increasing W
precursor foulant (at given T s )
back diffusion shear removal
Tw low kinetics
control
I - reduces dRf/dt
d small k « kt - - little effect
W high - I reduces dR/dt
Tw high precursor
I - increases dR/dt
diffusion
d large control - - *increases dR/dt
W low k » kt - I complex
* same dependency of dR/dt on Wand d as in Nijsing 18 and Fernandez-Baujin

and Solomon 21 models
<Pr (43)
where ~ = a function of deposit structure.

Watkinson and Epstein 19 included such a removal term in their mass
transfer-adhesion-release model to rationalise their experimental results
with both gas oils and sand-water slurries. Deposition from gas oils was
assumed to have been caused by the mass transfer of suspended particles
to the wall followed by adhesion of some particles to the wall. The
probability that a particle would stick to the wall, S, was assumed to be
dependent on temperature, according to the Arrhenius equation, Figure 10,
and inverse ly proportional to the hydrodynamie forces on the particle as
i t reached the wall. Hence:
(44)
a3(C b -C s )exp(-E/RTW)
(45)
vf~
where a. constants
l-
E activation energy for sticking probability, S
R universal gas constant
Tw wall temperature (absolute)
@ProcessEng
Equation (45) predicted correctly the dependency of initial fouling rate

on wall temperature and mass flow rate, as found by experiment 27 .
However, the model did not predict the correct dependency of the asymptotic
fouling resistance on flow rate.
309
Deposit removal terms were not included in the vapour phase coking
models of Jackman and Aris 20 and Sundaram and Froment 22 . This is reason-
able since coke forme d at high temperatures is not easily removed from
tube walls. Both these models invoked the quasi-steady state assumption,
ie since the cOking rate is ve ry much less than the precursor throughput,
the energy, continuity and pressure drop calculations did not contain
explicit time dependencies but were updated periodically for changes in
flow cross-sectional area arising as aresult of deposition. Simple first
order dependence of the coking rate on propylene concentration in the bulk
was assumed by Sundaram and Froment 22 , ie
A exp(-E/RTw ) Cb ~t
(46)
By taking incremental steps along the tube, Sundaram and Froment integrated
numerical ly the model equations to give predicted results which compared
well with plant data.
4. APPLICATION OF PREDICTIVE MODELS

The development of scientific models which ean predict the dependence of
fouling rates on time and on other key process parameters presents process
management with the opportunity to
(a) identify process control strategi es for minimising the impact af
fouling
(b) determine optimum cleaning cycles
(c) evaluate commercial anti-foulant and corrosion inhibition
treatments
(d) assess the value of alternative heat exchangers in reducing the
impact of fouling
MINERVA is a program developed at Bath 28 which incorporates process-
specific fouling modelS, such as those described above, into a personal
computer energy management and operability package, which will enable
technical management to adopt operational and design strategi es for mini-
mising the impact of fouling on their plants. An example screen display is
shown in Figure ll. The program has been developed to complement, not
replace, the existing range of heat transfer software through its ability
to predict the dynamie behaviour not only of individual exchangers but also
of existing and re-vamped series networks, such as the preheat exchanger
trains in the crude distillation units of oil refineries. As a concept,
the program has a much broader application in the process industries that
suffer from fouling. Its success as a simulator ve ry much depends on the
knowledge and ability to write the process-specific fouling sub-routine.
Indeed an important feature of MINERVA is the requirement to evaluate
fouling model coefficients from plant data.
5. CONCLUSION
Much in principle is known about the fundamental science of re action
fouling. Many models have been developed and continue to be tested with
laboratory and plant data. Despite this, the problems of reaction fouling
remain in the proces s industries.
@ProcessEng
6. ACKNOWLEDGEMENTS
The author is grateful to both the Science and Engineering Research
Council and BP International Ltd for continuing to support research on hydro-
carbon fouling at the Univers ity of Bath. The author is also indebted to
Dr Stan Kolaczkowski and Miss Imelda Downey for helpful comments made in
310
u u u u u
o O O O O
o
f'- f'-
O
CO
O O
ri
O
li)
N N N M M
furnace
+' . .,
ri
Ul QJ
'Cl
>:: ;:., .
ri
., QJ
..c:: O O ;:l fOl ;:l Ul
tJ, fOl 'Cl O O :> O O
.Pl1J ..,
;:l
'ri Ul +' .., +' )..< l1J 'tl
l1J l1J Ul +' l1J QJ Ul
" tJo QJ O ..c:: l1J Ul
)..< .o Pi tJo QJ
)..<
5
p.,
Exchanger HUMber(s); 234

Flowrate (lb.x1888); 728 1958 1658 1218
Step (weeks); 8 14 19 26
rf
: :: :;~ i j
~ l... ~...~ .. .•.~ ~...•. ~ .•• ~ •• ~ ~., ~ ~ ~ ~, j.. ~.........
~ ~., .. ;...~ .. ~ .. ~...>. "~."
8.88 •. ..•
::,: .. l., . . ... .. ...
.. .. .... .. •. J.", . . . l:.:..

","':~ 'TT ~:"'1~ '"[""'" ~("l
: : : ; : :
8.87 '1" 'r" .. ~ .. +.. ~ .. ~ .. ~ ...~ .. ;.. ~. "1'" j
4
.-.
I
r... : ..
o : 3
2
r:r:'H 8.888 "4 8 12 16 28 24 28 32 36 48

~~~83/87
HATD3 TiMe
==>
@ProcessEng
('"leeks)
Figure Il MINERVA simulation of reaction fouling in three exchangers

of acrude distillation unit (effect of changes in crude
throughput)
311
the preparation of this article and to the Institution of Chemical

Engineers for permission to publish Figure 2.
7. LIST OF SYMBOLS
constants in equations ktf mass transfer coefficient

(44) and (45), various units for foulant, m s-l
A pre-exponential, various units defined by equation (39)
concentration of reactant, M metal in equation (3)
precursor or oxygen in bulk
molar mass of deposit,
fluid, kg m- 3
kg kmor l
Cbf concentration of foulant in
molar mass of oxygen,
bulk fluid, kg m- 3
kg kmol- l
concentration of reactant, pre-
R universal gas constant,
cursor or oxygen at fluid/solid
kJ kmol-lK- l
interface, kg m- 3
fouling resistance
concentration of foulant at (kW m- 2 r l )-1
fluid/solid interface, kg m- 3
solution resistance, ohms
d tube diameter, m
sticking probability
D diffusivity of oxygen in bulk
fluid, m2 s- 1 Sherwood number
diffusivity of oxgyen in time, s
deposit, m2 s- 1
wall temperature, DC, K
E activation energy, kJ kmol- l
v average fluid velocitjf m s-l
E corr corrosion potential, volts
W mass flow rate, kg s-l
Ep passivation potential, volts
deposit thickness, m
f friction factor
valency in equation (3)
I corr corrosion current density,
amps cm- 2
deposit density, kg m- 3
Icrit critical current density,
amps cm- 2 T shear stress at wall,
kg m- l s- 2
passive current density,
amps cm- 2 deposition flux, kg m- 2 s- 1
mass flux of foulant, function of deposit
kg m- 2 s- 1 structure
mass flux of reactant or

Superscript:
precursor, kg m- 2 s- 1
k reaction velocity constant, + dimensionless variable
varions units
kf deposit thermal conductivity,
kW m-lK- l
@ProcessEng
kt mass transfer coefficient for

reactant, precursor or oxygen
m s-l
312
REFERENCES
l Somerscales, EFC, "Corrosion fouling", In FC'mling in Heat Exchange
Equipment, eds. Chenoweth, JM and Impagliazzo, M, Pub1. HTD-Vo1 17,
ASME, New York, 1981, pp 17-27
2 Lister, DH, "Corrosion products in power generating systems", In Fouling
of Heat Transfer Equipment , eds. Somerscales, EFC and Knudsen, JG,
Hemisphere, Washington, 19B1, pp 135-200
3 Froment, GF, "Fou1ing of heat transfer surfaces by coke f"rma"tion
in petrochemical reactors", In Fouling of Heat Transfer Equipment, eds.
Somerscales, EFC and Knudsen, JG, Hemisphere, Washington, 1981,
pp 411-435
4 Garrett-Price, BA, Smith, BA, Watts, RL, Knudsen, JG, Marner, WJ and
Suitor, JW, "Fouling of Heat Exchangers, Characteristics, Costs,
Prevention, Control and Removal", Noyes Publications, Park Ridge, NJ,
1985
5 Crittenden, BD, Kolaczkowski, ST and Hout, SA, "ModeIling hydrocarbon
fou1ing", Chem Eng Res & Des, 65(2), 171-179, 1987
6 Fitzer, E, Mueller, K and Schaeffer, W, "The chemistry of the pyrolytic
conversion of organic compounds to carbon", In Chemistry and Physics of
Carbon, Vo1 7, ed. Walker, PL jnr, Marcel Dekker, New York, 1971,
pp 237-383
7 Eaton, P and Lux, R, "Laboratory fouling test apparatus for hydro carbon
feedstocks", In Fouling in Heat Exchange Equipment, eds. Suitor, JWand
Pritchard, AM, Pub1. HTD-Vol 35, ASME, New York, 1984, pp 33-42
8 Lenz, RW, "Polymerisation mechanisms and processes", In Kirk-Othmer
Encyc10pedia of Chemica1 Technology, Vol 18, Wi1ey, New York, 1982,
pp 720-744
9 Fryer, pJ and Slater, NKH, "Tbe simulation of heat exchanger control
with tube-side chemical reaction fouling", Chem Eng Sci, il, 2363-2372,
1986
10 Ross, TK, "Corrosion and heat transfer - areview", Brit Corr J, .?...
131-142, 19E7
Il Dillon, RL, "Observations on the mechanisms and kinetics of aqueous
aluminium corrosion", Corrosion, l2, 13t-16t, 1959
12 Butler, G, "The inf1uence of movement on corrosion", Proc 3rd Int
Conf on Meta11ic Corrosion, Vo1 l, Moscow, 1966, pp 271-280
13 Mahato, BK, Voora, SK and Shemi1t, LW, "Steel pipe corrosion under flow
conditions: An isothermal corre1ation for a mass transfer model",
Corrosion Science, ~, 173-193, 1968
14 Ga11oway, TR, "Heat transfer fou1ing through growth of calcareous film
deposits" , Int J Heat Mass Transfer, 16, 443-460, 1973
15 Khai1ov, VS, Chimishkyan, AL, Akimov, SA and Glebov, MB, "Sorne aspects
of the action of a corrosive stream on a heat transfer surface",

J App1 Chem USSR, 48, 2059-2063, 1975
16 Nelson, WL, "Fouling of heat exchangers", Refiner and Nat Gas Man,
Q(7), 271-276, 1934
17 Atkins, GT, "What to do about high coking rates", Petro/Chem Engr,
~(4), 20-25, 1962
18 Nijsing, R, "Diffusiona1 and Kinetic Phenomena Associated with
@ProcessEng
Fou1ing", Euratom Report EUR 543e, 1964

19 Watkinson, AP and Epstein, N, "Particu1ate fouling of sensible heat
exchangers", Proc 4th Int Heat Transfer Conf, Paris, Vol l, Paper HE
1.6, Elsevier, Amsterdam, 1970
313
20 Jackman, A and Aris, R, "Optimal control for pyrolytic reactors",

Proc 4th Euro Symp on Chemical Reaction Engineering, Pergamon, Oxford,
1971, pp 411-419
21 Fernandez-Baujin, JM and Solomon, SM, "An industrial application of
pyrolysis technology: Lummus SRT III Module", In Industrial and
Laboratory Pyrolyses, eds. Albright, LF and Crynes, BL, ACS Symp Series
No 32, ACS, Washington, 1976, pp 345-372
22 Sundaram, KM and Froment, GF, "Kinetics of coke deposition in the
thermal cracking of propane", Chem Eng Sci, 2±, 635-644, 1979
23 Crittenden, BD and Kolaczkowski, ST, "Mass transfer and chemical
kinetics in hydrocarbon fouling", In Fouling - Science or Art? I Corr
Sci and Tech/IChemE, London, 1979, pp 169-187
24 Crittenden, BD and Kolaczkowski, ST, "Energy savings through the
accurate prediction of heat transfer fouling resistances", In Energy
for Industry, ed. O'Callaghan, PW, Pergamon, Oxford, 1979, pp 257-266
25 Kern, DQ and Seaton, RE, "A theoretical analysis of thermal surfaee
fouling", Brit Chem Engng, i, 258-262, 1959
26 Crittenden, BD, Hout, SA and Alderman, NJ, "Model experiments of
chemical reaction fouling" Chem Eng Res & Des, 65(2), 165-170, 1987
27 Watkinson, AP and Epstein, N, "Gas oil fouling in a sensible heat
exchanger", Chem Eng Prog Symp Ser, 65(92), 84-90, 1969
28 Crittenden, BD, Kolaczkowski, ST andVarley, R, "Efficient use of
energy in oil refinery exchange: networks subject to fouling", paper to
be presented at IChemE Symposium on Innovation in Process Energy
Utilisation, Bath, September 1987
@ProcessEng
CHEMICAL REACTION FOULING OF HEAT EXCHANGERS
B. D. CRITTENDEN

UNIVERSITY OF BATH
BATH BA2 7AY
UNITED KINGDOM
1. INTRODUCTION
Chemical reaction fouling ean occur to varying degrees in any process
environment in which hydrocarbons, or other reactive organic species, are
heated. Particular problem areas include:
(a) oil refinery heat exchangers
(b) jet fuel stability
(c) polymerisation reactors
(d) steam cracking furnaces (reviewed by Froment 1 )
(e) food processing (discussed elsewhere in this book)
Nobody is certain what the total financial penalties are with this type of
fouling. However, in 1979 the Exxon Chemical Company2 reported that the
estimated annual expense for proces s-side fouling on a hypothetical
100,000 bbl/day (~ 13500 tonne/day) oilrefinery was nearly $10 million.
Table l shows the breakdown of fouling-related expenses into additional
energy consumption (process fuel cost = $0.0096 per kWh), loss in through-
put (margin =
$2/bbl), maintenance and cleaning for four important units
on the refinery. The estimates show that about half of the total cost is
attributable to fouling in the crude distillation unit (CDU) in which all
of the incoming crude oil is heated from ambient conditions to elevated
temperatures (over 350°C) in a netvlOr}~ of 8hell and tube exchangers and
furnaces. A sketch of a typical CDU preheat exchanger train is shown in
Figure 1.
There is no reason to doubt that the Exxon estimates are applicable to
European refineries as well. Making no allowance for recent falls in
energy prices, estimates of process-side fouling costs in refineries in
NATO countries are given in Table 2. It is clear that abetter understand-
ing of hydrocarbon fouling could lead to substantial savings in terms of
reta ine d throughput and reduced energy demand.
Chemical re action fouling rates are strongly dependent upon temperature,

pressure and composition, particularly on the concentration and type of
trace level constituents which might include solid contaminants. Tempera-
ture has an important effect, but not always in the simple way in which
individual chemical reaction rate constants depend on temperature.
Deposition which is often severe enough to cause significant reductions
in throughput or frequent shut-downs for cleaning ean occur not only at
@ProcessEng
very high temperatures (up to 1200K) in vapour phase cracking furnaces,

but also at much lower temperatures (up to 650K) in liquid phase CDU
preheat exchangers and column reboilers. Pressure, vaporisation, flow
rate and corrosion are additional complicating factors.
315
L. F.Melo et al. (eds.), Fouling Science and Technology, 315-332.

316
TABLE l Hypothetica1 typica1 refinery fou1ing re1ated expenses
Fou1ing re1ated expenses ($x10- 3)

Capacity
maintenance
Energy Throughput Total
(bb1/day) & c1eaning
crude unit 100,000 1020 3730 35 4785

hydrotreaters 45,000 535 510 25 1070
visbreaker 10,000 1695 420 120 2235
reformer 25,000 1070 700 15 1785
4320 5360 195 9875
o
~
crude
---40'"
oil
o
19
Figure l Typica1 crude disti11ation unit preheat exchanger train

TPA = top pump-around HGO heavy gas oi1
BPA = bottom pump-around LGO light gas oil
@ProcessEng
KERO = kerosene RES hot atmospheric residue

317
TABLE 2 Estimated fouling related expenses (FRE) for NATO countries
*1985 refining capacity FRE

(tonne/day) $ M per anmlIn
Belgim 89,000 66
Canada 253,000 187
Denrnark 23,000 17
France 266,000 197
Greece 53,000 39
Iceland - -
ltaly 374,000 277
Luxembourg - -
'Ihe Netherlands 200,000 148
Norway 33,000 24
Portugal 40,000 30
Spain 162,000 89
Turkey 63,000 47
United Kingdom 253,000 138
USA 2,082,000 1,540
West Germany 264,000 195
4,155,000 2,994
* Source: Institute of Petroleum (1987)

2. DEPOSITS
A large number of adjectives has been used to describe the appearance
of deposits. Hard coke tends to be found in higher temperature applica-
tions whilst soft, soot-like, waxy or tarry deposits, which are sometimes
relative ly easy to remove by means of high velocity fluids, are generally
found in lower temperature applications. Coke has a high thermal conduc-
tivity (typically 0.8 wm- 1 K- 1 ) relative to that of a hydrocarbon fluid
(typically 0.15 Wm-1K- 1 liquid; 0.015 Wm-1K- 1 vapour). Therefore the
thermal resistance of a porous deposit is likely to be controlled by the
fraction of fluid trapped within the deposit structure. With time any
hydrocarbon deposit ean be expected to age on contact with high temperature
surfaces and turn progressively into tenacious high molecular coke-like
material, perhaps via resins (mol weight < 5000) and asphaltenes (1000 <
mol weight < 300,000)3.
Apart from oil-soluble fractions 3 , high ash contents, sometimes in
exces s of 80%, are found in deposits from CDU preheat exchangers 3 ,
desulphuriser preheat exchangers 4 and naphtha vaporisers 5 . Salts of Na,
Fe, Ca and Mg are found in CDU exchanger deposits, the Na coming from a
combination of incomplete desalting of the crude and alkali injection
af ter the desalter to prevent HCl formation from the hydrolysis of CaC12
and MgC12' salts which are associated with the aqueous fraction of crude
oil. Fe salts arise from corrosion both within the refinery and prior to
delivery of the oil. Other elements found in deposits include S, Pb, Cu,
Ni, Zn, Si, Mn 3 - 6 .
@ProcessEng
Deposit morphology is dependent upon processing conditions 7 . Fine

po rous structures of near-spherical particles occur at lower temperatures,
particularly when fuels are saturated with air or oxygen 7 - 9 . Filamentary-,
plate- and varnish-like structures occur with deoxygenated fuels 7 ,8 or at
higher temperatures 9 - 10 .
318
TABLE 3 Effect of time t on fouling resistances Rf
type plot example situations ref
CDU exchangers 11
naphtha reboilers 12
absorption oil coolers 12
visbreaker 13
~
Rf coker 13
linear crudes, crude fractions 14
aviation kerosene 15
gas oil sensible heating 6
kerosene vaporiser 9
t
jet fuel coking 16
styrene solution polymerisation 17
Rf~
CDU exchangers 11
(a) falling rate gas oil/catalyst slurry
(b) asymptotic exchangers 12
(b) gas oil sensible heating 6
crude oil laboratory tests 3
t
~
falling rate Rf vapour phase thermal 38,
+ linear cracking 39
3. FACTORS AFFECTING FOULING RATES

Example temporal variations in fouling resistances are shown in Table 3.
In general, it is not possible to determine whether or not an initial
linear behaviour would eventually yield either a falling rate or an
asymptotic behaviour, given a sufficiently long period of operation.
3.1 Temperature
Since the mechanisms by which reaction fouling occurs are complex, a
simple dependence of fouling rate on temperature cannot always be expected.
However, a number of studies indicate that the rate increases exponentially

with absolute temperature 6 ,7,14,17,18. Data are often fitted graphically
to Arrhenius-type equations 6 ,17,18, ie
deposition (or fouling) rate a exp (-E/RTw ) (l)
An example is shown in Figure 2; example activation energies for the

@ProcessEng
fouling rate-temperature plots are:

319
sour gas oils 6 146 < Tw < 204 °e E 120 kJ mol- 1

pure n-paraffins 1 8 93 < Tw < 260 °e E 40 kJ mol- 1
dilute solution styrene
polymerisation 1 7 22 < Tw < 98 °e E 39 kJ mol- 1
kerosene vapour 9 350 < Tw < 630 °e E 70 kJ mol- 1
liquid jet fuels 16 149 < Tw < 260 °e E 42 kJ mol- 1
More complex plots of the shape shown in Figure 3 have also been found in
three studies:
air-saturated jet fuels 19 350 < T* < 425 °e
vaporising n-hexadecane 2O T* 320 °e
air-saturated vaporising 9
kerosene 260 < T* < 302 °e
In each case the reason given for the abrupt decrease in deposition rate
at a temperature equal to T* was associated with the transition from a
liquid phase to a vapour phase on the heated surface. Other experimental
results show that trace levels of 02 7 ,19, sulphur compounds 21 ,22, nitrogen
compounds 23 and other species complicate the deposition rate-temperature
relationships.
3.2 eomposition
4
Species present in only trace quantities can pla important roles in the
deterioration of hydro carbon feedstocks in storage 2 -26. The extent of the
deterioration depends not only on the bulk hydrocarbon composition, but
also on the presence of dissolved oxygen, organic compounds containing O,
S and N, and on trace metal eontaminants. Thermally cracked feedstocks can
beparticularly unstable 26 ,27. From their free energies of formation
several conclusions ean be drawn 28 about the relative stabilities of pure
Q) Q)
~c~:,
.j..l
ro
.j..l
ro H
H
T!\
I': I':
o o
"ri "ri
.j..l .j..l
"ri "ri
Ul Ul
o o
P.. P..
Q) Q)
'O 'O
e 14
~ ~
o e 16 o
ri
ri
liT liT
@ProcessEng
Figure 2 Effeet of temperature on Figure 3 Arrhenius plot

deposition rate from pure showing ehange of
n-paraffins l 8 mechanism 9, 19,2 O
320
hydrocarbons, and hence their likelihood to foul hot surfaces:

(a) below 800K, low molecular weight paraffins are the most stable
hydro carbon s with methane showing the highest stability;
(b) above 1100K, aroma ti c hydrocarbons become the most stable
hydrocarbons;
(c) above 1100K, the stability of olefins lies between that of
paraffins and aromatics;
(d) the stability of paraffins decreases with increasing carbon
number;
(e) at high temperatures the stabilities of olefins decrease with
increasing carbon number;
(f) alkylated aromatics are less stable that their unsubstituted
counterparts;
(g) the stability of aromatics decreases with increasing length of
the side chain;
(h) the stability of aromatics increases with increasing numbers of
rings.
The thermal stability of pure and blended hydrocarbons, oil fractions, and
jet fuels has been studied extensively. The folIowing observations have
been made regarding deposit formation on hot surfaces:
(a) In variance with the prediction (a) above, Figure 2 shows that
the deposition rate from n-paraffins decreases with increasing
carbon number from 10 to 16 18 .
(b) For a given temperature and carbon number, chain branching of
paraffins increases the deposition rate 18 •
(c) In general, the presence of an aromatic or naphthene (at 10%
w/w) inhibits the deposition rate from n-decane between 366 and
450K, the inhibition becoming less pronounced at higher temp-
eratures. The effect is also a function of the additive
structure 18 •
(d) In general, the addition of an olefin (at 10% w/w) increases
the deposition rate from n-decane, the effect being a function
of olefin structure 18 •
(e) The addition of asphaltenes (mole weight between 1000 and
300,000) to oils promotes fouling whereas the addition of
resins (mole weight < 5000) is less deleterious 3 . Both the
concentration and solubility of asphaltenes are important
factors.
(f) Rigorous exclusion of dissolved oxygen or air substantially
reduces or even eliminates deposition 3 ,7,9,19,30. With most
fuels the greatest reduction in deposition rate occurs in the
liquid phase 9 ,19. However, rigorous deoxygenation by itself
to suppress deposition depends on the type and concentration of
trace sulphur compounds present 22 •

(g) The addition of organic peroxides to deoxygenated hydro carbon s
is highly detrimenta1 23 and provides experimental support for
the theory that the thermal degradation of liquid hydro carbon s
occurs via a free-radical autoxidation mechanism.
(h) Sulphur compounds (at 1000 ppm s w/w), which are known to
break down to form free-radicals promote deposition from
@ProcessEng
oxygenated jet fuels 21 . Example compounds are thioIs, sulphides,

dissulphides and some condensed thiophenes. Diphenyl sulphide
and dibenzothiophene are not deleterious 21 . Free sulphur,
dissulphides, polysulphides and in particular thiophenol
promote sludge formation from fuel oils in storage, whilst
321
thiophens, ali,hatic mercaptans and aliphatic sulphides have

littie effect 2 ,31.
(i) The structure of the hydrocarbon to which sulphur compounds are
added is important as wel1 32 . The thermal decomposition rates
of n-paraffins and naphthenes may be reduced whilst the
decomposition rates of i-paraffins may be accelerated.
Unpredicted kinetic phenomena frequently occur when mixtures of
two or more substances are allowed to react simultaneously3Z.
(j) Small amounts of nitrogen compounds affect the stability of
fuel oils in storage 33 . Pyridines and pyrroles both cause
deposits to be formed, the latter being the most deleterious.
(k) Metal chlor ides such as FeC13, CaClz and MgCIZ which hydrolyse
to produce acids substantially increase the rate of fouling
from hydrocarbons 3 . The effects of HCl and dodecylbenzene
sulphonic acid are dramatic 3 .
(l) The nature of the metal sur face strongly influences deposition
rates. Copper and a titanium alloy (containing vanadium) are
particularly deleterious 34 . Copper has pronounced effects on
the stability of feedstocks in storage 25 ,Z6.
(m) The addition of 50 ppm of metal in the form of acetylacetonates
increases the deposition rate from a jet fuel by a factor of
between 40 and 120. The Cu complex results in a greater
increase than complexes of Fe, Ni or Co 34 .
3.3 Pressure and vaporisation

Pressure can exert a complex effect on deposition rates 9 ,19,35, even
though the rate of thermal decomposition of hydrocarbons generaily
increases with increasing pressure 35 . Oxygen is a complicating factor in
the rate-pressure-vaporisation relationship9,36. Substantial circum-
ferential variations in the initial fouling rate during the vaporisation of
air-saturated kerosene were found at various pressures in the range l to
2.5 bar 37 . The highest rate was at the bottom of the horizontal furnace
tube where the temperature was the lowest, but where the liquid phase
tended to flow. It was postulated 37 that the release of air bubbles at
the hot surface was responsibie for the relatively high fouling rates at
locations close to the onset of vaporisation. Later work 9 confirmed that
the fouling rates general ly increased with pressure, but were reduced
marked ly either bydecreasing the feedstock oxygen content or by raising
the wall superheat. The results of both studies 9 ,37 were consistent with
fouling occurring predominantly via autoxidation and cracking-synthesis
mechanisms for the liquid and vapour phases, respectively.
3.4 Flow rate

It is a general ly accepted rule in the oil and chemical industries that
the problem of hydrocarbon fouling can be alleviated to some extent by the
use of higher velocities. Indeed TEMA 40 presents design fouling resistances
which show this trend. However, as Table 4 shows, not all laboratory and
industri al observations con form to this simple rule. In addition, the
foliowing important factors should be taken into account:
(a) whether the fouling rate could be control led completely or
@ProcessEng
partially by mass transfer of reactants or precursors to the

hot surface 16 ,17,43,44; mass transfer rates increase with
increasing velocity;
(b) whether the laminar sub-layer becomes disturbed by the deposit
roughness 15 ;
@ProcessEng
TABLE 4 Effect of flow rate on deposition rate W

N
N
Dependence of
Tube Temperature
deposition Flow rate
Authors System studied riameter range Comments
rate on increa- range
(m) (oC)
ing flow rate
Nelson desalted, wet & not to greater
decreases 0.3<ms- 1 <2.1 industrial plant data
(1958)41 corrosive crude specified than 260
oils
Chantry & forced circula- not not
decreases 3<ms- 1 <10
Church tion reboilers specified specified
(1958)42
various gas,
TEMA not <O.6ms- 1 to
(1968) 40 decreases gasoline and
specified -18 to >260 >1.2ms- 1
refinery streams
Watkinson &
liquid sour 9800 < RE
Epstein decreases 0.0087 146 to 204
gas oils < 41,900
(1969)6
Smith liquid aviation 0.0021 - 4500 < Re I
increases 160 to 260 ASTM fuel coker I
(1969) 15 kerosene 0.0028 < 10,000
Chen and
cracking furnacE not kinetics may control
Maddock increases 0.05 -
for ethylene 900 to 1000 specified at lower temperatures
(1973) 43 0.2
Fernandez- vapour phase
not not comparison of model
Baujin increases pyrolysis of high
specified specified with plant data
(1976)44 naphtha and
light gas oil
Vranos et al liquid jet 0.0018 - 600 < Re (Re) 0.6
increases 149 to 260 rate et
(1981)16 fuels 0.0048 < 10,000
vapour phase
Shah et al increases or 0.0046 - O l<space<l maximum in rate-
(1976) 38 thermal crack- 750 to 800 . time S
decreases 0.0064 flow rate relationship
ing of n-octane
Crittenden dilute solution
increases or 1000 < Re maximum in rate-
et al polymerisation 0.02 22 to 249
decreases < 5200 flow rate relationship
(1987) 17 of styrene
323
(c) the effect of tube diameter, or other geometri c aspects; in one

study, deposition rates were higher in tubes of small diameter 38 ;
(d) the effect of changes in surface temperature which arise from
changes in flow rates. This is an important factor in assessing
Smith's results 15 ,17.
Watkinson and Epstein 6 measured fouling rates from sour gas oils (~0.7% S)
in a small heat exchanger operated at constant heat flux. Fouling resis-
tances increased to asymptotic values except at the lowest flow rates for
which high wall temperatures were developed. Fouling resistances were
correlated with time by the equation proposed originally by Kern and
Seaton 45 : 00
R f (l - exp{-St}) (2)
The following dependencies on mass flow rate were found:
00
Rf et W- 2 (3)
S et W (4)
dR f (o) et exp (-E/RTw ) (5)
dt
These results show that there are two advantages to be gained from operation
at high flow rates. Firstly, the asymptotic fouling resistance R~ is
reduced considerably, whilst the rate of approach to the asymptote is
increased. Secondly, the film heat transfer coefficient is increased,
and therefore the surface temperature, at which fouling reactions are
generally assumed to occur, is reduced for a given heat flux and bulk
temperature:
Tw Tb + ~ (6)
Watkinson and Epstein 46 also reported that by increasing W for a given q,
but without cleaning between changes, the increase in overall heat transfer
coefficient could be fully accounted for by the change in the film heat
transfer coefficient as given by the Sieder-Tate equation. It was concluded
that successive increases in flow rate, and hence wall shear stress, did
not result in a decrease in the fouling resistance due to possible scouring
by the liquid.
The use of high velocities should be considered at the design stage,
because for a given exchanger in which the process stream outlet tempera-
ture is to be maintained, the duty, and hence the heat flux, are proport-
ional to W, whilst the film heat transfer coefficient is proportional only
to GO. 8 . Thus:
Tb + (constant)WO. 2 (7)
In this situation the surface temperature can be increased by increasing

the flow rate.
Figure 4 shows the dependency of the initial rate of fouling from the
dilute solution polymerisation of styrene on both surface temperature and
flow rate 17 . At the highest temperatures, it was postulated that mass
transfer of the styrene monomer to the hot wall played an important role
in the control of the fouling rate. At lower temperatures and higher flow
@ProcessEng
rates, reaction kinetics were believed to control the overall deposition

rate. The results have been modelled 47 in terms of styrene mass transfer
and kinetics for deposition and polystyrene mass transfer for removal. A
discussion is presented in this book, in the paper "Basic Science and
Models of Reaction Fouling". It is interesting to note that for the vapour
phase coking of n-octane at very much higher temperatures 38 , a maximum
324
1.4
1.2
./210
LO
• • 190
J~ /
0.8
.~ . • 170
0.6
. ....--. 150
.~
----_.
0.4
.-.
.-- ----"_.-
t
120
0.2 . • • • -. 100
--- • e _ _ ..
• • ... • .... 75
35
O
100 300 500 700
mass veloeity kg m- 2 s-l
Figure 4 Initial rate of fouling from dilute solution polymerisation of

styrene
in the rate-flow rate relationship is also observed. Mass transfer effeets

are considered to be responsible for other observations of fouling rates
being inereased by inereasing flow rate 16 ,43,44.
3.5 Corrosion
Corrosion fouling ean make a major contribution to the overall fouling
of refinery units; iron salts normally represent 20 to 50% of the deposits
@ProcessEng
but this percentage ean be much greater when light erudes are processed.
Corrosion roughens the surface, thereby providing nueleation sites for
other meehanisms of fouling. Corrosion in heat exehangers in hydro carbon
service is often established during storage of the equipment prior to
eommissioning, but ean eontinue during normal operation beneath other
types of fouling deposits. In severe cases the eorrosion may eause the
deposits to leave the exchanger surface.
325
Corrosion foullng rates are also affected by composition, temperature

and flow rate. Hardness and pH nf aqueous fractions have an important
bearing. Corrosive salts are primarily chlorides and sulphates. Chloride
ions interfere with the development of protective scales and encourage the
breakdown of passive films. Free carbon dioxide, generally set by the
CO~-/HC03 equilibrium, is undesirable, since it lowers the pH. The
influence of pH however is very specific to the metal concerned. For
example, in aqueous solutions, the corrosion rate of steel is a minimum
at pH = 12, above which the rate increases as soluble products are formed.
For 6.0 ~ pH ~ 9.5, the corrosion rate is largely constant, but the rate
increases again for pH < 4.
Oxygen is the most significant dissolved gas, since it is the most
usual cathodic reactant in neutral solutions. The rate of corrosion of
active metals in near-neutral solutions is proportional to the oxygen
concentration. However, deoxygenation is not always advantageous, since
a certain cathodic current availability is essential for the formation and
maintenance of a protective passive film.
Increasing the flow rate reduces the diffusion boundary layer to
increase the limiting current density of the cathodic reaction, Figure 5.
On an active metal, the corrosion rate increases up to a maximum value,
Figure 6. Very low flow rates have little effect, except to reduce the
the tendency towards localised corrosion. At higher flow rates, up to
Re = 2000,
corrosion rate a ;n (8)
l
where v average fluid velocity and n = 3 for flow in pipes. For
turbulent flow the exponent tends towards unity. At very high velocities
erosion can occur. With active/passive materials, the effect of flow
depends on the behaviour at low flow conditions. If Ic is les s than the
low flow limiting current density, Figure 7, the material is stably
passive and flow rate has littie effect (CD on Figure 8). If Ic is greater
than the low flow limiting current density, there are two stable inter-
sections of the anode and cathode curves (I and II), so that repair of
mechanical damage to a passive film is not possible and the whole surface
may move into an active condition. In this case the corrosion rate is a
function of the flow velocity initially (AB of Figure 8), until the
limiting current density equals Ic' af ter which the corrosion rate falls
to the passive value and further increases in velocity have little effect.
For most materials normally used in the passive state the velocity at
which the change in behaviour occurs is quite low, eg18:8 stainless steels
are prone to pitting corrosion in sea-water at low flow rates, but at
velocities > 1.5 ms- 1 excellent corrosion resistance is achieved.
The increased availability of oxygen at high solution flow rates can
cause materials which are normally in an active state to become passive.

For example, the corrosion product of mild steel is not very protective.
Higher velocities lead to a more stable and adherent product and passiv-
ation occurs. Very high velocities may however result in erosion and
spalling.
Corrosion is an electrochemical reaction and therefore it might be
expected that its rate would increase significantly with surface tempera-
@ProcessEng
ture. However, this effect is significant only when the process is not
control led by oxygen transfer, ie at high velocities and with very thin
deposits. The sharp decrease in the solubility of oxygen at higher
temperatures is a factor which could lower rather than increase corrosion
rates.
326
OH
M2 +
H
(lJ
~.-
[il -l-l
,.., ..,
rO
rO .::
·ri
-l-l
.::
(lJ
-l-l
O
·ri
Ul
O
..,..,
/
O
~ O
U
V1 V2 V3 V4 Vs
current I velocity v
Figure 5 Figure 6
Effect of solution flow on eorrosion of aetive metal
OH H
[il
(lJ
,.., -l-l
..,co
rO
·ri
-l-l .::
.:: O
(J) ·ri
-l-l Ul B
O O
H
'"" H
O
U
Ic D
I\..rr C • •
eurrent I veloeity v
Figure 7 Figure 8
Effect of solution flow on corrosion of active/passive metal
4. THE ACQUISITION OF SCIENTIFIC DATA

Data from laboratory-scale experiments is invaluable for quickly testin~
the comparative fouling tendencies of hydrocarbons under a wide range of
conditions. Test apparatus based on the thermal or pressure changes
across small tubes, annuli, hot wires, filters, or stirred tanks are often
used to obtain rapid estimates of the effectiveness of antifoulant
chamicals 3 ,4,7,48,49. .
@ProcessEng
Nonetheless industrial plant data is still necessary for the under-

standing of reaction fouling and for the testing of scientific models,
since the laboratory simulation is fraught with problems. For example,
because fouling in refinery heat exchangers ean take weeks oreven months
to reaeh signifieant levels, it is usually necessary in the laboratory to
modify one or more of the operating parameters so that an accelerated test
327
lasting only hours or days can be achieved 9 . A common approach is to use

actual feedstocks and realistic temperatures, pressures and metallurgy,
but to greatly reduce the fluid flow rate and thereby to reduce the equip-
ment size, power requirements and problems of safety. The philosophy
genera l ly is that since chemical reaction fouling occurs close to or at
the exchanger surface, that is within the laminar sub-Iayer, the main
stream velocity will have littIe impact on the overall deposition process.
The evidence reported above shows however that the dependency of a fouling
rate on flow rate ean be complex. In addition, experiments which depend
on greatly reduced flow rates often yield deposits which are dissimilar in
composition to those found in industrial exchangers; for example, the
laboratory-scale deposits from crude oils generaIly have unrealistically
high organic contents. The objective of the collaborative research
between the chemical engineering departments of the Univers ity of Bath and
BP International Ltd is to gain a fundamental understanding of the complex
dependencies of fouling rates in crude oil preheat exchangers on key
operating parameters. The objective is to be achieved by testing funda-
mental scientific models with actual plant data which will be acquired
from a typical large crude distillation unit. The principal measurements
taken on a regular basis at the refinery are:
(a) inlet and out let temperatures on tube and shell sides of all
exchangers;
(b) all flow rates;
(c) samples of all tube-side and shell-side streams for laboratory
analyses to yield key physical property data and other
important information such as asphaltene content, sulphur
content, oxygen content, inorganic content eta
This information is supplemented by routine data recorded by refinery
operators and by crude assay data. Many practical problems are encountered
however. These are, for example,
(a) frequent changes in crude source
(b) frequent mixing of different crude types, slops eta
(c) use of caustic injection to control pH
(d) occasional use of water washing
(e) impact of occasionally taking out some exchangers from the
preheat train for cleaning or maintenance
(f) errors in temperature and flow measurements which require
considerable care in the assessment of the thermal dutY of each
exchanger.
5. PREVENTIVE AND REMEDIAL ACTIONS

Each fouling problem is highly individual and so no single general
treatment method is available. Control of reaction fouling may be
effected by one or more of the folIowing:

(a) prevention of solids formation
(b) prevention of solids agglomeration
(c) removal of solid deposits.
Mitigating techniques which are used especially within the oil and
petrochemical industries are:
(a) control of process variables, eg
@ProcessEng
(i) minimise surfaee temperatures,

(ii) use high velocities, provided that deposition rates are
not control led by mass transfer,
(iii) avoid vaporisation, if possible, by control of temperature
and pressure.
328
(b) eliminate salt and inorganic content of feedstock, by use of

desalters;
(c) eliminate oxygen and air from the feedstock by purging,
stripping, inert gas blanketting or by adding oxygen scavengers;
(d) avoid the detrimental effects of sulphur and nitrogen compounds
by means of free-radical scavengers;
(e) avoid the use of unsaturated hydrocarbons, or use antipolymerant
additives;
(f) eliminate particulate material from the feedstock;
(g) control corrosion via selective metallurgy and/or inhibitor
chemicals;
(h) coat the heat transfer surfaces with, for example, thin films
of thermosetting resins or powdered coatings;
(i) use tube inserts which not only improve heat transfer rates
but also reduce residence times of foulant precursors at hot
surfaces
(j) avoid slugs of sludge, which is normaIly present in crude oil
storage tanks, from traveIling through heat exchangers and
desalters.
Many proprietary antifoulant formulations are available commercially.
These chemical additives, injected into a process stream at low concen-
tration, are normal ly built around a base dispersant. Additives or surfaee
coatings work effectively only in the temperature range for which they
have been developed 29 ,48, and ean be efficient only if applied in the
correct concentrations 4 ,49, their functions being many:
(a) dispersant - prevents small particles from agglomerating and
sticking to equipment and mayaIso cause disintegration and
removal of deposits, if loose. Dispersants are normaIly long
chain polymeric molecules with a polar group which attaches to
a site of opposite polarity on the partieles, thereby producing
a hydrocarbon film which isolates them from other particles or
the tube metal surface.
(b) anti-corrosion - usually film-forming compounds for minimising
the growth of corrosion produets and inhibiting the formation
of organic molecules where metal ions catalyse polymerisation
reactions etc. A film-forming molecule contains a polar head
group which adsorbs onto the metal surfaee leaving the rest of
the molecule, usually a long hydrophobic oil-soluble chain,
extending into the oil. Water droplets which contain soluble
inorganic salts should also be prevented from reaching the wall.
(c) metal co-ordination, metal chelation, sequestration - deactivates
metal ions which would otherwise catalyse free-radical polyrnerie
reactions.
(d) anti-oxidation - anti-oxidants are effective by destroying

peroxides or by reacting with free-radicals, thereby preventing
autoxidation reactions. Antipolymerants are similar but only
react via the free-radical trapping mechanism.
(e) detergency - detergents are similar to dispersants but are more
polar and ionic, usually being long chain carboxylic acids or
their salts. The polar head groups are attached to the polar
@ProcessEng
sludgeparticleswhich are then solubilised in the hydrocarbon

by the oil-soluble hydrocarbon chains.
(f) neutralisation - chemical reaction between the additive and
fouling precursors, coupled with pH control to neutralise
troublesome compounds.
329
Relative to the overall cost of fouling, the cos t of antifoulant chemicals

appears to be smal1 2 . However, there are reports that these chemicals are
not always effective. For example, whilst the addition of various anti-
oxidants, including alkyl substituted phenols and a phenylenediamine,
reduced the deposition rate from jet fuels, the use of rust preventatives
and metal deactivators increased the deposition rate above 175 °C 29
Results were also unsatisfactory when a water soluble antifoulant chemical
was injected in to wash water which was mixed with crude oil before the
preheat exchangers and desalter of a crude unit 50 . Laboratory trials are
therefore strongly recommended before industrial application.
Many methods, physical, chemical or a combination, are available to
remo ve chemical reaction fouling deposits. The success of any particular
method or combination of methods depends very much on the nature of the
deposits, eg tenacity, organic content, inorganic content etc. Whilst
chemical cleaning is likely to be cheaper than mechanical cleaning, due to
a lower manpower requirement, the effectiveness of chemical cleaning is
variable. Chemical methods include the folIowing:
(a) chemical soaking and/or circulation
(b) steam-air decoking
(c) control led combustion
Physical methods include the folIowing:
(a) pure ly mechanical methods, eg rodding, scraping etc
(b) hydrodynamic methods, eg high velocity liquid jets with or
without abrasive material.
6. CONCLUSION
Chemical reaction fouling in the process industries can be an expensive
problem. Many parameters which affect deposition rates are affected
themselves by the progress of deposition. Despite the diversity of process
environments in which chemical reaction fouling is an operational problem,
there are clear trends in the effect of key process parameters such as
temperature and feedstock oxygen content. However, the effect of flow rate
is complex.
7. ACKNOWLEDGEMENT
The author is grateful to both the Science and Engineering Research
Council and to BP International Ltd for continuing to support research on
hydro carbon fouling at the University of Bath. The author is also indebted
to Dr Stan Kolaczkowski and Miss Imelda Downey for helpful comments made
in the preparation of this article and to the Institution of Chemical
Engineers for permission to publish Figure 4.
8. LIST OF SYMBOLS
E activation energy, kJ kmol- l T* transition temperature, DC, K
E corrosion potential, volts v average fluid velocity, ms- l
h heat transfer coefficient, kW m- 2 K- l W mass flow rate, kg s-l
I corrosion current density, amps cm- 2 S reciprocal time constant in
Ic critical current density, amps cm- 2 asymptotic fouling models
n exponent in equation (8)
q heat flux kW m- 2
@ProcessEng
universal qas constant kJ kmol-lK- l

fouling re;istance (kW m- 2 K- l )-1
time, s
°
bulk temperature, DC' K
wall temperature, C, K
330
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15 Smith, JD, "Fuel for the supersonic transport: effects of deposits on
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16 Vranos, A, Marteney, pJ and Knight, BA, "Determination of coking rate
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18 Taylor, WF, "Kinetics of deposit formation from hydrocarbons: fuel
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20 Vranos, A, "Influence of film boiling on the thermal decomposition of
@ProcessEng
vaporizing n-hexadecane", Ind Engng Chem Prod Res Dev, 20, 167-169,
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21 Taylor, WF and Wallace, TJ, "Kinetics of deposit formation from hydro-
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2. Effect of trace sulfur compounds", Ind Engng Chem Prod Res Dev,
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24 Brooks, BT, "The chemistry of gasolines particularly with respect to
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25 Pedersen, CJ, "Inhibition of deterioration of cracked gasoline during
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26 Walters, EL, Minor, HB and Yabroff, DL, "Chemistry of gum formation in
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27 Johnson, CR, Fink, DF and Nixon, AC-;-"Stability of aircraft turbine
fuels", Ind Engng Chem, 46, 2166-2173, 1954
28 Fitzer, E, Mueller, K andSchaeffer, W, "The chemistry of the pyrolytic
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29 Taylor, WF, "Kinetics of deposit formation from hydrocarbons:
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30 Taylor, WF and Wallace, TJ, "Kinetics of deposit formation from hydro-
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31 Thompson, RB, Druge, LW and Chenicek, JA, "Stability of fuel oils in
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33 Thompson, RB, Chenicek, JA, Druge, LW and Symon, T, "Stability of fuel
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~, 935-939, 1951
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geneous and homogeneous metal effects", J Appl Chem, 18, 251-254, 1968
35 Fabuss, BM, Kafesjian, R, Smith, JO and Satterfield, CN, "Thermal
decomposition rates of saturated cyclic hydrocarbons", Ind Engng Chem
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36 Watt, JJ, Evans, A and Hibbard, R, "Fouling Characteristics of ASTM
Jet A Fuel when heated to 700°F in a Simulated Heat Exchanger Tube",
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37 Crittenden, BD and Khater, E~m, "Fouling in a hydro carbon vaporizer",
IChemE Symp Ser No 86, IChemE, Rugby, 1984, pp 401-414
38 Shah, YT, Stuart, EB and Sheth, KD, "Coke formation during thermal
cracking of n-octane", Ind Engng Chem Proc Des Dev, l2, 518-524, 1976
39 Sundaram, KF and Froment, GF, "Kinetics of coke deposition in the

therma1 cracking of propane", Chem Eng Sci, li, 635-644, 1979
40 Tubu1ar Exchangers Manufacturers' Association 1978 Standards, TEMA,
New York, pp 138-142
41 Nelson, WL, "Petroleum Refinery Engineering", 4th edition, McGraw-Hil1,
New York, 1958, p 549
42 Chantry, WA and Church, DM, "Design of high ve10city forced circu1ation
@ProcessEng
reboi1ers for fou1ing service", Chem Engng Prog, ~ (10), 64-67, 1958
43 Chen, J and Maddock, MJ, "How much spare heater for ethylene p1ants?",
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332
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of pyrolysis technology: Lummus SRT III Module", In Industrial and
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No 32, Washington, 1976, pp 345-372
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46 Watkinson, AP and Epstein, N, "Particulate fouling of sensible
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Paper HE 1.6, Elsevier, Amsterdam, 1970
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carbon fouling", Chem Eng Res & Des, 65 (2), 171-179, 1987
48 Hausler, RH,. "New test will show fouling tendency of process
streams", Oil Gas J, 2l (23), 56-63, 1973
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reduce preheat-exchanger fouling" , Oil Gas J, 63 (18), 117-122, 1965
50 Lawler, D, "Fouling by crude oil in refinery heat exchangers",
Proc. Conf. Fouling: Science or Art? I Corr Sci and Tech/I Chem E,
London, 1979, pp 155-168
@ProcessEng
FOULING FROM LIGHT HYDROCARBONS ON METAL SURFACES
Luis Sousa Lobo
Departamento de Quimica
Universidade Nova de Lisboa
2825 MONTE DE CAPARICA, PORTUGAL
l. INTRODUCTION
Fouling from hydrocarbons on metal surfaces is an important problem

and occurs in many and diverse industrial situations. In some cases,
hydrocarbon mixtures contain significant amounts of inorganic matter (eg.
sulfur and organo-metallic compounds) and particles in suspension. This
may give rise to combined and complex fouling processes. In this paper we
deal with mechanisms of fouling from hydrocarbons only.
The fouling process is usually followed by measuring the change of the

over all heat transfer coefficient, Uf' and comparing it with the original
value Uo. The fouling resistance is defined as
l
Uo
Measuring the change of Rf with time dRf/dt, we usually get assymptotic

curves, useful for design and operating purposes. This, however, is
difficult to predict in the absence of careful work duplicating the experi
mental conditions that might be encountered. -
The process of chemical reaction fouling is a combination of heat and

mass transfer and chemical reactions. The rates of chemical reactions are
difficult to predict.
The reactions to be considered in this context are both the catalytic

surface reactions and the fluid phase homogeneous reactions. In fact, a
precursor chemical species may not be present at the inlet of the heat
exchanger and rather be an intermediate formed under the conditions
prevailing in the exchanger.
We may perhaps state that in chemical reaction fouling the equipment

must be in principle be regarded as:
l) A heat exchanger
2) A flow reactor (tubular or other)
@ProcessEng
3) A catalytic surface
In Fig.l, possible profiles are shown for temperature (T), velocity (u)
and concentration of the fou1ing species. This species might be formed
inside the exchanger by a homogeneous reaction, its concentration profile
across the tubes may be comp1ex, as aresult of the higher temperature in
333
334
Hot stream(possible fluid reactions)

Surfaee of the coke layer
Coke layer
Metal (catalyst) surfaee
Tube wall
Cold stream
FIG.I - HEAT EXCHANGER TUBE WITH CHEMICAL REACTION FOULING
--
M B M B MB
L
oC;-- IN
L __
OUT OUT
IN _ _
B
Lobo et al.(3) Froment et al. (S)
BATCH OR FLOW CSTR

REACTOR
@ProcessEng
LaCava et al. (4)

FLOW; PERIODIC REMOVAL OF SAMPLE FLOW WITII LINING(L)
FIG.2 - ARRANGEMENTS TO STUDY KlNETICS OFFOULING ON FOILS

(M-foil ;F-furnace ;MB-microbalance suspension ;L-lining) •
335
the centre of the tube, of the higher residence time for the stream
flowing or stagnant near the wall, and due to convertion in solid deposit.
Under different conditions, various profiles can be observed. Inpyrolysis
furnaces, the gas film at the tube wall is overheated and this might
favour the formation of the fouling precursors.
As a first approach in modeIling the processes we may consider the

usual mass balance for diffusion through the film and for the surface
reaction (l ,Z) .
Assuming that the reaction is first order (n=l) and that fouling resistan-
ce is proportional to the amount of deposit formed (dRf/dt ~ Ut ), we get,
by eliminating C
dR s
f Cte
dt l/K t + l/K
This is the usual result of adding the resistances of two first orde r
processes in series, namely diffusion to the surface and surface reaction.
With fuel oils at high temperatures , it is observed that a "tarry

layer" and a "coke layer" are formed, and in this case a more elaborate
model is required(Z). With light hydrocarbons however, only a coke layer
is formed, and the kinetics of.deposition show zero order up to tempera-
tures of the order of SOOOC. This will be discussed later in detail.
If zero order kinetics is observed, this means that mass transfer is

not limiting. So, the process is controlled by a concentration independent
surface reaction. In such conditions understanding the kinetics of both
fluid phase and surface reactions is then the key factor to model, control
or minimize fouling.
Z. EXPERlMENTAL TECHNIQUES
In early experiments the measurement of the weight (W) of coke deposited

as a function of time, was made by the cumbersome method of burning out the
deposit and evaluating W from the envolved COZ, by absorption or by GLC.
Introduction of thermogravimetric methods enables a continuous recording of
either W or dW/dt with time. With a sensitive microbalance it is possibIe
to study in detail the kinetics (3), including induction and acceleratory

periods whenever they are observed. Fig.Z shows some arrangements that have
been used to suit particular needs. Arrangements Z-B and Z-C were used for
high temperatures deposition studies (pyrolysis). With Z-C, wall or lining
effect on gas phase reactions can be tested(4). Z-B shows a CSTR reactor
designed to operate under a well known surface to volume ratio (5). This
is known to be important in pyrolysis. Analysis of the gas products is
made by GLC.
@ProcessEng
Together with the kinetic studies, a large number of thechniques are now
available to study the nature of the deposit. These include optical and
electron microscopy (TEM,SEM) and X-ray diffraction. In situ TEM and SEM
have given a large amount of information about gas/solid reactions. Other
336
A SEM x 1,350 2
W = 25 ]Jg/cm B SEM x 1,500
W = 400 ]Jg/cm2
T 595°C; Po = 147 torr T 615°C; Po = 150 torr
c
SEM x 3,050 D SEM x 4,000

T=s500C; P0=100 torr; PH =30 torr T 600°C; Po = 149 torr
FIG.3 - ELECTRON MICROSCOPY PICTURES OF DEPOSITS

@ProcessEng
FORMED ON IRON FROM BUTENE (3,6)

337
techniques provide information about the solid surfaces, particularly LEED

patterns, Auger spectra (AES) and X-rays photoelectron microscopy (XPS).
With a microbalance it is also possible to operate by temperature progra-
med sur face reaction (TPSR), usually by using hydrogen. This technique
gives information about the nature and about types of deposits in the
sample.
Figures 3 and 4 show SEM and TEM pictures of deposits formed on iron
and nickel from light hydrocarbons. This visual and microstructural
observations, together with kinetic studies, provide the basis for
establishing mechanisms for the fouling process.
In Fig.3-A we see the initial deposit formed on an iron foil from

butene. For long deposition times, the deposit shows various forms
that seem to grow from the bottom (Fig.3-B,D). In the presence of both
butene and hydrogen, nucleation on the surface seems to be inhibited and
to take place instead under the surface possibly at grain boundaries (Fig.
3-C).
an nickel foils the deposits show different features. In the absence of

hydrogen, fouling from olefins is very slow. Under high magnification,areas
of nucleation can be observed (Fig.4-A). In the presence of hydrogen,
nucleation takes place immediately in restricted areas (Fig.4-B) from where
carbon growth takes place (Fig.4-C). Growth proceeds at a fast deposition
rate for long times. Thick deposits can be observed (Fig.4-D).
3. SCOPE aF THE PROBLEM
Carbon formation from carbon bearing gases (hydrocarbons and CO mainly)

has been the object of many studies in the last three decades. The
importance of this type of reaction is enormous, as can be seen from Table
I. In most cases, carbon formation is a nuis.ance.
The mechanism of this reaction is frequently misunderstood. In fact it

diverges from normal heterogeneous catalysis in the fact that we have three
phases, and mass transfer processes ofaparticular type must be considered.
Also,carbon gasification should be regarded as the opposite of fouling,

and the mechanisms operating in both cases have points in common.
4. KlNETICS aF FOULING
In studying fouling from hydrocarbons on metals it is convenient to

consider two regions with respect to temperature : a) Ca talytic
region (low temperatures , up to ca. GOOOC), free metal or a metal carbide
bein8 the stable bulk phase; b) Pyrolytic region (high temperatures ,
above ca. 600 0 C). These limits of temperatures vary for different systems
and different conditions. This paper deals mainly with catalytic fouling.
@ProcessEng
Fig.S shows the kinetics of carbon deposition formed on nickel from

various light hydrocarbons. Fast deposition is observed from unsaturated
hydrocarbons. Ole fins require the presence of hydrogen to give rise to fast
deposition rates. Induction and acceleratory periods are observed under
certain conditions. Deposition from aromatic hydrocarbons on nickel
supported catalyst can also attain high rates under conditions of steam
338
A TEM x 35,500
W = 25 jlg/cm2
B SEM x 1,600
W = 14 jlg/cm2
T 540°C; Po = 48 torr T=5500C; P 0=25 torr; PH=25 torr
c SEM x 800
W = 300 jlg/cm 2
D SEM x 270
W = 3,000 jlg/ cm2
T 523°C; Po = 153 torr T = 556°C; Po = 50 torr
@ProcessEng
FIG.4 - ELECTRON MICROSCOPY PICTURES OF DEPOSITS

FORMED ON NICKEL FROM BUTENE (3).
@ProcessEng
IABLE I - PROCESSES IN WHICH CHEMICAL REACTION FOULING ON
METALS IS INVOLVED
AREA PROCESS!UNIT CONDITIONS References
Methanation,hidrodesulphurisation, From 100 to 800 0C. From 2

Industrial Catalysis reforming, steam reforming, to 50 ats. Fe, Co, Ni, Mo, (7)
acetylene hydrogenation ,Fischer-Tropsch. on support.
Coraphite corrosion at high

Nuclear Reactors Gas cooled nuclear reactors. temperatures, fouling of
exchangers at low temperature~
Heat Transfer Heat exchangers, boilers , condensers ,

Variable.
furnaces, tubing, reactor walls.
Pyrolysis Cracking, steam cracking. 600 to 11000C,usually steel. (8,9)
Aircrafts Jet fuel in storage and in fuel wing (lO)

250 to 6500C.
tanks (supersonic).
Bosch process + electrolysis to C02!CO!H2!CH4!H20 mixtures (11)

Space Ships on Fe, Co, Ni, up to 700 0C.
recover 02 from metabolic C02.
Meta11urgy Carburization(hardening) of steels. CO, CH4, 600 0C or higher •
""
'Cl
""
340
70 . - - - - - - - - - - - - - - - ,
35r--------------~
500QC
ETHYLENE. 25 torr 550QC
ACETYLEN!:. 100 tor r
HYDROGEN. 100 torr ~ HYDROGEN, 25 tor r
bl 60 NS 30
.5
---:;
u
O l)
'"
~ SO 25
'"
H
ti)
O Ol
E-<
""
Ol
'" 40
H
ti)
~ 70
5 l-BUTEN!:, 100
HYDROGEN, 100 '"'"
~
..: 5
...
u lO
~ 15
O
...
U
5 H
20 O 10
~ ~
H
s. IO. '50 200
TIME (min)
250 300 10 15 2' 25 3.
TIME (min)
FIG.5 FIG.6
KlNETICS OF FOULING ON ANICKEL FOULING FROM OLE FINS ON ANICKEL
FOIL FROM LIGHT HIDROCARBONS FOIL: EFFECT OF PRE-TREATMENT ON
(weight vs. time, as recorded NUCLEATION (weight vs. time, as
in a microbal ance) (3) • recorded in a microbalance)(3,12).
50
'"2
°E IRON COBALT
N
l-BUTEIÆ. 100 torr l-BUTENE, 100 torr
HYDROGEN. 100 torr
.c:co
E
HYDROGEN, 100 torr
-:;
z
;:
;::
'"oo- 25
Ol
Q
'"
o
!:l
;:i
400· C 450· C
I
so 100
TIXE' (min)
TIME (min)
@ProcessEng
FIG.7 FlG.S
RATE OF FOULING FROM RATE OF FOULING FROM
BUTENE ON IRON SHOWING BUTEC'Æ ON COBAL T SHOWING
FAST INITIAL DEPOSITION (13). FAST I:-JITL.;.L DEPOSITION (14).
341
reforming(8).
Fig.6 shows the early stages of deposition from an olefin . The dramatic
effect of pre-conditioning the metal surfaee prior to the admission of the
reactant ean be observed. Note that the weight scale is expanded 1,000
times with respect to figure 5. The ole fin and hydrogen are admitted in
sequence (batch conditions). The effect of the order of admission of the
two gases is noted. The acceleratory period is followed by a steady state
deposition lasting for several hours: apparently indefinitely.
With nickel, we observe always an acceleration of the rate at the

beginning, followed by steady state deposition. On iron and cobalt,however,
we observe fast deposition rates at the beginning~followed by deceleration
(Figs.7 and 8) (13,14). A comparison of the rates on Fe, Co and Ni from both
acetylene and l-butene under standard conditions is presented in Tab1e II
(14). Both the maximum rate (rmax) and the rate in the final steady state
regime (r ss ) are tabled.
The rates of deposition change with temperature in a surprising fashion.

In Fig.9, the Arrhenius plots for the deposition from butene on Fe, Ni and
Co are shown. This effect was first observed for deposition from olefins
(3) and acetylene (15) on nickel, and later found to be common for
deposition from unsaturated hydrocarbons on iron (13) and cobalt (14) as
well.
Three regions of temperature may be considered in the Arrhenius plots,

as shown in Fig.9-C, with the foliowing remarks:
a) In region I (low temperatures) the rate is independent of both

hydrocarbon and hydrogen pressure (order zero) and independent
of the nature of the olefin used as fou1ing agent.
b) Region II shows a negative activation energy: the rate decreases
with increasing temperatures. The order is now one for both
reactants. A maximum in rate, T , is observed, as shown inFig.9.
c) In region III the order is one for fou1ing from ole fins and two
with acetylene. This is in faet a gas phase pyrolytic process,
almost independent of the nature of the surface.
Deposition on various other metals is negligib1e as compared to

deposition on Fe, Co and Ni (3).
In short, two features shou1d be retained:

a) Fou1ing is very fast from unsaturated hydrocarbons in the

presence of hydrogen, on Ni, Co and Fe, in this order of
decreasing importance.
b) The order zero observed means that even traces of ole fins ean
1ead to similar rates of fouling.
To stress this point, the case of nickel wi11 be taken as an examp1e. If

@ProcessEng
the pressure is reduced by a factor of 10- 2 to l torr, the declining part

of the Arrhenius curve in Fig.9-C will shift to the right. This is due to
the order one observed in regions II and III. The point of maximum rate is
now TH. If the pressure is reduced again by a factor of 10- 2 , T~ is the new
maximum. We ean estimate now that even at the partial pressure of 10- 2 torr
342
50
,......
,...... .....~ 100
.....
~
s
I
S N
S
50 I
NS (J
I
......Q()
.....
(J
Q()
10
\
\ ;:::l.
;:::l. \ I '-'
\ I ~
\' 10
5
~
~
~ 5
600 500 400 600 500 400
A TEMPERATURE (oC) 8 TEMPERATURE (oC)
BUTENE/COBALT (14) BUTENE/IRON (13)
100 ,......
Ul
~
::l
? 50 o
..... ..c::
S -<:t
N N
S S
......Q()
(J
......
(J
Q()
;:::l.
;:::l.
10 '-'
~ ~
~
H
5 ;il 10
c
700 600 500 400 500 400. 300 200
TEMPERÅTURE (OC)
D
BUTENE/NICKEL (3,16) JET FUEL/ STEEL (la)
@ProcessEng
FIG.9 - RATE OF FOULING FROM HYDROCARBONS ON METALS AS A FUNCTION

ON METALS AS A FUNCTION OF TEMPERATURE (ARRHENlUS PLOT).
(FIG. 9D - Adapted, with permission from ref.10, copyright
American Chemical Society)
343
'Fe Co Ni
r (~g/cm2min) 10 205 112
C2 H2 r~~\~g/ cm 2 min) 2 20 85
Ea (Kcal/mole) (21-24) 32 31
r (~g/cm2min) 20 22 50
C4 H8 r;~x(~g/ cm 2 min) 2 15 50
Ea (Ked/mole) 45 34 29
TABLE II-RATES OF FOULING FROM ACETYLENE AND l-BUTENE ON Fe,

Co AND Ni AT SOooC (PHyd = 100 torr, PH2 = 100 torr)
AND ACTIVATION ENERGIES IN TRE RANGE 400-S000C(14).
l ;j.vf
1000
j I /
jO;1 Il
500
-iJ/
</"0 J" yo "';
< <I • " "0 ..,. ..
I I"''' !/ ~lu;
'E
,100
~
-50
• °
il ;0/
/d !)(
I° /
I
o
/ r
10
W =: K t "
A B
10 SO 100
TIME {tJ min. 10 50 100
TIME (t J min
FIG. 10 - LOG/LOG PLOT OF TRE ACCELERATORY PERIOD FOR FOULING ON

NICKEL, SHOWING GOOD FITTING TO A POWER LAW W = K t n (3,17).
(---, line of instantaneous nucleation/constant deposition rate)
TIME
O
til.
11 '" 2 WVM?Zt22WZ??vzmØ
llU. 11>. .f)

@ProcessEng
A B
FIG. 11 - SIMPLE MODELS FOR TRE PROCESS OF GROWTR OF TRE DEPOSIT:

A) CONSTANT SPEED OF NUCLEATION AND TRREE DIMENSIONAL GROWTH:
B) INSTANTANEOUS NUCLEATION AND UNIDlMENSIONAL GROWTH(17).
344
4_l0- 5 atm= l Pa) at 400 o C, fouling rates of 5 ~g/em2 min or 175 g/m 2 h ean
be observed from hydrocarbon mixtures eontaining only traces of olefins.
Similar ealeulations ean be made for iron or eobalt. Traces of acetylene
may have an even stronger fouling effeet (cf. Fig.5 and Table 2).
In studies of thermal eraeking of propane, Sundaram and Froment(5)

eoneluded that the initially predominant eatalytie fouling was due to the
olefins formed by eraeking, and not to propane itself, in agreement with
our previous work.
5. MECHANISMS OF TRE FOULING REACTION
5.1 Aeeeleratory period
The initial induetion and aeeeleratory periods for the deposition from
olefins on nickel ean be aecurately followed using a high sensitivity
microbalance (Fig.6). An appropriate law to describe this aceeleratory
process is a power law of the type W = Kt n . The fitting of sueh a law for
eurves B and C of Fig.6 is shown in Fig.lO-B. The fitting is excelent and
the folIowing laws are obtained:
I W = 3.5 t1. 3 for instantaneous nueleation
II W =4 x 10- 4 t 3.9 for progressive nueleation
In these equations, W is in ~g/em2 and t in minutes. This effect of the

order of admition of the reaetants on the aeceleratory period , during whieh
nucleation of the new phase (carbon) is taking plaee is observed at 550 oC.
For lower temperatures nueleation is slower (Fig.lO-A). We see again that
values for the exponent n between ca. l to 4 are observed.
This ean be explained by simple models for nueleation and growth as

shown previously(16) :
dy W de
dt"e
The rate of nueleation dy/dt per unit metal surfaee S is assumed to be

constant in time dy/dt = S kg. The weight at time t of a nueleus of density
~ born at time e is obvious ly gi ven by We = f' k l k2 k3 (t- e) 3. The K are the
rates of growth in each direction (three dimensional). The law W = Kt 4 is
then obtained.
The two extreme cases of laws found to model the aeeeleratory period can
be visualized in a simple way as shown in Fig.ll.
Values of the aetivation energy for K have been estimated(17), and can
be as high as 400 keal. This is not surprising, as this K is in faet the
@ProcessEng
produet of several rate constants (K=kg kl k2 k3), and reflects the high
energy barrier involved in the nueleation process of a new solid phase. The
dramatic effeet of temperature on nueleation is a consequence of this very
high aetivation energy.
345
METAL
PART IC LE
METAL
CRYSTAL LlTE
~ ~ t jo
(AfteON OEPOSIT
---""""'W/ø'I'/////~ //t'I'U/t'/I'///'/'Ir/'/t'/,'///
~~~ ~
c c METAL c FOIL c
FIG.l2 - CATALYTIC FOULING OCCURS BY EXTRUSION IN VARlOUS FORMS, AS
SHOWN. GAS DECOMPOSITION FORMS CARBON ATOMS WHICH DIFFUSE
THROuGH THE BULK OF THE ME TAL TO GROWTH AREAS (3).
301 HYDROGEN - PROPYLENE ATMOSPHERES
T> 900·C .,-pyrolyll( (ok.

~~,,!!!!~,:---P~ y r OIyti C (ok e
Ni or Cu
cOke____ .
/
/ ·\1 \\I\~.l!.Alloy
+-carOld.
mie
cok e
(oke - - - f=-~=-carblde
sCdle
Ni Cu Allo\'
50: 1 HYDROGEN - PROPYLENE ATMOSPHERES T= 900·C

@ProcessEng
FIG.13 - SCHEMATIC REPRESENTATION OF COKE MORPHOLOGIES OBSERVED

IN HYDROGEN-PROPYLENE ATMOSPHERES (Reprinted from ref.
27, by caurtesy af Chapman & Hall)
346
5.2 Steady-state fouling rate
Based an our kinetic work an nickel we proposed in 1971 (3) a mechanism

involving surface decomposition af the hydrocarbon an the metal forming
carbon atoms, followed by bulk diffusion af carbon. This carbon grows as a
new solid phase in areas where nucleation had aiready taken place, as
shawn in Fig.12 (3).
Fouling may continue indefinitely by ane af the proces ses shawn in Fig.
12. Columns such as seen in slow deposition an iran (Fig.3-B) and nickel,
grow from the bottom. Thick fast deposits can grow by detachment af nickel
crystallites ar small nickel particles. This latter case is common with
deposited metal films and supported metal catalysts. On metal surfaces,
other forms af growth predominate (Figs.3 and 4) (3,6). It is obvious that
surface nucleation favours columnar growth (Fig.3-A and B), while
nucleation in grain boundaries tend to detach metal particles which may
grow continuously.
The proposed mechanism explains most kinetic features observed,

including the orders af reaction and the negative activation energy in
region II (Fig.9). This mechanism has received support from several
authors (19,20,21) and has been extended to the cases af iran (13,22) and
cobalt (14).
A comprehensive discussion af the mechanism af carbon formation an

catalysts is presented in this monograph by Bernardo (18).
5.3 High temperature fouling
At high temperatures (above ca. 600 0 C) gas phase pyrolysis occurs.

Extensive gas phase chain reactions take place (23). At the same time, gas
phase carbon is formed ("Saot") . Several mechanisms have been proposed to
explain this,and reviews an the subject are available (23,24). The walls
can have an effect an the chain reaction process. This explains same
"liner" effects that can be felt downstream in a tube (4). In adition, gas
phase carbon deposits an the walls and recrystallization may occur,
changing the structure and properties af this deposit (25). This effect is
particularly noticeable an Fe, Co, Ni and steels. In this case, although
the surface does not act as a catalyst for the fouling reaction it does
have a strong effect an the deposit formed.
The mechanism af fouling in this region af temperatures is discussed

by LaCava (26).
In a transition range af temperatures (700 to 800 0 C) interaction

between catalytic fouling and pyrolytic fouling is observed on the above
mentioned metals and its alloys. Fig.13, taken from the work of Jackson,
Trimm and Young illustrates this point (27).We note that internal carbides
are formed in the steel alloys at high temperatures and high hydrogen
partial pressures. Burning off the deposit mayaiso remove carbon inside
the metal structure, weakening the alloy. Af ter several cycles of
@ProcessEng
operation and cleaning, severe corrosion might result.

347
6. REACTION FOULING IN HEAT EXCHANGERS
In monitoring reaction fouling in heat exchangers, a plot of Rf vs. time

is usually made. The increase in Rf is the result of various factors though.
As aresult of deposit formation, the surface temperature drops to lower
values. The surface reaction will be slower then. On the other hand,
changes in surface roughness have an effect in mass and heat transfer in
the film. For constant mass flowrate the velocity may increase if there is
an appreciable reduction of the cross section of the tubes. This will
increase NRe and lower the residence time. The net result of all the
changes that progressively occur during fouling is difficult to predict,
unless reliable information exists concerning the various steps involved.
The effect of wall temperature is well documented. It is a critical

parameter affecting fouling rates. The intrinsic fouling rate is usually
an exponential function of temperature. It has been observed that in some
cases the deposition rate drops quickly above certain temperature (1,10,28).
It might not be a coincidence that the Arrhenius plot found by Taylor for
jet fuels (10) is very similar to the ones reported by Lobo (3,13,14,15,16)
for unsaturated hydrocarbons on Fe, Ni and Co (Cf. Fig.9).
The effect of dissolved oxygen on fouling from jet fuels and naphtas is
well known d too. The break point temperature for fouling may increase by
100 or 200 C by introducing an oxygen stripper. As mentioned previouly,
olefins seem to be the principal foulants. Production of olefins in
petroleum process streams by oxidative dehydrogenation is known (28):
Free radicals are required as initiators. Sulphur and nitrogen compounds

may play a role in that. A synergism between sulphur, nitrogen and olefin
concentration was reported by Taylor (reported inlO). At high temperatures,
the free-radical prevailing reactions are particularly sensitive to the
presence of oxygen. On the other hand, the oxygen potential may alter the
metal surface and change its activity. This is known to occur with stain-
less steel under pyrolysis conditions.
With gas mixtures, mass transfer limitations are only expected at very
high temperatures , ·With liquid fuels, limitations may be present at low G
(mass flow rate). However, other effects may be expected. Increasing the
residence time may allow higher conversion to an intermediate foulant,
increasing fouling, as observed by Shah (29). For very low G (high resi-
dence time), mass transfer control may be present. So, a maximum fouling
rate for intermediate G could be thus explained (2,29). However, low G
can also increase the volume of fluid in the film which is exposed to high
temperatures, increasing fouling, in line with a suggestion by Nelson (30).
Either the effect of low G on a possible fluid phase reaction rate or the
effect on mass transfer may be predominat. This will depend on whether the
foulant is already present in the bulk fluid or is being formed at the
@ProcessEng
higher temperatures and higher residence times prevailing in the film near
the wall.
In refineries, fouling occurs in various types of equipment and on

catalysts. Heat exchanger fouling is in some cases a major problem, as on
the charge side of Hydrobon and Platforming combined feed exchanger
348
equipment. Attempts to m~n~m~ze fouling include: l) Whenever possible,

charging freshly processed material; 2) Eliminating air from stored
straight-run or cracked stocks by rerunning thecharge or by airstripping;
3) Avoid contamination of stored naphtas by blanketing with nitrogen or
natural gas; 4) Use of additives; 5) Use of higher alloy equipment,
especiaily with charges containing reactive sulfur compounds.
7. CONCLUSIONS
Chemical reaction fouling is a complex process. As refered, a heat

exchanger can be regarded as a flow reactor 01' as a catalytic surface as
well.
When studying fouling in a particular system, it is certainly useful to

know Rf vs. t for various conditions. However, beyond a certain point, this
approach will not lead us to abetter understanding of the process. It
might be a good strategy to follow the sequence:
l) Study the fluid phase reactions that might be involved. High

resolution analyticai techniques may be required.
2) Study the catalytic surface reaction, and the morphology and
heat resistance of the deposits formed, under constant tempera-
ture conditions.
3) Integrate the previous information with mass and heat transfer
rate estimates to get a prediction of Rf vs. t to fit the data.
This involves modeiling in a quasi steady-state situation.
Toconclude, may I recall that fouling includes the foliowing steps in

series:
a) Possibie fluid phase reactions.

b) Diffusion of the foulant(s) to the surface.
c) Adsorption.
d) Surface reaction, and desorption of products.
e) Bulk (or surface) diffusion.
f) Nucleation.
g) Growth of the deposit.
By abating any of these steps we may reduce or eliminate fouling.
8. AKNOWLEDGEMENTS
The author aknowledges a current research grant from JNICT under

contract number 304.86-ll7/FCI and financial support from PETROGAL.
9. REFERENCES
(l) Crittenden B.D., "Basic Science and Models of Reaction Fouling", this
monograph.
@ProcessEng
(2) Crittenden B.D., Chem.Eng.Res.Des., 65,171-179,1987.

(3) Lobo L.S., Ph.D. Thesis, University of London, 1971.
(4) LaCava A., Ph.D. Thesis, University of London, 1977.
(5) Sundaresan K.M., Froment G.F., Chem.Eng. Science, 34, 635-644,1979.
(6) Lobo L.S., Trimm D.L., Proceedings of the Vth Ibero-American Symp.
Catal., Lisbon, Vol. 2, 350-354, 1979.
349
(7) Denny P.J., Twigg M.V., "Catalyst Deactivation", Ed.B.Delmon, Elsevier,

1980.
(8) Holmen A., Lindvaag O.A., Trimm D.L., A.C.S. Meeting 45,1982.
(9) Trimm D.L., Chem.Eng. Process 18, 137, 1984.
(10) Taylor W.F., Ind.Eng.Chem.Prod.Res.Develop., 13, 133-138, 1974.
(Il) Manning M.P., Garmirian J.E., Reid C.R., Ind.Eng.Chem. Process Des.Dev.
21, 404-409, 1982.
(12) Lobo L.S., Trirnrn D.L., J.Cat. 29, 15-19, 1973.
(13) Bernardo C.A., Lobo L.S., Proceedings of the Vth Ibero-American Symp.
Catal., Lisbon, Vol. 2,355-358,1979.
(14) Bernardo C.A., Lobo L.S., Catalyst Deactivation, Ed.Delmon and
Froment, Elsevier, 409-420, 1980.
(15) Lobo L.S., Trirnrn D.L., Nature 234,15-16,1971.
(16) Lobo L.S., Trirnrn D.L., Figueiredo J.L., Proc. of the 5th International
Congr.Catal., 2, 1125-1137, 1973.
(17) Lobo L.S., Proceed. III Ibero-American Symp.Cat., 1972, Acta Scient.
Venezolana, 24, Sup. 2, 219-222, 1973.
(18) Bernardo C .A. "The fouling of catalysts", this monograph.
(19) Baker R.T.K., Barber M.A., Harris P.S., Feates F.S., Waite R.J., J.
Catal. , 26, 51-62, 1972.
(20) Rostrup-Nielsen, J.R. and Trirnrn D.L., J.Catal. 48, 155-165, 1977.
(2L) Figueiredo, J.L., "Progress in Catalyst Deactivation", NATO ASI,
Nijhoff Pub., 1982.
(22) Cooper B.J., Trimm D.L., J.Catal., 62, 35-43, 1980.
(23) Palmer H.B., Cullis C.F., Chemistry and Physics of Carbon, Vol. l,
1965.
(24) Trirnrn D.L., Progress in Catalyst Deactivation, NATO ASI, Ed.J.L. Fi-
gueiredo, Nijhoff Publishers, 1982.
(25) Derbyshire F.J., Trirnrn D.L., Proc. IV London Int.Conf. on Carbon, 95,
1974.
(26) LaCava, A.I., "Droplets and Filaments", this monograph.
(27) Jackson P.R.S., Trirnrn D.L., Young D.J., J.Mat.Sci., 21, 3125-3134,
1986.
(28) Richard Braun, Materials Performance, 35, 1977.
(29) Shah Y.T., Stuart E.B., Sheth K.D., Ind.Eng.Chem., Proc.Des. and Dev.,
15, 518, 1976.
(30) Nelson W.L., Petroleum Refining Engineering, McGraw Hill, 1979.
@ProcessEng
FOULING OF CATALYSTS.
INDUSTRIAL EXAMPLES.
J.R. Rostrup-Nielsen
HALDOR TOPSØE A/S

NymØllevej 55
DK-2800 Lyngby
CLASSIFICATION OF CATALYST FOULING PHENOMENA

Catalyst deactivation is of great importance for industri-
al catalysis. Design criteria for many catalytic processes are
dictated from deactivation phenomena rather than from the ac-
tivity of the catalyst.
A catalyst may deactivate for several reasons, such as:
- poisoning (site blockage), by preferred adsorption of a
tracecomponent, or by the formation of carbonaceous de-
posits as a side reaction,
- sintering, by los s of active surface area caused by cry-
stal growth or modification of support,
- solid state reactions, involving the active component,
- fouling by the formation or deposition of solids.
The literature on catalyst deactivation {1,2,3,4) focuses
on phenomena caused by blockage of the active sites, the im-
pact on the intrinsic activity and selectivity, and the inter-
action with the diffusion of reactants into the porous cata-
lyst system (pore mouth poisoning). Ve ry little has dealt with
the effect of fouling by the build-up of bulk solid phases
although this phenomenon is of increasing industrial interest.
Fouling may result from different phenomena:
- Solids formed by competitive side reaction
Carbon formation is the most typical example known in many hy-

drocarbon reactions (5,6) such as catalytic cracking (7), plat-
formin~ (6), hydrodesulphurization (8), steam reforming (9,10),
and dehydrogenation (5). Carbon formation is also observed in
hydrocarbon synthesis such as methanation (11), Fischer-Tropsch
@ProcessEng
351

352
synthesis (12), and conversion of methanol into hydrocarbons

(13). The carbon formation is promoted either by the acidity
of the catalyst or by the presence of transition metals. The
mechanism and the resulting effect depends strongly on type
of catalyst and reaction. Carbon formation may result in site
blockage as well as fouling.
- Conversion of impurities in feed to solids
An important industrial example is the conversion of metal or-
ganic compounds in residue resulting in deposition of metals
in hydrodesulphurization catalysts (6,8).
Other examples can be related to volatile metal compounds
being formed at one location in the plant, and typically to be
decomposed in downstream units. Iron and nickel carbonyles (11)
may be formed in units working at high partial pressures of
carbon monoxide, and the metal will be deposited at higher
temperature on the catalyst resulting in pore blocking. The
metals may change the selectivity by favouring hydrocarbon
synthesis or carbon formation. Volatile silicum compounds may
be formed at high partial pres sure of steam and typically de-
compose at low temperatures resulting in fouling of catalysts
and heat exchangers (10).
Impurities in process steam may similarily be deposited
at high temperatures.
- Dust
Dust may originate from the process feed such as for industrial
flue gas processes (14), sulphuric acid plants based on roast-
ing of ore, plants based on coal gasification, in particular
for catalytic reactors operating on raw gas (11), and simply
from carry-over of catalyst dust.
It may be useful to separate the effects of fouling by:
- bui Id-up of solids inside the catalyst particles leading
to pore mouth blocking, and
- build-up of solids between the catalyst particles resulting
in increasing pres sure drop in the catalyst bed.
2 INTRAPARTICLE FOULING
2.1 Pore Mouth Blockage

As mentioned above, the literature on catalyst deactiva-
tion deals mainly with the effects of site blockage, and the
classical work by Wheeler (16) formed the basis for later ad-
vanced mathematical treatment of the interaction of diffusion
and site blockage (3,7). Most analyses are based on constant
diffusion coefficients. However, when pore blockage is involved,
the diffusion coefficient changes and the re~ults depend on
structural aspects of the pore system as illustrated by Beeck-
@ProcessEng
man and Froment (3,17). This makes a quantitative analysis

extremely difficult except for idealized systems.
353
2.2 Steam Reforming

The impact of the pore volume distribution on intrapar-
ticle fouling is illustrated by carbon formation on a catalyst
for steam reforming of naphtha (18).
Fig. 1 shows analysis of the radial distribution of car-
bon in a ring-shaped catalyst which was exposed to coking con-
ditions in a pilot test. The carbon is accumulated close to
the external surface which is not surprising in view of the
low effectiveness factor for the reforming reaction at indu-
strial conditions (10). The catalyst was able to operate with
no sign of deactivation, nor increased pres sure drop.
:[m
20
I I
~ I~I
i
...!i;....
i! 10
...
u
~
u
0.5 1.0 1.5

DISTANCE FROM EXTBlNAL SURFACE mm
Fig. 1. Steam reforming. Radial profile

in ring-shaped steam reforming cata-
lyst af ter mono tube pilot test at
coking conditions (J.R. Rostrup-Nielsen
( 1 8) ).
Fig. 2 shows the pore volume distribution of the catalyst

before and af ter regeneration. Apparently, the presence of coke
is reflected only by formation of a small amount of pores with
small ratios properly reflecting pore mouth blocking. On this
basis, only marginal change of the diffusivity in the catalyst
should be expected. The catalyst is characterized by the pre-
@ProcessEng
sence of a dual pore system with micro as well as macro-pores.

354
700
o P1
600 x P1 AFTER REGENERATION
500
400
300
200
100
Fig. 2. Steam reforming. Pore volume distribution of

catalyst referred to in Fig. 1. Before and af ter
burn-off of carbon (J.R. Rostrup-Nielsen (18) ).
Surface area Porosity
max/g ml/~
- Before regeneration 13.8 218
- Af ter regeneration 9.8 263
When the experiment was repeated with a catalyst of the

same composition, but without the macropores, deactivation
was observed (18). This behaviour can be explained by assuming
that the cata~yst, with micropores only, is more sensitive to
pore blockage whereas the large macropores in the other cata-
lyst ensures transport of the feed into the micropore system.
2.3 Hydrodesulphurization
For hydrodesulphurization (HDS) of heavy residue, the si-
tuation is more complex, because the build-up of carbon is ac-
companied by deposition of metals (nickel and vanadium) result-
ing from decomposition of metal organic compounds being present

in the heaviest (asphaltene) fraction of residium (6,8,19).
These deposits lead to restrictions of the diffusion of
the reactant molecyles, and eventually the deposits block the
pores resulting in irreversible deactivation of the HDS cata-
lyst. The removal of the metals (hydrodemetallization HDM) is
in fact intended in order to produce a purified oil fraction.
@ProcessEng
During operation, metal sulphides and coke being deposited

in the catalyst pores can amount to more than the weight of the
catalyst itself. The distribution of deposited metals in the
catalyst varies with process conditions as well as with the in-
dividual metals. Vanadium has a tendency to be accumulated near
the particle surface whereas nickel is more uniformly deposited
355
as illustrated by the electron microprobe analysis in Fig. 3

(8) .
METALS UPTAKE =0.31 g /g FRESH CAT.
Fig. 3. HDS of resid. Microprobe profile analysis of

1/32" catalyst pellet. (A.C. Jacobsen et al. (7».
It was found (19,20) that the ratio of the average vana-

dium concentration to the maximum vanadium concentration de-
pends mainly on type of feedstock and catalyst, but was only
slightly influenced by the severity of operation (the HDS-rate).
Surprisingly, it was found that the spent catalyst did not in-
dicate a complete closure of the catalyst pores.
On this basis, Hannerup and Jacobsen (19) proposed a model
illustrated in Fig. 4 for a single pore of length R , in a
spherical particle of radius R . The model assumes ~hat 1)
the outer part of the pores lo8ses HDS activity quite early
in the run, and 2) diffusion restrictions in the same part of
the pore increase gradually with the steady accumulation of
metal sulphides.
The HDS reaction proceeds with a first order rate constant
k. in the uncontaminated pore of the particle with radius AoR ,
wEereas in the outer part of the pore, (l-A) R , no reaction o
occurs. All the vanadium is uniformly depositea in this inac-

tive shell of the particle and the effective diffusion coeffi-
cient is reduced from the initialvalue of D to moD, where l-m
is the fractional reduction in the open pore cross-sessional
area. On this basis, an expression for the HDS-rate per volume
of catalyst can be derived (19), by expressing that the HDS-
rate in the non-contaminated core should be equal to the trans-
@ProcessEng
port rate through the inactive shell.

356
(1)
Integration of (1) gives a eorrelation C = f (C ), whieh is

inserted in the rate expression (left siåe of (9». This re-
sults in the following expression for the maximum HDS-rate
(i.e. ~ 7 00) per volume eatalyst pellet:
3m'D'A • C k •C (2 )
r HDS ' max 2 o max o
R '(1-A)
o
For a given severity (k i = K ), there is a maximum value of the

pore bloekage 1-m above whigh the reaetion rate eannot be main-
tained. The minim8m value m is found from (2):
o
1-A (3)
min -A-
Model Pore
~
V
Outer
Surfaee
I Center
of
Sphere
I
I AR
I-
I mD
: 'R
I
D
:I I Diffusivity
I
I
I
Co
O I
I
C<;
K
I Activlty
Concentration
Fig. 4. Model for fouling of HDS eatalyst

(P.N. Hannerup et al. (19».
In industrial reaetors, the eonversion is maintained by

inereasing the temperature (and k ) allowing a higher value
@ProcessEng
of m , min. A typieal temperatureOtime plot (8) is shown in

Fig.oS. The shape ean be predieted by the model (19),
357
II
STIPULATED max. TEMP.
1
CATALYST AGE
Fig. 5. Hydrotreating of resid. Typical run plots for

different catalyst fillings (A.C. Jacobsen et al (8».
I High activity, small pores: cat. A.

II Low activity, large pores: cat. B.
III Combined bed, inlet A/exit B.
A catalyst with small pores (low D) will have high acti-

vity af ter initial deactivation due to low penetration (1-A) of
metal and for the same reason it will have a low capacity for
metals meaning a short life of the bed for removal of metals
(HDM). A catalyst with large pores will allow higher penetra-
tion of metals, and therefore reduce HDS-activity. This means
that activity for HDS and capacity for HDM are inversely re-
lated.
A further increase in pore size will further reduce acti-
vity and eventuaily lead to reduction in theoreticai metal ca-
pacity for a given severity. This follows from eq. (3) showing
that (1-A) affects m at high penetrations. The factor (1-A)/A
means that there is ~n optimum pore size catalyst for each ope-
ration.
By using more than one type of catalyst in a composite bed,
one can in many cases obtain a longer life than with a single
catalyst as illustrated in Fig. 5. Low HDS-activity and high
metal capacity catalysts are used in the front end, and high
HDS-activity and low metal capacity catalysts are used further
down. This means that the composition of the optimum catalyst
bed should be tailored for each feedstock and for the operation
in question.
@ProcessEng
358
3 INTERPARTICLE FOULING
3.1 Pressure Drop
Deposition of solids between the catalyst particles re-
sults in increased pressure drop and often in uneven flow di-
stribution. The rate of deposition will depend on local resi-
dence time and in some cases temperature, i.e. fouling, is
more pronounced at sheltered positions and (for coke) at high
temperatures. When solids are accumulated between the particles
in the catalyst bed, the pres sure drop increases more than pro-
portionally with the accumulated amount. This follows from the
Leva equation (3) which, for turbulent gas flow, has the fol-
lowing form:
1 (4 )
0.35
Pp,s
The pressure drop depends on the equivalent particle dia-
meter on a surface basis, d (= 6 V /S ), and strongly on
p, s p p
the void fraction with a factor 1-E/c:3.
3.2 Hydrodesulphurization and Ring-shaped Pellets

Examples of typical accelerating pres sure drop curves are
shown in Fig. 6. The data refers to hydrodesulphurization of
resids (21). In parallel to the blockage of the pore system
described in section 2, deposits accumulate in between the par-
ticles. Fig. 6 clearly illustrates the importance of a high
void fraction obtained by using rings instead of cylinders. A
bed filled with rings has a void fraction 0.5 - 0.55, to be
compared with 0.40 for cylinders and 0.30 for spheres. As a re-
sult, ring-shaped HDS catalysts have been successfully instal-
Ied as top layer for many residium HDS reactors (21).
3.3 Sulphuric Acid

Sulphuric acid converters represeut a similar example on
the benefits by using ring-shaped catalysts at conditions for
interparticle fouling. Sulphuric acid plants are typically
operating on dust containing gas from metallugicai smelters
(5). Sulphuric acid converters are also used to remove S02
from flue gases (15,23), Fig. 7, which in most cases repre-

sents a potential for fouling.
@ProcessEng
359
eo
1/32-in. cylindere
3/16-in. ringe /
1/32- in.
cylindere
20
2 4 6
Run length, months
Fig. 6. HDS of resid. Catalyst shape and pressure

drop (B.M. Moyse (21).
The estimation of pres sure drop is very
complex for a trickle bed HDS-reactor and
eq. (4) cannot be used directly. Special
models for two phase flows must be applied
(22). (Reproduced with permission from (21».
WSA-2 DENOX
PLANT
AIR------t{I)f;t...J
375
WSA TOWER
COAL
DE-NO x DE-SO x
NH 3 02
NO x- - N 2 S02- S03
NH3~N2
@ProcessEng
Fig. 7. Flue gas cleaning. Unit for combined re-

moval of S02 and NO x (SNOX Process).
360
The alkali promoted vanadium catalyst acts as a ve ry ef-

fective dust filter owing to the vanadium, potassium sulphate
melt being the active phase distributed on the surface of the
support (5,23). Whereas the dust particles may pas s unhindered
through a layer of ceramic bodies often placed on top of the
bed, then practically all the dust in the feed gas is usually
trapped in the upper 5-10 cm of the sulphuric acid catalyst
bed (23). This eventuaily results in a blocking of the gas
passage making a change out or cleaning of the catalyst neces-
sary.
For the same penetration depth of dust, Schoubye e t al.
(23) found that the time on stream, for building up a critical
pres sure drop was 50-60% longer for 10/4 x 7 mm rings (d
p,s
6.3 mm) than for a 6 x 6 mm cylinders. If a bed of 6x6 mm cy-
linder was topped off with about 10 cm of large 20 mm rings
(d = 12.8 mm), the on stream time was prolonged by 75%.
p, s
This is illustrated by the data shown in Table 1.
Table 1. Effect of using 20 mm catalyst rings on top

of first bed (P. Schoubye et al. (23».
(Reproduced with permission from (23».
Catalyst on Amount of dus t Pressure drop, nwn H20

Duration top of 1st bed found by end of run (at same flow rate)
kg/m 2 start of run end of run
16 months 6x6nwn 6.3 70 > 600

eyl inders
dp,s =6nwn
18 months 20/8-15 nwn 6.8 70 70-80

rings
dp,s = 12.8 nwn
3.4 Flue Gas Cleaning

Flue gas cleaning involves catalytic proces ses for removal

of nitrogen oxides (14), and in some cases also for removal of
sulphur oxides (15). These units must operate at low pres sure
drop because of the low pressure of the boiler flue gas. Units
for coal fired boilers must operate in the presence of dust.
@ProcessEng
361
The most common method of removing nitrogen oxides (deNO)

is the selective catalytic reduction (SCR) by which NO is re~
duced to nitrogen by the addition of ammonia and sulphUr oxides
to ammonia sulphate which may deposit on the catalyst or on the
equipment (14). In the combined catalytic removal of NO and
SO (SNOX Process, Fig. 7) (15), the excess ammonia is &xidized
inXthe SO removal step, thus reducing the risk for sulphate
fouling. x
In order to minimize pres sure drop and the risk of foul-
ing, the catalyst bed is shaped in a honey-comb with parallel
flow channeis, which have a high void fraction, E, of ca. 0.7.
Moreover, the honey-comb design leaves no shelter for dust ac-
c u mu l a t i o n. A t YP i c a l d e s i g n (24 ) i s s h o wn i n F i g. 8.
Flue gas inlet
Catalyst unit
Cleaned gas
Fig. 8. NO x plant. Typical arrangement.

(R. Ishimoto et al. (24». (Reproduced with
permission from (24».
The fouling phenomena depend on whether the catalyst is

placed upstream (high dust operation 10-20 g dust/Nm 3 ) or down

stream (low dust operation 0.05 - 0.1 g dust/Nm 3 ) of the elec-
trostatic filter (Fig. 9).
Fouling characteristics of the two systems are compared
in Table 2 (14). The increase of pressure drop depends on ho-
ney-comb dimensions and design, as well as dust characteristics.
In some cases, the dust in high dust operation may be able to
@ProcessEng
clean (brush) the catalyst surface. If so, the catalyst should,

of course, be resistant to abrasion.
362
High Duat
NH3
Low Duat
Fig. 9. Flue gas cleaning. DeNO for low and high dust
operation. Coal fired b~iler.
SCR reactor for selective catalytic reduction
APH air preheater
ESP electrostatic precipitator (filter)
Table 2. Comparison of high dust and low dust systems

for coal fired boilers (J. Ando (14».
High-dust system Low-dust system
Catalyst erosion by dust More Less

Dust deposit in reactor Less More
Ammonium bisulfate deposit

in air preheater Less More
Contamination of fly ash
by ammonium compounds Possible None
Cost of ESP Less More
Nature of ESP Suitable to medium Suitable to low
and high-sulfur sul fur coal
@ProcessEng
coals
363
In the high dust case, ammonium bisulphate may deposit

on the ash particles passing through the air preheater. In
the low dust case, the bisulphate may deposit on the equip-
ment (APH). Also, the fine particles left in the dust may more
easily accumulate on the catalyst (14».
3.5 Autoexhaust Catalysis

Autoexhaust catalysis may remind about flue gas cleaning,
although there is normaily less air in surplus. Again, the
honey-comb shape is preferred to minimize the pres sure drop,
the effects of fouling, and heating up time during st~rt.
The potential for fouling is big, when leaded gasoline is
used. It can be estimated that an average midsize car - over a
period of five years (100000 km) operating on leaded gasoline
(7 tons, 0.4 g/Pb/l, 300 ppm S) will be exposed to 4 kg of
lead and 3.5 kg of S02' to be compared with the 1-2 g of noble
metal in the catalyst bed.
The deactivation mechanisms are complex. Lead is known
to poison the catalyst, but at moderate contents (25,26), the
uptake of lead (probably as PbS0 4 ) results in no significant
change of the effective diffusiv~ty. At high contents (ca.
0.5 g/l), the catalyst is plugged with lead-uptake of 10-30 wt%
(25). Alkyl halides (ethylene dibromide or chloride) are often
added with the lead as "scavengers" (27) to form volatile lead
halides. Thereby, deposition of lead may be eliminated. How-
ever, the lead hal ides penetrate the catalyst more effectively
resulting in a higher degree of poisoning (site blockage) (27),
and in presence of sulphur, the hal ides will be converted into
lead sulphate on the catalyst. Thus, the "scavengers" may harm
the catalyst (27). On this background, practical solutions fo-
cus on the use of lead-free gasoline for autoexhaust cleaning.
Base metal catalysts are sensitive to sulphur which re-
acts with these base metals forming sulphates (25). The effects
may be reduced by operating at temperatures above the decompo-
sition temperatures of the sulphates in question.
Fouling is a severe problem in catalysts for diesel ex-
haust from cars as aresult of excessive soot accumulation on
the catalyst at low temperatures (25).
4 FOULING AND INDUSTRIAL OPERATION

For many processes, the fouling of the catalyst and the
necessity of removing deposits causing it, is one of the most

serious problems encountered in the design of the process.
Fundamentally different solutions to this problem are used.
4.1 Periodic Regeneration
In many situations, a continuous progress of deactivation
due to the fouling can be tolerated (28). One example is the
@ProcessEng
coking of the zeolite catalyst ZSM-5 for the methanol to gaso-

line process.Very big amounts of coke (20%) are accumulated
on the surface of the zeolite crystals embedded in the cata-
lyst particles. As aresult, the temperature profil e in the
adiabatic reactor moves slowly through the bed resulting even-
364
tuaIly in break-through of unconverted methanol (13). Af ter

regeneration, by controlled burn-off of the coke, the operation
cycle ean be repeated. For the Mobil MTG Process, life cycles
of ca. 4 weeks have been reported (13). In Fig. 10, results
are shown for the integrated gasoline process, TIGAS (29), in
which the hydrogen retards the deactivation rat-e-.----
NORMALlSED
TEMPERATURE
l00~--------------~~~~----------~
75
50
25
20 40 60 100
Fig. 10. Synthetic gasoline by TIGAS Process.

Progression of temperature profiles.
(J. Topp-Joergensen (29».
Other proces ses such as dehydrogenation of butane over

chromia/alumina catalysts (f.inst. Houdry process) show much
shorter operating cycles (5). Several reactors are used in
parallel and each reactor operates adiabatically. Af ter 5-10
minutes, the feed is switched to another reactor. The first
reactor is purged with steam, and carbon deposits are burned
off in air which reheats the bed. The catalyst is re-reduced,

and the cycle is repeated.
In case of metal depositions such as on resid HDS/HDM
catalysts, regeneration is not possible, but the top of the
catalyst can be removed and exposed to "skimming" (30), re-
moving agglomerated catalyst particles. However, the additio-
nal cycle time gained will become progressively shorter af ter
@ProcessEng
each skimming because of the gradually increasing fouling of

the remaining part of the bed.
365
Dust aeeumulated on sulphurie aeid eatalyst ean be re-

moved by simple sieving (21) and in many situations, dust ae-
eumulating in deNa -eatalyst ean be removed by blowing with
air (14). ----x
4.2 Continuous Regeneration

For some reaetions, eoking is so fast that the operating
eyele is within seeonds. This is true for eatalytie eraeking
using zeolite eatalysts and a fluid bed reaetor with eonti-
nuous regeneration (5,6). In faet, reaetions are so fast that
they take plaee aiready in the transfer line as utilized in
the riser eraeker (5). The feed is mixed with and evaporized
by eontaet with hot regenerated eatalyst and passes upwards
in a vertieal pipe. Contaet times of the order 2-4 seeonds
are aehieved. The eatalyst is separated from the proeess stream
and exposed to regeneration in another fluid bed reaetor.
Other examples of fluid bed teehnology with eontinuous
regeneration of the eatalyst are the MTO proces s for conver-
sion of methanol into olefins (31) and the Synthol proeess
for Fiseher-Tropseh synthesis (12). A typieal arrangement is
shown in Fig. 11:
Flue gas Produet
Regenerator
Cooler
Make- up
catalyst
air (+ N2 ) -
' - - - - - -...-air
(N 2 )
Feed
Fig. 11. Typieal arrangement for eontinuous regene-

ration in fluid bed reaetors (in eatalytie
eraeking, the regenerated eatalyst is added
to the feed stream)
4.3 Elimination of Carbon Formation

@ProcessEng
Carbon formation ean be eliminated by seleetion of "safe"

reaetion conditions. This solution is preferred when fouling
has a serious impaet on the heat transfer rate.
366
A typical example is tubular steam reforming of hydrocar-

bons for the manufacture of synthesis gas. Carbon formation
would easily result in maldistribution of flow or build up of
carbon on the tube walls, resulting in "hot tubes" and strong-
ly reduced tube life (9,10).
5 CONCLUSION
Catalyst fouling is a dominating phenomena in many cata-
lyst applications, including several technologies of increasing
importance such as hydrotreating of heavy oil fractions, flue
gas cleaning and co al conversion.
There is a need for abetter understanding of man y fouling
phenomena such as correlation between pore structure, pore
plugging and resulting catalyst activity, and the impact of
dust characteristics on the extent of fouling.
ACKNOWLEDGEMENT
Thanks are given to Mr. B. Cooper, Mr. K. Johansen, and
Mr. P. Morsing for helpful discussions.
LIST OF SYMBOLS
C concentration
d equivalent sphere diameter
p, s
D diffusion coefficient
g gravity constant
G mass velocity
km rate constant
m blockage parameter (Fig. 3)
pres sure
reaction rate
radial distance
pellet radius
pore radius
particle surface
temperature
void fraction in bed
penetration parameter (Fig. 3)
viscosity R
Thiele modulus (~ = ~ Vk!D)
REFERENCES
1. Bartholomew, C.H., Chem.Eng. 91 (23), 96 (1984).

@ProcessEng
2. "Deactivation and Poisoning ofCatalysts" (Oudar, J. and

Wise, H. eds.), M. Dekker, New York 1985.
3. Froment, G.F. and Bischoff, K.B., "Chemical Reactor
Analysis and Design", John Wiley & Sons, New York 1979.
367
4. "Progress in Catalyst Deactivation" (Figueiredo, J.1. ed.),

Martinus Nijhoff Publ., The Hague 1972.
5. Satterfield, C.N., "Heterogeneous Catalysis in Practice",
McGraw Hill, New York 1980.
6. Gates, B.C., Katzer, J.R. and Schuit, G.C.A., "Chemistry
of Catalytic Processes", McGraw Hill, New York 1980.
7. Butt, J.B., Adv.Chem.Ser. 109, 259 (1972).
8. Jacobsen, A.C., Cooper, B.-alld Hannerup, P.N., PD18,
paper No. 3, 12th World Petrol. Congr. , Houston 1987.
9. Rostrup-Nielsen, J.R. This monograph.
10. Rostrup-Nielsen, J.R. in "Catalysis, Science and Techno-
logy, Vol. 5 (Anderson, J.R. and Boudart, M. eds.),
Springer Verlag, Berlin 1983, Chap. 1.
11. Rostrup-Nielsen, J.R. and Højlund Nielsen, P.E., Ref. (2),
Chap. 7.
12. Dry, M. in Ref. (10), Vol. 1, Chap. 4.
13. Yurchak, S., Voltz, S.E. and Warner, J.P. Ind.Eng.Chem.
Process Des. Dev. 18,527 (1979).
14. Ando, J. in "Proc.-"NO Symposium, Univ. Karlsruhe 1985
(Rentz, O., Issle, P. iind Weibel, M. eds.), Karlsruhe
1985, Chap. A.
15. Kildsig, F., and Schoubye, P. in "NO -Bildung und NO
Minderung bei Dampferzeugen flir fossfie Brennstoffe"X
VGB Handbuch, Essen 1986.
16. Wheeler, A. in "Catalysis", Vol. 2 (Emmett, P.H. ed.),
Reinhold, New York 1955, Chap. 2.
17. Froment, G.F. in: Ref. (4), p. 103.
18. Rostrup-Nielsen, J.R. "Steam Reforming Catalysts",
Teknisk Forlag, Copenhagen 1975.
19. Hannerup, P.N, and Jacobsen, A.C., ACS Div. Petro Chem.
Preprints, ~ (3) 576 (1983).
20. Tamm, P.W., Harnsberger, H.F. and Brigde, A.G. Ind.
Chem. Eng. Process. Des. Dev., 20, 262 (1981).
21. Moyse, B. Oil Gas J. 82, Dec. 3~ 164 (1984).
22. Cooper, B.C., Donnis,~.B.1., and Moyse, B., Oil Gas J.,
84, Dec. 8, 39 (1986).
23. SChoubye, P. and Albjerg, A., Sulphur 138, 34 (1978).
24. Ishimoto, R., Miyamae, S. Ref. (14), Chap. N.
25. Kummer, J.T. Prog. Energy Combust. Sci., 6, 177 (1980).
26. Shelef, M., Otto, K., and Otto, N.C., Adv-:- Catal., 'l:J...,
311 (1978).
27. Diwell, A.F. and Harrison, B., Plat.Met.Rev., ~, 142
( 1 981) .
28. Rostrup-Nielsen, J .R., Skov, A., and Christiansen, 1.J.

App l. Ca tal., Q, 71 (1986).
29. Topp-Joergensen, J. in Proc. World Methanol Conference,
Frankfurt, Crocco & Assoc. Ine., p. XVII-l.
30. Moyse, B., Oil Gas J., ~, Sept. 15, 108 (1986).
31. Gould, R.M., Avidan, A.A., Sofo, J.1., Chang, C.D., and
Socha, R.F., Paper presented at ACS Symposium "Methanol
@ProcessEng
as a Raw Material for Fuels and Chemicals", June 1986,

Florida.
TRE FOULING OF CATALYSTS BY DEPOSITION OF FILAMENTOUS CARBON
C. A. BERNARDO
Centro de Quimica Pura e Aplicada (I.N.I.C.), Universidade do Minho

4719 Braga Codex, PORTUGAL
1. INTRODUCTION
Catalysts tend to loose act~v~ty under the specific conditions of their
operation. Consideration of this deactivation affects not only the prepara-
tion of the catalysts but also, in many cases, the design of the very pro-
ces s in which they are used. Deactivation studies are, thus, of great impor-
tance and a number of authoritative monographs and reviews have been publi-
shed (1 - 4). Deactivation may be brought about by many factors. The majors
ones are:
i) Strong adsorption of a poison on an active site, that changes the
nature of the catalytic surface, diminishing the number of sites available
for the reaction. Catalyst poisoning is frequently a selective, irreversi-
ble process. Sulphur compounds, mercury (for metals) and alkali (for stoi-
chiometric acidic catalysts) are common poisons.
ii) Solid state transformations,either sintering or solid state chemi-
cal phenomena. The former means the diminution of the surface area of the
active species or the support by aggregation of crystallites. The latter re-
fers to phase transformations or formation of new chemical compounds.
iii) Formation of solid deposits, either by physical deposition or by
a process involving adsorption, chemical reaction and growth on the surface
of the catalysts. The term fouling is applied to this particular type of
deactivation.
Frequently more than one of these processes concur to deactivate a ca-
talyst. Rowever, it is of theoreticaI as well as prat icaI interest to consi-
der their effect and possibIe remedy separately. An example of this is pre-
sented in Table 1 for the different types of catalysts.
As indicated in the Table, fouling can be originated by dust, metals
and coke. Dust results from the proces s itself (roasting of ore to R2S04,
gasification of coal, etc.) or from the catalyst as a carryover. Metals may
be deposited by conversion of organo-metallic impurities or by decomposi-
tion of inorganic volatile compounds, such as iron and nickel carbonyls. for-
med up-stream in the plant. Coke is originated by competitive side re~ctions

of liquid or gaseous hydrocarbon feedstocks (or carbon bearing gases), lea-
ding to deactivation of active sites or pore blocking.
A review of industrial examples of catalyst fouling is presented in
other part of this monograph, together with a detail ed study of carbon for-
mation in the steam reforming process (5). The present contribution is main-
ly concerned with fundamental aspects of coking (carbon formation) and rege~
@ProcessEng
neration (carbon gasification) of catalysts.

Carbon deposition, the most ubiquitous form of catalyst deactivation,
can occur through different mechanisms, depending on factors such as the na-
tures of the parent hydrocarbon and the catalyst and the reaction conditions.
Carbon can also grow on any hot metallic surface thatpossesses catalytic ac-
369

370
TABLE 1. Catalyst deactivation and re-activation processes (repro-

duced from ref. 4 by courtesy of Martinus Nijhoff Publi-
shers)
Catalyst Deactivation as a result af possibie remedy
Metals sintering high temperatures redistribution may be

poss ibly enhanced by gas possibIe
Addition af stabiliser
poisoning compounds af elements af By oxidation ar reduction
Groups VB & VrB
metal ions af 5 ar more Regeneration difficult
cl electrons Change to a more peison resistant
catalyst
fouling eoke hurn off
adjust size of surfaee ensemble
dus ting/metals deposition may be difficult to remove
Metal oxides sintering high temperatures possibly addition of stabilisers
(stoichiometric) enhanced by gas
poisoning alkali re-acidification
fouling coke burn off
metals (.e.g. Ni) add a metal poison
met<; Ideposits difficult to remove
Metal oxides sin tering high temperatures add stabilisers
(noo-
stoichiometric) poisoning valency stabilising poison may be difficult to regenerate
fouling les s likely oxidation of coke
inorganic foulants may be
difficult to remove
tivity, such as the steel surfaces of reactors and tubes that are common in
chemical industry plants. At high temperatures (above 900 K) carbon can be
formed in the gas phase by thermal cracking of hydrocarbons, a process that
is essentiaIly non-catalytic. Due to the severity of the operational condi-
tions coking of the equipment is unavoidable, although the proces s can be
minimized by additivation to the feed (6). In some cases, metallic surfaces
contribute to high temperature coking by affecting the concentration of the
free radicaIs leading to carbon (7,8). This is evident in Figure 1, which
shows that the nature of the metal liner applied to a silica reactor influ-
ences the rate of carbon deposited on a copper foil (catalytically inert)
placed down-stream. Catalytically active liners enhance the concentration
of gas-phase intermediates which, in turn, bring about an acceleration of
the deposition on the foil (8,9).
30 LINERS
o none
RATE OF CARBON
'c:EZO • Cu
t. Ni
N ~ Fe
DEPOSITION '~
0110
:::a.
@ProcessEng
Z-INLET RESIDENCE Tlt04E (sec)

FIG. 1. Effect of metal liners on the rate of carbon deposition on a copper
foil from n-butane at 1073 K (from ref. 8 by courtesy of Pergamon
Jourr,als Ltd.)
371
2. THE CHARACTERISTICS OF CARBON DEPOSITS

Carbon deposits can present a range of different structures, from near-
ly amorphous to highly crystalline. As stated before, high temperature py-
rolytic deposits can be formed either homogeneously or heterogeneously, lea-
ding to Boot (gas phase) and Burface carbon, respectively. Soot is produced
in spherical particles, believed to contain aromatic macromolecules, which
tend to increase in size, condense and deposit on the reactor walls. A de-
tailed description of a probable mechanism for this process is described in
other chapter of this monograph (7). In general, surface carbons have big-
ger crystallites, lower interlayer spacings and higher densities than soot.
The nature of the surface appears to be thecontrolling factor determining the
crystallinity of this type of carbon. On some metallic surfaces, like nickel,
iron and cobalt, highly crystalline deposits can be formed at relatively
lower temperatures. These catalytic carbons may present three dimensional
order, together with considerable crystallite size.
Typical properties and parameters of various types of carbon are lis-
ted in Table 2, compared with those of the stable allotrope of carbon, gra-
phite.
Catalytic carbons can also be characterised according to their appea-
rance and morphology. Fibrous carbon (also called filamentous or whisker
carbon) is probably the more well known. Carbon whiskers are usually long
and thin (up to 7 ~m long and more than 10 nm wide), have a hollow core and a
metal] icparticle at the tip. The diameter of the particle is close to that
of the fiber. The carbon is constituted by stacked, curved graphite layers,
with the axis of the basal planes paralel to that of the filament. Figure 2
shows filamentous carbon formed on a nickel catalyst. In the next section
the mechanism of whisker carbon formation will be discussed in detail.
On a typical carbon deposit more than one structure is usually present.
In deposits formed at high temperatures, carbons layed-down at earlier sta-
ges tend to be harder, more graphitic and have an higher C/H ratio than la-
ter ones. The latter can contain a range of polycyclic aromatic compounds,
indicative of possibIe surface reactions leading to carbon. In Table 3 a
list of compounds tentatively identified by mass spectrometry in the depo-
sits formed by condensation of the efluent gases of thermal cracking of
n-butane is presented (9). Catalytic carbon deposits may, similarly, contain
carbon whiskers together with less crystalline structures.
TABLE 2. Typical properties of carbon deposits

(fromref.10).
Type of Temp d spacing Lc La C/H Densit~

Carbon (OC) (OA) (OA) (atomic) (g cm- )
Gas phase 1000 3.61-3.70 12.2 42 8 -
Surface 1000 3.46-3.54 28 51 80 2.00

@ProcessEng
Catalytic 600 3.37 200 400 20 -
Graphite - 3.35 co co co 2.26

372
FIG. 2. Electron micrograph of filamentous carbon formed at 750 K on a sup-

ported nickel catalyst from CH 4
3. THE COKING OF CATALYSTS

Carbonaceous materials can deposit on all types of catalyst. The mecha-
nism of coking, however, depends on the nature of the catalyst. Thus, metal
oxides form carbon via acid catalysed polymerisation reactions, whereas in
metallic (or bi-functional) catalysts coke is formed through a mechanism
that will be described ahead.
Aromatic hydrocarb~ are the main source of coking of silica-alumina
catalysts, and a correlation has been established between their basicity
and the coke deposited, as shown in Figure 3.
Olefi~,present in the feed or formed during paraffin cracking, are al-
so major contributors to the coking of oxide catalysts. The route to carbon
my involve a series of sequential Diels-Alder additions, catalysed by Lewis

acid sites (12), schematically represented in Figure 4.
The deposits formed on oxide catalysts contain a significant amount of
aromatics, the C/H ratio depending on the specific conditions fortheir for-
mation. In the case of acid zeolite catalysts, factors like the Si0 2 /Al 2 0 3
ratio and, ab ove all, pore structure can affect the degree of coking. For
example, pore sizes that exclude aromatics lead to minimum amounts of coke
@ProcessEng
during conversion af a mixed benzene: n-hexane feed (13).

Bifunctional catalysts, like platinum-alumina for catalytic reforming
to produce hydrocarbons of higher octane number, can form carbon either in
the acidic or in the metallic sites. In fact, platinum catalyses hydrogena-
tion-dehydrogenation reactions that can lead to coke from benzene and cyclo-
hexane. Concurrently, alumina can catalyse coke formation from paraffins,
possibly via reactions to olefinic intermediates (14).
373
TABLE 3. Compounds formed in the thermal cracking of

n-butane.
Note the increasing C/H ratio (from ref. 9)
mIe Possibie compound No. af mlc Poss ibI€' compound No. nf

rings r lOgS
128 Naphthalene 302 Dibenzopyrene

142 Me thylnapht halene 326 Benzant hant hrene
152 Diphenylene 328 Di benzochrysene
154 Diphenyl 340 Dibenzonapht hant hrene
166 Fluorene 350 Benzocoronene
168 Methyldiphenyl 352 Tribenzpyrene
178 Phenanthrene, Anthracene 354 Dihyd rod ibenzopentacene
180 Methylfluorene 364 Methyl benzcoronene
182 C 2 -Diphenyl 366 Met hy l t ribenzpyrene
192 Met hy lphenant hrene 374 Di benzoperopyrene
194 C2 -Fluorene J 76 Di henzant hrant hrene
202 Pyrene 378 Tr i benzochrysene
204 Dihydropyrene J9C Het hyld i henzant hrant hrene
216 Methylpyrene 400 Dihenzocoronene
218 Me t hylci ihydropyrene 402 Tet rahenzopyrene
Benzof luoranthene 4/5 404 C2 -o ihE'nzant hant hrene

22(-
Cbrysene 426 Tr i henzant hrant hrene

228
p-Terphenyl 428 Octacene
230
440 Het hy l t r ihenzant hrant hrene
240 Naphthanthrene
Benzopyrene 442 Methyloctacene

252
450 Tr i benzoe o ronene 10
254 Met hy lnapht han t hrene
Naphthoperinapht hene 452 Pent ahenzopyrene
266
478 Nonaeene
278 Benzochrysene
528 Hexahenzot r i pheny l ene 10
276 Anthant hrene
578 Undecaeene 11
290 Benzonapht hant hrene
300 Coronene
Of greater interestin the context of this monograph is the formation

of carbon deposits on transition metals that are the construction materials
of the reactors in the chemical industry. This will be dealt with in the
next sec tion.
3.1. Carbon formation on nickel, iron,cobalt and their alloys

The formation of carbon deposits on transition metals is the most im-

portant cause of fouling of equipment in the chemical industry. The unders-
tanding of the mechanism af their formation can help to find means to dimi-
nish (or even to prevent) this effect.
The most striking feature of this phenomenon is that coke can be depa-
sited without deactivating the metal for further carbon growth. This leads
to massive deposits that can cause serious operational problems.
Catalytic coke formation has been studied for many years. However,most
@ProcessEng
of the earlier studies were mainly concerned with morphological aspects of

the deposits (15,16). Labo and co-workers were the first to report experi-
ments in which carbon deposition was measured continuously, by means of a
microbalance technique (17-21). Using a batch reactor operating at low pres-
sure, the weight of carbon formed on nickel and iron foils from the decom-
374
C 4
o
-;;;
c: 2
ou
-O
>-
~
·;~n
CO
~
-6
0
-8 0":0'
00 CH
_OCH~
-10 L-........L_....L._L-........L_....L.----''--------'-----'
O 4 8 12 16 20 24 28 32
C o k e on catalyst (wt.Of.)
FIG. 3. Correlation between the basicity of hydrocarbon and the coking of
cracking catalysts (from ref. 11 by courtesy of the Americam Chemi-
cal Society, Copyright (1962) A.C.S.)
position of olefins and paraffins was recorded as a function of time. Long

periods of steady-state deposition were observed (see Figure 5), allowing
e,H s
@ @--O @-@
t l
eS p- 0-0 ".,
C~-_~~ e~e~
Il) ~ --- ~J ~
oco -
12b)
-n. 000
2a.2b
(-C(e -
e
©re
e
@ProcessEng
- IW)
FIG. 4. Mechanisms for the formation of coke precursors on acidic zeolite

catalysts from butadiene (from ref.12 by courtesy of Elsevier Pu-
blishing Co.)
375
ACETYLENE. 100 to!"!"

'"
E 5Od'c
~ 100
Cl
~
in
~
11.1
Cl
Z
O
GI
~ 50
u
IL
O
100 200 300

TIME ( min)
FIG. 5. Carbon deposition from C2H~:H2 mixtures at 773 K (from ref.21 by

courtesy of Academic Press)
for the determination of activation energies and reaction orders with res-
pect to the hydrocarbon and hydrogen.
The characteristics of the deposition and the kinetic results obtained
are summarised in Figure 6, relative to acetylene decomposition (21).
As explained in the Figure, in the first temperature zone (up to ca
800 K) ,the available data can be explained by a mechanism envolving the fol-
lowing steps (17, 19):
i) adsorption of the hydrocarbon on the metal surface;
ii) production of adsorbed surface species by hydrogenolysis and dehy-
drogenation reactions;
iii) migration of carbon atoms through nickel to.active growth areas,
such as grain boundaries, where precipitation occurs;
iv) separation of nickel crystallites from the foil, transported with
the growing carbon, ensuring a quasi-constant surface for the reaction(and,
hence, the steady-state of deposition).
The kinetic data are consistent with the rate controIling step being
the diffusion of carbon through nickel.
In the intermediate temperature zone (800-810K) the decrease in the ra-

tes was explained by the enhanced desorption of hydrocarbons and hydrogen
caused by the increase in temperature (18). Later, the irreversible deacti-
vation observed in this zone was attributed to a thin layer of graphitic
carbon covering the surface (22). This layer may result from surface nucle-
ation,leading to encapsulation of the active sites by carbon and to decrea-
se in the rate of coking. High partial pressuresof hydrogen could prevent
the deactivation effect, through the gasification of the surface carbon(10,
@ProcessEng
22) •
In the high temperature zone (above 870 K) the deposition rates increa-
se again with temperature. Carbon is now formed in the gas phase by pyrQ~
lysis and subsequently deposited on the surface (18). This is confirmed by
the results shown in Figure 7 that correspond to a thermogravimetric study
of the nickel catalysed decomposition of n-hexane with on-line gas cromato-
376
MECHANISM:
Amorphous ...!L1C-i=P
carbon ~ H2
Graphite
======
1
9
l[
1 2 !~
(C1l~H2+2C
Graphite
~
( ~ICkel 1011 ar particle~ )
ARRHENIUS PLOT:
In k
3
klnetlcs observed
L~--~~~----600L------5~OOL--------4~OLJ---------
1!r--
FIG. 6.Mechanism proposed by Lobo and co-workers, including the folIowing
steps: 1) and 2) adsorption and desorption of acetylene; 3) and 4)
surface decomposition and reformation; 5) carbon diffusion in Ni;6)
and 7) H2 desorption and adsorption; 8) pyrolysis; 9) carbon lay-
-down on the surface. ;'The nature of adsorbed species is not stated
(from ref. 21 by courtesy of Academic Press)
graphic analysis of the outlet gases (8). The gas-phase conversion ~ncrea
ses significantly above 900 K and is independent of the presence of the ca-
talyst. Figure 7 can be compared with Figure 6 and it should be noticed
that for n-hexane, as for acetylene, a significant amount of carbon is for-
med below 900 K on the metal foil. This corresponds to the catalytic decom-
position. The carbon formed above 900 K should be originated via gas phase
intermediates, as the conversion to olefinic hydrocarbons is important in

this temperature zone.
The me.chanism for catalytic carbon growth was proposed independently by
Baker and co-workers, that used Controlled Atmosphere Electron Microscopy
(CAEM) to study the decomposition of acetylene on nickel (23) and iron, co-
balt and chromium (24). The technique involves an electron microscope with
areaction chamber with means to display on a television monitor and record
@ProcessEng
on video tape images of carbon filaments gro1>Jing (25). In this way linear
growth rates of individual carbon filaments can be measured by frame-by-fra-
me analysis of the video film. In the decomposition of acetylene on nickel,
carbon filaments (similar to those shown in Figure 2) were observed to grow
with nickel particles at the tip, ab ove 850 K. These filaments possessed a
graphitic skin and a less organized core and their growth rate was indepen-
dent of the partial pres sure of the hydrocarbon (23). The activation ener-
377
z --; 100
O ~
cD
~ o'"
15Cl: E tJ. Run 19
o ..... D RlI1 20 no H2
~ Ul
..J O RJn 21 no catalyst. no H2
.....
~
Ul
I O
.....
Ul
IJ..
I Products refer to Run 19 only
O >-
Z Z
Q
..... Ul
~ Cl:
~
8 'i ><
loOO 500 fro 700
TEMPERATURE (oe)
FIG. 7. Composition of the outlet gases vs. temperature. Catalyst: Ni foil;
Feed: 3.9 cm 3 (STP)s-1, Xc H14=O.09, xH2=0.50 (from ref.8 by courte-
sy of Pergamon Journals Ltg.)
gies determined lead to avalue of 145 kj mol- 1 , in agreement with the ac-
tivation energy determined for the cobalt catalysed decomposition, but di f-
fering from that for iron (24).
A significant contribution to the understanding of the mechanism of
"wisker carbon" growth was given by Rostrup-Nielsen (26). He was able to ex-
plain the deviation between the equilibrium constant obtained with the sys-
tem:
Cfilaments+2H2= CH4 (1)
and that based on graphite data. In the former case greater partial pressu-
res of methane can be present without carbon formation. This was explained
by contributionsof the surface energy of the filament and the disordered
structure of the carbon.
As the filament has the same diameter as the particle at its tip, the
foliowing correlation can be obtained for the deviation, 6G c :
b Gc = bGofilament - bGOgraphite = ~ +]J 1, (2)
where ]J" represents the contribution from structural defects and dNi is the
diameter of the larger particles in the particle size distribution for each
system.
In alater publication, the concentration gradient responsibie for the
diffusion of carbon was explained by the difference of solubilities of car-
bon at the nickel-graphite and at the nickel-gas interfaces (27). This was
based on information found in the literature that the activity of carbon in
a metal depends on the composition of the gas phase adjacent to the metal
surface. Further improvements of the mechanism will be discussed ahead.
Evidence that diffusion of carbon through nickel plays a role in cata-
ly tic carbon formation was presented by Bernardo et al. (28, 29). A very
thin single crystal nickel foil pre-coated in ane face with amorphous carbon
@ProcessEng
was put in contact with acetylene at ca 750 K. The sequence of experiments

involved is presented in Figure 8. Micrographs of the nickel single crystal
faces before and af ter acetylene decomposition (run 3) are shown in Figure
9.
Although some carbon islands are observed on the uncoated face, most
378
BEFORE REACnON GRONTH [LRING REACTlON
~ }
Clean cryslal
RUN 1 0'1 boIh sides
foil
80th surfaces
~ }
RUN 2 cO/ered No deposi lion
by carbon
One surface
RUN 3
A~ 8 pre-coaled
by carbon
} IOn pre-coaled surface I
One surface
pre-coaled
RUN 4
A ~ 8
+ ameallng
for 5 min.
al 900°C I On bolh sides
FIG. 8. Catalytic growth of carbon on nickel crystal foils with different

pre-treatments (from ref. Z8 by courtesy of Pergamon Journals Ltd.)
of the deposition occurred on the pre-coated face. This clearly means that
the carbon formed on the clean face (the only one catalytically active)must
have diffused through the nickel to grow on the opposite face.
The different types of carbon present in the deposits formed on suppor-
ted nickel catalysts were characterised by Mc Carty, Wise and co-workers by
means of a temperature-programmed surface reaction technique (30, 31). They
found that the carbon deposited by the decomposition of hydrocarbons or car-
bon monoxide exhibits several states (types), identified by the temperatu-
res corresponding to the maxima in methane (or co, etc) production. These
temperatures, Tp ' that give an indication of the reactivity of each type
of carbon (lower Tp ' higher reactivity and vice-versa), are listed in Table
4 for the decompos~tion of CZH4.
Coupling this information with electron microscopy observations, the
å and å'states were identified as filamentous carbon and the encapsulating
carbon referred to before.
With all these different contributions it is now possibie to have a
coherent idea of the mechanism of filamentous carbon growth, its characte-
ristics and reactivity. Comprehensive reviews that describe in greater de-
tail the mechanism of catalytic carbon formation can be found in the lite-
rature (3Z,33). Still, some conflicting aspects remain.
Manning et al. studied by thermogravimetry the rate and equilibrium of
carbon formation from CH4 ,CO,COZ,H;P and HZ mixtures on Ni/Al Z0 3 and Co metal
catalysts (34). They state that the deviation af the equilibrium constant
from graphite equilibrium was due to a carbide intermediate that continuous-
ly decomposed into carbon and metal. In a recent series of publications,
Geus and co-workers reported extensive studies of filamenroæcarbon growth
on silica supported nickel and iron catalysts (35-37). By means of thermo-
magnetic and gas-phase analyses, temperature-programmed hydrogenation and
@ProcessEng
electron microscope techniques, they reached the foliowing conclusions:

i) Before the formation of carbon filaments the metal is substantially
transformed into a non-magnetic phase (indicating the formation of a bulk
carbide); the decrease of the saturation magnetization is only partially re-
covered when the growth starts;
ii) The equilibria determined for the different systems correspond to
379
FIG. 9. Optical micrographs of the nickel crystal foil before and af ter run
3: a) and b) uncoated and coated faces before the reaction; b) and
c) same faces af ter reaction.
the calculated equilibria for relevant metal-carbides;

iii) The contributions from the surface energy and from the structural
deffects were not enough to explain the observed deviation from graphite e-
quilibrium, thus contradicting the explanation of Rostrup-Nielsen (26).
These authors concluded that carbon formation on nickel and iron takes
place through an unstable, intermediate bulk carbide that determines the e-
quilibria and continuously decomposes into carbon and metal during filament
growth.
@ProcessEng
In a very recent work on the thermodynamics and mechanism of carbon fi-

lament formation on Fe, Ni and Ni-Gu catalysts, Alstrup was able to refute
most of the above arguments (38,39). Re pointed out that the carbide-equili-
brium hypothesis is not able to explain the correlation shown in eqn. (2)
380
TABLE 4. States of carbon identified on carbon deposited on a Ni/Al Z0 3

catalyst from CZH4' Heating rate: 0.9 Ks-l.Gas: HZ (from
ref. 31 by courtesy of the American Chemical Society)
State Identification Tp (K) CZH4 exposure

temperature (K)
Cl, , Chemisorbed carbon 410± 15 573 - 1073
Cl, Chemisorbed carbon 48O:!: Z5 573 - 1073
Y Nickel carbide 550 573
B Polymer carbon 660± 30 573 - 773

o' Filamentous carbon 875:!: ZO 773 - 873
o Encapsulating carbon 960:: 15 873 - lZ73
E Platelet (?) carbon llZ0:: ZO 873 - lZ73
and also the reversibility of the filament growth process (Z6,40). An ele-
gant calculation showed that the lass of magnetization measured during fi-
lament growth corresponds to the quenching of the moments of the outer sur-
face atoms of nickel particles with 5nm diameter (38). Thus, in the case of
nickel, no bulk carbide is present during steady-state deposition (but on-
ly a "surfaee carbide"). He also demonstrated that there is no coincidence
between tha data for Ni3C equilibrium and the equilibrium results of Geus
and co-workers and other authors(Z6,35,40). Finally, by considering the con-
tribution of the elastic energy stored on the curved basal graphite planes
forming the filaments, he was able to explain the difference between their
free energies of formation and that of graphite.
As aresult of these ideas, Alstrup proposed a modification of the tra-
ditional mechanism for filament growth, that involves the foliowing steps:
1. Surfaee reaction producing carbon atoms on the metal surface;
Z. Migration of carbon atoms into the bulk of the particle, leading to
supersaturation of the metal and the formation of an unstable carbide;
3. Decomposition of the carbide into metal and carbon, that seggrega-
tes out forming the first part of the filament (induetion period);
4. Growth of the filament by seggregation of carbon, af ter diffusion
from the residual "surfaee carbide" (steady-state growth).
This mechanism in now able to explain most of the available experimen-
tal evidence.
In the case of iron, Yang et al. proposed a model based on a surfaee
carbide to explain the low activity for catalytic carbon formation (41).The-
re is experimental evidence, however, that under certain conditions fila-

mentous carbon ean grow on carbon with the same general character is tics as
in the case of nickel (14). In a review of the deposition of carbon on tran-
sition metals it is suggested that, below 873 K, the process is controlled
by the diffusion of carbon through the metal (14). At higher temperatures
the surfaee decomposition of the gas could be rate determining.
In any case, the possibility of the existence of stable carbides at the
@ProcessEng
temperature of the deposition, indicates that they ean playan important ro-
le in the process.ln faet, the kinetics of carburisation or decarburisation
may be rate determining under a given set of reaction conditions.
The growth of filaments on cobalt is not very fast, one explanation
being that it is inhibited by the simultaneous formation of amorphous car-
bon (4Z). The reaction is strongly affected by the operating conditions
381
(namely the hydrocarbon pressure and the temperature) and no filaments are
produced below 1200 K. At lower temperatures (below 750 K ) there is eviden-
ce that bulk diffusion of carbon in the metal may be involved in the growth
of filaments and possibly be rate controIling (43).
As stated before, the deposition of carbon on iron and nickel alloys
is of great importance, as they are the engineering materials for most of
the equipment utilized in the chemical industry. This is the case of HK40,
the usual alloy for high temperature operation (24.5% Cr, 21.6% Ni, 1.8% Si,
1.1% Mn and 51% Fe). In processes such as steam cracking, coke can be depo-
sited either by gas-phase or by surface reactions. Carbon accumulates on the
surface leading to tube blocking or to inefficiency in the operation of heat
transfer equipment. Carbon can also dissolve in the metal, diffuse and form
metallic carbides. This leads to a decrease in the strength of the alloy
structure (44). A micrograph of a carburised alloy is shown in Figure 10.
Although alloys can be decoked by gasification, the reaction leads to
considerable disruption of the surface. A more efficient solution to the
problem of coking is prevention. At high temperature, coking of the reactor
walls can be diminished to some extent by additivation to the feed or by
coating the surface with elements, such as aluminium and silicon, that re-
duce carburisation. Coking of catalysts can also be diminished in various
ways, that will be described in the next section.
3.2. ControIling the deposition of carbon

The coking of catalysts can be decreased by controIling the operation
conditions. For instance, the use of excess steam in the steam reforming
reaction leads to minimal carbon formation. However, this lowers the yield
of the desired products and makes it necessary to use bigger reformers and
more energy to heat and condense the fluids. Hence, a minimum steam to car-
bon ratio is normaIly used. Centrol of the diameter of the nickel crystalli-
te particle can be an efficient way to reduce the deposition of carbon fi-
laments, by increasing their free energy of formation (see eqn. (2)\ The
formulation of the catalyst is another means to reduce coking, for instance,
by addition of alkali or magnesia to enhance steam adsorption (26).
Another technique to minimize carbon formation in tte reforming process
@ProcessEng
FIG. 10. Micrograph of a carburised alloy. Magn. 500x (from ref. 44 by cour-
tesy of Martinus Nijhoff Publishers)
382
is the so called "ensemble control" by sulphur passivation (45,46). As "en-

semble control" is described by Rostrup-Nielsen elsewhere in this monograph
(5), only minimal reference will be made to it here. In essence, the techni-
que assumes that above a given sulphur coverage, the sites for carbon forma-
tion are blocked at a greater extent than those necessary for reforming.
This implies that a larger ensemble of surface atoms is needed for the for-
mer reaction.
The same "ensemble control" effect can be achieved by alloying nickel
with copper (40). However, although coking is much reduced it is not comple-
te ly prevented, as shown in Figure 11.
The morphology of the carbon deposited can also be strikingly altered
by sulphur passivation or alloying (40,45), and a new structure, dubbed "oc-
topus carbon", can be observed. An exemple of this structure is presented
in Figure 12.
As observed in Figure 12, in the "octopus carbon" structure various fi-
laments are attached to the same metallic particle. This has a much bigger
diameter than the filaments and presents many facets, lacking the "pear"
shape which is typical of "whisker carbon".
The carbon observed in the Figure is also more amorphous and less den-
1.0,"
~. Ni-Cu/SIO.
~,
\\
>
6
~
\
\0,
\
\~;:~-------o
!::
()
~
c
()
~
---
z
~
0.1\ .',
\ -----II
~
\
z
Q
~
0.01 ° Tolal
~ hydrogen
•
~ • Slrongly adsorbed hydrogen
w
II: 6 Reforming. T=823 K
w g Deposilion
le
wilh sleam. Tz 823 K
~
....
w • Deposllion
II:
without ateam , T- 773 K
o 0.1 0.2 0.3 0.4 0.5

@ProcessEng
COPPER ATOMIC FRACTION
FIG. 11. Reforming and deposition rates on Ni-eu relative to those for the
100% Ni/Si0 2 catalyst as function of the copper content of the
alloys. Also shown are the relative amounts of hydrogen chemisor-
bed on the catalysts (from ref. 40 by courtesy of Academic Press)
383
FIG. 12. Electron micrograph of "octopus carbon" formed at 800 K on a suppor-

ted Ni-Cu catalyst (25 at.%Cu) from CH4 (from ref.48 by courtesy of
Academic Press)
se. This probably explains why a significant amount of carbon was observed
in CAEM experiments to deposit on a 50% Ni-Cu catalyst, contrarily to the
results of Figure 12 (47).
The reactivity of the carbon formed on Ni-Cu/Si0 2 catalysts was studied
by temperature-programmed hydrogenation (48). The results obtained for a ran-
ge of copper concentrations are presented in Figure 13.
By means of electron microscopy observations it was possibIe to ascribe
the first peak in each run to "whisker carbon" and the second, corres-
300r---------~----------------------------------------------~
at%Cu
... o o
III
.,"- 200 A 0.1
S2
)(
II)
• 1
~ , 10
!i:
Cl
iii
...
~
100 · 25
O
• 50
W
ti o 80
@ProcessEng
II:
900 1000 1100 1200 1300

TIK
FIG. 13. Temperature-programmed hydrogenation of carbon deposited on Ni-Cu
catalysts. Heatingrate: 0.1Ks-1, PH2 = 50 KPa, N2 as balance (from
ref.48 by courtesy of Academic Press)
384
ponding to higher temperatures, to "octopus carbon". This order of reactivi-

ty was explained by the smaller role that the metal should play in the ga-
sification of the latter structure (48). It ean be observed in the Figure
that, from run to run, the temperatures corresponding to the maxima in the
hydrogenation spectra, Tp, increase with the eopper concentration. It was
possibIe to demonstrate by a simple calculation that this is due to the con-
comitant decrease of the surface concentration of dissociated hydrogen, BH:
T~ =[b(E a + 6HH)]/AR exp (Ea/RT). eR (3)
In eqn. (3), b is a constant, A is a pre-exponential factor, Ea is the acti-
vation energy for surface hydrogenation of the different adsorbed carbon
species and 6H H is the heat of adsorption. As BH decreases with the copper
concentration (see Figure 11), it can be concluded from the equation that
the peak temperature will vary in the opposite way(49).
4. REGENERATION OF FOULED CATALYSTS

Regeneration of fouled catalysts ean be achieved in a number of ways.
We will concern ourselves only with the reactivation of coked catalysts and
in particular, of those based on transition metals.
Heavily coked catalysts mayeither be replaced or regenerated, depen-
ding on the economics of the process. Regeneration can be achieved by gasi-
fication with air, steam, carbon dioxide or hydrogen, according to the fol-
lowing simplified reaction schemes:
C + 02 = CO 2 (4)
C + H20 CO + H2 (5)
C + CO 2 2CO (6)
C + 2H2 CH4 (7)
02 is the more effective gasifying agent but the reaction is highly exother-
mic and it may lead to sintering of the catalyst. In practice, it is neces-
sary to control the gasification conditions, for which mixtures of air and
steam are used, nitrogen acting as diluent. The characteristics of the gasi-
fication depend on the catalyst and the nature of the carbon deposit. In ge-
neral, older deposits are harder to gasify. This is due to the increase in
the C/H ratio caused by surface dehydrogenation reactions af ter the initial
lay-down (see section 2.). The gasification specifity justifies that littIe
general information exists on the regeneration of coked catalysts (44), al-
though it can be eas ily found about particular systems (see, for instance,
reference 50).
Gasification of filamentous carbon deposited on iron and nickel has
been studied for many years. In 1972 Baker et al. were able to follow by
CAEM the oxygen gasification of "whisker carbon" filaments grown on nickel
(23). Most of the studies done since then coupled thermogravimetry and e-
lectron microscopy techniques and have recent ly been reviewed (51). The most
interesting feature of the gasification of filaments is the occurrence of
long periods of near constant rate, as was the case for deposition.
Typical gasification curves on nickel are presented in Figure 14. Iden-
tical curves were obtained for iron.
The long periods of constant rate allowed the determination of kinetic
parameters. These, together with the observed characteristics of the reac-
@ProcessEng
tion, lead to the proposal of a mechanism for the gasification of carbon

filaments catalysed by nickel, that is the reverse of that for deposition
described in section 3.1 (52). It involves the folIowing steps:
1. Dissociative adsorption of the gas on the metal;
2. Supply of carbon atoms to the surface, by diffusion through the
385
30
ca
E
20
10
o 50 100 150 min

FIG. 14. Gasification of carbon on nickel foils by C02'PcO =51.5 kPa (from
ref. 51 by courtesy of Martinus Nijhoff Publisheri)
bulk of the metal particle;

3. Surfaee reaction between the adsorbed gas and carbon atoms.
This mechanismimplies that carbon diffusion in nickel plays a role in
the gasification catalysed by nickel, a vue that has been endorsed by other
authors (53,54). Renee, if a common step is occurring in opposite directions
in the deposition and gasification of carbon filaments, then it should be
possibIe to reverse these processes. This hypothesis was tested in a series
of CAEM experiments in which carbon filaments were, sequentially, grown by
acetylene decomposition, hydrogenated, and grown again (55). The results ob-
tained are schematically represented in Figure 15. During hydrogenation the
metal particle moved down within the skin of some of the filaments, while
the inner core was gasified. When hydrogen was replaced by acetylene, the
particles that had catalysed gasification reversed direction and proceeded
to infill the core of the original filament. These observations give strong
support to the vue that bulk diffusion of carbon is, in faet, involved in
the gasification of carbon filaments on nickel.
Tha data obtained for the gasification of carbon filaments formed on
iron are more difficult to interpret. This is due to the existence of vari-
I
@ProcessEng
I
I H2 out Deposition
Gasification
I (2 H2 in ( 2nd (yde)
FIG. 15. Gasification and growth of carbon filaments (from ref. 55).
386
ous solid phases, such as oxides and carbides, that depend on the nature of
the gaseous environment. In the presence of C02' gasification is hindered
by the formation of FeO (51), which, in turn, is an active precursor for
carbon formation (56). These findings may indicate that equipment made with
iron-rich alloys can be progressively more difficult to decoke af ter the
first gasification.
5. CONCLUSIONS
Coking, as other forms of deactivation, severely restricts the utili-
zation of catalysts, affecting not only their formulation but also, in many
cases, the design of the process in which they are used.
Carbon deposition leads to serious operation problems, lowering the
yield of the desired reactions and also the performance of the equipment
(mechanical strenght, heat transfer characteristics, pressure drop, etc.).
There are three usual ways of dealing with this problem: i) modification of
the catalyst or the surface, ii) control of the operation conditions and
iii) regeneration. In some cases, like the sulphur passivated reforming,
the first procedure mayensure operation without excessive coking. In other
cases, the control of the operation conditions (like the carbon to steam ra-
tio in steam reforming) may lead to the same result. Usually a combination
of the two procedures is necessary and, even so, af ter some time, the cata-
lyst has to be replaced or regenerated. Due to the characteristics of coking,
general solutions tend to be scarce and most of the available data concerns
a particular type of reaction and catalyst. In some cases, however, like
the formation of filamentous carbon, a base of knowledge has been establi-
shed which leads to a more general understanding of the process.
6. REFERENCES
1. "Catalyst Deactivation" (Delmon, B. and Froment, G.F., eds.), Elsevier
Publ., Amsterdam (1980).
2. "Progress in Catalyst Deactivation" (Figueiredo, J.L., ed.), Martinus
Nijhoff Publ., The Hague (1982).
3. "Deactivation and Poisoning of Catalysts" (Oudar, J. and Wise, H.. ,eds.),
Marcel Dekker, New York (1985).
4. Trimm, D. L., "Introduction to Catalyst Deactivation" in Progess in Ca-
talyst Deactivation (Figueiredo,J.L., ed.), p.3-22, Martinus Nijhoff
Publish., The Hague (1982).
5. Rostrup-Nielsen, J.R., "Fouling of Catalysts.lndustrial Examples" and
"Carbon Limits in Steam Reforming", this monograph.
6. Froment, G.F., "Fouling of Heat Transfer Surfacesby Coke Formation" in
Fouling of Heat Transfer Equipment (E.F.C. Somerscales and J.G. Knutsen,
eds.), p.411-435, Hemisphere Publishing Corp., New York (1981).
7. LaCava, A.I., "Droplets and Filaments: on the Fouling of Metal Surfaces
by Carboneous Materials from Hydrocarbon Gases above 850 K", this mono-
graph.
8. LaCava, A.I., Bernardo, C.A. and Trimm, D.L., "Studies of Deactivation
of Metals by Carbon. Deposition", Carbon 20, 3, 219-223 (1982).
9. LaCava, A.I., "Pyrolysis and Thermal Hydrogasification of Hydrocarbons",
Ph.D. Thesis, University of London. (1976).
10.Figueiredo, J.L., "Carbon Formation on Steam Reforming Catalysts", Ph.D.
@ProcessEng
Thesis, University of London (1975).

l1.Appleby, W.G., Gibson, J.W. and Good, G.M., "Coke Formation in Catalytic
Cracking", Ind. and Eng. Chem.-Process Design and Development, 1,2,
102-110 (1962).
387
12. Langner, B.E. and Meyer, S., "The Mechanism of Coke Formation in the
Reaction of Butadiene on Calcined NaHN4-Y" in Catalyst Deactivation(Del_
mon, B. and Froment, G.F., eds.,), p. 91-102, Elsevier Scientific Publi-
shing Co., Amsterdam (1980).
13. Rolman, L.D. and Dennis, F.W., "Constraints on Carbon Formation on Zeo-
lite Catalysts", in Progress in Catalyst Deactivation (Figueiredo, J.L.,
ed.), p. 81-91, Martinus Nijhoff Publish., The Hague (1982).
14. Trimm, D.L., "Carbon Formation on Metals other than Nickel and on Alloys"
in Progress in Catalyst Deactivation(Figueiredo, J.L., ed.), p.65-79,
Martinus Nijhoff Publish., The Hague (1982).
15. Presland, A.E.B. and Walker Jr., P.L., "Growth of Single-Crystal Graphi-
te by Pyrolysis of Acetylene over Metal s", Carbon 7, 1-8 (1969).
16. Tesner, P.A., Robinovich, E.Y., Refalkes, I.S. and Arefieva, E.F., "For_
mation of Carbon Fibres From Acetylene" , Carbon 8, 435-442 (1970).
17. Lobo, L.S., "Carbon Formation From Hydrocarbons on Metals", Ph.D. The-
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18. Lobo, L.S. and Trimm, D.L., "Complex Temperature Dependencies of the Ra-
te of Carbon Deposition on Nickel", Nature 234, 44, 15-16 (1971).
19. Lobo, L.S., Trimm, D.L. and Figueiredo, J.L., "Kinetics and Mechanism
of Carbon Formation from Hydrocarbons on Metals" Proceed. 5th Int.Cong.
Catal, Miami, 2, p. 1125-1137, North-Holland/American Elsevier, London/
/New'i'ork (1973).
20. Lobo, L.S. and Trimm, D.L., "Carbon Formation from Light Hydrocarbons
on Nickel", J. Catal 29, 1, 15-19 (1973).
21. Bernardo, C.A. and Lobo, L.S., "Kinetics of Carbon Formation from Ace-
tyl ene on Nickel", J. Catal. 37, 267-278 (1975).
22. Figueiredo, J.L. and Trimm, D.L., "Low Temperature Carbon Deposition on
Nickel" Proceed. 4th Int. Carbon and Graphite Ceni., London, p.314-317,
Society of Chemical Industry, London (1974).
23. Baker, R.T.K., Barber, M.A., Feates, F.S., Harris, P.S. and Waite, R.J.,
"Nucleation and Growth of Carbon Deposits from the Nickel Catalyzed De-
composition of Acetylene", J. Catal. 26, 51-62 (1972).
24. Baker, R.T.K., Harris, P.S., Thomas, R.B. and Waite, R.J., "Formation
of Filamentous Carbon from Iron, Cobalt and Chromium Catalyzed Decom-
position of Acetylene", J. Catal. 30, 86-95 (1973).
25. Baker, R.T.K., "In-Situ Electron Microscopy Studies of Catalyst Parti-
de Behaviour", Catal. Rev. - ScL Eng. 19,2, 161-209 (1979).
26. Rostrup-Nielsen, J.R., "Equilibria of Decomposition Reactions of Carbon
Monoxide and Methane over Nickel Catalysts", J. Catal. 27, 343-356(1972).
27. Rostrup-Nielsen, J.R. and Trimm, D.L., "Mechanism of Carbon Formation
on Nickel-Containing Catalysts", J. Catal. 48, 155-165 (1977).
28. Bernardo, C.A. and Lobo, L.S., "Evidence that Carbon Formation from Ace-
tyl ene on Nickel involves Bulk Diffusion", Carbon 14, 287-288 (1976).
29. Bernardo, C.A., "Carbon Formation and Removal in the Context of Nickel
Catalysts", Ph.D. Thesis, University of London (1977).
30. McCarty, J.G. and Wise, H., "Hydrogenation of Surface Carbon on Alumina
Supported Nickel ", J. Catal. 57, 406-416 (1979).
31. McCarty, J.G., Hou, P.Y., Sheridan, D., andWise, H., "Reactivity of
Surface Carbon on Nickel Catalysts. Temperature-Programmed Surface Re-
@ProcessEng
action with Hydrogen and Water", Am. Chem. Soc.-Symp. Series 202, 253-
-282 (1982).
32. Baker, R.T.K. and Harris, P.S., "The Formation of Filamentous Carbon",
in Chemistry andPhysics of Carbon (Walker Jr., P.L. and Thrower, P.A.,
eds.), 14, p.83-165, Marcel Dekker, New-York (1978).
388
33. Figueiredo, J.L., "Carbon Formation and Gasification on Nickel" in Pro-

gress in Catalyst Deactivation (Figueiredo, J.L., ed.), p.45-63, Marti-
nus Nijhoff Publish., The Hague (1982).
34. Manning, M.P., Gamirian, J.E. and Reid, R.C., "Carbon Deposition Studies
Using Ni and Co Catalysts", Ind. Eng. Chem.-Process Des.Dev. 21, 404-409
(1982).
35. deBokx, P.K., Kock, A.J.H.M., BoelIaard, E., Klop, W. and Geus, J.W.,
"The Formation of FilamentOJs Carbon on Iron and Nickel Catalysts. I. Ther-
modynamics", J. Catal. 96, 454-467 (1985).
36. Kock, A.J.H.M., deBokx, P.K., BoelIaard, E., Klop, W. and Geus, J.W.,
"The Formation of Filamentous Carbon on Iron and Nickel Catalysts. II.
Mechanism", J. Ca tal. 96, 468-480 (1985).
37. BoelIaard, E., deBokx, P.K., Kock, A.J.H.M. and Geus, J.W., "The Forma-
tion of FilamentousCarbon on Iron and Nickel Catalysts. III. Morphology",
J. Catal. 96, 481-490 (1985).
38. Alstrup, I., "On the Thermodynamics and Mechanism of Carbon Filament
Growth on Nickel, Iron and Ni-Cu Alloy Catalysts" ~n publication in J.
Catalysis.
39. Alstrup, I., "Models for Carbon Filament Growth on Nickel, Iron and Ni-
-Cu Alloy Catalysts", Abstracts of the 18th Biennial Conf. on Carbon,
Worcester (1987).
40. Bernardo, C.A., Alstrup, 1., and Rostrup-Nielsen, J .R., "Carbon Deposi-
tion and Methane Steam Reforming on Silica-Supported Ni-Cu Catalysts",
J. Catal. 96, 2, 517-534 (1985).
41. Yang, K.L. and Yang, R.T., "The Acceleration and Retarding Effects of
Hydrogen on Carbon Deposition on Metal Surfaces", Carbon 24, 6, 687-693,
(1986).
42. Baker, R.T.K., Gadsby, G.R., Thomas, R.B. and Waite, R.J., "The Produc-
tion and Properties of FilamentcusCarbon", Carbon 13, 211-214 (1975).
43. Bernardo, C.A. and Lobo, L.S., "Kinetics of Carbon Formation from Ace-
tylene and 1-Butene on Cobalt" in Catalyst Deactivation (Delmon, B. and
Froment, G.F., eds.), p. 409-420, Elsevier Scientific Publishing Co.,
Amsterdam (1980).
44. Trimm, D.L., "Coke Formation and Gasification on Refineries" in Carbon
and Coal Gasification (Figueiredo, J.L. and Moulijn, J.A., eds.), p.
523-541, Martinus Nijhoff Publish., Dordrecht (1986).
45. Rostrup-Nielsen, J .R., "Sulphur-Passivation Nickel Catalysts for Carbon-
Free Steam Reforming of Methane", J. Catal. 85, 31-43 (1984).
46. Andersen, N.T., Topsøe, F., Alstrup, I. and Rostrup-Nielsen, J.R., "Sta-
tisticaI Models for Ensemble Control by Alloying and Poisoning of Cata-
lysts. I. Mathematical Assumptions and Derivations", in publication in
J. Catalysis.
47. Baker, R.T.K., private communication.

48. Tavares, M.T., Bernardo, C.A., Alstrup, I. and Rostrup-Nielsen, J.R.,
"Reactivity of Carbon Deposited on Ni-Cu Alloy Catalysts from the
Decomposition of Methane", J. Catal. 100, 545-548 (1986).
49. Alstrup, I., Rostrup-Nielsen, J.R. and Bernardo, C.A., "Formation of
Octopus Carbon on Sulphur and Copper Modified Nickel Catalysts", Abs-
tracts of the 18th Biennial Conf. on Carbon, Worcester (1987).
@ProcessEng
50. Franck, J.P. and Martino, G., "Deactivation and Regeneration of Cataly-
tic-Reforming Catalysts" in Progress in Catalyst Deactivation (Figueire-
do, J.L., ed.), p. 355-397, Martinus Nijhoff Publish., The Hague (1982).
51. Figueiredo, J.L., Bernardo, C.A. and Orfao, J.J.M., "Gasification of
Carbon Deposited on Metallic Catalysts", in Carbon and Coal Gasification
(Figueiredo, J. L. and Moul ijn, J.A., eds.), p. 269-287, Martinus Nijhoff
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Publish., Dordrecht (1986).

52. Figueiredo, J.L. and Trirnrn. D.L., "Casification of Carbon Deposited on
Nickel Catalysts", J. Catal. 40, 154-159 (1975).
53. Nishiyama, Y., and Tamai, Y., "Deposition of Carbon and its Hydrogena-
tion Catalyzed by Nickel", Carbon 14,13-17 (1976).
54. Audier, M., Coulon, M. and Bonnetain, L., "Hydrogenation of Catalytic
Carbons Obtained by CO Disproportionation or CH4 Decomposition on Nickel"
Carbon 17, 391-394 (1979).
55. Bernardo, C.A., Figueiredo, J.L., Chludzinski, J.J. and Baker, R.T.K.,
"Crowth and Casification of Carbon Filaments From Nickel", Abstracts of
the 18th Biennial Conf. on Carbon, Worcester (1987).
56. Baker, R.T.K., Alonzo, J.R., Dumesic, J.A. and Yates, D.J.C., "Effect
of the Surfaee State of Iron on Filamentous Carbon Formation", J. Catal.
77, 74-84 (1982).
@ProcessEng
DROPLETS AND FILAMENTS: ON THE FOULING OF METAL SURFACES BY CARBONACEOUS
MATERlAL FROM HYDROCARBON GASES ABOVE 850 K
ALBERTO I. LACAVA
Department of Chemical Engineering, The City University of New York, NY

10031 and The BOC Group Inc., Group Technical Center, 100 Mountain Ave.,
Murray Hill, NJ 07974, U.S.A.
l. INTRODUCTION
Carbon fouling of surfaces is known to increase pres sure drops, reduce
heat transfer coefficients and weaken the mechanical strength of process
equipment. Carbon-containing vapors or gases tend to form or deposit
carbon on equipment walls through a variety of chemical and physical steps.
Some of the mechanisms of carbonaceous deposit formation and growth
challenge the imagination of the investigator with their complexity. Some
aspects of catalytic filament growth, which were elaborated upon in a
previous lecture of this Institute Cl) are so surprising to the scientist,
so difficult to explain and the different explanations to prove, that the
current discussion of the different theories that have been proposed may
continue for years to come.
Carbonaceous materials can deposit or grow on surfaces through several

different mechanisms. This paper will show cases where carbonaceous
deposits were formed at high temperatures Cabove 850 K), through a catalytic
filament growing mechanism on a catalytic metal substrate. This is a
temperature where catalytic carbon is not usually formed (see for example
ref. 2, table I). Evidence is presented here to show that there are
operating conditions and reactants which allow for catalytic carbon
formation at these high temperatures.
Even better known is the fact that carbonaceous deposits can form due
to homogeneous chemical reactions at temperatures above 800 K. Under some
conditions of temperature and hydrocarbon concentrations, a homogeneous
chemical reaction mechanism forms liquid droplets in the gas phase. These
deposit on the surrounding surfaces, and are further carbonized to form coke
(3). Although this is not the only mechanism through which a non-catalytic
type of carbon can be formed, it is a very interesting (and unexpected)
phenomenon that can produce coke fouling in a wide variety of reaction
vessels and environments.
@ProcessEng
391

392
In this paper, experimental information on droplet formation and

deposition is presented giving n-butane/hydrogen and benzene/hydrogen as
examples. The effects of the process variables (temperature, hydrogen
concentration, reactant concentration and residence time) are reviewed using
results from laboratory experiments.
The surface to volume ratio of the reaction environment (vessel) is

found to modi fy the supply and demand balance for carbon-forming
intermediates. As a result, carbon formation rates may change considerably
when scaling up or down to a reacting system with a different surface to
volume ratio. Experiments showing this effect and a model explaining it are
also presented and discussed below.
2. EXPERIMENTAL
The results described in this paper were obtained using a tubular flow
microbalance reactor, described in reference (4). Further details on
experimental techniques, materials and reactants have been given in
references (5) and (6).
3. CASES OF HIGH TEMPERATURE CATALYTIC CARBON FORMATION

The growth of catalytic carbon at temperatures higher than 850 K was
studied in a flow reactor where benzene, diluted with hydrogen, was passed,
forming carbonaceous filament deposits on iron and nickel foils (See photo
in Figure l ).
FIGURE l: Carbon deposit on a Fe foil at 898 K from benzene diluted with

hydrogen. SEM photograph showing filament growth (9350X)
Under these high temperature conditions, hydrogen was found to play a

marked effect accelerating the rate of filament growth. Figure 2 shows the
@ProcessEng
effect of hydrogen partial pres sure on the rate of carbon formation. It is

to be noted that the rate has been shown to be of third orde r with respect
to hydrogen on nickel catalytic surfaces and of first order on iron surfaces
for these experiments (6)
393
The reaction order with respect to the hydro carbon concentration tends
to be positive at high temperature conditions.
Ul
"'E"
U
008 l
!
/
006 ..,i
IT
Ul
"'E"
Ol
004 ~ ,/
002 ~
/"
0/
O t--4--
.
ru ~
-iJ
m O .2 .4 .5 .8
IT
H2 Partial Press. atm

FIGURE 2: Hydrogen effect on catalytic C formation on Ni. Benzene: 0.132
atm, total pressure atmospheric pressure, 923 K, Helium used as diluent .
. 00004 'I
.000035 '0\
.00003 i
I o
.0000251' \
. 00002
.000015:
j' o
\
.....co
Q.l
.00001 I \ ____ o~o

o:
.000005 ----.,-
O-+'--~--r----,---~-,
O 20 40 60 80 100
% Butane in H2
FIGURE 3: Effect of reactant concentration in H2 on catalytic C formation.

Reactant: n-butane, 1073 K, Ni surface, 1.66 s gas residence time.
If the hydrocarbon is diluted with hydrogen, however, the effect of

increasing hydrocarbon concentration and simultaneously reducing the
concentration of hydrogen is quite unpredictable. See for example, figure 3
above.
@ProcessEng
The plot should start at zero rate at zero concentration of hydrocarbon

Cn-butane in this case). Experimental limitations precluded the gathering
of data at low hydrocarbon concentration, but the rate of carbon formation
394
should increase and go through a maximum, as shown by a dot ted line in

Figure 3. At concentrations above the maximum, experiments show a decrease
of the carbon formation rate with an increase in hydrocarbon concentration.
A second, minor maximum appears in the region of 50% concentration of
n-butane. Since there is no explanation for this effect, experiments were
repeated several times. The effect appeared every time on nickel foils, and
it was found to be even more marked on iron catalytic surfaces.
Carbon formation from different paraffins and olefins goes through a

maximum at temperatures in the range of 800 to 910 K (l, 2, 5, 6, 7, 8, 9).
In the present work, benzene was found to present amaximum rate of carbon
formation at a temperature as high as about 950 K. Figure 3 show the
temperature effect. The rate of carbon formation increases with temperature
up to about 950 K ( zone I, see reference 10), af ter the maximum, there is a
region in the curve with apparent negative activation energy ( zone II).
Note that at higher temperatures, the rate of coke formation should increase
again due to the gas phase formation of carbon (zone III) .
u
.008, II
Ol rJ \
en
E
u
/
u
. OO~ ,
CT
en
---= ,,/ \
,
.§
....,
Ol
.002 ~ / ,
"'D-D_
m
er Oi 4~ I
750 800 850 900 950 1000 1050 1100
Temperature, K
FIGURE 4: Temperature effect on the rate of C formation on Ni. Benzene:
0.132 atm, total pressure: atmospheric, diluent: hydrogen.
In the case of benzene (a relatively stable molecule), however,

decomposition reactions only become significant above 1100 K and are not
observed in Figure 3.
The experimental results described above show that catalytic carbon

formation can occur even at temperatures as high as 1000 K, given the
presence of hydrogen, the right catalytic surface and the right carbon
source (hydrocarbon). At higher temperatures, the gas phase formation of
coke precursors becomes dominant. Examples of this mechanism are given
below.
@ProcessEng
395
4. GAS PHASE ORIGINATED COKE

Under a certain set of conditions, hydrocarbons will undergo gas phase
reactions that will tend to form coke deposits on the surfaces exposed to
the reacting gas or vapor. The deposition does not depend upon a large
measure on the nature of the surface where the deposit is being formed, and
is, for all practical purposes, non-catalytic (5, Il, 12).
An interesting feature of this mechanism of carbon formation is that it

behaves quite in the opposite way from catalytic carbon formation. For
example, increased hydrogen partial pres sure tends to accelerate catalytic
carbon formation under certain conditions .
. 000035
.00003
en
......... .000025
ru
e
u
......... .00002
Cl
.§ .000015
.00001
Ol
0"--0 -D-
......
co
o::
.000005
O -~
O 20 40 60 BO 100
H2 in Feed
FIGURE 5: Hydrogen partial pres sure in gas phase carbon formation.
Deposits on Cu foil, 1073 K, gas residence time: 5.25 s, feed: 25 %
n-butane, total pressure: atmospheric, diluent: He
Increased hydrogen partial pressure, in contrast, will decrease the

rate of gas phase originated carbon formation. The effect becomes obvious
when comparing Figure 2 with Figure 5 above.
The gas phase residence time has no bearing on catalytic reactions,

such as catalytic carbon formation, and has no noticeable effect on the
rates of formation measured (See Fig. 5 in reference 6). On the other side,
gas phase originated carbon formation depends strongly on the gas phase
residence time, as shown in Figure 6 below. Note also that the rate curve
does not go through the origin, indicating a complex sequence of phenomena

as the route towards carbon. One or more intermediate compound s are likely
to be formed before carbon is finally deposited on the surfaces (3). This
matter will be explored further in the discussion of this paper.
Another difference between gas phase and catalytic carbon formation

is shown in the results of the effect of reactant concentration in hydrogen.
@ProcessEng
396
.00025 ~
.0002 -
.00015-
.0001 -
.00005 -
O+1----,-1----,-----r----r---,----~T--_r_l
1.5 2 2.5 3 3.5 4 4.5 5
Res. Time, s
FIGURE 6: Effect of gas residence time on gas phase carbon formation.

Deposits on a Cu foil, 1073 K, pure n-butane feed, pressure: atmospheric
.000025 l
/~"-
I
I
en .00002 ~
---
C\J
E
LJ .000015-
---"" .00001 "
.§
...,
Cl>
/'
OOOOO~ IT~---T-~~T -----,-
n::J
ex:
. --l
O 20 40 60 80 100 120
Reactant % in H2
FIGURE 7: Effect of reactant concentration on gas phase coke formation.

n-butane in H2, 1.31 s gas residence time, surface: Cu foil, 1073 K
Figure 3 above can be compared with Figure 7 to see the contrast. In

both cases carbon is formed under the same set of conditions, but in the
last figure a Cu foil is used Cwhich does not tend to form catalytic
carbon). The overall effect in Figure 7 is an increase in the rate of
carbon formation with increased hydrocarbon concentration. In contrast with
Figure 3, no negative slope or maxima appear in this case.
@ProcessEng
397
The effect of temperature on gas phase carbon formation is simpler than

in the catalytic formation case. Figure 8 shows the absence of a maximum or
negative activation energy region in the plot. (Compare Figure 4 with Figure
8)
,002,
Ul
---
ru
e
0015 J
u
---
Cl
.§
,00 1~
I
Cl)
......
co
,0005 1
a::
OI
1025 1050 1075 1100 1125 1150 1175 1200
Temperature, K
FIGURE 8: Effect of temperature on gas phase coke formation, 50% n-butane in

H2, 6.13 s residence time, surface: Cu foil
Gas phase originated carbon formation is the result of a set of

homogeneous chemical reactions. As such, the rate of fouling by coking is
affected by the interaction of the surfaces with the gas reacting
environment.
This effect i's very important, because S/V is a strong function of the
scale of the equipment or the presence of packing in it. Scaling up or down
into a new piece of equipment, which is equivalent to changing S/V, can
strongly affect the rate of carbon formation on the equipment surfaces.
Figure 9 shows the S/V effect on the gas phase carbon deposition on a Cu
surface. The rate of carbon deposition, per unit area of surface, decreases
with an increase of the total area exposed to the hydrocarbon reacting gas.
According to Figure 9, if carbon formation rates were measured in a

laboratory equipment (high S/V) and found to be small, when scaling-up into
a large r vessel (low S/V), the rates of fouling by coking could be much
higher.
@ProcessEng
Figure 10 shows the topography of the gas phase originated coke. The
deposit looks as if drops of a liquid material have deposited on the foil
surface.
398
.00025
\D
\"---0_
Ul
E
.0002
<..J
O'
'"
........
.00015-
Ol
.§ .0001 -
....,
Cl>
!tl
er:
.00005 ,
f'
Il,.'
2.5 5 7.5 10 12 15 17 20 22
s/v U/cm)
FIGURE 9: Vessel surface to volume ratio effect 50% n-butan e in HZ, Cu

screen used to change S/V, Cu foil collection surface, 1073 K, 6 s gas
residence time
The presence of smaller particles or droplets suggests that the larger

drops are formed by the aggregat ion and melting together of smaller, gas
phase originated droplets. How these smaller droplets may form in the gas
phase and how the kinetic of deposition may be explained and modeled is one
of the subjects of the discussion below.
FIGURE 10: SEM photograph of a gas phase originated coke deposit. Surface:
Cu, benzene in HZ, magnification 1870 x.
@ProcessEng
399
5. DISCUSSION
5.1 High temperature catalytic carbon formation
The mechanism of catalytic carbon formation has been described in a
previous paper of this Institute (l) and in several excellent reviews (2, 8,
9, 13). The general mechanism does not need further discussion here.
With regards to the accelerating effect of hydrogen on the kinetics of

carbon formation, a high temperature effect, several explanations have been
advanced.
The encapsulation theory (2, 5, 7, 8) proposes that carbonaceous

material encapsulates active sites. Hydrogen would act by removing the
carbonaceous material from the active sites, either by gasifying the carbon
capsule or by mobilizing carbon fragments away from the active sites.
The hydrogenolysis step theory (6) complements the encapsulation

theory, claiming that under some conditions, a hydrogenolysis step is
involved in the production of atomic carbon. Hydrogenolysis is a necessary
step to produce atomic carbon from hydrocarbons (except methane) because it
is the mechanism that breaks carbon-carbon bonds. Atomic carbon is the
species that dissolves and diffuses through the metal crystallite that
generates the carbon filament. Hydrogen is necessary for the hydrogenolysis
step and an increase in hydrogen concentration would accelerate the reaction
rate (see the example below).
This theory was used by LaCava et al. (6) to explain the third order
kinetics of carbon formation from benzene on nickel with respect to
hydrogen. The postulat ed steps are:
Benzene + S ~I B.S (a), Equilibrium
B.S + 3 H2 (b), Hydrogenolysis,

in equilibrium
I<~ Carbon + S + 6 H2
r.S ----~~~~~ (c) Rate limiting
The rate expression, deduced from the above mechanism is:
3
k3 Kl K2 Ct [HC] [H2]
Rc k3 [r.S] (d)
3
( l + Kl [HC] + Kl K2 [HC] [H2] )
The above expression will reduce to third order with respect to

hydrogen at low surface coverages of H2.
A recent paper by Yang et al. (14) proposes a low activity carbide

model. According to this paper, surface carbide is a poor catalyst for
carbon formation. Experiments show that the use of hydrogen to clean the
@ProcessEng
surface carbide increases the rate of carbon formation considerably.

400
The theory, based upon experiments performed on iron, can explain the
increase of rate with increased hydrogen. This theory, however, does not
explain why the rate of carbon formation is third order with respect to
hydrogen on nickel and first order on iron. It seems obvious that the
formation of a nickel carbide may regulate the rate determining step under
some set of conditions. It is also possibie that the other two mechanisms
described above could limit the rate under other sets of conditions.
5.2 Gas phase originated carbon formation.

The theories that try to explain the gas phase originated surface
carbon formation, start by postulating homogeneous chemical reactions that
tend to build a carbon forming intermediate (3, 5, 8). The intermediate (or
family of intermediates) does interact with the surface, either through a
physical (5 ) or a chemical process (12). An alternative mechanism is
the droplet formation, where the intermediate physically condenses into
droplets in the gas phase and these droplets deposit on surfaces forming
coke (3).
The foliowing is a summary of a model for droplet surface carbon

formation proposed by the author and coworkers (3, 5).
Building the carbon-forming intermediate: Macromolecules are formed in

the gas phase, as a consequence of homogeneous chemical reactions. For the
case of n-butane and benzene pyrolysis, the intermediates are assumed to be
macromolecules of polycyclic aromatic hydrocarbons, formed in abundance
during pyrolysis of both compounds (5, 8, Il). The steps in the formation
of macromolecules is a complex sequence (see a discussion in references 5
and Il on the chemical steps involved in the formation of these
macromolecules). The foliowing steps are a simplified model that captures
the essential points:
HC- RI. (e) (Radicai generation)
RI. + H2 ~ RH + H. (f) (Radicai deactivation by H2)
RI. l/n M (g) (Macromolecule formation)
The concentration of hydrocarbon along areaction vessel can be

obtained integrating the conservation equation:
d [HC]
-kl [HC] (h)
d t
with initial conditions [HC]=[HCO] at t O
Af ter integration of (h),
[HC] = [HCO] exp(-kl t) (i)

@ProcessEng
401
With the applieation of the steady-state hypothesis to the radieal RI.

and af ter rearrangement and integration of the resulting equations, the
eoneentration of maeromoleeules is deseribed by:
(l/n) [HCO] (1- exp(-kl t»

[M] (j)
(l + (k2/k3) [H2] )
Forming the droplets: The eoneentration of maeromoleeules will

inerease in the gas phase until it reaehes the eoneentration [M*l, the
saturation level, at the time t* (15). At that point (af ter reaehing some
supersaturation level) droplets are formed. Maeromoleeules formed af ter t*
will eontribute to the growth of the droplets, but without forming new
droplets. The mass eoneentration of droplets, af ter nueleation (total mass
of partieles/volume of the reaeting vessel), eould be expressed as:
[c] = ([M]-[M*]) Mwm (k)
where Mwm is the moleeular weight of the maeromoleeules.
Depositing the droplets: The deposition of droplets on the surfaee is

produeed by Brownian motion (or diffusion). The rate would be given by Red
= ke [C] or:
(l/n) Mwm [HCO] (exp(-kl t*)-exp(-kl t»

Re ke (l)
(l + (k2/k3) [H2]
Equation (l) ean be simplified for short residenee times, to yield:
(l/n) Mwm [HCO] kl (t - t*)

Re ke (m)
(l + (k2/k3) [H2] )
This last equation has most of the features to explain the experimental
results given above (Figures 5 through 10). The negative effeet of hydrogen
(Figure 5) appears in (m) through the denominator term. The linear
dependenee on residenee time, from avalue of time of about one seeond
(Figure 6) is given by the term (t - t*) in equation (m). Figure 7 is not
aeeurately deseribed by (m), beeause n-butane does not deeompose folIowing a
first order kinetie but a fraetional order. Carbon formation from benzene,
on the other hand, is quite well deseribed by a first order expression (15).
The temperature effeet of Figure 8, typieal of an Arrhenius behavior,

is deseribed by the temperature dependenee of kl in (m).
The effeet of the vessel surfaee to volume ratio (5) ean be explained
by writing the eonservation equation for maeromoleeules for a volume where
the deposition surfaee is large:
@ProcessEng
d [M]
- (S/V) Red + Rv (n)
d t
402
As in the previous case, the rate of generation of macromolecules Rv

will be given by: Rv = (l/n) [HCO] exp(-kl t)/ (l + (k2/k3) [H2] ).
Equation (n) can be integrated for some limiting cases of the values of
(S/V). For small (S/V), the model reduces to equations (l) and (m) and is
insensitive to S/V changes. For large values of S/V, the model yields:
-l
Rc (S/V) (l/n) kl [HCO] exp(-kl t) (o)
-l
The term (S/V) tends to agree with the shape of the curve on Figure
9. Equation (o) also predicts that at high S/V, the rate of coke deposition
would decrease with residence time (i.e. further down the reactor tube).
This is the opposite to what equation (m) predicts for low (S/V). It should
be noted that at high (S/V) macromolecules can directly condense or
chemically react with the surface to form coke. In such a case, droplets are
unlikely to be formed.
6. CONCLUSIONS
6.1 Practical Consequences of Droplets and Filaments Coke Fouling
There is a borderline operation zone which, in the experience of the
author, has been the source of unpleasant surprises and frustration for
research and development. There is a set of conditions where both catalytic
and gas phase carbon can be formed, and all that is needed to trigger
copious fouling from the droplet or from the filament mechanism is a
moderate change in the operating conditions. In many cases, changes are
introduced with the intention of reducing fouling by coke formation. And in
man y cases, all that is accomplished is an increase in fouling!
There are reports, especiaIly coming from industrial research and

development, of cases where a vessel is lined with an expensive inert
material to prevent a problem of fouling by catalytic formation of carbon
(filaments). When the lined vessel is tested, no filaments appear, but the
vessel gets rapidly filled and fouled with just another type of coke,
derived from the droplet formation and deposition mechanism! (This happened
in an actual case known to the author).
It is perfectly possibIe to reduce fouling by gas phase originated coke

(droplets) by decreasing the operating temperature slightly. But, if the
vessel has catalytic metal walls, this can achieve just the opposite result,
fouling the vessel with catalytic coke. To illustrate this point, suppose
that a unit is operating at the conditions of Figure 4 (around 1000 K) where

gas phase carbon is generated at a low rate. A temperature decrease of 50 K
would decrease gas phase originated carbon formation even further, but it
would put the unit to operate at 950 K, where the rate of catalytic carbon
formation hap pens to be at its maximum. Rapid fouling will follow. On the
other side, it is possibIe to reduce catalytic carbon formation by raising
the temperature of the system (above the maximum in Figure 4), but these are
@ProcessEng
now the conditions where droplet coke can start forming rapidly (see Figure
8) •
403
lncreasing hydrogen concentration will tend to reduce gas phase

originated coke (droplets), but will tend to accelerate catalytic carbon
formation (filaments). Hydrogen concentration is another variable that can
affect the change from one mechanism to another and offers a potential
pitfall. lf one desires to reduce coking by increasing hydrogen, folIowing
Figure 5, conditions may be such that catalytic carbon will be increased as
shown in Figure 2 instead. A similar situation appears when trying to
modify the hydro carbon to hydrogen ratio. An engineer trying to reduce
carbon formation (filaments) in the conditions of Figure 3 by increasing the
hydrocarban to hydrogen ratio, has to have in mind that gas phase originated
carbon formation (droplets) will accelerate, as in Figure 7, tending to
defeat his purpose.
The conditions required for the unexpected changes of mechanism

described above are found in industrial practice. Hydrocarbon process
industries have operated for many years with coke formation fouling and have
learned how to minimize it or to somehow live with the phenomenon. The
potential for unexpected behavior is clear from the contents of this paper
and the work of other researchers. Droplets or filaments (and other types
of carbon formation that have not been mentioned here) can appear, with its
sequel af unwelcame fouling problems, at the most unexpected time.
7. LIST OF SYMBOLS
HC Hydrocarbon species
I Carbon forming intermediate
ki Kinetic constants
Ki Equilibrium constants
M Macromolecules
n Number of monomer units in a macromolecule
Rc Rate of carbon formation, (Kg/m2/s) or derived units
Rv Homogeneous rate of generation of macromolecules
S Surface site
S/V Surface to volume ratio (l/m)
t Residence time (s)
X.S Adsorbed species X
[xl Gas phase concentration of species X
8. REFERENCES
1- Bernardo, C. A., "Catalyst Fouling", NATO Advanced Study lnstitute:

Advances in Fouling Science and Technology, Alvor, Portugal, May 19-30,

1987.
2- Figueiredo, J. L., "Carbon Formation and Gasification on Nickel" in

"Progress in Catalyst Deactivation", p. 45-63, J. L. Figueiredo, Editor,
Martinus Nijhoff Publishers, Boston, 1982.
@ProcessEng
3- LaCava, A. I., E. D. Fernandez-Raone and Maritza Caraballo, "Mechanism of

Surface Carbon Formation During the Pyrolysis of Benzene in the presence
404
of Hydrogen", in "Coke Formation on Metal Surfaces" , p. 109-121, L. F.

Albright and R. T. K. Baker, Editors, ACS Symposium Series 202,
Washington D. C., 1982
4- LaCava, A. L, D. L. Trimm and C. Turner, "Microbalance Studies in Flow

Reactors", Thermochimica Acta, 24, 273-280, 1978
5- LaCava, A.,"Pyrolysis and Thermal Hydrogasification of Hydrocarbons", Ph.

D. Thesis, Univers it y of London, 1977.
6- LaCava, A. I., E. D. Fernandez-Raone, L. L. Isaacs and M. Caraballo,

"Effect of Hydrogen on the Iron and Nickel Catalyzed Formation of Carbon
from Benzene", in "Coke Formation on Metal Surfaces", p. 89-107, L. F.
Albright and R. T. K. Baker, Editors, ACS Symposium Series 202,
Washington D. C., 1982.
7- LaCava, A. L, C. A. Bernardo and D. L. Trimm, "Studies of Deactivation

of Metals by Carbon Deposition", Carbon, 20 (3),pp. 219-223, 1983.
8- Trimm, D. L., "The Formation and Removal of Coke from Nickel Catalyst" ,
Catal. Rev.-Sci. Eng.,16(2), 155-189, 1977
9- Trimm, D. L., "Carbon Formation on Metals other than Nickel and on

Alloys" in "Progress in Catalyst Deactivation", p. 65-79, J. L.
Figueiredo, Editor, Martinus Nijhoff Publishers, Boston, 1982
10-Figueiredo, J., "Carbon Formation on Steam Reforming Catalysts", Ph.D.

Thesis, University of London, 1975
ll-Trimm, D. L., "Coke Formation in the Gas Phase and in Surfaces" in

"Progress in Catalyst Deactivation", p. 31-43, J. L. Figueiredo, Editor,
Martinus Nijhoff Publishers, Boston, 1982
12-LaCava, A. L and D. L. Trimm, "The Growth of Carbon Particles During

Pyrolysis", Carbon, 16, (6), 505, 1978
13- Baker, R. T. K., P. S. Harris, "The Formation of Filamentous Carbon", in

"Chemistry and Physics of Carbon", vol. 14, p. 83, Marcel Dekker, 1978
14-Yang, K. L. and R. T. Yang, "The Accelerating and Retarding Effects of

Hydrogen on Carbon Deposition on Metal Surfaces", Carbon, Vol. 24, No 6,
pp. 687-693, 1986.
15-Lahaye, J., Prado G. and Donnet, J. B., "Nucleation and Growth of Carbon
Black Particles During Thermal Decomposition of Benzene", Carbon, 12, 27,
1974.
@ProcessEng
CARBON LIMITS IN STEAM REFORMING
J.R. Rostrup-Nielsen
HALDOR TOPS0E A/S

Nymøllevej 55
DK-2800 Lyngby
THE STEAM REFORMING PROCESS
1.1 Industrial Application

Steam reforming is an essential process for the manufac-
ture of synthesis gas and hydrogen from hydrocarbons (1). Its
applications are widespread in the petrochemical industry as
well as iil the energy related industries. Most of the world
ammonia production is based on steam reforming of hydrocarbons
with natural gas being the preferred feedstock. In the petro-
chemical industry, steam reforming is used for production of
syngas for methanol, oxo-synthesis, and for Cl-chemistry reac-
tions such as synthesis of acetic acid, etc. Oil refineries
use hydrogen from steam reforming for desulphurization and hy-
drocracking.
The steam reforming proces s may become an important ele-
ment in solving the problem of the huge amounts of associated
gas being produced jointly with oil production. The gas may be
converted either into methanol or synthetic liquid hydrocarbons
(2). Other applications include conversion of hydrocarbons for
fuel cells (3) or advanced energy transfer systems, in which
nuclear heat or solar energy are absorbed by the endother~ic
steam reforming proces s (1).
1.2 The Tubular Reformer

The steam reforming proces s converts hydrocarbons into

mixtures of hydrogen, carbon monoxide, carbon dioxide, and me-
thane:
@ProcessEng
405

406
o
C H + n (-LlH 298 < O) (1)
n m
(-LlH~98= 41.2 kJ mol-l) (2)
(-LlH~98 = 206.2 kJ mol-l) (3)
Natural gas is the dominating feedstock, but also refinery off

gases, LPG and liquid hydrocarbons are being used. The reaction
is carried out over a supported nickel catalyst with typical in-
let and exit temperatures of SOOoC and 800 0 C or above, respec-
tively. In order to supply the heat for the overall endothermic
reaction, the catalyst is loaded into a number of high alloy
tubes placed inside a furnace. This reactor is called a tubular
reformer (Fig. 1). A typical reformer may contain 40 to 400
tubes with internal diameter in the range 70-160 mm and a heat-
ed length of 6-12 m depending of furnace type. The maximum al-
lowed stress value in the tubes is strongly influenced by the
maximum tube wall temperature and by the maximum heat flux.
Even a slight increase in the maximum tube wall temperature
may result in a serious decline of the expected tube life (1).
Fig. 1. Reformer furnace

@ProcessEng
407
In a typical ammonia plant, about 50% of the heat produced

by combustion in the burners is transferred through the refor-
mer tubes, and absorbed by the process (60% for reaction, 40%
for temperature increase). The other half of the fired dut y is
recovered in the waste heat channel of the reformer.
2 CARBON FORMATION
2.1 Reactions
The reforming reactions may be accompanied by reactions
forming carbon:
+
2 CO ->- C + CO 2 172.4 kj mol-l) (4 )
o -1
(-~H298 = -74.9 kj mol ) (5 )
CnH m ->- "carbonaceous deposits" + xH 2 (6 )
These reactions compete with the reforming reactions on the

nickel surface and they lead to the formation of filamentous
carbon. The carbon grows typically in a whisker-like structure
(4,5,6) with a nickel particle at the top as shown in Fig. 2,
and the strong whiskers may result in break-down of a catalyst
particle. The growth rate of the carbon whiskers is indepen-
dent of time, meaning that large amounts of carbon can accumu-
late. This behaviour is in contrast to the carbon formation in
catalytic cracking where the carbon deactivates the active
sites forming the carbon (7).
@ProcessEng
Fig. 2. Whisker carbon on steam reforming catalyst.

408
At high temperatures (> 650 o C), the higher hydrocarbons

may react in parallel to reaction (1), by thermal cracking
(steam cracking) to olefins (1,8), which mayeasily form coke.
This can deposit either as dense scales on the tubewalls or as
deposits encapsulating the catalyst particles and eventually
filling out the void between the particles.
2.2 Impact of Carbon Formation on Reformer Operation

The reforming reaction is a complex interaction of heat
transfer, reaction kinetics and mechanical constraints. Strong,
axial and radial temperature gradients are present in the cata-
lyst bed (1).
The balance between heat input through the reformer tubes
and the heat consumption in the endothermic reforming reaction
is the central problem in steam reforming. Carbon formation may
lead to break-down of the catalyst, and the build-up of carbon
deposits. Degraded catalyst may cause partial or total blockage
of some tubes resulting in development of "hot spots", "hot
bands" or total ly hot tubes. The uneven flow distribution will
cause a self-accelerating situation with further overheating of
the hot tubes.
Therefore, carbon formation cannot be tolerated in tubu-
lar reformers. The important problem is whether or not carbon
is forrned and not the rate at which it is formed.
2.3 Carbon Limits

It is important to explore the limits of the steam reform-
ing reaction. When these are known, it is possible to establish
safe design for optimum conditions. For reforming of methane,
there are three different carbon limits to consider, Fig. 3:
Carbon Limits
SPARG
<: More Critical Conditions
Steady State Kinetics
c B A
Fig. 3. Carbon limits.

@ProcessEng
Limit A corresponds to conditions in the reformer where kine-

tics allow methane to decompose into carbon instead of reacting
~ith steam, even if thermodynamics predict no carbon formation.
Carbon formation is then a question of kinetics, local process
conditions and reformer design.
409
Limit B is dictated by !~~E~~~Y~~~~~~~ Carbon will be formed

if the equilibrated gas shows affinity for carbon. The limit
is a function of the O/C, H/C and inert/C ratio of the gas as
well as pressure.
Limit C is aresult of control led ~~!E~~E_E~~~~~~!~~~ of the

reforming catalyst as practiced in the SPARG process (9).
3 KINETIC CARBON LIMIT. CARBON LIMIT A.

3.1 Steady State Activity of Carbon
Carbon Limit A is aresult of a kinetic balance between
methane reacting to carbon and to gas.
HZO
~-
CH ---+ Gas
4---+
-<C--- Carbon
Of course, it is not possibIe in a close thermodynamic

system, unless carbon limit B is violated, but in an op en sy-
stem carbon may be stable in a steady state, and the accumu-
lation of carbon may continue. In principle, the carb~n limit
is dictated by the steady state activity of carbon, ac' on the
nickel surface (1).
According to the whisker carbon mechanism (4,5,6), adsor-
bed carbon atoms will be dissolved into the nickel crystals.
Above the saturation value, carbon will nucleate corresponding
to a carbon activity, a = 1. If the rates of the reforming
reactions are zero, theCcarbon activity, a O is expressed by:
c
o
a K (8 )
c P
in which K is the equilibrium constant for reaction (5). If

a O > 1, cafbon should result, but at high rates of the steam
r~forming reaction, the adsorbed carbon atoms on the surface
and hence the concentration of carbon in the nickel crystals
is decreased. The resulting steady state activity of carbon,

aS, may then become less than one and carbon formation is eli-
mrnated.
aS can be expressed by balancing the rate of carbon for-
mation~ r , without the presence of steam with the rate of
gasificatron, r , of the adsorbed carbon atoms in presence of
steam (1): g
@ProcessEng
410
r (9)
c
ex
r
g
k a
g c
(0-*) k
g
a
c . kga <(:::0 }
O
(10)
in which (0-*) is the s~rface concentration of adsorbed oxygen.

For r =r , a becomes ae and eq. (9) and eq. (10) yields:
g c c
o
a
s c ( 11)
a
c
k -(2+ex')
1+ g PH
~ 2
-c
Carbon may be formed when aS> 1. This means that carbon

may be eliminated even when the ~as above the catalyst shows
affinity for decomposition of methane (a o > O). A large value
of the steam adsorption constant on the §atalyst, K , decreases
the steady state activity aS (1). The strong retardYng effect
on the coking rate from met~ane of small amounts of steam and
carbon dioxide is demonstrated in Fig. 4 (1).
0.10,------------------,
Vl
~~ 0.08
O)
E
-;; 0.06
C)
•
~.
Vl
g 0.04 . [0 2
-o
~
o
ru 0.02
o
<::<:
o 0.002 0.004 0.006 0.008 0.010 0.012
Fig. 4. Influence of steam and carbon dioxide on methane

decomposition. Thermogravimetric studies.
@ProcessEng
411
3.2 Simplified Approach

Quantitative calculations of the steady state activity of
carbon may be difficult. A simplified (and conservative) cri-
terion for carbon free operation is to require that a~ at any
position in the reformer must not show affinity for methane
decomposition, i.e. a O < 1.
a O is eas ily cal~ulated from the equilibrium constant,K ,
for re~ction (5) and the gas analysis. This criterion should P
consider not only the axial temperature profile, but also take
into consideration the radial temperature gradients.
Fig. 5 shows how the catalyst temperature at the tube wall
(T CW ) is higher than the carbon limit temperature (T M) at the 10-
cation 1-4 m from the tube inlet, resulting in potential for a
"hot band".
TM is the temperature above which the actual gas has affi-
nit y for methane decomposition (reaction (5» in to carbon. It
increases with distance from inlet as the methane concentra-
tion decreases. (The calculation assumes no radial concentra-
tion gradient which is normal at the typical high mass veloci-
ties).
It is evident that the risk for carbon formation depends
on TCW-T CM , i.e. the radial temperature gradient or the heat
flux proYile in the reformer (1).
1450 - , - - - - - - - - - - - - - - - - ,
1350
1250
~ 1150
::J
10
a;
E1050
~
950
850
7504---~----._--~----._--_.----~
o 2 4 6 8 10
Zlm
Fig. 5. Carbon Limit A and catalyst temperature.

For the endothermic decomposition, reaction (5),
there is a temperature, TM, for a given gas com-
@ProcessEng
position above which there is potential for car-

bon. (Reproduced with permission from (1».
412
A more quantitative approach to the problem requires the

use of a two dimensional (pseudo homogeneous) computer model
describing the mass and heat transfer in the reformer tube.
Fig. 6 shows radial temperature profiles in an ammonia plant
running at boosted capacity with a low activity catalyst (1).
The catalyst temperature (Te) exceeds the carbon limit tempe-
rature (T M) close to the tUDe wall, which means potential for
carbon formation by methane decomposition.
The catalyst mean temperature (TeM) stays below the car-
bon limit temperature, which means that carbon would not have
been predicted by a simple one-dimensional description, disre-
garding radial gradients.
With a highly active catalyst, the temperature level in
the reformer is lowered, and calculations showed no formation
of carbon (1).
1000
~
Q;
:; 990
n;
Q;
c.
E 980
~
970
O 025 0.50 0.75 100
Relative distance from tube axis. R,/R o
Fig. &. Radial gradients and carbon formation.

Ammonia plant at boosted capacity.
3 m from tube inlet. Potential for carbon
for T > TM. (Reproduced with permission from
(1)).cat
3.3 Higher Hydrocarbons

If the feed gas contains higher hydrocarbons, the reac-
tion scheme (7) is replaced by irreversible reactions:
@ProcessEng
H2 0, H2
e n Hm ------,>>- Ga s
------,>>- ea r b o n
413
In this situation, a~ is always above 1 as long as the hydro-

carbons have not been converted. Therefore, the conservative
criterion applied above for steam reforming of methane would
predict carbon formation. Special catalåsts are required to
depress the steady state of activity, a (1). This is achieved
by aiming at high values of K'. Additioå of alkali or use of
active magnesia for enhanced ~team adsorption have been used
in industry (1).
For a given catalyst and hydrocarbon feedstock, a correla-
tion can be established between a critical steam to carbon ra-
tio below which carbon will result (1). This ratio will in-
crease with the temperature as shown in Fig. 7. For carbon-free
operation, the actual steam to hydrocarbon ratio should be
higher than the critical ratio at all positions in the refor-
mer. Again, it is important to consider the radial temperature
gradient s which result in higher potential carbon formation
in the tube wall.
A naphtha reforming catalyst

B natural gas reforming catalyst
l normal activitY:7
2 pOIsoned; /2
/
_-i----- _L--8
.
.----
-- :::"
. A
...
... _::::':::.~.
Temperalure
Fig. 7. Critical and actual steam to hydro carbon ratio

for higher hydrocarbons.
Potential for carbon when the actual ratio is
lower than the critical ratio.
(Reproduced with permission from (1)).
4 THERMODYNAMIC LIMITS. CARBON LIMIT B.

4.1 Principle of Equilibrated Gas
"Carbon is formed when the gas shows affinity for carbon
@ProcessEng
formation af ter the establishment of the methane and the shift

equilibria".
This principle of equilibrated gas (1) is no law of nature.
It is merelyarule of thumb. Carbon Limit C re~resents an ex-
ception, and the reverse statement is not true as indicated by
the carbon Limit A.
414
The thermodynamic data to be used for carbon are influen-

ced by the morphology of the carbon formed on the catalyst (1).
This results in lower equilibrium constants than calculated on
the basis of graphite, which again corresponds to higher con-
tents of carbon monoxide or methane before formation of carbon.
Fig. 8 shows data for the methane decomposition. Similar
results were obtained for the Boudouard reaction (1).
,
TEMP °C
700 650 600 550 500 450 400
Kp
10
.~
.~
x~
•
CATALYST ~ GRAPHITE
0.1
.'\
0.9 1.0 1.1 1.2

\.
1.3 1.4 1.5 1.6
10 3/T K·'
0.0 1 ~--:-':;;---:-':--:-'::"-7::--:'-:----::'"::---,'"::---.J
Fig. 8. Equilibrium constants for decomposition

of methane.
The deviation from graphite thermodynamics ean be ascribed

partly to the contribution from the surfaee energy of the whis-
ker (1,6). The diameter of the whisker is equal to that of the
nickel crystal. Renee, the nickel crystal size may influence
the supersaturation to form carbon as illustrated in Fig. 9.
@ProcessEng
@ProcessEng
10,---------------------------,
H/C
9 9 ~
/
8 8 f- .0f
(,01,
7 '
6
6
'oE 5
..., 15
""u
Cl
<I
4
3
3 ro
2 , C
O ,y
åGe - 2korffiix + IJ*
2~ o Ni/MgO '(·C
• • other types ~
5.0 "T'
O' O/C
'" 2 3
.!:!2' CO RATIO IN PRODUCT GAS
o 20 40 60 80
OUTLET TEMPERATURE =900·C (1650·Fj
1()3 D;riax/nm-1
OUTLET PRESSURE = 5 kg Icm2g (71 psig
FIG. 9, Deviation from graphite and FIG. 10, Equilibrium diagram. Carbon Limit B.
nickel crystal size, SOOoC. Curve 1: graphite data
CH 4 decomposition on various Curve 2: whisker carbon (aged catalyst)
catalysts. (Reproduced with permission from (9».
(Reproduced with permission
from (1».
.j:>.
u.
416
The atom ratios O/C and H/C are used as axes. The straight
line increasing from H/C = 4 represents all mixtures of steam
and methane, whereas the lower line represents all mixtures of
carbon dioxide and methane.
The dotted lines show conditions (O/C and H/C) resulting
in the indicated H 2 /CO ratio in the reformer exit gas.
The selection of process parameters is limited by the po-
tential for carbon formation. Curve 1 shows carbon limit B
calculated by the "principle of equilibrated gas" on basis of
graphite data for carbon. For O/C and H/C ratios below the
values indicated by the curve, there is thermodynamic poten-
tial for the formation of graphite.
However, as mentioned above, the tbermodynamic calcula-
tion should take into consideration the deviation of the car-
bon structure from ideal graphite. If so, curve 1 should be re-
placed by curve 2, which allows coke-free operation at lower
O/C and H/C ratios. The position of curve 2 depends on the type
of catalyst and demonstrates the importance of selection of
the right catalyst. Note that curves 1 and 2 are related to
the specific examples and that the curves do not give informa-
tion at which temperature level carbon is to be expected. They
just indicate whether there is potential for carbon formation
in the temperature range and pres sure range applied in the re-
former.
As discussed earlier, carbon limit A may become a problem
before approaching carbon limit B.
The SPARG principle (9) allows operation to the left side
of carbon limit B, curve 2.
Examples of thermodynamic carbon limits expressed as tem-
perature intervals with potential for carbon are shown in
Table 1 for mixtures of steam and methane. The critical steam
to methane ratio is below 1.2, and the potential for carbon
is highest at low pressure.
Table 1. Carbon limits.
PRESSURE J BAR
H;z0/CH4
1 2 3
0.8 545- 564- 919-
0.9 574- 605-770 -

925-
1.0 634-674 - -
1.1 - - -
@ProcessEng
This means that for a practical reformer operation, car-

bon limit B will seldom represent a problem with the exception
of reformers for manufacture of reducing gas for direct reduc-
tion of iron ore (1,10).
417
4.2 Carbon Limits for C02~reforming
The increasing interest for Cl-chemistry has created a

need for syngases with low H2/CO ratio. This can be obtained
by adding CO 2 to the reformer feedstock:
2CO + 2H 2 ( 13)
The H/c ratio in eq. (13) is l , whereas the ratio ln eq. (1)
is 3 for methane
However, the presence of CO 2 in the feedstock results in
more critical conditions because of the lower H/c ratio.
The ratio of H2 /CO in the reformer exit gas can be esti-
mated by thermodynamic calculations knowing the atomic ratio
olc and H/c in the feed stream, and the pres sure aDd tempera-
ture at the reformer exit. The results of the calculations may
be presented in equilibrium chart (9) as shown in Fig. 10 for
a given pressure.
5 SULPHUR PASSIVATED REFORHING

5.1 Ensemble Control
Sulphur passivated reforming as practiced in the TopsØe
SPARG process (9) solves the problem of carbon formation by
"ensemble control" which means that the sites for carbon for-
mation are blocked while sufficient sites for the reforming
reactions are maintained. This effect is obtained by adding
sulphur to the process feed.
The chemisorption of hydrogen sulphide is well understood
as aresult of numerous studies of well-defined surfaces (11,
12). Above a certain coverage, islands of well-ordered struc-
ture are formed which may be considered as a two-dimensional
sulphide with the Ni-S bonds being stronger than the Ni-Ni
bonds. The composition of the saturation layer, which does not
vary significanil y from face to face, corresponds to ca. 0.5
sulphur atom per nickel atom for the (100) surface and to ca.
0.4 on the dense (111) surface (Fig. 11).
The sulphur coverage below saturation is determined by the
H2 S/H 2 ratio in the gas. Experimental data correlates with li-
near lsobars (1,13):
-5 -5
8 1.45-9.53 10
0 oT+4.17 0 10 oT o ln(H 2 S/H 2 ) (14)
s
The data (9,14) shown in Fig. 12 illustrates how the rate

of carbon formation decreases more (with the power ca. 6.5)
with sulphur coverage than does the reforming rate (with the
power ca. 3). In terms of simple Langmuir kinetics, Fig. 12
@ProcessEng
indicates that the ensemble for the reforming reaction is smal-

ler than those required for the normal dissolution - precipi-
tation nucleation of the carbon whisker. The reaction sequence
for methane dissociation on the nickel surface may be written
as:
418
CH + * ~ CH - * ~ C - * ~ C - * ~ {C,NI} ~ C-whisker (15)

4 n x n m p
with increasing size of the required ensemble, i.e. n < m < p.

For a non-poisoned catalyst, methane may well be completely
dissociated(l), C-*p beingthe surface intermediate for the
reforming reaction. However, at high sulphur coverage, the *p
ensemble is eliminated and the intermediate may become CHx-*n
or C-*m.
A more detailed statisticai analysis (15,16) was made of
the correlation between the build-up of the sulphur monolayer
and the concentration of ensembles of given size and shape.
This model considered that the surface grid of poison atoms
does not coincide with the grid of surface metal atoms and that
the poison atoms m~y deactivate more than the nearest neighbors
of metal atoms. When applying this model, the ensembles shown
in Fig. 11 would correspond to the observations in Fig. 12 (16).
Fig. 11. Ensembles for reforming and carbon formation

on nickel (111) surface. Sulphur atoms are
ch~mi~orbedoin a two-dimensional lattice,
p/3x/3 - 30 , and it is assumed that each

sulphur atom deactivated the nickel atoms
within a radius of 2/13 (16). The non-filled
triangles show sulphur atoms which may poison
the ensemble. The number of these atoms, k, is
related iO
the ensemble concentration (14,16) =
Zq(I-8 s ) .
@ProcessEng
419
Coking rate Retorming rate

re rA
mol/g/h mol/g/h
1.0
0/=2.7
10-3 0.1
L -________________ 0.05.
1-Gs
Free Ni-surface
Fig. 12. Reaction rates and sulphur coverages. Thermo-

gravimetric studies. The slopes are related
to the exposure numbers (Fig. 11).
The necessity of a larger ensemble for dis solution of car-

bon in the nickel than for activating methane corresponds to
observations in surface physics (11). Adsorbed carbon atoms
result in adistortion of the metal atom geometry (11,17) as
illustrated in Fig. 13, whereas the bonding of CH and CH 2 ra-
dicals on the nickel atoms requires only 3-4 free nickel atoms
(11,18). Also, it is well known from surface physics (19) that
chemisorbed sulphur inhibits the segration (and hence dissolu-
tion) of carbon atoms. In simple terms, the two-dimensional
surface sulphide prevents the necessary distortion of the sur-
face shown in Fig. 13.
The ensemble control principle was studied also for nickel
copper alloys (20) and similar trends were observed. However,

the nickel-copper system does not allow stable copper concentra-
tions at the nickel Burface sufficient for eliminating the en-
sembles for carbon nucleation.
@ProcessEng
420
Fig. 13. Adsorption of carbon atoms on nickel (100)

surface. Distortion of the top layer of
nickel atoms. The small circles represent
carbon atoms in fourfold hollows.
5.2 Elimination of Carbon

Studies leading to the SPARG proces s (9,11) demonstrated
that carbon free operation could be obtained above a cettain
sulphur coverage at conditions which without sulphur would
otherwise result in carbon formation. However, the retarding
effect of sulphur is a dynamic phenomenon as illustrated in
Fig. 12 (14), meaning that carbon may be formed at certain con-
dit ions in spite of sulphur passivation - although at strongly
reduced rates (14).
AIso, the morphology of the carbon is changed from the
normal whisker carbon (Fig. 2) to a more amorphous structure
termed "Octopus Carbon" (14,20,21) with several threads grow-
ing from the same nickel crystal.
Laboratory and full size monotube reformer tests were used
for determining the effective operation limits (carbon limit C)
left of curve 2 in Fig. 10, not to be surpassed.
5.3 Industrial Aspects

It is obvious that operation on the left side of curve 2
in Fig. 10 results in more economical conditions (lower steam
and CO 2 addition for a given H 2 to CO ratio). The conventional

processes are limited by carbon limits A and B. Examples of
operating conditions for the SPARG process which have been
demonstrated in a full si~e monotube process demonstration
plant are listed in Table 2 (9). Operation with mixtures of
CO 2 and methane without steam is also possible.
@ProcessEng
421
Table 2. SPARG tests Ln full size monotube reformer.
Duration, MS 630 200 1720 5x200 300 300

O/C 1.15 1.27 1.32 1.15 1.07 1.43
H/C 6.30 3.40 3.71 3.30 2.97 1.14
H2O/CH4 1.15 0.96 0.91 0.73 0.50 O
C0 2/CH4 O 0.64 0.59 0.77 0.80 2.5
P, exit, hrr 1-6 6 5.6 1 9.0
T, exit 950 900 880 925 935 900
5.4 Sulphur Passivation of Tube Walls

The impact of sulphur on carbon formation is observed also
for other systems. It is well known (22) that the presence of
sulphur in the feed to steam crackers for pyrolysis of hydro-
carbons to olefins significantly reduces the coke formation on
tube walls. Also, sulphur may inhibit carbonization of con-
struction materials (23).
The product gas resulting from operating conditions with
ve ry low H 20/CH 4 and CO 2 /CH 4 ratios has a high content of CO.
This means that belowa certain temperature, TB' the gas will
have potential for carbon formation by the (exothermic) Bou-
douard reaction (reaction (4». With high contents of CO, this
temperature may be sufficient to promote the reaction on tube
wall.
Temperature loss in the reformer out let system may ac-
cordingly bring the product gas below TB' i.e. into an area
where carbon is formed. These conditions may also result in
severe corrosion of the outlet system by metal dusting (23).
Studies have proven a strong retarding effect of sulphur
on metal dusting corrosion (23). This was also demonstrated in
the mono tube reformer (9) when operating on non-SPARG, but se-
vere conditions. The lack of sulphur in the product gas re-
sulted in a substantial formation of carbon in the reformer
outlet hairpin. However, the carbon formation was eliminated
by adding sulphur to the ou~let hairpin.
The sulphur present in the SPARG product gas inhibits the

formation of carbon in the outlet system, even if the operating
conditions predict that carbon formation is possible.
6 REGENERATION OF COKED CATALYSTS

Rapid formation of whisker carbon can result in break-down
(spalling) of the catalyst and accumulation of carbon. The spal-
@ProcessEng
ling can result in break-down of the outer part of the particle

into powder. The result is an increasing pres sure drop and the
development of hot tubes. However, if whisker carbon is formed
at a ve ry slow rate, significant amounts may build up in the
422
catalyst without harming the performance of the reformer (1).

The formation of pyrolytic carbon can result in coke de-
posits at the tube wall and consequently in a reduced heat
transfer coefficient, which may cause the development of a
"hot band". The catalyst particles can be encapsulated, which
results in increased pres sure drop. However, the encapsulation
does not harm the catalyst particles (1,24).
Therefore, it is possibie in many situations to regenerate
the catalyst and to re-establish satisfactory performance of
the reformer. The whisker carbon is highly reactive and may be
gasified by means of hydrogen, carbon dioxide, and steam with
nickel as catalyst. Steam is the most effective gasifying agent.
o -1
(-6H 298 = -132 kj mol ) ( 16 )
Non-aged whisker carbon may be removed simply by increasing

the steam-to-carbon ratio, at the same time maintaining the
catalyst in a reduced state. Low pres sure favours reaction (16).
The whisker structure will collapse with time and be con-
verted into a more dense layer of carbon, which may be difficult
to remove under reducing conditions. Regeneration in steam can
be carried out at temperatures around 600-700 o C or higher, de-
pending on the ageing of the deposits. However, with the addi-
tion of a small percentage of air, the burn off of carbon is
easily performed at a temperature above ca. 4S0 0 C. The addition
of air should be well controlled to minimize the local over-
heating of the catalyst caused by the heat produced from oxi-
dation of the nickel and the carbon.
In an industrial plant, the progress of the regeneration
can eas ily be followed by analysis of the exit gas from th2
reformer. An example (1) is shown in Fig. 14. The addition of
air is increased as the production of CO 2 decreases. In this
way, overheating can be controlled.
2.0 r----------------.., 10
CO z Ivol.%
~ Air in steom I vol.% .--- 8
C) 1.5 I
r-.J
> ~
"- "-
(l)
"'O 5 E
D
x
o
"'O
lO (l)
u;
r- I. .<:=
C
C) I '-
LJ
L... I «
D
0.5 I
LJ
r----' 2
_ _ _ _ ..JI
O
00 2 3 l. 5 6 7
Time Ih
@ProcessEng
Fig. 14. Regeneration for carbon formation in industrial

reformer. Analyses of dry exit gas (1).
423
REFERENCES
1. Rostrup-Nielsen, J .R. In "Catalysis, Science and Technology"
(Anderson, J.R. and Boudart, M. eds.), Springer, Vol. 5,
Berlin 1983, Chap. 1.
2. Topp-Joergensen, J. and Rostrup-Nielsen, J.R. Oil & Gas
J., 84 (20), 68 (1986).
3. StahY-;- H., Rostrup-Nielsen, J.R., and Udengaard, N.R.,
Proc. 1985 Fuel Cell Seminar, Tucson, Arizona, Courtesy
Assoc., Washington 1985, p. 83.
4. Rostrup-Nielsen, J.R. and Trimm, D.L., J. Catal. 48, 155
(1977). -
5. Baker, R.T.K. and Harris, P.S. In: "Chemistry and Physics
of Carbon", Vol. 14 (Walker, P.L. Jr. and Thrower, P.A.
eds.), Dekker, New York 1978, p. 83.
6. Alstrup, I., J. Catal. (in press).
7. Butt, J.B., Adv. Chem. Ser. 109,259 (1972).
8. de Blieck, J.L. and Groosens-;-A.G., Hydrocarbon Process.
50 (3) 76 (1971).
9. Dibbern, H.C., Olesen, P., Rostrup-Nielsen, J.R., Toettrup,
P.B. and Udengaard, N.R., Hydrocarbon Process., ~ (1), 71
(1986).
10. TopsØe, H. and Rostrup-Nielsen, J.R., Sean. J. Metallurgy
8, 168 (1979).
11. Wise, H., McCarty, J. and Oudar, J. In "Deactivation and
Poisoning of Catalysts" (Wise, H. and Oudar, J. eds.),
Dekker, New York 1985, Chap. 1.
12. Bartholomew, C.H., Agrawal, P.K. and Katzer, J.R., Advan.
Catal. 31, 131 (1982).
13. Alstrup~I., Rostrup-Nielsen, J.R. and Roen, S., Appl.Catal.
1,303 (1981).
14. Rostrup-Nielsen, J.R., J. Catal. 85, 31 (1984).
15. Andersen, N.T., Topsøe, F., Alstrup, I. and Rostrup-Nielsen,
J.R., J. Catal., 104, xxx (1987).
16. Rostrup-Nielsen, J.R. and Alstrup, I., Proc. "10th North
Amer. Catalysis Soc. Meeting", San Diego, May 1987, Else-
vier, Amsterdam (in press).
17. Onuferko, J.H., Woodruff, D.P., and Holland, B.W., Surfaee
Sci., 87, 357 (1979).
1 8. De mu t h-,-J . E. a n d I b a c h, H., S u r f a c e S c i. 7 8, p. 2 3 8 (1 9 7 8) .
19. Ramanathan, R., Quinlan, M., and Wise, H.~Chem. Phys.
Lett. 106, 87 (1984).
20. Bernardo, C.A., Alstrup, I. and Rostrup-Nielsen, J.R.
J. Catal., 96, 517 (1985).

21. Bernardo, C~., Alstrup, I. and Rostrup-Nielsen, J.R.
Proc. "17th Biannual Carbon Conferenee", Worchester,
July 19-24, 1987.
22. Mol, A., Hydrocarbon Process., 53 (2), 115 (1974).
23. Barnes, J., Corish, J., Franck,F., and Norton, J.F.,
Oxid.Met., 24,85 (1985).
@ProcessEng
24. Rostrup-NielSen, J.R. This monograph.

424
LIST OF SYMBOLS
a carbon activity
c
o
a carbon activity with no gas phase reactions
c
s
a carbon activity at steady state (with gas phase
c
H enthalpy
k exposure number
k k rate constant for carbon formation and reverse
c' -C
reaction
k rate constant for gasification
g
K equilibrium constant
P
K adsorption constant for steam
w
p partial pressure
p probability
q weighting factor
r reaction rate
r rate of carbon formation
c
r rate of gasification
g
r reaction rate of non-poisoned catalyst
o
R passivation range
P
T temperature
TB carbon limit temperature for reaction (4).

Fixed gas composition. C for T<T B
T catalyst temperature
c
T catalyst temperaeure at tube wall
cw
T catalyst mean temperature
cm
T CM carbon limit temperature for reaction (5).
Fixed gas composition. C for T>T M
Z distance in tube
a,a' numbers
es sulphur cover age
@ProcessEng
CARBON DEPOSITION IN STEAM-CRACKING
J.L. FIGUEIREDO, M.L.G.M. PINTO
Faculdade de Engenharia, Porto, Portugal
l. INTRODUCTION
The pyrolysis of paraffinic feedstocks to produce olefins in the steam-
-cracking process is ~ecompanied by the formation of tars and "coke", which
accumulate on the reactor walls. As aresult, the pressure drop increases
and the heat transfer accross the wall decreases. To maintain the heat flux,
tube skin temperature must be increased, but eventuaily the process has to
be stopped and the surfaces decoked, by gasification of the carbonaceous
deposits (l).
Figure l shows a typical steam-cracking reactor/furnace unit. The hydro-
carbon feedstock (naphtha,ethane or gasoil) and steam are preheated in
the convection zone of the furnace and then pass through the coil in the
radiant zone where pyrolysis occurs at temperatures ranging from about
900 K at the inlet to 1100-1170 K at the exit. The thermal reactions are
rather unselective and produce the desired olefins among a variety of
other products. Olefins are very reactive, hence the effluent has to be
cooled very rapidly in the transfer-line heat exchanger (T.L.E.), placed
just af ter the furnace.
The materials of construction of the steam-cracking reactor tubes can
have a significative effect on the course of the reaction. Thus, the re--
actor wall can influence the cracking reactions, can act as a collecting
surface for carbon deposition or can catalyse the formation of carbon (2).
Heat resistant Fe-Ni-Cr alloys (,>lith other minor components) are generally
used, operating at skin temperatures of 1220-1300 K (3,4).
In the present chapter, coke deposits found in steam-cracking are des-
cribed, and the effect of the stat e of a Fe-Ni-Cr alloy surface on the
rates of carbon deposition from the pyrolysis of propene is investigated.
2. EXPERIMENTAL METHODS
Metal surfaces and coke deposits were examined in a JEOL JSM-35C
scanning electron microscope (SEM), and microanalysis performed with the
JEOL JSM-35 and TRACOR TN-2000 wavelength and energy dispersive X-ray
attachments (EDAX).
Kinetic data were determined in a microbalance flow reactor.
Sample foils of about 4 cm L geometric area and 0.17 mm thickness were
cut from a section of a steam-cracker tube made up of the alloy 36XS.
Identical specimens of Fe, Ni, Cu and HK40 alloy were also used for compa-
rison. The composition of the alloys is shown in Table l. The specimens
@ProcessEng
were suspended from a microbalance (C.I.Electronics Mk 2B) into a quartz

reactor, and the sample weight recorded continuously. A mixture of C3H6+N2
was passed over the sample with a flow rate of 0.16 rillllols- 1 , and the tempe-
rature controlled to within ± 2K. The temperature was varied frOld 1073-
-1173 K and the concentration of propene from 10-50% (by volume). Gasifi-
cation of the deposits was carried out with C02, H20 or air.
425
L. F. Melo et al. (eds.), Fouli/Jg Science and TechfUJlogy, 425-434.

426
Ai r ...._---+--::::>"
Hyd roca rbo n ...
Steam
.t:==:t::=::
l
Convect ion
zone
.---'-11.
Radiant
Fuel
zone
FURNACE
FIGURE 1. Schematic representation of the steam-cracker
TABLE 1. Compositions of the Fe-Ni-Cr alloys used (wt %)
Alloy Ni Cr c Nb w Si Mn
HK40 20.5 24.5 0.12 0.55 1.8

36XS 34.1 25.9 0.43 1.11 1. 52 1.6 1.2
3. RESULTS
3.1. Examination of coke deposits from steam~cracking
Coke deposits are forrned both in the coil and ~n the T.L.E .. Typical
samples shown in Figure 2 were collected a) from the coil; b) from the
inlet plate of T.L.E.; c) from inside the tubes of the T.L.E •.
Examination of the sample from the coil by SEM!EDAX showed the presence
of numerous filaments (Figure 3a) and significant amounts of metals (Figure
3b) on the surfaee originally exposed to the gas phase.

The deposit removed from the plate of the TLE showed a globular struc-
ture (Figure 4a) consisting of concentric layers of carbonaceous material
(Figure 4b). The deposit removed from the tubes contained regions of glo-
bular (Figure 4c) and sooty material (Figure 4d) where some filaments were
also observed.
Figure 5 shows the etched cross-section of a steam-cracker tube. The
@ProcessEng
inner surfaee is disrupted by intergranular fissures and the specimen is

carburized throughout its entire thickness, with the exception of a subsur-
face layer depleted in chromium and free from carbide precipitation.
427
Figure 2 - Coke deposits: from the eoil (right); from the TLE inlet plate
(top left) and tubes (bottom left). Seale=3 em
,Fe
,,
-1
"
""
""
""
S '""
ru
,i~
'::::11"'::::::'
er il:,
l::: Fe
@ProcessEng
,lHlHH::H::::::::!:,,:::: H: I " , :i l:::

,,::::::::::::::::::::::::::::::::::::::::,:::,1':1111
""1111111111'''''11111111111111111111111111111111111111111
::,
1111
er iim 11111
:::: Ni
b)
11111111111111'""111111\11111111111111111111111111111111"""'1111111 '" III'"
111111111111111111111111111111111111111'''''''''''"111111111''"11'''''"1'"'' ''''"
111111111111111111""11111111111111111111111111111""11111111111"1111111"""""'""""""'''' ,.,
""1
'''111111111111111''"1111111111111111111111111111''''''''1111111'"111'''111'"'"11111111''"11111111111"'" I""
"""""11111111'"'"1111111111111'"1111111111""""""'"11'""'111111111"""1IIIIIIIHI"''''''II''''''''''''''
"""""11111'111'""111111"""""11111111"""""""111111111""111,,,,,,,,,",",,"1'11,,,11,",",,,,,,,,,,,,,
'11""111111111111\11'1111'1111111111111111111'"11111111111",1"'''"1111111'"1111'""'"H'UIIIIIII',"IIIIII'I,II"!!"·"
'~'~~~'!!'!'II'flllll"II'I'II"'I"I'IIIIII'IIIII'I'I'"II'I'IIIIIIIIIII_IIIIIIIIIIII"~III'III"'IIIIII'III 1111111"1111"""'"
Figure 3 - Coke deposit from the eoil: a) SEM; b) EDAX

@ProcessEng
.joo
N
00
Figure 4 - Aspects of coke deposits from the TLE inlet plate (a,b) and tubes (c,d)
429
Figure 5 - Etched cross section of Figure 6 - Pyrolytic carbon deposit

a steam-cracker tube on copper
6
co 3
E
-o
ClJ
+'
Ul
o 4
CO-
ClJ
-o
c 2
o
..o
s-
ro
u 2
o 15
Time (min)
@ProcessEng
Figure 7 - Carbon deposition from 20% C3H6 + 80% N2 (by volume) on the
alloy 36XS at 1083 K (1), 1120 K (2) and 1171 K (3) and on the
a110y HK40 at 1104 K (4)
ri = initial rate; r s = final asymptotic rate
430
3.2. Carbon deposition

The carbon deposits obtained from propene pyrolysis on the alloy 36XS
were similar to those obtained over copper. and consisted of droplets more
or less joined together (Figure 6).
The amount of carbon deposited on the alloy 36XS was found to increase
linearly with time. i.e .• the rate of deposition was constant from the
beginning of the run (Figure 7). This was also observed with Ni and Cu. but
not with Fe or the HK40 alloy. With these specimens. the rate of deposition
was found to decrease from an initial value ri. to a final asyrnptotic rate
r s • as also shown in Figure 7. Deposition on previously coked foils pro-
ceeded at constant rate. with the same value as the r s determined on fresh
foils at the same temperature. The initial and final rates of deposition
measured at 1123 K or. different materials are shown in Table 2.
First order kinetics and an activation energy of 235 ± 15 kj/mol were
determined for carbon formation on the alloy 36XS.
The specimens were also submitted to pre-treatment under different con-
ditions. and examinedby SEM/EDAX before carbon deposition. A chromium
oxide layer was observed on top of the untreated surfaces (Figure 8); the
layer was thiner af ter 2 hours treatment in hydrogen at 973 K. and was not
found on samples pre-treated in steam at 1123 K for 8 hours. In this case,
crystals of FeO (Figure 9a) and needle-like formations rich in Cr and Si
(Figure 9b) were observed on the surface. The rates of carbon deposition
measured on these specimens are compared in Table 3.
TABLE 2. Initial (ri) and final (r s ) rates of carbon deposition at 1123 K

(flg. s-1.cm- 2)
Surface r. rs
1.
Fe 1. 90 0.45
Cu 0.42 0.42
Ni 0.40 0.40
36XS 0.45 0.45
HK40 1.08 0.47
TABLE 3. Rates of carbon deposition (flg.s-l.cm-2) on the alloy 36XS at

1108±5 K
Pre-treatment r. r
1. s
None 0.56 0.54

H2(2h)973 K 0.72 0.52
@ProcessEng
H20(8h)1123 K 1. 61 0.42
431
Figure 8 - Chromium oxide surfaee layer an the alloy 36XS

@ProcessEng
Figure 9 - Surfaee of the a110y 36XS af ter 8 honr treatment in H20 at

1123 K: a) FeO crysta1s; b) Cr and Si rich growths
432
3.3. Coking-decoking cycles

The effect of coking-decoking cycles was investigated by carrying out
successive deposition runs over the same sample, with intermediate removal
of the deposits by gasification. Both the initial and asymptotic rates of
carbon formation were determined.
Table 4 shows the results when the gasifying agent was C02; similar re-
sults were obtained with steam. Table 5 shows the results when air was
used to gasify the deposits. Examination of the specimens af ter gasifica-
tion with air showed the presence of an extensive chromium oxide layer over
the surface.
TABLE 4. Rates of carbon formation (Vg.s-1.cm-2) in deposition-gasification

cycles.
Deposition from 20% C3H6 at 1133 K
Gasification with 100% C02 at 1233 K
r. r
1 S
1st deposition 0.40 0.40

2nd deposition 0.64 0.45
3rd deposition 0.89 0.51
-l -2
TABLE 5. Rates on carbon formation (Vg. s .cm ) in deposition-gasification
cycles
Deposition from 20% C3H6 at 1133 K
First gasification with 100% air at 1233 K
Second gasification with 20% air at 1173 K
r. r
1 s
1st deposition 0.39 0.39

2nd deposition 0.33 0.37
3rd deposition 0.32 0.27
4. DISCUSSION AND CONCLUSIONS

As described in section 3, "coke" deposits are mixtures of materials
with different structures and origins. They may be classified by reference
to their mechanisms of formation as pyrolytic carbons (including soot and
surface carbon), tars and catalytic carbons (5).
Pyrolytic carbons and tars are formed at high temperature by free radi-
cal chain reactions, and they will deposit on any available surface, cata-
@ProcessEng
ly tic or inert. The detail ed mechanism of pyrolytic carbon formation has

been described in a previous chapter (6).
Catalytic carbons are produced at much lower temperatures, by heteroge-
nous surface reactions, the nature of the surface determining the nature
of the carbons formed. Carbon filaments carrying metal particles at their
tips are obtained on Fe, Ni, and Co by a mechanism which involves dissolu-
433
tion and diffusion through the metal, as discussed before (7). Conditions
that favour the formation of this kind of carbon deposit on the reactor
walls are particularly harmful because:
a) Carbon filaments aet as a filter, retaining greater amounts of gas-phase
carbon and tars (8);
b) Filamentous carbon deposits disrupt the surfaee by removing metal par-
ticles which are carried away with the filaments; the disrupted surfaee
will enhance coking in the folIowing cycles (9);
c) Dissolution and diffusion of carbon will also lead to carburization of
the alloy; upon subsequent decoking, removal of carbon from the grain boun-
daries ean lead to extensive metal dusting (10).
The kinetic results presented in Figure 7 and Table 2 show that the
alloy 36XS behaves as an inert surfaee while Fe and HK40 catalyse the for-
mation of carbon in the initial stages of the reaction. This effect disap-
pears when the surfaee of the specimen is coated with a film of carbon;
then the rate of deposition becomes similar to that obtained over inert
surfaces, and pyrolytic carbon is formed alone, at rate r s . This is confir-
med by the aspe et of the deposits and further supported by the close
agreement between the kinetic parameters determined in this study and those
reported for carbon formation from propene on a carbon substrate (11).
Copper is known to be an inert metal with respect to carbon deposition
(12) and so ri=r s (Table 2). On the other hand, nickel is a very active
catalyst for filamentous carbon formation (13,14). However, under the condi
tions of Table 2, only pyrolytic carbon was formed on nickel and ri=rs -
a1so. This is eas ily explained since it is known that the rate of carbon
deposition an nickel shows a maximum and a minimum with temperature (13,15)
and that the presence of hydrogen has opposite effects on the rates of pyro
ly tic and catalytic carbon formation (6,15). Thus, high temperatures and na
hydrogen in the feed favour pyrolytic carbon formation on nickel.
The behaviour of the alloy 36XS may now be explained in terms of the
state of its surfaee (16):
-when a chromium oxide layer is present on the surface, the alloy is passi-
vated, and only pyrolytic carbon is deposited (ri=r s );
-when the surfaee is enriched in iron and the chromium oxide layer is des-
troyed, there is catalytic activity for carbon formation, and ri>r s '
The results of coking-decoking cycles are consistent with this explana-
tion:
-In the first cycle, ri=r s ; in the subsequent cycles, ri>r s if the interme
diate gasification is carried out with C02 or H20; or ri~rs' if the depo~
sits are gasified with air.
It may be concluded that carbon formation on the alloy 36XS at tempera-

tures of l123±50 K is exclusively of pyrolytic nature, provided that a
chromium oxide layer is present on the surface. Reaction conditions which
destroy this protective layer promote the formation of filamentous carbon
in the initial stages.
@ProcessEng
ACKNOWLEDGEMENTS
The authors are indebted to Jose M.Orfao and Carlos M.Sa for their as-
sistance. This work was carried out at Centro de Engenharia QUlmica (INIC).
434
REFERENCES
l. Trirnm, DL: Coke Formation and Gasification in Refineries, in Carbon and

Coal Gasification. J.L.Figueiredo, J.A.Moulijn (eds.), Martinus Nijhoff,
Dordrecht, pp.523-54l,1986.
2. La Caya, AI, Bernardo, CA, Trirnm, DL: Studies of Deactivation of Metals
by Carbon Deposition. Carbon,20(3),2l9-223,1982.
3. Mol, A: How Various ParameterS-Affect Ethylene Cracker Run Lengths:
Hydrocarbon Processing,53(7),115-ll8,1974.
4. Schillmoller, CM, van den Bruck, UW: Furnace Alloys Update. Hydrocarbon
Processing,63(12),55-59,1984.
5. Figueiredo,-YL: Gasification of Carbon Deposits on Catalysts and Metal
Surfaces. Fuel,65,1377-l382,1986.
6. La Caya, AI: Droplets and Filaments: on the Fouling of Metal Surfaces by
Carbonaceous Material from Hydrocarbon Gases above 850 oK. This monograph
7. Bernardo, CA: The Fouling of Catalysts. This monograph.
8. Graff, MJ, Albright, LF: Coke Deposition from Acetyrene, Butadiene and
Benzene Decompositions at 500-900 °C on Solid Surfaces. Carbon,20(4),
319-330,1982. --
9. Figueiredo, JL, Orfao, JJt1: Morphology and Reactivity of Coke Deposits
on Metal Surfaces. Sprechsaal,119(12),1139-1142,1986.
10. Trirnm, DL: Control of Coking. Chem.Eng.Process.,18,137-148,1984.
ll. Hoffman, WP, Vastola, FJ, Walker Jr., PL: Pyrolysis of Propylene over
Carbon Active Sites - I. Kinetics. Carbon,23(2),151-l61,1985.
12. La Caya, AI: Pyrolysis and Thermal Hydrogasification of Hydrocarbons.
Ph.D.Thesis, Univ.London, 1977.
13. Lobo, LS, Trirnm, DL, Figueiredo, JL: Kinetics and Mechanism of Carbon
Formation from Hydrocarbons on Metals. Proc. 5th Int.Congress on
Catalysis, 11iami Beach, Florida, 1972, North-Holland, Amsterdam, vol.2,
pp. 1125-1137, 1973.
14. Baker, RTK, Barber, MA, Harris, PS, Feates, FS, Waite, RJ: Nucleation
and Growth of Carbon Deposits from the Nickel Catalyzed Decomposition of
Acetylene. J.Catal.,26,5l-62, 1972.
15. Figueiredo, JL: Carbon Formation and Gasification on Nickel, in Progress
in Catalyst Deactivation, J.L.Figueiredo (ed.), Martinus Nijhoff, The
Hague, pp. 45-63, 1982.
16. Jackson, PRS, Young, DJ, Trirnm, DL: Coke Formation on and Removal from
Metals and Heat-Resistant Alloys under Steam-Cracking Conditions. J.
Mater.Sci.,~, 4376-4384, 1986.
@ProcessEng
Chapter 8
Design and Operation af Heat Exchangers
@ProcessEng
BASIC RELATIONSHIPS FOR HEAT EXCHANGERS AND IMPACT OF FOULING ON DESIGN
S. Kakac and Ajay K. Agrawal

Department of Mechanical Engineering
University of Miami
Coral GabIes, Fl 33124, USA
1. INTRODUCTION
Heat exchanger is a device in which heat is transferred from a hot
fluid to a cold fluid. In its simplest form the two fluids mix and leave
at an intermediate temperature determined from the conservation of energy.
This device is not trulyaheat exchanger but rather a mixer. In most ap-
plications, the fluids do not mix with each other but transfer heat
through a separating wall which takes on a wide variety of geometries.
Three categories are normaIly used to classify heat exchangers. These are:
(a) recuperators
(b) regenerators
(c) direct-contact apparatus.
Recuperators are direct transfer type heat exchangers in which the
heat transfer occurs between two fluid streams at different temperatures,
separated by a thin solid wall (e.g. parting sheet, tube wall). Heat
transfer occurs by convection from the hotter fluid to the separating wall
surface, by conduction through the separating wall and by convection from
the separating wall surface to the cooler fluid; if one of the fluids is a
radiating gas, the thermal radiation also plays an important role in heat
exchange between the two fluids. The recuperators include air heaters,
economizers, evaporators, condensers, steam boilers, dry cooling towers,
etc.
Regenerators are heat exchangers in which the hot and the co Id fluids
flow through the same surface at different time intervals. The surface of
the regenerator first receives heat from the hot fluid and re leas es it
later to the cold fluid. Thus the proces s of heat transfer is transient,
i.e., temperature of both, the heating sur face and the fluids vary with
time during the heat transfer process. Both recuperators and regenerators
are surface type heat exchangers.
In direct-contact apparatus, the heat is transferred by complete or
partial physical mixing of the two fluid streams. Hot and cold fluids
entering separately in such an exchanger leave as a single mixed stream.
Applications include jet condensers, cooling towers of thermal and nuclear

power stations etc.
Some heat exchangers, such as those used in nuclear reactors,
electrical heaters include an internal heat source. A cooling fluid is
used to remove the heat energy liberated in the system. A detailed clas-
sification of heat exchangers is given by Shah [1].
In this work, the basic heat transfer relations for sizing and rating
two fluid recuperators, and the effect of fouling on heat transfer and
@ProcessEng
pressure drop are discussed. The term heat exchanger is used to designate
a recuperator. In obtaining expressions for the basic design methods, the
folIowing assumptions are made:
(a) The heat exchanger operates under steady-state, steady flow
conditions.
(b) Heat transfer to the surroundings are negligible.
437

438
FI~fJ=-_=_---=- 3 -
It
0
Fluid-I
( b)
Fluid-I
Fluid-2
inside
"----.:::....:,-J ..... tubes
(d)
(c)
FIGURE 1. Heat exchanger classification according to flow arrangements.

(a) parallel-flow (b) counterflow (c) single-pass crossflow (both fluids
@ProcessEng
unmixed) (d) crossflow heat exchanger (cold fluid unmixed, hot fluid
mixed).
439
(c) There is no heat generation in the heat exchanger.

(d) In counterflow and parallel-flow heat exchangers, the tempera-
ture of each fluid is uniform over the flow cross section; in
crossflow exchangers each fluid is considered mixed or unmixed
at the cross section depending upon the specifications.
(e) If there is a phase change in one of the fluid streams flowing
through the heat exchanger, it occurs at a constant pressure.
This is an idealization of a two-phase flow heat exchanger.
(f) The specific heat at constant pressure for each fluid is con-
stanto
(g) Longitudinal heat conduction in the fluid and the wall is neg-
ligibIe .
(h) The overall heat transfer coefficient between the fluids is
constant throughout the heat exchanger including the case of
phase change.
2. ARRANGEMENT OF FLOW PATH IN HEAT EXCHANGERS

A recuperator-type heat exchanger is classified according to the flow
direction of the fluid streams and the number of passes made by each fluid
as it passes through the heat exchanger. The heat exchangers may have the
folIowing patterns of flow:
(a) Parallel-flow with both fluids flowing in the same direction
(Fig. la).
(b) Counterflow with the two fluids flowing parallel to one another
but in opposite directions (Fig. Ib).
(c) Crossflow with the two fluids crossing each other (Fig. IC,d).
(d) Mixed flow where the fluids flow in parallel, in counter (Fig.
2a,b) and in multiple crossflow (Fig. 2c) in different parts of
the heat exchanger.
Shell-side fluid
Shell-side fluid
I ~~~~-
~~I~ _M'-';d.
fluid
(a ) ( b)
Shell-side fluid
I ~~~~~-
L_2-===C===I:===:I:~=f=1 -
i IJ
Tube -side fluid
@ProcessEng
( C)
FIGURE 2. Multipass and multipass crossflow arrangements. (a) 4-pass

tube, 2-pass shell (b) 6-pass tube, 3-pass shell (c) 2-pass tube, baffled
single-pass shell shell-and-tube heat exchangers.
440
3. BASIC EQUATIONS IN DESIGN

In addition to the basic heat transfer equations, the complete design
of a heat exchanger requires structural and economical considerations. The
purpose of the thermal analysis given here is to determine the heat trans-
fer surfaee area of the heat exchanger (sizing problem) and to conduet the
performance evaluation of a heat exchanger (rating problem; when the heat
exchanger is available, and it is necessary to find out the heat transfer,
pressure loss and outlet temperature of both fluids).
The temperature distribution in usual fluid-to-fluid heat transfer
proces ses is shown in Fig. 3 for various flow path arrangements. Referring
to Fig. 3, counterflow heat transfer with the two fluids flowing in op-
posite directions is shown as proces s (a), parallel-flow heat transfer
with the two fluids flowing in the same direction is shown as process (b),
heat transfer with the cold fluid at constant temperature (evaporator) is
shown as process (c), and heat transfer with hot fluid at constant tem-
perature (condenser) is shown as process (d). Besides the flow arrange-
ment, the temperature distribution depends upon the heat capacity ratio
(mc ) of the fluids.
p
r
T T
lIT,
l T
r
liT,
Thz j
T
lIT2
l
TC2
lIT2
Te
~ TCI
O --l dA ~ O --l dA ~ L
Surfaee area. A L Surface area. A
T T
Thi Thi
Thz
TCI TC1
TCI
@ProcessEng
O O
Surfoce orea. A L Surface area. A L
FIGURE 3. Fluid temperature variation in parallel and counter flow,

evaporator and condenser type heat exchangers.
441
For an open system under the steady-state conditions, with negligible

potential and kinetic energy changes, the change in enthalpy of one of the
fluid streams is determined by the energy balance (Fig. 4):
5Q = rn. di (1)
where rn. is the mass flow rate, i is the specific enthalpy and 5Q is
the rate of heat transfer to the fluid. Integration of Eq. (l) gives:
Q (2)
where the subscripts l and 2 designate the inlet and the outlet
values, respectively. Equation (2) holds for all the processes shown in
Fig. 3. Note that Q is negative for the hot fluid. Assuming negligible
heat transfer between the exchanger and its surroundings, the integration
of Eq. (l) for hot and cold fluids gives:
(3)
and
(4)
where the subscripts h and c refer to the hot and the cold fluids,
respectively. If the fluids do not undergo a phase change and have con-
stant specific heat (di = c dT), Eqs. (3) and (4) ean be written as:
p
Q (5)
and
Q (rn. c p ) c (T c 2- T l)
c
(6)
Heat transfer
surfaee area
@ProcessEng
FIGURE 4. Overall energy balances for the hot and cold fluids of a two
fluid heat exchanger.
442
As can be seen from Fig.3, the temperature difference between the hot
and the co Id fluids, !'.T = (T h - T ~, varies along the heat exchanger.
Therefore, in the heat transfer analysis of heat exchangers, it is con-
venient to establish an appropriate mean temperature difference between
the hot and the cold fluids such that the total heat transfer rate, Q, be-
tween the fluids can be determined from the folIowing equation:
(7)
where A is the total heat transfer surface area and U is the average
overall heat transfer coefficient based on A.!'.T is a function of fluid
m
inlet and outlet temperatures. A specific form of !'.Tm must be obtained.
Equations (S), (6) and (7) are the basic equations for thermal
analysis of a heat exchanger under the steady state conditions. If the
heat transfer rate, Q, is known from Eq. (S) or (6), then Eq. (7) is used
to calculate the heat transfer surface area, A. Hence, the problem of cal-
culating the heat transfer surface area comes down to determining the
overall heat transfer coefficient, U, and the mean temperature difference,
!'.T .
m
4. OVERALL HEAT TRANSFER COEFFICIENT

The overall heat transfer coefficient for a single, smooth, clean
plain wall can be written as:
U A = (8)
where Rt is the total thermal resistance to heat transfer between the two
fluids and t is the thickness of the wall; hi and h o are the heat trans-
fer coefficients for the inside and the outside flows, respectively.
For single, smooth, clean tubular heat exchanger the overall heat
transfer coefficient is given as:
U A
o o
U.A.
~ ~
(9)
Most heat exchanger surfaces tend to acquire an additional heat

transfer resistance which increases with time. This mayeither be a thin
surface oxidation layer or, at the other extreme, a thick crust deposit,
such as in steam condensers using sea water. This effect can be taken into
consideration by introducing an additional thermal resistance, termed as
the fouling resistance, Rs ' The fouling resistance depends upon the tem-
perature level, fluid velocity, sur face type and the length of service of
the heat exchanger [2-4]. We de fine a scale coefficient of heat transfer,
h s ' in terms of thermal resis~ance of the scale as:
!'.T
s
@ProcessEng
R (10)
s Q
where A is the heat transfer surface area before the scaling began, and
!'.T s is the temperature drop through the scale. Rf l/h s is termed as the
fouling factor (i.e., unit fouling resistance).
443
We now eonsider the heat transfer aeross a heat exehanger wall whieh
is fouled by deposit formation on both the inside and the outside sur-
faees. The total thermal resistanee, Rt , ean be expressed as:
(11)
The overall heat transfer eoeffieient depends on whether it is based

on the eold or the hot side surfaee area, sinee Uo~ U i if Ao~ Ai. The wall
resistanee, Rw ' is obtained from the following equations:
tikA for a plane wall (12a)

R
w
{ for a tube wall (12b)
Fins are often added to the surfaees exposed to either of the fluids.
By inereasing the surfaee area, the fins reduee the resistanee to eonvee-
tion heat transfer. A separating wall may be finned on one or both sides
(Fig.5). The heat transfer takes plaee from the fins (subseript f in the
equations that follow) as well as from the unfinned portion of the wall
(subseript u). Introdueing the fin effieieney, ryf' the total heat transfer
ean be expressed as:
Q (13 )
Using hu~ hf~ h, and rearranging Eq. (13), we get:
Q h A [1 - (14)
Fin
Fin surfaee area , Af

_-----Unfinned area , Au
@ProcessEng
FIGURE 5. Finned Wall.

M4
or
(15)
where ryo [l-(l-ryf)Af/A] which is calle d the overall surface efficiency,

and A = Au + Af.
As seen from Eq. (15), the thermal resistance at the finned surface
is l/ryoh A ; this is the combined surface resistance of the finned and the
unfinned area.
Therefore, the overall thermal resistance to the heat transfer is
given by:
l l Rfi Rfo l
ij~A~ ---h--A-- + R + A + ---A-- + -ry--A--h-- (16)
ryo{~ { {
~ ~
W ·'oi i
fi ~
·'00 o 00 o o
~ ~
Contact resistance may be finite between the tube and the fin or be-
tween the plate and the fin. In such a case, the contact resistance terms
can be added in Eq. (16).
In heat exchanger applications, the overall heat transfer coefficient
is usually based on the outer surface area (cold or hot side). Eq. (16)
can be represented in terms of the overall heat transfer coefficient based
on the outside surface area of the wall as:
uo (17)
The expressions of ryf for a variety of fin configurations are avail-

able in the literature [5]. For a straight or pin fin of length, L, and
uniform thickness, C, having an adiabatic tip, the fin efficiency is given
by:
tanh(ml)
--mI---- (18)
with m = J2h/ck f (19)
For unfinned, tubular heat exchanger of Figs. (la, b) and 2, Eq. (16)
reduces to:
uo (20)
Therefore, the overall heat transfer coefficient may be determined

from the inside and outside heat transfer coefficients, fouling factors
and geometric parameters.
4.1 Order of Magnitude Df Thermal Resistances

The order of magni tude and the range of heat transfer coefficient, h,
@ProcessEng
for various flow conditions are given in Table l.

Example l. Determine the overall heat transfer coefficient for a 3
mm thick steel plate (k=SO W/mK) and the following liquid flow and fouling
conditions:
2 2 2
hi = 1800 W/m K, h o = 1250 W/m , Rfi = 0.0002 m K/W
445
TABLE 1. Order of magni tude of heat transfer coefficient, h
2
Fluid h, W/m K
Gases (Natural convection) 5-25

Flowing Gases 10-250
Flowing Liquids (non-metal) 100-10,000
Flowing Liquid metals 5,000-250,000
Boiling Liquids 1,000-250,000
Condensing Vapors 1,000-25,000
For a flat plane wall with fouling only on one side, Eq. (16) reduces to:
l
U (21)
Therefore, we get:
1
U ~ 1800
1
+ 0.0002 +
0.003 +
--50-
_l __
1250
0.00056 + 0.0002 + 0.00006 + 0.0008
In this example, none of the resistances is negligible.
Example 2. In example l, replaces one of the flowing liquid by flow-

ing gas (h o ~ 50 W/m 2K).
l l 0.003 1
U 1800 + 0.0002 + -50-- + 50
0.00056 + 0.0002 + 0.00006 + 0.02
In this example, only the gas side resistance is significant.

Example 3. In example 2, replace the flowing liquid by flowing gas

2
(hi ~ 25 W/m K).
l 1 0.003 l
U 25 + 0.0002 + -50-- + 50
@ProcessEng
Rt ~ 0.04 + 0.0002 + 0.00006 + 0.02
In this example, the wall and scale resistances are negligible.

446
5. LMTD METHOD FOR HEAT EXCHANGER ANALYSIS

Consider a simple counterflow or parallel-flow heat exchanger (Fig.
3a,b). The form of ~Tm in Eq. (7) may be determined by applying energy
balance to a differential element. From the differential form of Eqs. (5)
and (6) or from Eq. (l) the energy balance for adiabatic, steady-state
flow yields:
± (m c P ) c dT c (22a)
or
(22b)
where the hot fluid direction is taken as positive. C is the heat capacity
rate and (+) sign refers to the parallel flow. The heat transfer rate, 6Q,
across the heat transfer surfaee area, dA, may also be expressed as:
(23)
For counterflow exchanger, we get:
(24)
Substituting 6Q from Eq. (23) into Eq. (24), we obtain:
(25)
Integrating Eq. (25) over the length of the heat exchanger, for constant
U, Ch and Cc ' results
(26a)
or
(26b)
It is seen that the temperature distribution along the heat exchanger is

exponential. Furthermore, in a counterflow heat exchanger, the temperature
difference (Th-T c ) decreases in the direct ion of the flow if Ch < Cc ' but
increases if Ch > Cc (Fig. 6). Substituting Cc and Ch from Eq. (22) into
Eq. (26a) and solving for Q, we obtain:
@ProcessEng
Q U A (27)
or
447
T Cc<Ch I Cc = Cmin T
~r--------l TC1
Te
o Surfaee area I A
L o Surfaee area I A
L
FIGURE 6. Temperature variation for counterflow heat exchanger (a) Cc <

cc .
(28)
where ~Tl is the temperature difference between the two fluids at one
end of the heat exchanger and ~T2 at the other.
Comparison of the above expression with Eq. (7) reveals that the ap-
propriate average temperature difference between the hot and the cold
fluids, over the length of the heat exchanger is given by:
~Tl - ~T2
(29)
In(t;T~7t;T;)
which is called the log-mean temperature difference (LMTD). Accordingly,

the total heat transfer rate between the hot and the cold fluids, for all
single-pass flow arrangements shown in Fig. 3, is determined as:
(30)
For counterflow, with (mcp)h (mc ) , the LMTD is indeterminate

p c
since
For this case, it can be shown using L'hopital's rule that ~Tlm~ ~Tl~ ~T2.
Therefore:
@ProcessEng
(31)
Starting with Eq. (22), it can be shown that Eq. (28) is applicable for
parallel flow arrangement also. However, for the parallel flow heat ex-
changer, the end point temperature differences are defined as ~Tl ~ (T hi
Tc1 ) and ~T2 ~ (Th2 - Tc2 )·
448
For the same inlet and outlet temperatures, the log mean temperature
difference for the counterflow exceeds that for the parallel flow, i.e.
~Tl f > ~Tl f' The maximum temperature potential for heat transfer can
m,e m,p
only be obtained in a counterflow heat exchanger. Rence, the surface are a
required for a prescribed heat transfer rate is les s for the counterflow
than for the parallel-flow arrangement, assuming that the U is same. Also,
Tc2 can exceed Th2 for counterflow but not for parallel-flow.
5.1 Multipass and Crossflow Heat Exchangers

The LMTD obtained above is not applicable for the heat transfer
analysis of multipass and crossflow heat exchangers. The integration of
Eq. (23) for these flow arrangements is written as:
(32 )
where ~Tm is the true (or effective) mean temperature difference and it is
a function of fluid inlet and outlet temperatures. Generally ~Tm can be
obtained analytically in terms of the following quantities [6,7]:
(33)
with
p (34)
and
R (35)
where ~Tl f is the log-mean temperature difference corresponding to the

m,c
counterflow arrangement. P is the ratio of actual heat transfer to the
maximum possible heat transfer, i.e. the temperature effectiveness of the
heat exchanger. R is the ratio of the heat capacity rates of the hot and
the cold fluids.
For design purposes, Eq. (32) for multipass and crossflow heat ex-
changers is written as:
Q U A F ~Tlm,cf (36)
F is a nondimensional correction factor; it depends on the temperature ef-

fectiveness, P, the heat capacity rate ratio, R, and the flow arrangement:
@ProcessEng
F = .p(P,R flow arrangement) (37)
The correction factors in chart form have been prepared by Bowman,

Mueller and Nagle [7] for common multipass shell-and-tube, and crossflow
heat exchangers. In calculating P and R to determine F, it is immaterial
whether, the cold fluid flows through the shell or the tubes.
449
FIGURE 7. Temperature distribution in crossflow.
Generally, F is less then unit y for multipass and crossflow arrange-

ments; it is unit y for counterflow heat exchanger. It represents the de-
gree of departure of the true mean temperature difference from the LMTD
for the counterflow.
In a multipass or a crossflow arrangement, the fluid temperature may
not be uniform at a particular cross-section in the exchanger unless the
fluid is well mixed. For example, in crossflow, the hot and the cold
fluids may enter at uniform temperatures, but if there are channels in the
flow path to prevent mixing (Fig. lc), the exit temperature distributions
may be as shown in Fig. (7). If such channels are not present, the fluids
may be well mixed along the flow path and the exit temperatures nearly
uniform (Fig. ld). A similar stratification of temperature occurs in the
shell-and-tube multipass exchangers. A series of baffles may be required
if mixing of the shell fluid is to be obtained. Charts are available for
both mixed and unmixed fluids [6,8,9].
The preceeding analysis assumed the overall heat transfer coeffi-

cient, U, to be uniform throughout the exchanger. If U is not uniform, the
heat exchanger can be subdivided into sections. The heat transfer analysis
can be conducted by assuming a constant U in each subdivision.
6. E-NTU METHOD FOR HEAT EXCHANGER ANALYSIS

If the inlet or outlet temperatures of the fluid streams are not
known, a trial and error procedure should be applied for the LMTD method
in order to determine the value of LMTD which will satisfy the requirement
that the heat transferred in the heat exchanger [Eq. (7)] be equal to the
heat convected by the fluid [Eq. (5) or Eq. (6)]. To avoid the trial and
error procedure, the method of number of transfer units (NTU) based on the
concept of heat exchanger effectiveness may be used. The method is based
on the fact that the inlet or exit temperature differences in a heat ex-
@ProcessEng
changer depend on UA/C min and Cc/C h [see Eq. (26)].

Equations (3), (4) and (26) may be written in dimensionless form
resulting in the following dimensionless groups [6,10]:
(a) Capacity rate ratio:

450
(38)
where Cmin and Cmax are, respectively, the smaller and the larger of the
two heat capacities. C* O represents Cmin as finite and Cmax approach-

ing infinit y (condensing or evaporating fluid).
(b) Heat exchanger effectiveness:
€ ~ (39)
where Q is the actual heat transfer rate, and Qmax is the maximum pos-
sible heat transfer rate if an infinite heat transfer area were available
in a counterflow heat exchanger. The actual heat transfer for parallel and
counterflow heat exchangers is obtained from Eqs. (5) and (6) as:
(40)
The fluid which might undergo the maximum temperature difference,

(Thl-T cl ), has minimum heat capacity, Cmin . The maximum possibie heat
transfer is expressed as:
(4la)
or
(4lb)
which can be obtained only in a counterflow exchanger (Fig. 6). Therefore:
(42)
Equation (42) is valid for all heat exchanger flow arrangements.

For given € and O ,the actual heat transfer rate, Q, from Eq. (42)
'max
is:
Q ~ € (ffic ) . (Thl - T l) (43)

p m~n c
@ProcessEng
If the effectiveness of the heat exchanger and the fluid inIe t tem-
peratures are known, Eq. (43) provides an explicit expression for the heat
transfer rate through the heat exchanger.
451
(c) Number of transfer units:
NTU ~ ~-~ (44)

G •
ml.n
NTU designates the non-dimensional heat transfer size of the exchanger.
In the equations of the preceding section, assume that Gc > Gh . Hence

Gh Gmin and Gc Gmax With Eq. (44), Eq. (26) may be written as:
G •
(Thl - Tc2 ) exp [-NTU (± l - cml.~)] (45)
max
where (+) sign is for the counterflow and (-) sign is for the parallel
flow arrangement. With Eqs. (5), (6) and (42), Th2 and Tc2 in Eq. (45) can
be eliminated. Solving for €, we obtain, for counterflow:
(46)
If Gc < Gh (G c ~ Gmin , Gh ~ Gmax ) , the result is the same.

A similar analysis can be applied for parallel flow to obtain the
foliowing expression:
l-exp [-NTU(I+ Gmin/Gmax)]

----I-+c-~-7c------------- (47)
ml.n max
Two limiting cases are of interest:
NTU
€ ~
I+-NTU Counterflow (48)
l -2 NTU)
€ ~
"2(l-e Parallel Flow (49)
(b) Cmin/Gmax ~ 0, (Figs. (3c, d), boiler and condenser)

€ ~ l-e -NTU for parallel or counterflow (50)
It is noted from Eqs. (46) and (47) that
€ ~ ~(NTU, *
G , flow arrangement) (51)
@ProcessEng
Similar expressions have been developed for heat exchangers having

other flow arrangements, such as crossflow, multipass, etc. Representative
results are summarized in [3,8].
€-NTU relations are also available in graphical forms [10]. The fol-
lowing observations can be made by reviewing them:
452
(a) The heat exchanger effectiveness increases with increasing NTU for a
specified C . *
(b) The heat exchanger effectiveness increases with decreasing C* for a
specified NTU.
(c) For € < 40%, C* does not have a significant influence on the heat ex-
changer effectiveness.
(d) Because of the asymptotic nature of the €-NTU curves, a significant

increase in NTU and hence in the heat exchanger size is required for
a small increase in € at high values of €.
(e) Counterflow heat exchangers have the highest effectiveness, €, for

specified NTU and C * compared to that for all other flow arrange-
ments. Thus for a given NTU and C* , the maximum heat transfer is ob-
tained in counterflow.
7. HEAT EXCHANGER DESIGN CALCULATION

We have discussed two methods for performing heat exchanger thermal
analysis (Table 2). The rating and sizing of heat exchangers are two im-
portant problems encountered in the thermal analysis of the heat ex-
changers.
TABLE 2. Working Equations for LMTD, and €-NTU methods.
LMTD Method € -NTU Method
Q Q
LMTD
C •
1;T l Thl -T c2 1;T 2 Th2 -T cl C*
mln
C--- ~~_~12~~J:~
max (m cp)max
Tc2 -T cl Thl -Th2

U A l
NTU c--:-- UdA
p R
T~~:T~~ T~;:T~~ mln
C .
mln A
F ø(P, R, flow arrangement) € ~ ø(NTU, C* , flow arrangement)
The slzlng problem is concerned with the determination of the dimen-

@ProcessEng
sions of the heat exchanger i.e.; selecting an appropriate heat exchanger

type and determining its size to meet the specified hot and co Id fluid in-
let and outlet temperatures, flow rate and pressure drop requirements. For
example, if the inlet temperature and the mass flow rate of both the
fluids are known and the objective is to design a heat exchanger that will
453
give a desired fluid outlet temperature, the LMTD method can be used to
solve this problem using the following steps:
(a) Calculate Q and the unknown outlet temperature from Eqs. (5) or (6).
(b) Calculate ~Tlm from Eq. (29) and obtain the correction factor, F, if
necessary.
(c) Calculate overall heat transfer coefficient, U.
(d) Determine the surface area, A, from the Eq. (36).
€-NTU method may also be used for sizing problem and the procedure is
as follows:
(a) From the fluid inlet and outlet temperatures and mass flow rates cal-
culate the heat exchanger effectiveness using Eq. (42).
(b) Calculate capacity rate ratio, C* .
(c) Calculate the overall heat transfer coefficient, U.
(d) *
From €, C and the flow arrangement, determine NTU using chart or €-
NTU relations.
(e) From NTU, calculate the heat transfer surface area, A using Eq.
(44).
The rating problem is concerned with the determination of the heat

transfer rate, fluid outlet temperatures for prescribed fluid flow rates,
and the pressure drop in an existing heat exchanger; hence the heat trans-
fer surface area and the flow passage dimensions are available. LMTD
method may be used for rating pr0blems but computations are tedious, re-
quiring iteration, since the outlet temperatures are not known to calcu-
late LMTD. In such situations, the analysis can be simplified by using the
€-NTU method. The rating analysis with €-NTU method is as follows:
(a) Calculate the capacity ratio, C* and NTU.
(b) Determine the heat exchanger effectiveness, €, from €-NTU charts or
equations for the given heat exchanger and specified flow arrange-
ment.
(c) Knowing €, calculate the total heat transfer rate from Eq. (43).
(d) Calculate outlet temperatures from Eqs. (5) and (6).
€-NTU method is generally used in the design of compact heat ex-

changers for automotive, aircraft, air-conditioning and other industrial
applications where the inlet temperatures of the hot and cold fluids are
specified and the heat transfer rates are to be determined. In the
process, power and petrochemical industries traditionally LMTD method is
general ly used.
8. IMPACT OF FOULING ON HEAT EXCHANGER DESIGN

The design of heat exchangers for fouling service must take into ac-
count the effect of fouling on both heat transfer and pressure drop.
Fouling deposits reduce the effectiveness of a heat exchanger by reducing
the heat transfer and by impacting the pressure drop of the exchanger,
generally unfavourably but sometimes favourably. The impact of fouling on
the design of heat exchanger including both thermal and hydraulic con-
@ProcessEng
siderations, is treated in this section. More information on fouling in

single phase convective heat transfer can be found in [12].
8.1 Impact of Fouling on Heat Transfer

Process conditions usually set the heat dut Y and temperature dif-
ference at specific values. Fouling reduces the overall heat transfer
454
coefficient by adding therma1 resistance in the heat flow path, thus

making the surface are a an adjustab1e parameter to account for the reduc-
tion of the overall coefficient due to fou1ing. The impact of fou1ing on
the surface area as a function of the overall coefficient is shown in Fig.
8. It is not uncommon for the heat exchanger are a to increase 100 percent
due to fou1ing; in other words, fou1ing a110wances often account for more
than ha1f of the heat exchanger sur face area.
A circu1ar tube fou1ed on both the inside and the outside is shown in
Fig. 9 with the corresponding therma1 resistance circuit. The overall heat
transfer coefficient is given by Eq. (20). The addition of the fou1ing
resistance decreases the overall coefficient, therefore requiring more
heat transfer surface area.
Examp1e 4. A two-pass tube, baff1ed sing1e-pass she11, she11-and-
tube heat exchanger is used as a marine oi1 cooler. Coo1ing water (sea
water) flows through the tubes at 20°C at a rate of 8.164 kg/s, and leaves
at 32°C. Engine oi1 enters the she11-side at a rate of 20 kg/s. The in1et
and the outlet temperatures of the engine oi1 are 65°C and 55°C respec-
tive1y. The heat exchanger has 15.25 in. ID she11, 18-BWG, 0.75 in. OD
tubes. A total of 160 tubes are 1aid out on a 15/16 in. triangu1ar pitch.
Heat exchanger is designed according to TEMA standards.
2 -5 2
Q 409.4 kW, Rfo ~ 0.000176 m K/W, AoRw ~ 1.084 x 10 m K/W
2
h. 2767 W/m 2K, ho ~ 686 W/m K, ~Tm ~ 34°C, Ao/A i ~ 1.1476
1.
Keeping the she11-side and tube-side heat transfer coefficients, and

she11-side fou1ing factor constant and varying the tube-side fou1ing fac-
tor, the effect of fou1ing on heat transfer surface are a is shown in Tab1e
3.
TABLE 3. Marine Oi1 Coo1er Examp1e.
2 2 2 2 2
Rf i , m K/W Uc' W/m K Uf' W/m K Ac,m Af,m Af/A c
0.00004 531. 06 475.07 22.67 25.35 1.118

0.00005 531. 06 470.49 22.67 25.48 1.124
0.00006 531. 06 469.95 22.67 25.62 1.130
0.00007 531. 06 467.43 22.67 25.76 1.136
0.00008 531. 06 464.93 22.67 25.89 1.142
0.00009 531. 06 462.47 22.67 26.04 1.148
0.0001 531. 06 460.02 22.67 26.18 1.154
0.0002 531. 06 436.96 22.67 27.56 1. 215

0.0003 531. 06 416.09 22.67 28.94 1. 276
0.0004 531. 06 397.13 22.67 30.32 1. 337
0.0005 531. 06 379.82 22.67 31.70 1. 398
0.0006 531.06 363.96 22.67 33.08 1.459
0.0007 531.06 349.36 22.67 34.47 1.522
0.0008 531. 06 335.89 22.67 35.85 1. 581
@ProcessEng
455
Clean overall heat transfer eoeffieient Ue' (W/m 2K)
FIGURE 8. Effeet of fouling on surfaee area.
Outside
............ / fouling
deposit
Tj •
Inside fouling
deposit
....:-:..:.::::::-::::;::=:).•
TI
@ProcessEng
FIGURE 9. Sehematie drawing of a fouled tube.

456
Even though the fouling factors appear to be small in magnitude, they can
increase the required sur face area significantly. As another example, con-
sider the industrial heat exchanger in liquid-liquid service described in
Table 4. The clean area required for this exchanger is about 59 m2
However, if inside and outside fouling resistances of 0.000352 and
0.000176 m2 K/W, are used, the required area increases to 140 m2 or a 137%
increase. These seemingly low fouling resistances obviously have a sig-
nificant effect on the required sur face area with the impact depending on
the relative value of the overall coefficient.
TABLE 4. Industrial Heat Exchanger in Liquid-Liquid Service Example.
Quantity Value
Q 5861 kW
LMTD 42 K
R A 0.0000153 m2 K/W
w o
h 3974 W/m 2 K
o
h. 7380 W/m 2K
~
Rfo 0.000176 m2 K/W
Rfi 0.000352 m2 K/W
U 2366 W/m 2 K
c
Uf 996 W/m 2K
Af/A c 2.37
Ao/A i 1.15
Small fouling resistances such as those in the previous example will

not impact gas-to-gas heat exchangers significantly, since typical gas-
side heat transfer coefficients are much lower than those for liquids.
Unfortunately, most gas-side fouling factors are much large r and do sig-
nificantly affect the overall heat transfer coefficient of gas-to-gas ex-

changers. For example, consider a heat recovery unit in a hot flue gas
stream as indicated in Table 5. The gas-side coefficient is much lower
than the liquid-side coefficient so the overall coefficient is less. In
this example the clean are a required is 2633 m2 while the fouled required
area is 4229 m2 or a 61% increase.
@ProcessEng
8.2 Impact of Fouling on Pressure Drop

The impact of fouling on hydraulic performance is often neglected in
the design of heat exchangers. In tubular exchangers, the fouling layer
roughens the surface, decreases the inside diameter, and increases the
outside diameter of the tubes. A shell side deposit also impacts the shell
457
side flow pattern in some cases actually enhancing the exchanger perfor-
mance by plugging or reducing unwanted shell side fluid bypass streams.
The effects on the shell-side performance are not easy to quantify but the
tube-side effects are, and the remainder of this discussion will center
around the hydraulic effects of the tube-side fouling.
TABLE 5. Industrial Heat Recovery Unit Example.
Quantity Value
Q 5861 kW
LMTD 42 K
R A 0.0000153 m2 K/W
w o
2
h
o
57 W/m K
h. 7380 W/m 2K
l
Ao/A i 10.0
R fo 0.0088 m2 K/W
Rfi 0.0002 m2K/W
U 53 W/m 2K
c
33 W/m 2K
1. 61
Inside the tube, the fouling layer decreases the inside diameter and
roughens the surface resulting in:
(a) Pressure drop increase due to the roughened surface.

(b) Pres sure drop increase due to the reduced flow area.
(c) Velocity increase due to the reduced flow area.
An exaggerated schematic of the fouled surface is shown in Fig.lO.

To determine the effects of the fouling layer on the hydraulic per-
formance, a tube-side flow computational procedure is:
(a) Determine the clean pressure drop.

(b) Determine the fouling layer thickness.
(c) Determine the velocity under fouled conditions assuming constant
volumetric flow rate.
(d) Determine the pres sure drop under fouled conditions.
@ProcessEng
For turbulent flows, the friction factor for smooth anq rough tubes
is given by, respectively [11],
f 0.0014 + 0.125 Re- 0 . 32 (52)
f 0.0035 + 0.264 Re- 0 . 42 (53)

458
Clean Fouled
inside inside
diameter diameter
Fouling deposlt
FIGURE 10. Sketch of tube cross-section with fouling on inside.
The pres sure drop is calculated by
boP (54)
The fouling layer thickness is determined by considering the fouling

layer to be a cylindrical thermal resistance much in the same way that the
tube wall resistance is determined. The fouling resistance is [12]:
(55)
Eq. (55) is rearranged to express the fouled diameter as a function

of the fouling resistance:
(56 )
For most liquid-side deposits the thermal conductivity varies between 0.03
and 10 W/mK.
The use of this procedure and the effect on pres sure drop is best il-
lustrated by an example. Consider a shell-and-tube exchanger with 25.4 mm
OD, 16 BWG tubes using cooling tower water on the tube side. The water
flows at 1.83 m/s with a tube side fouling resistance of 0.000528 m2 K/W.
@ProcessEng
Table 6 summarizes the pressure drop contributions due to the increase in

the velocity and the roughness of the deposit. These results illustrate
that the changes in pressure drop associated with fouling deposits may be
substantial and must be considered when designing a tubular heat ex-
changer.
459
TABLE 6. Fouling Deposit Effect on Pres sure Drop Exarnple.
Pressure Drop, Pa % Change
Clean condition 1740

Fouled condition with
area reduction only 2545 46
Fouled condition with

area reduction and 2995 72
rough sur face
In gas-side service the effect of fouling on pres sure drop may be

more pronounced than that on heat transfer. For fully developed flow con-
ditions, Shah [8] has shown that:
(57)
For a fixed mass flow rate, there is a slight increase in h as the fouling
deposits build up due to increase in fluid velocity and deposit surface
roughness. However, the overall heat transfer coefficient reduces because
of the additional thermal resistance which depends on the thickness and
thermal conductivity of the deposit. Since ~p is inversely proportional
to Dh , the pressure drop for flow inside ducts is highly sensitive to
reductions in the hydraulic diameter due to fouling. However, for external
flows in tubular exchangers the hydraulic diameter depends on the tube and
layout geometry and can be relative ly large for heat recovery applica-
tions. In such cases the impact of fouling on pres sure drop may not be as
great as that on heat transfer.
CONCLUDING REMARKS
Although in this work LMTD and €-NTU methods are reviewed, P-NTU and
~-NTU methodsare also used in the design of heat exchangers which are
presented in [8]. Fouling in heat exchangers is the undesirable accumula-
tion of insulating material on heat transfer surfaces. Such deposits may
result at either liquid or gas side in a heat exchanger. In general, when
fouling occurs, the heat transfer decreases and the pressure drop in-
creases. Methods are available to predict these effects provided that ap-
propriate information on fouling is available. In this respect, the infor-
mation on the tabulated values of fouling resistance and thermal conduc-

tivity of deposits is important [12]. In cases where fouling is an-
ticipated or can not be avoided, the designer of the heat transfer equip-
ment can specify a number of prevention, mitigation, and accommodation
techniques to deal with the problem of fouling.
ACKNOWLEDGEMENTS
The authors gratefully acknowledge the assistance of Mr. Long Quan Fu
@ProcessEng
and Mr. Huanyi Zhang during the preparation of this article.

460
NOMENCLATURE
total heat transfer area on one side of a heat exchanger, m

2
2
clean heat transfer area of a heat exchanger, m
fin surface area on one side of a heat exchanger, or heat transfer
2
area with fouling, m
2
A unfinned surface are a on one side of a heat exchanger, m
u
c flow stream heat capacity rate, mcp, W/K
C * heat capacity rate ratio, Cmin/Cmax' dimensionless

C . minimum of C or Ch ' W/K
c
m~n
C maximum of C or Ch ' W/K

max c
c specific heat of fluid at constant pres sure , J/kgK
P
D equivalent diameter of flow passage, 4A/p, m
e
d. tube inside diameter, m
~
d tube outside diameter, m

o
F log-mean temperature difference correlation factor, dimensionless
2
f Fanning friction factor, [T W/( p u m/2)], dimensionless
G mass velocity, kg/m 2s

h heat transfer coefficient, W/m 2K
i enthalpy of the fluid, kj/kg
k thermal conductivity, W/mK
L length of the heat exchanger, m
l length of the fin, m
m fluid mass flow rate, kg/s
NTU number of heat transfer units, UA/C min , dimensionless
P temperature effectiveness of the cold side stream, defined by Eq.
(34), dimensionless
p perimeter, m
~p fluid static pressure drop on one side of a heat exchanger, Pa
Q heat transfer rate in the heat exchanger, W
R heat capacity rate ratio, defined by Eq. (35), dimensionless
2
inner surface fouling factor , m K/W
2
outer surface fouling factor, m K/W
total thermal resistance, m2K/W

wall thermal resistance, K/W
r radius of the tube, m
Re Reynolds number based on the hydraulic diameter, pUmDe/~' dimension-
@ProcessEng
less
T fluid temperature, K
Th hot fluid temperature, K
Tc cold fluid temperature, K
461
~T local temperature difference between the fluids, Th - Tc ' K

~Tlm log-mean temperature difference, defined by Eq. (29), K
~Tm true mean temperature difference, defined by Eq. (36), K
t thickness of the wall, m
U overall heat transfer coefficient, W/m 2K
U overall heat transfer coefficient for clean surface, W/m 2 K
c
Uf fouled overall heat transfer coefficient, W/m 2K
u fluid velocity, m/s
S fin thickness, m
heat exchanger effectiveness, defined by Eq. (42), dimensionless
ryf fin efficiency, dimensionless
extended surface efficiency, defined by Eq. (15), dimensionless
fluid dynamic viscosity coefficient, Pa.s
1/
. ..
k ~nemat~c .
v~scos~ty, m
2/ s
p fluid density, kg/m 3

r wall sheer stress, Pa
w
SUBSCRIPTS
c cold fluid side, or clean

cf counterflow
f fin, finned, friction or fouling
h hot fluid side
i inner
m mean
max maximurn
min minimum
o outer
s scale or shell side
t tube side
u unfinned
w wall
linlet
2 out let
REFERENCES
1. Shah, R.K., Classification of Heat Exchanger, in Heat Exchangers:Thermal-
-Hydraulic Fundamentals and Design, Eds. S. Kakac, A.E. Bergless and F.
Mayinger, pp. 9-46, Hemisphere, New York, 1981.

2. Chenoweth, J.M., and Impagliazzo (Eds.), Fouling in Heat Exchange Equip-
ment, ASME Symposium Voluma HTD-17, ASME, New York, 1981.
3. Kakac, S., Shah, R.K. and Bergless, A.E. (Eds.), Low Reynolds Number Flow
Heat Exchangers, pp. 21-72, Hemisphere, New York, 1981.
4. Kakac, S., Shah, R.K. and Aung, W. (Eds.) Handbook of Single phase Convec-
tive Heat Transfer, Chapters 4 and 18, John Wiley, New York, 1987.
@ProcessEng
5. Kern, D.Q. and Krauss, A.D., Extended Surface Heat Transfer, McGraw-Hill,
New York, 1972.
6. Kays, W.M. and London, A.L., Compact Heat Exchangers, 3rd Ed., McGraw-
-HilI, New York, 1984.
7. Bowrnan, R.A., Mueller, A.C. and Nagle, W.M., Mean Temperature Difference
in Design, Trans. ASME, Vol. 62, p,283, 1940.
8. Shah, R.K. and Mueller, A.C., Heat Exchangers, in Handbook of Heat Trans-
462
fer Applications, 2nd Ed., Eds. W.M., Rohsenow, J.P., Hartnett and E.N.
Ganic, Chapter 4, part 3, McGraw-Hill, New York, 1985.
9. Kakac, S., Bergless, A.E., and Mayinger, F. (Eds.), Heat Exchangers:Ther-
mal-Hydraulic Fundamentals and Design, Hemisphere, New York, 1981.
10.Kays, W.M., London, A.L. and Johnson, D.W., Gas Turbine plant Heat Exchan-
gers, ASME, New York, 1951.
11.Kern, D.Q., Proces s Heat Transfer, McGraw-Hill, New York, 1950.
12.Marner, W.J. and Suitor, J.W., Fouling with Convective Heat Transfer, in
Handbook of Single-Phase Convective Heat Transfer, Eds. S. Kakac, R.K.
Shah and W. Aung, Chapter 21, John Wiley, New York, 1987.
@ProcessEng
SELECTION OF HEAT EXCHANGERS
JAMES M. CHENOWETH

Alhambra, California U.S.A.
1. INTRODUCTION
The selection of the type of heat exchanger for a particular application is the firs t
essential step in the design process. From process considerations, the choice may be
obvious. However, in most instances several different types will work well. It then
becomes important to evaluate a number of options, requirements, and constraints
before making the selection. Much of the complication arises from the faet that heat
exchangers are part of a much larger interconnected system which often greatly
influences their ability to perform satisfactorily. Thus, for the selection to be made
correctly, many factors must be considered in addition to the obvious characteristics of
the process fluids, the amount of heat to be transferred, the temperatures and
pressures, weights, pressure drops, etc. In some instances, the consideration of other
external factors will dictate the type of exchanger.
Heat exchangers are made in a wide variety of configurations from house-sized
surfaee condensers to subminiature devices used for cooling electronic components.
Heat is generated inside some heat exchangers, such as a boiler, fired heater, or a
chemical reactor. In other heat exchangers, such as in a wet cooling tower, the hot and
cold fluid are in direct contact. However, most heat exchangers transfer heat from the
hot fluid to the cold fluid through some type of separating wall. Different heat
exchanger configurations of this latter type will be described briefly to illustrate the
range of possibilities.
Once the type has been selected, the heat exchanger needs to be sized to meet the
process requirements. But before this ean be done, it is essential to prepare a set of
specifications which define the expected performance, the anticipated process
conditions, and mechanical requirements. These specifications are then used to
perform the thermal/hydraulic rating and design. Since heat exchangers arealso
pres sure vessels, they must als o be designed to ens ure their mechanical integrity under
all operating conditions. The size and materials of construetion of the various
components influence the eventual firs t cost of the exchanger. Although many of the
calculations in the design process ean now be made using sophisticated computer
programs, they are not fully integrated. Many individuals, each an "expert" in his own
area of specialization and experience, become involved in the ultimate seleetion process.
Some speculations are made as to future trends in computerizing the selection of heat
exchangers using an overall "expert system" approach.
2. TYPES OF UNFIRED HEAT EXCHANGERS

The largest number of heat exchangers are those that are made in great numbers for
specialized applications. Produetion runs of thousands or even millions of nearly
@ProcessEng
identical units are common. Typical are the heat exchangers used as automotive
radiators, domestic and commerical air conditioners, furnaces, engine oil coolers, etc.
The selection process for these heat exchangers is highly specialized, proprietary, and
usually involves prooftesting a number of candidate designs. The final choice is greatly
influenced by haw well the exchanger satisfies the intended application, the ability to
duplicate a "good" design, and the cost af produetion.
463

464
On the other hand, more generalized procedures are utilized in the selection, sizing,
and fabrication if the exchanger is unique and intended for a particular application,
typical of the process and power industries. The amount of the engineering effort that
is expended for the evaluation of alternative designs depends upon whether the
exchanger can be sold at a high cost and/or ifsafety is involved. An example ofwhere
both are present is the selection of a heat exchanger for a nuclear power plant. The
emphasis of this paper will be on those heat exchangers that are custom engineered for
process plant applications. There are several excellent discussion~ [1,2] on the selection
of these exchangers available in the literature.
The folIowing types of unfired heat exchangers are among the most common, but
the list is partial and not meant to be complete:
• Double-Pipe Heat Exchanger. A

typical double-pipe heat exchanger consists
of one pipe placed concentrically inside
~!
another of larger diameter with appropriate
fittings to direct the flow from one section
to the next as shown in Fig. 1. Double-pipe
heat exchangers can be arranged in various -RETURN HEAD
series and parallel arrangements to meet

pressure drop and MTD requirements. The Rtproduted by permission of Hemisphere Publishing Company,@1983
major use of double-pipe exchangers is for
sensible heating or cooling of process fluids Figure 1 Double-Pipe Heat Exchanger [l]
where small heat transfer areas (to 50 m 2 )
are required. The major disadvantage is
that they are bulky and expensive per unit
of heat transfer surfa('e. CAARYING BAR
• Plate-and-Frame Heat Exchanger. A

typical plate-and-frame heat exchanger is
shown in Fig. 2. It consists of a series of
thin plates with corrugations which
separate the fluids. Appropriate design
and gasketing perrnit a stack of plates to be
held together by compression bolts joining
end plates. Since the flow passages are
quite small, strong eddying gives high heat
transfer coefficients, high pressure drops,
and high local shear which minimizes
fouling. These exchangers provide
relatively compact and lightweight heat ~
transfer surface. They are temperature and
,,,,"' ~ ~SION BOL T
pressure limited due to the construction
'od
details and the gasketing. They are

Reproduced by permission of Hemisphere Publishing Company,(f)1983
typically used for heat exchange between
two liquid streams. They are easily cleaned
and sterilized as they can be completely Figure 2 Exploded View of a Plate-and-
disassembled so they have wide application Frame Heat Exchanger [1)
in the food processing industry.
• Spiral Heat Exchanger. Spiral heat exchangers are forrned by rolling two long,
@ProcessEng
parallel plates into a spiral using a mandrel and welding the edges of adjacent plates to
form channeIs. The plates are held apart by raised bosses on one of the plates as shown
in Fig. 3. The two spiral paths introduce a secondary flow, increasing the heat transfer
and reducing fouling deposits. These heat exchangers are quite compact, but are
relatively expensive due to their specialized fabrication.
465
. ,~_~
•
Reproduted by permission of Hemisphere Publishinl CompOiilny.@1983
Figure 3 Diagrams of Three Spiral Heat Exchanger Configurations

• Lamella Heat Exchan er. The lamella
(Ramen type of heat exchanger consists of
a set of parallel, welded, thin plate channels
placed longitudinally in a shell. The
channels are welded into headers at each
end of the plate bundle which is allowed to
expand and contract independently of the
shell by the use of a packing gland at the
lower end as shown in Fig. 4. The shellside
flow is typically a single pass around the
plates. The plate bundle can be easily
removed for inspection and cleaning.
• Com act Plate Fin Heat Exchan ers.
The plate fin matrix heat exchanger offers
the most compact form of heat transfer
surface where the fluids must be kept
separated. They are usually assembled
from formed metal (often aluminum) sheets
into a matrix of channels separated by
parting sheets. The assembly with the
appropriate headers is clamped together in
a jig and the unit brazed into a strong,
rigid structure. This is illustrated in Fig. 5.
Compact heat exchangers offer extremely
high volumetric heat transfer surface Reproduced by permission of Hemisphere Publishing Company,@1983
density, but are limited in overall size and Figure 4 Lamella Plate Heat Exchanger 11)
the materials of construction. They also
must be used with nonfouling fluids as they
FLUID 2
are difficult to clean.

• Mechanically Aided Heat Exchangers.
Some heat transfer problems require
mechanical action at or near the heat
transfer surface to achieve acceptable heat
transfer rates. One type is a stirred tank FLUID 1
where the bulk fluid must be transported to
@ProcessEng
the heat transfer surface. One type of

stirred tank heat exchanger used for batch
proces ses is shown in Fig. 6. The main MATRIX 1
features of such a tank may be controlled Reproduced by permission of Hemisphere Publishine Company,()1983
more by the reaction kinetics
considerations than heat transfer. Another Figure 5 Compact Heat Exchanger 11)
type
466
type of mechanicalJy aided heat exchanger is one that uses a blade very dose to or
actualJy contacting the cylindrical heat transfer surface. The blade causes shearing
action on the fluid layer immediately adjacent to the heat transfer surfaces. One
configuration is shown in Fig. 7. The equipment is bulky, heavy, expensive, and
requires constant power input and frequent maintenance. This type of heat exchanger
is only used in extremely difficult applications.
,pz==l'III1===!><"" SHAFT
JACK ET WITH VESSEl

HEAT TRANSFER
MEDIUM
ANCHOR
AGITATOR
Reproduced by permission of Hemisphere Publishing Company,©1983 Reproduced by permission of Hemisphere Publishing Company,@1983
Figure 6 Stirred Tank with Anchor Figure 7 Scraped-Surface Heat

Agitator (1) Exchanger [1)
• Air-Cooled Heat Exchanger. This type
of heat exchanger is used to exchange heat
to the atmosphere. It typically uses high-
finned tubes to increase the surface area to
offset the relatively poor heat transfer
coefficients of the air, typically 10 to 200
times smaller than that for the tubeside
process fluid. Further, to satisfy the heat
balance requirements, it is necessary that DRIVER WITH V-BEL T
very large volumes of air must be blown or

drawn across the tubes. There are two
main types of air-cooled heat exchangers -
those with induced draft and those with
forced draft - as illustrated in Fig. 8. The
basic configuration is a large, shallow (3 to
12 tuberows) bank of high finned tubes (a) FQRCED ORAFT (b) INDUCEO DRAFT
attached to appropriate headers. The

design features of these exchangers include
the fan, plenum, and stack arrangements.
Reproduced by permission of Hemisphere PulHishin, Company,«)19a3
They do require constant power input, but
balance is achieved by changing the fan Figure 8 Air-Cooled Heat Exchangers [1)
speed or by shutting down selected cells
@ProcessEng
within a large array of air-cooled heat

exchangers. The cost is relatively high, and
the exchangers are quite bulky and require
considerable open space to operate
satisfactorily.
467
• Evaporative Cooling Towers. One AIR OUT

type of direct contact heat exchanger is the t t
evaporative cooling tower. In this type of
heat exchanger, hot cooling system water is
sprayed on to a fill structure where it comes
in contact with a countercurrent flow of air.
Some of the water evaporates and thereby
releases the heat of vaporization with the
net result that the remaining water is lal
cooled. A typical design is shown in Fig. 9.

Although some evaporative cooling towers
use a natural draft for air circulation, the
current practice is to use fans to produce a "'111111/ I1I111
forced draft. The successful operation of """" \ """ \
evaporative cooling towers is affected by IN

WATER_ =1~::;::::::~~~1
-:-:-
~
--
-:-:- ---~
the local elevaion, and the relative ,:-:-:PACKING :-:-=
humidity and temperature of the incoming
air. It is necessary to treat the water to AIR - r J f i i i l l l i i i lillii",! i:in~ AIR
IN ~_ :::::r- IN
prevent biological growth, and as the WATER_ ~~ ~-l
cooling water is cirC"ulated the minerals cm
ibi
ten d to concentrate. It is necessary,
therefore, to treat the water with corrosion
inhibitors and antifoulants and contimIaIly
supply makeup water for that which is
evaporated.
• Shell-and-Tube Process Heat
Exchangers. Shell-and-tube heat
exchangers are the most commonly used in
the process industries. A typical
configuration is shown in Fig. 10. A bundle
of tubes is supported by baffles spaced lel
along the length of the bundle. One fluid
flows inside the tubes in one or more Reproduud by permission of Hemisphere Publishing Company,©1983
passes, while the other fluid flows back and

Figure 9 Evaporative Cooling Tower [1)
forth across the outside of the tubes as
directed by the baffles. Shell-and-tube
/
configurations provide fairly large ratios of
heat transfer area to volume and weight.
They are used for sensible heat exchange,
condensing, and boiling. They are
'""". """''
l~
relatively easy to construct in a wide range '"""'~;'" ?~,7
of sizes, and are rugged enough to
TUBE-SIDE CHANNEL7
withstand normal fabrication, shipping,

and erection. The parts that most often ~~[i'21
II
: 11~l
fail - tubes and gaskets - can be replaced, I I I 11\
~ ~ JJ [Sl u~
and the heat transfer surfaces ean be O :
cleaned relatively easily. The large number ~ C \O:BAFFlES
TUBE SHEET
of options available using different shell . ." "","'" , , " " " " ,"o,"
styles, tubefield layouts, baffle

TUBE-SIDE CHANNEL
@ProcessEng
AND NOZZLES
arrangements, materials of construction,

etc. enable a shell-and-tube heat exchanger Reproduced by permission of Hemisphere Publishinl Company,@1983
to be "tailored" to meet a very wide range
af specifications. Figure 10 Shell-and-Tube Heat
Exchanger [1)
468
• Reboilers. Reboilers are specialized

process heat exchangers used to vaporize WEIR VAPOR OUT
fluids to be fed into distillation columns.
Many are horizontal shell-and-tube heat
exchangers with a U-tube bundle and an
oversized shell to assist the removal of
entrained liquid from the shellside boiling
two-phase mixture. These are called kettie
reboilers and are illustrated in Fig. Il.
Other re boilers have con ven tional shelIs .
Typically, vertical units have the boiling STEAM PARTITION
fluid inside the tubes, while horizontal OUT
units have the boiling fluid on the outside

of the tubes. A pump can be used to Reproduced by permission of Hemisphere Publishing Company,@1983
recirculate the liquid to the reboiler or the
flow can be accomplished by a Figure 11 Kettie Reboiler [1)
thermosiphon action. Other types of heat
exchangers, in addition to shell-and-tu be,
can be used as reboilers.
• Condensers. Although many different
WATER
styles of heat exchangers can be used as OUT VAPOR VAPOR VENT
condensers, some have unique features.
L---
~ J"
Process condensers may have the tc..~ I G
condensing on either the tube or the shell
side. One popular design uses a single
crosspass on the shell side so it is necessary t •
L
"
BAFFLE ROTATED 900
I i,
JfI~
D)
SPLIT RING
to get even shellside flow distribution of the WATER IN CONDENSATE HEAD
fluid entering the condenser as shown 1ll

Fig. 12.
Reproduced by permission af Hemisphere Publishing Company,CD19S3
Figure 12 Process Condenser [1)

• Feedwater Heaters. One of the most
complicated type of heat exchanger to
design and bui Id is the feedwater heater
used in steam power plants. This is
because it contains three separate heat
exchangers within the same shell - the
desuperheating zone, the condensing zone,
and the subcooling zone for the steam from
the turbine at very low pressure. The tube
bundle is typically of U-tube construction
and carries very high pressure water to be

preheated before return in g to the boilers.
A typical feedwater heater is shown in Fig.
13. These exchangers are subject to flow-
induced vibration, erosion, and venting CONDENSING ZONE
problems; but they are essential
components of the power plant proces s
@ProcessEng
cycle.
Figure 13 Feedwater Heater
469
• Surface Condensers. Another heat

exchanger found in power plants is the
specialized shell-and-tube heat exchanger
used for surface condensers where large
quantities of low pressure, subatmospheric
steam from the turbines must be condensed
with very low pressure drops to maintain
the efficiency of the power station. Surface
condensers often use nonuniform tubefield
arrangements with engineered steam lanes
(see Fig. 14) to ens ure uniform penetration
into the very large bundles. Specialized
care is taken to remove any noncondensable
buildup which will greatly deteriorate the
performance. The tubes carry the cooling
medium, usually water, and often have on-
line cleaning systems to keep the fouling to
an acceptable level.
Figure 14 Surface Condenser
As can be seen there are many characteristic features offered by these different
types of heat exchanger. The customer may specify the type of heat exchanger based
upon past experience. Or the designer may be given the option of selecting the most
promising candidates to investigate for the particular application. His decisions may
well be based upon the availability of reliable methods for him to size and predict the
performance for one type or another.
3. SELECTION OF HEAT EXCHANGER TYPE

The selection of the type of heat exchanger is narrowed down considerably once the
process conditions are defined. These describe the flow rates, the temperatures,
whether there is a phase change of the fluids, and the permissibIe pressure drop on both
sides of the exchanger. The character of the fluids suggests materials to minimize
corrosion and fouling problems. At times, the type of heat exchanger is given in the
specifications. However, there are often several types of heat exchanger that will satisfy
the process conditions, so the decision as to which is the most attractive depends upon
the thorough evaluation and comparison of the several candidates.
Bell [3] outlines six basic criteria that must be met for a successful heat exchanger
design. They are the folIowing:
a) The heat exchanger should satisfy the process requirements by

accomplishing the thermal change on the streams within the allowable
pressure drops, in the presence of fouling until the next scheduled cleaning.
b) The heat exchanger must withstand the service conditions of the plant
en vironmen t.
c) The exchanger must be maintainable.
d) The advantages of multisheIl arrangement with flexible valving and piping
@ProcessEng
for service should be evaluated for permitting maintenance without severe

plant upset.
e) Consideration as to constraints on size, weight, and servicing access.
f) The exchanger should cost as littIe as possible.
470
With these criteria in mind, let's assume that a shell-and-tube heat exchanger type
has been selected. Let's now look at the constraints placed upon the design by process
and mechanical specifications, the anticipated operation and maintenance procedures,
and their influence on the cost of the unit.
4. SPECIFICATIONS AND CONSTRAINTS

A customer decides upon which heat exchanger he will purchase by comparing the
offerings from several vendors based upon his set of specifications. The specifications
give process, mechanical, and performance requirements needed to design the heat
exchanger. They may be minimal or so specific that only the fabrication details and
cost are left to the vendor. For shell-and-tube heat exchangers, standardized
specification sheets are provided by TEMA [4] and APl [5] which cover most of the
usual considerations. These may be supplemented by specific additional requirements
of the customer. Since heat exchangers are pressure vessels, they must also meet
various safety codes and standards. In the United States these are provided by such
organizations as the American Society ofMechanical Engineers (ASME), the American
National Standards lnstitute (ANSI), the American Petroleum lnstitute (APl), the
Heat Exchange lnstitute (HEl), and the Tubular Exchanger Manufacturers Association
(TEMA).
Specification are the vital communications link between the customer and the
vendor to facilitate the procurement of the correct heat exchanger. U nfortunately,
some specifications are prepared with only partial or inaccurate information. The
implications of items entered into the specifications to the performance of the
exchanger throughout its useful life may not be appreciated. Often only a single design
operating condition is given, with no mention of other conditions such as start-up,
shutdown, and anticipated load swings. It is unusual that an exchanger is operated
only at the given design condition. The operating people need to review the
specifications to be sure that they have considered how the exchanger will be used in
combination with other exchangers and pieces of equipment. Provisions for
maintenance and cleaning and their impact on the operation of the plant need to be
incorporated in the requirements. Unrealistic constraints often result in oversized
equipment that is expensive, difficult to operate, and may foul unnecessarily. The
designer of the heat exchanger re lies on the specification to provide realistic process
conditions, physical properties, pressure drop limitations, etc.
It is important that all those who have information concerning the particular heat
exchanger application communicate this to the team that selects the appropriate type
of equipment and prepares the specification. This function is increasingly being
assumed by the ultimate customer; however, it is not uncomon for the
engineer/architect contractor to provide the specifications. Let's assume that a shell-
and-tube heat exchanger has been selected and a proper and comprehensive
specification has been prepared. The next step is to determine the configuration and
the size and predict its performance.
5. THERMAL-HYDRAULIC SELECTION, RATING, AND DESIGN

There are a number of features of a shell-and-tube heat exchanger that can be
varied to seek the "best" configuration for a particular application. These include the
shell style, the bundle and balle style, the tubefield layout, tube type, size, length, and
number, the nu mb er and location of nozzles, the number of tubepasses, the number of
crosspasses, etc. All of these influence the ability of the heat exchanger to satisfy the
specifications.
@ProcessEng
There are three uniquely different techniques for deciding upon which heat
exchanger is appropriate for a given application. The names for these are sometimes
used interchangeably; but that is incorrect as each represents adistinet aetivity. They
are called the "seleetion," the "rating," and the "design."
471
5.1 Selection means just that. It involves going to a manufacturer's catalog of

standard exchangers and selecting one that will meet the specific process requirements.
The exchanger mayeither be in stock or can be built quickly with minor variations, but
does not normally require additional mechanical design effort. Therefore, the unit is
less expensive than one that is tailored to meet a process specification. The exchanger
is probably somewhat overdesigned and may not provide a full thermal/hydraulic
performance balance for both process fluids. The selected configuration should be
rated again to verify that the anticipated performance will be met before agreeing to its
purchase.
5.2 Rating is a computational process which determines the thermal performance and
pres sure drops for the two specified streams flowing in a geometrically defined heat
exchanger. The rating process is shown schematically in Fig. 15. The inlet flow rates
and temperatures, the physical properties, and the heat exchanger configuration are
given as input. A rating procedure calculates either the out let temperatures and the
heat dut y (if the exchanger length is specified) or the required length of the exchanger
to accomplish the thermal change. In either case, the pressure drop for each stream is
also calculated.
FLOW RATES
TEMPERATU RES
PRESSURES
1.
RATING PROGRAM
GEOMETRY CALCULATIONS - OUTLET TEMPERATURES

(LENGTH FIXED)
--
EXCHANGER CONFIGURATION_ 2. HEAT TRANSFER CORRE-
LATlONS
FLUID PROP ERTIES LENGTH (DUTY FIXED)
3. PRES SURE DROP CORRE-
FOULlNG FA CTORS LATIONS PRES SURE DROPS
Reproduced by permission of Hemisphere Publishing CompanY.©1983
Figure 15 Schematic Diagram of a Rating Program [3)
Usually the exchanger chosen for rating is found to be deficient in one or another of
the requirements, and a different one must be chosen for the next rating iteration. If,
for example, the pres sure drops are too high, some modification must be made to
reduce them. One way is to increase the size of the heat exchanger shell. On the other
hand, the pressure drops may be much too low. Upon selecting a smaller shell, the heat
transfer coefficients mayaiso increase along with the pres sure drop to offset a reduction
in the heat transfer surface due to fewer tubes of a fixe d tube length. The relative
interplay among the numerous parameters is not always predictable without
undertaking the rating calculations.

However, once the thermal performance is acceptable and the pres sure drops are
within the maximum allowable, that exchanger configuration may be considered a
possibie selection. There usually are other configurations that als o meet all the process
requirements. The desire is to identify a number of these so that a final selection can
be made on the basis of other significant criteria, such as operation, maintenance, and
firs t cost of the exchanger .
@ProcessEng
5.3 Design is a procedure of selecting the "best" heat exchanger configuration and size
that meets the process requirements. It has been found that the most effective way to
accomplish this is through a process of successive ratings connected by a set of logic
that adjusts the heat exchanger configuration on the basis of a step-by-step procedure
so that the "best" configuration is not missed. The structure of the design logic is
472
shown schematically in Fig.

16. The degree of success of
this approach is dependent
upon the skill and care of
the decision making in
moving from one
configuration to the next. It
is easy to construct poorly
conceived tests w hich limit SELECTION OF A
TENTATIVE SET OF
the possibIe configurations EXCHANGER DESIGN
w hile screening out those PARAMETERS
that should be eliminated. MODIFICATION OF

Figure 17 illustrates one .-------~ ::~A~~~?~S
"design" logic that can be
used for heat exchanger
design. For a heat
exchanger with a fixed
length of tubes, the
minimum number of shelIs
in parallel and / or series of
the minimum diameter that
will satisfactorily transfer
the required heat within the
allowable pressure drop is
considered a "best" design Reprodu,ed by permission of Hemisphere Publishing Company,©1983
selection as it usually has
the lowest firs t cost. Figure 16 Basic Logic Structure for
Process Heat Exchanger Design [3)
RATING PROGRAM
INITIAL OUTPUT:
LENGTH OF LARGEST
DIAMETER SHELL. FEWEST
TUBE PASSES. GREATEST
BAFFLE SPACING
VES
ADD SHELL
IN PARALLEL
DECREASE SHELL
DIAMETER
*DENOTES THE LARGEST VALUE

OF THAT PARAMETER PERMITTED ADJUST INTERNAL
@ProcessEng
IN THE FINAL DESIGN. 0.;.:..;:.....______...., PARAMETERS TO

STANDARD VALUES
Reproduced by permission of Hemisphere Publishin& Company,@1983
Figure 17 Simplified Logic Structure for Configuration Modification

for Process Heat Exchanger Design [3)
473
6. SOMETIMES OVERLOOKED CONSIDERATIONS

Typieally the evolution of a heat exchanger design involves a number of people who
unfortunately may not eommunieate fully with one another. The proeess engineer
specifies requirements, but not equipment. The heat transfer equipment specialist
depends upon the information given in the proeess speeifieations whieh may be rigid
and laek information for operational conditions different from the design point. The
equipment designer is asked to provide a piece of equipment that satisfies mechanieal
codes and standards while providing for the performance indicated on the specification
sheet. The constructor is given the equipment to install with the correct connections
and instruments. The operator is given a plant after eommissioning by a crew of start-
up specialists. Re then must operate and maintain the plant so that it will produce the
required produet. The original process engineer and the heat transfer equipment
specialists get feedback from the plant operators only when the eguipment faBs to
operate satisfactorily. The loop is seldom completed when equipment works well or
beyond expectations.
The failure to eommunicate often leads to operational problems when some of the
folIowing design items for shell-and-tube heat exehangers are overlooked:
• Flow-Induced Vibration. The flow on the shell side of a shell-and-tube heat

exchanger ean eause the tubes to vibrate wildly or to develop a loud noise due to
aeoustic vibration. Tube leakage ean cause the exchanger to have to be shut down for
repairs. These problems ean be avoided, but they place design and operational
constraints that must be respected. Shorter unsupported tu be span lengths are
effective in preventing tube vibration. Deresonating baffles ean be installed to prevent
acoustic vibration.
• Impingement Devices. Impingement devides are required to prevent the erosion
of tubes directly below inlet nozzles. They are usually round or square plates mounted
inside the shell that deflect the incoming flow. Unless there is an adequate escape area,
extremely high local velocities develop that are known to exeite tube vibration
probierns. It is often necessary to remove rows of tubes to perrnit the impingement
devices to be correctly positioned.
• Tie Rods. Relatively thin tie rods are plaeed around the periphery of the tube
bundle to hold the baffles in place. Sleeves of appropriate length aet as spacers
between baffles. The tie rods are often located where shellside flow ean cause them to
vibrate. If the amplitude is large enough, the tie rods will impact with nearby tubes or
the shell wall. Both the tie rods and the spacers ean wear to the extent that the baffles
are no longer held in place. Heavier tie rods usually eliminate the problem.
• Vents and Drains. The proper placement of vents and drains will make the
difference as to whether or not many exchangers perform well. The buildup of
noncondensables in condensers with inadequate vents is a classic example of the
problem. Drains need to be sized not only to handle the liquid flows, but als o to
provide a path for the removal of debris during cleaning.
• Anticorrosion and antifouling fluid treatments It is unusual for the anticipated

anticorrosion and antifouling treatment programs to be defined at the time a heat
exchanger is being designed. If they are known, they are usually not incorporated in
the specifications. This ean lead to overlooking important connections and influences
the decisions about the extent of corrosion allowances desired and the setting of the
design fouling resistances. These items will influence the future operational history of
the exchanger .
@ProcessEng
• Cleaning Procedures. Even when fouling is anticipated, the plans for cleaning the
exchanger are not specified. Depending upon the technique to be used, different
allowances for valving, piping, and access should be provided. If the exchanger is in a
critical service, it may be justified to provide a spare exchanger and the necessary
piping to clean the exchanger without shutting down the plant. On-line cleaning
474
techniques may prove to be worth the added costs of equipment and complication of
the system design.
• Provisions for Instrumentation. The performance of a heat exchanger ean only be
verified if adequate provisions for temperature, pressure, and flow instrumentation are
provided. These add lit tie to the cos t of an exchanger if they are installed when it is
buiit. However, in the name of economy they are often omitted.
7. HEAT EXCHANGER MECHANICAL DESIGN

Heat exchangers are pressure vessels that must be built with integrity so that the
proces s fluids will not mix or be leaked to the surroundings. This means that heat
exchangers must be designed according to accepted codes and standards. Heat
exchangers in the United States follow the ASME Unfired Pressure Vessel Codes [6],
TEMA Standards [4], APl Codes [5], HEl Standards [7,8], etc. Similar codes and
standards exist in other countries around the world. These codes impose constraints
that influence the thermal/hydraulic performance of the heat exchangers.
Temperature and pres sure ranges dictate the types of closures, gaskets, allowances for
thermal expansions, tube-to-tubesheet connections, materials of construetion, etc. The
thickness of the various mechanical elements determines the weights, seismic loads on
foundations, and ultimately much of the cost of the heat exchanger . There are
computer programs that will perform the various calculations for a detailed mechanical
design so that a heat exchanger will comply with the applicable codes and standards.
These not only greatly expedite the necessary calculations, but als o ens ure that all
elements of the procedures are incorporated in the design calculations.
8. COSTING
Although rough costing of a heat exchanger ean be done without a detailed
mechanical design, it is needed before the final cost ean be established. There are a
number of proprietary programs that bui Id up the elements of cost for the engineering,
materiais, machining operations, assembling, fabricating, testing, and shipping. Some
of these are dynamic and reflect changes in raw materials and fabrication with time.
However, most are specific to the capabilities and costs of a particular manufacturer.
The competitiveness of the marketplaee also influences what will be considered an
acceptable markup for profit.
In many instances, a standard design will be found to be the least expensive.
However, it must be realized that the difference in first cos t may be offset by later
savings in operation and maintenance. The true cost of a heat exchanger incorporates
all of the expenses for providing the required heat transfer capability throughout the
life of the plant in which it is installed.
9. FUTURE TRENDS
With the advent of inexpensive, high-powered computers the future selection of
heat exchangers will probably re ly heavily on what are called "expert systems." These
are extensive suites of computer programs that not only perform the routine
calculations but also "think" through all of the interrelated elements in obtaining the
"best" design. Soler [9] has speculated that the folIowing four major modules are the
elements of sue h a system for the design of heat exchangers:
Architectural
Thermal-Hydraulic
@ProcessEng
Mechanical-Metallurgical
Operation and Maintenance
The expert system would re ly heavily on collecting the procedures and methods used
by experts in each of these areas and tying toget her an overall logic that would provide
the communication and interaction necessary to consider the numerous factors
475
involved. A schematic flow chart is given in Fig. 18. Such a program would require a
massive data base of information. Certainly, the computer technology is now available
to handle this task. Elements are scattered. The need is to interrogate the experts, to
develop the communications and logic programs, and to assemble the huge data base.
This is a massive task; but one that is greatly needed as the expertise for heat
exchanger design is rapidly being eroded.
Reproduc.ed by permission of the Ametican Society of Mechankal Encineers.
Figure 18 Schematic Diagram Showing the Integration Necessary

for an Expert System for Heat Exchangers [9J
10. CONCLUSIONS
The selection of the type of heat exchanger is often much easier than the
determination as to the size and configuration that "best" meets the many demands.
One of the difficulties encountered is the lack of communication between the
individuals that are involved in the specification, sizing, fabrication, erection,
operation, and maintenance. Each has a part of a very complicated puzzle. And each
part involves an economic impact on the final selection. When all of the pieces are in
place, it then becomes straightforward to select the "right" exchanger for a particular
application.
Acknowledgment
proprietary information nor does it necessarily represent HTRI recommendations for
design. Rather, it is intended to provide a helpful interpretation of published literature
@ProcessEng
in the light of HTRI experience in the same area.

476
References
1. Bell, K. J., "Types of Heat Exchangers and Their Applications," Section 3.1.2,
Heat Exchanger Design Handbook, Hemisphere, Washington, 1983.
2. Taborek, J., "Design Procedures for Segment ally Baffled Heat Exchangers,"
Section 3.3.10, Heat Exchanger Design Handbook, Hemisphere, Washington,
1983.
3. Bell, K. J., "Logic of the Design Process," Section 3.1.3, Heat Exchanger
Design Handbook, Hemisphere, Washington, 1983.
4. Tubular Exchanger Manufacturers Association (TEMA), Standards of Tubular
Exchanger Manufacturers Association, Sixth Edition, New York (1978).
5. American Petroleum Institute (APl), Heat Exchangers for General Refinery
Services, APl Standard 660, Third Edition, American Petroleum Institute,
Washington (1976).
6. American Society ofMechanical Engineers (ASME), ASME Boiler and Pressure
Vessel Code, Section VIII, Division 1, American Society of Mechanical
Engineers, New York (1977).
7. Heat Exchange Institute (HEl), Standards for Steam Surface Condensers, Heat
Exchange Institute, Inc., Seventh Edition, Cleveland (1978).
8. Heat Exchange Institute (HEl), Standards for Power Plant Heat Exchangers,
Heat Exchange Institute, Inc., First Edition, Cleveland (1980).
9. Soler, A. J., "Expert System for Design Integration - Application to the Total
Design of Shell and Tube Heat Exchangers," Thermal/Mechanical Heat
Exchanger Design - Karl Gardner Memorial Session, K. P. Singh and S. M.
Shenkmen (eds.), ASME HTD-Vol. 64, Anaheim (1986).
Figure 18 is reproduced by permission of the American Society of
Mechanical Engineers.
Figures, 1 to 12 and 15 to 18 are reproduced by permission of Hemisphere
Publishing Corporation, N.Y., U.S.A.
@ProcessEng
GENERAL DESIGN OF HEAT EXCHANGERS FOR FOULING CONDITIONS
JAMES M. CHENOWETH

Alhambra, California USA
1. INTRODUCTION
Not all heat exchangers have serious problems with fouling. Many operate
satisfactorily for long periods without being cleaned. Garret-Price et al. [1] assembled
Table 1 which identifies the kind and typical extent of fouling for fluids in various
industry groups. This is useful in determining which heat exchangers must seriously
consider fouling when they are being designed.
Some allowance for fouling must be provided in the design of a heat exchanger if
fouling is anticipated. There are different ways to provide this allowance. Design
fouling resistances, cleanliness factors, and a percent oversurfaee are the most usual
TABLE 1
Fouling of Heat Transfer Surfaces by Industry Groups (from Garrett-Price et al 11])
Type of fouling that occurs in heat Usual extent

lndustry group exchange equipment ofproblem
Food and kindred produets Chemical reaction Major

Crystallization (milk processing) Major
Biofouling Medium
Particulate (gas side) (spray drying) Minor/major
Corrosion Minar
Textile mill produets Particulate (cooling water)
Biofouling (cooling water)
lumber and wood produets Crystallization (liquor, cooling w.ter) Major
including paper and allied Particulate (process side, cooling water) Minar
produets Biofouling (cooling water) Minar
Chemical reaction (process side) Minar
Corrosion Medium
Chemical and allied Crystallization (process side, cooling water) Medium
Particulate (cooling water) (gas side) Minor/medium
Biofouling (cooling water) Medium
Chemical reaction (process side) Minor/major

Corrosion Medium
Petroleum refining and Chemical reaction (process side) Major
related industries Crystallization (cooling water) Medium
Particulate (cooling water, gas side) Minor/medium
Biofouling (cooling water) Medium
Conosion (process side) Medium
Stone, clay, glass, and Particulate (gas side) (heat recovery) Minor/major
@ProcessEng
concrete produets
Electric power produetion Biofouling (cooling water) Major
Crystallization (cooling water, boiler water) Medium
Particulate (furnace side) Major
Freezing (fum.ce·side slag formation) Major
Corrosion (air·cooled condensers) Minar
477

478
approaches that have been used. Regardless of the approach, the selection of
appropriate values re lies more on engineering judgement from past experience than on
an application of results from experimental research. It must be recognized that it is
extremely difficult to predict specific fouling behavior for most cases due to the large
number of unknown variables that ean materially alter the kind of fouling and its rate
ofbuildup.
Typically the sizing of heat exchangers is based upon given design specifications
which assume a steady operation. Fouling, on the other hand, is dynamic by its very
nature. To specify appropriate values to account for fouling requires the careful
examination of a large number of parameters. All too often, the designer concentrates
on the design conditions and fails to ex amine such important factors as the way the
exchanger is to be operated, the difficulty of cleaning, the desired time between
cleanings, the metallurgy of the components, the consequences the exchanger being
fouled, etc.
With the availability of sophisticated computer programs for the design and
evaluation of heat exchangers, the designer and the operator have access to
information needed to evaluate the impact of fouling. It is possibie to examine the
relative thermal resistances of the wall material, the heat transfer coefficients for the
individual fluids, and the fouling layers on both sides of the wall. With this
information intelligent changes in a design ean be made to mitigate fouling.
2. DESIGN FEATURES THA T MINIMIZE FOULING

One of the things to be considered in the design of a heat exchanger is the severity
of the anticipated fouling. If fouling will be significant, it may well control the
selection of the type of exchanger and its size. The thermal-hydraulic considerations
may be secondary. For example, brines from geothermal wells were found to contain
such a high mineral content that conventional heat exchangers plugged solid after a
few days of operation. For this application, direct contact heat exchangers proved to
be attractive. Or, in another case, fluidized-bed heat exchangers were selected where
the fluidized particle motion scours away the otherwise fouling buildup from the
imbedded tubes. Plate and frame heat exchangers are attractive for food processing
where fouling is anticipated as they ean be easily disassembled for cleaning and
sterilizing. Scraped heat exchangers improve the heat transfer by continuously
removing both fouling and the static fluid from the heat transfer surfaee as the blades
rotate. Since there are no locallow velocity regions in spiral heat exchangers, they are
particularly attractive for process stream with a high concentration of suspended
solids. On the other hand, compact and plate fin heat exchangers are norma Ily
avoided for fluids with a high fouling potential as they are difficult to clean. Although
each type of heat exchanger has special design features that ean reduce the impact of
fouling, those for shell-and-tube heat exchangers will be emphasized.
Type of Heat Exchanger. Probably the two most important decisions to be made
when designing shell-and-tube heat exchangers for fouling services are the selection of
the type of heat exchanger and choice of the fluid to place on the tube side. Shell-and-
tube heat exchangers come in a variety of types as illustrated in Fig. 1 which gives the
TEMA [2] designations for shell, front end, and rear end types. As ean be seen there
are man y possibie combinations. The "G," "H," and "K," are normally oriented
horizontally, while the others ean be oriented either horizontally or vertically.
Once the type of heat exchanger is selected, the allocation of the streams to the tube
side and the shell side must be made. In general, the more corrosive and/or the more
@ProcessEng
fouling fluid is placed on the tube side. A high pres sure fluid or one that ean be
expected to polymerize should also be placed on the tube side regardless of its fouling
character. The reasons for this are that it is less expensive to provide more exotic
materials on the tube side and it is easier to mechanically clean. If the exchanger has
straight tubes and the heads are removable, it is possibie to clean the tubes
mechanically without removing the bundle from the shell. Horizontal heat exchangers
479
are easier to dean meehanieally than vertieal ones. Chemieal deaning ean be done
equally well on either the tube or shell side and for exchangers oriented horizontally or
vertieally.
FRONT END REAR END

SHELL TYPES HEAD TYPES
STATlONARY HEAD TYPES
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@ProcessEng
CROSS FLOW EXTERNALLY SEALED

SPEClAL HIGH PRESSURE CLOSURE FLOATING TUBESHEET
FIGURE 1 TEMA (2) Shell, Front Head, and Rear Heat Types
"©1978 by Tubular Exr.hanger Manufacturers Association"
480
Operating Conditions. The operating conditions set by the process design define
the thermal-hydraulic requirements that must be met for the overall performance of a
heat exchanger. However, there are a number of combinations of parameters that will
satisfy the operating conditions. The designer has the opportun it y to select those that
will mitigate the effects of fouling. Experience has shown that higher velocities and
lower surfaee temperatures tend to reduce fouling. In addition, operation above the
dew point temperature for acid vapors and above the freeze point for fluids containing
waxes prevents corrosion and freeze fouling from occurring. By investigating
countercurrent and cocurrent flow and different tubepass arrangements it is often
possibIe to modify the local temperatures and velocities. A sacrifice in the thermal
performance or a penalty of increased pressure drop may be associated with design
changes desired to mitigate fouling.
Geometry Considerations. Shell-and-tube heat exchangers are widely used
because they ean be tailored to meet such a wide variety of requirements by changing
their geometry. For example there are different bame arrangements as shown in Fig.
2 which alter the shellside fluid flow path by trading increased pressure drop for
improved heat transfer. The spacing between baffles and the size of the baffle
windows further perrnit tuning a design. Those arrangements that eliminate stagnant
and low velocity regions where deposits ten d to accumulate have les s overall fouling.
This ean be seen in Fig. 3 which il!ustrates the observed fouling on the shel!side of two
smal! test heat exchangers that differed in their baffle spacing and bame window size.
Both were operated with the same shellside fluid, crossflow velocity, and surfaee
temperature. Fouling deposits were heavy in the regions of low velocity. These are
BAFFLE CUTS FOR SEGMENTAL BAFFLES
eJGGHorizontal Vertical
BAFFLE CUTS FOR MULTI-SEGMENTAL BAFFLES

Rotated
ti
DOUBLE SEGMENTAL
@ProcessEng
TRIPLE SEGMENTAL
FIGURE 2 Baffle Styles and Cut Orientation TEMA (2) Designations

"@1978 by Tubular Exchanger Manufacturers Association"
481
Exchanger E-l
Well Designed Tube Bundle
Exchanger E-2
Wide Baffle Spadng Bundle large Baffle Cut Bundle
FIGURE 3 Sketch of Observed Fouling Deposits in Two Different Heat Exchanger Configurations
areas which can experience local hot spots. As can be seen, the fouling deposit is far
from uniform on the shell side of a heat exchanger. Gilmore [3] suggests that baffle
cuts of 20 to 25 percent of the shell diameter are appropriate to minimize fouling. He
also recommends horizontal baffle cuts for liquids and gases and vertical cuts for
boiling and condensing.
There are an increasing number of different enhanced heat transfer surfaces for
tubes in shell-and-tube heat exchangers. Finned tubes having as few as 354 to as
manyas 1260 fins per meter are common in the process industries. Enhanced surfaces
tailored for boiling and condensing service are recognized as offering significant
improvements in performance. Internally and externally grooved straight and spiral
tubes increase the heat transfer particularly in laminar flow. It is often argued that
the least expensive way to provide an allowance for fouling is to use finned tubes and
put the more fouling fluid on the shell side. But with each of these tubes with
enhanced surfaces come questions as to w hether they will foul as quickly as plain
tubes, how they will perform when they become fouled, what are the appropriate
fouling resistances and surface are a definition, and how these surfaces ean be
effectively cleaned.
The geometry affects the thermal performance and must always be considered.
Many trends that improve the heat transfer als o minimize fouling. However, some
cause a thermal pen alt y that must often be offset by an increase in the first cost of an
exchanger. For example, it is easier to mechanically clean bundles with square or
@ProcessEng
rotated square tubefield layouts than those with triangular layouts. Also increasing
the tube pitch will provide wider lanes for hydraulic cleaning. However, these actions
ean lead to larger diameter heat exchanger shelIs that are more expensive to purehase.
Other parts of the heat exchanger , in addition to the heat transfer surfaces , need to
be examined for possibie ways for reducing fouling. For example, the clearances
between tube and baffle holes, baffles and shelIs along with the placement of tie rods,
seal strips, and seal rods ean do much to direct the shellside flow past the tubes and
482
prevent bypassing. Gillmore [3] warns that notches in the bottom of baffles are
potential problems because they permit undue bypassing between crosspasses. A ve ry
smooth surface finish on tubes such as that produced by electropolishing has been
shown to delay the initiation of fouling and facilitate the removal of the fouling layer.
Coatings are sometimes used to provide corrosion protection result in smooth tube
surfaces which are daimed to reduce fouling.
Maintenance, Control, and Cleaning. Having the folIowing information available
when the exchanger is being designed would be of great benefit: the type of fouling
anticipated, the difficulty to dean the tubes, the expected frequency of deaning, and
the anticipated fluid treatment plans. If they have not, the strategy for operation,
maintenance, control, and cleaning that should have a significant impact on the
design will not be considered. As aresult the appropriate allocation for fouling will be
nothing more than an educated guess. If the anticipated fouling will be severe, on-line
cleaning may be economically attractive. There are several available including the use
of circulating sponge rubber balls, wire or plastic brushes, thermal shocking, gas
bumping, etc. Intake screens and filters to remove unwanted suspended solids may be
warranted. Control to prevent biological growth is always justified. Corrosion
products and catalyst fines suspended in the process fluids ten d to deposit on heat
transfer surfaces. Additives to prevent or modify the character of the fouling deposits
should be determined. Otherwise, too much surface may be provided in an
anticipation of fouling buildup that does not materialize. It may then be very difficult
to control the heat exchanger to provide the desired performance, particularly when it
is put back onstream after cleaning.
Special Fouling Considerations. Some designers routinely increase fouling
resistance values to provide added safety to cover uncertainties in the heat transfer
predictions and the anticipated operating requirements. This leads to larger and more
expensive heat exchangers. (This may please the manufacturers but not the user.)
But this is a dangerous procedure. It can lead to heat exchangers that are so oversized
that they can not be operated at all. Further, an overspecification of the fouling
resistance will also prevent making the desirable design checks on the pressure drop
when the exchanger is fouled and the temperature evaluation when the exchanger is
cleaned. It is better practice to limit the fouling resistances to values that reflect the
fouling alone. Uncertainties can be accounted for in identified safety factors.
The metallurgy of the components of a heat exchanger need to be checked for their
corrosion properties and for their compatibility. Depending upon the process
requirements, some metals can be pretreated to minimize the attack from corrosive
fluids.
3. PROVIDING A FOULlNG ALLOWANCE
There are three basic ways to provide a fouling allowance. The first is to assign
fouling resistance, sometimes called "fouling factor ," for each of the fouling layers that
develop on the tube walls. These are usually different depending upon the fouling
characteristics of each fluid. By assigning these separately, it is possibie to determine

the influence of each on the overall thermal performance. The sum of these fouling
resistances is designated the total fouling resistance, Rft.
Another approach is to use a so called "cleanliness factor" to relate the overall heat
transfer coefficient when the exchanger is fouled to that when it is dean. This is a
convenient way to represent the performance of a heat exchanger dur in g operation.
However, it is subject to some differences in interpretation when using this approach
@ProcessEng
for design. It was developed for the steam power industry where the fluids are
typically steam and water and the fouling is concentrated on just one side of the
exchanger. Cleanliness factor can be related to the total fouling resistances under
limit ed conditions. The assumption has to be made that the film heat transfer
coefficients do not change between the clean and fouled operating conditions. Typical
designs are based upon a cleanliness factor of 85 percent.
483
A third approach is to assign a percent of added heat transfer surface to that

determined assuming no allowance for fouling. This approach requires a decision as to
how the surface should be added. The added surface implicitly fixes the equivalent
overall fouling resistance from the overall clean heat transfer coefficient for the design.
Those designers that add 15 to 25 percent additional surface to account for fouling
have in effect assigned overall fouling resistances. There are different ways in which
this surface is provided. Ifthe length of tubes is limited, more tubes can be added of
the same size and pitch to increase the shell diameter. This in turn alters the
velocities on both the tube and shell sides so it is necessary to rerate the design.
Another popular way of adding surface is to increase the tube length while retaining
the same bundle diameter. This will probably alter the number of crosspasses and the
baffle spacing. Both the shell side and the tube side pressure drops will be increased
for the same flow rate. The resulting effects on the heat transfer coefficients will
influence the performance of the exchanger. The new design with the increased
surface should be rerated with a computer program. The designer may decide to
assign a portion of the overall fouling resistance to one side or the other. It is usual for
a fouling thickness to be assigned so the increase in pressure drop when the exchanger
is fouled can not be predicted.
It is interesting to examine the implicit total fouling resistance when assigning 25
percent excess surface for various overall clean heat transfer coefficients. Table 2
shows that it may well be quite large.
TABLE 2
Implicit Overall Fouling Resistance for 25 Percent Excess Surfaee Area
(uo)c, Rft,
Wfm 2 K Btu/hr ft2 F m2 K/W hr ft 2 F/Btu
56.7 10 0.00176 0.010

283.7 50 0.00088 0.0050
567.5 100 0.00044 0.0025
1418.6 250 0.00018 0.0010
2837.3 500 0.00009 0.0005
All three approaches have been used successfully. Each has its advantages and
proponents. Most process heat exchangers are designed with fouling resistances.
Some large users prefer to specify a percentage of oversurface. On the other hand, the
power industry favors cleanliness factors. For the understanding of the effects of
fouling on the design process, the fouling resistance approach is preferable.
The designer may have several reasons for increasing the margin for "fouling" which
have nothing to do with the actual occurrence of fouling. It seems that this is one of
the most convenient ways to mask uncertainties. The exact performance required
may not be known or some doubt may exist about the properties of the fluids. Or it
may be a safeguard against any inaccuracies in the methods used to design the heat
exchanger. At times the purchaser may request that an overload factor be built into
the fouling allowance; however this would better be incorporated as a specified factor
for potential growth.
Specifying too much surface to provide for possibIe fouling is an invitation for that
much fouling to occur. For example, to compensate for the improved heat transfer
@ProcessEng
when an exchanger is clean, cooling water flow rates may be reduced and the surface
temperature allowed to rise. These trends are counterproductive and fouling will be
accelerated. Ir fouling is to be minimized, high velocities should be maintained by
recycling, if possible, when the exchanger is dean. It is important that start-up
conditions for a dean exchanger be carefulIy planned. Ir an exchanger is designed
with a large fouling resistance and operated at partial load conditions, rapid initial
fouling rates can occur.
484
Fouling resistances are usually specified by the user of the heat exchanger and
occasionally by the heat exchanger designer. The fabricator of the heat exchanger will
seldom accept the responsibility for the specification of fouling resistances. The user is
guided largely by previous experience, or lacking that, by the TEMA fouling
resistances. The user desires that the heat exchanger will perform at the required heat
dut y in the period between scheduled cleanings, usually during times of plant
shutdown and maintenance. Unscheduled shutdowns due to fouling are to be avoided.
The use of finite fouling resistance in the specifications of a heat exchanger leads to
surface area in excess of that needed to perform the same heat transfer dut y when the
exchanger is dean. The amount of excess surface is a funetion of U o' the overall heat
transfer eoefficient for the dean exehanger aeeording to the relations hip
(1)
where A o is the area required for the dean heat exehanger (R f = O) and Af is the area
required when a finite fouling factor is ineorporated in the design. As ean be seen in
Fig. 4, the amount of added surface is influeneed by both the size of the overall dean
heat transfer eoefficient, Uo' and the sum of the fouling resistanees, Rft. The
percentage of added surfaee will be small if U o is low regardless of how high the Rft is.
On the other hand, for a high U o' even a low Rft will result in a high pereentage of
added surface.
To illustrate the interrelationships of the parameters involved in the surface added
for fouling, it is interesting to start with Bell's [4] list of typieal values of Uf and
assigned Rtf for typieal industrial applieations in shell-and-tube heat exehangers.
These were used to determine the eomparable percent of surfaee added for fouling and
the results are listed in Table 3. Notice that the percent of added surface ranges from
a few pereent to over 80 percent. Certainly, the designer should evaluate the pereent
of added surfaee that is implicit ly specified when fouling resistances are assigned.
10 3
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@ProcessEng
Clean Overall Heat Transfer Coefficient, (Uole, Btu/hr ft 2 F
FIGURE 4 Area Added to Provide for Fouling

485
TABlE 3
Typical Design Overall Heat Transfer Coefficients, Fouling Resistances, and Added Surfaee
(from Chenoweth (16))
Rft , (Uo)f' (Uo)e' Added

First Fluid Second Fluid hr It 2 F ~ ~ Surface,
Btu hr It 2 F hr It 2 F percent
Water Water 0.0015 250 - 300 400 - 546 60.0 - 82.0

Gas, about 10 psig 0.001 15 - 20 15 - 20 1.5 - 2.0
Gas, about 100 psig 0.001 30 - 40 31 - 42 3.1 - 4.2
Gas, about 1000 psig 0.001 60 - 100 64 - 111 6.4 - 11.1
Light Organic Liquids 0.0015 125 - 175 154 - 238 23.1 - 35.7
Medium Organic Liquids 0.002 75 - 125 89 - 167 17.7 - 33.3
Heavy Organic Liquids 0.0025 40 - 75 44 - 64 11.1 - 16.0
Very Heavy Organ ic liquids
Heating 0.004 10 - 40 10 - 48 4.2 - 19.0
Cooling 0.004 5 - 15 5 - 16 2.0 - 6.4
Condensing Pure Vapors
light Organic 0.001 150 - 200 176 - 250 17.6 - 25.0
Medium Heavy Organics 0.001 100 - 150 111 177 11.1 - 17.7
Heavy Organics 0.002 75 - 100 88 - 125 17.6 - 25.0
Steam Gas, about 10 psig 0.0005 15 - 20 15 - 20 0.8 - 1.0
Gas, about 100 psig 0.0005 35 - 45 36 - 46 1.8 - 2.3
Gas, about 1000 psig 0.0005 70 - 110 73 - 116 3.6 - 5.8
Light Organic liquids 0.001 135 - 190 156 - 235 15.6 - 23.5
Medium Organic Liquids 0.0015 80 - 135 91 - 169 13.6 - 25.4
Heavy Organic liquids 0.002 45 - 80 50 - 95 9.9 - 19.0
Very Heavy Organic liquids 0.0035 15 - 45 28 - 54 9.7 - 18.7
Water 0.001 300 - 400 429 - 667 42.9 - 66.7
light Light Organic liquids 0.002 100 - 130 125 - 175 25.0 - 35.1
Organic Medium Organ ic liquids 0.0025 70 - 100 85 - 133 21.1 - 33.3
liquid Heavy Organic liquids
Heating 0.003 40 - 75 45 - 97 13.6 - 29.1
Cooling 0.003 25 - 50 27 - 59 8.1 - 17.6
Very Heavy Organic liquids
Heating 0.004 20 - 50 22 - 63 8.7 - 25.0
Cooling 0.004 5 _. 25 5 - 28 2.0 - 11.1
0.003 50 - 80 59 - 105 17.6 - 31.6
Medium Medium Organic liquids

Organic Heavy Organic Liquids
liquid Heating 0.0035 30 - 50 34 - 61 11.7 - 21.2
Cooling 0.0035 15 - 35 16 - 40 5.5 - 14.0
Very Heavy Organic liquids
Heating 0.0045 15 - 30 16 - 35 7.2 - 15.6
Cooling 0.0045 5 - 15 5 - 17 2.3 - 12.6
@ProcessEng
Heavy Organic Heavy Organic liquids 0.005 10 - 30 11 - 35 5.3 - 17.7

liquids Very Heavy Organic Liquids 0.006 5 - 15 5 - 18 3.1 - 9.9
To convert hr It 2 F /Btu to m 2 K/W multiply by 0.1762

Btu/hr It 2 F to W /m 2 K multiply by 5.6745
486
4. SOURCES OF FOULlNG DESIGN DATA

Knudsen [5] identified the major problem in the design of of heat exchangers as the
inability to obtain appropriate values of the fouling resistance to be included in the
overall heat transfer coefficient determination. Although there has been ongoing
fouling research, the results have not led to a comprehensive set of acceptable values
for design. The selection of fouling resistances for design remains more an art than a
science. Fouling resistance values are sometimes specified by the licensor of the
process for which the exchanger is to be used. However, most of the time the heat
exchanger purehaser faces a difficult task when selecting values to be used. For a
limited number of situations he may have the results of similar operational experience
to serve as a guide. But more often, he selects either what has been specified in the
past or what he ean extract from available published sources.
The most comprehensive source for shell-and-tube heat exchangers with worldwide
popularity is the Fouling Section in the Standards of the Tubular Exchanger
Manufacturers Association [2]. As is stated in this section, the values represent a
consensus of good industrial practice, but are to be used only when other information
is not available. When firs t assembled, the values reflected the state of the art in
defining heat transfer coefficients, fouling, and the acceptable cleaning schedules in
industrial plants. It is interesting to note that most of the values in the original 1941
edition remain unchanged in the latest 1978 edition. This is surprising as there have
been many improvements in predicting clean heat transfer coefficients for all types of
heat transfer processes.
The great majority of the TEMA fouling resistances are given as a single value from
a set of numbers with significant intervals between each. This reflects the
uncertainties in the values. Some of the parameters recognized to affect fouling are
not adequately considered. For example, the effects of flow velocity and temperature
are respected only for water and crude oils in rough steps (e.g. for water velocity
smaller or greater than 0.91 m/s (3 ft/sec)). Unfortunately, the temperature referred
to is that of the bulk fluid rather than that at the wall surfaee and shear stress would
have been more appropriate than velocity. Although the values given are typical of
those used by industry, they have not been verified by research measurements. There
is no distinction made as to whether they ean be used equally for tube side or shell
side, nor whether they apply to sensible heating or cooling, boiling, or condensation
heat transfer processes.
The TEMA fouling resistances provide a "cook book" selection without
consideration of many of the factors now recognized as significant in the prediction
and control of fouling. To an extent, they are ambiguous and fail to define the specific
conditions for which they are valid. It is surprising how well they have worked in
spite of their deficiencies. This is probably because heat exchangers ten d to foul to the
extent of their fouling resistances before design velocities are achieved resulting in a
self-fulfilling propheey.
A designer has few published sourees of fouling data that ean be used direetly for
design. The most quoted souree is the fouling resistanee tables assembled by TEMA,
but there is evident that these are inadequate. The refrigeration industry (ASHRAE)
and the utility power industry (HEl) have reeommendations for a limited number of
fluids and services used by them. But for most cases the designer is required to base
his specifieations on previous company experienee and these data are usually
proprietary. Selected references are discussed in the folIowing sections for fouling
resistanees found in the published literature.
@ProcessEng
Cooling Water Fouling. The most important consideration for eooling water is the
quality of the water itself. Biological fouling ean be prevented by proper applieation
of bioeides to the water. Knudsen [6] indicates that if quality is controlled using
available treatment, the asymptotic fouling resistanee should not be greater than
0.000088 m 2 K/W (0.0005 hr ft 2 F/Btu). However, ifthe water treatment gets our of
hand, it ean rapidly beeome many times higher. AIso, the buildup of fouling will be
minimized if the veloeity of cooling water on the tube side ean be maintained between
487
2.44 and 3.06 m/s (8 and 10 ft/see) when erosion is not a problem. This eompares
with Kern's [7] value of 0.91 m/s (3 ft/see) or the more recent reeommendation of
Taborek [8] of 1.83 m/s (6 ft/see). The use ofthe higher veloeities ensures that those
veloeity effeets that impede fouling will predominate over those whieh promote it.
Knudsen [6] indicates that with eooling waters from whieh calcium earbonate may be
deposited, the heat transfer surfaee temperature above 60 C (140 F) should be
avoided. '
Evaporator Fouling. Smith [9] states that although theoretieally fouling resistanees
ean be calculated, in praetiee neither the thiekness nor the thermal eonduetivity ean
be even roughly estimated, the latter being very dependent upon the composition and
the density of the deposit. The most useful souree of information is a test of existing
evaporators, the estimated resistanees of the wall and the two fluid films being
subtraeted from the measured total resistanee to give the sum of the inside and the
outside fouling resistanees. Sueh information will not be available for a new process.
Advantage should be taken of any pilot plant tests, whieh should be planned so that
data on fouling ean be obtained using the same type of evaporator operating at similar
temperatures. It has been found that the fouling information required to check a
design ean be obtained by earrying out a simple test on a single tube of full-seale
dimensions. The tube should be provided with a steam-heated jacket and fitted into
the pilot plant so that the boiling proeess fluid ean flow through it. Steam used for
heating provides virtually no fouling. The tests should be earried out at the
cireulation veloeity that will be used. Smith [9] suggests that reasonable values of
boiling fouling resistanees will range from 0.001 m 2 K/W for heavy seale deposits to
0.000 1 m 2 K/W for slight seale.
Reboiler Fouling. Palen [10] has tabulated in Table 4 the reeommendations for the
seleetion of reboiler type depending upon the antieipated fouling. He has als o
indieated reasonable values offouling resistanees for design as 0.000 18 m 2 K/W for
nonpolymerizing fluids, 0.000 09 m 2 K/W for fluids known to be dean and
nondegrading, and 0.000 5 - 0.000 7 m 2 K/W for polymerizing materiais. Additional
values are given in Table 5 by Palen and Small [U].
TABLE 4
Reboiler Selection Guide Based Upon Anticipated Fouling (adapted from Palen [10))
Horizontal Vertical
Process Kettle or Shell Side Tube Side Forced
Conditions Internal Thermosiphon Thermosiphon Flow
Anticipated Fouling
Clean Good Good Good Expensive

Moderate Risky Good Best Expensive
Heavy Poor Risky Best Good
Very Heavy Poor Poor Risky Best
Reproduted by permission of Hemisphere Publishing Company,@1983

@ProcessEng
Plate Heat Exchanger Fouling. Cooper and Usher [12] warn that fouling
resistanees for plate and frame heat exehangers are mueh smalle r than those for shell-
and-tube heat exehangers. They attribute this to the highly turbulent flow and the
small flow passages whieh produce high heat transfer eoeffieients. Their
reeommendation is that fouling resistanees for plate heat exehangers should be about
20-25 percent of tubular fouling resistanees. On the other hand, MeAteer and Bath
[13] suggest that they should be no more than 10 percent.
488
TABLE 5
Suggested Fouling Resistances Values for Reboilers (from Palen and Smal! [11])
Fouling Resistance Rf , m 2 K/W

Boiling Side
C1 -C S Normal Hydrocarbons O to 0.000 18
Heavier Normal Hydrocarbons 0.00018 to 0.00050
Diolefins and Polymerizing
Hydrocarbons 0.00050 to 0.00090
Heating Side
Condensing Steam O to 0.00009
Condensing Organics (without
Entrained Heavy Components) 0.00009 to 0.000 18
Sensible Heating, Organic
Liquids 0.00009 to 0.00035
Reproduced by permIssIon of Hemlsphere Pubhshmg Company,©1983
Pritchard [14] suggests the folIowing are the ramifications of the selection of the
fouling resistances for design.
• If the fouling resistance has been underestimated, the exchanger does not
perform and you are in trouble.
• If it has been overestimated, there are no operational problems unless the
exchanger blocks up through overcooling of a fluid such as tar - or the
accountants realize the substantial capital that might have been saved.
Current Foulin Desi n Practice Surve A joint committee of members from Heat
Transfer Research, Inc. HTRI and TEMA have been meeting to review the Fouling
Section in the TEMA Standards [2]. The main feature of the current Fouling Section
is the tabular values of fouling resistances. The objective of the committee is to review
the current section and make recommendations for consideration of a revision. In
addition, it is anticipated that a general discussion will be prepared to to be included
in the Recommended Good Practices Section that accompanies the Standards. The
final report edited by Chenoweth [15] will issue later this year.
Out of the HTRI/TEMA Joint Committee discussions, concern was expressed
about the ambiguity of the source and the limitations for the fouling resistances
included in the tables. It was recognized that more complete data should be provided
and that fouling resistances for design should have a range of values and not single-
values as now given in the tables. Further, the list in Table 6 of desired data for each
design fouling situation was prepared. It was realized that they were unlikely to be
assembled.
As another part of the activities of the HTRI/TEMA Joint Committee, five heat
exchanger manufacturers who are TEMA members were asked to supply the fouling
resistance values that had been specified on over 750 recent inquiries for shell-and-
tube heat exchangers. The data included the specified fouling resistances on both the
shell and tube side, the fluid designation, and the average bulk temperatures. From
these rat her typical data, it was possibIe to make some interesting observations.
@ProcessEng
The data were tabulated and grouped in a number of different ways. One of these
was the averages of the summations of the fouling resistances for both sides as
illustrated in Fig. 5. Note that the average combined fouling resistances are smallest
for vapor /vapor fluid combinations and the highest for liquid/liquid combinations.
The latter value of 0.00079 m 2 K/W (0.0045 hr ft2 F /Btu) is more than twice the
value of 0.000 38 m 2 K/W (0.0022) for the former. Values for the other fluid
combinations were somewhere in between. These average values are interesting in
489
TABLE 6
Data Desired for Fouling Resistances for Design
• Primary Fluid Name • Shellside Fluid Temperature Range

• Secodary Fluid Name • Shellside Fluid Velocity Range
• Primary Fluid Tubeside or Shellside • Shellside Design Fouling Resistance Range
• Description of Service • Types of Fouling Expected
• Tube Description • Fouling Layer Thermal Conductivity
• Range of Overall Clean Heat Transfer Coefficients • Fouling Layer Thickness Before Cleaning
• Estimated Tubewall Temperature • Ease of Fouling Layer Removal
• Tubeside Fluid Temperature Range • Effective Cleaning Procedures
• Tubeside Fluid Velocity Range • Period of Time Between Cleanings
• Tubeside Design Fouling Resistance Range • Special Considerations
that they reflect increases of 22.5 and 67.5 percent in heat transfer surfaee if the
combined fouling resistance is 0.000 79 m 2 K/W and the clean overall heat transfer
coefficients are 284 and 852 W /m 2 K, respectively. As can be seen from Fig. 4, the
percentage surface increase would be 11 and 33 percent for the same clean overall heat
transfer coefficients and a combined fouling resistance of 0.000 38 m 2 K/W.
Tubeside and Shellside

Combined Fouling
Resistance,
hr ft 2 F/Btu
Reproduced by permission of Hemisphere Publishing Company,@1981
FIGURE 5 Specified Average Combined Fouling Resistances (15)

5. UNCERTAINTIES AT THE TIME OF DESIGN

All too often there is a breakdown in the lines of communications. The designer is
seldom provided with adequate information about the anticipated operation of the
heat exchanger as a part of the overall plant. Re must make assumptions and may
fail to consider some important variables. As aresult he is unable to make intelligent
trade offs when significant fouling is antieipated. Therefore, the values for the fouling
allowance end up being somewhat arbitrarily assigned for the plant "design"
@ProcessEng
conditions.
Seldom is a plant operated uniquely at its design eonditions. Further, the effects of
fouling in many heat exchangers vary continuously throughout their operating eycle
until they are cleaned. Thus, the usual performance is different from that for which
the heat exchanger was designed. This ean lead to difficulties in the operating of heat
exchangers, particularly when they are first started up after being cleaned. This ean
be illustrated on Fig. 6 by Knudsen [5] which schematically indicates the relationship
490
Increasing
r
* ....
c::
Velocity ~
FIGURE 6 Effect of Velocity and Surfaee Temperature on the Asymptotic Fouling Resistance [5)
Reproduced by permission of the American Institute of Chemical Engineers
between surface temperature, veloeity, and asymptotie fouling resistanee for a typieal
cooling water. The design eonditions are indicated by point A. For the same heat
load the heat exchanger must be operated at point B when the exehanger is clean of
fouling. Notice this reflects an increase in surface temperature and a deerease in
veloeity - both tending toward increased fouling. However, it is possibIe to operate at
point C if the velocity can be inereased at the same time the surface temperature is
inereased to meet the required heat duty. The anticipated fouling will be les s than the
design, but a priee is paid to provide the higher velocity. As ean be seen, the way the
exchanger is operated influences the development of fouling.
There are a number of strategies for minimizing the impact of fouling. These include
the use and control of appropriate additives whieh may act as fouling inhibitors,
antisealants, dispersants, and acids. For fluids containing suspended solids filtering
ean do much to reduce the effects of fouling.
The trend has been for plant operators to increase the time between scheduled
turnarounds. This is, of course, the best time to clean offending heat exchangers. The
designer should be provided some indication as to the desired frequency of this
maintenanee operation and the anticipated means of off-line cleaning. There are a
nu mb er of different way to clean a fouled heat exchanger as indieated in Table 7. The
appropriate one to use is influenced by the rate at which fouling buiIds and how
difficult it is to remove. For heat exehangers that are critical to the plants operation
that are anticipated to have serious fouling problems and require frequent cleaning, an
on-line cleaning system may be eeonomieally attraetive.
6. SOMETIMES OVERLOOKED CONSIDERATIONS

There are many events that occur prior to the time a heat exchanger is first brought
into service that ean materially influence its later fouling behavior. These involve the
@ProcessEng
procedures followed in the construction, storage, erection, shakedown, and startup of

the exchanger. The care with whieh the exchanger is manufactured and the attention
to good fabrication praetice can ens ure that it meets the specifications. Preparation
for shipment and plant site storage should keep the exchanger internals from being
exposed to the elements and prevent corrosion. The erection should not damage the
exchanger and the connecting piping should be cleaned and checked for construction
491
TABlE 7
Various Techniques for C1eaning Heat Transfer Surfaces
On-line Techniques Scheduled Off-line Techniques
Use and Control of Disassembly and

Appropriate Additives Manual Cleaning
• Inhibitors
• Antiscalants lances
• Dispursants • liquid Jet
• Acids • Steam
• Air Jet
On-line Cleaning
• Sponge Balls Mechanical Cleaning
• Brushes • Drills
• Sonic Horns • Scrapers
• Sootblowers
• Chains and Sera pers Chemieal Cleaning
• Thermal Shoek
• Air Bumping
trash. Temporary screens should be provided to prevent extraneous items from

entering the exchanger. It is import an t that the fluids used for pressure testing and
shakedown be clean and treated. If the unit is to be temporarily be taken from
service, it should be thoroughly cleaned and if drained, dried and purged.
Provisions for cleaning are sometimes not considered at the time the heat exchanger
is being designed. All too often, the selection of the appropriate cleaning procedure is
an after the fact decision. Space and provisions for removing bundles need to be
provided. Valves to isolate the exchanger and eonnect cleaning service hoses should
be ineorporated if onsite chemical cleaning is anticipated. On-line cleaning systems
are available and most easily installed when a plant is initially eonstructed. The
assurance of continuous cleaning ean result in requiring a smaller fouling alIowanee.
Similarly, fluid treatment facilities should be provided for if they are needed.
It adds littie to the eost of a heat exchanger to provide adequate taps in the nozzles
for instrumentation at the time it is being buiit. Temperatures and pressures are
relatively easily obtained. Flow meter provisions are desirable, but less often
considered.
All too often, fouling is considered to be exclusively a thermal problem. AIIowances
for fouling are given as thermal fouling resistances and no mention is made of the
other equally as important manifestations, such as the thickness of the fouling layer or
its thermal conductivity. In part, this is due to the lack of identified values for either
of these parameters as they ean vary eonsiderably depending upon the eircumstances.
However, they are important design considerations. A table of approximate thermal
eonductivities of pure materials that ean constitute fouling deposits was assembled by
Knudsen [6J. Selected values have been reprodueed in Table 8 along with the
corresponding fouling layer thickness for an assumed design fouling resistance of 0.000
176 m 2 K/W (0.001 hr ft 2 F /Btu). Of course, this assumes that the design fouling
@ProcessEng
resistanee is tot ally associated with fouling and not design uneertainties, and that the
fouling layer is composed solely of the one material. In columns 3 and 4 are shown the
effects on the flow area and pressure drop if all of the fouling is on the sheII side of a
typieal sheII-and-tube heat exchanger bundle with 19 mm tubes and 24 mm pitch
(pitch-to-diameter ratio of 1.25). As ean be seen, the bundle pressure drop would
inerease more than 60 percent in some instanees for the assumed fouling.
492
TABLE 8
Approximate Thermal Conductivities of Some Materials Found in Fouling Layers
(from Knudsen [6))
Pure Material Thermal Layer Percent Added

Conduc!., Thick., Gap Pressure
Btu/hr It F in.• Remaining Drop •••
Open •• Percent
Water 0.35 0.00042 -- --

Biolilm 0.41 0.00049 99.48 1.0
Calcium Carbonate 1.70 0.0204 78.24 63.3
Calcium Sulfate 1.35 0.0162 82.87 46.1
Calcium Phosphate 1.50 0.0180 80.80 53.2
Magnesium Phosphate 1.25 0.0150 84.00 41.7
Magnetic Iren Oxide 1.66 0.0199 78.77 61.2
Analcite 0.70 0.0084 91.04 20.7
Hematite (boiler deposit) 0.35 0.0042 95.52 9.6
Calcite (boiler deposit) 0.54 0.0065 93.07 15.5
Gypsum (boiler deposit) 0.76 0.0091 90.29 22.7
Serpentine (boiler deposit) 0.60 0.0072 92.32 17.3
..
•••
Assuming a louling resistance 010.001 hr It 2 F /Btu
Assuming 3/4-in. tubes on 15/16-in. pitch
Assuming pressure drop varies as velocity squared
For many heat exchangers the physical presence of a fouling layer is of secondary
consideration as they experience few serious problems with fouling and operate
successfully between scheduled shutdowns for maintenance and cleaning. This is a
consequence of the common practice to cascade heat exchangers in parallel or series.
As fouling buiids in one, the load shifts on to the next. There is still more than
adequate thermal performance to meet the plant requirements which often are below
design conditions.
However, there are certain critical heat exchangers that present ongoing fouling
problems. There are some services where fouling ean not be avoided so alternative
plans to maintain heat exchanger availability must be sought. It is interesting to note
that the limiting consideration may be the available pressure drop rather than the
required heat transfer. When such a problem is recognized process engineers should
examine possibie re arrangement of the flow diagram that would reduce the problem.
Online c!eaning might be considered to lengthen the available run time. It may be
attractive to install a spare heat exchanger in parallel with the appropriate valves so
that one ean carry the load while the other is being cleaned.
Most of the expense of unscheduled downtime in a plant comes from the loss of
produetion. There are different causes including mechanical failure, instrumentation,
corrosion, and fouling. In some plants the largest costs are incurred due to failure of
heat exchangers. Discussions by the HTRI/TEMA Joint Committee [15] identified
@ProcessEng
that more exchangers are removed from service for unscheduled cleaning due to
pressure drop (pumping) limitations than from heat transfer considerations.
Good heat exchanger performance simulation computer programs facilitate
examining the impact of fouling at other than the design condition. It is known that
the exchanger will be oversized just after it has been cleaned. How quickly and to
493
what extent the exchanger fouls de pen ds upon how it is operated. Simulations to
develop an operational strategy should be a part of eve ry design. Conditions just
before cleaning should be simulated to verify that there is adequate pumping
available. This requires an assumption as to the thickness of the fouling layers. All
too often this is assumed to be zero while in reality it is significant and may well block
leakage streams which are present when the exchanger is clean. The result is a
redistribution of the major streams on the shell side of a heat exchanger.
7. ECONOMIC CONSIDERATIONS
The design of heat exchangers for fouling service involves a number of economic
considerations. It is possibIe to design most heat exchangers so that fouling is under
control. However, there will be services where continuing cleaning will be necessary
for satisfactory operation. The important faet is to recognize this situation when the
exchanger is being designed so that a cleaning scheme ean be provided that result in
the minimum negative impact on the overall plant operation.
The first cost may well rep res en t a small fraction of the overall cost for successful
performance throughout the operationallife of a heat exchanger. Providing addition al
surfaee to perrnit fouling to occur may not be justified when a smaller heat exchanger
with on-line cleaning or fluid treatment produces a lower overall cost. The relocation
of a heat exchanger within the process flow diagram should also be considered to
lessen the impact of fouling on the overall plant operation. Recirculating piping,
valves, eductors, and/or pumps do much to maintain high velocities, especiaIly
folIowing the cleaning of a heat exchanger, to mitigate fouling. Certainly, the desired
time between scheduled cleanings and the cost of unscheduled shutdowns due to
upsets in treatment procedures influence the overall cost.
The cost cycle for a heat exchanger from the standpoint of fouling should be
considered as starting with its initial design and only concluded when it is retired or
scrapped. The decision as to the selected design should be made on economic
grounds. The ultimate objective always is to provide the required heat dut y safely for
the least overall cost.
8. CONCLUSIONS
Almost all heat exchangers require some allowance for fouling. It is not easy to
dee ide upon the appropriate amount of fouling allowance to use. Although there are
different techniques for providing a fouling allowance, when possibIe it is advisable to
specify fouling resistances for both sides. There is limited availability of published
values of fouling resistances for heat exchanger design. Not all types of heat
exchangers are equally effective for fouling service. Geometry determines the local
velocity (shear stress) which in turn influences the fouling characteristics.
Many parameters are unknown so assumed when the fouling allowance was assigned
and these need to be verified before the final design is accepted. For example,
maintenance and plant downtime influence the desirable cleaning schedule.
Anticipated treatment plans modify appropriate fouling resistance values. Past

experience with identical exchangers in a similar service suggests the range of
reasonable values. Too often uncertainties are buried in the specification of the
fouling resistances. Fouling resistance values are single, design point values which
often do not reflect variations causerI by significant parameters. To be meaningful,
individual design fouling resistances with anticipated fouling layer thickness should be
specified for the designer.
@ProcessEng
A matrix simulation of off-design operating conditions should be calculated to

assure reasonable flexibility and to evaluate the probable effects of parameter
variation. It is important to develop a strategy for the startup and operation
folIowing the cleaning of an exchanger. Adequate consideration should be given to the
economics of operation and maintenance. Fouling control is too often a reaction to a
problem rat her than a carefully considered plan developed at the time of design.
494
Acknowledgment
proprietary information nor does it necessarily represent HTRI recommendations.
Rather , it is intended to provide a helpful interpretation of published literature in the
light of HTRI experience in the same area.
References
l. Garret-Price, B. A., Smith, S. A., Watts, R. L., and Knudsen, J. G., "Industrial
Fouling: Problem Characterization, Economic Assessment, and Review of
Prevention, Mitigation, and Accommodation Techniques," Report No. PNL-4883,
Pacific Northwest Laboratory, Richland, WA., Feb. 1984.
2. Tubular Exchanger Manufacturers Association (TEMA), "Thermal Standards,"
Standards of Tubular Exchanger Manufacturers Association, 6th Edition, New
York,1978.
3. Gilmour, C. H. "No Fooling - No Fouling," Chem. Engr. Prog., Vol. 61, No. 7, pp.
49-54 (1965).
4. Bell, K. J., "Preliminary Design of Shell and Tube Heat Exchangers," Heat
Exchangers: Thermal-Hydraulic Fundamentals and Design, S. Kakac, A. E.
Bergles, and F. Mayinger, eds., pp. 559-579, Hemisphere, Washington, 1981.
5. Knudsen, J. G., "Fouling of Heat Exchangers: Are We Solving the Problem?"
Chem. Engr. Prog., pp. 63-69 (1984).
6. Knudsen, J. G., "Fouling in Heat Exchangers," Section 3.17, Heat Exchanger
Design Handbook, Hemisphere, Washington, 1984.
7. Kern, D. Q., Process Heat Transfer, pp. 154, McGraw HiU, New York, 1950.
8. Taborek, J., "Design Procedures for Segment ally Baffled Heat Exchangers,"
Section 3.3.10, Heat Exchanger Design Handbook, Hemisphere, Washington, 1983.
9. Smith, R. A., "Estimation of Heat Transfer Coefficients: Evaporators," Section
3.5.7, Heat Exchanger Design Handbook, Hemisphere, Washington, 1983.
10. Palen, J. W., "Shell-and-Tube Reboilers," Section 3.6, Heat Exchanger Design
Handbook, Hemisphere, Washington, 1983.
11. Palen, J. W. and Small, W. M., (1964) "A New Way to Design KettIe and
Internal Reboilers," Hydrocarbon Proc., Vol. 43, No. 11, pp. 199 (1964).
12. Cooper, A. and Usher, J. D., "Fouling: Plate Heat Exchangers," Section 3.7.8,
Heat Exchanger Design Handbook, Hemisphere, Washington, 1983.
13. McAteer, E. and Bath, C., "Design Features to Avoid Fouling in Plate Heat
Exchangers," Proc. Fouling and Cleaning of Heat Exchangers, Paper 5, U. of
Liverpool, 1986.
14. Pritchard, A. M., "Prevention or Cure?" Fouling Prevention Digest, Vol. 5, No. 1
(1983).
15. Chenoweth, J. M., "Final Report, Joint HTRI/TEMA Committee to Review the
Fouling Section of the TEMA Standards," 1987.

16. Chenoweth, J. M., "Fouling Problems in Heat Exchangers," Heat Transfer in High
Technology and Power Engineering, pp. 406-419, Hemisphere, Washington, 1987.
Figure 6 is reproduced by permission of the American Institute of Chemical
@ProcessEng
Engineers, from Chem.Eng. Prog. 18(2), p. 65, Febr. 1984.

Figure 5 is reproduced by permission of Hemisphere Publishing Corporation
N.Y., U.S.A.
BASIC CONCEPTS IN HEAT EXCHANGER NETv]ORK MODELLING.
Peter Fryer
Dept. of Chemical Engineering,

Pembroke Street,
Cambridge, U.K.
I.INTRODUCTION: FOULING IN HEAT EXCHANGER NETWORK DESIGN.

Increasing energy costs have made it imperative to ensure
that as littie energyas possibie is consumed by a chemical
plant. Despite the recent fall in the cost of oil, it seems
certain that the general trend in energy costs over the next
few years will be steadily upward, and so design techniques
which can produce energy-efficient plant are of paramount
importance. Recent developments in process synthesis -defined
by (l) as "the act of determining the optimal interconnection
of processing units as well as the optimal type and design of
the units within a process system"- have resulted in large cost
savings, but have not considered the effects of fouling.
Umeda (2) has noted that process synthesis proceeds in five
stages: development, planning, basic design, detailed design,
and improvements. The results from any stage constrain the
feasible solutions to later stages. It is vital, therefore, to
consider as many options as possibie at as early a stage as
possible, so that the final plant can be optimal. Originally
the design of a chemical flowsheet was large ly intuitive. Over
the last ten years, however, new techniques of integrated
process design - where the flowsheet is designed as a whole
rather than as a series of independent units - amongst them the
"pinch" approach developed by Linnhoff and co-workers at ICI
and elsewhere ((3) gives a ful ler description of many of the
techniques described here), have made the synthesis and
analysis of energy- and cost-efficient flowsheets a much less
empirical business. These techniques began with the analysis of
heat exchanger networks, and have since been extended to the
design of whole flowsheets, including distillation and
mechanical power systems.
In this work we will be concerned primarily with the the

problem of heat exchanger network (HEN) design, a tractable
subset of the overall synthesis problem, and one in which the
effects of fouling are especiaily obvious. The problem was
first stated by Masso and Rudd (4):
A set of co Id streams initially at supply temperatures

TC IN are to be heated to target temperatures TC OUT ,
@ProcessEng
whilst a set of hot streams at TH IN are to be cooled to

target temperatures TH OUT . Determine the structure of a
network of heat exchangers, with additional heaters or
coolers, which will bring all the streams to their target
temperatures whilst minimising the cost of equipment,
steam, and cooling water.
495

496
The problem is simple to state, but much more difficult to

sol ve. The techniques developed to solve the problem do not
consider the possible effects of fouling, being concerned
largely with thermodynamic and topological fundamental s i the
structure of the network and stream flowrates, heat capacities
and temperatures, rather than with the compositions of those
streams. Additionally, exchangers are considered as black boxes
which carry out the required heat dut y, rather than as plant
items. The techniques have only recent ly reached a levelof
sophistication in which it is worthwhile to consider the
complex effects which fouling of individual flowsheet units
will have on the operation of the whole plant.
The effects of fouling on heat exchangers are well
documented elsewhere in this volume: the formation of deposit
within equipment decreases the heat transfer efficiency of that
equipment whilst increasing the pressure drop through the
system. The decrease in heat transfer coefficient due to
fouling is a complex function of many variables, such as
surfaee quality, fluid composition, fluid and surfaee
temperature and time. Fouling is a costly processi as well as
the obvious capital and maintenance costs incurred, the loss of
produetion while cleaning is performed ean also be significant.
Designs which minimise fouling are obviously advantageous.
The effect of fouling on a single exchanger is shown on an
enthalpy-temperature diagram in Figure l. The effect of fouling
is to decrease the amount of heat transferred, thus increasing
TH OUT and decreasing TC OUT . If the exchanger has a bypass
controller, the effect of fouling ean be mitigated, but
eventually the controller will become saturated and cleaning
will be needed.
In a network subject to
fouling, exchangers will
I
interact: the fouling of one
I part of the system may well
IT:' I
result in fouling elsewhere.
This ean be demonstrated
t
T
I ea5ily: consider Figure 2,
I which shows a section of a
I
I I heat exchanger network,
I containing two exchangers and
I three streams. The hot stream
I H loses heat to two cold
streams Cl and C2. Suppose
I
I that stream H is prone to
T," I reaction fouling, and that
----------+--
initially, such fouling is
I
I.. ~I
I concentrated in exchanger
Heat load before fouling
(l), which is hotter than
--Enthalpy---+ (2). The effect of this
fouling will be to reduce the
@ProcessEng
FIGURE l: Fouling of a single heat transferred, raising the

exchanger on an enthalpy- outlet temperature, and thus
temperature diagram. the temperature in exchanger
(2): this may well eventually
lead to fouling in that
exchanger, which would not
497
FIGURE 2: Section of a heat exchanger network.
TIN TOUT TOOT

IHl IHl IH2
T~
IC2
have been predicted had the designer considered each

individually.
The behaviour of networks suffering from fouling is thus
worthy of study. The eventual aim of current research is to
produce techniques which can enable the effects of fouling to
be included in heat exchanger network design. In some cases, it
may be that the effects of fouling can be neglected in
comparison to the requirement of maximum energy recovery (MER)
which is given first priority where utility costs dominate (5)
and which forms the basis of the pinch technique. However, in
industries where severe fouling occurs, the introduction of
fouling into existing network design techniques will be of
practical importance.
This problem can be approached in two ways: via analysis of
a given network to determine whether it is optimal, or ab
initio synthesis of an optimum system. Synthesis techniques,
whilst obviously much more useful than analysis ones, are much
harder to produce. Both types, however, require accurate
information on the fouling rate in individual heat exchangers,
in addition to reliable algorithms for the generation of
suitable networks. This paper first outlines techniques for the
design of cost-optimal networks and for analysing their
operability, and then reviews existing techniques for modeIling
the behaviour of heat exchangers undergoing fouling. The
introduction of fouling into network modeIling is described in
a companion paper (6).
2. HEAT EXCHANGER NETWORK SYNTHESIS

2.1 Techniques
A large number of techniques for HEN synthesis have been

described in the literature (1,7-9). It can be shown that even
for small networks, the possibIe numbers of networks is
enormous: efficient selection algorithms are vital. Early work
(4,10) used simple rules of thumb to generate networks which
could be subsequently optimised, an approach refinedby Shah
and Westerberg (Il) and Pho and Lapidus (12). The network
@ProcessEng
obtained depended on the definition of "optimal": with both

maximum energy recovery (6) and minimum area (13) networks
considered.
A key series of insights into the problem was made by
Hohmann (14), who showed that the minimum number of units in a
network was one less than the total number of streams in the
498
problem, and that the minimum utility needed could be found by

thermodynamic arguments. These discoveries greatly re duc e the
number of networks which need to be examined. This approach was
followed and refined by Linnhoff and Flower (15,16), who
developed analysis techniques from which were produced the
pinch process for network design (17,3). The technique
comprises simple algorithms which produce networks which
attempt to satisfy both maximum energy recovery (MER) and the
minimum number of heat exchangers compatibie with MER, and is
based on locating 'pinch' points within a network where a
minimum approach temperature exists. This approach, or variants
of it, forms the basis of modern design techniques, and has
been shown to yield large cost savings (18),
2.2 Network design: example

Although the pinch technique forms the basis for a number
of commercial computer programs, and the synthesis of
multistream systems can be complex, in its simplest form it can
be carried out by hand. It is thus ideal for the early stages
of design, where it is necessary to reject unworkable designs
as rapidlyas possible. To illustrate the technique, the
problem specified in Table 1 will be used as an example.
TABLE 1 : HEAT EXCHANGER PROBLEM
Supply Target Heat Capacity

Stream no. Temp. Temp. flow rate
(OC) (OC) (kW/K)
1 400 60 0.6
2 210 40 1.0
3 20 160 0.8
4 100 300 1.2
STAGE 1: Thermodynamic analysis.

The system must first be analysed thermodynamically. It
consists of four streams, two of which are to be cooled and two
heated: it is thus possibie to construct hot and co Id composite
streams, representing the nett amount of heat available at any
temperature for heating or cooling. For heat to be transferred
between two streams, there must be a temperature difference
between them. In any network, the selection of the minimum
temperature driving force, ~Tmin' is a crucial step. Here, 20 0 C
is selected.
In order to ens ure that ~Tmin is not violated, temperatures
are adjusted. Hot stream temperatures have ~Tmin/2 subtracted
from them, and co Id stream temperatures have ~Tmin/2 added.
Thus when the adjusted temperatures are equal, the true
temperatures differ by exactly ~Tmin. The composite streams
are shown on an enthalpy-temperature diagram in Figure 3. The
@ProcessEng
absolute enthalpy values are arbitrary, but the slope of the

lines at any temperature represents the heat capacity flowrate
of the composite stream: e.g. between 400 and 210 0 C the slope
of the hot composite is 0.6kW/K whilst between 210 and 60 0 C the
slope is 1.6kW/K, reflecting the sum of the two hot streams.
It is evident from the diagram that the two curves touch at
499
one point: this is the

Adjuste-d
pinch point, at which the
T (DC) ,G" temperature driving forces
1-',
400 are minimised, and heat
transfer is most
difficult. The pinch
divides the system in to
two halves: above the
300 Hot pinch, only external
Composite heating is reguired,
below, only external
Cold cooling is reguired. For
200 Composite MER, no heat is
trans fer red across the
pinch.
The composite curves now
100 allow the amount of heat
recovery possible to be
determined: it is the
PINCH overlap of the two
composite streams. The
regions outside the
-- Enthalpy~ overlap will reguire
FIGURE 3: Composite curves. utility heating or
cooling.
The selection of ~Tmin
is thus a key step. Small
~T . n leads to ve ry high
Iwer Q IQ
he~ recovery, but low
driving forces imply large
0.6 46 heat transfer area and
48
capital costs. Large ~Tmin
values result in low heat
-0.6 -66 recovery, but have small
Cl>
heat transfer area:
.... 200 -18 obviously, some
~- 0.4 12
cost-optimal solution
exists. Initially the
a.
E choice of ~Tmin was
~170 -6 arbitrary, based an design
intuition and experience.
~ -0.4 -24
Ul More recent work has
attempted to define
~
'0110 30 PI NCH
« - • selection criteria, based
TEMP.
08 48 either on are a (19) ar
overall cost (20) targets;
18 only a limited number af
designs need be
0.2 4 considered.
Systems can be solved by
@ProcessEng
Surplus = 22kW manipulation of the

l2 0·8 lO 0·6 composite curves, but in
Capaeity FICMls practice it is best to
(kW/"C) construct a "Problem
Table", Figure 4. On the
FIGURE 4: Problem table. adjusted temperature
500
scale, heat transfer can always occur in each interval, and

streams can thus be combined into common sources or sinks. A
heat cascade can thus be produced, with the energy requirements
or surpluses from one interval carried on to the next.
The pinch temperature can be immediately identified in
Figure 4. A negative flow of heat down a temperature gradient
is obviously impossible. So the largest magni tude negative flow
is set to zero, by importing 30kW above the pinch. The pinch
point of zero flow is then seen to be 1100 C, and 52kW is
rejected from the cascade. These are the MER utility loads:
addition of extra heat would result only in the need for extra
cooling, demonstrating why no heat should be transferred across
the pinch. These QHmin and QCmin values can be se en from Figure
3, but for a more complex system, composite curves are awkward
to construct, and temperature interval analysis lends itself
more readily to computer programs.
STAGE 2: Design for maximum energy recovery

Above the pinch all hot streams must be cooled from their
supply temperatures to the pinch and all cold streams heated
from the pinch to their target temperatures. This must be done
without utility cooling. Similar arguments apply below the
pinch: cold streams must be raised to the pinch and hot streams
cooled from the pinch, without utility heating.
Design thus starts at the pinch and moves out. It is
advantageous to match heat loads so that the whole need of one
stream is satisfied, i.e. to maximise the exchanger loads and
minimise the number of exchangers. To avoid infeasible matches
at the pinch; i.e. those in which heat exchange reduces the
temperature driving force below ~Tmin, exchangers just above
the pinch must have wH<wC, and those just below must have
wC>wH·
Consider the cold end. The whole of the heat required by
stream 3 can be supplied by stream 2; by the criterion above,
this is feasible. No other heat can be used: 52kW is thus
rejected to utility from the other two streams, as predicted
above.
At the hot end, the whole of the heat dut Y of 3 can be
supplied by stream 1, and the whole of the cooling of 2 can be
provided by stream 4. In both cases the match is feasible. The
remaining heat of stream 1 can then be transferred to 4,
leaving a 30kW heating load to raise 4 to the correct
temperature.
STAGE 3: Targeting for minimum number of units.

The MER solution has 7 units: 4 exchangers and 3
heaters/coolers, and is shown in Figure 5. However, it does not
contain the minimum number of units, shown by (11) to be
Umin=(N-1), where N is the total number of streams, including
utilities; here N=6, so Umin is 5. Two units could be removed.
@ProcessEng
These units are identified by tracing loops within the network;

there are two, shown in Figure 6. One incorporates the two
coolers, which we choose here not to break. The other loop
involves the four heat exchangers, one of which can be removed.
In general it is best to begin by considering the removal
of the exchanger with the smallest dut Y in the loop: here
501
PINCH
II 120·
II
210
2
2 o
åTmirf 2cfc
All temps in ·C.
All heat loads in kW
FIGURE 5: MER solution to the problem of table 1.

@ProcessEng
FIGURE 6: Two loops (A + Bj in the MER sOlution, showing

which exchangers could be removed.
502
16(t
åTmin
.= 20°C
All temps in ·C.
All heat loads in kW.
FIGURE 7: Solution of the problem of table l with three

exchangers.
exchanger (3). Examination of the loop shows that removal will
add 48kW to the loads on (l) and (4), whilst subtracting 48kW
from (2). This results in smaller 6T's than is allowed. 6T min
is restored by adjusting the heater and cooler loads, drawing
paths through the network to identify the effect of those
changes. As shown in figure 6, to restore the temperature match
in (l), Cl=15kW is needed, whilst to restore that in (2),
C2=12kW is needed: an extra 27kW of heating is thus needed. The
final network, with the minimum number of units, is given in
Figure 7.
2.4 Pinch design and fouling.

The above example has briefly summarised the pinch design
procedure: detailed explanations can be found elsewhere (3).
The method is both simple and rapid, and represents a major
advance in design. However, at no point are stream properties
other than capacity flowrate considered, save in discussion of
"forbidden matches" ((3),p75) between streams, where
interchange is forbidden due to possibIe corrosion or safety
problems.
3. OPERATING HEAT EXCHANGER NETWORKS

The above procedure generates networks which satisfy MER
and the consistant least number of units - or, at the cost of
greater energy use, fewer units. However, for systems
containing a large number of streams, a large number of
@ProcessEng
solutions are possible, each having similar costs. It is

necessary to adopt other criteria to select an optimum
solution.
Once a heat exchanger network has been designed and buiIt,
it must be operated. In practice, the final network must be
500
easy to control, and flexible enough to deal with both changes

in both input conditions and in the efficiency of heat
transfer. A number of authors have examined the problem uf
operability, and have developed ways to analyse and describe
the range of conditions under which the system can be operated.
As with the pinch method, the aim of these studies is to reject
unsuitable networks at as early a stage as possible (21).
A series of papers have been written concerning the concept
of "resilience". A network displays "static resilience" (22) if
it achieves maximum energy recovery (MER) , satisfies a chosen
6Tmin and attains stream target temperatures, in the face of
specified changes in (a) supply temperatures or (b) stream
flowrates. A resi1ience index (RI) describing the ability of
the network to cope with such changes has been defined (23,24).
Static resilience is a function solely of the structure of the
network, but does not discriminate between those streams whose
outputs it is important to maintain, and those which can change
without affecting system performance (21).
The control of networks is examined using the definition of
dynamic resi1ience: "the quality of the regulatory and the
serve behaviour of the plant by feedback" (25). Increasing the
heat transfer are a of a network may decrease dynamic resilience
(24), and ways in which design uncertainties can affect dynamic
resi1ience have been analysed (27).
Techniques for synthesis of resilient networks have been
developed (28), and it has been demonstrated (29) that pinch
design techniques tend to genera te resilient networks. Methods
have been devised (29) which identify resilient structures: the
specifieation of exehanger areas is left to some subsequent
design step. Beautyman and Cornish (30) present a method whieh
not only determines whether a network is resilient, but also
speeifies the necessary areas and bypass split fraetions: they
point out that the assumption (24) that 6T min cannot be
violated whatever the input conditions is unneeessary in
practice and therefore potential ly misleading.
Similar ideas to resilience are expressed by the ideas of
f1exibility, defined by Westerberg and Chen (31): a strueture
has adequate structural flexibility if the type of equipment
and its configuration allows it to meet required design
speeifieations. Grossmann and Morari (26) identify two aims of
a flexibility analysis: a feasibility test, to establish
whether a design can operate, and a flexibility index whieh
establishes the maximum parameter range which the design ean
tolerate. Such an index was defined by Swaney and Grossmann

(31) and has been applied to heat exchanger networks (33). It
is considered (33) to be a more accurate reflection of the
operability of the network, although more expensive in computer
time than the resilienee index.
Flexibility is also discus~ed by Kotjabasakis and Linnhoff
(34), who deve10p the work of Hohmann (14) in drawing up tables
@ProcessEng
to describe the behaviour of simple networks, to introduee the

eoneept of "sensitivity tables". Here the behaviour of network
temperatures is shown as a funetion of changes in stream flows
or exehanger areas: the tables can thus be used to analyse the
effeet of a particular ehange, and to identify the cheapest
solution to a particular problem. The eoneept has been applied
504
to network design and to fouling (35): this work is discussed

in the companion paper.
The above ideas allow networks to be analysed:
specifically, definition of a flexibility or resilience index
allows the problem to be defined in a way that can be dealt
with by computer, using a program which first generates
networks and then tests them for operability. Any attempt to
include the effects of fouling should proceed in a similar way.
4. MODELLING HEAT EXCHANGERS UNDERGOING FOULING

4.1 Introduction
The final design decision will be made on cost. The
techniques outlined ab ove produce networks which have low
capital and utility cost, but nothing can be said about their
response to fouling, which will involve both extra operating
and cleaning costs.
This problem requires more practical information than the
synthesis and analysis of mathematically idealised systems. If
the effect of fouling on networks is to be fully predicted,
rate laws for the change in heat transfer coefficient and
pressure drop as a function of time, temperature, flowrate and
foulant concentration must be available. In addition, the flow
and temperature distributions within each heat exchanger should
be known. Then, if the stream compositions are known, the
amount of fouling which can be expected from each stream under
process conditions can be calculated by combining the stream
and exchanger properties.
However, very little information of this type is available,
and approximations to real behaviour have to be made. This
section first outlines the need for accurate rate models, and
then reviews techniques for predicting the fouling of heat
exchangers.
4.2 Fouling rate models

A large amount of data has now been collected on fouling.
However, data obtained from industrial heat exchangers is
difficult to use to predict the fouling of other systems, as
the measured heat transfer coefficient represents an aver age of
different flow and temperature conditions. The fouling rate
obtained cannot, therefore, be associated with a specific
temperature, flowrate or composition. In addition, such data
may be extremely difficult to obtain, given the limitations of
production schedules (36).
Of more value in modelling fouling are experiments in which

the rate of fouling is measured under control led conditions
(37) . This data is more reliable, and can be obtained faster,
than that from large-scale equipment. Models which describe the
whole course of the fouling reaction (induction, fouling and
post-fouling stages) do not currently exist. However, some
progress has been made in describing the progress of fouling
@ProcessEng
af ter the induction period, and also in understanding the

processes taking place in the induction period. These models
are reviewed by other papers in this volume, and elsewhere
(38-40) .
505
4.3 Distributed parameter modeiling

The basic equation for a heat exchanger is
Q= fOUT
IN
A'h(TH -Te) .dx
where A' is the heat transfer are a per unit exchanger

length, h the local overall heat transfer coefficient, and TH
and Te the hot and cold fluid temperatures. In process
synthesis, heat exchangers and other plant items are commonly
regarded as black boxes which carry out a given task. If h is
constant both along the exchanger and with time the equation
can be greatly simplified and the black box assumption will be
appropriate. However, in a real exchanger undergoing fouling,
h, TH and Te will be all be functions of position and time, and
the presence of deposit will distort the flow in the exchanger.
The changes in temperature and flow patterns in the
exchanger may influence the subsequent fouling rate. This can
be shown by considering reaction fouling in an exchanger: the
hotter regions will foul first, decreasing local heat transfer
rates, and thus increasing the temperature in what were
initial ly cooler regions of the exchanger. That region will
thus begin to foul. Additionally, changes in the shear stress
distribution as aresult of deposition will in turn change the
fouling pattern, as low-shear areas are established in which
deposit removal is difficult.
Some modeiling technique which takes account of these
changes is obviously required. A distributed parameter model,
in which the variation of properties within the heat exchanger
are considered, must be used: once the variation of temperature
and flowrate is known, a local fouling model can be used to
predict the resulting behaviour. Existing numerical models of
heat exchangers do not examine the problem of fouling (41,42).
Two types of problem can be envisaged. If fouling is very
slow then the exchanger can be considered as a series of
quasi-steady state temperature and flow distributions which
gradually give rise to changes in fouling and thus fluid and
shell-side temperatures. Where fouling is rapid, however, the
above assumption will not be valid, and a more sophisticated
fouling model will be needed to replace the steady-state
approximation.
Equations for the distributed parameter modelling of
scaling have been derived (43), and scaling from calcium

sulphate in a tube modelled using the pseudo-steady state
approximation and solubility data (44). Hydrocarbon fouling,
has been model led in a heat exchanger divided into ten zones
(45), and the fouling of an exhaust heat recovery unit modelled
by dividing it into 48 segments, each of which was assumed to
foul uniformly (46). A control strategy for thermal gasoline
@ProcessEng
cracking furnaces in which coke deposits on the walls has been

examined (47); the furnace temperature was varied along the
length of the tube to keep the fluid-deposit interface
temperature constant throughout. The fouling rate was thus
constant at each point in the exchanger.
A technique, based on the method of characteristics, to
506
model the behaviour of a heat

1.4 exchanger suffering from rapid
fouling has been developed
1.2 (48,49). The method is a
Tw = 373
o
generalone, but was tested
::: 1.01---------:;7"""'-------1 using areaction fouling model
<T
for skimmed milk in a simple
0.8 double-tube exchanger. Both
control led and uncontrolled
0.6 operation were simulated. It
was found that exchangers in
o 0.2 0.4 0.6 0.8 1.0 which the temperature driving
Dlslance aLong exchanger force was initial ly small were
least affected by fouling, and
required less control action
l. O ,-------,----,-----,----,------, to keep their outlet
temperatures constant.
0.8 Figure 8 shows plots of Bi
(dimensionless fouling
0.6 resistance) and the ratio of
co heat flux before and af ter
0.4 fouling along two exchangers
[one 10m long Tw=373 K, one
0.2
3.7m long, Tw=390 K, both
designed to heat .25kg/s of
skimmed milk from 333 K to
o O 0.2 O.LI. 0.6 0.8 1.0 370.4 KJ. The shorter and
D"lonce aLc"g exchanger hotter exchanger fouls more
severely. It can be seen that
the effects of fouling on the
FIGURE 8: Plots of (i) heat fluid out let temperature in
flux and (ii) Bi for two heat the longer exchanger are
exchangers. lessened by an increase in
local heat flux in the exit
region. Here the decrease in fluid temperature caused by
fouling increases the local temperature driving force to such
an extent that the decrease in h is overcome. In the shorter
exchanger, where temperature driving forces were initially
high, the increase due to fouling is insufficient to overcome
the decrease in h, and so the heat flux af ter fouling is at all
places less than that before. Similar effects are found when
control action is applied. These effects agre e well with
practical operating experience, and will be shown in the
companion paper to be analogous to effects which occur in

networks.
5. FOULING OF NETWORKS.
The literature pertaining to network design and subsequent
operation has been briefly reviewed. The strategies which have
been developed were not designed to consider fouling:
@ProcessEng
initially, the design problem was sufficiently complex without

extra complications! However, simple and reliable techniques
for network design, based on thermodynamic concepts, now exist.
The above review has shown that incorporation of the costs
of fouling into network analysis would aid the designer in a
number of ways:
507
(a) consideration of the effect of forbidden fouling

matches -between, for example, highly temperature-
sensitive streams and streams of tao high (if reactian
fouling is possible) or too low (if solidification, for
example of long-chain hydrocarbons, occurs) temperature-
which, by constraining the number of designs and the
energy recovery possible, will simplify the problem.
(b) selection of an optimal 6T min will be affected by
fouling. Operating costs other than the utility required
are not considered explicitly by pinch design, although
the costs af fouling ean be considerable (50). The
importance of the temperature driving force in the
fouling af a single exchanger has been shown (48,49), and
similar effects may be expected far networks.
(c) a measure of the effect of fouling an the operability
of a netwark would enable flexibility and resiIience
analyses ta be extended to more realistic systems.
In addition, there is a strong connection between the

structure of the network and the chemical process of which the
network is a part. Simultaneous optimisatian of the chemical
pracess and the heat recovery system (for example ta adjust the
pinch point) will be better than sequentially optimising first
the proces s and then the heat recovery. Recent design
techniques (51-55) are based on the mixed-integer linear
prograrnrning (MILP) approach developed by Papoulis and Grossmann
(56-58), and show it is much more important to select the
correct operating conditions than to optimise a given set. This
approach is ideally suited to fouling analysis.
6. CONCLUSIONS.
The need for fouling to be considered in network design has
been shown, and an analysis of pinch design has demanstrated a
number of areas which may be affected by fouling.
Calculation of the effects of fouling require much more
specific knowledge of the process conditions than does the rest
af HEN design. In comparison to the techniques available for
the design of other parts of the plant (such as reaction or
separation equipment) the modeIling af fouling behaviour is
primitive, and more research is needed to integrate fouling
kinetics with exchanger models. However, models which are
repLesentative of the problems which fouling poses do exist: in
the companion paper, such models will be used to determine the
effects which fouling has on networks and to outline ways in

which analysis ean be condueted.
REFERENCES
Acknowlegements and nomenclature are given at the end af (6).

@ProcessEng
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@ProcessEng
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of optimum heat exchanger configurations. AIChE.J. 32 276.
1986.
34.Kotjabasaskis E and Linnhoff B: Sensitivity tables for the
design of flexible processes (1)- How much contingency in
heat exchanger networks is cost-effective? Chem.Eng.Res.Des,
64 197. 1986.
35.Kotjabasaskis E and Linnhoff B: Proces s design for
flexibility: an optimaloverdesign strategy for fouling and
multiple base cases. Process Optimisation Conf., Nottingham.
1987.
36.Merry H and Polley GT: Obtaining valid data on fouling
resistance. In "Fouling of Heat Transfer Equipment", ed
E.F.C.Somerscales and J.G.Knudsen, McGraw Hill. 83. 1981.
37.Somerscales EFC: The fouling of heat transfer equipment. In
"Fouling of Heat Transfer Equipment", ed E.F.C.Somerscales
and J.G. Knudsen, McGraw Hill. 1. 1981.
38.Epstein N: Fouling in heat exchangers. Proceedings of the
6th Int. Heat Transfer Conf., Vol 6. 1978.
39.Epstein N: Fouling: technical aspects (afterword to fouling
in heat exchangers). In "Fouling of Heat Transfer
Equipment" , ed E.F.C.Somerscales and J.G. Knudsen, McGraw
Hill. 31. 1981.

40.Knudsen JG: Fouling of heat exchangers: are we solving the
problem? Kern Award Lecture, 21st Nat.Heat.Transf.Conf.
Seattle. 1983.
41.Sha WT: Numerical modeiling of heat exchangers. In "Handbook
of heat and mass transfer - Vol 1" ed NP Cheremisinoff,
Gulf. 815 1986.
@ProcessEng
42.deBruijn H and Zijl W: Numerical simulation of shell-side

flow and temperature distribution in heat exchangers. In
"Handbook of heat and mass transfer - Vol 1" ed NP
Cheremisinoff, Gulf. 853 1986.
43.Clampett JB: Relative effect of deposited scale on transfer
of heat to salt water. J.lnst.Eng.Aust. 123. 1965.
510
44.Hoffman EJ: Fouling rates from the theory of simultaneous

heat and mass transfer. AIChE Ann. Meeting, Washington.
1969.
45.Hausler RH and Thalmeyer CE: Fouling and corrosion in feed
effluent exchangers: discussion of a new test method. APl
refining meeting, Chicago. 1975.
46.Chiapatta LM and Szetela EJ: A heat exchanger computational
procedure for temperature-dependent fouling. Chem.Eng.Comm.
16 189. 1982.
47.Sundarem SM and Froment GF: Kinetics of coke deposition in
the thermal cracking of propane. Chem.Eng.Sci. 34 635. 1979.
48.Fryer pJ and Slater NKH: A direct simulation procedure for
chemical reaction fouling in heat exchangers. Chem.Eng.J. 97
1985.
49.Fryer pJ and Slater NKH: The simulation of heat exchanger
control with tube-side chemical reaction fouling.
Chem.Eng.Sci., 41 2363. 1986.
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51.Duran MA and Grossmann lE: A mixed-integer nonlinear
programming algorithm for process synthesis. AIChE Ann.
Meeting, San Francisco. 1984.
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heat integration of chemical processes. AIChE.J. 32 1 123.
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Interactive software package for the synthesis and analysis
of resilient heat exchanger networks. Parts I and II.
Comp.Chem.Eng. 10 577-599. 1986.
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to Chem.Eng. 1987.
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optimisation approach in process synthesis. Parts I-III.
Comp.Chem.Eng. 7 695-734. 1983.
@ProcessEng
THE FOULING OF HEAT EXCHANGER NETWORKS
Peter Fryer
Department of Chemical Engineering

Pembroke Street,
Cambridge
1.INTRODUCTION
1.1 Robust heat exchanger networks
In the previous paper (1), the pinch method for heat
exchanger network (HEN) design, and the ways in which networks
are subsequently analysed for operability were described,
together with ways in which the modeIling of single exchangers
suffering from fouling has been performed. Here, these
techniques will be combined to investigate the effect of
fouling on networks, with the aim of developing simple and
rapid ways of analysing heat exchanger networks, so that those
whose response to fouling is unacceptable can be rejected.
To avoid confusion wlth other nomenclature, the response
of systems to fouling will be described in terms of
"robustness". A network will be considered robust to the
effects of fouling if:
(a) it resists the effects of fouling, and
(b) those effects which do occur are readily nullified
by cJntrol action.
This paper is concerned with ways in which robustness can
be defined, and in incorporating fouling into network design.
The work is divided into a number of sections. First, the
fouling of a single exchanger is considered, and the
mathematical sensitivity of an exchanger to fouling derived.
Two definitions of robustness are given, and their use
demonstrated via case studies on the fouling of simple
networks. ways in which the costs of fouling could be
incorporated into network design are also demonstrated. Much
of the work described below has been done at Cambridge since
1983, and further information can be found in refs (2-4).
1.2 Fouling models: simplifying assumptions

The previous paper has shown that accurate modeIling of
networks undergoing fouling needs both accurate local fouling

models and techniques for the incorporation of fouling into
distributed parameter modeIling of heat exchangers. The
present work seeks only to demonstrate the problems which
arise if fouling is ignored during network design, and so a
number of assumptions can be made to simplify and speed
network analysis.
@ProcessEng
1.2.1 Fouling models. In the absence of fully accurate

kinetic data the present work uses two simple fouling models
of practical interest. In one, the fouling rate is temperature
dependent, and in the other, it is not. The models are thus
representative UL most Lypes of fouling:
511

512
(a) areaction fouling model, based on the data obtained

by Fryer and Slater (5), who showed that fouling from
reconstituted skimmed milk could be associated with a
reaction whose activation energy was 89 kJ/mol, and
fitted the folIowing equation:
dBi ~ exp -E
<It Re RT
where Bi is a Biot number for fouling (the ratio of the

deposit conductive resistance to the convective heat
transfer resistance, also equal to RFU o ) and kd and kr
are constants.
(b) a deposition model, based on the results of Newson
et al (6), who showed that deposition of magnetite was
proportional to v O. 73 , implying mass transfer control.
The induction per iod prior to fouling is assumed constant
for each heat exchanger, so that each begins to foul at the
same time.
1.2.2 Heat exchanger models. For a first analysis of the
effects of fouling, the initial behaviour of heat exchangers
will be approximated by assuming:
(a) that design procedures such as those described in
the Heat Exchanger Design Handbook (7) lead to fluid
tubeside velocities which are of the same order of
magni tude (i.e. 1-2 m/s for liquids, 5-10 m/s for gases)
and to approximately similar film heat transfer
coefficients, for all heat exchangers in a network: i.e.
that Re is the same for all flows, and that for
particulate fouling the percentage change in U from its
unfouled value will be the same for each exchanger.
(b) that the variation of Re with time ean be negleeted.
(c) changes of temperature due to fouling do not
significantly affect the initial fouling rate.
(d) the fouling rate for reaction fouling ean be
estimated by assuming reaction at the mean temperature
of the hot stream in the exchanger
1.3 Accuracy of the approximations.

The assumptions described uLave grossly simplify exchanger
behaviour. Note especiaIly that the assumptions are more
realistic for particulate deposition than for reaction
fouling, since reaction foullng ean bo highly temperature-

dependent, the fouling rate doubling for a 10 K temperature
rise (for E= 89 kJ/mol, Tl=373K, T2=383K). However, they do
allow the effects of fouling, at least in the initial stages,
to be estimated rapidly. If a network performs badly in a
fouling analysis using the above assumptions, it is unlikely
to perform well in a full analysis.
@ProcessEng
The two fouling models, whilst simplified, represent a

wide range of real fouling types. If a specific example were
to be considered, obviously the fouling model appropriate to
those conditions should be used. Again, if a network reacts
badly to these idealised models, it is unlikely to do better
when faced by reality.
513
2.FOULING OF A SINGLE EXCHANGER

2.l.Sensitivity af an exchanger to fouling
The effect af fouling an a given exchanger can be
estimated via appropriate linearisation af the constituent
heat transfer eguations, fallowing the example af Donaldson et
al (8), and the suggestion af Asbjornsen and Haug (9). The
overall heat flow Q in a single-pass counter-current heat
exchanger can be related to the log mean temperature
difference by the familiar:
Q = UA lITl m [ 1)
and this heat increases the cold stream and decreases the hot
stream temperatures:
TH IN - Q/wH [ 2)
TC IN + Q/wC (3)
where w is the stream capacity flowrate. The above eguations

can be combined to yield:
Q = K - 1 (TH IN - TC IN ) [4]
K - 1
wH Wc
where
K = exp ( UA [ (l/wH) - (l/wC)) ) [ 5)
To determine the response af the system to change, these

eguations can be differentiated to give the coefficients of
the Taylor expansion for the change in Q resulting from
changes in input temperature, heat transfer coefficient or
heat transfer area:
åQ [ 6)
where
[ 7]
K 1
K/wH - l/wC
For the special case of Wc wH = w, the above eguations are

replaced by:
aT = UA/(l + UA/w) [ 8)
@ProcessEng
The expressions can be simplified by substituting back for

UA, producing expressions in terms of temperature and heat
load:
[ 9]
514
[10)
2.2 The response of an exchanger to fouling

The sensitivity analysis above is useful because it
indicates design methods by which the effects of fouling ean
be minimised:
(a) Small aUA values result in small changes in Q for a
given amount of fouling. Exchangers with small
temperature driving forces between hot and cold streams
will thus have abetter response to fouling than those
with large; low aUA values will be useful for exchangers
which are expected to foul severely.
(b) Large aT values ensure that any drift in inlet
temperature results in a large change in Q. Examination
of [10) shows that large Q and/or small THIN-TeIN values
are required for high aT. Large aT values will enable an
exchanger to compensate for fouling elsewhere in the
network. This will be especiaIly true if its aUA value
is small, so that changes in inlet temperature outweigh
changes due to fouling.
The analysis thus suggests ways to design exchangers;
those which are going to foul should have low aUA, and those
around them should have high aT, and, ideal ly low aUA as well.
However, there is a limit to the effect aT ean have. This ean
be shown by rewriting equation [10): as the heat load Q is
equal to WH(THIN_THOUT), and to We(TeOUT-TeIN):
(THIN-TeOUT)/(THIN-TeIN))
[ 11)
(THOUT-TeIN)/(THIN-TeIN))
thus aT/wH and aT/we ean never exceed 1: the response of an

exchanger to a single change in inlet temperature ean never be
greater than that change.
These effects are analogous to those aIready identified
in the heat exchanger models (10,11) discussed in the previous
paper, where exchangers were found to compensate internally
for the effects of fouling, providing that temperature driving
forces were sufficiently small.
Equations [9) and [10) do however show that simultaneous
high aT and low aUA will be difficult to achieve exe ep t in
large exchangers, as, for a given TH IN - TeIN, high Q and low
driving forces would be required. As before, networks which
are resistant to fouling may be of higher area, and thus

capital cost, than fouling-prone ones. It will thus be
necessary to tradeoff between capital and operating costs in
practice.
3 THE WAGES OF SYNERGY: NETWORKS UNDERGOING FOULING.

3.1 Interactions between exchangers.
@ProcessEng
As aresult of the analysis above, the behaviour of a

single exchanger ean be described: sensitivity coeffici.ents
ean be calculated ve ry rapidly by hand using equations [7) and
[8) if UA is available, or more rapidly via [9) and [10) if
all the temperatures are known. In networks, the effect of
fouling on one exchanger will be carried on to the next, with
515
TIN TOUT . OUT

IHl IHl TH2
TOUT
IC2
FIGURE 1: Section of a heat exchanger network.
synergistic results which could not have been predicted by

considering the effect of fouling on the two singly.
The sensitivity analysis both allows these effects to be
estimated rapidly, once the coefficients have been calculated,
and suggests ways of designing networks. For example, consider
the network in Figure 1: fouling of (1) by an amount åUA1
increases TH1 0UT by åQ1/wH = aUA1 åUA1/wH. The driving force
in exchanger (2) increases, and the change in heat load in
that exchanger becomes:
[12]
so the overall change in QH OUT is given by:
åQ [ 13]
which shows that high aT2 values will recover much of the
losses in (1): for example, this configuration would be
effective in minimising the effects of reaction fouling where
åUA 2 is much less than åUA1.
3.2 ModeIling the fouling of networks.

The coefficients are a useful design tool, illustrating
the factors which affect the response of heat exchangers to
fouling. They can however only be used in regions where the
Taylor expansion of equation [6] is appropriate, i.e. in the
initial stages of fouling. Equations similar to [13] can be

derived for any system, and solved either by hand or, for more
complex networks, via a simple linear equation-solving
routine.
Beyond this stage, computer calculations are necessary to
predict network conditions. Rigorous calculation using the
QUASILIN flowsheeting package (12,13) showed the linear
@ProcessEng
approximations to be within 1% of the full solution for up to

10% changes in U, and within 10% for changes of up to 25%.
Rapid analysis using the coefficients is thus reasonable even
for severe fouling. In calculating the effects of fouling
below, both QUASILIN and the coefficients have been used.
516
4. ROBUST HEAT EXCHANGER NETWORK ANALYSIS.

4.1. Passive response: A suitable measure of robustness.
Providing fouling rates are known, therefore, the passive
response of the system to fouling can be estimated. A
simplistic estimate of overall sensitivity to fouling could be
obtained by considering the special case where all the
exchangers in the network foul in equal proportion: i.e. the
response to particulate fouling, where the response of the
network could be defined as the change in the total heat
transferred per unit change in every U due to fouling.
However, this measure of robustness would be useless in
cases where exchangers foul to different extents, i.e. in
reaction fouling as described in 1.2.1. In practice, then,
before robustness can be determined in a given situation,
fouling rate laws must be known or suspected. Although
artificial, the response to uniform fouling does however offer
a measure of the network response, representing the most
testing fouling conditions.
It is now necessary to decide on a measure of robustness
by which networks can be judged. Some streams are control led
by heaters or coolers whilst some are left to drift: an
estimate of the response to fouling which takes account of
this is required. For those streams whose temperatures can be
regulated, the additional utility necessary is a measure of
robustness, whilst for those that cannot be regulated the
drift in temperature measures robustness. In practice,
maintenance of some stream temperatures may be more crucial
than others ("hard" and "soft" temperature targets (14)), but
this will depend on the given situation: here, an arbitrary
measure of robustness will be taken as the extra utility dut Y
which would be required to bring all the hot streams to their
target temperatures (by the First Law, the same amount is
needed to bring the co Id streams to their correct values) .
In the example below, the passive response to fouling is
studied using the two models of 1.2.1. The extra notional heat
load for a uniform decrease in U of 10% was used to
characterise the response to particulate fouling. For reaction
fouling the hottest exchanger was considered to foul by 10%,
with the others fouling in proportion according to their
temperatures.
4.2 Passive response: a case study.

Having developed a measure of robustness, it must now be
tested. We take as an example a problem which has been studied

by other authors in aresilience analysis. Table l shows the
problem specified as Example 2 of (15), and examined in (15)
and (16).
TABLE l: (i) Three exchanger problem.

@ProcessEng
Stream TIN (OC) TOUT (OC) W (kW/K)

Hl 470 350 8
H2 500 450 6
Cl 265 405 5
C2 300 420 7
517
This is a threshold problem (17), where the pinch is at

one end of the network rather than in the middle. Three
possibIe solutions are considered: Figure 2(i-iii) correspond
to Figs 4(b) and 5 of (15) and Figure 10(b) of (16)
respectively. In those papers the networks were examined for
static resiIience by changing TC2 IN between 300 and 380 o C,
and, whilst networks 3(ii) and (iii) were found to be
resilient over the whole range, network (i) was found to be
unresilient, as well as having a greater heat transfer are a
and thus cost.
Examination of Figure 2 shows three types of exchanger:
type O, where neither input temperature changes as aresult of
fouling (such as exchanger (3) in Fig. 2(i)), type l, where
one input changes (exchanger (3) in Fig. 2(ii)) and type 2,
where both input temperatures change (exchanger (2) in Fig.
2(i)). For hand calculations on these simple networks, type O
exchangers were solved first. The temperature changes produced
were then carried on as inputs to type l and 2 exchangers: the
advantage of this method, as opposed to computer calculation,
is that it mimics the passage of the effects of fouling
through the network and enables the designer to appreciate
where robustness to fouling arises.
Results are shown in Table 2. In both cases the
unresilient network is the most robust.
TABLE 2: Robustness of the networks of Figure 2
Network 2 (i) 2 (ii) 2 (iii)
Particulate: 35.5 51. 4 59.0

Reaction 14.5 25.6 32.4
(Figures show kW of heating necessary to return hot

streams to their prefouling values)
Examination of the networks shows that network 3(i)

responds best to fouling because af exchanger (2):
(a) it has low driving forces, so that aUA is ve ry low
(9.99 compared to c50 for exchangers in other networks).
(b) it is a type 2 exchanger: both input temperatures
change due to fouling.
These effects combine to make the network robust: in the case
of 10% particulate fouling, the heat load on exchanger (2) is
increased by 17.8 kW, compensating for the effects of fouling

elsewhere. For reaction fouling the effects are more obvious:
fouling is concentrated in exchangers (l) and (3), increasing
the driving force in (2) such that stream Hl is overcooled by
1.loC.
The case study has shown that robustness is a function
both of network structure and individual exchanger responses:
@ProcessEng
for network 2(i) the effect of fouling on streams Hl and Cl

can be mitigated by exchanger (2), providing its aT and aUA
are suitabl~. However, the other networks are structured such
that fouling in exchanger (l) cannot be mitigated by
subsequent passage through other exchangers: indeed, for
2(iii) the fouling of exchanger (2), by increasing the heat
518
FIGURE 2: Three solutions dut y of exchanger (3), reduces

to the problem of table l. the driving force for exchanger
(l), the absolute opposite of
what is required. In cases where
the structure of the network is
unsuitable designing individual
exchangers to resist fouling is
of littIe use.
(i) 4.3 Dynamic response: a further
definition of robustness.
The above example has shown
that some networks are more
robust than others under passive
conditions. In practice, bypass
control lers will be used to
maintain output conditions, and
networks will be robust until one
bypass saturates. The ease of
this control will depend on the
network structure.
To investigate the dynamic
response of networks to fouling,
another definition of robustness
(ii) is needed. Here the number and
effectiveness of feedback control
loops necessary to regulate the
~o,,----_ _--{ 350 network will be taken as a
measure.
t---+---t-{C 450
4.4 Dynamic response: case study.
4.4.1 Control of clean networks.
The control of the three networks
of Figure 2 will be examined. A
procedure has been outlined (18)
by which controlloops can be
incorporated into networks.
300 Figure 3 shows the networks of
C2 Figure 2 with such loops added to
control all the streams which do
not have heaters or coolers on
(iii) them.
It can be seen that, even
350 before the effects of fouling are

considered, network 3(iii) is not
easily operated: stream H2 can
only be control led by the
manipulation of exchanger (l), so
that steam Cl can only be
control led by manipulation of
@ProcessEng
exchanger (3), upstream of (l).

Networks 3(i) and (ii) are,
however, operable, at least in
300 the absence of fouling.
420 r-----="'-i C2
519
FIGURE 3: Control structures FIGURE 4: Control structures

for the networks af Fig. 2, for the networks af Fig. 2,
assuming steady feed. assuming unsteady feed.
(i) (i)
H2~--~-----+--~ H2r---~-----+--~
(ii) (ii)
Hl~-------1 Hl~-------1
r--'--~--~~IC
)----+---+--{C
}-------------1 C2 )-'-------1 C2
( iii) (iii)
Hl~-----'{
r--.-~---+~T
@ProcessEng
}-------------1 C2 }----------{ C2
520
4.4.2 Control of fouling. The control of the two remaining

networks during fouling is now examined. Network 3(i) is
satisfactory. However, consider fouling of network 3(ii): as
exchanger (2) fouls, TC2 0UT falls, so the bypass on exchanger
(1) must be manipulated. The case study networks were chosen
with TC2 IN = 300 0 C, so the cooler dut Y is initial ly zero. The
decrease in TH2 0UT cannot, therefore, be accommodated by the
cooler, and network 3(ii) is inoperable. Although the
vividness of this example is a function of the choice of
network, and is to a large sense artificial, the phenomenon is
general: the effects of fouling may wellovercool or overheat
streams. This possibility should be accounted for in design.
4.4.3 Regulatory control and fouling. Next consider the
combination of fouling and input fluctuations in temperature,
so that the network control system is required to compensate
for both. As the coolers are here ineffective for such
control, they must be omitted: Figure 4 shows the resulting
networks, in which three bypasses are needed. By the arguments
of 4.4.1, only network (i) is operable.
4.5 Robustness and design.

Two possible definitions of robustness have been given.
The first, where passive response is examined, is a relative
measure, selecting the most robust of the networks: it is thus
analogous to the resilience or flexibility indices discussed
earlier (1). In practice, network response depends on the type
of fouling present, and the designer may attach a greater
priority to the maintenance of some stream temperatures than
to others. Construction of an absolute definition of
robustness on this basis is thus impossible. However, the
second definition is an absolute measure: networks can be
rejected outright.
Methods of analysing networks to select those most robust
to fouling have been demonstrated, and it has been shown that
the resilience of a network to load changes does not imply
robustness to fouling. This is not surprising: the arbitrary
changes in inlet conditions considered by Morari and
colleagues are independent of one another, whereas the changes
in U caused by fouling, governed by a rate law, occur within
the network rather than being imposed from outside. There is
no real connection between the two analyses.
Combination of the two definitions will allow the designer
to determine the effect of fouling on a network. Here, hand
methods have been presented by which a selection can be made

between simple networks, although the method is well suited to
computer analysis.
5. THE COSTS OF FOULING.
5.1 Cost balances.

@ProcessEng
The above example has shown that a fouling analysis can

give useful results, and allow robust networks to be
identified. Although it will be cheaper to operate, the robust
network is much more expensive to build (IUA=22.3kW/K) than
the two others (IUA about 15kW/K). The optimum network will be
521
selected on a compromise between capital and operating costs.

As with the fouling models, cost information is highly
problem-specific, and it is almost impossible to provide
realistic data. This section aims only to indicate general
ways of including the cost of fouling into network design:
therefore, only ve ry simple cost data and an equally simple
example will be used.
S.2 Case study.

The problem to be studied is given in Table 3: three
streams are to be cooled and three heated.
TABLE 3:~Tmin selection problem.
Stream Initial Final Capacity

Temp. (OC) Temp. (OC) Flowrate (kW/K)
l 200 60 30
2 220 30 SO
3 ISO 70 80
4 110 160 100
S IS 13S 60
6 40 220 40
A simplified version of the cost data of (19) will be

used: the cost of heat transfer are a is taken as E9S00(AO.47),
(A measured in m2 ), and the costs of hot and co Id utility are
Sx10- 3 E/MJ and Sx10- S E/MJ respectively. The optimum network
will be chosen on the basis of minimising the sum of the
PINCH = 110'
200'
~~--------~4 ~---+------------~
40·
6
@ProcessEng
l---------j
~IGURE s: Solution to the problem of table 3.

522
capital cost plus l

FIGURE 6: Variation of heat load
years operating costs.
and area with ~Tmin. Heater and cooler costs
Mea will be neglected,
(10'ma)
rn together with any
~ cleaning costs.
20
o The MER network
3 1fi designed to solve the
e. problem is shown in
O" Figure 5: for
oo.
20% o.
convenience, it has not
15
Fouling c
11)
been relaxed to the
minimum number of
2 6" units. By the
Q
S- definition of
S
\O
robustness in 4.3 and
lO described above, the
10% system is operable. A
Fouling range of networks,
based on this
structure, were
calculated for ~Tmin
5 values between 5 and
20 o C. Slight changes in
5 lO 15 20 the structure are
l,Tmin (DC) needed at the extrema
of the problem: for
FIGURE 7: The effect of fouling ~T . =20 o c heat
on the optimal ~Tmin. ex~anger (l) is
unnecessary, and for
~Tmin=SO an extra
exchanger is needed
between streams l and
5, replacing the cool er
20°'0 on 1. The total areas
FOULlNG required (assuming
10
U=1000 W/m 2 ) are shown
in Figure 6.
Unsurprisingly,
increasing ~Tmin
decreases the network
I Effect area: however, the
of amount of utility
ti) \ Fouling
.. on required increases from

o
u optimal 300kW hot and 1MW cold
~Tmin at SOC to 2.7MW hot and
3.4MW cold at 20 o C.
It is first necessary
9 to cost the networks in
the absence of fouling.
When the relevant
@ProcessEng
capital and operating

costs are added
together, as shown in
20 Figure 7, the optimal
5
~Tmin is found to be
523
about 14 o C.
The optimum ~Tmin has been calculated solelyon utility
cost. The effect af fou1ing an the networks must next be
studied. Fouling af up to 20% was considered, and the results,
in terms af the theoretical extra utility required (measure af
robustness af section 4.1), are given in Figure 6. The amount
af extra utility needed rises with ~Tmin: for 20% fouling, up
to an extra 300kW are required.
The cost af this extra utility must now be estimated. If
it is assumed that all the streams will be brought to their
correct temperatures elsewhere in the system, in plant items
not considered in the network diagram, then the extra utility
needed can be costed using the same utility costs as befare.
If this assumption is made, and the costs af fouling added to
the overall network costs, then the optimum ~Tmin decreases,
to about 11.5 0 C for 10% fouling and to c 10 0 C for 20% fouling,
as can be seen in Figure 6. On another, equal1y simplistic
cost base, similar answers are obtained: if 20% fouling were
expected, ane solution is to add 20% extra area to each
exchanger. Sample calculation suggests this extra area costs
about the same as the national utility cost (within about
E5000 for ~Tmin=100C, for example), indicating a similar shift
in ~Tmin.
5.3 Realistic costings.
The example above contains a number af questionable
assumptions, not least because an unrelaxed network has been
used. However, it indicates that the costs af fouling can form
an important part af an overall cost analysis, and be
significant in the selection af the cost-optima1 network. The
shift in ~Tmin required to produce an optimal network for a
given fouling problem will be a function af the accounting
practices used in design: for example, if operating costs over
5 years are considered, 5% fouling reduces ~Tmin by about 5 0 C.
For a given plant situation, a more rational cost scheme
wou1d af course be used: it would be known what streams were
expected to foul, which outlet temperatures were important to
maintain, and much more cost data would be available. Such
data could be used in a hand analysis ar as part af a computer
package.
6.THE FOULING OF HEAT EXCHANGER NETWORKS.

6.1 Sensitivity analysis.
The above sections have outlined the analysis af networks

for robustness to fouling, via sensitivity analysis first af
individual heat exchangers, and then af the whole network. The
technique is appropriate both to design and retrofit. A
similar approach to general network ana1ysis has been reported
by Kotjabasaskis and Linnhoff (20), who describe the
construction af "Sensitivity Tables" which chart the response
@ProcessEng
af network exit temperatures to the change in values af

process variables such as temperature and flowrate. Elegant
use af the tables in a fouling analysis has been reported (21)
for the design af a network where ane exchanger is expected to
foul severely: they allow possible solutions to a problem to
be rapidly compared, and offer many advantages to a designer.
524
The construction of such tables is a useful step, and

necessary to ca1culate the overall network response. One
advantage of the present analysis, however, is that the
identification of individual exchanger sensitivities enables
the regions of the network which produce robustness to fouling
to be readily identified. This is important in both network
and individual heat exchanger design.
As Parker and Smith (19) point out, however, sensitivity
analyses are of limited use in isolation: ideally, such
analysis should take p1ace in an integrated environment, where
the process and the heat recovery system are designed
concurrently. An elegant method for performing such
sensitivity analysis will shortly be published (22).
6.2 A strategy for robust network design.

A series of illustrations has demonstrated the importance
of considering exchanger fouling in network analysis. Although
further work is needed before fouling can be fully
incorporated in design, the following general strategy is
appropriate:
(a)PROBLEM DEFINITION: It is first necessary to know,

for the given problem, what rate of fouling is expected,
or, if the kinetics are unknown, what levelof fouling
is acceptable by the network.
(b)NETWORK DESIGN: The pinch algorithms can then be used
to produce acceptable solutions.
(c)CONTROL ANALYSIS: First analyse the control
structures necessary for each network, and reject any
unacceptable networks.
(d)EFFECT OF FOULING: For those networks not rejected in
(c), calculate aT and aUA for each exchanger, and thus
the robustness to the expected amount of fouling.
(e)COST ANALYSIS: Select the cheapest network (on the
chosen cost basis) of those considered in (d).
It wou1d be possible to write software to carry out the

ab ove scheme, or to implement it by hand. Since fouling will
not be a crucial factor in every design, however, it may be
more appropriate to incorporate the above strategy into
existing programs, such as those developed for the design of
resilent networks (RESHEX (23,24)). The use of the strategy in
programs such as MI DAS (19) which simultaneously optimise both
the process and the heat recovery system would be especially

useful.
No algorithm has yet been developed for the ab initio
design of robust networks. One area which should be
investigated further is the effects of preferential matching
between streams to produce "type 2" exchangers during the
design step. Further work here may yield interesting results.
@ProcessEng
7. CONCLUSIONS.
The importance of fouling in heat exchanger design has
been examined using simple but representative fouling models.
The sensitivity of an individual exchanger to fouling has been
derived, and the ways in which heat exchangers interact in
525
networks illustrated.
Two definitions of robustness have been given: one, a
relative measure, is based on the response of the network to
the fouling which is expected. The second, based on the
controllability of the network, is an absolute measure. The
use of the definitions has been demonstrated, and they have
been shown to select different networks than a conventional
resiIience analysis.
Robust networks will be of greater area, and thus capital
cost, than unrobust networks. The effect of the costs of
fouling must thus be included in any design calculation:
fouling has been shown to affect the position of the optimal
lITmin in a network.
8.ACKNOWLEDGEMENTS.
Portions of this work were originally undertaken in
collaboration with Dr NKH Slater and Dr WR Paterson, and their
assistance, together with that of Dr W Morton with QUASILIN,
is gratefully acknowledged. The assistance of Dr WR Paterson
in the preparation of this manuscript was especiaIly helpful,
as were discussions with Dr DC Woodcock and Dr GJ Smith of
ICI. "The Wages of Synergy" is the title of a story by
Theodore Sturgeon.
NOMENCLATURE
aUA Sensitivity to change in UA [K]

aT Sensitivity to change in temperature [kW/K]
A Heat transfer area [m 2 ]
A' Heat transfer area per unit length [m]
Bi Biot number
E Activation energy [kJ/moIK]
k Rate constant [s-l]
h Film heat transfer coefficient [kW/m 2 K]
K Factor defined by equation [5]
N Number of streams
t Time [s]
R Gas constant [kJ /mol]
T Temperature [K or °C]
llTl m Log mean temperature difference [K or °C]
ilTmin Minimum approach temperature [OC]
U Overall heat transfer coefficient [kW/m 2 K]
Umin Minimum number of units

q Heat flux [kW/m 2 ]
Q Heat flow [kW]
v Mean velocity [m/s]
w Heat capacity flowrate [kW/K]
x Distance [m]
@ProcessEng
Superscripts and subscripts.
c Cold
C Cold stream
d Deposition
h Hot
H Hot stream
526
IN rnlet
o Prior to fouling
OUT Out let
r Removal
REFERENCES
1.Fryer PJ: Basic concepts in heat exchanger network modeIling.

This conference. 1988.
2.Fryer PJ, Paterson WR and Slater NKH: The robustness of
fouling heat exchanger networks and its relation to
resilience. To be published in ChERD. 1987.
3.Fryer PJ: ModeIling heat exchanger fouling. PhD Thesis, Univ.
of Cambridge. 1986.
4.Phillips S and Stroud TP: The design of robust heat exchanger
networks. Part II Tripos reports, Univ. of Cambridge Dept. of
Chem. Eng. 1987.
5.Fryer pJ and Slater NKH: Reaction fouling from food fluids.
In "Fouling of Heat Transfer Equipment" ed AM Pritchard and
JW Suitor, ASME HTD-35. 1984.
6.Newson IH, Bott TR and Hussain Cl: studies of magnetite
deposition from a flowing suspension. Chem.Eng.Comm. 39 3.
1983.
7.Schlunder EO(ed): Heat exchanger design handbook. McGraw
HUL 1984.
8.Donaldson RAB, Paterson WR and Ponton JW: Design of complex
heat recovery networks: synthesis, simulation and
uncertainty. IChemE. Symp. Ser. No 40. 15-1. 1976.
9.Asbjornsen OA and Haug M: Choice of variables and
approximations in the optimisation of heat exchanger
networks. PSE 85. IChemE Symp.Ser. No 82. 209. 1985.
10.Fryer pJ and Slater NKH: A direct simulation procedure for
chemical reaction fouling in heat exchangers. Chem.Eng.J.
97.1985.
11.Fryer pJ and Slater NKH: The simulation of heat exchanger
control with tube-side reaction fouling. Chem.Eng.Sci. 41
2363. 1986.
12,13.Hutchison HP, Jackson DJ and Morton W: The development of
an equation-oriented flowsheet simulation and optimisation
package. I. The QUASILIN program. II. Results.
Comp.Chem.Eng. 10 1987.
14.Fisher WR and Douglas JM: Analysis of proces s operability at
the preliminary design stage. Comp.Chem.Eng. 9 499. 1985.
15.Saboo AK and Morari M: design of resilient processing

plants-III Some new results on heat exchanger synthesis.
Chem.Eng.Sci. 39 579. 1984.
16.Townsend DW and Morari M: Resiliency of heat exchanger
networks: an objective compatibIe with minimum cost. AIChE.
Ann. Meeting, San Francisco. 1984.
17.Linnhoff B, Townsend DW, Boland D, Hewitt GF, Thomas BEA,
@ProcessEng
Guy AR and Marsland RH: A user guide on proces s integration

for the efficient use of energy. IChemE. 1982
18.Linnhoff B and Kotjabasaskis E: Design of operable heat
exchanger networks. First UK Heat Transfer Conf., IChemE
Symp. Ser. No 86, 599. 1984.
19.Parker D and Smith GJ: MIDAS: A software pac kage for heat
527
exchanger network targeting, design and analysis. Submitted

to Chem.Eng .. 1987.
20.Kotjabasaskis E and Linnhoff B: Sensitivity tables for the
design af flexible processes (1)- How much contingemcy in
heat exchanger networks is cost-effective?
Chem.Eng.Res.Des., 64 197. 1986.
21.Kotjabasaskis E and Linnhoff B: Process design for
flexibility: an optimum overdesign strategy for fouling and
multiple base cases. Paper presented at IChemE Process
Optimisation Conf., Nottingham. 1987.
22.Paterson WR, Lester GA and Harris BA: to be submitted, 1987.
23,24.Saboo AK, Morari M and Colberg RD: RESHEX - An
interactive software pac kage for the synthesis and analysis
af resilient heat exchanger networks. Parts I and II. Camp.
Chem.Eng. 10 6 577-599. 1986.
@ProcessEng
COMPENSATING FOR FOULING IN HEAT EXCHANGER NETWORKS
E. KOTJABASAKIS AND B. LINNHOFF, UNIVERSITY OF MANCHESTER INSTITUTE OF

SCIENCE AND TECHNOLOGY, MANCHESTER M60 lQD, UNITED KINGDOM
INTRODUCTION
Fouling of heat transfer area is expensive. A survey in 1979 showed

that the annual costs associated with fouling of heat exchangers in oil
refineries exceeded $4,500,000,000 (l). Refineries represent only a minor
proportion of the total fouling related expense in industry and we can
safely assume that the understanding and control of fouling is important.
There is clear incentive for the development of good practices.
Fouling influences the way in which chemical plants are designed and
operated. practically every heat exchanger manufactured includes an
allowance for fouling through the 'fouling factor' (2). Depending on the
nature of plant, the fouling factor might result in significant additional
capital expenditure. In 1977, for the UK only, additional capital cost
was estimated to be in the order of $200,000,000 per annum (3). Plant
operation is also affected and indeed is sometimes governed by fouling
problems. The same report (3) estimated that effects of fouling such as
additional fuel costs, maintenance costs, use of anti-foulants, plant down-
time, reduced throughput, etc., add up to a total fouling related cost of
approximately $800,000,000 per annum in the UK (at 1977 prices) .
Understandably then, fouling attracts much research. HTRI undertook
an extensive research programme aimed at obtaining information that would
allow the engineer to improve the design of exchangers subjected to fouling
(4). The UK Government funded a similar programme a few years later (3).
Much work is done on finding new and better additives. International
Symposia total ly related to exchanger fouling have been mounted (5). Much
of this research is no doubt worthwhile. An understanding of fouling
mechanisms is vital if the effects are to be minimised. More accurate data
on fouling will result in improved designs. Additives that reduce fouling
will almost always find a market.
So there is considerable effort devoted to the development of methods
both for reducing and predicting the effects of fouling. These methods
are important. They help reduce overdesign margins and plan for improved
plant operation.
The present paper starts with the observation that all these methods
are based on the implicit assumption that fouling is counteracted by over-
designing the fouling equipment. Once overdesigned, the fouled equipment
per forms to the same capacity/throughput as the - smaller size - clean
@ProcessEng
equipment would have done.

In this paper we introduce an alternative approach. Most processes
are integrated structures of equipment. During design, alternatives often
exist for the selection of individual equipment sizes and trade-offs. The
designer may specify one piece of equipment to be smaller at the expense
of another one being larger. In this paper we will argue that there are
529
L. F. Melo el al. (eds.), Fouling Science and TechMlogy, 529-554.

530
many good reasons why, if a piece of equipment is subjected to fouling, it

should be made smaller rather than larger. This can be done by "trading
off", i.e. by increasing in size other pieces of equipment which are not
subject to fouling. In other words, we advocate the foliowing simple
concept: we need to oversize to compensate for fouling but let us oversize
the non-fouling equipment.
TYPICAL PROBLEM
Figure l shows the simplified flowsheet of a vacuum distillation unit.
The relevant heat exchanger network is shown in Figure 2 using the grid
representation proposed by Linnhoff (6). Data describing the current
operation of the plant are given in Table la.
The plant is to be retrofitted to operate on a different dut y for a
single campaign once ayear. The length of the campaign is approximately
two months. A new feedstock is to be used. Flowrates within the plant
need to be increased and some temperatures are changed. As mentioned in
the introduction, Case B is described as a set of deviations from Case A.
The data describing CASE B are given in Table lb.
Case B operation has another complication. The temperature of stream
l is increased significantly (see Table Ib) and this is known to result in
exchanger fouling at temperatures in excess of 280 deg. Thus, exchanger
no. l in Figure 2 will operate clean during Case A operation but will be
subjected to fouling, to a significant extent, during Case B operation.
The design objective for the retrofit is to find the cheapest project,
in terms of energy and capital costs (see Table 2), which will enable in
future both Case A and Case B operation. All specified flows and temper-
atures must be maintained. Fouling and cleaning requirements (it usually
takes two days to clean a heat exchanger) must be taken into account and
plant downtime, which is very costly, must be avoided.
To assess what is "cheapest" we define the "Total Additional Cost",
- l
analogous to reference l, as:
Total
Additional
r,mualioed coo,
of Capital for + [nnual CO] ~Energy
of Energy -
Annual Cost of
before
! Cost retrofit af ter retrofit,
L
retrofit, Case A only
!
L J Case (A+B)
We suggest that an engineer might tackle this problem by first

simulating the performance of the existing plant for Case B. The results
of such a simulation are shown in Figure 3. The target temperatures (TT)
for streams l, 2, and 4 have been maintained by increased use of utilities.
The target temperature of stream 3 cannot be maintained using existing
equipment. Consequently, the engineer might specify a new heater for

stream 3, see Figure 4.
Next, the engineer would need to specify overdesign on exchanger l
to counteract the fouling problem. The extent of overdesign is not
immmediately clear. Plant operation must be considered: downtime should
be avoided, even while an exchanger is cleaned. The capital cost of new
area must be weighed against operating costs, based on non-constant
@ProcessEng
operating conditions.
The rate of fouling is known. There is a reduction in the overall
heat transfer coefficient of 1% per day. A quick simulation shows that
the performance of exchanger no. l has deteriorated af ter less than fort y
days of Case B operation such that the load on the furnace exceeds its
maximum firing capacity (9200kW). At that point, the plant can no longer
531
operate. By the same token, it is clear that the plant cannot operate
with exchanger l off-line for cleaning. It follows that we need either:
* a new furnace, or
* additional surface area in exchanger l, installed in parallel
to the existing exchanger.
A new furnace is too expensive. So the remaining question is what
should be the size of the required new exchanger?
There is a trade-off between capital cost, operating cost and
cleaning cost. To keep the example simple we will base our calculations
on the minimum additional surface area required. This is easily
determined. It is the smallest clean unit that will allow the plant to
operate within the furnace firing limit (Figure 5). The result is
450 sq.m.
We have achieved an operable overall design for Case A and Case B
subject to fouling. The Total Additional Cost for the retrofit is
$ 50 , OOO/annum.
SENSITIVITY TABLES
In a previous publication (7) we introduced a new approach to the
cost effective provision of contingency in heat exchanger networks. It
was based on simple "Sensitivity Tables" which enable the engineer to:
(i) evaluate the passive response of a network to deviations in
feed temperatures, flowrates, heat transfer coefficients etc.
(ii) evaluate all possibie design changes to eliminate unwanted
passive responses.
A Brief Review
The heat balance equations for a single heat exchanger are:
Q CPH (TI T 2)
where: TI hot inlet temperature; T 2 = hot outlet temperature
T3 cold inlet temperature; T 4 = cold outlet temperature
and the design equation is:

Q = UA (L'lT LM )
These equations can be transformed to give:

(l - RB)T 2 + (B - 1)RT 3 + (R - l)T l O
R(l - RB)T 4 + (B - l)RT l + (R - 1)BRT 3 = O

where:
R
@ProcessEng
and:
B exp [IUA/CP c) (R - l]
532
The equations are linear with respect to temperature but non-linear

with respect to heat capacity flowrate and the heat exchanger parameters
(D and A). If we know the exchanger parameters, the heat capacity
flowrates, and any two of the four temperatures, we ean solve the equations
without iteration to find the outer two temperatures.
For networks of heat exchangers we ean exploit the duplication of
temperatures between exchangers and ean describe the overall network by a
system of simultaneous equations which again ean be solved without
iteration. Thus, if we know all exchanger parameters, all heat capacity
flowrates, and network inlet temperatures only, we ean calculate all
remaining temperatures in a network. This holds true for any feasible
network, with or without loops (7).
Non-linear effects such as non-linear enthalpy-temperature
relationships, variations in local heat transfer coefficient, etc, are
handled eas ily through the use of linearised sub-units (8).
The solution of the simultaneous equations requires only simple
software (8). The result ean be a simple but effective simulator which ean
be used with ease. However, an even more useful result exists.
We ean solve the equations to obtain "unit network responses" for any
input deviations and we ean generate tables showing the correlation between
inlet temperatures, flowrates, exchanger parameters, etc, deviations and
their effects throughout the network (7). These "Sensitivity Tables" ean
be used for the rapid screening of sensitivities.
Three kinds of Sensitivity Tables are required for the full analysis
of a system. They are the:
T(TS) Sensitivity Table
T(CP) Sensitivity Tables
and: T(DA) Sensitivity Tables
The tables are used in an apparently naive manner. Individual effects
are simply added together with total disregard of non-linearities and
interaction effects. This has the appearance of a non-linear problem
being treated as linear. The appearance is misleading. Rather, the tables
establish sensitivities within range s and linearised sections. The errors
generated are small. The results are, within reason, "accurate". The
simplicity of the approach gives the user a near-exact birds-eye view of an
otherwise intractably complex problem. Naturaily the chosen design options
should finally be confirmed through modeiling and simulation. However,
overall errors in Total Additional Cost are usually found to be less than
5% and optimal solutions identified quickly are confirmed as such even af ter
protracted and "exhaustive search" using traditional simulation.
Sensitivity Tables for the Example Problem

We wiI1 now genera te the relevant Sensitivity Tables for our example
problem.
T(TS) Sensitivity TabIe

A single table (Table 3) is sufficient to provide all correlations
between changes in all supply temperatures (TS) and the respons e in all
other network temperatures (T). Given that the transformed base equations
@ProcessEng
are l.inear wi th respect to temperatures , the table gi ves exact resul ts

for any combina·~:ion of changes over any range of deviation.
The temperature notation used in Table 3 is explained in Figure 6.
The correlation factors listed are simple multiplication terms. The use of
the table is simple. For instance, we ean see at a glance that if supply
temperature TSl changes by 10 deg then temperature T14 changes by 0.7 deg.
533
If supply temperature TS2 changes by 10 deg then T14 changes by 2.27 deg,
etc.
T(CP) Sensitivity Tables

The system of equations is non-linear with respect to heat capacity
flowrates (Cp). Therefore, we need one T(CP) Sensitivity Table for each
stream if the effects of non-linearities are to be minimised. Each of
these tables will cover a range of flow variations about the base case.
A typical T(CP) Sensitivity Table is shown in Table 4. It applies
to stream l of our example problem. It lists temperature deviations as
opposed to correlation factors. For instance, it tells us that if the
heat capacity flowrate of stream l is increased by 30% then temperature
T14 would increase by 3.53 deg, etc.
T(UA) Sensitivity Tables

The system of equations is also non-linear with respect to the
exchanger parameters (UA). Thus, as in the case of flow, we need several
tables. In this case we need one for each exchanger, covering a range of
possible deviations in exchanger (UA) from the base case.
Using the T(UA) Sensitivity Tables we can consider operational factors
such as fouling and the influence of flow upon overall heat transfer
coefficient. We can also consider changes in design parameters such as
area and overall heat transfer coefficient.
The T(UA) Sensitivity Tables for our problem are given in Tables 5a-d.
Again, they contain temperature deviations and not correlation factors.
APPLYING SENSITIVITY TABLES

In this section, we will work with the Sensitivity Tables to solve
our problem. First, we will address the new alternative dut y (Case B) ,
ignoring fouling. Second, we will address fouling.
Case B Operation
We apply the tables in two stages. The determination of the passive
network response is followed by the selection of a suitable design change.
Passive Response
The passive response is the final steady state condition of the
existing network given the specified deviations from base case (see Table
l). It could be determined from simulation. Alternatively, we can use the
Sensitivity Tables.
As mentioned ealier, traditional simulation indicated that all but the
target temperature on stream 3 could be maintained through the use of
additional utilities in existing exchangers (see Figure 3). The short fall
on target temperature 3 was 7.35 deg. Let us see what the tables tell us.
Individual effects can be determined from the T(TS) and T(CP) Tables.
For instance, for the increase in supply temperature l (40 deg) Table 3
tells us that the associated change in target temperature 3 (T14, see
Figure 6) is:
6T 14 (TS1) = (0.069). (40) = 2.76 deg.
@ProcessEng
The other effects are also quickly established. They are listed in
Table 6. As stated previously, the overall effect is found by simple-
minded addition. A shortfall of 7.2 deg is predicted. There is a
difference between this result and that obtained from full simulation of
less that 3%.
534
The Tables are both quick and simple to use and can be used repeatedly
for other network temperatures to establish the full passive response. This
may or may not be important, depending on the availability of a simulator.
It should be borne in mind however, that the tables need only be computed
once at the beginning of a project. Thereafter, the engineer is at liberty
to test responses to the full without recourse to a computer.
Design Changes
In our example problem all four target temperatures need to be
maintained. Three of these (TT1, TT2 and TT4) are easily maintained using
existing coolers and heater. The remaining one (TT3, or T14 in Figure 6)
should probably be maintained differently as no heater or cooler is
situated conveniently.
The usual method of building flexibility into a heat exchanger network
is by oversizing exchangers and the provision of bypasses. The T(UA)
Sensitivity Tables give the necessary information for identifying and
evaluating such options (7). They identify the effect of changes in
exchanger parameters on every temperature in the network. Consequently,
they allow us to easily discuss every possibie design option - even the
non-obvious ones. The use of the Tables is now in a reverse manner to that
for determining passive response. The objective is to cancel undesirable
elements of the passive network response. In other words, in our problem,
we are looking for changes in the "effective area" (7) of any exchanger such
that 6T 14 = +7.2 deg.
Inspece:.ion of the T(UA) Sensitivity Tables shows us that there are
four alternatives (in addition to the "obvious" solution involving a
heater) :
Heat exchanger l 6 (UA1) -82% Bypass
Heat exchanger 2 6(UA2) -23% Bypass
Heat exchanger 3 6 (UA3) +66% Additional Area
Heat exchanger 4 6(UM) +40% Additional Area
Using the Tables we see all these options at a glance. In contrast,

the use of simulation would be cumbersome. We would have to run too many
cases to be practical. Ultimately, we would need to make some intuitive
choices and cross our fingers. It is this ability of the Tables to show
all options at a glanee, the "birds-eye view", that sets them apart from
simulation. Simulation is a modeiling tool. The Tables are also a design
tool.
To evaluate the overall cost implications of the four options
identified we need to know the overall passive response of the entire
network for each of the options (7) when overlaid with initial passive
response. Once more, this information is easily obtained from the Tables or
from simulation. To enable a final assessment of accuracy to be made we
stick, for the time being, to the use of the Tables.
The "Total Additional Costs" of the four options is as follows:
Heat exchanger l 190,000 $/year
Heat exchanger 2 73,000 $/year
@ProcessEng

Heater of Stream 3 85,000 $/year
535
In Figure 7 we show the Total Additional Cost of each of the options

as a function of the Case B annual operating time. Using the Tables this
information is quickly obtained. It ean be seen that for Case B opera ting
periods of two months per year or more the option involving heat exchanger
4 is cheapest. For shorter annual operating periods the option involving
heat exchanger 2 is cheapest.
We would venture that the cheapest solution, i.e. overdesign of
exchanger 4 (Figure 7), comes somewhat of a surprise and may not have been
identified without the use of the Tables. The "obvious" solution
(installation of a heater on stream 3) is 20% more expensive.
Finally we assess the errors associated with the use of the Tables
for Total Additional Cost. Comparing it to the results of full simulation
we found it to be around 3%.
Fouling
The traditional approach to fouling is to add are a for contingency in
the exchanger which is subjected to fouling. Is this the right approach?
There is an interaction between exchanger design and fouling rate. It has
been found in some notorious cases that an increase in exchanger size to
cope with fouling has resulted in lower velocities, etc., and therefore an
increased rate of fouling! Secondly, we should recognise that the
additional area is installed in a position where its effective use is
impaired of necessity by fouling. Could we do better?
Why not ask the question "Can we cope with fouling by installing
additional area in positions in the network other than where the fouling
occurs?".
Sensitivity Tables help us again to implement this idea. They help us
to evaluate the ways in which exchangers interact within the network.
Fouling ean be described as a reduction in UA of a particular exchanger.
We ean determine its effect from the Tables as a passive response and
subsequently we ean use the Tables to identify design changes elsewhere to
overcome the effect.
Let us apply the Tables in this fashion to our example problem. As
described above, there are two major operational concerns in our problem:
* the furnace firing capacity may be limiting
* we need to avoid plant downtime, even during cleaning.
From the information given in the T(UA) tables we ean construet
Figure 8, which shows the effect of changes in the effective area of
exchangers l, 2 and 4 on the furnace inlet temperature. We see that we ean
compensate for the effects of fouling in three ways:
* additional area in the fouled unit (exchanger l)
* additional area in exchanger 2
* additional area in exchanger 4.
The cheapest option appears to be an increase in the are a of

exchanger 4. This option is significantly better than simply oversizing
the fouling exchanger (exchanger l). Next we must decide how much over-
design of exchanger 4 is required and how often exchanger l should be
cleaned. The two factors are closely related.
First we need to establish whether it is possible to remove exchanger
l for cleaning whilst maintaining plant operation. The Tables tell us that
@ProcessEng
this is now possible, but only if the overdesign on exchanger 4 is large.

This leaves us with two possible choices:
l) We ean place new area in two locations: exchanger 4 for Case B
operation and some fouling correction; and a new exchanger parallel to
exchanger l to permit cleaning. This would imply an operating
536
strategy analogous to that used earlier (Figure 5) but with lower

capital cost implications.
2) We can place new area solely on exchanger 4. We would not remove
exchanger l for cleaning until the production campaign (Case B) has
finished. While exchanger l is cleaned (during Case A operation) we
can keep the plant on line due to exchanger 4 being now larger.
This choice of options requires some detailed cost trade-off
calculations. The first option was found to be more expensive than the
second.
The chosen option is again evaluated with the Sensitivity Tables.
For the purpose of comparison with the solution found earlier (Figure 5) we
have based our calculations on the minimum additional surface are a required
on exchanger 4. The results are shown in Figure 9 in the terms of
operating policy and furnace duty. The minimum overqesign on exchanger 4
is 330 sq.m.
This final solution as found using the Tables has a Total Additional
Cost of $-42,000/year. It is $92,000/year cheaper than the "straight-
forward" solution derived earlier (see Table 7) .
DISCUSSION
The Sensitivity Tables

In the example presented the error associated with the use of
Sensitivity Tables related to full simulation was found to be around 3%.
General experience from practical application of the Tables indicates that
the error in estimating Total Additional Cost is usually les s than 10%, and
often less than 5%.
The purist might be worried. Errors of this magni tude may affect
comparisons. However, let us bear in mind that the screening of options is
used in the present context for the early rejection of alternatives whose
differences in Total Additional Cost typically exceeds 50%. The Tables
ensure that all options are seen early, leading to the safe rejections of
most. If necessary, more than one of the cheaper solutions can be ful ly
evaluated using detailed simulation.
In essence the Tables present a "birds-eye" picture. The engineer
gains a full understanding of available options and is able to evolve a
practical, and perhaps non-obvious, solution with confidence and little
effort.
Simulation does not present an alternative. It does not provide this
"birds-eye" view. Too many repeated calculations would be required to build
up an overall picture. The appropriate use of simulation is for final
design validation, not for the invention part of the design.
Compensating for Fouling through Network Interactions

To the authors' best awareness, this concept has not been previously
suggested in the literature. There have been several papers addressing the
behaviour of a given network to fouling (e.g. ref. 9). However, these
papers only ex amine network respons e for given installed areas. When
compensation is considered, the approach is invariably to install
additional area in the exchangers which foul. The present paper suggests to
@ProcessEng
install the additional area systematically and perhaps elsewhere in the

network.
In the example presented we have seen that the traditional treatment
of fouling (i.e. through concentrating on the unit in which fouling occurs)
is not always the best solution. Fouling can be compensated for through
additional are a in "clean" units using network interactions. Why invest
537
in extra heat transfer area that is going to foul?

This simple idea could have a far reaching economic impact.
Dealing with fouling by seeking to avoid it (e.g. chemical additives
etc.) is an active area of research. However, it is a complex problem.
Headway is being made in specific areas but a general solution is not in
sight.
In this paper we present an alternative and a practical approach that
works today:
Once we have identified that fouling will occur let us compensate
for it in places other than the unit which fouls. Let us then
consider the overall sensitivities in the integrated process. Let
us examine network interactions and check cheaper possibie solutions.
All this can be done by inspection and simulation. However,
Sensitivity Tables are nice ly suited for the task.
Research on Fouling
Let us now ask what the potential benefits are from traditional
research and development work on fouling in relation to the design of heat
exchangers, and process networks, as discussed here.
There are three main areas of research and development which have
implications for the industrial designer. These are:
* Additives
* Study of fouling mechanisms
* Better prediction of fouling rates and effective resistances
The varying degrees, research and products on the market all relate
to specific circumstances. A particular additive helps reduce fouling in
one application but not the other. A particular exchanger geometry
minimises fouling for one process dut y but not the other. Also, most
prediction methods are specific. The fact that results are specific, often
poses a problem for the industrial designer. While fouling mechanisms, for
example, may be well understood for a given range in velocity, his design
may fall outside this range. Often the very fact that the (remaining)
fouling has to be compensated for is responsibie for designs away from
traditional values. And with less certainty about effects, a higher
fouling factor is used, resulting in even more off-range designs, resulting
in less certainty, etc.
The message here is simple. Network interactions, as discussed in
the present paper, can be used not only to identify where in the network to
place the overdesign for compensation but also to identify whether gains
are to be made by designing the fouling equipment deliberately for
conditions of most certainty. Depending on additives, fouling models,
prediction charts, etc. available, the gains can be significant indeed.
CONCLUSIONS
Fouling can be considered to be a deviation in the operating
condition of a plant. As such it can be considered to be a "flexibility"
problem.
Sensitivity Tables exist for flexibility problems in design. In this
paper their use has been demonstrated for heat exchanger networks. They are
quick and simple to apply. They give an overview of all options available
@ProcessEng
to the designer. Sometimes, good options are non-obvious. The Tables are
accurate enough for the easy recognition of such non-obvious but cheap
solutions.
Full simulation is not suited for this task. The proper use of
simulation is in final design validation. The use of repeated simulation
for invention should be the last re sort if all other means of invention
538
have failed.
The cost of fouling in the process industries is high. The incentive
to reduce these costs is real. One option that has not been recognised to
date, as far as the authors are aware, is the use of exchanger interactions
in design to compensate for the effects of fouling. In the immediate term
this could provide the quickest route to a practical reduction in
industrial fouling costs. The benefits are difficult to estimate. What is
easy to say is that they will be vast.
ACKNOWLEDGEMENTS
Thanks are due to the Bodossakis Foundation, the Onassis Foundation
and the Process Integration Research Consortium who supported
Mr Kotjabasakis's research at UMIST. BASF, Union Carbide, and Dow helped
this work greatly by providing meaningful industrial case studies.
Special thanks are due to Dr G T Polley for his help and constructive
criticism in preparing the manuscript.
REFERENCES
l. Van Nostrand W.L., Leah J.R. and Havuska J.L. "Economic penalities
associated with the fouling of refinery heat transfer equipment",
Int.Conf. on Fouling of Heat Transfer Equipment, Rensselaer
Polytechnic Institute, 1979.
2. TEMA. Standards of the Tubular Exchanger Manufacturers Association.
6th Edn., New York, N.Y., 1978.
3. Pritchard A.M. "An investigation of fouling and anti-fouling measures
in the British Isles", Int.Conf. on Fouling of Heat Transfer
Equipment, 1979.
4. Taborek J., Aoki T., Ritter R.B. and Palen J.W. "Fouling: The major
unresolved problem in heat transfer", CEP Febuary 1972, pp59-78.
5. Fouling of Heat Transfer Equipment, Hemisphere 1981, Proceedings of
Intl.Conf. on Fouling of Heat Transfer Equipment, Rensselear, 1979.
6. Linnhoff B. ph.D. Thesis 1979, Leeds (UK).
7. Kotjabasakis E. and Linnhoff B. "Sensitivity Tables for the Design of
Flexible Processes", Chem.Eng.Res.Dev., Vol. 64, pp197-211, May, 1986.
8. Kotjabasakis E., Ph.D. Thesis, UMIST, 1987.
9. Fryer P.J., Paterson W.R. and Slater N.K.E., unpublished manuscript,
University of Cambridge, 1985.
@ProcessEng
539
TABLE 1
Stream data describing current plant operation (CASE A) and the

new alternative dut y (CASE B).
CASE A (10 MONTHS/YEAR)
S T R E A M D A T A
STREAM No. TS TT CP (kW/oC) h (kW/m 2 0C)
1 285 218 81.49 0.35

218 150 69.71 0.28
150 120 66.97 0.24
2 272 151 49.17 0.50

151 75 44.41 0.41
75 40 43.29 0.40
(a)
3 55 115 55.87 0.38
4 40 102 76.45 0.33

102 175 81.51 0.41
175 236 89.51 0.47
236 315 97.10 0.53
CASE B (2 MONTHS/YEAR)
STREAM No. TS TT CP (kW /oC) h (kW/m 2 oC )
1 +40° - +30% -
2 _20° - +10% -
(b)
- - -
@ProcessEng
3 +20%
4 - - +20% -
540
TABLE 2
Cost Data
Cost of Heat Transfer Area
*Process/process exchangers, heaters:

Installed cost ($): 26,000 + 330 (A)0.95
A: area of exchanger in m2
*Air coolers:
InstalIed cost ($): 2,000 (A)0.76
A: area of cooler in m2 ,
bare tube surfaee are a based on:
U = 400 W/m 2 k
MTD = ! Ti - 12°C
Ti = process strcam inIet temperature
*Life time of equipment: 2 years
Cost of UtiIities
*Fuel cost 2.6 $/GJ

Furnace efficiency: 0.75
*Steam: 54 psig, 140°C
Cost of steam: 5.8 $/tonne = 12.25 $/MWhr
Heat transfer film coefficient: 6 kw/m 2 oC
*Cost for air coolers operation = 0.8 $/MWhr
*Annual operating time: 8,500 hrs/year
Downtime
To be avoided
@ProcessEng
541
TABLE 3
The "T(TS) Sensitivity Table" gives the correlation between changes

in stream supply temperatures (~TSi) and the resulting changes of
network temperatures (~Ti)
Example of use: If ~TSl
then ~T8 = (0.445) (+10)
/ ~TSl ~TS2 ~TS3 ~'rs4
åT 6 .445 .296 .000 .256
ål'
.275 .184 .000 .541
9
å'l' 10 .211 .141 .000 .461
åT 11 .110 .362 .000 .528
åT 12 .023 .076 .790 .111
åT 13 .008 .028 .267 .040
åT 14 .069 .227 .372 .332
åT 15 .155 .104 .000 .741

~T 16 .088 .489 .000 .423
åT 17 .594 .219 .000 .188
åT 18 .375 .137 .0000 .119

@ProcessEng
542
TABLE 4
The "T(CP) Sensitivity Table" for stream 1 gives the correlation between
changes in its heat capacity flowrate (~~Pl) and the resulting changes in
network temperatures (~Ti)
Example of use: If ~CPl = -10% then,

~T8 = -6.11 °c
lICPl -40\ -30\ -20\ -10\ 0\ 10\ 20\ 30\ 40\
liT O -30.64 -2l. 35 -13.19 -6.11 .00 5.29 9.88 13.89 17.41
liT 9 -45.08 _-32.01 -20.16 -9.51 .00 0.50 16.10 22.91 29.01
liT 10 -45.16 -32.64 -20.87 -9.98 .00 9.11 17.41 24.97 . 31.87
liT 11 -12.03 -8.40 -5.21 -2.43 .00 2.12 3.98 5.62 7.08
liT 12 -2.52 -l. 76 -l.09 -.51 .00 .44 .04 l.10 1.49
liT 13 -.92 -.64 -.40 -.19 .00 .16 .30 .43 .54
liT 14 -7.56 -5.27 -3.27 ,..1.52 .00 1. 33 2.50 3.53 4.45
hT 15 -16.90 -11. 80 -7.32 -3.41 .00 2.90 5.60 7.90 9.55
liT 16 -9.64 -6.73 -4.10 -1.94 .00 l. 70 3.19 4.51 5.68
liT 17 -17.31 -1l.42 -6.77 -3.04 .00 2.51 4.60 6.37 7.87
liT 1il -10.92 -7.21 -4.27 -l.92 .00 1.50 2.90 4.02 4.99
@ProcessEng
543
TABLE 5
The "T(UA) Sensitivity Tables" give the correlation between changes

in (UA!) at a given exchanger (i) and the resulting changes in net-
work temperatures (~Ti).
Examples of use: I f ~UA1 = +20%

Le. (UA I ) (1.2) (UA 1 ) base case
then, -5.8°C
6UA 1 -an -001 -.os -20' OS 4201 6UA 2 -201 -101 OS ti Ol nOl .sOl
,T.
,T.
U.O
27.1
21.
n.z
o 10.1
IO. o ...
T.I 0.0
O. o
-'.e
-3.a ...
aT. -4.5
-2.0T
-2. JO
-1.33
.00
.00
I.U
1.10
3 .• '
2 .••
11.00
l,OO
ar,. 20.t 13.3 T.T 3 •• 0.0 -2.' liT •• 2.21 -1.03 .00 .tO ..0& a."
"T" IO. t 0.3 •• O I.e O. O - .. 4 .61" 0.97 '.eJ .00 -'.04 -T." -ID."
AT,.
.. ti.
Ar ..
2.3
o.•
e.t
I.'
... ... ...

O••
o.e
o.•
o ••
0.1
1.1
O. O
O. O
0.0
-0.3
-o.
-0.0
l
AT ••
AT,.
AT,.
2.09 .
.'0
6.21
...
O.tf
2.01
.00
.00
.00
-.85
-.,a
-J.U
-1.50
-.5' .
"".TI
-2.2'
-.'2
-I.U
.r ..
., ..
.r, •
15.3
O.T
-31.2 -10.8
...
t. T •• e
3.'
-II .•
l ••
-a.l
0.0
0.0
0.0
-'.0
-1.1
•• I
AT,.
AT,_
6T,.
-1.02
-7.'.
-3. (O
-.1~
-'.15'
-1.51
.00
.00
.00 1.34
.00
:J. 00
1.23
IS. Il
2.158
I."
'.20
:I.U
., .. -19.T -12.5 -T.' -3.2 O. o 2.e 6T,. -2.15 -I. 00 .00 .&1 1.03 •• 31
(a)
6U"3 "201 OS UOI HOl tOOI uos 6UA 4 -101 os tlOI .201 flOI HOl
......
aT. .00 .00 .00 .00 .00 .00 -1.00 .00 ... 1 2.05 '.31 15.'0
....
AT. .00 .00 .00 .00 .00 .00
3.n .00 -3.20 -0.35 -8.2' -12.01
A',. .00 .00 .00 .00 .00 • DO
.u,. 2." .00 -2.51 - -f." -'.21
.. TtI .00 .00 .00 .00 .00 .00 -3.23
6Tn .00 3.10 0.0& '.12 11.47
" .. •. 01 • 00 -'.03 -O •• 1 -fl.O -o.a 6T,. -.80 .00 .e5 1.21 1.15 J.U
.r ..
-'.5 ..,
AT ..
Ion
43.90
.00
.00
-1.32
a,ID
-'.33
•• 09 ...
-3.1
T••
6T,.
6T'4
-.25
-2.00
• 00
.00
.2 •
1.15 3.71
.CO .eT
1S.5' f.ao
.T ..
.T .•
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
.00
",T .. -'.00 .00 C.35 •. U 12." U.II
6T •• -2.63 .00 2.41 c .•• '.or '.lf

arn- .00 .00 .00 .00 .00 .00 -1.17
6T ... .00 1.11 J.16 3.111 C. JO
,t,. .00 .00 .00 .00 .00 .00 6T,. -.74 .00 .70 1.36 I." J .••
@ProcessEng
(c)
544
TABLE 6
The change in temperature T14 resulting from CASE B operation is found

by the addition of the individual effects from each deviation.
Effect of change in TS 1 :
Table 3, 6T l = +40°C
lITl4 = (0.069) (+40) +2.76°
Effect of change in TS 2 :
Table 3, lITS 2 = -20°C
lITl4 = (0.227) (-20) -4.54°
Effect of change in CPl:
Table 4, 6CP1 = +30%
lIT14 = +3.53°
Effect of change in CP 2 :
lICP 2 +10%
lITl4 +7.2°
lICP 3 +20%
lITl4 -7.95°
li CP 4 +20%
6T14 -8.2°
The overall effect is:
li Tl4 (+2.76) + (-4.54) + (+3.53) + (+7.2) + (-7.95) + (-8.2)
li Tl4
@ProcessEng
545
TABLE 7
Comparison of the two solutions
Capital Energy Total

Investment Cost Additional
($/yr) Difference Cost
($/yr) ($/yr)
SOLUTION 1 144,000 -94,000 50,000
SOLUTION 2 65,000 -107,000 -42,000
SOLUTION 2 as
a percentage 55% 14% n.a.
of SOLUTION 1
SOLUTION l: Design using a traditional approach (Figure 5)
SOLUTION 2: Design using Sensitivity Tables (Figure 9)
Annualised cosJ
Capital Investment [ of Capital for
retrofit
Energy cost Difference

[
AnnUal Cost
Energy af ter
0J [
AnnUal Cost 0J.
Energy before
retrofit retrofit
Case (A+B) Case A only
@ProcessEng
@ProcessEng
Ul
...
0\
HP SHAH
TOP PRODUCT
BFW --_I--- lRECYCLE
BOTTOM
PRODUCT
PRIMARY
FE ED
FIGURE 1
~implified flowsheet for a Vacuum Distillation Unit.

547
265"
1~----(
272"
1I11~-----:---i
115 0
315 0
236 0
5460 5950 4740
7671
FIGURE 2
The existing network before retrofi t {.CASE A}

@ProcessEng
548
1 '------{
252
lIJ-----:-----t
0
8028
FIGURE 3
The "passive response". TT1. TT 2 .and TT 4 are maintained

by utility exchangers. TT3 is reduced by 7.4°C.
@ProcessEng
549
1J - - - - - - t
252 0
lI1----:----t
8028
FIGURE 4
The "obvious" solution: install a steam heater on

stream 3 for CASE B operation.
@ProcessEng
550
rn
( a)
firina limit defines

Furnace minilflum size af t he
Dut Y (kw) new unit (1A)
9200
~
_____________ H____ _________ _
F
( b)
6960 D
CASE A
5700 C
26 30 60 days
FIGURE 5
a) The final design using a traditional approach. In addition

to the new heater on Strearn 3 a new unit (lA) is required to
cornpensate for fouling. Total Additional Cost: $50,000.
b) Operating policy during CASE B.
C: Operation starts
@ProcessEng
D: (lA) out for cleaning

F: (lA) returned and (1) out for cleaning
H: (1) returned
551
T1
1
T2
2
T14
T18 T17
FIGURE 6
Temperature numbering system for the Sensitivity Tables.

@ProcessEng
552
(lJ1-----:--
(a )
•
Total Additional
Cost ($/yr)
20QOOO
( b)
Exchanger 4
2 Case B operating time

(monlhs )
FIGURE 7
Design for CASE (A and B) without fouling

@ProcessEng
a) The cheapest alternative is to overdesign

exchanger 4.
b) The effect of CASE B operating time on
Total Additional Cost.
553
Exchanger 4
\ Exchanger1
+ 1O~
- 500 500
FIGURE B
The effect of fouling in exchanger 1 on furnace inlet temperature

(bottom left) and the effect of increase in effective area of
@ProcessEng
exchangers 1, 2 and 4 on furnace inlet temperature (top left).

The reductlon of the effective area on exchanger 1 because of
fouling (bottom left) ean be offset by the sma1lest amount of
additional area if this is instalied on exchanger 4.
554
( a)
firing limit defines

Furnace min overdesign on
Dut Y( kw) Exchanger 4
9,200 . - - - - - - - - - - - - - /- - - - - - E
- -F- - - -
8,700
( b)
CASE A
o 60 days
FIGURE 9
a) The final deBign aB derived with the Sensitivity TableB.
Overdesign exchanger 4 for CASE B operation aB well aB for

fouling. Total Additional Cost: $-42,000/year.
b) Operating policy:
C: CASE B operation startB
D: End of CASE B operation. Exchanger 1 fouled by 601,
removal for cleaning.
E: CASE A operation. Exchanger l Btill out for cleaning.
@ProcessEng
F: Exchanger l returned.
@ProcessEng
Chapter 9
Food Processing Fouling
FOULING BY MILK AND DAIRY PRODUCT AND CLEANING OF HEAT EXCHANGE SURFACES
M. LALANDE*, F. RENE**
* INRA, L.G.I.A. - 59651 Villeneuve d'Ascq cedex

** BSN, C.I.R.D.C. - 92253 Le Plessis Robinson
1. INTRODUCTION
Among processes of food engineering, heat transfer plays a key role.
The use of heat exchangers is of such frequent occurence that they
appeared in every step of industrial transformations and underwent a
constant evolution. Different kinds of equipment, corresponding to
specific use conditions according to concerned fields of using are
available, among which, just to mention the best known ones : tubular
exchangers, shell an tubes exchangers, plate heat exchangers, spiral flow
exchangers, scraped surface exchangers and platular exchangers. Their
function will be to transmit heat flux to one or between two fluids
according to a given thermal specification. The princip les of heat
transmission are conduction, convection, evaporation, condensation and
radiation, whatever the state of the involved fluids (gaz or liquid state)
or changing phase in course of treatment. However, while flow and heat
transmission in exchangers are now well-known phenomena in the simplest
cases, fouling of surfaces remains one of the major problems not yet
completely solved (47).This is especially true in the case of food
liquids containing thermosensitive compounds such as milk, for example.
Thus, in dairy industry, special attention and constant care are focused
on thermal treatments and especially on sterilization processes.
Fouling of heat transfer sur face s is one of the most observed
experimental facts when such a transfer is performed through a wall.
Consequently, reducing of heat fluxes and increasing of pres sure drops are
generally observed. In food industry this implies to set up cleaning
procedures so that the soiled surface recovers its original conditions of
cleanliness and hygiene (41). Therefore, the accurate knowledge of
kinetics involved in fouling and cleaning proces ses is of great interest
to explain and modelize the fouling and cleaning dynamics observed as well
under research laboratory conditions as under industrial conditions. The
ability to predict such dynamics with sufficient accuracy is one of the
essential way to realize process optimization.

In food area processing of milk products represents a large part of
production. The quantities of treated milk or derivative s used in
preparation of milky products are important and are generally heat
processed in plate heat exchangers with temperatures ranging from 70°C
(pasteurization) up to 130°C (cooking of milky dessert) or 140°C (UHT milk
sterilization). Milk appears in thi s process as a particularly fouling
@ProcessEng
product. That is the reason why fouling and cleaning of exchangers have
been widely studied by different research teams.
This paper presents a review of recent progress made from the study and
the understanding of fouling and cleaning of exchangers mechanisms
together with heat exchange surfaces dealing with milk components and
their relation with observed dynamics.
557

558
2. METHODS USED TO STUDY FOULING AND CLEANING AND THEIR DYNAMICS

2.1. Methods used for large-scale (pilot plant or industrial)
experimentation
According to SANDU et al. (41), fouling (cleaning) dynamics define the
increase (decrease) in thickness of the fouled layer on a heat transfer
surface as a function of position and time for a given set of design and
proces s parameters, and finally yields the time dependence of the fouling
resistance and pres sure drop in the heat exchanger subject to fouling. For
this reason the most widely employed methods were, in near all studied
cases of fouling by dairy product, overall methods based, on the one hand,
on the measurement of fouling resistance -deduced from overall heat
transfer coefficient determination- (30, 25, 2, 10) and on the other hand
on the measurement of mean thickness of the deposit-deduced from overall
pres sure drop (25, 17). These methods are an adaptation of classical
methods used in chemical engineering (22, 23). They lead to the foliowing
expressions :
R
f
l/U - l/U o (1 )
1/2 d [1 -(oP /opn (2)

o o
n ~ 1/3 for plates

n ~ 1/5 for tubes
These methods allow to follow the dynamics of the fouling/cleaning

process which is generaily expressed by the equation (11)
dm /dt =
f
ød - ør (3)
In the case of milk the correlations between R , y and m have been
empiricallyestablished by CORRIEU et al. (7) ahd LALANDEfand CORRIEU
(25) during fouling experimentations applied to milk pasteurization in a
plate heat exchanger :
m f>f·A'Yf = ~f·A.kf·Rf
f
(4 )
1030 Kg.m- 3 ; Rf = 0.7 -1
w.m .K
-1
The determination of fouling resistance, suitable to follow the fouling

process, cannot be used for measuring the cleaning since the steady-state
statement for use of heat transfer equations is seldom respected during
cleaning procedure. That is the reason why the pressure drop method has
been widely employed in order to follow simultaneously fouling and
cleaning, especiaily during industrial experimentation (8).
Another method was developed by GALLOT-LAVALLEE et al. (12) especiaily

devoted to the investigation of cleaning dynamics. It consisted in fitting
an optical sensor at the output of a milk pasteurizer which measured
cleaning rate on-line. This sensor required a previous calibration with a
suspension of milk deposits to convert its electrical signal in to a
deposit concentration.
@ProcessEng
2.2. Methods used for laboratory investigations

Often, another purpose for using these methods was the building of
laboratory devices, either to investigate on-line dynamics in relation
559
with the main parameters acting on fouling (nature of fluid, surface

temperature, hydrodynamic of flow), or to study interactions between
surfaces and heated milk products. In the first case, the fouling
characteristic determined is always the fouling resistance because such
experimental device is general ly of so small a size that pressure drop is
not sufficiently accurate to be used. This fouling resistance was
general ly obtained from electrically heated systems (4, 52) by the well-
known equation (23)
R
f
= T
wf
-T
wo
/q (5)
In the second case, on-line measurements of dynamics were not the major
aim of studies. The main purpose was to design devices able to provide
samples of a fouled surface obtained in temperature gradient conditions
which would permit to analyse the composition of deposit layers and the
nature of their interaction with the sur face (39, 49).
Nevertheless, evolution of deposit amounts versus time can be estimated
by these devices by weighing the amount of deposit collected onto samples
at various steps of the procedure.
In the same way, cleaning dynamics were studied by JENNINGS (20). The
methodology was based on cleaning small stainless steel samples removed
and replaced eve ry now and then into a pipe submitted to a known-flow of
detergent. The determination of the soil removal was done by a radioactive
counting (milk being previously labelled to 32 p . Nevertheless, this kind
of method poses a major problem to establish a dynamic as it necessitates
frequent interruptions of the cleaning process.
3. EXPERIMENTAL FOULING DYNAMICS

While milk is always heat pretreated whatever its transformation
process, other products, derivating from milk are also of industrial
interest (cream,whey ultrafiltration permeate and retentate, milky
desserts ... ). That is the reason why the behaviour of such products as to
their ablity to foul heat exchange surfaces has now been more and more
studied as well as milk behaviour itself.
3.1. Case of milk
Af ter the previous works of BELL and SANDERS (1), LYSTER (31) and
BURTON (5), the first study of milk fouling dynamic using fouling
measurement methods at a pilot plant scale has been investigated by LUND
and BIXBY (30). Then other researchers (24, 25, lO, 16, 15, 27, 40) have
also studied the dynamic of fouling by milk.
If we compare the results to those obtained in the chemical engineering
field (11) the first thing to be original is the fact that this dynamic
when temperature ranges from 65° to 115°C and with constant heat flux
conditions follows an increasing rate regime and not a linear or

asymptotic one. This particular behaviour has been interpreted by LALANDE
and CORRIEU (25) as a chemical reaction fouling with an autocatalytic rate.
The determination of a general law able to render this behaviour posed
first some difficulties to LUND and BIXBY (30) who fitted several possibie
equations to their experimental results and final ly chose to express the
dynamic as
@ProcessEng
R
f
= R
fo
e
~t
(6)
Further LALANDE and CORRIEU (25) then ROIGNANT et al. (40) agreed to
establish, on the basis of long run time experiments (up to 6 hours), that
560
the growth of milk deposits was close from time to the power 2 (between 1.
85 and 2.05)
m
f
ae (7)
This implies, in terms of heterogeneous reaction, that the deposition
flux is governed by an autocatalytic reaction with a 0.5 order
ep = b m 1/2 (8 )
d f
Concerning the main parameters which influence tids deposi tion flux,
all the authors previously mentioned have established the key role played
by the bulk temperature at which milk is heated and the temperature
gradient. No influence of any removal shear stress has been clearly
evidenced. On the contrary the milk itself has always been considered as
acting strongly on the fouling level in given temperature and flow rate
conditions. Among the different characteristics of milk which could
influence fouling, pH, bacterial count and some seasonal variations have
been widely cited. On this basis, LALANDE and CORRIEU (25), taking into
account experimental results obtained over more than one year during milk
pasteurization, established the foliowing model for the rate constant b :
b = a
1
C
NH3
+ a
2
exp (a
3
IT s ) (9)
where C is
the ammoniac concentration in milk before processing -
traduci~~ the action of bacteria- and T the temperature at the deposit
surface. T was computed from heat exchange data set (bulk temperatures,
flow rates S and temperature gradients). This "T " approach summarizes in
fact the influence of the temperature difference (oT) for given
hydrodynamic conditions.
In the temperature range from 120°C to 140°C (case of U.H.T.
sterilization) dynamic of fouling seems more complex since a linear as
well as a falling or a slightly increasing rate behaviour has been
observed (15, 27). But these experiments have been made at semi-industrial
scale and the stability of fouling conditions was not evident.
3.2. Case of milk derivatives

The most important investigated fluids directly related to milk were
whey (10, 16, 9, 17) whipping cream (35, 18) chocolate flavoured desserts
(38). With the aim of understanding the mechanisms of fouling by milk
components some other special fluids were prepared from whey or cream :
whey + citrate, desalted whey, UF permeate (decalcified or not), phosphate
+ calcium solutions (10, 17, 9) UF retentate x 2 (40) whipping cream with
a modified casein/whey protein ratio (35). The different results obtained

from these experiments related to mechanisms will be discussed in the
foliowing part 4. But, aiready, we can conclude from these works that, as
soon as proteins (and especiaily whey proteins) are presents in the fluids,
dynamics follow an increasing shape (as for milk) while, when solutions
are purely mineral, dynamic is linear.
This indicates that the autocatalytic rate regime previously mentioned
@ProcessEng
is mainly related to protein behaviour.
4. FOULING KINETICS AND MECHANISMS OF FOULING BY MILK COMPONENTS

Milk is a complex food product, concerning as well its composition as
its physicochemistry (50). On a chemical point of view, milk contains
561
several hundreds of components. It would be unrealistic to hope that it is

possibIe to build fouling models taking into account all components
present in milk even if their properties and interactions when heated
would be known. Nevertheless, a valuable approach consists first in
considering milk composition refering to its main components. GeneraIly to
obtain a reproducible raw material to be processed, industrial people try
to standardize milk composition (fat, protein, dry matter). It is a well-
known fact that milk composition varies according to the collect area and
seasons (5).
To summarize, we will say that milk is composed of two phases, one
containing soluble compounds (whey proteins, carbohydrates, salts), the
other being a particulate phase which contains molecular associations
appearing as soluble (fat globules and casein micelles). Factors as pH,
ionic strength, dissolved gazes, contribute more or les s to change the
ability of milk to give deposits onto surfaces when heated (5, 25, 21, 46,
44, 34). Table 1 represents milk composition in its main components (33).
4.1. Study of structure and composition of deposits

An important analyticaI work on structure and composition of deposited
material (5, 31, 27) preceded first the understanding of fouling
mechanisms by milk.
The main result of these studies demonstrates that the deposit
composition is not homotetical to milk composition (Table 1). It does not
contain any carbohydrates, it has low-fat content, its protein phase is
mainly composed of soluble proteins and its mineral phase is represented
by calcium salt precipitates (essentiaIly phosphates). The authors agree
to say that heat exchanger sections containing the most worrying deposit
deal with temperatures ranging around 100°C. In thi s case, the deposit is
composed of 50 to 60 % of protein, 30 to 35 % of minerals and 15 to 20 %
of fat. This deposit looks like a spongy deposit, with low density which
causes the major disadvantage of the exchanger functioning that is to say
an increasing of pres sure drops. In sections where temperatures range from
130°C to 140°C (sterilization) the deposit looks completely different as
well as its composition. The deposited layer has a high density and
corresponds to the well-known "milkstone". Its composition shows up to 75
%of minerals. The use of modern techniques as Scanning (or Transmission)
Electron Microscopy as well as histochemical techniques, biochemical
analyses (e1ectrophoresis, High Pres sure Liquid Chromatography) and
spectroscopy methods (Infra Red and Xray Photoelectron Spectroscopy)
permitted recently (48,28, 49, 9) to improve the knowledge of fouling
mechanisms by milk components.
4.2. Kinetics and mechanisms

It is a well-known fact that mineral fouling in the case of milk is due

to an inverse solubility of calcium phosphate (5, 27). The equilibrium of
Ca/P in liquid phase is a complex system (3). From the composition of the
analysed deposit, calcium phosphate in deposit appears to be calcium
phosphate dihydrates (CaHPO ,2H O) and octocalcium phosphates (Ca H (POA)6'
5H O) with eventually hYd~oxy~patite onto surface (Ca (P0 4 ) OH)8 ~hich is
th~ least soluble form (41). Protein fouling is mJinly due to protein
@ProcessEng
aggregation resulting from disulphide interchange reaction (-SH/S-S). This

has been evidenced by studies concerning the milk protein denaturation and
its possibIe relation with fouling as well in the case of milk as in the
case of whipping cream (28, 18, 35).
Among proteins being highly heat-sensitive (immoglobulins, BSA, ~-
562
lactoglobulin and a-lactalbumine), ~-lactoglobulin seems to be main ly

involved in deposit formation (28. since its amount in milk deposit
represents 50 % of protein phase. Globulins represent 23 % and caseins 18
% (48).
TABLE 1 Comparison between whole milk composition and deposit
composition collected from fouling obtained during milk pasteurization in
a plate heat exchanger.
Deposit composition
Composition Milk composition LALANDE et al.
(1984, 1985)
(g/100 g of dry matter) (LYSTER, 1979)
heating holding
section section
Lactose 37.6
Fat 30.4 15.8 25.2
Protein 26.4 53.8 58.8
Casein 20.8 16.1 4.3

Whey protein
R>-lg 2.5 24.2 22.4
a-la 1.3 3.5 2.3
IgG+BSA 0.8 9.9 8.4
Minerals 5.6 26.8 10.0
Calcium Phosphate 3.4 21.4 8.0
R>-lactoglobulin (R>-lg) represents the most abundant part of the total

serum protein, but the particularity which is most interesting concerns
its behaviour when the temperature increases. According to LYSTER (33),
below 40°C ~-lg is a dimer of two identical subunits, each of which has a
molecular weight of 18 300 and contains disulphide bridges and one free
sulphydryl (-SH) group, normaily unreactive. But when raising the
temperature the dimers dissociate and between 60°C and 70°C a large
conformation change occurs which is accompanied by the unmasking of the -
SH group. This change is of great importance in milk since it allows the

unmasked -SH groups to react with disulphide bonds on other protein
molecules. These disulphide interchange reactions involve R>-lg itself (51)
but mayaiso concern other milk proteins containing disulphide bonds.
Since above 70°C, the denaturation becomes irreversible, it is suggested
that, as aresult of these chain-reactions, polymers of high molecular
weight might be formed, including the denatured forms of the different
@ProcessEng
molecules containing disulphide bonds (33). For example, in heated milk, -

SH groups supplied by ~-lg react with disulphide bonds of a-lactalbumin
and the product of the reaction is a mixed disulphide of the denatured
forms of the two proteins (33).It is also known that the -SH group of R>-lg
can react with the disulphide bonds of K-casein when the two pure proteins
563
are heated together on their own (53). This aggregation reaction also
appears with protein of fat globule membrane (50). Whether quite the same
reactions occur in heated milk, although suggested by LYSTER (33) is not
entirely clear but at leas t we can suppose that this possibIe interaction
would exist. Although immunoglobulins contain disulphide bonds, nothing is
known about their possibIe interaction with -SH group of ~-lg. The three
major types (IgG, IgA and IgM) are heterogeneous with respect to their
heat stability (33). Nevertheless, they are rather less stable than ~-lg
and partly denatured by pasteurization. Thus, no other component of milk
is modified by heat as dramatically as are the serum proteins.
In milk and whey (32, 19, 29) or pure solution (36) the kinetics of the
irreversible denaturation of ~-lg follow second order rate equations and
show a rather sharp change in activation energy at about 90°C (32, 19) ) ;
below this temperature the activation energy is about 300 KJ/mole, on an
average,for milk and whey (32, 29) and about 500 KJ/mole for pure solution
(36) , but above it, it is about 40 KJ/mole (32, 19).From this, it is
clear that irreversible denaturation of ~-lg in milk, that is to say in
presence of other proteins containing disulphide bonds, is a complex
reaction and almost certainly consists in at least two consecutive
reactions with different temperature dependencies.Measurements of ~-lg
denaturation rate in presence of p-chloromercuribenzoate (32), a specific
reagent for -SH groups, show that the apparent rate of denaturation is
slowed down dramatically in presence of p-chloromercuribenzoate,
suggesting that disulphide interchange catalyzed by -SH is the rate-
determining reaction below 90°C. Above 90°C the rate determining reaction
is the denaturation reaction
denaturation
heat
~-lg -----) ~-lg* (activated SH)
b
1
aggregat ion
~-lg* + ~-lg (or a-la, or K-casein or fat globule) ------) aggregates

b
2
b ) b for T < 90°C

bl < b 2 for T ) 90°C
1 2
The relation this mechanism might have with the fouling process on a
heated surfaee has been put forward by SKUDDER et al. (45). During UHT
treatment of milk in a pilot-scale plate heat exchanger, the authors
showed that a decreasing of the concentration of free -SH groups in milk

reduces markedly the amount of protein deposited on the heated surface.
The reduction in the levelof free -SH groups was ob tai ned by adding to
milk K-iodate which was supposed to aet by a rapid oxydation of the -SH
group as soon as they become free under the influence of heat.
Although no reaction scheme, involving the right protein components and
particularly their interactions with minerals and fat, has been
@ProcessEng
established through all these observations, it seems, nevertheless,

obvious that thermal denaturation of ~-lactoglobulin plays a key role in
the fouling process, at least during the growth of the fouled layer af ter
it has been initiated.
564
Thus, the fouling mechanisms could be described as an heterogenous

reaction of aggregation (~-lg, a-la, caseins, fat globules) onto the
surface. The calcium phosphate is necessary to the growth of deposit by
creating "carboxylate" bounds (9) between protein aggregates and
precipitated minerals. Nevertheless, the rate of reaction is fixed by
protein aggregation which is directly related to SH groups concentration
(maximum at 90°C). The autocatalytic behaviour could be explain by an
increasing of the reactive surface when the deposit is growing up since
the structure of deposit is spongy. This mechanisms can be extended to
whey when it contains protein especiaIly ~-lg. As soon as protein are
removed from solutions the fouling dynamic follows a linear relationship
in agreement with the classical behaviour of inverse solubility of salts
(11) .
5. CLEANING MECHANISMS AND KINETICS

5.1. Introduction
The mechanisms involved in cleaning proces s and the resulting kinetics
are essential aspects of the topic. Only the understanding of these
questions may lead to an improvement of the theoreticai bases, to a non-
empirical design of cleaning units and to a modelization and optimization
of industrial cleaning operations.
However, there is a very large difference between the scarcity of our
theoreticai knowledge and the industrial practice : cleaning proces ses are
applied every day in food processing plants. Owing to their experience and
to empirical approaches, the food engineers have found efficient solutions
to problems which have not been solved yet theoretically. Analysis of the
scientific literature confirms this impression. Thus, most of the
empiri cal studies describe the applications of various cleaning methods
(choice of cleaning agents, working conditions, etc ... ). They do not
contribute to improve the fundamental knowledge. Some theoreticaI studies
on the absorption, the detergency and the physical and chemical phenomena
involved, may improve our understanding of the processes although they
have been conducted in another field than that of the food industry.
However, only studies including the fundamental aspects of cleaning and
their practical applications may lead to the understanding of the
mechanisms involved and the modelization of the phenomena. Consequently,
the research results reported here have been obtained by a restricted
number of research teams. Let us however mention that the last few years,
this theme has gained in interest.
5.2. Cleaning mechanisms and kinetics

Let us first emphasize the importance of the energy phenomema involved
in soiling and cleaning processes. JENNINGS (20) analysing studies made on
cleaning of textiles was the first specialist in the food and agricultural
industry to understand this aspect of the problem. He concluded that the
cleanliness of a surface is a non natural state and that soiling is a
spontaneous phenomenon corresponding to a decrease in the free energy of
the system. Cleaning, therefore, requires an energy supply large enough to
cut the substrate soil bond.
The balance between the forces of attraction and repulsion established
between the different soil particles, highly influenced by the distance
@ProcessEng
between these particles, and the surface phenomena involved in the soil-
surface interface are main factors for the formation or not of a solid
soil.
This energy approach concerns not only the beginning of the soiling
565
process and the end of the cleaning process (surface-soil interface) but
also the accumulation or progressive elimination of the soil (liquid-soil
interface). Although the aggregat ion bonds between soil molecules may be
weaker than those of the adhesion to the surface, they are control led by
similar energy phenomena.
On the basis of these analyses and observations, HARPER (14) was the
first to explain, in a clear but theoreticai way, a cleaning mechanism
divided into several steps. The main points are the foliowing :
- a step during which the cleaning solution enters into close contact with
the soil to be eliminated.
- a step of wetting and penetration of the soil by the cleaning solution
and reaction of the latter with the soil components.
- a step during which the products of the reaction are dispersed in the
cleaning solution by diffusion, defloculation and emulsification or other
mechanisms.
This mechanism can only be associated to experimentally observable

cleaning kinetics for a given soil, a given cleaning product and a given
shape of the equipement to be cleaned the different chemical and
physical kinetics involved at each step of the process have been
established and their respective importance defined.
The hydrodynamics of the experimental devices used to study cleaning,
either at the laboratory or at the pilot unit scale, and the transfer of
matter in connexion with this, are rather well known, whereas this is not
the case for the phenomena of wetting, penetration and reaction between
soil components and cleaning products, especiaily if considering their
potential complexity. This is the reason why this whole mechanism has
never been evidenced experimentally.
Studies devoted to milk soils have been made by JENNINGS (20),
SCHLUSSLER (43) and GALLOT-LAVALLEE (12, 13). In all these studies, the
soils are heterogeneous and in similar amounts (from 0.05 to 0.4 kg/m 2 )
but there are great differences in the way in which they have been
obtained and in the cleaning conditions.
SCHLUSSLER (43) studied milk, butter-milk and chocolate milk soils
which were dried and deposited on glass samples immerged in to a stirred
vessel containing the cleaning solution. He was limited by his evaluation
method (wettability of the surface), the response of which was only
positive or negative and he therefore determined experimentally the length
of cleaning required to eliminate any soil whose initial amount was known.
He deduced an average cleaning rate which was assumed to be constant. As
the procedure did not supply any cleaning rate according to time, a
kinetic study of the phenomenon could not be made and it was therefore
assimilated to a zero order reaction. He obtained mean cleaning rate

ranging from 0.16 to 1.3 kg.s- 1 .m 2 • This led to cleaning lengths ranging
from 30 to 150 seconds. On the basis of this, he studied the influence of
some parameters acting upon the rate of the cleaning process (temperature,
concentration and nature of the detergents, mechanical action, nature of
the soil, state of the surface).
JENNINGS (20) studied the cleaning of stainless steel disks inserted
@ProcessEng
into cylindric pipes parallel to the direction of the circulating solution.

Using a radioactive counting, he obtained cleaning rates according to time
by multiplying the experiments of variable length. He concluded that the
rate of soil elimination (Ø) was proportional to the soil amount (m )
present on the surface at each moment and to the concentration bf
566
hydroxide ion (COH -) and he deduced the relation 10 with the following
restrictions :
ør = b 3 .mf .COH (10)
- the model can only be applied to the elimination of about 60 %of the
initial soil. The authors considered that at the end of the elimination
process particular bonds with the surface occured more or les s
significantly, impairing the validity of the model;
- the influence of the soda concentration was studied over a very
restricted range (O to 0.6 %).
Accordingly, no generalization can be made and relation (11),

corresponding to a first order reaction relative to the amount of soil
present (mf)' is more currently admitted
ø = bf .m with b' b C (11 )

3 f 3 3 OH
This expression assumes that the rate of soil elimination is

proportional to the amount of soil present and decreases with time of
cleaning. This is only possible if the penetration of the cleaning
solution in to the soil is instantaneous. The parameters acting upon the
cleaning process were studied. The temperature, soda concentration and
mechanical effect influence the value of the cleaning rate constant, bf ,
located between 0.01 and 0.2 S-l in the experimental conditions of t~e
author.
GALLOT-LAVALLEE (13) and LALANDE et al. (27) studied the cleaning with
soda of milk deposit (small fouled tubes of 20 cm length and 1 inch
diameter). They adopted a cleaning procedure in an open ring using an
optic sensor placed at the outlet of the soiled system and allowing to
follow cleaning according to real time. They showed that the cleaning rate,
meas ure d in terms of appearance of soil in the cleaning solution, was
initially null. This observation supports the theoretical mechanism
suggested by HARPER (14) and provides the possibility of suggesting that
the penetration of the cleaning solution into the soil is not
instantaneous. According to this, the au thors suggested a reactional model
including two serial steps in which the soil goes through an intermediate
state before being eliminated with the cleaning solution. First step which
characterizes reaction between soil and detergent was of zero order and
second step which characterizes removal by diffusion of modified soil
(intermediate) was of first order. On the basis of these hypotheses, the
kinetic is governed by the relations 12 and 13 :
b (l-exp(b t)) for t < mfro Ib 5 (12)

5 6
b (exp(b (m Ib)) -1) exp( -b t) for t > mfIo Ib 5 (13)

5 6 fIo 5 5
Among the many parameters affecting the process, the au thors studied
the temperature, concentration and circulation rate of the soda solution
used. From these three parameters and the initial mass of soil to be
cleaned (m ), they established an empirical mathematical modelof the
@ProcessEng
two rate cb~stants.

More recently PERLAT (37) studying the cleaning of a plate heat
exchanger of semi-industrial size proposed for equation 13 to replace the
diffusion mechanism of the second step by aspalling mechanism adapted
567
from KERN and SEATON (22) and CLEAVER and YATES (6)
ø = b
7
T.m
fz
(14)
This model cannot be analytically integrated to give an analyticai

expression of equation 14, as for equation 12 and 13. Nevertheless, it can
be numerically integrated. This has been done by PERLAT (37) by taking
into account the mass repartition of milk deposit onto the surface of a
milk pasteurizer. The simulation of the cleaning dynamics of the
pasteurizer by this model in different cleaning conditions fit remarkably
to experimental results collected with the optical sensor used by GALLOT-
LAVALLEE et al. (12). Thus, this model is of great interest to predict the
overall cleaning rate of industrial pasteurizers.
TABLE 2 : Main models established for cleaning of milk deposit.
Reaction order Model Authors
zero
I --> F ør bo SCHLUSSLER (43)
first
1--> F ø b mf COH
3
JENNINGS (20)
Two first sequential GALLOT-LAVALLEE et al.

I --> Z --> F (13)
One zero, one first - for t < mfIo Ib 5

sequential
I --> Z --> F LALANDE et al. (27)
- for t> m
fIo
Ib 5
ø b (e b6 mfIo_ 1 ) e -b5 t
5
Differential model ørI b" C

3
no specific order PERLAT (37)
OH
sequential ørF b
7
T m
fz
1--> Z --> F
ørZ ørF - ørI
@ProcessEng
5.3. Parameters affecting the cleaning kinetics

Many studies show that a great number of parameters affect the kinetics
of cleaning. Among the parameters studied, the detergent concentration,
the cleaning temperature and the chemical action play a main and
568
complementary role as they represent the three principal forms of energy

required to remove soil. Opposite to that, the cleaning time should not be
considered as an independent variable as it depends directly on all the
other variables characterizing the cleaning process.
5.3.1. Effect of the nature and concentration of cleaning solutions
It is generaIly admitted that all detergents are not equally effective
for all soils. Consequently, the composition of the cleaning compounds
will be determined according to the nature and type of soil. according to
some well defined rules. We will not insist more on this aspect of the
problem and especiaIly because detergent manufacturers are exeeIling in
the establishment of formulas.
The conclusion of JENNINGS (20) determining a direct proportional it y
between soil removal rate in its first stage and soda concentration, can
only be accepted when thi s concentration is lower than 0.6 %. Before that,
several authors had shown that the cleaning rate increased with the
detergent concentration until a limit concentration beyond which it
remained constant or decreased. SCHLUSSLER (43) confirmed this rule
pointing out that the mean cleaning rate of mildly alkaline detergents
increases generaIly with concentration more slowly and for a longer time
than that of strongly alkaline detergents, but never reaches such high
values (2 to 2.5 mg/s versus 3.5 to 4 mg/s). Thus, the optimum
concentrations of strongly alkaline detergents range around 1 %whereas
they may exceed 3 % in the case of midI y alkaline detergents.
GALLOT-LAVALLEE (13) also confirmed the beneficial effect of an
increase in the soda concentration upon the cleaning of whole raw milk
soils. LALANDE et al. (27) as SCHLUSSLER (43) noticed a decrease in the
cleaning rate above a given threshold.
5.3.2. Effect of the temperature
JENNINGS (20) and GALLOT-LAVALLEE (13) during assays on milk soils made
between 36 and 82°C and between 55 and 95°C respectively observed that the
logarithm of the cleaning rate constant varied linearly as a function of
the reciprocal of the absolute temperature. This corresponds to expressing
the temperature effect by ARRHENIUS's law (relation 15) :
log b = (E/T) + Cte (15)
SCHLUSSLER (43) obtained a similar result by considering the mean

cleaning rate (Ø table II). In addition, he showed that the constants
indicating the effect of temperature varied according to the nature of the
deposit. Thus, the mean removal rate of buttermilk is very sensitive to an
elevation of the temperature whereas that of the milk is much less
affected. Curiously the latter reaches its maximum at 65°C while the
maximum mean cleaning rate of other produets tested (buttermilk,
evaporated milk, cocoa) is reached around temperature of 85 to 90°C.

SCHLUSSLER (43) deduced two mathematical models from his results
indicating the mean cleaning rate Ø (relation 16) and the time t required
for cleaning (relation 17) according to the detergent concentration (c)
and the absolute cleaning temperature (T) :
Ø = b eac+~/T (16)
@ProcessEng
r 8
t = b /eac+~/T (17)
9
b , b, a and ~ are constants depending on the nature of the detergent and

o~ tt'le soil.
569
SCHLUSSLER (43) concluded that the effect of increasing temperature is

alway favourable, but in proportions varying with the cleaning compound
and the type of soil. In the case of homogeneous reactions, the cleaning
rate constant may be multiplied by a factor ranging between two and four
when the temperature increases by 10°C, but the multiplying factor is much
lower in the case of heterogeneous reactions (for milk, JENNINGS (20)
observed a factor of 1.6 and GALLOT-LAVALLEE (12) a factor of 1.7). This
result seems to indicate that in this case the physico-chemical mechanisms
are the limitting step reactions since the corresponding activation energy
is about 50 kJ/mole.
Thus, like the observation made about the detergent concentration, no
model seems to be fitted in all cases to describe the effect of the
temperature on the cleaning rate. It is undeniable that the combination
"detergent concentration-cleaning temperature" presents an optimum
situation but in the state of present knowledge the latter cannot be
accurately predetermined theoretically and must be determined
experimentally.
5.3.3. Role of the mechanical action
Many authors studying the influence of flow rate, velocity or
turbulence on the cleaning rate have shown the favourable role of the
mechanical effect. However, JENNINGS (20) and SCHLUSSLER (43) agre ed on
the existence of a mlnlmum threshold beyond which it is negligible. For
instance, in a pipeline, JENNINGS (20) characterized this threshold by a
REYNOLDS number equal to 25.000.
The diffusion model may explain theroetically the effect observed since
the velocity increase reduces the thickness of the interface (6). However,
SCHLUSSLER (43) admits that this phenomenon may be masked by a
simultaneous increase in the shear stress exerted by the cleaning solution
on soil. Although these two hypotheses show the same trends, the second
one seems to correspond better to the reality of the mechanical action
which is best expressed by the shear stress. This shear stress,
proportional to the pressure drop cannot be highly increased without
supplementary energy expenditure.
PERLAT (37) established recently a cleaning modelof a deposit
collected from milk pasteurization. This model included as second step of
the reactional scheme aspalling mechanism which included a shear stress
effect (equation 14). The b coefficient appeared af ter identification to
be independant of all parafueters except for temperature. This result
demonstrates that aspalling mechanism can render correctly a mechanical
effect for cleaning of milk deposit af ter the detergent has reacted with
the soil. The temperature dependance of b (which could represent the
cohesion strength of the deposit) was express~d by an activation energy of
20 KJ/mole.
ACKNOWLEDGEMENTS
The authors thank Miss S. GOUDEBRANCHE from CERTIA for her translation
assistance.
@ProcessEng
570
LIST OF SYMBOLS
Activation energy - E
Area (surface area) - A
Concentration - c
(Surface) concentration - c
(Bulk) concentration - c
Coefficient : b
- convective heat transfer - h
- overall heat transfer - U
- overall heat transfer, under clean conditions - U
Diameter - d o
Particle diameter - d
Molecular (Brownian) &iffusivity - D
Turbulent diffusivity - E B
Density - e
Density of fouling layer - ef
Deposition flux - ø
Distance in the lon~itudinal direction - y
Distance in the transversal direction - x
Friction factor - f
Heat transfer rate - Q
Heat flux - q
Heat of reaction - OH
Length - L T
Mass flow rate - W
Mass of deposit - mf
Pressure - P
Radius, Radial distance - r
Removal flux - ø
Specific heat atrconstant pres sure - c
p
Shear stress - T
Sur face tension - a
Temperature - T
Time - t
Thermal conductivity - k
Thermal conductivity of the wall - k
Thermal conductivity of the fouling layer - k
f
Thermal resistance of the wall - R
Thermal resistance of the fouling layer - R
f
Thickness of the fouling layer - Yf
Dynamic viscosity - p
Average fluid velocity - v
Local fluid velocity - v

Friction velocity - v*
Volume - V
SUBSCRIPTS :
f - fouled conditions
o - clean conditions
w - wall
@ProcessEng
s - surface
p - particle
SUPERCRIPTS :
• + dimensionless variable
571
REFERENCES :
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temperature-short-time heater by preheating milk and whey. J. of Dairy
Science, 27, 499-504, 1944.
2. Bouman S, Lund, DB, Driessen FM, Schmidt DG Growth of
thermoresistant Streptococci and deposition of milk constituants on
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806-812, 1982.
3. Brule G : Les mineraux du lait. Rev. Lait. Fr., 400, 61-65, 1981.
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the deposit of milk solids on a heated surface. Journal of Dairy
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8. Corrieu G, Lalande M, Ferret R : Mesure en ligne de l'encrassement et
du nettoyage d'un sterilisateur U.H.T. industriel. Journal of Food
Engineering, 5, 231-248, 1986.
9. Daufin G, Labbe JP, Quemarais A, Brule G, Michel F, Roignant M, Priol
M: Fouling of a heat exchange surface by whey, milk and model fluids.
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liquids. Neth. Milk Dairy J., 37, 139-148, 1983.
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Equipement, Mc GRAW HILL, New-York, 701-734, 1979.
12. Gallot-lavallee T, Lalande M, Corrieu G: An optical method to study
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13. Gallot-Lavallee T, Lalande M, Corrieu G : Cleaning kinetics modelling
of holding tubes fouled during milk pasteurization. J. Food Process
Eng. 7,123-142, 1984.
14. Harper WJ : Sanitation in dairy food plants. Food Sanitation, GUTHRIE
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15. Hawran LJ, Jones VA, Swartzel KR : Fouling during U.H.T. processing
and subsequent sedimentation during storage of milk. Summer Meeting of
the American Institute of Chemical Engineers, August 19-22,
Philadelphia, P.A.,1984.
16. Hege WU Uber die Bildung von Ablagerungen beim Erhitzen von Milch
und Molke. University of Technology Munich, Thesis, 1984.
17. Hiddink J Fouling of a plate heat exchanger by sweet whey and its
ultrafiltration permeate. Second International Conference on fouling
and cleaning in Food Processing, Madison, U.S.A., 14-17 July, 1985.
18. Hiddink J, Lalande M, Maas AJR, Streuper A Heat treatment of
whipping cream. 1. Fouling of the pasteurization equipment.
@ProcessEng
Milchwissenschaft, 41, 9, 542-546, 1986.

19. Hillier RM, Lyster RLJ : Whey protein denaturation in heated milk and
cheese whey. Journal of Dairy Research, 46, 95-102, 1979.
20. Jennings WG Theory and practice of hard surfaee cleaning. Advanced
Food Research, 14, 325-458, 1965
572
21. Joshi RM, Patel AA Heat-induced deposit formation and its

relationship to heat stability in a blend of recombined and fresh milk.
Journal of Dairy Research, 53, 323-328, 1986.
22. Kern DQ, Seaton RE : A theoreticai analysis of thermal surface fouling.
Brit. Chem. Eng., 4, 258-262, 1959.
23. Knudesn JG Apparatus and techniques for measurement of fouling of
heat transfer surfaces. Fouling of heat transfer Equipment, Mc GRAW
HILL, New York, 57-81, 1979.
24. Lalande M, Corrieu G : Investigations of fouling during heat treatment
of milk in a plate heat exchanger. Food Process Engineering, Applied
Science Publishers, London, 1, 419-423, 1980.
25. Lalande M, Corrieu G Fouling of a plate heat exchanger by milk.
Fundamentals and Applications of Surface Phenomena Associated with
Fouling and Cleaning in Food Processing. HALLSTROM, LUND, TRAGARDH
editors, Lund University, Sweden, 279-288, 1981.
26. Lalande M, Tissier JP, Corrieu G : Fouling of a plate heat exchanger
used in ultra high temperature sterilization of milk. Journal af Dairy
Research, 51, 123-142, 1984.
27. Lalande M, Gallot-Lavallee T, Corrieu G : Chemical reactions and mass
transfer associated with cleaning of heat exchange surfaces fouled by
milk deposits. Engineering and Food, Vol. 1, Ed. B. McKenna, Elsevier
Applied Science Publishers Ltd, London, pp. 59-68, 1984.
28. Lalande M, Tissier JP, Corrieu G : Fouling of heat transfer surfaces
related to ~-lactoglobulin denaturation during heat processing of milk.
Biotechnology Progress, 1, 2, 131-139, 1985.
29. Levieux D Heat denaturation of whey proteins. Comparative studies
with physical and immunologi cal methods. Annales des Recherches
Veterinaires, 11, 89-97, 1980.
30. Lund DB, Bixby D : Fouling of heat exchange surfaces by milk. Process
Biochemistry, 11, 52-55, 1975.
31. Lyster RLJ : The composition of milk deposits in a UHT plant. Journal
of Dairy Research, 32, 203-208, 1965.
32. Lyster RLJ The denaturation of a-Iactoglobulin and ~-lactoglobulin
in heated milk. Journal of Dairy Research, 37, 223-243, 1970.
33. Lyster RLJ : Milk and dairy products. In : Effects of heating on food-
stuffs, 353-368. Applied Science Publishers, London, 1979.
34. Marshall RJ Effects of iodate, hydrogen peroxyde and dichromate on
the denaturation of whey proteins in heated milk. Journal of Dairy
Research, 53, 89-95, 1986.
35. Mass AJR, Lalande M, Hiddink J : Fouling of a plate heat exchanger by
whipping cream. Fouling and Cleaning in Food Processing, LUND,PLETT,
SANDU editors, University of Madison, Wisconsin, U.S.A. 217-225, 1985.
36. Park KH, Lund DB Differential scanning calorimetric method for

obtaining kinetic data on protein denaturation. Presented at the
Midwest Food Processing Conference. Sept. 27-28, Minneapolis, MN, USA,
1982.
37. Perlat MN Etude du nettoyage des echangeurs å plaques destines å la
pasteurisation et å la sterilisation å ultra haute temperature du lait.
These de Docteur-Ingenieur, UST 1, Lille, France, 1986.
38. Rene F, Leuliet JC, Goldberg M, Lalande M Encrassement d'un
@ProcessEng
echangeur de chaleur å plaques lors du traitement U.H.T. d'un produit

lacte chocolate. Comparaison avec le lait. A paraitre dans Le Lait,
1987.
39. Roignant M, Daufin G, Michel F : Dispositif experimental pour etudier
l'encrassement des echangeurs de chaleur alimentaires. Lait, 63, 363-
573
390, 1983.
40. Roignant M, Daufin G, Michel F, Kerherve FL, Brule G : Traitement
thermique de retentat (x2) d'ultrafiltration de lait dans un echangeur
a plaques aspects thermiques, hydrodynamiques et encrassement par
comparaison au lait et au lactoserum. Le Lait, 66, 3, 207-232, 1986.
41. Sandu C, Lund D Fouling of heating surfaces. Chemical reaction
fouling due to milk. Fouling and Cleaning in Food Processing, LUND,
PLETT, SANDU editors, University of Madison, Wisconsin, U.S.A., 122-
167, 1985.
42. Sandu C, Lund D, Plett EA : Fouling and cleaning of heat exchangers -a
definition of terms. Fouling and Cleaning in Food Processing, LUND ,
PLETT,SANDU editors, University of Madison, Wisconsin, U.S.A., 3-21,
1985.-SAWYER W.H. Complex between ~-lactoglobulin and K-casein. A
review. Journal of Dairy Science, 52, 9, 1347-1355, 1969.
43. Schlussler HJ Zur reinigung fester oberflachen in der lebensmittel
industrie. Milchwissenschaft, 25, 3, 133-149, 1970.
44. Singh H, Fox PF Heat stability of milk : further study on the pH
dependent dissociation of micellar K-casein. Journal of Dairy Research,
53, 237-248, 1986.
45. Skudder PJ, Thomas EL, Pavey JA, Perkin AG Effects of adding
potassium iodate to milk before UHT treatment. I-Reduction in the
amount of deposit on the heated surfaces. Journal of Dairy Research,
48, 99-113, 1981.
46. Skudder PJ, Brooker BE, Bonsey AD, Alvarez Guerrero NR : Effect of pH
on the formation of deposit from milk on heated surfaces during ultra
high temperature processing. Journal of Dairy Research, 53, 75-87,
1986.
47. Taborek J, Aoki T, Ritter RB, Palen JW, Knudsen JG : Fouling : the
major unresolved problem in heat transfer. Chem. Eng. Prog., 68, 2,59-
67, 1972.
48. Tissier JP, Lalande M, Corrieu G: A study of milk deposit on heat
exchange surface during U.H.T. treatment. Engineering and Food, Mc
KENNA, Elsevier Applied Science Publishers, New-York, U.S.A., 1, 49-58,
1984.
49. Tissier JP, Lalande M: Experimental device and methods for studying
milk deposit formation on heat exchange surfaces. Biotechnology
Progress, 2, 4, 218-229 1986.
50. Walstra P, Jeness R : Dairy chemistry and physics. John WILLEY & Sons,
New York, U.S.A., 1984.
51. Watanabe K, H Klostermeyer : Heat induced changes in sulphydryl and
disulphide levels of -lactoalbumin A and the formation of polymers.
Journal of Dairy Research, 43, 411-418, 1976.
52. Ling AC, Lund DB : Apparatus for studying fouling of heated sur face s
by biological fluids. J. Food Sc., 43, 390-403, 1965.

53. Sawyer WH: Complex between ~-lactoglobulin and k-casein. A review. J.
of Dairy Research, 52, 9, 1347-1355, 1969.
@ProcessEng
ON-LINE MEASUREMENT OF FOULING AND CLEANING OF INDUSTRIAL U.H.T. EXCHANGERS
G. CORRIEUl, M. LALANDE2, F. FERRET2

1. INRA-L.G.P.B.A.A. - 78850 THIVERVAL GRIGNON
2. INRA-L.G.I.A. - 59651 VILLENEUVE D'ASCQ CEDEX
1. INTRODUCTION
Fouling has long been regarded as a major outstanding problem in the

field of heat exchangers <Taborek et al., 1972a, b) and especially in
food processing industries. This is due firstly to the thermosensitivity
of numerous constituents of food products (proteins, inorganic salts,
vitamins, etc.), and secondly because the thermic stabilization necessary
to ensure the upkeeping of their quality may be performed in very
different ways. In this regard the dairy industry can be taken as a good
example. Indeed, milk, cream, som e sweets desserts prove to act as severe
fouling vectors when undergoing pasteurization sterilization and
eventually concentration. In order to ensure the satisfactory hygienic
quality of the installations and subsequently of the products processed,
costly and time consuming cleaning procesures have to be set up.
Studies carried out on the evaluation and understanding of fouling and

cleaning phenomena first made significant progresses towards the years
1965-1970 (Jennings, 1965 Lyster, 1965 ; Burton, 1968 ; Schlussler et
al., 1970). In the recent years,further to a long stagnation period and
thanks to the improvements in existing investigation means, considerable
and decisive progress was achieved (Gallot-Lavallee et al., 1984 ; Hege
1984 ; Lalande et al., 1984a, b, 1985 ; Nassauer et Kessler, 1985 ; Plett,
1985). Composition and distribution of depositions as well as kinetics
and mechanisms involved were concerned.
The outcome of such advancement for industrial process remain
nevertheless limited as in the end they have a bearing only on the design
of heat exchanger (pasteurizers, sterilizers) and on their operating
principle (difference in product processed and service fluid temperatures,
cleaning method).
Based on earlier experiments carried out on a small pilot scale (Corrieu

et al., 1979; Lalande et Corrieu, 1979), it seemed interesting to design
an on-line fouling sensor for industrial milk sterilisers working at an
Ultra High Temperature (UHT) and according to the indirect heat exchanger
process. To our knowledge, no other similar experiment has ever been
attempted, eventhough some laboratory tests were former ly reported on
(Burton , 1966 Ling et Lund, 1978 ; Fryer et al., 1985 ; Zel ver et al.,
@ProcessEng
1985) .
The aim of this paper is to provide a description of the sensor as well

as areport on results obtained in factory both during the processing
(fouling) and the cleaning phases.
575

576
2. EQUIPMENTS AND METHODS
2.1. Measuring principle of the sterilizer degree of fouling
The evaluation of fouling in an heat exchanger by two different methods

has former ly been described (Corrieu et al., 1979). The first method is
based on the determination of the global heat transfer coefficient in a
given section of the exchanger. A comparison of that with the
corresponding calculated value considering the equipment is clean, gives
the thermic resistance (expressed in m2 .K.W- 1 ) generated by the fouling
and hampering the heat exchange.
The second method takes into account the hydrodynamic functioning of the
heat exchanger. For a given flowrate of milk, a reduction of the
exchanger hydraulic diameter due to fouling, generates an increase of the
pressure drop.
The differential pressure (~Po) of a clean plate exchanger is expressed

as follows :
(1)
f, the friction coefficient is proportional to Reynolds number,

(2 )
In view of the particular geometry of a plate heat exchanger (n "passes"

rectangular channel of which the hydraulic diameter is roughly twice the
space between plates : D = 2d), the relation becomes :
flp o = (8Ln/D03F).k,.Rek2.~.Q2 (3)
The degree of fouling (~) is defined by the folIowing expression (see fig.
1) :
~ = Wo - D)/D o ( 4)
This represents, at a given time, the ratio of the difference in

hydraulic diameter of clean and fouled exchanger to the initial hydraulic
diameter.
Thus ~ O when the exchanger is clean (D Do) and ~ in case of

complete blockage.
Considering ÅP and D are respectively the differential pressure and

hydraulic diameter, then at any given time, ~ ean be expressed as a
function of the differential pressure, using relations (3) and (4) :
~ =1 - (5 )
@ProcessEng
This last relation is the one used to determine, on-line the degree of
fouling. Tt implies the measuring of the effective differential pressure
(tiP) and the calculation of~~ (relation (3», for the concerned section
577
of the heat exchanger. Relation (3) may be written in a simpIer way

(6 )
I deposit
I pl2te
Jont d d
D
FIGURE 1. Schematic drawing of one channe l cross-section of a dirty

plate exchanger.
K depends essentiaIly on the geometry and on the configuration of the

exchanger. This coefficient ought to be clearly identified at the
beginning of the trial runs in order to adjust the initial value of ~ at
zero.
Fluid density (~) at working temperature is general ly known while the
flowrate (Q) measurement is high ly recommendable if not imperious.
2.2. Description of the eguipment

2.2.1. U.H.T. Sterilizer
rmi I k inlet
P2 P3
~P1
,d D
~ ~ -
,
-
80 12] 140 95
5° C
-
-
energy recovery heat in9 area
.a;e~•.•.• : ,- - - - -,I .. . <. . '":

:' ~
122 142'
20° C 95 : I
,
service
,, hot Ib
l .
, . . ..... .. .l,."w?tEir. . ...., .....
fluid
• •• " • •j • • • • •
•• , ••• I
. .. :
('
·· ,(
@ProcessEng
packaging ~
FIGURE 2. UHT sterilizer schematic drawing.
Pl,P2,P3 : 3 pressure sensors ; D flowmeter.
578
The industrial sterilizer used to run tests with the fouling sensor is a
plate heat exchanger marketed by APV (Ultramatic II), schematically
represented in Fig. 2. Depending on production imperatives, full fat or
half-skimmed milk can be processed at a flowrate of 10 m3 /h. First
homogenized at a 200 atm pressure under a temperature of 80°C, the milk
is packaged straighaway af ter sterilization.
The installation is working continuously (24 hours a day) except for a
30h stop at week end. Production is stopped every two to three weeks and
the sterilizer is dismentled to check its cleanliness. Any defective
gasket is then re-stuck or replaced.
Three cleaning procedure are performed over a 24 hours cycle (refer to
Table 1). Two of these taking place towards the 7 th and 15th working
hours last for approximatively 35 mn and correspond to an intermediate
cleaning. The third one is the final cleaning lasting about 2 hours.
Whereas intermediate cleaning is realized in the normal production
conditions, final cleaning does includes a sterilization stage before
production is resumed.
TABLE 1. Specifications of intermediate and final cleaning.
Intermediate cleaning Final cleaning
Initial rinsing : Initial rinsing

water : 140°C - 5 min. water : 70°C - 10 min.
Alkaline rinsing : Acid rinsing :
NaOh (2 %) : 140°C - 10 min. HN0 3 (1.5 %) : 80°C - 5 min.
with recycling without recycling
Intermediate rinsing Intermediate rinsing :
water : 140°C - 5 min. water ; 80°C - 10 min.
Acid rinsing : Alkaline rinsing :
HN0 3 (1.5 %) : 140°C - 10 min. NaOH (2 %) : 80°C - 20 min.
with recycling With recycling
Last rinsing : Intermediate rinsing :
water : 140°C - 5 min. water : 80°C - 10 min.
Resumption of production Acid rinsing
HN0 3 (1.5 %) 80°C - 15 min.
with recycling.
Last rinsing and temperature
raising :
water 20 min.
Sterilization
Water under pression
140°C - 30 min.
Total duration : 35 min. Total duration : 120 min.
@ProcessEng
579
2.2.2.The sensor
The sensor ensuring the on-line determination of the sterilizer fouling
is a complex device consisting of
(a) Three relative pressure transmitters (range O-lO bar, accuracy +

or - 0.5 %) direct ly set on the sterilizer, in respect of hygienic
constraints and in such a way that static pressures are measured.
(b) An electromagnetic flowmeter (range 0-20 m3 /h, accuracy + or - 0.5

%>.
(c) A microprocessor system ensuring the input of measurement data,

their conversion in physical values and subsequently their
processing to finally get the ~ values.
The flowmeter (D) and pressure transmitters (Pl, P2, P3) are instalied as
shown on Fig. 2. The complete assembly diagram is represented on Fig. 3.
The three pressure transmitters allow the determination of the

differential pressure existing in both sections of the sterilizer most
liable to get fouled i.e. the heat recovery zone (where milk is preheated
from 80 to 120°C by means of a service fluid) and the heating zone (where
milk is heated from 120 to 140°C by means of pressurized hot water). The
respective degrees of fouling determined are ~, and ~2.
These are in faet average values of the degrees of fouling. Indeed

deposition is not uniformely distributed on the respective 34.8 and 41.8
m2 exchange surfaces. Although this phenomen has not been studied on the
industrial heat exchanger, it was clearly demonstrated at a pilot scale
(Tissier et al., 1984).
Pl
A. digital display
A D. flowmeter
E. recorder
lo printer
P2
MP A MP. microprocessor
P. pressure sensor
A
P3
@ProcessEng
D E
EIGURE 3. Schematic drawing of complete installation.

580
Fouling of the heat recovery zone consists of a whitish and spongy type
of deposition characterized by a particularly high protein content (50 to
60 % of the dry matter weight). It is maximum in the section where the
milk temperature lies between 105 and 115°C. On the contrary deposition
occuring in the heating zone is dense and yellowish, with an inorganic
matter content averaging 70 % of dry weight and increasing with the
processed milk temperature (Tissier et al., 1984).
3. RESULTS AND DISCUSSION
3.1. Evaluation of fouling during milk processing
A recording of the fouling degree evolution given by the sensor over a

complete production cycle of sterilized milk is shown on Fig. 4.
7
2 6
rn
c 5
~
~
4
~
~ 3
o
L 2
~
c
rn
~
O
0-1 0-2 [~J 0-3 0-4 0-5
FIGURE 4. Example of recording given by the sensor during milk

sterilization.
~, and ~2 : respective degrees of fouling in heat recovery
heating zones.
The degree of fouling in the heat recovery section (~,) first rises
slowly to suddently increase rapidly. Such kinetics of fouling are
similar to those which can be observed and modelized in the case of milk
pasteurization where a protein rich deposition also eccurs (Lalande et
al. , 1985). The final value of ~, record ed and shown on Fig. 4 is 0.43.
Several months of survey show ed that final values of a" reached af ter
more than 7 hours of milk processing, were situated between 0.2 and 0.5.
This last value corresponding approximately to the semi blocking-up of
the exchanger (or at least of som e of the plates), is only rarely
exceeded and can be considered as a reasonable limit at which the
necessity of cleaning becomes imperious.
The degree of fouling in the heating zone (~2) rises more regularly but
@ProcessEng
not linearly however. The final value of a2 is 0.26. Observations over

several months of operation show ed that final values of ~2 reached af ter
7 hours of production ranged from 0.15 to 0.45.
581
As a matter of fact eventhough for the first 4 to 5 hours of processing

~2 is usually higher than ~1' it rarely happens that such a situation
lasts till the cleaning limit. This occurs only in case of a very small
deposition in the heat recovery zone or of a very rapid fouling of the
heating zone. Fig. 5 shows recordings made during three successive
production cycles over a 26h period and clearly illustrates the various
situations that can be encountered.
(a) In the first cycle, ~, is very weak at the beginning and only
grows moderately, even af ter 6 hours of production. On the
contrarY'~2 is important and increases much more suiftly than in
the example of Fig. 4.
(b) The second cycle represents the prevailing type of evolution of
fouling with quite high values of ~, and ~2'
(c) The third cycle appears as a medium evolution in comparison with
the first and second ones and it was only by the merest chance
that final values of ~, and ~2 came 50 close (respectively 0.4 and
0.375) .
Such various occurences clearly show that even over a limited period of
time, the quality of the milk processed plays a major role in the
evolution of fouling in both sections under survey. This result is
confirmed by the fact that the final values of ~, and ~2 obtained may
vary by a factor of 1 to 2.5 and even 3.
Unfortunately, as the reported trial runs were carried out in an

individual setting, the influence of the milk quality could not be
studied.
As can be noted, initial values of ~, and ~2 are never nil and range from
0.03 to 0.09. The reason is that the zero adjustement of the sensor is
realized with water in clean sterilizer whereas the circulation of milk
induces a slightly larger pressure drop due to a significantly higher
viscosity.
To avoid such inconvenience f:. Po ought to be systematically calculated,

taking account of the density and viscosity of fluids processed (water,
milk and cleaning solutions) and entered in the microprocessor software.
This would have implied the development of a much more elaborated one.
The specification conditions, i.e. the realization of a sensor featured
for an industriQl application, led us to neglect such phenomenon.
3.2. Evolution of the sterilizer cleaning.
Two intermediate cleanings, performed according to the procedure

described in Table 1, are carried out between the three cycles shown on
Fig. 5. Their short duration excludes any detailed analysis except for
the observation of the cleaning efficacy confirmed by the decrease of ~,
@ProcessEng
and ~2 values close to zero.

582
25
20
15
.2
w
E
I-
1O I--==-'--~.,-.--- _ _~
cycle 1
o 0-1 0-2 0-3 0-4 0-5

degree or fouling ~
FIGURE 5. Example of recording given by the sensor during three

sucessives production/intermediate cleaning cycles.
Based on recording made at high speed, we succeeded in obtaining cleaning
evolution curves much more easy to interpret. A typical intermediate
cleaning recording is shown on Fig. 6. It first represents the a, and a 2
degrees of fouling during produetion. The corresponding final values
reached are 0.44 and 0.155. The time scale is modified as indicated in
Fig. 6 for the intermediate cleaning phase. During the initial water
rinsing a, and a2 remain approximately at the same level. Then the

alkaline solution (2 %, 140°C) provokes a sudden decrease of a, down to a
stable value, averaging 0.03 to 0.05, within 3 to 4 minutes.
Simultaneously, a 2 increases slightly (a2 = 0.22). Such rise proved
@ProcessEng
583
systematic and can be explained by a modification occuring in the

inorganic deposit structure.
Foliowing the intermediate rinsing, the action of the nitric acid (1.5 %,
140°C) causes an abrupt decrease of a2 down to avalue nearing zero
within a couple of minutes only. Simultaneously a, reaches an identical
value. At that stage, the sterilizer may be considered as perfectly clean.
Such conclusion was ascertained several times by dismantling the
exchanger and checking visually the cleanliness of the plates.
On several occasions, the final value of a, or a2 remained above 0.03

af ter an intermediate cleaning. This generaily indicated a defective
cleaning which in fact can easily be cured by circulating the most
appropriate detergent solution for a few additional minutes.
15
HN03
c
E
w Dl
E (;
~ c:
ro
5'
lJ
W
ro
u
w
E
'-
w
5 c
o
6
5 i
.t:
4 c:
w a
E 3
~
lJ
~
::J
u
2 a
cl:
O
@ProcessEng
O-l 0-2 0-3 0-4 0-5

degree af faul ing ~
FIGURE 6. Recording given by the sensor during the successive processing
and intermediate cleaning phases.
584
In connection with this, the results obtained with cleaning of the

industrial sterilizer confirm the observations we had made at the pilot
scale (Perlat et al., 1985). The protein rich deposit appearing in heat
recovery zone is, to a large extend, expelled by the alkaline solution.
On the other hand that detergent do es not have any significant effect on
the inorganic matter deposition forming in the heating zone, which in
turn is eliminated only by the acid detergent. At the same time it does
complement the action of soda in the heat recovery zone. Nevertheless
using the acid detergent before the alkalin detergent -the interest of
which was demonstrated at a cleaning temperature of 80°C (Perlat et al.,
1985)- do es not seem to present any significant advantages at 140°C.
In addition to confirming the efficiency of the sensor on site, the

follow-up of the cleaning procedure leads to several major remarks to be
made
(a) Whatever the type of deposition cleaning proves to be extremely

rapid. It se ems that the nclosed loopn (recycling of detergent
solutions) cleaning practice commonly used in industrial
installations had concealed such phenomenon and subsequently
often induced too lenghty cleaning cycles. Moreover the
circulation of cleaning and rinsing solutions through long
tubings spread out in factories does not contribute to solve
such a problem.
(b) There is one detergent specific to each kind of deposition. Any

intermediate cleaning with a single detergent, be it acid or
alkaline, ought to be proscribed.
(c) The advantage of an intermediate cleaning performed at 140°C,

and foliowing the procedure indicated in Table l, is to
preserve the sterility of the installation without disturbing
the thermic program. Besides that, it proves especiaily
efficient as aresult of the activation of cleaning kinetics at
high temperatures (Gallot-Lavallee et al., 1984). Insofar as
the sterilizer gaskets and plates withstand such treatments,
then the final cleaning at 80°C could possibly be avoided and
the productive capacity of UHT installations could therefore be
significantly increased. Concurrently, the frequency of
necessary dismantling of the whole sterilizer, which is always
a costly and lengthy task, could also be dramatically limited
as the sensor does provide reliable information on the cleaning
efficacy.
4. CONCLUSIONS
Thanks to an adequatly programmed microprocessor device, simple

measurements of static pressures and of processing through-put, enable
the evalutation, on-line and in real time, of the degree of fouling
developping in heat exchangers used for industrial food processing.
@ProcessEng
When fitted onto a plate heat exchanger designed for the industrial
production of sterile milk using the UHT method, such a sensor allows the
evaluation of the degree of fouling in sections of the sterilizer where
585
deposition is most liable to develop, i.e. the heat-recovery zone through

which the milk temperature is raised from 80 to 120°C and to allow its
immediate industrialization and distribution. The sensor enables a
continuous follow-up both of the degree of fouling increase during
the processing phase and of the action of the cleaning procedures. In the
first case, the kinetics of fouling given by the sensor to provide
valuable information on the influence of the processed milk antecedents
(age, refrigeration and collection, etc ... ) on deposition conditions.
Moreover, the maximum degrees of fouling not to be exceeded can also be
determined and should average 0.5.
Any overriding value would be detrimental to the satisfactory running of
the sterilizer and to the quality of the milk produced. Areliable
appreciation of the cleaning procedure quality, thus of the sterilizer
cleanliness, looks as the major advantage brought forth by the
utilization of this sensor all the more as the dismentling frequency of
the exchanger is thus significantly reduced. However, the study of
optimal cleaning conditions (detergents'effect depending on their
composition, concentration and temperature in relation with the type of
deposition; duration and link up of sequences including rinsing ;
integration of data provided by the sensor into the automatic device
monitoring the installation, etc ... ) susceptible of generating
considerable increase in production capacity, still remains to be
undertaken.
Finally, the adaptation of such a type of sensor to other heat exchanger
(tubular exchanger), to other heat treatments (such as pasteurization)
and to other products (milky desserts, fruit JUlces, etc ... ) may be
foreseen in the short term whereas its application to other processes
(membrane separation, evaporation, etc ... ) looks more delicate and would
require additional studies.
ACKNOWLEDGEHENTS
The authors sincerely thank M. Domlnlque Loonis for his essential

contribution to the industrial testing the Managing Board and the
technical executives of the "Cooperative Laitiere des Quatre Cantons" (59-
Le Quesnoy-France) where trials where carried out. But for their interest
in such study and their active participation, the project of our sensor
would never have been finalized/concretized; the Agence Francaise pour
la Maitrise de l'Energie (AFME) and the Nord-Pas de CaIa is region for
their financial support and the SERES Company (13762 Aix les Milles)
who is caring for the manufacturing and distribution of the sensor.
LIST OF SYMBOLS
Exchanger hydraulic diameter - D

Space between plates - d
Deposit thickness - e
friction coefficient - f
@ProcessEng
Exchanger effective length - L

Width of a rectangular channel - l
Recycling pass number inside exchanger - n
Product flow rate - Q
586
Reynolds number - Re
Product average speed - v
Degree of fouling - ~
Differential pressure - f::, p
Product density - p
Coefficients - k, k" k 2
Refer to clean exchanger -å Po , Do
REFERENCES
1. Burton H. : A comparison between a hot-wire laboratory apparatus and

a plate heat exchanger for determining the sensitivity of milk to
deposit formation. J. Dairy Res., 33, 317-24, 1966.
2. Burton H. Reviews of the progress of Dairy Science. Deposits form
whole milk in heat treatment plant a review and discussion. J.
Dairy Res., 35, 317-30, 1968.
3. Corrieu G., Lalande M., Ferret R. : New monitoring equipment for the
control and automation of milk pasteurization plants. Food Process
Engineering, Vol. l, Elsevier Applied Science Publishers Ltd, London,
pp. 165-71, 1979.
4. Fryer P.J., Pritchard A.M., Slater N.K.H. and Laws J.F. : An on-line
fouling sensor for the food processing industry. lInd International
Conference on Fouling and cleaning in Food Processing. Universite de
madison-Wisconsin, pp. 203-16, 1985.
5. Gallot-Lavallee T., Lalande M. et Corrieu G. : Cleaning kinetics
modeling of holding tubes fouled during milk pasteurization. J. Food
Proc.Eng. 7, 123-42, 1984.
6. Hege W.G. : Uber die Bildung von Ablaerungen beim Erhitzen von Milch
und Molke. These de Dr Ing., Universite de Munich-Weihenstephan, 1984.
7. Jennings, W.G. Theory and practice of hear-surface cleaning, Adv.
Food Res., 14, 325-58, 1984.
8. Lalande M., Corrieu G. : Procede de controle de l'encrassement et du
decrassage d'un materiel. Appareil de mesure du degre d'encrassement
d'un materiel. Brevet depose le 13/4/79 sous le numero 79/09.969,
1979.
9. Lalande M., Tissier J.P., Corrieu G. Fouling of a plate heat
exchanger used in ultra-high-temperature sterilization of milk. J.
Dairy Res., 51, 568-77, 1984a.
10. Lalande M., Gallot-Lavallee T., Corrieu G. : Chemical reactions and
mass transfer associated with cleaning of heat exchange surfaces
fouled by milk deposits. Engineering and Food, Vol. l, ed. B. McKenna,
Elsevier Applied Science Publishers Ltd, London, pp. 59-68, 1984b.
11. Lalande M., Tissier J.P. Corrieu G. : Fouling of heat transfer
surfaces related to B-lactoglobulin denaturation during heat

processing of milk. Biotech. Progress, 1, 2, 131-9, 1985.
12. Ling A.C., Lund D.B. Apparatus for studying fouling of heat ed
surfaces by biological fluids. J. Food. Sc., 43, 390-403, 1978.
13. Lyster R.L.J. The composition of milk deposits in an ultra-high-
temperature plant. J. Dairy Res., 32, 203-8, 1965.
14. Nassauer J., Kessler H.G. Adsorption of proteins and micro-
@ProcessEng
organisms on stainless steel surfaces. Food Engineering and Process

Applications, Eds. M. LE MAGUER and J. PELEN, Elsevier Applied
Science Publishers, LONDON, l, 211-220, 1986.
15. Perlat M.N., Lalande M., Corrieu G. Cleaning of UHT plants -
587
Influence of cleaning solutions according to deposit composition.

Food Engineering and Process Applications, Eds. M. LE MAGUER and J.
PELEN, Elsevier Applied Science Publ ishers , LONDON, 2, 521-529, 1986.
16. Plett E.A. Optimization of rinsing in the CIP procedure. Food
Engineering and Process Appl icat ions , Eds. M. LE MAGUER and J. PELEN,
Elsevier Applied Science Publishers, LONDON, 2, 531-538, 1986.
17. Schlussler H.J., Hierath D., Scharf R. : Versuche zur quantitativen
Bestimung von Verschmutzungen in Reinigungslosungen. I.
Flaschenreinigungslangen Brawissenschaft, 23, 3, 81, 1970.
18. Taborek J., Aoki T., Ritter R.B., Palen J.W., Knudsen J.G. : Fouling
: the major unresolved problem in heat transfer. Chem. Eng. Prog.,68,
2, 59-67, 1972a.
19. Taborek J., Aoki T., Ritter R.B., Palen J.W., Knudsen J.G.
Predictive methods for fouling behaviour. Chem. Eng. Prog. 68, (7),
69-78,1972b.
20. Tissier J.P., Lalande M., Corrieu G. : A study of milk deposits on
heat exchange surface during UHT treatment. Engineering and Food, Vol.
1 ed. B. McKenna, Elsevier Applied Science Publishers Ltd, London, pp.
49-58, 1984.
21. Zelver N., Roe F.L., Characklis W.G. Potential for monitoring
fouling in the food industry. lInd International Conference on
Fouling and Cleaning in Food Processing, Universite de Madison-
Wisconsin, pp. 225-62, 1985.
@ProcessEng
Chapter 10
Fouling in Industrial Water Systems
@ProcessEng
EFFECTIVENESS OF BIOCIDES
A. MARSHALL AND T.R. BOTT

DEARBORN CHEMICALS LTD., THE UNIVERSITY OF BIRMINGHAM,
WIDNES, BIRMINGHAM,
ENGLAND. ENGLAND.
1. INTRODUCTION
In nature, microbes normal ly live in harmonious balance, but when
unusual conditions occur such as an increase in temperature, a plentiful
supply of nutrients or over concentration of water, those organisms which
can adapt to the new conditions over-develop leading to problems.
There are three distinct microbial effects which are then possible:-
i) Fouling - caused by microbial growth which will restrict flow, cause
blockage of pipelines and system waterways, and foul heat transfer
surfaces.
ii) Corrosion - will occur where microbial or other deposits are present.
iii) Public health problems can occur where pathogenic bacteria are
contaminating the system, e.g. Legionnaires Disease.
These effects can occur in most man-made water systems such as:-
open or closed cooling systems
once-through circuits
low temperature heating circuits
storage tanks
2. FOULING
In order to maintain maximum plant efficiency it is necessary to
maintain clean heat transfer surfaces • The deposition of organic and
inorganic materials causes significant reductions in plant performance.
It is commonly accepted that the fouling of systems is caused by:-
i) Inorganic scale: due to precipitation of calcium/magnesium salts
from water or iron oxide which results from
system corrosion.
ii) Suspended solids: due to the deposition of suspended particulate
matter at low flowareas.
iii) Organic deposits: normaIly due to process contamination such as
oil.
iv) Biological fouling: this results from the excessive growth and
development of three lower forms of plant life -
algae, fungi and bacteria.
Algae growth usually occurs in sections of the cooling tower exposed to
sunlight. Fungi include all simple plants not containing chlorophyl1.
In industrial systems fungal growths are generaIly encountered ab ove the
water line.
@ProcessEng
Båcteria are the smallest, yet most prolific and troublesome forms of
life in cooling water systems. Bacteria multiply at an awesome rate by
cell division.
Microbiological growths in cooling systems can cause a number of
problems, such as reduced heat transfer, plugging of distribution lines,
blockage of filters, corrosion of system metals and deterioration of
cooling tower timber.
591

592
3. CORROSION
Microbiologically produced deposits promote corrosion of metal surfaces
in the folIowing ways:-
i) They accelerate pitting corrosion by the de-polarising action of
oxygen released during their metabolic process.
ii) They accelerate pitting corrosion by producing areas of potential
difference on the metal surface.
Hi) They shield the metal surface from the action of inhibitors.
iv) The oxygen-free conditions produced beneath fouling layers enable
anaerobic bacteria, such as sulphate-reducing bacteria to thrive.
They use sulphates in metabolic reactions and produce corrosive
hydrogen sulphide.
4. PUBLIC HEALTH
The microbiological species that can exist within the cooling systems
and other man-made water systems can give rise to a number of diseases.
One such disease which can be contacted from bacteria in cooling systems,
is Legionnaires Disease.
Legionnaries' Disease is a form of pneumonia which is caused by the
bacterium Legionella pneumophila. There are at least twenty two species
of the family Legionella, the most common one associated with disease in
man being sero-group 1. It is known that Legionella pneumophila is a
ubiquitous bacterium which has been recovered from mud, rivers and other
natural collections of water. Although incidence of the disease is
relatively rare - indeed Legionella pneumoni a has been found to represent
only 2-6% of all pneumoni as seen in hospital, the bacteria has been found
to proliferate in man-made water systems such as piped water and
recirculating cooling water. Infection results from inhalation of an
aerosol of water containing the bacteria and therefore the maintenance of
correct water side conditions which will minimise the growth of bacteria
in the water system is of importance.
5. MICROBIOLOGICAL CONTROL
The primary objectives of any microbiological control programme are:-
i) the removal of anyexisting biological deposits.
ii) the prevention of excessive growth of species of micro-organisms
that will either cause corrosion, the formation of further deposits
or be a danger to public health.
5.1 Biofouling Removal
Deposit removal is essential prior to the introduction of an on-going
programme to control general microbiological growth.
An initial appraisal will indicate the need for an off-line cleaning
procedure.
Using an off-line procedure the cleaning can be undertaken using

dispersants and biocides, some of which also have dispersant properties.
The selected programme is dependant upon the nature of the deposit and
i ts sever i ty. Cationic biocides/bj ~dispersants have been shown to be
particularly effective in suspending the biological mass for removal by
draining from the system or by introducing a high blowdown volume on the
circuit.
@ProcessEng
If it is not possibIe to shut down the system, then an on-line clean

using biodispersants and biocides should be undertaken. During the clean
a high blowdown should be used to remove debris from the system and
prevent re-deposition of slime masses.
5.2 On-Going Procedures
Cleaning and sterilisation procedures should be followed by a planned
593
control programme using microbiological control chemicals.

There are a large number of such biocides and they have been generaIly
classified as either oxidising or non-oxidising. In the former group
there is chlorine, bromine, hypochlorites, chloroisocyanurates, chlor ine
dioxide and ozone. The non-oxidising biocides most commonly used are
based on amines, organo-metallic compounds, quaternary ammonium
compounds, organo-sulphur compound, thiazolone derivatives, and many
others.
An ideal biocide should meet the folIowing requirements:-
i) Active against a wide range of microbes
ii) Possess a low order of toxicity to human and aquatic life
iii) Biodegradable
iv) Non-corrosive
v) Is not deactivated by inorganic or organic deposits in the system
vi) Does not deactivate corrosion inhibi tors and/or scale preventatives
used as part of the general water treatment programme.
6. OXIDISING BIOCIDES
6.1 Chlorine
W1,en chlor ine gas encounters water, i t hydrolyses to form two acids,
PiPochlorous and hydrochloric acid, respectively.
HOCI + HC1
Hypochlorous acid will ionise according to this reversible

reaction:-
HOCI H+ + OC1-
The amount of hypochlorous acid, as opposed to hypochlorite ion,

determines the biocidal efficacy.
The pH of the cooling water is directly responsible for the extent of
ionisation of hypochlorous acid. The acid state is favoured by low pH.
As shown in Figure l, at pH 5.0, there will be very little ionisation.
At pH 7.5 there will be approximately equal amounts of acid and
hypochlorite ion. Chlorine becomes ineffective as a microbicide at pH
9.5 or greater, as aresult of total ionisation. A pH range of 6.5 - 7.0
is considered practical for chlorine-based microbial control programmes,
since lower pH values would increase system corrosion.
Hypochlorous acid is an extremely powerful oxidising agent. It easily
diffuses through the cell walls of micro-organisms, and reacts with the
cytoplasm to produce chemically stable ni trogen-chlorine bonds wi th the
cell proteins. Chlorine oxidises the active sites on certain coenzyme

sulphydryl groups which constitute intermediate steps in the production
of adenosine triphosphate, which is essential to respiration.
Hypochlorous acid is estimated to be twenty times more reactive
(effective) as a microbicide than the hypochlorite ion.
6.1.1 Advantages of Chlorine. The attraction of chlorine as a
microbicide is its low in-use toxicity. It can, therefore be used in
@ProcessEng
potable water and applications which require low toxicity such as food
processing.
Chlor ine has a relatively low unit cost and under ideal conditions, pH
6.0 - 7.5, the dose rate required is only 1 ppm.
Minimal disposal problems are encountered with the use of chlor ine.
6.1.2 Disadvantages of Chlorine. The major disadvantages of chlorine
594
relate to its efficacy as a biocide in industrial cooling systems and

these briefly are as follows:-
Effectiveness at high pH. The trend is towards operation of cooling
systems at higher cycles of concentration, without acid dosing, and hence
higher system water pH values. Chlorine becomes progressively less
effective as a biocide as the pH increase ab ove pH 7.5. This can lead to
significantly higher doses of chlor ine being required to achieve some
degree of microbiological control.
Effectiveness against slime forming bacteria. Chlor ine is
particularly poor at penetrating microbiological slimes and in preventing
the development of slime forming bacteria. Experience has shown that
sulphate reducing bacteria can become a problem when the use of chlor ine
has allowed slimes to develop.
Chlorine Demand. Chlorine being a strong oxidising agent will react
with oxidisable material in the cooling water. The presence of
oxidisable materiaIs, such as process contaminants, organics,
microbiological slimes or ammonia could lead to excessive amounts of
chlorine being required to produce a free chlorine reserve.
Corrosion. When chlor ine dissolves in water it produces an acid
solution. The over zealous dosing of chlor ine can give rise to corrosion
problems.
Attack of Cooling Tower Timber. The use of chlor ine where timber
cooling towers are instalIed can result in delignification of the timber
which significantly reduces the life time of the tower.
6.2 Hypochlorites
These are salts of hypochlorous acid and when the two commonly used,
sodium or calcium, hypochlorites are added to cooling water systems they
function in much the same way as chlorine.
6.3 Chloroisocyanurates
These organo-chlorine compounds are gaining increased acceptance to many
smaller plants which prefer an oxidising biocide approach.
Chemically, chloroisocyanurates are compounds which hydrolyze in water to
slowly release chlor ine and cyanuric acid.
6.4 Chlorine Dioxide
Chlorine dioxide dose not form hypochlorous acid in water, as does
chlor ine • It exists as dissolved chlorine dioxide in solution and is
generaIly les s reactive as a biocide, however, it is more effective than
chlorine in the higher pH ranges.
Since it is an explosive gas, the compound is usually produced on site,
by mixing a strong chlor ine solution with sodium chlorite.
C12 + 2NaCl02 ~ 2NaCl + 2Cl02
In smaller installations, chlor ine dioxide may be generated by mixing
hydrochloric acid and sodium hypochlorite with sodium chlorite.
HCl + HOCl + 2NaCl02 ----7 2Cl02 + 2NaCl + H20

Generally, chlor ine dioxide is more expensive to use than normal
chlorination. However, in cooling systems contaminated with ammonia or
organic material it should be considered because it has lower organic
demand than many other oxidising biocides.
6.5 Bromine
In a similar manner to chlor ine the dissolution of bromine in water
@ProcessEng
results in the production of hypobromous acid.

Bromine has several advantages over chlorine, the major one being that as
shown by Figure 2 the equilibrium for HO Br .--.. H+ + OBr-is at a
higher pH than the corresponding hypochlorous acid ionisation. This
means that bromine can be used effectively at higher pH values than
chlorine.
595
Both bromine and chlor ine react with ammonia in water to form bromamines
and chloramines. Figure 3 shows the effect of ammonia on the efficacy of
chlorine and bromine on E co1i in the presence of ammonia. Chloramines
are re1ative1y ineffective microbicides but bromamines are extreme1y
effective microbicides.
A convenient way of introducing bromine into coo1ing systems is in the
form of halogenated hydantoins. The most common1y used being 1- bromo -
3 - ch1oro - 5, 5 - di methy1 hydantoin which hydrolyses in water to
produce both hypoch1orous and hypobromous acid together with di methy1
hydantoin.
7. NON-OXIDISING BIOCIDES
In many situations, non-oxidising biocides prove to be more effective
than their oxidising counterparts. They can be used in conjunction with
oxidising biocides for broader control. Many p1ants ch10rinate and add a
non-oxidising biocide once or twice per week to achieve microbiological
control.
7.1 Isothiazo1ones
Isothiazo1ones are effective broad spectrum biocides which have activity
across a broad pH range and degrade to eco1ogica11y acceptable substances.
They are initia11y biostatic due to the inhibition of macromo1ecu1ar
synthesis such as protein and RNA. Ce11 membrane integrity and microbia1
catabo1ism are not immediate1y affected. U1timate1y, they are biocida1
and ce11 death occurs af ter a few hours contact time.
7.2 Quaternary Ammonium Sa1ts
These cationic surface active chemica1s are organica11y substituted
nitrogen compounds. The general structure of these cationic biocides is
t3 -:; -R~
shown be1ow:
_ _- hal ide-
"R" represents alkyl, ary1 or heterocyc1ic radica1 substituent containing

8 to 25 carbon atoms bonde d to a nitrogen atom.
Quaternaries are generally most effective against a1gae and bacteria in
alkaline pH ranges. Their biostatic action is attributed to their
cationic charge, which forms an e1ectrostatic bond with the negative ly
charged sites on the ce11 wa11. The e1ectrostatic bonds create stresses
in the ce11 wa11, causing ce11 1ysis and death. The quaternaries a1so
cause ce11 death through protein denaturation, by distorting the
permeabi1ity of the ce11 wa11, which reduces the normal flow of
1ife-sustaining nutrients into the ce11.
A number of problems limit the use of these compounds. Their activity
level drops in systems heavi1y fou1ed with dirt, oi1 and debris. Because
of their sur face activity, "quats" wi11 emu1sify oi1, instead of
participating in ce11 wa11 bonding; a competing mechanism with weakens
the control programme. In addtion, overfeed of "quats" may cause
extensive foam.
7.3 Organo-Su1phur Compounds
A variety of organo-su1phur microbicide formulations are available for
@ProcessEng
use in coo1ing water systems, and a1though their mechanisms of

microbicida1 activity are quite simi1ar, the pH ranges affecting their
efficacy are quite different.
In general, the organo-su1phur compounds function as microbicides by
either competitive1y or non-competitive1y inhibiting ce11 growth.
596
The competitive inhibition action of organo-sulphurs closely resembles

that of chelating agents. Normally , in microbial respiration, a low
energy ferric (Fe 3 +) cytochrome, accepts an electron and is transformed
to a high energy, ferrous (Fe 2 +) cytochrome, state. These reactions
result in the generation of energy required for life.
The competitive-inhibiting type of orgao-sulphurs remove the ferric
(Fe 3 +) ion from the re action by complexing it as an iron salt. Removal
of the iron ion from the cytochrome stops the transfer of energy and
causes immediate cell death.
Non-competi ti ve inhibition caused by certain organo-sulphur compounds,
consists, in its elementary form, of nothing more than inducing the
micro-organism to accept a chemical substance that will eventually lead
to its destruction. MicI'obial death is brought about by acceptance of an
organo-sulphur compound, sufficiently similar in structure to the
essential metabolite that it will combine with the appropriate enzyme
protein, but sufficiently different that it will not produce the required
life-sustaining reaction.
7.3.1 Methylene Bisthiocyanate This organo-sulphur compound is
effective in inhibiting algae, fungi and bacteria, most notably the
sulphate reducing Desulfovibrio species. Since it is a competitive
inhibiting microbicide, it inactivates the electron transfer cytochromes
of the micro-organism. The thiocyanate fragment, NCS-CH2-SCN, of the
methylene ester of thiocyanic acid reacts to block the transfer of
electrons in the micro-organism, resulting in cell death.
Although methylene bisthiocyanate is a very effective microbicide in
cooling water systems, it is not very soluble in water and therefore is
usually formulated with dispersants. The dispersants enable it to
function as an effective microbicide throughout the water system and
enhance its penetrability of algal and bacterial slime layers.
Methylene bisthiocyanage is pH sensitive and rapidly hydrolyses in pH
ranges above 8.0. For this reason it is not recommended for use in
systems where the recirculating water pH generally exceeds 8.0.
7.3.2 Sulphones and Thiones. These are non-competitive organo-sulphur
microbicides • In water, they decompose to form solutions similar to
microbial metabolites, but which are actually metabolite analogues and
consequently cause cell death. As with all organo-sulphurs, they are pH
sensitive, with the former most reactive in cooling water as a range of
6.5 - 7.5, and the latter in pH range of 7 - 8.
7.3.3 Sodium dimethyldithiocarbamate and Disodium ethylene
bisdi thiocarbarnate. These are organo-sulphur compounds which
possess excellent microbicidal capabilities. They are readily soluble in
water and function best at pH 7 and above. .
7.4 Organo-Dibrominated Compounds
Recent developments have led to the introduction of certain organic

dibrominated compounds which function as broad spectrum biocides, being
particularly effective against bacteria. These compounds have short
hal f-lives degrading to substances of significantly lower toxicity and
hence increased ecological acceptability.
7.5 Organo-Tin Compounds
Environrnental concern over heavy metals has limited their use in recent
@ProcessEng
years. Generally,they have been effective as cooling water- microbicides

when used in the range of l - 2 ppm.
However, organo-tin compounds are known fOl their toxicity to algae,
moulds and wood-rotting organisms. They are characterised by a least one
tin-carbon bond per molecule.
Organo-tin compounds function best in the alkaline pH range s and are
597
often combined with quaternary ammonium compounds or complex amines to

improve their dispersant abilities. Formulations of this type provide
synergistic activity, with the total microbicidal efficacy exceeding that
expected of any individual ingredient.
8. ALGAL CONTROL
Algae require air and light in order to grow, and their growth usually
appears initially in the form of microbial slime. They play a key role
in the propagation of bacteria and fungi since they produce organic
material from atmospheric carbon dioxide, using light as an energy
source. The organic material so produced acts as nutrients for futher
microbial growth, particularly of bacteria. For this reason the
efficient c.ontrol of algal activity is vital to the success of any
programme designed to control microbiological growth in natural waters.
8.1 Triazines
Triazines have been used for many years as the basis of herbicides. Some
triazines are used for weed control in aguatic systems and in general
they are active over a wide pH range. Triazines act as algal control
agents by inhibiting the reactions which produce starch in the cell
structure. The triazines are thus essentiaIly algaest&tic in action.
9. SUMMARY
The over-development of microbiological growths in man-made water
systems lead to fouling, corrosion and public health problems. The
microbiological species which cause these problems are algal, fungi and
bacteria. A microbiological control programme should be applied where
possibIe in man-made water systems. The primary objectives of the
control programme are the removal of anyexisting biological deposits and
the prevention of excessive growths that will cause corrosion, the
formation of further deposits or be a danger to public health.
There are a large number of biocides which can be used in control
programmes • They can be generaIly classified as ei ther oxidising or
non-oxidising. The oxidising biocides include chlorine, bromine
hypochlorites, chloroisocyanurates, chlor ine dioxide and ozone. The
non-oxidising biocides most commonly used are based on amines,
organo-metallic compounds, guaternary ammonium compounds, organo-sulphur
compounds and thiazolone derivatives.
@ProcessEng
598
FIGURE 1
EFFECT OF pH ON THE DISSOCIATION

ØF HVPOCHI.DROUS ACIDS
100
l
110
i
II
IO
I
70 II
,~ IO
150
!
I
;
I
I
I I
•
40
æ
!I
20
I
I
10
I
o !
10
pH VALlIE
@ProcessEng
599
FIGURE 2
HYPOHAlOUS ACID CONCENTRATION VB pH
100
IO
eD
70
Cl
~ eD
!
I"
SO
40
30
20
10
O
e 7 7.8 e 1 1.8 10
pH
@ProcessEng
@ProcessEng
600
CASE STUDY - CLEAN-UP OF A COKE OVEN COOLING SYSTEM
A. MARSHALL AND G.E. IBBOTSON, AND T.R. BOTT

DEARBORN CHEMICALS LTD., THE UNIVERSITY OF BIRMINGHAM,
WIDNES, BIRMINGHAM,
ENGLAND. ENGLAND.
l. INTRODUCTION
The primary coolers of a coke oven cooling system were found to be
fouled with a black slime material and this case study details the
programme of removal and clean-up of the system over a twenty day period.
2. PROBLEM IDENTIFICATION
2.1 Plant Inspection
The cooling system consists of a three cell mechanical draught timber
tower which cools twenty shell and tube heat exchangers that are arranged
in five banks of four heat exchangers. The process liquor flows through
the tubes and the cooling water flows through the shell of the exchanger.
Inspection of the tube bundles in March, 1986 revealed slimy grey/black
deposits with a thickness of about 4 mm. No significant smell was
apparent and the deposit appeared to be only loosely attached to the tube
surface.
Removal of the slime deposit showed the Hyform 409 tubes to be generaIly
in a clean condition. Areas of localised corrosion had been initiated
under the deposit and these were in greatest density in the areas where
the tubes had surface damage produced during manufacture.
The mild steel shell and baffle plates showed extensive build-up of
corrosion products.
2.2 Laboratory Investigations
The biological activity of the deposit and water was assessed and the
results are shown in Table 1. An analysis was also carried out on the
deposit, the results of which are shown in Table 2.
The cooling water had a general ly acceptable levelof total aerobic
counts of between 10 4 and 10 5 org/ml. Analysis of the deposit
indicated that it was predominantly biological in nature. The total
aerobic count was about 10 7 org/ml and nitrifying, denitrifying and
sulphate reducing bacteria were identified as being present in the
deposit. Further analysis indicated the presence of Pseudomonads, E.coli

and Klebsiella.
Analysis of the deposit indicated that about 50" of the volume was
biological in nature. The rest comprised of inorganic materials such as
calcium phosphate, iron oxide and calcium alumino silicate.
2.3 Assessment of the Problem
In the past, the system had mild steel heat exchanger tubes and was
@ProcessEng
treated with a phosphate based corrosion inhibitor. The corrosion

inhibitor over a period of some 10 years had failed to provide adequate
protection and the tube bundles had severely corroded to an extent that
they required replacing. The tube bundles were replaced in 1985 and were
fabricated in Hyform 409. The use of the corrosion inhibitor was
terminated and the system was treated periodically with biocide.
The two objectives in treating this cooling system were to minimise
601

602
corrosion and protect the huge capital investment in the Hyform 409 tube
bundles, and provide clean heat transfer surfaces to ensure that the coke
oven gas temperatures leaving the plant were acceptable.
Clearly, the current regime was not achieving this objective. The
deposit on the heat transfer surfaces was found to be a mixture of
biological slimes and inorganic solids. The deposit provides a suitable
environment for anaerobic bacteria such as sulphate reducing and
nitrifying bacteria. The presence of these acid producing bacteria,
together with the possibility of under deposit corrosion as aresult of
differential aeration cells being established, has resulted in the
initiation of localised corrosion on the heat exchanger tubes.
The presence of the deposit was also having a marked detrimental effect
on heat transfer capability.
The system required a treatment programme which would remove the deposit
quickly and then an on-going treatment which would prevent re-growth and
subsequent deposition.
3. TREATMENT PROGRAMME
3.1 Clean-up Treatment
A twenty day cleaning regime was implemented based on the following
treatments:-
i) Flomate 781 - antifou1ant dispersant dosed at 200 ppm through-out the
twenty days.
ii) Biomate 795 - biodispersant dosed at 200 ppm through-out the twenty
days.
iii) Biomate 755 - oxidising biocide dosed to give l ppm free chlorine on
Day 3, 9 and 18.
iv) Biomate 792 - non-oxidising biocide which is specific for anaerobic
bacteria dosed at 100 ppm on Days 4 and 5.
3.2 On-going Treatment
i) Flomate 781 - antifoulant dosed to maintain 50 ppm
ii) Biomate 795 - dosed once per week at 50 ppm
iii) Biomate 5793 - oxidising biocide which re leases both chlorine and
bromine dosed at 2 ppm.
4. MONITORING
The progress of the clean-up was monitored on a daily basis using the
following:-
i) Biological activity - samples were taken periodically for laboratory
assessment of total aerobic counts and identification of specific
species. The Bioscan (ATP method) was used on-site to give rapid
information on system biological status.
ii) Corrosion rates - corrosion coupons were installed in the cooling
tower pond and in an ASTM rack for measurement of corrosion rates. A

probe was installed in the system to allow instantaneous measurement of
corrosion rate and pitting index.
iii) Water parameters - the water was analysed daily for dissolved solids
content, but more specific analysis of suspended solids, iron, chlorine,
phosphate and treatment reserves ...ere carried out on a more frequent
basis.
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5. SYSTEM CLEAN-UP
5.1 Results
Figures l and 2 show the biological counts, measured with the Bioscan,
for days 2, 3, 4 and 5. Figure 3 shows the biological counts, measured
with the Bioscan, from the start of the trial through to day 10.
603
Tables 3 and 4 show the biological counts measured in the laboratory.

Figure 4 shows the phosphate concentration through-out the clean-up.
Figure 5 shows the suspended solids in the system through-out the trial
and Figure 6 shows the mild steel corrosion and pitting rates monitored
with the instantaneous corrosion rate meter.
The tube bundle s were inspected and photographed at the beginning, during
and at the end of the clean-up.
Figure 7 shows photographs of the tube bundle in No. 3 cooler atthe start
of the clean-up. Figure 8 and Figure 9 show photographs on Day 11 and on
Day 20, respectively.
5.2 Discussion of Clean-up
5.2.1 Biological Actiyity. The biological counts, measured by the
Bioscan, indicate that the addition of dispersants and the oxidising
biocide were having the desired effect of disruption of the slime
matrix. Figure 2 shows the increase in the bacterial population as a
result of applying Biomate 755 which is an oxidising biocide. The
bacterial population in the slime is higher than in the bulk water.
Hence, disruption of the slime results in higher counts in the water.
The application of Biomate 792 on Day 4 produced a dramatic reduction in
bacterial counts such that the system was virtually sterile 6 hours af ter
the addition of Biomate 792. The laboratory analysis of samples taken on
Day 5 showed very low counts and the absence of sulphate reducing
bacteria. The bacterial counts on Day 6 and 11 showed slightly higher
levels indicating that some re-infection was occurring, either from the
atmosphere by the air scrubbing action of the tower or from the make-up
water. Thus, indicating the need for an effective on-going
microbiological treatment.
5.2.2 Water Parameters. The two parameters which gave an indication of
the progress of the clean-up were the phosphate concentration, since the
deposit contained about 6' phosphate, and the suspended solids level.
Figure 4 indicates that the phosphate concentration increased from the
beginning of the clean-up programme and reached a peak on Day 5. Figure
5 shows that the suspended solids also increased from the beginning of
the trial and also reached a peak on Day 5.
The quantity of material removed was estimated from the suspended solids
level and the water loss calculations. On Days 4 and 5 it was estimated
that a total weight of 450 Kgs of material was dispersed into the bulk of
the water. This was removed from the system by extensive bleed-off in
order to prevent re-deposition of the dispersed material.
During the following 15 days it was estimated that a further 480 Kgs was
removed.
5.2.3 Corrosion Monitoring. The corrosion rates measured during the
clean-up are shown in Figure 6. An acceptable general corrosion rate and
low pitting index was measured through-out the per iod of the clean-up.
5.2.4 Visual Inspections. Figures 7 - 9 show the photographs taken on
Days l, 11 and 20 of the clean-up and clearly show the significant
removal of deposit that has occurred as aresult of the clean-up
programme. Much of the are a of the tubes are completely free of
deposits. The clean-up produced improved heat transfer and reduced the
risk from under deposit corrosion.
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6. ON-GOING TREATMENT
The on-going microbiological control was achieved by dosing Biomate
5793. This is a white solid supplied in the form of pellets which
dissolve in water to give hypobromous and hypochlorous acids, which are
both effective biocides.
604
The amount of hypobromous and hypochlorous acids formed depends on the

flow velocity and temperature of the water flowinq throuqh the pellet bed
and the volume of the pellet bed. Therefore, to enable accurate dosinq
and control of Biomate 5793 the Biofeeder dispensinq unit has been
developed.
The coke oven system was fitted with a Biofeeder, a schematic diagram of
which is shown in Fiqure 10.
Table 5 shows the biologi cal counts achieved in the system since the
on-qoinq treatment was initiated. The bacterial counts have been
sufficiently low to ens ure that no further foulinq of the heat exchanqers
has occurred.
Corrosion rate measurements on both coupons and instantaneous corrosion
rate meter indicate acceptable qeneral corrosion rates and pittinq
indices.
Figure 11 shows photoqraphs of the tube bundle s af ter 12 months operation
on the on-qoinq treatment. The tubes are especiaIly clean and free from
deposits.
7. SUMMARY
This paper qives details of a successful clean-up of a coke oven coolinq
system usinq a combination of dispersants toqether with oxidisinq and
non-oxidisinq biocides to remove a deposit which consisted of inorqanic
materials bound toqether with bioloqically produced slimes.
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TABLE l
BIOLOGICAL A.NALysrs PRE CLEAN-UP
SAMPLE TYPE TOTAL AEROBlC COUNT ORG/Ml S.R.B. IRON BACTERIA DENITRIFYING BACTERIA NITRIFYING BACTERIA
37°C 30°C 20°C
WATER 8.3 " 10 4 3.5 x 10 5 4.0 x 10 5 .Ve .Ve .Ve .Ve
SLIME 6.6 x 10 6 3.5 li: 10 6 1.3 x 10 6 .Ve .Ve .Ve .Ve
O>-
O
U>
606
TABLE 2
DEPOSIT ANALYSIS - PRE-CLEAN-UP
Residua1 Af ter Dryinq (to constant weiqht at 105°C)
Iqnition Loss at 6000C 52.2'\
Acid Inso1ub1es (aqua reqia) 10.3'\
Carbonate as C02 1'\
5.6'\
Calcium as CaO 10.5'\
13.2'\
13.2'\
Silica as Si0 2 7.6'\

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TABLE 3
BIOLOGICAL ANALYSIS - POST CLEAN-UP
TOTAL AEROBIC COUNT 370C - WATER SAMPLES
DAY TIME POSITION OF SAMPLING
COOLER No. 3 TOWER
09.34 1.8 x 105 9.0 x 105
10.45 2.0 x 105 1.3 x 105
11.45 1.6 x 105 8.7 x 10 4
Day l 2.00 1.1 x 105 1.0 x 105
4.00 8.7 x 10 4 5.8 x 10 4
6.00 3.3 x 105 1.2 x 10 4
09.00 3.7 x 10 4 4.0 x 10 4
11.00 2.9 x 10 4 1.0 x 105
Day 2 3.30 4.0 x 10 4 5.8 x 10 4

4.30 9.7 x 10 4 7.5 x 10 4

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g
00
TABLE 4
BIOLOGICAL ANALYSIS - POST CLEAN-UP
TRIAL DAY PSEUDOMONADS TOTAL AEROBIC COUNT ORG/Ml S.R.B. IRON BACTERIA DENITRIFYING BACTERIA NITRIFYING BACTERIA
37°C 30°C 20°C
Day -Ve 2.8 x 10 2 3.1 " 10 3 40 -Ve -Ve -Ve -Ve
Day 6.2 " 10 2 2.6 x 10 3 6.2 x 10 3 6.8 x 10 4 -Ve -Ve -Ve -Ve
Day 11 1.2 " 105 5.9 x 10 4 2.1 x 105 2.4 x 105 -Ve -Ve -Ve -Ve
609
TABLE 5
COKE OVEN COOLING SYSTEM
ON GOING TREATMENT
DATE TOTAL AEROBIC COUNT (org/ml)
37°C 30°C 22°C
11.07.86 2.3 x 10 2 3.4 x 10 2 3.7 x 10 2
19.08.86 3.3 x 10 3 4.8 x 10 3 4.0 x 10 3
15.10.86 3.6 x 10 4 4.9 x 10 4 4.9 x 10 4
24.11.86 8.8 x 10 3 9.8 x 10 3 8.3 x 10 3
19.02.87 8.2 x 10 4 5.1 x 10 4 5.0 x 10 4

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610
fICURE 1
COKE OVEN COOLIt'>JG SYSTEM

elOCOUNTS AT THE TOWER
1.28
1.27
J
1.26
1.25
1.24
E 1.23
.......
(/)"
'""
:::E c
(/).2 1.22
\
z=
,,---
<:::E
a:: 1.21
O
1.2
~
1.19
1.18
1.17
\
1.16 -I T---'--'T-,- - r - - -
2 3 4 5 6 7 8 9 10 11
HOURS
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611
nCURE 2
COKE OVEN COOLlNG SYSTEM
1.7 -----_..
BIOCOUNTS AT THE TOWER
r
, .6
1.5
1.4
il
1.3
DAY )
1.2
~,
1.1
E
,-,....
:::;; "c
Ul 0.9
"s
Ul.2
z==
<:::;; 0.8
~'-'
Il:: 0.7
o
0.6
0.5
0.4
0.3
0.2
0.1
o
2 3 4 5 6 7 8 9 10 11
HOURS
D 19/3/86 + 20/3/86
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612
nGURE J

BIOCOUNTS AT THE TOWER
2 -
1 -
o
2 3 4 5 6 7 8 9 10 11 12
DAYS OF CLEAN-UP
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FICURE 4
613
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614
fIGURE 5
615
FIGURE 6

CORRATOR MEASUREMENTS·
7
2 :3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20
DAYS OF CLEAN-UP
D CORROSION RATE + prmNG INDEX
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FIGURE 7
INSPECTION PHOTOGRAPHS AT THE START OF THE CLEAN-UP PROGRAMME
111
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617
FIGURE 8
INSPECTION PHOTOGRAPHS DAY 11
III ,
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618
FIGURE 9
INSPECTION PHOTOGRAPHS DAY 20
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619
FIGURE 10
SCHEMATIC DIAGRAM OF BIOFEEDER
- Inlet
\-
3/4" BSP.
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620
fIGURE 11
PHOTOGRAPHS Af TER 12 MONTHS OPERATION

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CORROSION FOULING: LIQUID SIDE
E.F.C. SOMERSCALES
RENSSELAER POLYTECHNIC INSTITUTE, TROY, N.Y. 12180-3590 USA
l. INTRODUCTION
1.1. Occurrence and importanceof corrosion fouling
When any metallie heat transfer surfaee is exposed to a corrosive liquid
medium the produets of corrosion ean foul the surface, provided the pH of
that medium is not such as to dissolve the corrosion products as they are
formed. Corrosion commences immediately a surfaee is brought into contact
with the corrodant. Furthermore, the corrosion products are such a potent
foulant that an effect on the heat transfer is observed immediately (for
example, Somerscales, 1981). Not only are the effects of corrosion fouling
probably quicker to appear than those of other categories of fouling, but
their ultimate effect on heat transfer is as great as that of other cate-
gories of fouling. Particularly important examples of corrosion fouling
occur in electronic cooling systems, in solar collectors, and in the heat
exchangers used in the Ocean Thermal Energy Conversion (OTEC) system. These
examples are doubly important because designers will frequently attempt
to minimize corrosion (most likely not for heat transfer reasons) by choos-
ing materials of high corrosion resistance and employing a clean coolant
(thereby minimizing other categories of fouling), such as water.
This paper is intended to review the current state of knowledge of corro-
sion fouling of heat transfer surfaces exposed to liquid corrodants, in
particular, because of its technical importance, water.
2. FOULING BY AQUEOUS CORROSION PRODUCTS

2.1 Effects of fouling
In the remainder of this paper it will be assumed that the effect of the
corrosion fouling deposit is to add a thermal resistance (Rf) to the con-
vective thermal resistance (Re) at the heat transfer surface, so the total
thermal resistance (R) is given by
R (la)
or R ( Ib)
The overall thermal resistance is related to the heat flux (q) by

@ProcessEng
Ts -T
=
00
q (2)
R
Corrosion fouling ean also affect the fluid friet ion characteristics of
the heat transfer surfaces, because, typically, roughness of the surfaee
is increased, which, in turn changes the friction factor (f), where
621

622
2
LiP
(3a)
L
and f (3b)
2
p
w
v
The pres sure drop mayaiso be affected by fouling, not only because of
its effect on the friction factor, but because of the reduction in the flow
cross section caused by deposits on the duct wall.
2.2 The electrochemical basis of corrosion
The corrosion fouling of a heat transfer surface involves two simultaneous
electro-chemical reactions. These occur at anodic and cathodic portions
of the surface, which can be visualized as an array of very small areas
(perhaps of the order of magni tude of a single crystal) with the areas of
different polarity mixed in some random fashion. An electric circuit is
imagined to join pairs of anodes and cathodes and thi s serves as a path for
electric charge transport (electric current flow). Charge transport in the
metal is by electrons, and in the corrodent by ionized species. For uniform
corrosion, that is, corrosion over the whole sur face rat her than corrosion
confined to particular areas (e.g. cracks and crevices), the chemical and
physical proces ses occurring at either the cathodic or anodic regions con-
trol the rate of corrosion.
In thi s paper it will be assumed that the heat transfer sur face is ex-
posed to a flowing stream of oxygenated water with pH between 4 and 10
(typical for natura 1 waters). In this case the foliowing overall reaction
is obtained
(4a)
The metal hydroxides shown on the right hand side of equation (4a) consti-
tute the fouling deposit. It is clear from this equation that the rate
of growth of these hydroxides, and hence of the fouling deposit, depends
on the rate of transport (dmOl/dt) of oxygen to the corroding surface. So
we can write for the rate of growth (dmg/dt) of the fouling deposit on the
sur face
dm
~ (4b)
dt
Equation (4b) indicates that a mathematical modelof corrosion fouling

would have to take into account the rate of oxygen transport to the heat
transfer surface and its rate of reaction at the surface. This observation
forms the basis of a mathematical modelof corrosion fouling presented
below, but before considering the model the available data on corrosion
fouling will be reviewed.
@ProcessEng
2.3 Available empirical data

Table I summarizes the results of measurements of corrosion fouling on
heat transfer surfaces. These have been subdivided into field and labora-
tory tests.
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Tab1e I. Observed Therma1 Resistances
Rf at Conelusion
of test * Type of
Duration of Category of
Reference Materia1 Test [m 2 °C/W] Fouling Test
McA11ister et al -3
90-10 Cu-Ni 100 days 6.0 x 10 In situ corrosion Fie1d **
(1961) A1uminum-brass -3 fouling
8.0 x 10
Admira1ty bras s
-3
304 Stain1ess stee1 8.0 x 10
-3
1.5 x 10
Griess et al -4 Laboratory
A1uminum a110ys 300-500 hours 7.0 x 10 - situ
In - - corrosion
(1964) (Aver age) fouling
-3 Fie1d
Gutzeit Admira1ty brass 40 days 9.0 x 10 In situ corrosion
(1965 ) A1uminum fouling
-4
Ritter and Copper alloy 706 1000 hours 1. 70 x 10 - situ
In - - corrosion Fie1d **
Suitor fouling
(1976) -5.7 x 10- 4
Characklis Unknown 100 hours 1. 8 x 10 -4 Microbia1 Laboratory

(1981 )
Parryet al -4 Precipitation Fie1d

Admira1ity bras s Unknown 2.5 x 10
(1981 )
* Assumed Rf R - Re' where R convective heat transfer coefficient on c1ean surface.

c
** Specimens exposed to seawater or river water, so other categories of fou1ing may be present.
a-
N
'"
624
3. MATHEMATICAL MODEL
3.1 Introduction
Experience indicates that the most effective way to obtain arealistic,
and hopefully complete, list of the governing variables is to formulate
a mathematical modelof the process. Such a model is presented here. Some
of the assumptions employed in its formulation may appear to be rather du-
bious, but this is considered to be of secondary importance to the main
objective of rationally identifying the controiling variables of corrosion
fouling. Once these variables have been established it is possibie to for-
mulate an effective programme of research. In addition the mathematical
model can serve as an effective means for formulating dimensionless groups
of the governing variables. Such groups serve as a basis for presenting
empirical data and theoreticai results in the most general way.
To formulate a modelof corrosion fouling it is necessary to determine
the quantities h, T s ' Pf, kf and mf that appear in equations (Ib) and (3b).
It is not anticipated that with the current understanding of heat transfer
and momentum transfer at a rough surface that the coefficient of heat trans-
fer (h) and the shear stress (T S ) at the deposit-water interface could be
obtained theoretically. The deposit density (Pf) and the deposit thermal
conductivity (kf) are likewise not amenable to theoreticai calculation.
It is, therefore, assumed that information on these quantities is available
from elsewhere, and the mathematical model will be concerned with the de-
termination of the mass (mf) of the fouling deposit.
The mass (mf) of the fouling deposit is obtained by integration from a
differential equation describing the rate of growth (dmf/dt) of the fouling
deposit. This is based on the model original ly proposed by Kern and Seaton
(19s9a,b) for precipitation fouling. This views the net effect of fouling
as the result of competing growth (subscript g) and removal (subscript r)
processes, that is
dm dm
~ r
(5)
dt dt
The growth and removal processes are considered in more detail below.
3.2 Growth proces s
From the discussion above of the chemical aspects of the corrosion proces s
it is clear that the rate of growth of the fouling deposit depends on the
rate of transport of oxygen to the corroding surface and the rate of the
corrosion reaction. It will be assumed for the purpose of this discussion
that the corrosion reaction is a firs t order chemical reaction.
Oxygen is transported to the corrosion site in two steps: (a) transport
from the bulk of the water to the interface between the deposit and the
water; (b) diffusion of oxygen through the fouling deposit to the metal
surface.
If the corrosion reaction rate (ktl) can be assumed to be much larger
than the other transport resistances, which also means that all the oxygen
is consumed immediately on arrival at the site of the corrosion reaction,
then
@ProcessEng
dm
~ (6)
dt
where Kl [= (4/z) (Mg/Ml)] is the molar mass ratio.

625
3.3 Removal process

Removal of the fouling deposit involves the transport of species away
from the corroding surface and a re lease "reaction". Littie is known about
re lease processes, but it is helpful to assume that the rate of removal
of the fouling deposit involves a first order release reaction (rate con-
stant K~) and a transport process (mass transfer coefficient K acting t)
in series.
In order to demonstrate the way in which a mathematical modelof corrosion
fouling can be used to guide research, and to assist in the interpretation
and application of empirical data, consideration will be restricted to de-
posit removal by dissolution (material leaves in ionic form). In this case
Dillon (1959), with some supporting experimental evidence, has proposed
that
dm
r
(7)
dt
where C is an empirical constant; Pf = mass density of the fouling deposit.
4. APPLICATION OF DIMENSIONLESS GROUPS OF VARIABLES TO CORROSION FOULING

4.1 Determination of the dimensionless groups
Combining equation (5), (6) and (7) we have
(8)
To put thi s differential equation in terms of the fouling deposit thermal

resistance (Rf) we use mf = PfkfRf and 6 = kfRf.
Assuming, for simplicity, that the fouling deposit thermal conductivity
(kf) and density (Pf) are constant (for consistency we will also assume
that the diffusivity,dDOl' of oxygen in the deposit, the mass transfer co-
efficient, Ktl' and the removal rate, C, are independent of time) then equa-
tion (8) becomes
(9)
To complete the mathematical statement of the rate of growth of the foul-

ing deposit an initial condition is required. It will be assumed that the
surfaee is initially clean so Rf(O) = O.
Using the method of Smith, Pike and Murrill (1970), equation (9) and the
associated initial condition can be put in dimensionless form [see Somer-
scales (1987) l
- D (10)
dT
@ProcessEng
Initial condition: Rf + (O) = O.

Equation (10) implies
( 11)
626
According to equation (11), a problem that original ly involved one inde-

pendent variable (t), and seven parameters (Pf,kf,ktl' Ol,Kl,cbl,C) has
been reduced to one independent variable (T ) and two parameters (Shl,f).
The advantages in test planning, and in presenting experi'lental and theo-
reticai results should be obvious.
4.2 Example
The usefulness of the dimensionless relation given in equation (11) will
be demonstrated by applying it to empirical results that are available in
the literature [Griess et al (1960,196la,b»).
8
Griess et al 1961b (test
A14) ; å Griess et al 1961b
200 (test A21) ; O
Griess et al
(196la); 0 Griess et al
to (1960).
f--'"
,
f--'"
w
et:
150
IO'
::J
~
et:
LU 0 0
Q.
::;; 0°&'.
LU 00 &'.
f--
LU 100 0&'.
U 0
tf
et:
10- 1
00&'.
::J
Ul [']
d"l
~ DE 0&'. [']
LU Bi.
&'. 0
Ul
<{
50
LU 0
et: [']
u
;;;;; [']
10- 2
['] [']
100 200
TIME (hours)
FIGURE 1. Plots of increase

in surface temperature during
corrosion fouling tests on alu-
minum alloys: see the original
FIGURE 2. Dimensionless plot
references or Somerscales (1987)
of data in Figure 1; key as
for experimental details.
in Figure 1.
The published data is in the form of measured temperatures at the fouled

surfaee. The test seetion was an eleetrieally heated aluminum duet, whieh
was exposed to flowing oxygenated water (further details of the experimental

apparatus are available in the original publieation). The measurements
that are to be generalized by plotting in terms of dimensionless groups
are show in in Figure 1. Sinee the observed quantity is the temperature
(T s ) of the test surfaee the analysis of the preeeeding sub-seetion must
be reeast in terms of thi s new variable [see Somerseales (1987»). This
leads to the foliowing form of equation (11)
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DE
H-K
B" ) (12 )
1 ~6
627
The data from Figure 1 are replotted in Figure 2 in dimensionless form using
the groupings indicated in equation (12). This shows that data from three
of the tests ean be consolidated, but a fourth set of data (test A14) re-
mains outside the group. The reason for this is not clear, but an examina-
tion of the original data shows that the deposit was much thinner in test
A14 than the other tests.
5. EXPERIMENTAL TECHNIQVES FOR STVDYING CORROSION FOVLING
5.1 Introduetion
The author has described elsewhere (Somerscales, 1981) the steps that
might be followed in a comprehensive, ideal experimental investigation of
a given category of fouling. It is appropriate to review the experimental
methods used to study corrosion fouling by classifying them in this way.
Thus
(a) Preliminary experiments to assess the tendency of a fluid stream
to cause corrosion fouling and to obtain a broad indication of the
controiling variables.
(b) Tests to provide immediate design and operational data on corrosion
fouling. The output of the test would be in the form of overall
coefficients of heat transfer (V), fouling factors (Rf), and fric-
tion factors (f).
(c) Detailed studies of the subsidiary processes of corrosion fouling,
e.g., oxygen transport, deposit removal, corrosion reaction rate
constants, etc., and measurements of the properties of the materials
involved in the fouling, such as, oxygen diffusion rates, fouling
deposit mechanical properties, fouling deposit thermal properties,
and so on.
(d) Experiments to ascertain the accuracy of a model proposed for corro-
sion fouling. Tests of this type would, preferably, be carried out
under field conditions, but failing that, in the laboratory under
simulated field conditions.
For each one of these stages in the overall investigation the foliowing
must be considered:
(a) Nature of the test fluids: from the actual fouling stream, or an
artificial corrodant.
(b) Closed or op en system: once through fluid flow or a recirculating
system.
(c) Time scale: acceleration of the tests is very desirable provided
the appropriate techniques ean be identified.
(d) Apparatus: type and size.
5.2 Examples
5.2.1 Preliminary experiments: heated wire apparatus. In order to in-
vestigate the significance and nature of corrosion fouling without the com-
plicating presence of other categories of fouling, the author and his stu-
dents have reported a number of tests [Somerscales and Kassemi (1984),

Somerscales, Dugan and Tse (1985)] using a heat ed wire apparatus. This
provides a simple, low cost technique for assessing the significance and
character of corrosion fouling. The apparatus is shown in Figure 3.
The test specimens are in the form of small diameter (about 1 mm) wire
arranged in the form of a Vand exposed to a flowing stream of water. The
wire is heated electrically and the power (Q = 12R e ) dissipated to the
@ProcessEng
water and the surfaee temperature (T s ) of the wire ean be determined from
its electrical resistance. The latter is obtained from the known electri-
cal resistance-temperature characteristics of the wire, which are determin-
ed by calibration (see below).
The measurements of the wire temperature (T s ), the electrical power dis-
sipated (Q) by the wire, and the bulk temperature (Tb) of the water are
628
used to determine the resistance (R) to heat transfer between the wire and
the water according to equation (2). The fouling thermal resistance (Rf)
is determined from the measured value of R assuming that its magni tude when
the wire is first exposed to the flowing water is equal to the convective
thermal resistance (Re). Then Rf ean be obtained immediately from equation
(la) •
@)-
(5)---- - ---- --
@-
D--~
FrGURE 3. Heated wire apparatus.

1. Pyrex glass pipe (15cm long x l5cm diameter); 2. Acrylic plastic
upper cover; 3. Acrylic plastic lower cover; 4. Aluminum flanges;
5. The wire specimen; 6. Terminal blocks (same material as the wire
specimen); 7. O-ring seals; 8. Cylindrical acrylic plastic baffle;
9. Fluid inlet; 10. Mercury-in-glass thermometer [reproduced from
Somerscales, E.F.C., & M. Kasserni, Trans. Arner. Soc. Mech. Engrs.
[cl, Vol. 109, pp. 267-271, 1987].
SYMBOL SPECIMEN
------
f:, 4
o 5
(> 7
9
" 6
'V
() 8
100 200 300 400

TIME (HOURSI
FrGURE 4. Variation of corrosion fouling thermal resistance (Rf)
with time on 1010 carbon steel exposed to distilled water (pH =
6.5 ± 0.4, Tb = 24 0 C) saturated with atmospheric oxygen [reproduced
@ProcessEng
from Somerscales, E.F.C., & M. Kasserni, Trans. Arner. Soc. Mech. Engrs.
[Cl, Vol. 109, pp. 267-271, 1987].
629
The chemical state and temperature of the water in the test chamber are
maintained by continually circulating it through a non-metallic closed loop.
Because the electrical resistance of the wire specimen is very low (about
50 milliohms), variations in contact resistance at the different connection
points in the electrical circuit can have a significant effect on the meas-
ured electrical resistance. To avoid this difficulty measurements are made
by a Kelvin bridge, which is a standard technique for measuring very low
electrical resistances.
The electrical resistance-temperature relation of the wire was found to
be linear over the temperature range (20 0 C to 80 0 C), thus
R a + bT (13)
e
The wire was calibrated af ter it had been instalied in the test chamber.
A low current (1 amp) was used and deoxygenated water was circulated through
the test chamber and loop. A precision mercury-in-glass thermometer, also
employed to determine the bulk water temperature during the actual corrosion
fouling tests, was used as a calibration standard.
As the specimen corrodes during the course of a corrosion test, the con-
stant a of equation (13) increases, but constant b remains unchanged. The
wire, therefore, was recalibrated each time a measurement of its temperature
(T s ) was made.
The results of tests on mild steel made with thi s apparatus are shown
in Figure 4.
5.2.2 Immediate design and operating data tests: IBM thermal conduction
module cold plate tests. Tests intended to provide engineering data for
design purposes and in order to formulate operating procedures for heat
transfer equipment subject to fouling almost invariably rely on the so-
called Wilson method (see Knudsen 1981) to determine the fouling thermal
resistance (Rf). That this may not necessarily be the best technique became
clear in a recent series of measurements, (Somerscales, Bahar and Gilgert,
1986) conducted in the author's laboratory, of corrosion fouling in the
water channels of the IBM Thermal Conduction Module (TCM) co Id plate (see
Blodgett and Barber, 1982). The total thermal resistance (R) at a clean
(R = Ro) and fouled (R = Rt ) heat transfer surface can be written, respec-
tively
(14a)
(14b)
where it has been assumed, foliowing Wilson (1915), that the convective
thermal resistance (R c ) is proportional to the inverse of the mean fluid

velocity (U) raised to some power (n) depending on the flow situation.
In equations (14) the quantity Rcond is the thermal resistance between the
temperature sensor, presumably located just below the test surface, and
the interface between the test surface and the deposit of corrosion products.
Although the Wilson method is wide ly used in measurements of the fouling
thermal resistance, it is not necessarily the best method. The two differ-
@ProcessEng
ent methods that can be used will be called methods I and II, respectively.
In method I, if we write equations (14) as ~
R a (ISa)
o o
630
(1Sb)
where a o and at denote Reond and Reond + Rf' respeetively, and also the
intereepts on the R-axis of Figure 5. Then if bo' b t are constants
R = a - a (16)
f t o
This is the standard Wilson method for determining the fouling thermal re-
sistanee (Rf)'
R,
at - - .
ao Rcond
1/V"
FIGURE 5. The Wilson method of determining Rf·
Method II applies if the constants bo and b t in equations (14) and (15)

ean be assumed equal, within the uneertainty (wb) of the determination of
b. Then at any eonvenient value of l/U n
(17)
If Rt and Ro are based on measurements at one value of l/Un then it cannot

have the quality of the determination of Rf by method I (Wilson's method),
beeause the latter is based on measurements at more than one value of l/Uno
However, if measurements are made at several values of l/Un and appropriate
forms of equations (15) are fitted to the data (preferably by the method
of least squares) then the preeision of the determination of Rf using equa-
tion (17) ean be greatly improved. In faet, in eertain eireumstanees, sueh
as those found in fouling by eomparatively light deposits, method II [equa-
tion (17)] has abetter preeision than method I [equation (16)].
It ean be shown [Somerseales (1986)] that the preeisions (WRf) of the
determination of the two methods of determining Rf are given by
(18)
where N is the number of data points used in the determination of equations

(6) by least squares and x = l/vn , and C = [l + Nx 2 /E(x - x)2]1/2 (Method
@ProcessEng
I), and C = 1 (Method II).

It is clear from equation (18) that the preeision of Method II is superior
to that of Method I, provided bo and b t are equal. This assumption would
have to be tested in eaeh applieation of Method II [see Somerseales et al
(1986) for details].
631
5.2.3 Detailed studies of corrosion fouling processes: deposit removal

processes. The discussion above has indicated the measurements that must
be made if a satisfactory modelof this category of fouling is to be con-
structed. The indicated research program is extensive and the research
conducted to date has only been of comparatively limited extent. This sec-
tion will describe brie fly an example of an investigationof a fundamental
fouling process, namely, the study of deposit removal processes.
It is clear from the earlier review of deposit removal processes that
our knowledge of this topic is very limited and has very weak observational
foundations. Consequently, the application of mathematical models of foul-
ing to the prediction of the fouling performance of heat transfer equipment
are subject to considerable uncertainty because of the specula.tive component
associated with estimates of the rate of deposit removal. In view of this,
a research programme, supported by the National Science Foundation, has
been started under the writer's direction to improve our empirical under-
standing of corrosion fouling deposit removal and to assist in the construc-
tion of an adequate modelof the process. While the emphasis of this re-
search is on corrosion fouling, the results should be of significance to
fouling in general.
The apparatus consists of an annular test section (22.2 mm ID, 38.1 mm OD)
shown in Figure 6. The outer surface is glass, which allows direct observa-
tion of the fouling deposit on the test surface. The latter consists of
a 305 mm length of mild steel tube of 22.2 mm OD arranged concentrically
with the outer glass tube. The test surface is connected to two 635 mm
lengths of PVC tubing by a threaded connector, so when assembled it has
the appearance of a long length of plastic tubing with a short, central
length, which is the steel test surface. The test section is mounted ver-
tically to ens u re circumferential symmetry of the flow conditions. Water
enters the test section at the lower end and flows upward over the test
surface.
@'t>
JJ
6
FIGURE 6. Apparatus for measuring the removal rate of

@ProcessEng
corrosion fouling.
1. Reservoir; 2. Pump; 3. Flowmeter; 4. Oxygen electrode;
5. pH electrode; 6. Heat exchanger; 7. Test section;
8. Test specimen; 9. Particulate filter; 10. Activated
resin bed; 11. Particulate filter; 12. Vent; 13. Vent;
14. Packed tower; 15. Air inlet; 16. Camera and lights;
17. Drain.
632
Immediately on leaving the test section the water passes through a pleated
polypropylene cartridge filter that traps the iron oxide released from the
test surface in particulate form down to 0.5 ~m diameter. It then passes
to an activated resin bed [Dowex CCR-2-H (weak acidic type) or Rohm and
Haas Amberlite IRC-7l8 (chelating type)] that separate s dissolved material.
A third filter, identical to the first, is ar range d downstream of the resin
bed where it will trap any remaining solid material. These filters (both
cartridge type and resin bed) can be removed from service at appropriate
intervals and the amount of material trapped by the filter can then be de-
termined. This is done by washing the filters with dilute hydrochloric
acid (this, incidentally, reactivates the resin and cleans the mechanical
filter so that both may be used again). The iron content of the solution
of filter washings is then determined by adding l, 10 phenanthroline and
measuring the colour change in a spectrophotometer. Development of the
chemical analysis procedure is now complete and data on deposit removal
should start to become available in the next few months.
6. SUMMARY AND CONCLUSIONS
This paper has presented a very brief survey of certain aspects of corro-
sion fouling. It is broadly divided into two parts, the firs t dealing with
the fundamental physical and chemical mechanisms of corrosion fouling, and
the second describing, by way of examples, various measurement techniques
that can and have been employed in the study of corrosion fouling.
The discussion of fundamental mechanisms made use of a simple mathematical
modelof corrosion fouling in order to show how the various basic processes
are related. This model was then put in dimensionless terms, and .the value
of this technique for experimental planning, and for the presentation of
experimental and theoreticai results was demonstrated.
The review of experimental methods opened with a discussion of the heated
wire method which is a simple, low cost procedure for carrying out prelimi-
nary investigations of corrosion fouling. The very wide ly used Wilson
method for measuring fouling thermal resistance was assessed from the point
of view of the precision of the technique. It was shown that in certain
circumstances it may not be the best method for determining the fouling
thermal resistance.
The final example of experimental methods dealt with an investigation
of deposit removal processes that is currently underway in the author's
laboratory. This has as its objective an elucidation of one of the funda-
mental processes of corrosion fouling, and fouling in general. The empiri-
cal study of such fundamental processes is currently the most important
problem facing engineers and scientists concerned with the fouling of heat
transfer surfaces. Without a proper understanding of thi s aspect of fouling
it is very unlikely that any useful progress will be made toward the formu-
lation of practical methods for designing and operating heat transfer equip-
ment subject to fouling.
7. DEDICATION
This paper is dedicated to the memory of Benjamin E. Linder, a mechanical
engineer who wanted to improve the quality of life in Nicaragua.
@ProcessEng
8. LIST OF SYMBOLS
A heat transfer area m2

calibration constant equation (13) ohms
constant in the Wilson equation [equation (ISa)] for the clean surface
m2 °C/W
633
constant in the Wilson equation [equation (15b)] for the fouled surface
m2 °C/W
deposit Biot number = qdH/kf(Tso-Tb) dimensionless
calibration constant equation (13) ohms/oC
constant in the Wilson equation [equation (ISa)] for the clean surface
m2 0C/W - (m/s)n
constant in the Wilson equation [equation (15b)] for the fouled sur-
face m2 0C/W - (m/s)n
c rate of removal of corrosion products m/s; constant in equation (18)
dimensionless
cbl concentration of oxygen in the bulk of the water kg/m 3
D dimensionless deposit removal number = CpfdH/cbl 01
01 diffusivity of oxygen in the deposit of corrosion products m2 /s
dH hydraulic diameter of duct m
E dimensionless temperature = (Ts-Tso)/(Tso-Tb)
f Blasius (Moody) friction factor dimensionless
h coefficient of convection heat transfer at the deposit-fluid interface
W/m 2 °c
l electric current amps
Kl molar mass ratio = (4z)(Hm/Ml) dimensionless
kf thermal conductivity of the fouling deposit W/moC
ktl mass transfer coefficient for oxygen m/s
L length of duct m
Ml molar mass of oxygen (chemical species 1) kg/mol
Mm molar mass of metal kg/mol
mf mass of fouling deposit per unit area kg/m 2
mg mass of fouling deposit formed per area kg/m 2
mr mass of fouling deposit removed per unit area kg/m 2
N number of data points dimensionless
n exponent in the Wilson equation [equations (14) and (15)] dimensionless
Q heat flow W
q heat flux W/m 2
R total thermal resistance m2 °C/W
Rc convective thermal resistance at the deposit-fluid interface m2 °C/W
Re wire electrical resistance ohms
Rf thermal resistance of fouling deposit m2 °C/W
R+ dimensionless fouling deposit thermal resistance = Rfkf/dH
f
Ro total thermal resistance at a clean surface m2 °C/W
Rt total thermal resistance at a fouled sur face m2 °C/W
Shl Sherwood number for oxygen transport = ktld H/ 01 dimensionless
Tb bulk temperature of the water °c
Ts temperature at the fouled heat transfer sur face °c
Tso temperature at the clean heat transfer sur face °c

t time s
V fluid velocity in equations (14) and (15) m/s
v fluid velocity averaged over duct cross section m/s
x l/Un sn/mn
X average of highest and lowest values of x sn/mn
z valency of metal dimensionless
@ProcessEng
nP pressure drop in a duct of length L Pa

6 fouling deposit thickness m
Pf mass density of fouling de~osit kg/m 3
Pw mass density of water kg/m
T dimensionless time = tCbl Ol/PfdH
TS shear stress at deposit-water interface N/m 2
WRf precision of Rf m2 °C/W
w~
precision of measured value of total thermal resistance
(R) m2 °C/W
634
9. REFERENCES
l. Blodgett, A.J., & D.R. Barbour, 1982, Thermal Conduction Module: A

High Performance Multi-Layer Ceramic Pac kage , IBM J. Res. Develop.,
Vol. 26, pp. 30-36.
2. Characklis, W.G., 1981, Microbial Fouling: A Process Analysis, in

Fouling of Heat Transfer Equipment, pp. 251-291, edited by E.F.C.
Somerscales and J.G. Knudsen, Hemisphere Publishing Corporation,
Washington, D.C.
3. Dillon, R.L., 1959, Dissolution of Aluminum Oxide as a Regulating

Factor in Aqueous Aluminum Corrosion, in AEC-Euratom Conference on
Aqueous Corrosion of Reactor Materiais, pp. 134-152, Report TID-7587,
Atomic Energy Commission, Washington, D.C.
4. Griess, J.C., H.C. Savage, T.H. Mauney, & J.L. English, 1960, Effect
of Heat Flux on the Corrosion of Aluminum by Water. Part I. Experi-
mental Equipment and Preliminary Test Results, Atomic Energy Commission,
Report ORNL-2939, Oak Ridge National Laboratory, Oak Ridge, Tenn.
5. Griess, J.C., H.C. Savage, T.H. Mauney, J.L. English, & J.G. Rainwater,
1961a, Effect of Heat Flux on the Corrosion of Aluminum by Water.
Part II. Influence of Water Temperature, Velocity, and pH on Corrosion-
Product Formation, Atomic Energy Commission, Report ORNL-3056, Oak
Ridge National Laboratory, Oak Ridge, Tenn.
6. Griess, J.C., H.C. Savage, J.G. Rainwater, T.H. Mauney, & J.L. English,
1961b, Effect of Heat Flux on the Corrosion of Aluminum by Water.
Part III. Final Report on Tests Relative to the High-Flux Isotope
Reactor, Atomic Energy Commission, Report ORNL-3230, Oak Ridge National
Laboratory, Oak Ridge, Tenn.
7. Griess, J.C., H.C. Savage, & J.L. English, Effect of Heat Flux on the
Corrosion of Aluminum by Water. Part IV. Tests Relative to the Ad-
vanced Test Reactor and Correlation with Previous Results, Atomic Energy
Commission, Report ORNL-354l, Oak Ridge National Laboratory, Oak Ridge,
Tenn.
8. Gutzeit, J., 1965, Corrosion and Fouling of Admiralty, Aluminum, and

Steel Tubes in Open Recirculating Cooling Water Systems, Materials
Protection, Vol. 4, July, pp. 28-34.
9. Kern, D.Q., & R.E. Seaton, 1959a, Remedy for Equipment Fouling: High,
Constant Water Velocity, Chemical Engineering, Vol. 66, August, pp.
126-128.
10. Kern, D.Q., & R.E. Seaton, 1959b, Sur face Fouling: How to Calculate
Limits, Chemical Engineering Progress, Vol. 55, No. 6, pp. 71-73.
@ProcessEng
11; Knudsen, J.G., 1981, Apparatus and Techniques for Measurement of Fouling
of Heat Transfer Surfaces, in Fouling of Heat Transfer Equipment, pp.
57-81, edited by E.F.C. Somerscales and J.G. Knudsen, Hemisphere Publish-
ing Corporation, Washington, D.C.
635
12. MeAliister, R.A., D.H. Eastham, N.A. Dougherty, & M. Hollier, 1961,
A Study of Scaling and Corrosion in Condenser Tubes Exposed to River
Water, Corrosion, Vol. 17, pp. 579t-588t.
13. Parry, D.J., D. Hawthorn, & A. Rantell, 1981, Fouling of Power Station
Condensers within the Midlands Region of the C.E.G.B., in Fouling of
Heat Transfer Equipment, pp. 569-586, edited by E.F.C. Somerscales
and J.G. Knudsen, Hemisphere Publishing Corporation, Washington, D.C.
14. Ritter, R.B., & J.W. Suitor, 1976, Fouling Research on Copper and Its
Alloys - Seawater Studies, INCRA Project No. 214A (January 1974-February
1976), Heat Transfer Research Ine., Alhambra, Calif.
15. Smith, C.L., R.W. Pike, & P.W. Murrill, 1970, Formulation and Optimiza-
tion of Mathematical Models, International Publishing Co., Scranton, Pa.
16. Somerscales, E.F.C., 1981, Introduetion and Summary: The Fouling of

Heat Transfer Equipment, in Fouling of Heat Transfer Equipment, pp.
1-27, edited by E.F.C. Somerscales and J.G. Knudsen, Hemisphere Publish-
ing Corporation, Washington, D.C.
17. Somerscales, E.F.C., & M. Kasserni, 1984, Fouling Due to In-Situ Corro-
sion Produets, in Fouling in Heat Exchange Equipment, pp. 1-9, edited
by J.W. Suitor and A.M. Pritchard, American Society of Mechanical
Engineers, New York, N.Y.
18. Somerscales, E.F.C., T.E. Dugan, & S.T. Tse, 1985, Corrosion Fouling
on Aluminum Heat Transfer Surfaces, in Proceedings: Condenser Bio-
fouling Control-State-of-the-Art Symposium, pp. 2-87 to 2-96, edited
by W. Chow and Y.G. Massaili, Electric Power Research Institute, Palo
Alto, Calif.
19. Somerscales, E.F.C., D. Bahar, & T.C. Gilgert, 1986, A Sensitive Tech-
nique for the Detection and Measurement of Fouling Deposits in Liquid-
Cooled Multi-Chip Modules, ASME paper No. 86-HT-7, presented at the
Joint AIAA/ASME Thermo-physics and Heat Transfer Conference, Boston,
Mass., June 2-4.
20. Somerscales, E.F.C., 1987, Fundamental Ideas on Corrosion Testing in

the Presence of Heat Transfer, Brit. Corr. J., Vol. 21, pp. 213-220.
21. Wilson, E.E., 1915, A Basis for Rational Design of Heat Transfer Appara-
tus, Trans. Arner. Soc. Mech. Engrs., Vol. 37, pp. 47-82.
@ProcessEng
AVOIDING FOULING AND CORROSION IN WATER COOLED HEAT EXCHANGERS: THE EXPERT
SYSTEM APPROACH
ALLEN E. FELTZIN'~*, HARVY GARCIA1', and ALBERTO L LACAVA'~
*,~ Airco Industrial Gases, 575 Mountain Avenue, Murray Hill, N.J. 07974
,~ The BOC Group Inc., Group Technical Center, 100 Mountain Avenue, Murray
Hill, N.J., 07974
1 .INTRODUCTION
Traditionally, cooling water treatment for open recirculating industri-
al systems involves control of four areas: corrosion, mineral scaling, fou-
ling, and biological growth. In air separation plants, over half the cos t of
production is associated with electrical power requirements to drive multi-
-stage compressors. Clean heat transfer surfaces on interstage gas coolers
are essential to efficient operation. Maintenance (cleaning) of heat trans-
fer equipment represents a penalty in terms of lost production·and increased
labor.
The four areas of water treatment control mentioned above may be re-de-
fined af ter Epstein (1) as specific types of fouling:
Corrosion Fouling
Precipitation Fouling
Particulate Fouling
Biological Fouling
Each of these will be discussed briefly, along with methods of treatment
and monitoring techniques. A computerized "expert system" serves as a useful
tool to integrate the myriad data from the monitoring programs, provide a
diagnosis, and organize a logical stepwise approach to problem solving.
1.1. Corrosion Fouling
In near neutral, aqueous environments typified by most cooling waters,
corrosion of mild steel or copper alloys proceeds by:
a) dissolution of metal at the anode, MO~MZ+ Ze-
Z = 1, copper = 2, iron
b) reduction of molecular oxygen and production of hydroxyl iron at the
cathode: O2 + 2 H20 + 4e- _4 OH-
By application of suitable corrosion inhibitors (chromates, molydbates,
phosphates, azoles, etc.) one or both of these reactions is stifled (but not
eliminated) by formation of a tight, protective film. Relative to the uninhi-

bited case, successful inhibition can reduce corrosion rates by 2-3 orders
of magnitude.
In the case of steel corrosion, the locally high pH at the cathode ul-
timately precipitates iron trihydroxide which forms a "tubercule" over the
anode. The Fe+ 3 generated by in situ corrosion and subsequent oxidation may
precipitate with orthophosphate.-rn-moderate and high hardness waters, cal-
cium is also usually present as a major constituent of these deposits.
@ProcessEng
Using nominal 12 inch pipe as an example, and assuming no transport of

iron out of the system, a corrosion rate of 1 mill per year (1 mpy) equates
to a deposit weight of 40 pounds of iron per 1,000 ft 2 of pipe wall.
Feed of polyphosphate based inhibitors must be carefully regulated, and
system retention times of 3 days are not recommended if revers ion to ortho-
637

638
phosphate is to be controlled.
Monitoring methods consists of corrosion coupons, instantaneous corro-
sion rate meters, test heat exchangers, usually with steam as the process
fluid, and corrosion monitors od the type described by Knudsen (3). The prin-
ciple of operation is essentiaIly that of using an electrically heated, con-
centric rod fitted to close tolerances inside a specimen tube which is gene-
rally of mild steel, admiralty brass, ar stainless steel metallurgy. Cooling
water, (preferably warmer return water) circulates through an annulus formed
by the outer surfaee of the tube and the inner surfaee of a surrounding glass
jacket. Both flow rate and voltage to the heating element are control led to
simulate conditions in a gas intercooler with water on the shell side. (Fi-
gure 1).
1.2. Precipitation Fouling
This form of fouling initiates in the bulk water and is a crystalliza-
tion of substances exceeding their allowed solubility. Calcium carbonate and
calcium sulphate have inverse solubilities, i.e., they precipitate preferen-
tiaIly on hot surfaces. Magnesium silicate scales, which form from adsorption
of silica into magnesium hydroxide, ean be extremely tenacious, requiring hy-
drofluoric acid or mechanical abrasion for removal (4). Control of precipi-
tation fouling devolves largely on the use of low molecular weight polymers
and crystal distortion agents such as phosphonates. It is of interest to no-
te that deposits of both calcium acrylate and calcium phosphonate have been
observed where the corresponding scale control agent was overfed.
Unlike inhibitor protective films, which are exceedingly thin (from a
single monolayer to several thousand angstroms), precipitation fouling pro-
duces thick, insulating deposits deleterious to heat transfer. Most deposits
are not particulary adept at stifling corrosion. In faet, they tend to crea-
te differential aeration cells and allow the influx and concentration of ag-
gressive ions such as chloride, which ean cause pitting.
With the trend towards higher pH programs and the tendency towards
higher cycling in cooling waters, the importance of controIling this type of
fouling has increased dramatically.
1.3. Particulate Fouling
This type of fouling encompasses contamination by dust and debris, bio-
logical and scale deposits which have sloughed off from elsewhere in the
CorrosiOD Monitor
GtASS JACKETED
SPEClMEN
HOLDER
ELECTRICAL
HEATING
mnmm~~~~~~~~~~~~fflFmm~~~D
ROTAMKTER
@ProcessEng
FIG. 1.
639
system - in short, deposition of material aIready present as a solid in the

water. In air separation plants, the gas pressures at higher stages ofcom-
pression require the gas to be on the tubeside for reasons of economics.Most
oxygen service has gas on the tubeside. Rence, with cooling water on the
shell side, air plants are susceptible to particulate fouling aggravated by
low folw conditions. The most common method of control is mechanical filtra-
tion; sidestream sand or multi-media filters are generaIly sized for 4-7% of
the cooling tower recirculation rate. If greater accuracy is desired in cal-
culating sidestream requirements, the folIowing may be used:(2)
F = ~~~~ = ~~ x BD B~ ~~~:~~~a(t~~~~) :~:

(existing SS - desired SS) x 100
SS = suspended solids, ppm R
existing SS
Cyclone or centrifugal separators can also be employed. Centrifugal se-
parators require that the contaminant to be removed be heavier than water
and particle size removal is down to ca. 70 microns. Sand filters will remo-
ve down to ca. 50 microns and multi-media, because of higher flow rates per
sq. foot, can approach 8 microns. In the chemical realm, charge repulsion
type polymers and surface active agents have been applied successfully, but
the surfactant may require the use of a defoamer in conjunction. Usually,
suspended solids loading before and af ter the filter is periodically che-
cked to monitor performance. Reated tube monitors similar to the corrosion
monitor described earlier have also been employed. By using multiple tubes
in series, exchangers with high water inlet to outlet temperatures may be
simulated (5).
1.4. Biological Fouling
This type of fouling occurs as aresult of system contamination by al-
gae, aerobic and anaerob ic bacteria, and fungi. In recent years, it has be-
come recognized that there is a fundamental difference between floating
(planktonic) bacteria and adherent (sessile) bacteria in terms of their res-
ponse to biocides. Sessile bacteria play a key role in mettalic corrosion,
which is foundto occur in highly organized microbial communities. Anaero-
bic sulfate reducing bacteria can thrive underneath thick biofilms formed
by aerobic bacteria which serve to exclude and consume oxygen (6). Biologi-
cal control is addressed by the use of many different biocides, which are
grouped into two major categories: oxidizing and non-oxidizing. Chlorine gas
or sodium hypochlorite (bleac~ react in water to form hypochlorous acid, a
strong oxidizing agent, which is not selective as to the organic species it
will attack or combine with. Rence, in high demand systems, such as those
contaminated by oil or ammonia, it may be uneconomical to feed enough chlo-
rine to take care of the biological matter. Non-oxidizing biocides such as
isothiazolin, methylene-bis thiocyanate, and organo-tin compounds can be
effective; each has their own special technology of application.
The most common (and easiest) monitoring method for biological activi-
ty is still based on planktonic bacterial counts, and that is, to use an
agar coated dip slide and incubation. Sessile monitoring by techniques such
as the Robbins device (7) have recently become available.
1.5. Approach Temperatures
In an air separation plant, one of the simplest, yet most important
items of information is the cooler approach temperature, i.e., the differen-
@ProcessEng
ce between the gas discharge temperature from the cooler and the cooling wa-
ter supply temperature. Gas intercoolers are general ly designed for an ap-
proach of between 7 and 15 0 F. If fouling is present in any form, the approach
temperature will rise once the normal fouling alowance has been exceeded.
GeneraIly speaking, a 5 0 F rise in approach will incur a 1% power penalty on
640
the next stage of compreension. Multi-stage air and nitrogen compressors for
air separation plants are typically in the 5,000-20,000 HP range. Each gas
cooler approach is logged at least daily. A summary of representative data
input from the total cooling water system follows:
1.6. Control Program (Measurement of Proces s Variables)
Specific methods of monitoring are used to assess the degree of control
attained in the four general areas aiready reviewed.
This involves a multi-faceted approach. A general representation of the
data required is shown in the Table 1.
From this introduction, two things immediately become clear:
- The phenomena are interactive and overlapping. A biological condition
promotes corrosion, biological films can trap suspended solids, corro-
si~n products can form precipitates with inhibitors and dispersants,
etc.
- The variety of data that can be gathered from all of these monitoring
techniques requires intelligent organization and a method of drawing
correct inferences to optimize water treatment control.
2. EXPERT-COMPUTER-USER INTERACTION
Water treatment is a complex, expert-based science. A detailed knowle-
dge of the delicate chemical and physical balance of the system is required
for the development of economical water treatment programs which will pro-
tect heat transfer surfaces and distribution piping.
Of course, experts are a scare, valuable resource whose skilis are
usually required in many other endeavors in any company. It would be imprac-
tical to have a cooling water treatment expert in every plant.
TABLE
Monitoring category Minimum Frequency

COBROSg,l
-Corrrosion rales Irom admlratty or mild steel 1 set every 60 davs .
coupons and heated lube specimens. Visual inspection weekly.
- Inslanlaneous corrosion rate readings (corrater) Inlermillenl.
APPROACH lEM'ERADJBES Logged daily
PARTICULATEEQUUNG
-Suspended solids checked in and out ol . Every 60 days
sideslream fitter.
pREClprrAI!ON EQULlNG
- Visual inspection ol appearance ol healed lube Onæaweek
specimen, sighl glasses, ooollng lower deck.
BIO!.OGICAL FOUUNG
- Aerobic bacteria counls (dip slide). Onæ/Momh
- Visual inspection ol lower. Onæ lweek
CHEMlCAL ANALYSES
- Conductivity
Calcium hardness
pH
@ProcessEng
Inhibitor level no
Frae chlonne
Chlorides As. required
Silica - lrøn - Copper
641
This is precisely a situation for which expert systems provide invalua-

ble help. An expert system can simulate a human expert, performing water
treatment diagnoses and recommending procedures to bring the system to nor-
maloperating conditions.
In order to achieve this, water treatment expertise has to be program-
med into the expert system knowledge base. A user, typically an operator or
a plant engineer, "consults" the expert system at the plant to troubleshoot
the cooling water system.
This approach has been followed by the authors in selected plants that
AIRCO operates in the USA. This paper surnmarizes the approach and the expe-
rience with this application of Expert Systems.
3. EXPERT SYSTEMS
Knowledge oriented programs have been one of the most popular applica-
tions of artifical intelligence. Several research groups have built specia-
lized systems to solve problems in medicaI diagnosis and treatment, identi-
fication of chemical structures, geological exploration, and equipment trou-
bleshooting among others (8).
These programs, know as Expert Systems, allow computers to simulate the
human reasoning process, handling incomplete information and heuristic know-
ledge, enabling people to analyze complex problems and make decisions.
Expert Systems serve as a tool for efficient problem solving and augment
the capabilities of the end user while providing training and education. A
computerized consultative system can hel p to de-skil l the task and dissemi-
nate information.
A typical session with a knowledge based system simulates a consulta-
tion with a real expert in the fieId. In response to a set of program
prompts, data has to be provided. This information is used to restrict the
initial solution search space to a few possibIe solutions within a domain
or context and to set some goals that will allow the search to proceed fur-
ther. Simulating the human expert, the computer will try to narrow the solu-
tion space by asking additional information or evidence, increasing the cer-
tainty of some goals and rejecting others in proportion to the amount and
quality of new information provided.
The user may interrupt the session at any time to ask WHY the program
is asking for a particular piece of evidence or HOW a particular conclusion
was arrived at, making this interactive process a very formative experience.
3.1. The Approach Used In The Present Work
In order to perform cooling water treatment troubleshooting, informa-
tion has to be given to the expert system. The information provided to the
expert system considered here was surnrnarized in Table 1.
Figure 2 gives an overview of the expert system operation.
Results from chemical analysis, the corrosion monitor, corrosion cou-
pons and visual inspection of the cooling tower are entered into the expert
system. The inference eng ine scans the knowledge base to produce a diagnos-
tic of the situation. There are four possibIe outcomes:
- Modification of Control Parameters: The expert system recornrnends that
the setpoint of plant controllers be adjusted to return the plant to
normaloperating conditions.
- Recalibrate instruments: The expert system has determined, through
internal checks, that one or more instruments may be out of calibra-
@ProcessEng
tion and should be re-calibrated.

- Insufficient Data: Additional tests are required to reach a conclu-
sion. The expert system asks for specific analyses.
- Normal operation: The plant is under control and no change is requi-
642
TROUBLESHOOTING
FIG. 2. Expert systems operation
red at the moment.

In building the expert system, a commercially available program was
used as a "sheIl". The "sheIl" contains most parts of the expert system
with exception of the knowledge base.
The knowledge base, composed of "if" ••• "then" rules, was based upon the
fault tree of the cooling water treatment system. Examples, based on frag-
ments of the tree are given next, to illustrate the operation of the expert
system.
4. FAULT TREE ANALYSIS

To illustrate the analysis and knowledge structure of the expert system,
which is stored in the form of rules, two examples have been selected. This
structure comprises a "fault tree" of deductive reasoning or logic. Portions
of the fault tree have been represented in Figures 3 and 4.
CYCJ.&
HIGH
INCOMPLETE
@ProcessEng
INFORMATION
CONTROLLER TO ANALYZE
CALIBRATED CONTROLLER
REDUCE CYCLES PERFORMANCE
FIG. 3. Failure Analysis on Conduc,tivity Controller

643
TOTALCYa.ES
TEST
=
NOEVIDENCE
OF PREClPITAnON
FIG. 4. Phosphate Analysis Fault Tree
The first example shows the failure analysis for a conductivity control-
'ler out of calibration. In the second example, the procedure to verify de-
composition of phosphate based inhibitors is illustrated.
4.1 •. Example One
4.1,.'1. Importance of Conductivity Controller Calibration
The conductivity control ler maintains the level ,of dissolved chernicals
in the system by blowdown discharge of a stream of circulating water. When-
eve r conductivity readings fall outside of the specified control range, the
blowdown is adjusted to increase or decrease concentration of dissolved so-
lids.
It is 'clear then, that the conductivi,ty controller plays an important
role in keeping proces s economicswithin expected ranges by direct manipula-
tion of the concentration of dissolved solids. Continued deviations will ha-
ve repercussions in the final cos t of the program.
As a normal operational procedure, the conductivity controller should
be c'<ilibrated at least once a month with standard solution or a reference

meter but this does not guarantee performance. If the system is found to be
out of specification, an experienced wat.er treatment representative would
question whether the conductivity cell is measuring the correct value or
not. Using common sense and a few "ru1:es of thumb" the staus of the control-
ler calibration can be inferred from sys,tem readings.
4.1.2. Detecting Deviations In Conductivity
A part of the mass balance related to water and chemical consumption is
@ProcessEng
the number of times the makeup is concentrated in the system, represented

by the value of cycles and .evaluated using the ratio of concentration sys-
tem/makeup for a given chemical species, typically calcium, chloride, sili-
:ca.
644
Cycles are calculated using both conductivity and ratio of soluble che-
mical species, and it is from this feature that deviations in conductivity
calibration can be detected when comparing numerical results from both me-
thods.
In general, calcium hardness ratio is used to calculate cycles. This
value can be used to compare evaluation by conductivity. For illustrative
purposes, suppose that cycles by calcium are low, and there is no evidence
of calcium precipitation in the system. Furthermore, as shown in Figure 3,
a high conductivity value has been detected in the controller, hence the
evaluation of cycles using conductivity ratio will also be expected to be
high (based on the fact that makeup water has almost constant characteris-
t ic s) .
If the difference between cycles by conductivity ratio and cycles by
chemical species (calcium) exceeds a certain tolerance, then the indication
is that one of the methods is failing.
At this point, a third calculation can be used to backup initial num-
bers using either chlorides or silica readings and evaluating their respec-
tive cycles.
The agreement (within a specified margin) of one of the results with
this third evaluation implies the failure of the other method by exclusion.
In this example, the value in question is the one obtained from conduc-
tivity controller information. Since this value is probably erroneous, the
logical action to follow is to calibrate the equipment.
4.2. Example Two
4.2.1. Phosphate Analysis
This second example shmvs how the expert system deals with the detec-
tion of potentiaIly severe problems in systems having phosphate as the main
inhibitor.
Polyphosphate is a delicate molecule which suffers a spontaneous degra-
dation process known as recersion, where long polymeric molecular units
break down, generating eventuaIly the monomer constituent, orthophosphate.
In this proces s polyphosphate loses its corrosion inhibition characte-
ristics.
When the system is at optimum conditions, reversion rates are control-
led and the ratio of polymeric phosphate to orthophosphate remains fixed.
The revers ion proces s can be accelerated by different conditions such
as pH upsets, biological contamination, long retention times, or high ther-
mal loads. Generally, phosphate systems work in a moderate alkaline envi-
ronment and can eas ily precipitate in the form of metal phosphates (cal-
cium, iron, etc.) when excessive levels of orthophosphate are present.
4.2.2. Problem Detection And Analysis
The parameter used to detect problems involving polyphosphate is the
concentration of orthophosphate. The procedures for orthophosphate detection
are fairly standard, economical and sufficiently accurate for use in the
fieId.
Additionally, since orthophosphate is the molecule produced by degra-
dation and is the agent involved in scaling situations, it appears to be the
ideal candidate to track potential problems.
When the othophosphate reading is detected out of specification one of
the folIowing problems may be present:
@ProcessEng
a) Polymer Reversion
b) Overfeed/Underfeed Of Inhibitor
c) Precipitation And Scaling
d) Excessive Cycling
The key to identifying the cause of the upset in concentration is pro-
645
vided by evaluating system parameters by eyeles of eoneentration and true

polyphosphate eoneentration.
For example, suppose that a high orthophosphate reading is obtained and
the eyeles of eoneentration are low. At low cycles, the expected concentra-
tion of any dissolved species should be low. The possibility of either over-
feed, or reversion to explain the high level deteeted would then receive mo-
re weight than other eonceivable explanations.
If information on polyphosphate level is available, the possibIe expla-
nation could be as follows:
- For high polyphosphate reading, overfeed of produet is suspeeted and
the high concentration of orthophosphate is eaused by the normal po-
lymeric reversion process.
- For low polyphosphate reading, the excess orthophosphate could be ex-
plained by an increase in the rate of polymer deeomposition.
- If no information on polyphosphate concentration is available the
program will signal what the possibIe causes are (1 or 2) and the
risks assumed if the problem is not evaluated and corrected.
Additional tests will be recommended to reach a conclusion.
5. CASE HISTORIES/DISCUSSIONS
At the time of this writing, some half dozen Airco plants are utilizing
the expert system as an aid to managing their water treatment programs. We
consider her e two examples, whieh show in effeet, that the expert system,
with the same data input, was able to render a more thorough analysis than
that indieated on the corresponding vendor service report.
5.1. Case 1.
The service report shown in Figure 5 was submitted by the vendor and
advises the plant to simultaneously increase the blowdown and the feed of
polyphosphate inhibitor. These actions are not in concert, and will have the
effect of wasting chemicals.
Increasing the blowdown will also probably drop the levelof chromate
below its required minimum, resulting in the need to increase its feed as
well. This is a pendulum approach to control.
With the identical data input, the expert system in contrast offers
the diagnosis shown in Figure 6.
CHROMATE POLYPHOSPHATE PROGRAM

SERVICE REPORT
TEST TESTRESULT CONTROL LIMITS
pH 6.3 6.5 - 7.0

Conduetance
micromho.
2100 1600 - 1800
Chromate 15.4 15 - 20
ppm
Phosphate 1.5 2- 4
e:e m
-The pH of the system is low. Please decrease feed of acid.
@ProcessEng
-The Conductivity of the system is High. Please ~

blowdown from the system.
-The phosphate residual is low . Please ~ feed
of phosphate inhibitor.
FIG. 5.Cromate Polyphosphate program - Service Report

646
VALUES BASED ON o - 10 SYSTEM VALUES
1. TIIERE IS NOT ENOUGH INFORMATION TO CALCULATE CYCl.ES 8

AND ANAL VZE CONDUCTIVIlY CONTROLLER PERFORMANCE.
2. IT IS RECOMMENDED TO CHECK BLOWDOWN SYSTEM 8
3. POSSIBLE DEVIATION IN CONDUCTIVITY READING 8
4. DECREASE ACID FEED BY SET POINT ADJUSTMENT IN CONTROLLER. 8
FIG. 6. Expert System Output For Case 1.
It is suggesting that the ratio of cycles by conductivity in both the

makeup and cooling tower be compared with the ratio obtained by calcium or
chloride. Renee, before taking actions which may not be required and which
are mutually incompatible, additional testing must be performed.
The detailed "rule" by which the expert system "reasons" that not
enough information on cycles is available for a valid conclusion is shown
in Figure 7.
The service report in Figure 8 shows several glaring errors and contra-
dictions.
5.2. Case 2.
Cycles by conductivity ratio show 8.3, cycles by hardness are reported
as 6 1/2 - this is in error - the cycle ratio is 5.5. by total hardness, 5.4
by calcium hardness, and 5.1 by chlorides. The observation certainly ought
to be made that the conductivity reading is suspect. A free chlorine res i-
dual of zero also deserves some comment as to cause or rectification.
The Figure 9 is an output from the expert system.
The expert system addresses:
a) The discrepancy in average cycles determined by chemical testing of
hardness and chlorides vs. conductivity measurements.
b) The need to verify whether any chlorine is present by running total
chlorine.
c) The need to adjust pR increasing acid feed slightly.
d) The conductivity controller should be re-calibrated.
RULE NUMBER 58
IF Conductivity is above specification or below specification
2. Conductivity controlIer is assumed out of calibration

3 ChemicaI analysis of makeup and circulating water is not available
THEN There is not enough informalion Io calculale cycles and anaLyze

conduclivily controller performance . probability 9110
2 Levelof confidence on conductivity controller performance
probability ·211 O
3 II is recommended Io check cycles probability 9110
@ProcessEng
4 If you have Io evaluale cycles: Circulaling and makeup waler

analysis is required probability 9110
FIG. 7. Rule Number 58

647
TEST MAKEUP SYSTEM LIMITS
pH 7.0 7.9 7.4 - 7.8
Total Hardness
38 210 300
ppm C.C03
Calcium
ppm C.C03 26 140
14 71
Chloride
ppm Cl
100 830 800

Conductivity
micromhos
I..101ybdenum 9 8 - 10
ppm MoOi
Free chlorine o o
ppm
6.5 CYCLES BASED aN HARDNESS
FIG. 8. Molybdate/Zinc/Azole
As we continue to test the expert system and receive feedback from

plants , the knowledge base will continue to grow and it is estimated that
another 50 rules minimum will beadded within the year bringing the total
to 250.
Ultimately, feedback at the plant level will determine the utility of
VALUES BASED ON o - 10 SYSTEM VALUES
1. Confidence in cycles by chemical tesling has a level 9

2. Cycles evaluation has detected a possibie calibratioD ;problem in 9
conductivity controller.
3. Very low free chlorine detected. It is recommended to run total 8

chlorine test.
4. Calibrate meter probe and/Dr controller with standard solution. 8

Compare with standarization meter read ing.
5. Increase aeid feed by set point adjustment in controller 8

6. Increase chlotination. 7
7. Decrease blowdown by adjusting controller set point. 7
8. Average cycles of concentration based in chemicals = 5.23
@ProcessEng
9. Cycles of concentration based in conductivity = 8.30

10. Difference in cycles by conductivity and c1:lemical analysis = 3.07
FIG. 9. Expert System Output for Case 2.

648
the expert system approach to plant water treatment operations. Initial

feedback thus far has been very positive.
6. CONCLUSIONS
The success of any operating water treatment program depends on the ca-
re and attention given to control of the process variables.
The complexity of the interactive nature of fouling and the amount of
data generated by monitoring requires some system for organization and ana-
lysis.
Analysis requires a certain levelof experience and expertise, applica-
tion of heuristic knowledge, "rules of thumb" , logic, and cornrnon sense.
From examples cited, the expert system ean offer a thorough analysis
consistent with good water treatment applications technology, as would be
expected from an experienced, capable service representative.
The program is not "static", i.e., its knowledge base ean be increased
by addition of rules so that new experiences ean be accornrnodated.
The ultimate utility of the expert system as a tool relies on proper
feedback from plant locations as end users.
REFERENCES
1. Epstein, Norman. "Fouling of Heat Exchangers, Fouling of Heat Transfer
Equipment", P. 795, McGraw-Hill International Book Company, Hemisphere
Publishing Corporation, 1981.
2. TPC Publication No. 1, "Cooling Water Treatment Manual, Section 2 - Depo-
sits, Scale and Foulants", National Association of Corrosion Engineers,
1971 .
3. Knudsen, Jarnes G., "Apparatus and Techniques for Measurement of Fouling
of Heat Transfer Surfaces, Fouling of Heat Transfer Equipment", P. 57,
McGraw-Hill International Book Company, Hemisphere Publishing Corpora-
tion, 1981.
4. Brooke, Maxey, "Magnesium Silicate Scale In Circulating Cooling System",
Paper Number 327, Corrocion '84, April 2-6, 1984.
5. Oberhofer, Alfred W., and Fulks, Kenneth E., "A Cooling Water Fouling
Evaluation Unit", Fouling of Heat Transfer Equipment, P. 95, McGraw-Hill
International Book Company, Hemisphere Publishing Corporation, 1981.
6. Costerton, J.W., Geesy, G.G., and Jones, P.A., "Bacterial Biofilm in Re-
lation to Internal Corrosion Monitoring and Bioeide Strategies", Corro-
sion '87, March 9-13, 1987.
7. McCoy, W.F., Bryers, J.D., Robbins, J., Costerton, J.W., "Observations
of fouling biofilm formation", Canadian Journal of Microbiology, Vol. 43,
910-17,1981.
8. Weiss, S.M., Kulikowski, C.A., "A Practical Guide to Designing Expert
Systems", Rowrnan & Allanheld Publishing Corporation, 1984.
@ProcessEng
FOULING OF GEOTHERMAL ENERGY SYSTEMS
S. H. Chan
Department of Mechanica1 Engineering
University of Wisconsin--Mi1waukee
Mi1waukee, Wisconsin, U.S.A. 53201
1. INTRODUCTION
Like fou1ing problems in general [1-4]. fou1ing remains as one of the
key unreso1ved problems in geotherma1 energy app1 ications. The major
contributors to geotherma1 fou1ing are the sca1ings of si1ica and calcium
carbonate [5,6]. This is as aresult of the fact that si1ica is one of
the primary components of the earth's crust and so are calcium compounds
i n s orne a rea s .
Calcium scaling in geothermal plants is largely driven by pressure re-
ductions through fluid transmission devices such as those produced in
valves, constrictions or flow measuring instruments. When the pressure
of the brine solution decreases rapidly, carbon dioxide gas is evolved
from the brine due to its decrease in solubi1ity. This increases the pH
of the brine which increases the carbonate concentration and causes the
deposition and crystal growth of calcium carbonate. The kinetics of this
reaction are very fast, causing scale formation immediately downstream of
such pressure drops [5]. In some cases this has caused the plugging of
the valves , pressure taps and flow instruments [7]. Since calcium car-
bonate solubility decreases with increasing temperature (retrograde
solubility) , calcium carbonate scale is also found on heated surfaces
such as cooling tower water sca1ing.
Silica scaling is much different. Silica solubility increases with an
increase in brine temperature (prograde solubility). Silica, being satu-
rated in geotherma1 brines in the downho1e environment in the monomeric
state, can become supersaturated as the brine is cooled through the heat
exchanger or when part of the brine is flashed into steam. The supersatu-
ration causes precipitation of silica in an amorphous form on heat exchan-
ger surfaces, separators, well lines and discharged lines.
Analytical modell ing of scale formation in general has been reviewed
recent1y [8-12]. Due to the complexity of the fouling process, no
genera1ized predictive corre1ation for the design of heat transfer equip-
ment has yet been established. Some work has been done on the kinetics
and crystallization [13-17] as well as on modelling and corre1ations of

calcium carbonate deposit formation [18-26]. Though the majority of these
studies are concerned with coo1ing water fouling or fouling in evaporator
and heat exchanger tubes, the fundamental s of calcium carbonate fouling
from geothermal brine shou1d be the same. As to silica scale, the depos-
ition mechanism is more complicated than that of calcium carbonate scale
[27, 28). Its comp1ex kinetics have begun to attract fundamental research
@ProcessEng
recent1y [29-35) and few modelings or corre1ations are available [36-45].

In the following, the recent advances and re1ated fundamentals in calcium
carbonate and si1ica fou1ing are reviewed and summarized.
649
L. F. Melo et al. (eds.), Fouling Science and Technology, 649..<>67.

650
2. DEPOSITION OF CALCIUM CARBONATE

2.1 Solubility of Calcium Carbonate
Calcium carbonate solubility increases with decreasing temperature
[5]. At a given temperature, the solubility of calcite in a solution in
equilibrium with a vapor phase increases with increasing C02 pressure
[35]. Figure 1 shows the solubility surface of calcite in the system
CaC03-C02-H20 at temperatures of up to 300°C and with a C02 pressure of up
to 70 atm [35]. Natural brine often contains significant amounts of other
constituents, like NaCl. The presence of NaCl increases the solubility
of calcite in hydrothermal solutions [35].
2.2 Solubility Product of CaC03
The solubility product of CaC03 is a criterion for the scaling of
CaC03. It is defined by the equilibrium constant for the reaction
.... ++ -
cac0 3( s).... Ca + C0 3 ( 1)
in three possible ways:

K = a C ++ a CO = (2a)
sp a 3
( 2b)
or
(2c)
If the concentration product of ions Ca++' and COj is larger than the
so l ubil i ty product (Ksp), the sca 1e of CaC03 wi 11 occur due to the
supersaturation of CaC03. Otherwise, the solution is undersaturated and
will not form the scale. The solubility product is influenced by tempera-
ture, ionic strength and pressure. Its values can be found in [46].
2.3 Langelier Saturation Index
The Langelier Saturation Index and Ryznar Stabil it y Index can provide
rough indications about supersaturation and potential for forming CaC03
scale. The Langelier Saturation Index (L.I.) is defined as the difference
between the pH of water and the theoretical value of the pH of water satu-
rated with CaC03, denoted by pHs, i.e.,
L. I. = pH - pHs ( 3)
Langelier [47] reported that if the L.I. is zero the water is just satu-
rated with CaC03; if positive, the water is supersaturated with respect
to CaC03 and has a tendency to depos it CaC03 sca l e; if negati ve, the
@ProcessEng
water is undersaturated and has a tendency to dissolve CaC03.

2.4 Ryznar Stability Index
Ryznar tried to give a quantitative index of the amount of CaC03
scale that would be formed by a water at any temperature up to 200°F.
651
The Ryznar Stability Index [48] is defined by

s. I. = 2pHs - pH (4 )
Water is considered scale forming when the index is less than 6.0. The
continued use of this index shows that though lacking any fundamental
justification, it provides a useful guide for practical purposes, but its
highly empirical character should be noted [11]. In the following, models
that can quantitatively predict the scale formation are summarized.
2.5 Quantitative Modelings of Deposition of Calcium Carbonate Scale on
Heat Transfer Surfaces
a. Kern and Seaton Type of Model
The deposition-removal modelof scale deposits introduced by Kern and
Seaton [49-51]
( 5)
was applied by Watkinson and Martinez [18] to model the rate of scale for-
mation when a prepared hard water containing calcium carbonate in dilute
sus pens i on runs through a tube heated by a condens i ng s team on the out-
side. The deposition term was from Reitzer [52] who considered the term
for inverse solubility salts to be dependent on the supersaturation raised
to a power n
td = K (C - C )n/ p (6)
R b s s
where Cb and Cs are theo bulk concentration and solubility, respec-
tively. Assuming the lnverse temperature-solubility relationship,
Cb-Cs = b(T s -T8) with b a constant and expressing the scale-water inter-
face temperature Ts i n terms of the wa 11 temperature , Tw' and bul k
temperature, T8' Eq. (5) becomes
(7)
where T and h are, respectively, the shear stress and heat transfer co-
efficient and where the removal term due to Kern [50] was used. The cry-
sta11ization rate constant as a function of the scale surface temperature
Ts was from an Arrhenius equation,
(8)
The asymptotic fouling resistance was obtained by setting dx/dt o and

was correlated by a least square fit of data to finally yield
@ProcessEng
5 9X10 19 (T -T *)2
. w B *
u2 exp(-17540/T s ) (9)
652
where R1 ~ x/Kf and the superscripts n_n and n*n designate the
average and asymptotic values, respectively. The above can be used to
evaluate the effects of certain variables (u, TB, etc.) on the carbonate
scale formation on the inside of a heated heat exchanger tube with a con-
stant wall temperature.
b. Surface Reaction Control led and Diffusion Control led Models
Before surface reaction and diffusion of ions are discussed, the rele-
vant chemical reaction equations in brine containing calcium and C02
should be mentioned. In the C02-H20 system, their reactions are
based on three equilibria [46)
(10)
(11 )
and
( 12)
At high pH, the dissolved aqueous C02 will mostly remain in the form of
C03: thus calcium reacts with carbonate ion C03 to form the deposition
of calcium carbonate by
++ =
Ca + C0 3 ~ cac0 3(S) (13)
At low pH, most of the dissolved C02 remain in HC03. The overall
mechanism of the deposition is considered to be [21),
which can be obtained by combining Eqs. (11-13).

Due to the complicated phenomena of CaC03 deposition, it is diffi-
cult to derive a set of theoretical equations to describe these phenomena.
However, it is possible to model them by using empirical equations. To
describe quantitatively ionic wall deposition of CaC03, consider two
mechanisms, a convective diffusional mechanism and a surface crystalliza-
tion reaction mechanism. From the data on kinetics of bulk precipitation
[14-17) and of wall deposition [20-23), the most plausible surface reac-
tion model describing ionic wall deposition of CaC03 over a wide range
of pH conditions is:
( 1 5)
where the index i refers to scale-brine interfacial conditions, dictated

@ProcessEng
by the convective diffusion rate.

During the deposition, C03 and C~+ ions have to diffuse from
the bulk fluid to surface to form the scale. If the diffusion rate is
considered to be fast compared to the surface reaction rate, the ion con-
centrations at the interface can be approximated by that of the bulk
653
fluid. Then the rate of scale formation, in accordance with the reaction
controlled model, is simply
( 16)
where the crystallization rate coefficient KR is usually determined

empirically in the form given in Eq. (B).
On the other hand, if the diffusion of ions is slow compared to the
surfaee reaction rate, the scale formation becomes diffusion controlled.
Hasson and Perl [23] have examined the CaC03 fouling on a heated
tube for a water containing Ca++ and HC03 ions which flowed over a heated
tube forming a laminar falling film. Since the pH value is low (between
7.1 to B.2), the diffusion of ions Ca++, HC03, C03 and C02 was consid-
ered, with the ions diffusing from the water toward the tube surfaee for
chemical reaction while C02 gas generated at the surfaee diffusing out-
ward. They obtained the following local deposition flux equation:
( 17)
where the coefficients Cij and the mass transfer coefficients KDI are
given in [23]. The calculated deposition fluxes at the outlet conditions
of the falling film based on Eq. (17) have been compared with experi-
menta l data for 9 test runs and the agreement i s found to be withi n
± 25%.
3. DEPOSITION OF SILICA SCALE

3.1 The Solubility of Silica
Silica exists in both the crystalline and amorphous states [5, 53].
Because many possible ordered arrangements of tetrahedra joined by corners
are possible, silica forms various crystal structures--polymorphs. The
solubilities of the different polymorphs of silica in saturated water at
various saturation temperatures are given in Fig. 2. The solubility of
the polymorphs increases with increasing temperature up to 300·C; af ter
this temperature the solubility decreases. Generally speaking, silica has
prograde solubility. It ean be seen that amorphous silica is more soluble
than quartz at all temperatures, but both exhibit similar temperature
dependencies. The concentration of silica in geothermal brines is
usually controlled by the solubil it y of quartz and downhole temperature
[5,54] so that silica is generally present as quartz [5,54]. However,
under most conditions, it appears that silica precipitates as relatively

pure amorphous silica [5, 30-33] whatever the original silica source may
beo The reason is that the kinetics of quartz crystallization below
300·C is much slower than that of amorphous silica [29].
Since the solubility of silica does not involve ionic quantities, it
is not strongly affected by pressure [55].
Other than temperature , pH and sa l i nit y ean have s i gn ifi ean t effects
@ProcessEng
on the solubility of silica. Figure (3) shows that at low pH, the solu-
bil it Y remains constant, but beyond a limit, the solubility increases
drastically with pH values [35, 56].
When salinity of brine is changed due to the addition of salts in the
pure water, the magnitude of the activity of water decreases and so does
654
the solubility of silica. Figure 4 shows that the solubility of amor-

phous silica decreases as the amount of additional NaCL increases at
various temperatures.
3.2 Proces ses of Silica Polymerization and Physical Phenomena of the
Oeposition of Silica Scale
The high concentration of silica in most geothermal brines causes the
brine solution to become supersaturated when extracted from the well.
This supersaturation is thought to be the main factor in the deposition
of silica scale in geothermal energy processes. Usually, silica precipi-
tates from geothermal brines as amorphous silica or amorphous silicates.
If the supersaturation factor is large, say, 2.5 or higher, homogeneous
nucleation occurs and rapid polymerization and precipitation may follow.
Otherwise, relatively slow heterogeneous nucleation and the deposition of
dissolved silica directly on solid surfaces become the dominant polymeri-
zation proces ses . The product of the latter process is a dense vitreous
s il i ca. At higher temperatures , thi s process may produce sca l e at a
significant rate.
There are two different types of deposition of silica in the Si02-H20
system, namely, the depositions from monomeric silicic acid and colloidal
particles. Monomeric silicic acid forms an impervious glass-like film,
whereas colloidal particles form a porous film, often white and opaque
when dried [28]. The phenomena from both types of deposition are so
complicated that, so far, neither has been modeled successfully to yield
a general empirical equation for predicting the silica deposition in the
geothermal field. In the following, an analytical model recently proposed
by Chan et al. [39] is described.
3.3 A Oeposition Model for Silica Scale
The basis of the analytical model [39] is from a kinetic study by
Bohlman et al. [29] on simulated geothermal brines in an isothermal system
(isothermal in the sense that the supersaturated brine and the deposition
surfaces are at the same temperature). They summarized the kinetic reac-
tion rate of silica deposits by a correlation which shows that the appar-
ent rate constant is independent of system temperature over the range of
60 to 100"C and that the apparent kinetic reaction orders for hydroxide
ion concentration and the supersaturation of Si(OH)4 are 0.7 and 2,
respectively.
Considering that silica scale deposition is probably not diffusion
controlled but instead is surface reaction controlled, the kinetic equa-
tion for an isothermal system [29] may be appl icable to nonisothermal
systems provided provisions are made for thermal-hydraulic effects.
Therefore, Chan et aL [39] proposed that the rate change of foul i ng
resistance due to deposition be given as
m2 "C (18)
kw h
@ProcessEng
where Cb is the bulk concentration of amorphous silica (Si02), CeI is the

equilibrium solubility of amorphous silica evaluated at the scale-brine
interface temperature, and COH- is the bulk molality concentration of
OH- ions in the brine. All concentrations are in units of molality
(m). The reaction order of silica (Si02) can be taken as P = 2, the
655
same as the isothermal system. The other correlation constants, KR and q,

are obtained experimentally as KR = 0.9954 and q = 0.862. As in iso-
thermal systems, the supersaturation and pH effects are explicitly ac-
counted for in Eq. (18). In addition, salinity and thermal-hydraulic
effects can also be accounted for as described below.
Since the surface kinetic reaction is assumed to be the controll ing
mechanism for sil ica deposition, the brine convective diffusion and the
heat transfer from the hotter, supersaturated brine to the cooler deposi-
tion surface should not affect the deposition mechanism. They can, how-
ever, alter the scale-brine interface temperature, Ts ' which in turn
has a direct bearing on the deposition rate because the equilibrium solu-
bil it y, CeI, in Eq. (18) is a strong function of temperature. In other
words, the model proposed here accounts for thermal-hydraulic effects by
evaluating CeI at the interface temperature Ts . Normally, overall
heat transfer coefficients Ui, and the inlet and outlet temperatures of
brine and coolant are measured and reported in the literature [36]. Then
the interface temperature can be deri ved from the simple energy balance:
( 19)
where hi is the brine side heat transfer coefficient, LMTD is the log
mean temperature difference across a heat exchanger and Tm is the mean
temperature of the brine (T m = (Ti in + Ti out)/2).
The salinity effect due to the presence of impurities other than silica
are included in the model by evaluating the equilibrium solubility from
(20)
where Co in units of molality is the equilibrium solubility of amor-

phous silica in pure water at the interface temperature [58], i.e.,
The activity of pure water is one and the activity of water aH O in NaCl
solution can be evaluated from [50], 2
log aH O = -0.0157 ~ I (22)
2
where I is the ionic strength of all ion components in the brine
= ! 1: C,. Z2,. (23)

2 i
with Ci and Zi standing for, respectively, molality and ionic strength of

ion i. The osmotic coefficient for water solutions of NaCl can be found
@ProcessEng
from Ref. 59 which provides a table of the coefficient as a function of

temperature and salt (NaCl) concentration. The salt concentration can be
replaced by the ionic strength of the brine if all the ions in the brine
are assumed to have the same effect on the osmotic coefficient as NaCl
salt.
656
To include the effect of sal inity on the concentration of hydroxide

ions, COH- in Eq. (18), COH- is calculated from
log C = log Q + pH + log y (24)

OH- W H+
Qw is the disassociation quotient of water which is a function of tem-
perature and ionic strength [60]. The molal activity coefficient of H+
ion is calculated from [61],
( 25)
with
where & is the dielectric constant of pure water [62, 63].

The density of the brine solution is evaluated from
Pb = Pw + 0.0073 wto (1+1.6 x 10- 6 Tc 2)
with weight percentage, wt, calculated from the total dissolved solids
(TOS). Finally, it is noted that Tc and T in the above equations are
evaluated at the interface temperature Ts in units of °C and oK,
respectively.
In general, foul ing curves can be classified into three types--the
linear, falling rate, and asymptotic types. For the linear type, the de-
position model given by Eq. (18) seems to be sufficient. As to the fall-
ing rate and asymptotic types, the deposition term has been modified and
the removal term has been added [68] as
(26)
and
( 27)
where Re is the Reynolds number. The complete model for the rate change
of fouling resistance can then be calculated from
@ProcessEng
m2 °C (28)
kw h
Again, the reaction order is taken as 2, Le., p = 2. Other correlation
constants are k1 = 1.65, k2 = 0.94, k3 = 2.34 x 10-9 , a = 0.005,
657
b = 4 and q ~ 0.1 As to be seen later, the model 's predictions agree with
experimental data of fouling resistance induced by synthetic brines.
3.4 Experimental Results of Geothermal Brine Fouling

Several previous investigations have reported experimental results for
fouling heat transfer with geothermal brines in tubular heat exchangers.
Tests of two ten foot (3.05 m) horizontal one inch (2.54 cm) titanium
tubes were run for 92 hours and showed a &0% loss in heat transfer coef-
ficient [42]. Vertical stainless and carbon steel tubes of 1/2" O.D., 18"
long using natural and synthetic brines were tested [&4]. Little scaling
resulted when the brine was kept in the liquid phase. A test of four, 20
foot long she 11 and tube heat exchangers us i ng l" t itan i um tubes wa s re-
ported using natural brine [37]. In most instances, linearly increasing
fouling resistance was observed due to a silica based scale. Experiments
with twenty foot long horizontal double pipe heat exchangers were made and
the observed linear fouling rates were used to design a 5 MW demonstration
plant [&5]. Studies [3&] conducted in Icel~nd were performed at two sites
with heat exchangers of the same design but differing flow conditions.
At one site, linear fouling was observed but an induction period was in-
dicated at the other site. Geothermal testings in Taiwan [&&-&7] indi-
cated that s il i ca concentrat i on i n bri ne seemed to be undersaturated and
time dependent, possibly influenced by heavy rainfa11, and that little
fouling was found in the heat exchanger for most of the time.
An extensive study of fouling with synthetic brines on horizontal, six
foot long, 1/4 inch titanium pipes was conducted at Oak Ridge National Lab
(ORNL) and reported by Bohlman et al. [45] The heat exchangers were
operated i n seri es and overa 11 therma l res i stances were reported whi ch
varied widely from exchanger to exchanger.
These results are far from conclusive. The complexity of geothermal
brine fouling needs a systematic, comprehensive series of experiments to
study parameters of importance, the number of wh i ch i s staggeri ng, i n-
cluding various chemical, material, thermal and hydraulic variables.
Recently, a geothermal brine loop has been designed and built in the
Geothermal Test Laboratory at the University of Wisconsin--Milwaukee
[39-41] to investigate the effects of silica supersaturation, brine pH,
Reynolds number and contents of sodium, chloride and other ions on forma-
tion of silica scale. The entire loop system is made of corrosion re-
sistant materials which are capable of withstanding the high pressure,
high temperature and corrosive environment that is associated with a
geothermal brine energy system. The loop is heavily instrumented to
yield both overall and local fouling resistances for all experiments.
The results of five typical experiments using synthetic brine are
presented in Figs. 5 and &. The thermal hydraulic conditions and chemis-
try for each run are given in Tables l and 2, respectively. Runs A to C
used distilled dionized water at a pH of & and a variation in NaCl con-
centration. Runs D and DO used sodium acetate as a buffer to change the
pH of the brine to above 7.
In comparing the results of these runs the effect of sodium chloride
concentration wi11 be examined first. In runs A, B and C, the NaCl con-
@ProcessEng
centration varied from 0.0,0.1 to 1.0 molar, respectively. The linear

fouling rates (Table 3) indicate a nonlinear relationship between the
NaCl concentration and fouling rate. This is unexpected. One would
expect the fouling rate to increase with concentration. One explanation
for the higher fouling rate in run B could be the higher pH of &.8. Since
pH is a major variable affecting fouling, it may overshadow the NaCl con-
658
centration. Another explanation might be that the tube was not chemically
cleaned prior to runnlng. Therefore, silica nucleation sites could have
been present prior to the experiment, which would accelerate the fouling
process. Run B may have to be repeated because of these factors.
The effect of pH is not completely clear at this time, since runs D
and DO (pH above 7) had asymptotic fouling rates while those with a pH
below 7 had linear fouling rates. However, a comparison of run B to runs
A and C would indicate that a higher pH increases the fouling rate as
described earlier.
To demons trate the effect of Reynolds number, run s D and DO can be
compared. If the data between 20 and 100 hours is ignored in run DO, both
curves have the same shape. However, the asymptotic fouling resistance
in run DO is 4&&% higher than that of run D (see Table 3). This corres-
ponds to a 32% lower Reynolds number in run DO. Therefore the lower
Reynolds number increased the fouling rate in this brine chemistry. This
would confirm Wahl's [&4] conclusion and refute others [3&, 42].
The characteristic shapes of the fouling curves show an induction
period for the runs with NaCl and an initial drop in resistance for the
run s with NaAc. With the exception of TT1B (the induction period of which
is not as clearly defined as others with a spoon shape), experiments C, D
and DO show that the induction period is reduced as pH increases, in
agreement with the batch type of experiments [31,34]. The initial drop
in resistance was reported in [3&,45]. It is explained as an initial en-
hancement in heat transfer caused by scale induced turbulence which is
eventually overcome by the increasing thermal resistance of the deposit.
All curves then proceed with increasing fouling functions, i.e., linear
or asymptotic.
Figure & shows the transient local thermal fouling resistance at dif-
ferent locations in the heat exchanger for run TT1-0. This has the same
shape as the Hl-o overa 11 curve i n Fi gure 5. In compari ng the curves,
there is a drop in the rate of change and in the asymptotically achieved
value of resistance at 148 hours, as the heat exchanger length (this re-
fers to distance from the inlet of the heat exchanger) increases. Figure
7 is a graph of the asymptotically foul ing resistance at the end versus
heat exchanger length. The asymptotic value of resistance is reached
faster at the exit than at the inlet locations. For other runs, the local
curves have the same shape as the overall curves. For example, for the
runs without NaAc (TTlA to TTlC), both local curves and overall curves
appear to be linear. From a regression analysis undertaken to obtain the
local fouling rate (dRfi/dt). it is found that the fouling rate de-
creases with a decrease in heat exchanger length. Figure 7 also shows the
variation in fouling rate versus heat exchanger length for run Hl-C.
This contradicts the findings that fouling was heavier at the exit [3&].
A quantitative analysis of the scale was carried out by removing the
deposit from the heat transfer surface with a high pressure water jet.
The major component of the scale in all runs is silica, in agreement with
a survey of brine scales made by Wahl [5].
Even with the high sodium and chlorine content of runs B and C little
of these constituents was found in the scale. However, their presence in
the brine makes a great difference in the fouling rate as seen in Table 3.
@ProcessEng
3.5 Comparison Between Analytical Predictions and Experimental Results

The analytical model given by Eq. (18) is used to correlate or to pre-
dict silica fouling from natural and synthetic brines. The data and ex-
perimental conditions of silica deposition rate on heat transfer surfaces
659
at two geothermal fields in Iceland as reported in [36] appear to be of

sufficient detail that meaningful calculations can be made to incorporate
supersaturation, pH factor, salinity and thermal-hydraulic effects in the
model.
Figure 8 shows that the experimental deposition rates of silica from
both fields can be correlated surprisingly well by Eq. (18). As discussed
before, a second order of reaction for dissolved silica (i.e., p = 2) has
been assumed. However, the comparison of the analytical calculations with
the synthetic brine data is much less satisfactory (see Figs. 5 and 6).
However, the comparison of analytical calculations based on Eq. (18) with
synthetic brine data is satisfactory only for the linear type of profiles
(see TT1-B and TT1-C in Fig. 5) but not the ones with asymptotic behavior
(TT1-D and TT1-DO). The latter can nevertheless be predicted better by
the model described in Eqs. (26-28). A representative comparison is shown
in Fig. 6 where comparisons are made with the six detailed local fouling
resistances at various locations on the heat exchanger of run TT1-D.
4. CONClUSIONS
An extensive review and a survey have been made regarding the funda-
mental information relevant to silica and calcium carbonate deposition in
aqueous solution. Recent advances in analytical mOdelling and experimen-
tal measurements of both types of scale deposit have also been reviewed
and discussed. Comparisons between analytical predictions with existing
data are encouraging but are not yet all satisfactory. Due to the complex
nature of geothermal fouling and because relatively few quantitative mea-
surements are available, continuation of systematic measurements wi 11 be
helpful to further refinement of fouling models.
ACKNOWlEDGEMENT
This research was sponsored by the National Science Foundation (NSF
C8T-8311788-02).
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!iB. iyznar,. J. W., "'P. !lJ0~,j lr,!lex for Determinlng Amm.mt of Calcium Car-
i~lla'te :"c:c,le Formed by a Water, OD J0utnal--tlmerh:a Uater Works As-"
, Vc1. 3~.1944, . 412-486.
"9. : ",r:1, S".B'ton. L, "S,Jrface foul in!;1'"'-r'ow te Ca1t1.iJEile
Cli~mh:al neetll1\J ress, \!l(l;. 55, Nr.
50. KerIl, . 2nd S~~atm" IL iL, ;"1'1 Heoretita ,i\!nalysls of HJGT'i::<il

:Surface rC!ll ng, il 3dtish Chemicai iEng1neeH1Clg, \~o'i. 4,
. 25J-":62.
51. Kern, l}. ., i'heat Exchanger lJes"lgn for l'ounng Service," Ci,em'lcal
Eng1neer1ng Progress, Vol. 62, No. l, 1966, PD. 51-56.
52. Reitzer, B. J., "Rate of Scale Formation 1n Tubular Heat [xchanger,"
:1 It: C:'Ct'ocess Ges'lgn and !}evelopment, \101. 3, No. 4, ~%4"
pp. 345-348.
53. Krauskopf, IC B., "Dissolution and PrecipHation of Silica at Low
Temperature," Geochimica et Cosmochimica Acta, Vol. lO, 1956,
pp. -1-26.
54.-1offmann, !'L "O "Brine Cnemistry-Scaiing and Corroslon---,Seothermal
:'!$eBrC~ Stud)! in the Salton Sea Region Df Ca~1fornia.· Env'ronmenta
Cua11ty Laboratory. California Instttute Df Technology. EOL MEMORAN-
;~.ljM No. 14, 'J975.
55. :11 i il ro, F. J .• "The Effect of Pressure on tne Solubiiity of MineralS
io ltJater and Seawater," Geochimica et Cosmochimica Acta, Vol. '~!i,
982, PP. 11-22.
56. Okamota, G., Okura, T. and Goto, K., "Properties of Silica in Water,"
Geochimica et Cosmochimica Acta, Vol. 12, 1957, pp. 123-132.
57. Chen, CoLA. and Marshall, W., "Amorphous Silica Solubilities IV.
Behavior in Pure Water and Aqueous Sodium Chloride, Sodium Sulfate,
Magnesium Chloride, and Magnesium Sulfate Solutions up to 350°C,"
Geochimica et Cosmochimica Acta, Vol. 46, 1982, pp. 279-287.
58. Fournier, R. P. and Rowe, J. J., "The Solubility of Amorphous Silica

in Water at High Temperatures and Pressure," American Mineralogist,
Vol. 52, 1977, PP. 1052-1056.
59. Lin, C. and Lindsay, W. T., "Thermodynamics of Sodium Chloride Solu-
tions at High Temperature," J. of Solution Chemistry, Vol. l, No. l,
1972, pp. 45-69.
60. Busey, R. H. and Mesmer, R. E., "The Ionization of Water in NaCl
@ProcessEng
Media to 300°C," J. of Solution Chemistry, Vol. 5, No. 2, 1976,

pp. 147-152.
61. Truesde 11, A. H. and Jones, B. F., "Water, A Computer Program for
Calcu1ating Chemica1 Equilibria of Natural Waters," J. Research U.S.
Geol. Survey, Vol. 2, No. 2, 1974, pp. 233-248.
663
62. Malmberg. C. G. and Maryott. A. A., "Dieleetric Constant of Water

from O· to 100·C," J. of Research of the National Bureau of Stand-
ards, Vol. 56, No. l, 1956, pp. 1-8.
63. Akerlof, G. C. and Ashry, H. I., "The Dieleetric Constant of Water
at Hi gh Temperatures and i n Equil ibri um with Its Vapor," Am. Chem.
Soc. J., Vol. 72, 1950, pp. 2044-2847.
64. Wah1, E. F., Yen, l. K. and Bartel, W. J., "Silica Sca1e Control in
Geothermal Brines," Office of Saline Water, U.S. Department of Int.,
Washington, D.C., #14-30-3-41 1974.
65. Mines, G. L. and Neill, D. I., "Analysis of Raft River Heat Exchanger
Fouling Data Using a Multivariate Regression Technique," EG' & G.
Ine., Idaho Falls, Idaho, 1978.
66. Chou, S. F. and Lin, C. C.• "Transient Fouling Heat Transfer in
Geotherma l Energy, " Proceed i ngs of 1982 Sympos i um on Transport
Phenomena and Application, Taipei, Taiwan, 1982, pp. 14-27.
67. Chou, S. F., "An Experimenta l Study on the Geotherma l Foul i ng i n
Heat Exchanger ," Proceed i ngs of 1985 Sympos i um on Transport Ph eno-
mena and App1ications, Taipei, Taiwan, 1985, pp. 184-189.
68. Chan, S. H., Zhou, D. Z., and Neusen, K. F., "An Ana1ytical Modelof
Si1ica Fou1ing," To be presented at the National Heat Transfer Con-
ference, Pittsburg, PA, August 9-12, 1987.
TABlE l - Thennal Hydraulic Conditions i n Foul i ng Experiments
Run # Reb Tbin fl Tbout 2 Te in Tcout2 Mbgal/min. Mc Uo(t=O) ttp hr

TTl-A 73.130 330.0 254.5 160.7 162.6 4.15 169.5 478.2 150
TTl-B 77 .500 327.8 254.1 159.6 161.6 4.30 168.5 477 .1 133
TTl-C 75.790 329.3 256.0 160.4 162.3 4.21 167.8 460.5 193
TTl-0 76,150 328.7 256.6 161.4 163.3 4.23 168.9 459.3 148
TTl-00 51,920 330.8 241.5 159.3 161.4 3.00 110.0 397.5 193
1. 5ubscrlpts: b = brine; c = eoolant; 2. At beginning of run; 3. Reb based on

Di. Tb and w~ter prope,ties. Uo In StUI/H' ft 2 F; 'tp = test period.
TABlE 2 - Ch ... le.l C_o,Jtlon lo Foul1'Q 'xp.. I ..,nts
TABlE 3 - Cemparlson of Foullng Beha.ior

51021 NaC1 2 NaAe \'OS3
Run I pH
H1-A 0.0111 5.9 670

(670) Characteristic Percent
fou11ng 1ncrease Pf kf
H1-B 0.009B 0.1 6.8 &440 behavior in bp across Btu . Ib
(590) ( 58500) Run # and I/alue heat exchanger hr.ft 4 .hr
H1-C 0.0095 1.0 5.B 59070

(570) ( 58500) TTl-A Linear 0.227 1 o
TTl-B Linear 3.489 1 lOO 19.52
H1-0 0.0109 0.1 7.l 14250 Hl-C Linear 1.314 1 64 11.79
(660) (13610) TT1-0 Asymptot i c 2. SOl 193 54.24
@ProcessEng
711-00 Asymptotic 14.16 2 317 24.7B

Hl-DO 0.0113 0.1 7.4 14290
(680) (13610)
1Unear Fouling Rate (hr. ft2 . F/Btu/hr) x 10- 6
2Fou11ng Re,lstanee at End of Run (hr. ft 2 . F/Btu)
1. Saturation concentrat1on. 2. Units of Molarlty and x 10 4
(ppm) 3. Total dlssolved solid. ppm
664
2000
ILlCA
1500
2.4 ,8-CRISTOBALITE
..... 2.0 iG-
>- 1.6 G-
!::
...J c /, V 1.2
«
1000
CtW.CEDOHY
2.4
ID
::J ~ 2.0 ~ !.iL
08
52
...J
...J
O "
'O
lA
1.6 ;;
0.4
50 (/)
(Il
1.2 ;;
W
1:11 IO O 500
>< 0.8 ti,
!:: "1:11 r-200 TEMPERA-
(.J 0.4
...J / / / TURE ("e)
'"
(.J 00 20 40 60 ~OO
o OL--50.t-...I<!:OO=----.J15LO-2.Loo,..--2-':-50::--:3~00:-::--=350~--'
C02 PRES SURE (atm)
TEMPERATURE (·C)
:=ig. l The Solubility Surfaee of Fig. 2 Solubilities of Various

Calcite in the System CaC0 3 - Silica Phases at Various
C0 2H20 between 50° and 300°C Saturation Temperatures and
pH = 7 [35J.
and between and 70 atm CO 2 °
[35J.
Cl)
=> >-
O
I 1400 t:
--l
a.. CD
l..L... 1200
O ::J
~ ....... 1000
--l
O >. 0.04
<l ~ Cl) +-
l..L... 800 <l 52 0.03

O O o
>- 600 ::J E
t-
--lO
t'-I
400
U5
Cl)
0.02 -~~
250
iI::iU5
=> 200
=>
O 0·01 ~20rr
-1
O
I
a.. 15 0::
a::
O O
Cl)
5 6 7 8 9 O
IO II ~ O 2 3 4 5 6 7 8
<l
PH Nael (molel it y)
Fig. 3 Solubility of Amorphous Silica Fig. 4 ~~olal Solubil ity of Amorphous

as a Function of pH at Various Sil ica in Aqueous NaCl,
@ProcessEng
Temperatures [48J. solutions, 25-300°C

665
4
Run TTI-A
Run
A
TTI-B
C
, B
!Ill
00
o
~ Gto0 o o e.u<l[)
~";,~'1f~DoifJj:",'f~~""
-I
-2
, '2l
o
- - Analyticai
-1
O 20 40 60 80 100 120 140 160 180 200
Time Ihrsl
4
Run TTI-D
o Run TTI-C
~~~
D o,p> o
'l;"I?~0 C
",0
~~
~
w - - Analyticai
'-'
:z:
c:( -2
l-
V)
Ul -3
W O 20 40 60 80 100 120 140 160 180 200
0";::
<.':l
Time Ihrsl
:z: 25r----------~--~-~----__,700 i
--'
::J 650
O Run TTI-DO
'-'- S
;;;
20 600
--'
c:(
::;: 550
er:
W
:c 15
I-
--'
--'
c:( IO
er:
r """
W
>
O
-- Analyticai
20 40 60 80 100 120 140 160 180 200

@ProcessEng
Time IhrsJ
FiJ. ~ Overall Fouling Results and Model Prediction

based an Eq. (18).
666
X"1. l FT
-I
-2
-3
10 20 30 40 50 50 70 80 90 100 110 120 130 140 150
T IMF (hrs)
X-4. l FT
D X"6. l FT
+ X"'7.1 FT
w 6 X"'S. l FT
U
;z
~
(/")
>-<
(/")
w
a:
(Cl
z
>-<
....J
:::>
o -I
LL
....J
c:r:
::E
a: -3
w
::r: 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150
f- TIME (hrs)
....J
c:r:
u
o
....J
Fig. 6 Local Fouling Results and Model Predications

based on Eqs. (26-28).
@ProcessEng
667
u',--------------------------------- 3.4)
II
!iU" HI-C
o
o
Ul
1.0
'"
i
~
Il!
li:
6 ~~
5 ~
4
~ =>
O
!
:ol-
OCD l
lJ.., ' -
lL. Run TTI-D -1.0 .!
U-l<
'F~
+-' "
O ~"
+..) }---,
N
4 6 8
-2.0
9
1
o'Ll-
E*
AC~
Heat Exchmger Lengtil IltI
~'::~~
Fig. 7 Variation of Local Fouling
\.D
"~
,-;
'i<
Cd --',
~ ..) r:..~
rd :r.:
rx ~
G"'l~
C ~"i~
~~" Ll __
:-.3 ~
o C'o'
lJ..,i<
i~
n::l CL
GJ1<
'"
1---
.,-. :::c
C o. COH- (moiality)
-.J "'---
Fig. 8 CorrclaLc'; e 1: S11 iea Dspcs·;tion

Outd flt'cn; l\,;,() bEGtht-~rmal rields

@ProcessEng
GEOTHERMAL WATER SCALING IN HEAT EXCHANGERS
S. ULKU, M. TOKSOY, A.C. GURSES
Mechanical Engineering Department, Dokuz "

Eylul University Bornova-
IzmirjTurkey.
1. INTRODUCTION
Geothermal fluid produced in geothermal wells generaIly contains
various amounts of impurities as dissolved solids and gases; and the
quality of it varies from potable to heavily brined. The recovery of heat
from such brines is adversely affected by scaling which originates from
carbonates, silicates, sulphites and oxides. Heat exchangers are essential
equipment responsibIe for the whole energy recovery system, and scaling is
the main drawback limiting the economical feasibility of the operation due
to the additional thermal resistance created. Since the overall resistance
to heat transfer is described as:
l l ygf r -r. ypf l

o ~
--- + +--- + , +
U~gf h .A f kgf(A'gf) kw(A'w) kpf(A pf) h (A f)
g g p p
By determining the thermal conductivity and the thickness of the scale it
is possibIe to establish the effect of additional resistance due to the
scale formation.
The rate of scale formation is a complex function of heat dut y,
flowrate, geometry, the particular characteristics of the fluid, and the
transfer surfaces. Depending upon the properties of the fluid, the deposit
may originate from the dirt present in the fluid, crystallization of
dissolved constituents present in the fluid, chemical reactions within the
fluid or corrosion produets formed as aresult of reaction between the
fluid and the construetion material. Of course the strict solution for the
fouling problem is the elimination of the fouling agent from the fluid.
Although this is a problem for the fouling related to the circulating
secondary fluid, it is not possibIe for the geothermal fluid. Maintaining
high velocity operation is also not sufficient for controIling the
geothermal scaling. The selection of the proper type of heat exchanger,

appears as the only way for minimizing scaling. Shell and tube, plate,
down hole heat exchangers are the main types of heat transfer equipment
currently used in geothermal applications. Shell and tube heat exchangers
are being used in a limited number of geothermal applications where
geothermal fluid is placed in the tubes which ean be cleaned physically or
chemically without removing the bundle. When specialized materials are not
required they become quite economic; but they are not suitable for heavily
@ProcessEng
brined geothermal fluids. For fluids having a high tendency to scale

formation, two special designs of shell and tube heat exchangers, fluidized
bed, (Figure l) and APEX (Advanced Geothermal Energy Primary Heat
Exchanger) have been developed. In the fluidized bed type, the geothermal
fluid passes through the shell side where a bed of particles surrounds the
669

670
tube bundle. The particles fluidized by the geothermal fluid provide a

I .GEOTHERMAL FLU ID OUT
I
SECONDARY
/ " " ", - SECONDARY
FLUID OUT FLUID IN
\
I n n I\
GEOTHERMAL FLUID IN
FIGURE 1. Fluidized bed heat exchanger
scrubbing action for the prevention of scaling. Additionally the rate of

heat transfer is increased due to increased mixing. In the APEX type, also
a scrubbing agent is used, but here it is injected into the geothermal
fluid as it enters the tubes and it is removed from the stream at the exit
of the heat exchanger.
Recently plate heat exchangers have found widespread application; due
to the high induced turbulence between the plates, bui Id up of the fouling
is minimized. It has even been shown that fouling resistance on the plates
is less than half that of tubular heat exchangers (2). When cleaning is
required; they ean be easily opened, cleaned and returned to service. They
may be constructed from various materials and they appear to have economic
advantages when specialized materials are required for corrosive fluids
(Figure 2).
@ProcessEng
FIGURE 2. Plate heat exchanger

671
For small scale applications in shallow resource areas «200 m),

dowrillole heat exchangers are located within the wellbore (Figure 3). This
type of heat exchanger is very simple in design and consists of pipes or
tubes in a U shape, suspended in the cased borehole. Perforations in the
well casing just below the water level, and near the bottom provide a
convective flow of geothermal fluid. A secondary fluid is circulated
through the exchanger for the recovery of thermal energy. Downhole heat
exchangers have superior advantages related to scale formation, and the
disposal problem.
-2
U Tube (Diameter",6x10 m)
Par.king
Perforations (Depth:~8-22 m)
-1
Casing (Diameter:.v2.3x10 m)
Perforations (Depth :.12-100 m)
FIGURE 3. Downhole heat exchanger (Izmir-Balcova)
There are also some other systems, such as direct contact heat
exchangers, where geothermal fluid is brough into direct contact with
another fluid which vaporizes at the appropriate temperature. These types
are not yet commercial and they are still in the development stage.
2. GEOTHERMAL ENERGY APPLICATIONS IN TURKEY

Turkey is located on the Alpine-Himalayan tectonic belt; and all the
available data suggests the existence of high geothermal energy potential.

Various fieids have been located which are promising for the recovery of
thermal energy and various installations are planned for these regions.
Characteristics of some of the fieids are given in Table l (3).
Even though the geothermal fluids have a high degree of scaling,
potential utilization of the resource for heating purposes has been applied
for 10 years. Presently geothermal energy is not being used at a
@ProcessEng
significant level in Turkey; although it has found wide application in

other countries. The firs t geothermal resource was located in 1963
(Balcova-IZMIR) but it was not utilized till 1982 due to the extensive
scale problem. The first geothermal field in Turkey, suitable for
electricity generation, was discovered in 1968 (DENIZLI-Ki-zildere) and a
geothermal power plant with a capacity of 20.4 MW was constructed in this
@ProcessEng
~
-.J
N
TABLE l: Characteristics of geotherma1 fie1ds in Turkey
NAME aF pH TEMP. T.D.S. COMPOSITION aF DISCHARGED WATER (in ppm)

FIELD °c mg/1
+ + ++ ++ ++ Li +
Na + K NH4 Ca Mg Ba HC0 3 C0 3 S04 Cl Si0 2
Kizi1dere
DENIZLI 8,9 212 5020 1400 148 3,6 2,2 0.0 28 2117 336 714 122 550
(Second reservoir)
Germeneik
AYDIN 8,3 200 4400 1335 45 3,8 6,4 1,0 45 1324 246 37 1586 8 305
(Second reservoir)
Omer-Gecek
7,4 106 4500 1510 116 5,4 143 la 9,1 952 180 487 1790 125
AFYON
Baleova
8,7 124 1230 380 29 1,03 12 7 2,8 567 6 174 192 1,6 145
IZMIR
Seferihisar
IZMIR 7,5 137 19938 6400 650 5,55 425 129 17 88 0.0 323 1/348 15.4 140
(First reservoir)
Tuz1a
CANAKKALE 7,0 173 70000 22250 2125 2,66 5715 lal 35 55 0.0 176 44140 74 123
(First reservoir)
Kizi1cahamam
7,6 105 2072 670 66 l.3 41 42 8.3 1512 0.0 122 243 112
ANKARA
673
are a (3) and it beeame operational in 1985. Sealing however, is a real

problem ehallenging the eeonomie feasibility of the operation.
In the Baleova-IZMIR and Omer-Geeek/AFYON fields, downhole heat
exchanger systems were used for the reeovery of thermal energy (Figures
3,4). In the systems water, as the seeondary fluid, is eireulated through
a elos ed loop ineluding the U tubes, for heating purposes. The wells were
sealed from the atmosphere.
Using down-hole heat exehangers and sealing the well easing from the
atmosphere, the geothermal water sealing was prevented, espeeiaIly in the
lower regions of the heat exehangers. In these wells some small degree of
sealing mainly due to the formation of GaG0 3 , was observed only in the
upper regions. Sealing is elosely related to the G0 2 eontent and the
solubility of this GO in the geothermal water. As seen from the table the
pH values of the geottermal water are in the range of 7-8.9, indieating the
existenee of G0 2 mostly in the form of HG0 3 whieh may be related to the
Temperature 8 OuL
Pressure Measurement
\
Flow 9x10- 3rn 3/s

Pres sure
Temperature 50°C
Measurement
FIGURE 4. Down hole heat exchanger system applieation (Izmir-Baleova)
effeet of pressure on the reaetion:

The greater the pressure, the higher the amount of soluble HG0 3 , present
(the lower the amount of insoluble GaG0 3 ) in the medium. In the upper
regions when the pres sure is lowered, the gaseous carbon dioxide. G0 2 , will
be forme d and if it is allowed to leave the well, insoluble GaG0 3 (and some
MgG0 3 ) is forme d eausing extensive seale deposits. By sealing ~n G0 2 , the
@ProcessEng
formaton of seale is minimized and the system is in operation w~thout

signifieant problems due to seale.
3. RESULTS AND DISGUSSION

Downhole heat exehangers with well sealing appear to be the effeetive
type of heat exehangers in shallow « 200 m) geothermal fieIds for the
674
recovery of thermal energy. By testing them in two regions it was possibIe

to recover energy, equivalent to 3400 tonnes coal/year or 1400 tonnes fuel
oil/year. Previously it had not been possibIe to recover energy in these
regions due to the formation of scale having thermal conductivity values
measured as 1.5 W/mK. The scale blocked the system as well as decreasing
the overall heat transfer coefficient. The decrease in the overall
coefficient with increase in the thickness of the scale is given in Figure
5 for he2t exchangers h2ving initial co 2fficients for clean surfaces of
0.35 kW/m K, 2.80 kW/m K and 5.70 kW/m K. With the increase in scale
thickness, the advantage of high total coefficient and feasibility of the
recovery system rapidly diminishes.
(mYJK)
6000 (Il» V o =3S0 W/rrfK
~
( X) - Ve =2800 W/m K
(o) - Ur;; = 5700 W/dK

/,500
3000
+'
C
....;
ID
.U
...;
4-
4-
ID
D
'-'
~
ro
'-
<D
>
co .01 .02 .03 {m}
Scale Thickness
FIGURE 5. Change of overall heat transfer coefficient with geothermal

scaling.
@ProcessEng
675
LIST aF STI~BOLS 2
A Transfer Araa, m 2
A' Mean Transfer Area, m
Coefficient 2
h Convective ~,eat transfer, ~/m K
U Overall heat transfer" \>J/m- K
Q Heat transfer rate, W/mL
r Radius of the tube, m
k Thermal conductivity, W/m IZ
kW Thermal conductivity et the Hall, \J/m K
le;: Thermal COIl'lGctivity f:Juling of layer, H/m "
Yf Thicknes5 Gf tne LlUling layer, IT
SUBSCRIPTS
f fouled condicions
g geothermal fluid
i inside
m mean
o outside
p process or secondery fluid
w wall
REFERENCES
1. Reistad G.M., Direct App1ication af Geotherma1 EnergYI ARRE, New York,

1980.
2. Cooper A, Usher D., Heat Exchangers 3.7.9, Hemisph.ere, Pub.Corp. Ne\<"
York, 1983.
3. Simsek S., Geothermal Activity in Turkey, UNo Workshop on the
Development and Exploitation of Geothermal Energy ,Ieelan:!., 1986.
@ProcessEng
@ProcessEng
Chapter 11
Fouling in Furnaces
HIGH TEMPERATURE FOULING: THE NATURE OF DEPOSITS
J. HOWARTH AND T.R. BOTT
Chemical Engineering Department, University of Birmingham, PO Box 363,

Edgbaston, Birmingham, Bls 2TT. UK.
l. INTRODUCTION
Fouling may be grouped into three temperature regimes: (l)
1. Low Temperature <530 oK
2. Intermediate 530-1100 oK
3. High Temperature >1l00 oK
High temperature fouling will be considered here to cover group 3 and
the higher temperature end of group 2.
High temperature fouling occurs almost exclusively with combustion
gases, sometimes containing extraneous material resulting from direct
contact between the combustion gases and the object being heated. Fouling
is experienced both in waste heat recovery and utility power generation or
proces s steam raising. In the glass industry for instance, combustion air
is preheated using the exhaust gases from the melting furnace. Although
fired by natural gas, these exhaust gases, at a temperature of l800 o K,
cause severe fouling of the regenerator type heat exchangers that are
cornrnonly used. This is due to material entrained in the exhaust gases.
Only utility power generation, process steam raising and municipal waste
incineration will be examined in this document. In these situations, the
term "fouling" is used slightly differently to its gener ic usage describing
deposition on a heat transfer surface. "Fouling" has come to refer to
deposition in the convective gas passes of boilers. Deposition in radiant
sections, where molten or flowing deposits may form, is referred to as
"slagging". Figure 1.1 shows a schematic representation of a typical 500
MW pulverised-coal-fired-boiler, with flame, flue gas and metal
te~peratures at selected points als o indicated. 120 MW units are similar
except for their smaller furnace enclosures and the abs~nce of the radiant
superheaters. Clearly the distinction between low, intermediate and high
temperature regimes is rather arbitrary in a boiler of this kind. Zone A
would be prone to slagging, particularly those areas with reducing
conditions and that experience flame impingement. Zone B may develop·
sintered deposits, ie. having the particles partially fused together. In
Zone C the deposits that form are more loosely held together. The deposits
in Zone D are considered to be low temperature. The type of firing in
utility power plant ean drastically affect the nature of the deposits.
Figure 1.2 shows a typical cyclone fired unit. It is an essential design
feature in these plant to trap as much mineral matter as possible in the
cyclone itself. Combination oil and gas units closely resemble pf furnaces
in layout, but solely gas-fired units need little precaution against
@ProcessEng
fouling. They therefore have smaller total volume of enclosure, and only
heat transfer/draught loss need be considered in arranging the heating
surfaces.
A further type of coal-fired unit is the stoker furnace as shown in
Figure 1.3. These are now more usually associated with the smaller boilers
679

680
8°9-950 K metal temperature
radiant reheater
superhea ter
platens
(secondary and
primary)
750-800 K metal
tempera ture
furnace
wall tube zone A
650-750 K
p.f
burners
_::r: _
-~-
-~-
air heater
FIGURE l.l. Schematic representation of a 500 MW pulverised-coal fired

boiler e
Reproduced by permission of Hemisphere Publishing Corporation; E. Raask 1985.
Secondary
superheater ---Reheat superheater
- PrimaI"J superhea ters

D
D
D - ~conomiser
c cyclone
--Gas outlet
C
air heater
@ProcessEng
--Air in1et
c
Slag tank
FIGURE 1.2. Schematic representation of a cyclone-fired boiler

681
used for process steam raising, and are capable of burning a wide range of
coal type. In these units most of the ash is discharged from the grate to
an ash hopper in fairly large, fused pieces. However, some of the fuel is
burned in suspension over the grate, and a considerable quantity of ash is
entrained in the flue gas and is swept over in the gas stream. This
material is often collected in hoppers and re-injected as it may contain
unburnt material.
The amount of fouling experienced in a steam raising plant will of
course largely depend on the ash content of the fuel. The national average
for the percentage ash content of coals used in U.K. power stations is
approximately 16% (dry basis). The relationship between percent ash as
determined in the laboratory at <llOOoK over a ger iod of a few hours, and
actual combustion residues from firing at 2000 K over a per iod of about 2
seconds is not a simple one. However, their masses are roughly equal. A
600 MW unit burning 7000 tonnes of bituminous co al per day, produces 1000
tonnes of ash (2). Other estimates indicate that a 300 MW unit firing 10%
ash bituminous coal at 2600 tonnes per day, will be exposed to 260 tonnes
of ash per day (3).
In pulverised fuel-firing, the combustion residue is distributed such
that 76% is removed in the precipitators, 20% from the furnace, and about
4% willIeave by the stack (2). These figures contain the material removed
from heating surfaces by sootblowing and which therefore constitute the
fouling deposits. The accumulation of unwanted deposits, at least in
moderate ly fouling systems, is reduced or prevented by the use of the
technique referred to as "sootblowing". The method simply involves
continuous or intermittent application of jets of steam or air to the
affected parts. In modern plant this is often automatic. At these rates
of throughput of potential foulant even a small percentage of retention on
heating surfaces constitutes a considerable degree of fouling. Estimates
suggest that in pulverised fuel-firing, 15-30% of the ash is captured by
furnace walls and superheater tube bundles, ie. 150-300 tonnes of deposit
per day in a 600 MW unit! This figure represents the sum of the deposit
accumulations that occur between sootblowing.
Cyclone firing contrasts sharply with pulverised fuel firing. Here 75-
85% of the combustion residue is captured by the furnace walls and
superheater tube bundles. Approximately 70% however is removed via the
slag tap from the cyclone itself, i.e. 50-150 tonnes per day of superheater
deposit has to be controlled by the sootblowers.
The disposal of municipal waste by incineration is now far and away the
cheapest method of disposal, (4). In 1980 in the Federal Republic of
Germany, 30% of municipal waste was incinerated (5). In 1981, 65% was
incinerated in Japan (6). Fouling is only a problem of course in plant
with heat recovery. Of the 200 plant in Europe, 95% have heat recovery,
whereas of the 50 in the U.K. only 4 have heat recovery. The Edmonton
plant fires 1150 tonnes/day, which amounts to 13% of London refuse,
producing 120 tonnes/day of preciptator ash, and 225 tonnes/days of other
residuals (4). Figure 1.4 shows a schematic representation of a typical
refuse incinerator with an inclined grate.
The rate of deposit formation can be illustrated by examining the
deposition occurring on cooled probes, ~~serte~2i~lthe gas stream. Slag
@ProcessEng
deposits may form at a rate of 5-10 x 10 kg m s -6 SUP:2h:fter deposits

have been measured forming at rates of 10-30 x 10 kg m s (7) both
these in pulverised fuel-firing. If these estimatzs held for the furnace
wall and superheater ZUbes of a unit having 300 m of heating sur face in
the furnace, and 300 m of superheater tube surface, they would represent
260 tonnes and 0.75 tonnes of deposit per day respectively, roughly
682
stack
FIGURE 1. 3. Schematic representation of a stoker furnace. (A trave11ing-

grate spreader-stoker with overthrow rotor and forward ash
discharge) .
re fuse hopper to electrical

precipi tatars
@ProcessEng
FIGURE 1.4. Schematic representation of a waterwa11 refuse incinerator.

683
-3
comparable to ~he figures given earlierc For density values of 2000 kg m
and 1000 kg m for slag and sinter respectively, this would represent 43
cms and 0.2 cms of slag and sinter per day respectively, if no sootblowing
was carried out. Four sootblowings per day would still allow for
intermittent accumulations of 65 tonnes within the furnace. Not only the
potential effects on heat transfer may be appreciated from these figures,
but also the additional structural load which the equipment has to
accornrnodate.
The effect of these deposits on heat transfer is illustrated in Figure
1.5 showing the change in percentage heat flow relative to clean surfaces,
resulting from the deposition of fused, and loose particulate ash deposits.
The fused deposit has less effect per unit thickness than the loose ash. A
sintered deposit would lie somewhere between the two. The cause of this
difference is related to the thermal radiation and heat transfer properties
of the different deposits. Listed in Table 1.1 are the thermal
conductivities of deposits etc.
deposit thickness mm
A particulate ash
B fused deposit
'---
FIGURE 1.5. The effect of furnace wall deposit on heat transfer

Reproduced by permission of Hemisphere Publishing Corporation; E Raask 1985.
Table 1.1. Properties affecting Heat Transfer
Substance Thermal Emittance

conductivity
Metal 40
Oxide 10 0.82
Deposit:initial 0.03 0.20
unsintered 0.1 0.60

sintered 1.1 0.75
@ProcessEng
slag 3.0 0.80
Air 0.05
684
Remarkably the initial submicron deposit formed on a cooled probe has a

lower thermal conductivity than air. This mayaiso be the case with loose
ash, depending on the source fuel. Also listed in Table 1.1 are the
emissivity values (a dimensionless ratio). It can be seen that with such a
low ability to absorb thermal radiation and its very low thermal
conductivity, the initial deposit is a very effective heat barrier. Slag
deposits have an ability to absorb heat by radiation similar to that of the
tube oxide coatings, but a rather lower thermal conductivity. Figure 1.6
shows the thermal gradients that develop across typical furnace wall and
superheater tubes af ter deposit formation. Whilst slag deposits appear to
constitute rather less of a thermal barrier than unsintered ash, a fused
slag constitutes a captive surface capable of a very high capture
efficiency, and hence of rapdily developing very thick deposits. They can
also be very corrosive. Actually most coal-fired boilers have furnace
enclosures that are 40% larger by volume than equivalently rated oil-fired
units, in order to allow for the effect of fireside deposits in reducing
heat flux. Problems develop when heat flux is reduced by more than 40% and
the furnace exit temperatures rise too high.
superheater tube furnace-wall tube

ALKALI
SULPHA TE
FLAME
FLUE
INTERNAL Ha50 Kj
METAL GAS
SCALE METAL
(~lJOO KI OXIOE ASH
I
I
I
I
i
I
I
I
I
I
STEAM I
WATER I
FLOW I
,,/0 750-950 K
/
'065;;//OI~15 K
915 K 615 Kr I
HEAT FLUX
.. HEAT FLUX
400 kW m-l
100 kW m- 2
FIGURE 1.6. Thermal gradients across tube deposits
The effects of deposits on heat transfer are important, but possibly a

more serious problem created by fouling is the enforced outage of plant
resulting from severely reduced air circulation ie. from increased pressure
drop that results from massive deposition. Certain boi ler designs are more
prone to suffer from this problem, for instance firetube designs. However,
@ProcessEng
uncontrollable fouling may result in almost any plant, if suitable

conditions are allowed to arise and persist unchecked.
2. FLAME REACTIONS OF THE MINERAL COMPONENTS IN FUEL

In a plllverised fuel boiler, within a per iod of 2-Ss, the mineral
matter contained in the fuel is totally transformed. An understanding of
685
the reaetions involved in this transformation is neeessary in order to

understand the nature of the deposition proces s and the final nature of the
deposits themselves. The reaetions oeeurring during eoal-firing serve as a
basis for understanding those oeeurring in eombustion of other fuels.
Briefly eoal mineral matter may be elassified into two groups:
l. Inherent
2. Adventitious
The adventitious mineral matter may be redueed by eoal preparation
plant, and is largely eomposed of roof, floor and dirt band material. The
inherent mineral matter has a more intimate eontaet with the eoal and is
homogenously distributed through the eoal body. The nature of the inherent
mineral matter ehanges with ehanging co al rank (i.e. from lignite to
anthraeite). The inherent mineral matter in low rank eoals is largely
earbonate (aragonite - GaG0 3 , and ankerite - GaG03 .FeG0 3 ) and
organometallie eompounds, whereas in bituminious eoals tne earbonates
ealeite, siderite (FeG0 3 ) and dolomite, and sulphides dominate.
The mineral matter in bituminous pulverised-fuel is mainly silieeous,
being dominated by clay minerals (mainly, illite and kaolinite) mica
(mainly museovite) and quartz. In the UK, pulverised fuel is ground sueh
that 70% is smaller than 76 ~m. Figure 2.1 shows the distribution of
mineral eomponents with partiele size. The layer silieates eoneentrate in
the <20 ~m fraetion. Quartz and earbonate eoneentrate in the 20-70 ~m
fraetion, and pyrite in the 10-45 ~m fraetion. Ghlorides tend to be
uniformly distributed. In terms of partiele density, the elean eoal,
middlings, and mineral fraetion constitute 56.4, 27.5 and 16.1% by weight
respeetively of an average UK pulverised fuel (16.4% ash) (7). The elean
eoal is eomposed of 95% eombustible matter, and the mineral fraetion only
10% eombustible matter. Despite this eaeh partiele of elean eoal eontains
several hundred smaller particles of mineral matter. Middlings will
contain several thousand particles of mineral matter per partiele of
pulverised fuel. The intimaey of eontaet between the mineral partieles,
i.e. their eoneentration within a single partiele of burning pulverised
fuel has an important effeet on the reaetions that take plaee.
10
z
o
E
~ A aluminosilieates
~
B quartz
8
~ 10 G pyrite
o
~
z D earbonates
u
~
E chlorides
~
1.0 1.5 1.0
LOG lO PARTlCLE SIZE,"m

@ProcessEng
FIGURE 2.1. The distribution of mineral species versus partiele size

in a UK pulverised eoal
686
Inherent mineraI matter, in close contaet with eoal, usually attains a

higher temperature during combustion than the surrounding flue gas. The
mineral particles are in close proximity, and fusion and ehemieal
interaetions are very likely. They would normal ly experienee a redueing
environment for a cCTIsiderable part of their residence time in the furnaee,
thus making the more easily volatilised oxidation states more likely.
Extraneous mineral matter on the other hand tends to behave as one
isolated particle, and will be at a slightly lower temperature than the
surrounding flue gas. It may experienee either oxidising or redueing
conditions.
In Figure 2.2. is shown the estimated temperature profile for two
particle sizes during pulverised fuel eombustion in a 500 MW unit. The
small particles attain the maximum flame temperature within Is. Notice the
very fast hea·ting cooling that occurs in this type of firing. Figure
2.3 ~bows the ~~rnpeTe-~re required for spheroidisation of various partiele
eizes ef 5i11cate minerals ° Remembering that clay minerals are
eOTJ.centrated in the o:-inwc size f:nlCtions and that these attain the highest
tempera·tures it saemsc.EaC tbe~' will certainly fuse al thcugh elays are also
an important comroneT,t oE the adventititous mineral matter Actually all o
bL~t the l;"rgest ~uartz pardc.le:s fuse and beeome spherieal iE the flame.
2000 0.1 J.l1l1 (top curve) to 100

)JIll (bottom curve)
500 MW pulverised coaI fired unit
A combustion chamber and heat

exchange chambers
1000 TI electrical precipitator~ ~Åd
chimney
f.-r~~-L", 'ef ?artic::les ir; pulveriseå fuel firing

jJ"nll~ssion of Hemisphere Publishing Corporation; E. Raask 1985.
---l
°0 '
- _o _ _
I
Hlite
I
b ::;: muscovi te
C native quartz
1/
I / !) chlorite
100 ~
J
@ProcessEng
L
Q li 50 ,DO
PARTlCLE RA01U5. ~m
neURE 2.3. Temperature of spherical shape transformations

687
By the time that a temperature of 1700 0 K has been reached, over 95% of the
mineral particles in burning coal will have fused.
An interesting feature of the silicate chemistry in p.f.a. (pulvervised
fuel ash) is the formation of cenospheres and plurospheres. These are
hollow spheres sometimes containing many smaller spheres. They are
probably forrned as aresult of gas evolution within the molten material.
They form only a very small fraction by weight of p.f.a. however, and are
therefore relatively unimportant.
Very littie silica is volatilised during pulverised fuel-firing, but up
to 4% of the total silica may be volatilised in the higher temperature-
cyclone furnaces.
Non-silicate minerals behave rather differently. Unlike the silicate
minerals they undergo thermal fracture and decomposition as well as some
fusion.
Pyrite (FeS 2 ) decomposes on heating to pyrrhotite (FeS) and S2' The
FeS thus forrned melts and rapidly oxidizes to FeO and S02:
2 FeS 2 2 FeS + S2
2 FeS + 302 2 FeO + 2 S02
The presence in p.f.a. of spherical particles of iron oxide confinns

the existence of a temporary molten FeS phase prior to oxidation, as the
melting points of iron oxides are too high f~r their spheroidisation in a
pulverised fuel furnace.
All of the carbonate minerals fragment and decompose on heating.
Ankerite (GaG0 3 .FeG0 3 .Mg.G0 3 ) and siderite fragment into 0.1 - l ~m
particles. GaO and MgO form from calcite and magnesite respectively. The
fate of these oxides varies. FeS0 4 is thermally unstable, but the FeO
forrned as above, is very reactive, dissolving in molten silicate very
easily. This also happens with some of the GaO and MgO, but most of these
particles react with SO and oxygen to form the respective sulphates.
NaGl is the dominan€ chloride mineral in most coals. Due to its water
solubility it is present in pre-dried pulverised fuel as small crystals af
NaGl dispersed evenly throughout the fuel. TI,e volatilisation of these
crystals is complete within 0.5s in the flarne. Sorne of this volatilised
NaGl will form sulphate, as below;
The rest interacts with molten silicates.

What has been described so far is the formation in the pulverised fuel
flame of a high temperature cloud of particles cornposed of melting
silicates and sulphides, oxidizing sulphides, vaporizing NaGl, fragmenting
and decomposing carbonates, and the formation of a sulphating oxide fume,
all in various combinations with burning coke particles. Those embedded in
burning coke will undergo extensive coalescence and chemical interaction.
@ProcessEng
It is the fate of this high temperature cloud of particles that will decide
the nature of the fouling deposits. Some of the more important reactions
that have aiready been mentioned will now be considered in more detail.
An observation of far reaching importance is that while practically all
of the potassium in coal minerals is in combinations that should be stable
at high temperature, some of this potassium is in fact volatilised. This
688
has been shown to be due to the interaction of volatile sodiurn chlor ide and
potassiurn-containing alurnino-silicates. Despite the several hundred or
several thousand particles of mineral matter per particle of coal, only 4
or 5 particles of ash are produced per particle of coal. This is due to
the extensive fusion and coalescence of flame-borne alumino-silicates.
They are als o likely to have reacted with other materials such as FeO, GaO
and MgO, resulting in spheres with reduced viscosity. Volatilised sodiurn
reacts with these fused silicate particles, resulting in an exchange
reaction in which potassiurn is volatilised. Enhanced by the lower
viscosity, potassiurn diffuses from the body of the particle to the
constantly depleted surface. It is found that up to 40% of the silicate
potassiurn may be volatilised in this way. Approximately half of the
volatile sodiurn is captured by silicates. The rest forms sulphate,
although if the ratio of ash:Na is very high there may be no formation of
Na 2 So 4 at all.
It has been observed that up to 25% of the total nurnber of sulphate
particles are formed in a captive manne r on the surface of silicate ash
particle (7). This could be due to the direct sulphation of captured
sodiurn and non-volatilised potassiurn present in the sur face of potassiurn
containing alurnino-silicates (e.g. particles of vitrified illite). It
could also be due to sulphation of volatile NaGl and KGl that have been
captured by fused silicate particles that are low in alkali (e.g. molten
kaolinite). The normaIly highly siliceous ash particles have a too
strongly developed and relatively immobile silicate network structure for
the sulphate and silicate phases to be miscible at normal combustion
temperatures. Hence the formation of these submicron sulphate particles as
a separate phase on the silicate surfaces.
It has been estimated that in the firing of a coal containing 65% 23 _~
flue gas containing 13% G0 2 at l200 0 K would contain an amazing 4xlO m
particles of sulphate, w~th an average equivalent spherical diameter of
0.12 ~m (7). The reduction in the count of particles due to captive
sulphate formation is balanced by the GaS04 particles that are not included
in the calculation.
It is important to appreciate that at l200 0 K over half of the total
Na2S0~ and KJ S0 4 are still in the vapour phase.
Tne sulpnat~on reaction can be studied using probes. If the reaction
is incomplete, NaGl will be deposited on a probe placed in the superheater
section of the boiler. Observations indicate that if the residence time is
greater than 2s, ie. in boilers over 100 MW in size, the reaction will be
complete, and no chloride will be deposited on the superheaters.
The rate of sulphate deposition is related in a two-fold manner to the
chloride content of the pulverised fuel. In Figure 2.4 it can be seen that
sulphate deposition increases rapidly af ter the chlor ide content
indicates that the sodiurn levels are high enough to saturate all of the
silicate present with Na 2 0, and Na 2 S0 4 deposition therefore increases
markedly.
The study now passes into a region where the silicate particles with
their submicron sulphate passenger particles have solidified. Most of the
oxide furne will have sulphated or reacted with silicates (FeO furne may have
formed feric oxide particles), but where there are still some volatile
@ProcessEng
alkali species. The proces s of deposition may now be considered.

689
15,..------------::--,
A Na2 S04
Reproduced by permission of
Hemisphere Pub1ishing Corporation;
05 E. Raask 1985.
FIGURE 2.4. The rate of sulphate deposition on a cooled superheater probe,

versus the chloride content of coal.
3. DEPOSIT FORMATION
3.1. Slagging
As was mentioned earlier, deposition in the radiant sections of the
boilers, if the deposit is molten, is referred to as slagging. In Figure
1.6, the thermal gradient that develops across a furnace-tube deposit was
shown. The very high radiant heat flux and the high sur face temperatures
of the deposit are the cause of the high rates of deposition that are
experienced in slagging zones.
A slag deposit is a fused homogeneous mass, containing a variable
number of different sized gas bubbles. These result from the delayed burn-
out of encapsulated coke particles. Slag may therefore be quite porous in
its early stages, but it will become more dens e as it ages, and the gas
bubbles slowly escape.
A common observation is that slag deposits are porous next to the tube
surface, to which they are only loosely adhered, whilst the outer part is
totally fused. The po rous layer may be the result of initial deposition of
submicron sulphate-rich material. This actually forms the initial deposit
on most heat transfer surfaces in the boiler, and results in part from the
steep thermal gradient between the gas stream and the deposit-free tube
surface. As was mentioned earlier this initial deposit is a very effective
insulator. It may eas ily acquire a molten surface particularly in the
radiant section, thus forming the initial captive sur face to which
impinging particles stick and slag. However, its lower viscosity renders
it unable to support any great thickness of deposit. If this layer freezes
as aresult of thermal shielding by subsequent particulate ash deposition,
this effect will disappear
Slag formation is sometimes ho.wever associated with inertial impaction
of molten or surface fused particles onto furnace walls. Because of this,
it was hoped that the melting behaviour of laboratory-prepared coal ash
would enable the prediction of slagging propensity. Whilst the method has
@ProcessEng
confirmed that ashes with high fusion temperatures tend not to slag, it has
a poor record in predicting slagging propensity with less extreme coal
ashes. For instance use of the Initial Deformation Temperature by plant
operators has given only about 40% accuracy of prediction (3). Slightly
more success has been obtained using slagging indices based on the chemical
composition of the ash, for instance the slagging factor, defined as (in
per cents):
690
NazO + KZO + Fe Z0 3 + CaO + MgO

Fs x S
SiO Z + Al Z0 3 + TiO Z
This formula represents the ratio of the pyrochemically basic (or

fluxing) components to the acidic (or refractory) components, with extra
weight given to the pyritic iron content (most of the sulphur in bituminous
coal is pyritic). Still, only 50% accuracy of prediction has been achieved
using this approach (3). It reflects the observation that one of the
important mechanisms in slag formation particularly with high sulphur
coals, is the inertial impaction of unoxidised molten FeS particles, the
residue of the thermal decomposition of pyrite. This is likely to occur
with large pyrite particles that have insufficient time to oxidize before
they' impact, and where flame impingement occurs. A layer of molten FeS can
form the necessary captive surface for rapid build up of deposit. The
importance of iron in slagging can be seen by comparing the composition of
laboratory ash, fly ash and furnace slag given in Table 3.1., although this
is a fairly extreme example.
An important feature of the chem~!f.try of iron in silicate slags is its
oxidation state. Iron present as Fe tends to lower all four ash fusion
temperatures (Initial Deformation Temperature, Softening 3~mperature,
HemisphericalTemperature and Fusion Temperature) whilst as Fe it raises
all four temperatures. This explains the observation that ash fusion
temperatures obtained under oxidizing conditions are higher than those
under reducing conditions , often by by 2.~ much 3~s ZOOoK for Initial
Deformation Temperatures. The ratio af Fe to Fe also has considerable
effect on slag vi~-l:0sity, as shown in Figure 3.1. The source of this
effect is that Fe in Fe 2 0 1 behaves rather like AI Z0 3 in forming units
that are isomorphous witn SiO Z units, and thus extend the developing
network structure in th.e slag, and thereby increase the viscosity. FeO on
the other hand tends to reduce this network formation.
Slag viscosity is an important parameter in selecting a fuel for
cyclone furnaces. These furnaces (along with other "wet bottom" furnaces)
are designed to capture as much ash as possible on tbe walls of the cyclone
itself, this being ~~n~tantly drained off via the slag tap. Slags with a
viscosity of 25 kgm s or below have been found to be suitable. However
this must be achieved at a temperature lower than normal cyclone operating
temperatures, ie. <1700 o K, in order to give reasonable slag flow under
reduced load.
Viscosity is als o important in deciding the effectiveness of
sootblowers. Slags with a steep viscosity:temperature curve are plastic
over a narrow temperature range, whereas the converse is true for slags
with more gradual slopes. Plastic slags are very difficult to remove by
conventional sootblowing techniques.

It is common practice to reduce load during periods of low demand, in
order to shed slag from furnace walls. The thermal shock produced by load
reduction is often sufficient to dislodge deposits due to different rates
of shrinkage of slag and metal.
The deposits described in the next section are sintered deposits. As
the surface temperature of these deposits approaches that of the gas stream
@ProcessEng
with increasing thickness of deposit, it is likely that a slagged surface

will result, particularly in radiant sections high in the boiler.
3.Z. Fouling of superheaters

An important target in boiler design is that the furnace exit
temperature should be below the lowest Initial Deformation Temperature (ie
691
Table 3.1. The cornposition of furnace slag cornpared to other material~
constituent Lab. Ash Fly Ash Furnace

slag
Si0 2 36.5 54.4 14.5
A1 20 3 12.5 26.1 6.0
Fe 20 3 24.0 13.9 71.2
CaO 8.4 1.7 <0.1
MgO <0.1 0.5 0.2
Na~/; <o 1 <0.1 <c -

KrO .1 0 6 3.0 2.9
L
S03 12. =l 0.9 (; o
Reproduced by perm:lssicn af Hemisphere Publishing CorporatioD.) E" ~Lao;;:< ',S n::: '
Ferric percentage ~ Fez 03 + LIl Fe O + 1.43 Fe
slag
5GOO
PSRCENTAGE~
68,,78
S:02
2 4959
]J jj
'J/,C"
20
1 3~= 16
FsZ03 " .
L
"
: i02_ LI
CaO 5.6
1'1g0 0.7
NazO 3.9
K2 0 .'},2
111 00 1600 1800
@ProcessEng
Temperature K
FIGURE 3.1. The effect of iron oxidation state on slag viscosity.

(Ref. 2)
692
under reducing conditions) for the chosen fuel. This is in order to limit
the rate of deposition in the superheaters by precluding the presence of a
captive surface deposit. A very common type of deposit that develops on
not only radiant (in the large units) but also convective superheaters, is
a sintered deposit, i.e. where some particle integrity is lost due to
interparticle bonding resulting from partial fusion.
Before discussing the likely causes of these deposits, their physical
and chemical natures will be described.
Superheater fouling can be illustrated by observing the deposition
taking place on a cooled probe placed in the superheater or preheater tube
banks. Fig 3.2. shows that the probe is initially entirely coated in a
submicron unsintered dust, containing a large proportion sulphates,
Probably deposited by eletrophoresic or thermphoresic mechanisms. This
deposition ceases fairly quickly because of the effective insulating
qualities of this deposit (see section 1). Further deposition takes place
mainly on the upstream sur face of the probe by inertial impaction. This
impacted material is composed of a distinct particle size range, from 1-10
~m with a peak at about 8 ~m. Smaller particles have insufficient inertia
to escape the stream lines around the probe, whereas larger particles have
sufficient energy to rebound. This type of deposition will obviously be
controlled by gas stream velocity, the aerodynamic properties of the
particles (i.e. effective diameter, density) the diameter of the probe,
and the particulate loading of the gas stream, if the surface remains non-
captive, and the deposit homogenous throughout.
If the probe is left in the gas stream for 14 days or more at a gas
stream temperature of l360K and metal temperature of 840 o K, the deposit is
seen to develop a layered structure which is usual for a superheater
deposit (2). These deposits are typically made up of a thin inner layer
next to the tube surface and a layer on top of this having a composition
close to that of the fly ash. There is good reason to believe that a
liquid phase exists in the inner layer under normaloperating conditions.
Table 3.2 shows the chemical composition of a typical superheater deposit,
obtained from a boi ler fired with an USA bituminous coal. The inner layer
shows an enrichment in Na, and K and sulphate, and a depletion in Si, Al
and Ca, and rather surprisingly Fe. The composition of the outer layer is
fairly close to that of the fly ash, except for slight enrichment in Ca and
S04. Two further developments are often observed. Firstly the inner layer
is seen to migrate to the sides of the tube (as shown in Figure 3.3.),
leaving the outer layer, dominated by silicates, in contact with tube-metal
oxide-coating. This outer layer remains po rous but becomes sintered, and
under certain circumstances massive. These observations may be summarized:
The development of a two-layered structure with an inner layer dominated by
sulphate (with, Na K enrichment) and showing evidence of a molten phase at
operating temperature, and an outer layer comprising a sintered porous

silicate body with enrichment of Ca and some S03 relative to the fly ash.
The mechanism by which these deposits develop is now fairly well
understood. It is known that approximately half of the total sulphate is
still in the vapour phase in the region of the superheater tubes at
approximately 1200 K. It is thought that these sulphates diffuse through
the porous undifferentiated impacted deposit toward the cooled metal
@ProcessEng
surface. However, sulphates are unstable at high temperature in the

presence of silicates, and they decompose, for example
693
O- O· A = initial submicron deposit
- F
,
,,
. . ~'
• F
. '
'
:
:
B = probe deposit af ter 15 minutes
(al (bl c = aerodynamie wedge of sintered

deposit
F = flow direction
- F
Reproduced by permission
of Hemisphere Publishing
Corporation; E. Raask
1985.
(cl
FIGURE 3.2. Ash deposition on a coo1ed superheater probe.

A initial unsegregated
ash deposit
B separated sulphate
and silicote
C = displaced sulphate
phase and silicote
- metal oxide bond
Reproduced by permission
of Hemisphere Publishing
Corporation; E. Raask
1985.
FIGURE 3.3. Sequence of formation of a 1ayered superheater deposit.
Tab1e 3.2. Superheater deposit and !lY ash composition from bituminous
coa1 ~ firing
Constituent Fly Ash Superheater deposit

outer inner
SiO 37.4 36.2 15.9

A1 2 3 3 15.3 12.9 9.0
F: 3 0 3 20.8 19.9 1l.8

T~ 2 l.0 l.1 0.5
CaD 5.2 9.1 3.9
MgO 0.9 l.0 0.8
3.8 4.3 5.9
~a3° 2.7 2.4 9.0
!~J 9.6 13.1 43.3

@ProcessEng
3.3
n.d = not determined
(Ref. 2)
694
Table 3.3. Thermal stability of sulphates in the presence of molten
Substance Temperature
(K)
K2 S0 4 1450
Na 2 S0 4 1300
CaS0 4 1150
MgS04 1000
The temperature at which this reaction takes place depends on the

particular sulphate in question, as shown in Table 3.3. (These figures will
change for different gas phase composition). It can be seen that CaS0 4 and
MgS0 4 will decompose whilst K?S04 and Na2So~ will not. This explains the
observation that sodium, poEassium and sulphate concentrate in the inner
layer, and also the sintering of the silicate layer resulting from the
enrichment of fluxing components in the surface of the silicate particles
because of the above reactions.
It was mentioned earlier that sulphate and silicate phases are
immiscible under pulverised fuel firing conditions, hence the separation of
the molten sulphate-rich layer, and its migration to the cooler areas of
the deposit at the edges of the tube. The sulphate content of this inner
layer is actually greater than the amounts suggested by the stoichiometry
of sulphate in simple combination with the alkali metals. An obvious
explanation of this is that the molten sulphates have absorbed further S03
with the formation of pyrosulphate
Na 2 S0 4 + S03
K2 S0 4 + S03
The high S03 levels necessary for this reaction (15 ppm for K, and 2000
ppm for Na at 680 K) could have arisen from the catalytic oxidation of S02
by Fe 2 0 3 , or from the silicate-sulphate reaction;
However, the pyrosulphates have never been detected. Instead, the mixed
alkali sulphates are believed to be present:
3 Na 2 S0 4 + Fe 2 0 3 + 3S03 2Na 3 Fe(S04)3
3 K2 S0 4 + Fe 2 0 3 + 3S0 3 2K 3 Fe(S04)3
K2 S0 4 + A1 2 0 3 + 3S03 2K Al(S04)3
@ProcessEng
These complex sulphate mixtures can be very corrosive, and typical

superheater corrosion is displaced to either side of the upstream tube
face, foliowing the distribution of the inner sulphate layer of the
deposit. Mildly corrosive sulphate deposits are typically composed of 50%
Ca + MgS04 , 25% Na 2 S04 + K2 S0 4 and 25% (Na, K)Fe(S04)2. A highly corrosive
695
deposit contained 50% KAL(S04)?' 30%(NaK)Fe(S04)2 5% Na 2 S0 4 + K2 S0 4 and 10%

CaS04 (7). The K2 0 contene of corrosive deposits was between 9-11%,
compared with 1-2.5% for the marginal ly corrosive deposits. It is certain
that these complex sulphates form in situ, as they are destroyed in the gas
stream at about 10000K. Despite the admixture of Fe 20 3 and A1 20 in the
sulphate, it is still molten at operating temperatures. If the Sd 3 levels
in the deposit fall for any reason, the complex sulphates may revert to
simple sulphates and iron oxide/alumina. The exact mechanism of corrosion
is not fully understood. S03 is favoured as the principal oxidant. The
rate of formation or destruction of the protective oxide coating is
important, as is its porosity. It also seems likely that sulphides may
form and that sulphidation corrosion as well as oxidation may occur.
The sintering propert y of the outer layer of superheater deposits has
the important effect of increasing their resistance to removal by
sootblowing, and it is this propert y that is most relevant to the plant
operator. Clearly the degree of sintering is important in deciding the
strength of the deposit, but the rate at which sintering occurs will decide
how often sootblowing is needed to prevent uncontrollable build up. This
is decided by the viscosity-temperature relationship of the particle
surfaces, and is therefore determined by the flue gas temperature, the
thickness of the deposit (and hence its temperature), the concentration of
the sulphate species, etc.
The discussion so far has concentrated on pulverised fuel-firing of
bituminous coals in dry bottom furnaces. Many utility boilers are fired
with lower rank coals (i.e. lignites, sub-bituminous coals, or the brown
coals of W. Germany and Australia). These coals contain very different
mineral matter combinations to higher rank coals. Lignites and sub-
bituminous coals have a highly porous matrix that is able to hold large
quantities of exchangeable cations. Most low rank coals have CaO > 10.0%
in the ash, and occassionally up to 35%, hence the observation that CaS0 4
is the chief mineral in low temperature ashes. The Na?O content is more
variable but may be as high as 10.0%, as may MgO. Sulphate (as SO)
contents vary from 10-30%. The Si0 2 + A1 20 3 contents are again quiEe
variable but are usually < 40% of the ash, unlLke bituminous coals where it
is normally between 60-90% of the ash.
Low rank coal mineral matter is therefore dominated by sodium,
magnesium and calcium in organometallic combination and to a les ser extent
as carbonates. Iron is present as pyrite, organometallic-Fe and ankerite.
Silicates are less important than in higher rank coals and usually <40%
ash. Exchangeable Na tends to behave like water soluble NaCl in bituminous
coals in that it volatilises in the furnace and is then either sulphated or
it combines with silicates. Exchangeable calcium and iron form oxide fume
particles of CaO and FeO. The overall mechanism of sintered superheater
deposition is similar to that described earlier except that sodium plays

the dominant role in the sulphate and silicate chemistry. There is an
important relationship however between the sodium and calcium. At lower
levels of calcium, the sintering proces s is enhanced because of the
combined effects of calcium and sodium reducing the viscosity of silicate
particles. At higher levels of calcium however, deposit formation is
retarded. This is possibly due to the formation of crystalline silicate
@ProcessEng
species in the otherwise glas sy silicate particles. Plagioclase feldspars

(e.g. anorthite CaA1 2 Si 2 0 S ) and melilite have been detected, both also
likely to contain sodium Ln the lattice. The residual glassy material has
increased viscosity because of this process of depletion of bases from the
glassy phase and hence sintering is reduced. It is frequently observed
that CaS0 4 crystals grow throughout the porous sintered matrix, and this
696
may strengthen the deposits further. The smaller amounts of silicate and
the absence of densification of the deposits by incipient slagging leave
these deposits with quite a low density. Bridging of tube passages by
deposit is therefore easier as not such a strong bond to tube-metal oxide
is required as that needed for the heavier more siliceous deposits. These
deposits are also more resistant to shedding by thermal shock.
In a similar way to slagging, the prediction of fouling from knowledge
of the composition and properties of the coal ash has met with only partial
success. For instance the strength of laboratory sintered fly ash relates
to the propensity to form bonded deposits. However two coals with ve ry
different sinter strengths shown in Figure 3.4. have very similar ash
fusion properties.(2)
Ash fusion properties LD.T. H.T. F.T.

Coal A 1327 1366 1688
Coal B 1320 1383 1644
'"
Q)
~
1O
..,o:
Q)
....
<Il":
<Il'"
..... Ol I
o »e
4
fi:;::~
gp ·.3
..,
Q)
~
Ul
1000 1700
Temperature K
FIGURE 3.4. Sinter strength for two coals with similar ash fusion
properties.
Various fouling indices have been developed for instance; (in per
cent) .
Na 20 + K20 + CaO + MgO + Fe 20 3 Basic Comp.
Si0 2 + A1 20 3 + Ti0 2
x Na O'"
2 acid comp
x Na °
2
basic components
x Na 20 (water soluble)
Ff.sol
acid components
Plant operators report only 50% and 53% accuracy of fouling prediction
for these two indices, (3) although the accuracy was considerably improved
when used in conjunction with a boi ler parameter, for instance excess air,
or rate of steam generation per unit area.
@ProcessEng
Refuse incineration presents a much more complex fouling problem from

the chemical standpoint. Whilst there are special cases in coal firing
where either chlorides or heavy metals are important components of the
deposition, they are both very common in many deposits from refuse firing.
The results in Table 3.4. give the composition of probe deposits from a
refuse-fired plant in the U.K. Also included are gas-borne particulates
@ProcessEng
Table 3.4. Elemental composition of probe deposits from refuse incineration
----
I Na 20 MgO A1 20 3 Si0 2 p03 s03 cl K2 0 CaO Ti0 2 cr 20 3 Fe 20 3 NiO ZnO
I
FURNACE l 1. 22 1. 37 6.88 10.2 0.79 13 .52 21.44 11. 37 23.68 1.24 0.32 2.74 0.29 4.93
upstream
deposit 2.13 1.11 4.97 11.03 1.80 29.52 7.25 13.29 12.69 1.42 0.77 5.33 0.63 8.26
downstream
particulate 1. 37 2.47 14.38 27.90 2.57 7.77 2.3 3.01 27.57 2.64 0.7l 4.90 0.20 1.96
FURNACE 2 1.67 1.01 5.89 11.98 1.41 31.09 5.08 13 .33 22.36 1.34 0.7l 3.13 0.47 4.76
upstream
deposit 1.46 1.43 6.40 14.63 1.89 32.42 1.13 6.54 26.33 1.65 0.02 4.17 - 1.87
downstream
particulate 1.86 2.52 13.10 27.51 2.87 9.14 2.64 4.30 24.50 1.84 1.45 5.35 0.23 2.72
Fly ash ignition 2.99 2.11 8.96 18.1 1.56 11. 78 3.89 4.92 30.07 2.22 0.53 8.74 0.44 3.67
residue
(Data used by permission of NEL, East Kilbride, Glasgow)

$
-.)
698
sampled near the cooled probe, and the precipitator ash. The notable
features of these deposits are the low Si0 2 and A1 2 0 3 contents relative
to the particulates, and the enrichment of sulphate, cfiloride and potassium
and less obviously calcium. Visually the deposits consisted of hard
impacted materiaion the upstream face, of a grey or whitish colour.
Downstream the deposit was very loosely held together and was rather darker
in colour.
S.E.M. studies show the presence of large numbers of spherical
particles in an apparently porous structure, and a smaller number of lath
like structures. Most of the particles are encrusted in a coating of much
smaller particles, which apparently extend into a crystalline bonding
matrix.
Point analysis of the larger, cleaner spheres revealed a variety of
composition, including Fe 20 1 , partly sulphated CaO and (Ca, Mg,
K)A1 2 0 1 .2Si0 2 . No larger parcicles containing potassium, chloride or
sulpfiace as the major components were detected. This suggests that the
enrichment of K, Ca, Cl and S04 was due to the cementing particles.
A similar mode of deposition has been detected with certain low rank US
coals, where CaS0 4 crystals are seen to permeate the po rous matrix and
provide some of the deposit strength.
The cementing particles appear to be sub-micron in size, and are
probably deposited by diffusion mechanisms. Although the gas stream
temperature at this point is only 9s0-l0s0 o K (i.e. below the sulphate
dewpoint temperature of about 11sO-1200 o K) there may still be some
condensation of alkali metal salts involved in this process. This is more
likely to occur with alkali chlorides than sulphates because of the much
higher saturation vapour pressure of chlorides at these temperatures.
The fly ash, and gas stream particulates from this incinerator gave pH
readings of 11.0 and 10.5 respectively, chemical analysis suggesting the
presence of CaO. It may be that some oxide fume particles are deposited in
the boiler, although they will probably not remain as such in a deposit for
very long, as they will be sulphated.
Boiler deposits from refuse incineration are known to be potentiaily
very corrosive and this phenomenon has been studied in some detail.
Corrosion by elemental chlorine (formed within the deposit by oxidation of
HCl released by sulphation of deposited alkali chlorides) or by the alkali
trisulphates (e.g. K3 Fe(S04)3' formed in a manne r described earlier, both
seem equally likely, as layers of FeC1 2 and sulphate enriched layers have
both been detected in deposits. The proces s of bonded deposit formation in
siliceous coal deposits was shown to be closely linked to the formation of
corrosive deposits, where the sulphate that managed to diffuse straight
through the deposit, concentrated at the surface and under the correct gas
phase conditions (i.e. Pso 2 ) form corrosive mixed sulphates. A mechanism
by which corrosion in refuse deposits may occur is a follows: (8)
within the ( KCl + S02 + 1/202 + H2 0 ~ K2 S0 4 + HCl

deposit (
(2HCl + 1/2°2 ~ H2 0 + C1 2
C1 2 + Fe ~ FeC1 2
@ProcessEng
The role of Zinc in lowering the melting point of particular chloride

mixtures has been linked to the corrosiveness of boiler deposits under
refuse firing. Molten phases within the deposit could possibly destroy the
protective oxide coatings on tube metal surfaces, and enhance corrosion
rates. Zinc was detected in fairly high concentrations in all of the
699
deposits from this UK incinerator. A1most every partic1e examined showed

some enrichment of zinc relative to the fly ash. There was no
concentration of zinc detected in the corrosion 1ayers of those deposits.
No mel ting behaviour was detected in a deposit up to a temperature of
a1most 1150K, a1though this does not prec1ude such behaviour in other
deposits, where very low temperature melting behaviour has been detected.
4. TRE PREDICTION OF FOULING

Most attempts to predict boi ler fou1ing depend on using the fou1ing
indices based on the chemica1 composition of the ash, or on physica1
properties such as ash fusion temperatures or sinter strength. Some degree
of success has been obtained using this approach, particu1ar1y where the
parameter is used in conjunction with a description of the actua1 firing
situation, for instance the combustion intens it y as described by steam
raised/unit are a of furnace.
For instance Figure 4.1. shows the deposition rate for three coa1s
versus temperature, a10ng with the ash burden in the flue gas for each
coa1. C1ear1y deposition here is not re1ated to the amount of fou1ant
present in the gas stream. Instead it re la tes to the high fou1ing index
resu1ting from the high CaO and Fe 2 0 3 content of the ash.
lO Ash burden gm-3
Coal A 3.9
'7 Coal B 3.2
, lO
Coal C 4.2
~
~
~
z
o
;::
!"
soo '00 1000
TEMPERATURE, K
FIGURE 4.1. Ash deposition rate for three different coa1s

Reproduced by permission of Hemisphere Publishing Corporation; E. Raask 1985
In another examp1e it has been found that in firing a high sodium coal
blended with a very high ash coa1 in order to give an overall ash content
of 16% in the pu1verised fue1, if the ash fa11s toa low due to incorrect
blending (i.e. giving a reduced ash burden in the gas stream) the fou1ing
increases as aresult of the increase in uncombined sodium.
In contrast the resu1ts given in Tab1e 3.4. may be re-examined. These
@ProcessEng
two furnaces were firing very simi1ar fue1 as shown by the very simi1ar
particu1ate composition. The deposits were very different, however, in
their contents of chloride and su1phate. On examining the rate of mass
gain on probes in these furnaces, it was clear that the deposit containing
high levels of chloride was accumu1ating about four times faster than the
high su1phate deposit, and the difference in deposition rate cou1d have
700
related to their very different chemistry. However the particulate loading

of the flue gas in the high chloride furnace was als o found to be four
times higher, providing a more reasonable explanation of the different
deposition rates. It is sometimes seen in the literature that calculated
deposition rates are corrected or normalised to allow for such differences
in ash burden, whilst at the same time looking for chemical explanations of
fouling rates. It maybe that a combined approach giving due weight to the
physical transport processes that deliver particles to the fouling surface
may have more succes s in the important area of fouling prediction.
5. CONCLUSION
This brief survey shows the complexity of the phenomenon of high
temperature fouling. Combustion of other fuels, eg. oil or diesel throws
up whole new aspects to the problem. Boiler design, different techniques
of plant operation, continuous fouling monitoring or the use of anti-
fouling fuel additives are some of the areas in which significant progress
has been made in alleviating the problems associated with fouling. As the
availability of non-fouling or slightly-fouling fuels becomes less, it is
increasingly likely that fuel more susceptible to causing to fouling will
be burned, making an understanding of the mechanisms and chemical proces ses
involved more urgently needed.
REFERENCES
1. Garrett-Price, B.A. et al. (1985). Fouling of Heat Exchang3rs. P.48,

Noyes Publications.
2. Steam: Its generation and use. Babcock and Wilcox.
3. Barrett, R.E. et al. (1984). Slagging and Fouling as Related to Coal
and Boiler Parameters. Engineering Foundation Third Conference on
Slagging and Fouling Due to Impurities in Combustion Gases. Copper
Mountain, Colorado.
4. Smart, J.H.S. (1986). The Greater London Council's Refuse-Fired Power
Station. Proc. Instn. Mech. Engrs. 200 (A4) 1986.
5. Halbritter, G. et al. (1984). Comparison of the Stack Emissions from
Waste Incineration Facilities and Coal Fired Heating Power Stations.
In: Recycling International Ed. K.J. Thome-Kozmionsky EF-Verlag fur
Energie-und Umwelttechnik GmbH.
6. Kabayashi, Y. (1984). Present Status of Resource and Energy
Utilization in Japan's Municipal Solid Waste Management. In: Recycling
International Ed. K.J. Thome-Kozmionsky EF-Verlag fur Energie-und
Emwelttechnik GmbH.
7. Raask, Erich (1985). Mineral Impurities in Coal Combustion p. 208
Hemisphere.
8. Vaughan, D.A. Krause, H.H. and Boyd, W.K. (1978). Chloride Corrosion
and its Inhibition in Refuse Firing. In: Ash Deposits and Corrosion
due to Impurities in Combustion Gases. Ed. R.W. Bryers. Proc. Int.
Conf. on Ash Deposits and Corrosion From Impurities in Combustion
Gases. Eng. Foundation.
@ProcessEng
HIGH TEMPERATURE GAS-SIDE FOULING CASE STUDY
A. TSADOS AND T.R. BOTT
Chemical Engineering Department, University of Birmingham, P.O. Box 363,

Edgbaston, Birmingham, BIS 2TT.
l. INTRODUCTION
Fouling of surfaces exposed to a flowing gas stream, occurs due to
both physical and chemical processes. The main fouling mechanisms are
particulate, corrosion and chemical reaction fouling. Particulate fouling
is a physical process, involving both mass and heat transfer to the sur-
face. It also depends on the physical properties of gas, its velocity and
the particle size distribution.
Particulate fouling ean take place with the folIowing mechanisms:
a) inertial impaction
b) particle diffusion
c) thermal diffusion
d) vapour diffusion
2. FOULING PROBLEMS IN(l~FUSE INCINERATION

Miller and Krause made an extensive study of field and laboratory
problems of incineration exhaust deposits and corrosion using a probe.
They identified all the chloride present in the deposit as NaCl, with
higher concentrations found at positions of lower surfaee temperature.
The concentration of the chloride in the deposit was 2 per cent by weight
and that in the corrosion produet scale was l per cent by weight.
Microprobe analysis of the interface between the deposit and metal showed
chloride being next to the metal of corroded tubes, suggesting a possibIe
reaction of a chl?2tde salt with the metal.
Krause et al , using the same probe, reported on a study of the
effect of refuse composition on deposition and corrosion rates. The
investigation involved mixing a certain amount of PVC with the refuse, and
then obtaining data using the corroison probe, for test periods up to 10
hours. The chloride content of the deposit increased with increasing PVC
content, but decreased with increasing metal temperature. The gas
temperature also affected its concentration, with lower chloride values
being observed at higher gas temperatures. Phase studies of these
deposits by X-ray diffraction, revealed the existence of iron chloride at

the metal surface, below the protective oxide layer which separates the
deposit from the test surface. (l)
The experimental results of Krause et al were obtained from rela-
tively short probe exposures to the flue gases (about 10 hours). In that
period, corrosion rates were increasing and should not be extrapolated to
predict long term corrosion effects. During previous tests, exposure time
@ProcessEng
was 800 hours, during which the corrosion rate reached an asymptotic
value.
3y
Sulphur bearing compounds playan imp ? ant role in corrosion at low
and high temperatures. A study by Kaiser revealed half the amount of
701

702
sulphur from refuse to leave the incinerator as grate residue, one fourth
in the collected and emitted fly-ash and one fourth in the stack gases as
SO. Pyrosulphates and bisulphates are very corrosive salts at about
3000G due to their low melting points(4). The presence of a liquid phase
on the metal tube is of great importance since corrosion reactions, which
are electrochemical in nature, take place more readily in lt3yids than in
solids or gases. The bisulphate and pyrosulphate salts can react with
the tube metal to form iron sulphide.
An interesting observation made by Krause et al(6), was that addition
of sulphur to domestic refuse, can produce a marked decrease in the
overall corrosion rates with carbon steels and stainless steels. These
tests were carried out at an incineration plant using a corrosion probe.
The sulphur content was increased from the normallevels of 0.2 per cent
to 1.0 and 1.7 per cent. The amount of SO? and sulphate compounds was
increased but the chloride content of Ehe deposits was reduced
significantly. This latter observation was put forward as an explanation
for the reduced corrosion rates, as the sulphates are more stable than the
chloride.
The deleterious effects of lead and zinc salts, particularly chlor ide ,
result from the formation of liquid phase. When these salts are mixed
with other low melting chlorides (NaGl, KGl) they form eutectic mixtures,
which exist tll)the molten state at even lower temperatures. The sources
of Pb and Zn in the refuse are the plastics to which they are added as
thermal stabilisers, and metal scrap. Lead has been reported(r~ exist in
concentrations of 20 per cent by weight in the corrosion scale .
3. THE N.E.L. PROBE AND ASSOGIATED EQUIPMENT

The fouling potential of incineration exhaust streams was studied
with the N.E.L. fouling probe. The sample collection pieces are 50 mm
long and 25 mm in diameter and are cooled by water or air. The tempera-
ture of the sample collection pieces is measured by inserting
thermocouples in 0.5 mm bore wells drilled axially into the metal. Data
collection and recording is performed with an automat i c data acquisition
system, instalIed in a caravan which can be positioned close to the test
location.
Frequent determinations of the particulate concentration in the gas
stream are made with a cascade impactor, which also provides the
aerodynamic particle size and size distribution. It can be used in gas
streams up to 42s o G. Gas-stream velocity is determined with a pitot-
static tube.
The problems encountered in refuse incineration exhaust environments,
where the N.E.L. probe has been used to obtain fouling data during this
study, are different to the problems of coal firing systems. This is due
to the very different character of the fuel and variability; the plastic
content of domestic refuse is an important consideration.

The N.E.L. probe was used at two different sites for evaluation of the
fouling potential of the exhaust streams.
4. TESTS AT THE GOVENTRY WASTE REDUGTION UNIT

4.1. The test site (Fig. l)
The fouling probe was used at the Goventry Waste Reduction Unit of the
@ProcessEng
former West Midlands Gounty Gouncil. This unit is a domestic refuse

incinerator with very littIe commercial refuse. The refuse is transferred
from the storage bunker into a feeding chute and into the furnace. The
refuse burns on a chain grate and the exhaust gases, af ter making a 180 0
703
Boiler drum
Combustion
ehamber
Feed
ehute
Duet to
Stoker --Æt-=- ehimney
CD Fouling probe position

® Dewpoint probe position
FIGURE l. Flow Diagram of the Coventry Waste-Reduction Unit
1800r-------------------------------~
Ol
E
:;: 1400
.c.
Ol
.~ 1000
8.
VI
600
CII
O
200
O 2 3
l. 5 6
Time (hrs)
FIGURE 2. Deposit Weight as a Function of Time at Different

Surfaee Temperatures. Coventry Incineration Plant.
Total Deposit.
@ProcessEng
704
bend pas s through the tubes of a shell and tube heat exchanger. The
6
temperatu e of the gases before passing through the heat exchanger is
about 800 e, and is reduced to 300 0 e on exit. The gases are then passed
through an electrostatic precipitator before being discharged to the
atmosphere. The position where the fouling probe was inserted into the
exhaust was upstream of the heat exchanger (Fig. 1), which was used to
raise steam by extracting heat from the flue gases.
Problems in the heat exchanger due to fouling soon showed themselves
during operation (7). Solids accumulated on the water side face of the
lower tube sheet due to poor water recirculation. In addition fouling was
occurring on the gas side face of the same tube plate, alleged to be
sulphate deposition. Erosion of the tube sheet was als o taking place.
The fouling resulted in:
1. Overheating of the tubesheet and weld cracks.
2. Thinning of the tube sheet, in some areas by as much as half the
original thickness.
3. Loss of operating draught (up to 180 mm WG).
4. Excessive and difficult cleaning requirements.
4.2. Fouling probe tests and results
Due to the fouling problems mentioned in the previous section an
examination of the gas side fouling was made.
The tests carried out at eoventry's incineration plant were mainly
mass deposition tests. The duration of the tests varied between 1/2 hour
and 6 hours. The specimen surface temperature was controlled between
270 0 e and 800 o e. The flue gas temperature at the position where the probe
was inserted into the duct, was normaIly around BOOoe. Flue gas tempera-
ture fluctuations were inevitable due to the variability of the refuse
burnt, operating conditions and to the decreasing fuel input, as the heat
exchanger, further downstream of the test site, became fouled. Both air
and water supplies were available to provide cooling of the test sections.
The nature of the upstream deposit was very different from that
downstream and this pattern was followed in all the tests. The upstream
deposit was thin (0.5 mm), dark, hard and uneven and could not be easily
removed. Washing had littIe effect in cleaning the surface to its
original condition. The downstream deposit was light coloured, soft,
uniform and powdery. The top part of the deposit could be easily blown
off the surface. Some degree of corrosion on the sur face was evident.
During tests at higher surface temperatures, both the upstream and
downstream deposits were darker in colour.
The total amount of deposit collected during each test is plotted for
different times in Fig. 2. Although some experimental scatter is evident,
a linear increase of deposit weight with time is noticed. A plot of
deposition rate against surface temperature shows a very steep increase of
the deposition rate from 27s o e up to 4s0 o e, (Fig. 3). This suggests the
existence of low-melting substances which provide a "sticky" surface for
further entrapment of particles. The considerable scatter of the five
data points in the range 600 o e-82s o e is probably due to the initial high
deposition rate, the value of which seems to level off with time, af ter
first hour of exposure. Similar plots (Figs. 4, 5) for the upstream
and downstream deposition rate show the same tendency.
@ProcessEng
Typical results of chemical analyses of an upstream (lU) and a

downstream (10) deposit are shown in Table 1. The analysis of a deposit
705
("Il
'5 11,. x x
'L..
L:.
12 x x
Ol
E x
10
Q)
.......
oL..
x x
8
c
o
x
6 x ;::x
x
.......
'Vi
o
a. l,.
Q)
o
O 300 400 500 600 700 800 900
Surfaee temperature (Oe)
FIGURE 3, Deposition Rate as a Function of Surfaee Temperature.

Coventry Incineration Plant. Total Deposit.
N 20 l -
Ix
X
lE
u 18 - X
T
I
L.
.c 16 r- X
01
E. 14 - X
....<Il X
E! 12 - X
c
o 10 "-
.... ~x
!xx
X
VI
o 8-
o.
O
<Il
6r- X lX X
X
I I I I I J
300 400 500 600 700 800 900
Surfaee temperature (Oel

@ProcessEng
FIGURE 4. Deposition Rate as a Function of Surfaee Temperature.

Coventry Incineration Plant. Upstream Deposit.
706
9
X
'"E 8
I
u
f-
T L- 7 f- x
.c x X x
E6 f- x XX
X
25 f- x~
X
Cl X
L-
x
f-x X
.§ l. X X
.~ 3 f-
o. X
~ 2 I-- I I I I I I
300 1.00 500 600 700 800 900
FIGURE 5. Deposition Rate as a Function af Surfaee Temperature.

Coventry Incineration Plant. Downstream Deposit.
Sewage
sludge
Refuse
l.. To electrostatic
precipitator
and stack
Ash
FIGURE 6. Flow Diagram of Alloa Incineration Plant

@ProcessEng
707
TABLE 1. Chemical Analysis of Deposit Coventry Incineration Plant
Percentage Mass
lU ID G
Element (upstream) (downstream) (Refractory wall deposit)
Fe 16.00 16.00 1.15

Pb 1. 50 2.00 N/D
Zn 2.5 2.75 2.75
Al 2.78 2.36 5.01
Ca 2.65 N/D 2.55
Mg 1.43 0.78 1.43
Cr 2.38 1.10 N/D
K 6.51 3.62 5.90
taken from the sur face of the refractory lined walls upstream of the heat
exchanger, is also shown (G). The high iron content of the deposit indi-
cates that it consists mainly of corrosion products, while the small
amount found in the refractory deposit, suggests that littIe iron is
volatilized from the refuse. The presence of chromium in the deposit
further supports the fact that corrosion takes place at the metal deposit
interface. Lead concentration was higher in the lower temperature
deposit. This may reflect higher volatility of compounds containing that
element at high temperatures. The ab ove mentioned chemical analysis was
carried out for deposits collected at surface temperatures varying between
260-400 o C.
The high exhaust gas temperature (800 o C) at the location of the probe
made particle size analysis and gas velocity measurements impossible. Any
attempt to "infer" these data from data gathered at other points could be
misleading where particle size distribution is concerned. Particle agglo-
meration is likely to take place as the dust burden moves through the
plant. At the same time some particulate matter will be "filtered out"
due to deposition in the plant. Because of the wide variation in flow
area, and problems of assessing temperature distribution, precise estimates
of gas velocity at the probe location ahead of the exchanger would be
extremely difficult. Nevertheless "practical" fouling data in the loca-
tion would be helpful for design and operation purposes. These factors
limited any further treatment of the results based on calculation of the
probe collection efficiency.
4.3 Redesign of the boi ler
The unsatisfactory fire tube boiler was replaced with a water tube
boiler of more conventional design. The target of 4000 hours operat}~n

between "shut downs" for major cleaning was exceeded by a large margin .
5. TESTS AT ALLOA INCINERATION PLANT

5.1. The test site
The N.E.L. probe has been used to obtain fouling data at the Bowhouse
Incinerator plant operated by Clackmannan District Council, Alloa (Fig.6).
@ProcessEng
Combined incineration of refuse and sewage sludge takes place in a multi-

hearth furnace. Sludge is fed into the uppermost hearth and refuse is
introduced at the first combustion hearth. The wet sludge is fed
downwards through the furnace by a motor driven, revolving, insulated
central shaft, to which radial arms with rabble teeth are attached. Com-
708
bustion of refuse occurs mainly in the first combustion hearth, and the
gas 5s evaporate the sludge moisture, thus reducing the temperature to 400-
600 C. (8)
5.2. Fouling probe tests and results
Before carrying out the mass accumulation tests, preliminary trials
were carried out using a special probe design, which could test a number
of test sections of different material. These tests were both longer in
duration (up to l week) and covered a wider range of surfaee temperatures
than the subsequent mass accumulation tests. On the basis of simple
comparisons, 316 stainless steel was chosen as the most suitable material
for the tests, free of any corrosion effects.
Measurements of mass accumulation on the P60be test sections were
carried out at surfaee temperatures between 150 C and 450 0 C - the gas
stream temperature. The fouling probe was positioned in the vertical
section of the duet which carried the exhaust gases upwards towards the
electrostatic precipitator. Cooling water sprays are positioned
downstream of the test location, to lower the gas temperature before
entering the electrostatic precipitator.
Part way through the test programme, the plant configuration was
modified and the cooling water sprays were moved further downstream from
the test location. The nature of the deposits changed as a result, and it
is necessary to differentiate between the two sets of data obtained. With
the sprays in position l, the deposits were hard and dark in colour, and
could not be eas ily removed by water washing or scraping. With the sprays
more remote in position 2, the deposits were lighter and powdery with
relatively weak adhesive forces.
There was no corrosion on the metal test sections used in these tests.
The low chromium content of the deposit (Table 2) is further evidence.
TABLE 2. Chemical Analysis of Deposits Alloa Incineration Plant
Percentage Mass
Element Upstream deposit Downstream deposit
Si 7.33 6.63
Al 4.46 4.45
Fe 7.00 6.09
K 0.63 0.61
Na 1.49 1. 05
Co 3.53 3.13
Ni 1.25 1.06
Cr 0.93 0.81
Mg 0.78 0.67
S04 2.21 1. 35
Cl 18.00 20.00
Therefore, it may be assumed that only physical mechanisms are

@ProcessEng
responsibie for the accumulation of materiaion the probe. From a

particle size analysis (Fig. 7), the "mass medium diameter" was 3/lm,
suggesting that inertical impaction mechanism was responsibie for the
upstream deposit. In all these tests, the downstream deposit mass was
much greater than the upstream deposit. Since the overall deposition
709
0·1
~ 0·2
å. 0·5
o 1
c 2
c x
.c.
..... 5
10
\Il
\Il
~
<1.1 20
Ol
.....c
c
<1.1
40
U
L-
<1.1 60
Cl.
80<1.1
>
.....
c 90
~
E 95~
u 98
99
2 0·5 03
Equivalent aerodynamic diameter.
Op .50. (pm)
FIGURE 7. Cumulative Percentage Less Than D S ' as a Function of

D S ' Alloa Incineration Plant. p, O
p, O
110
L:" 100
~ 90
Ol
E 80
2 70
e 60
c
o 50
~
111 40
o
o. 30 -
cv
o 20
@ProcessEng
10 >'X-
o 150 200 250 300
FIGURE 8. Deposition Rate as a Function of Surfaee Temperature.
Alloa Incineration Plant. First Set of Data.
710
150.------------------------------------,
o 150°C
x 190-205°C
Ol + 250°C
E
• 300°C
~ 100
Ol
ijj
o
~
.....
1/1
o
g- 50
.J<---
Cl x
OL-__L-__L -__~__J __ _~_ _~_ _~--~---L--~

•
023 4 5 6
Time (hrs)
FIGURE 9. Deposit Weight as a Function of Time at Different Surfaee

Temperatures. Alloa Incineration Plant. First Set of
Data.
200
Ol
.5. 150
....
.c
Ol
'ijj
....~
'iij
100 x x
o
a.
GI X
Cl x
50
/x
X
x
00
FIGURE la. Deposit Weight as a Function of Time. Alloa Incineration

@ProcessEng
Plant. Second Set of Data.

711
process was not found to be a strong function of thermophoresis, it was

clear that sedimentation fouling was the major mechanism determining the
overall fouling rate. It is only when the temperature difference between
the gas stream and the surface becomes more than 200 o C, that thermphoresis
becomes significant (Fig. 8). In Fig. 8, it can be seen that as the
surface temperature decreases to lSOoC- corresponding to a temperature
difference of 2S0 o C- then the deposition is eliminated at this tempera-
ture, as the gas dew point was measured at 78 o C. The chlorine content of
the deposit is typical of exhaust streams of incinerators burning sewage
sludge.
The different amounts of deposit obtained during the two different
positions of the water sprays are presented in Figs 9 and 10. The first
set of data shows a linear increase of foulant mass with time, for a given
isotherm. The second set of data (Fig. 10), shows a higher rate of
deposition and the amount of deposit is not influenced by the temperatures
difference between surface and gas stream. The strong deposit formed with
the sprays in position 1, suggest, that some degree of intermittent up-
stream migration of water had occured from position 1, and produced a
marked influence on the nature of the deposit.
The results obtained from the two different studies show the effect
of the gas temperature on both the amount the nature of the deposit.
Data obtained from Coventry Waste Reduction Unit suggest that chemical
reaction fouling and inertial impaction are the main deposition
mechanisms. The deposition rate increases up to surface temperatures of
about SOOOC, indicating the possibie existence of liquid phases at that
temperature. Results from Alloa Incineration plant support the view that
physical deposition of particles takes placed without anyevidence of
corrosion. The higher deposition rates at the lower sur face temperatures
can be attributed to increased thermal diffusion as the temperature diffe-
rential between the surface and the exhaust stream becomes larger.
The data collected from the two incineration plants indicate the
importance of temperature, particle size distribution, mode of operation,
and plant geometry on the potential fouling problem.
These limited data are of value for the conceptual design of future
incineration plant. Further plant studies are envisaged in order to
obtain a more comprehensive set of data, which will provide abetter
understanding of the effects of ~he different variables.
REFERENCES
1. Miller, P.D., Krause, H.H., "Factors influencing the corrosion of

boiler steels in Municipal Incinerators", Corrosion NACE, Vol. 27, No.

1, Jan. 1971, pp 3l-4S.
2. Krause, H.H., Vaughan, O.A., Boyd, W.K., "Chloride corrosion and its
inhibition in refuse firing", from "Ash deposits and corrosion due to
impurities in combustion gases", R.W. Bryers (Ed.), pp. 473.
3. Kaiser, E.R., "The sulphur balance of incinerators", J. of Air Pollu-
tion Control Assoc., Vol. 18, 1968, pp. 171-174.
@ProcessEng
4. Kerekes, Z.E., Bryers, R.W., Sommerland, R.E., "Corrosion mechanisms

in refuse-fired steam generators related to superheath tube failures",
from "Proceedings of the 1972 National Incinerator Conference", pp.
l20-13S.
S. Krause, H.H., Vaughan, O.A., Miller, P.D., "Corrosion and deposits
712
from combustion of solid waste", J. of Eng. for Power, July 1974, pp.
216-222.
6. Krause, H.H., Vaughan, O.A., Boyd, W.K., "Corrosion and deposits from
combustion of solid waste: Part III: Effects of sulphur on boiler tube
metals", J. of Eng. for Power, July 1975, pp. 448-452.
7. Hall, G.S., Knowles, M.J.D., "Good design and operation reaps benefits
on UK refuse incineration boilers over the last ten years".
Proceedings of Symposium "Energy recovery from reguse incineration",
Institution of Mechanical Engineers, University of Strathclyde, 1985.
8. Tsados, A., Ewart, W. R., Isdale, J., Bott, T. R., "Measurement of
fouling in domestic refuse incineration plant", presented at the 22nd
National Heat Transfer Conference and Exhibition, Niagara Falls, New
York, August 5-8, 1984.
ACKNOWLEDGEMENTS
The author wishes to express his thanks to his friends for the
technical help provided by J.D. Isdale, W.R. Ewart and N. Glen. He would
also like to acknowledge finance provided by the U.K. Department of Trade
and Industry (National Engineering Laboratory), which enabled this work to
be undertaken. The substantial help provided by personnel at the Alloa,
Coventry plants is also much appreciated.
@ProcessEng
@ProcessEng
COOLING WATER FOULING - Summary of Discussion
Paul Watkinson
A brief introduction to cooling water fouling problems was presented

by the chairman who stressed that at least three mechanisms were usually
operative in cooling water fouling - precipitation, particulate and
biological fouling. Thus, interactions between fouling types are
important. Cooling water systems of different designs e.g. single pass
or recirculating will affect the cooling water chemistry and treatment
and hence impact on the relative importance of the different
mechanisms.
Fouling Data on Cooling Waters
A large set of experimental data on some 17 waters has been collected
and published by J. Knudsen and co-workers. J. Chenoweth presented some
of this data on effects of surface temeprature, velocity, and tube
materiais. J.G.T. Savelkoul showed some experimental results of fouling
of carbon steel heat exchangers by phosphonate and polymer treated
cooling water at concentration factors of 5 to 6. While his conclusions
agreed with recent work of Knudsen on polymer quality for stabilization,
general fouling behaviour was different in that af ter 50 day runs of
continuous fouling no asymptotes were reached. Deposits were calcium
phosphates. H. Merry described the experience at a large generating
station which was tubed half in aluminum brass and half in titanium.
Water was at a concentration factor of 1.65 and CaC0 3 scaling was
expected. Fouling was higher on the titanium tubes where the deposit
was composed of particulates plus calcite, than on the aluminum brass
tubes where a combination of biofilm and particulate was found. Surface
charge effects were suspected of contributing to this difference.
Similar effects with aluminum brass versus titanium were reported by
others in the audience however American experience with sea-water was
just the opposite. The need for understanding charge and surface
effects to explain fouling on different materials is evident.
Interpretation of Fouling Data
N. Epstein gave an interpretation of Rf * vs Ts data of Dunqi and

Knudsen[l] to separate the scale strength temperature dependence from
that of the fouling rate. The former decreases with temperature whereas
the latter increases, and thus plots of lnR f * vs l/T. lump together
opposing effects. S.H. Chan queried the use of the Kern-Seaton equation
for situations where the wall temperature is not constant, or where
deposits are rough. P. Fryer also questioned the appropriateness,
@ProcessEng
validity and relevance of the Kern-Seaton equation, as well as the

strong temperature depen~ence of the scaling rate dependence. In
response it was pointed out that the asymptotic equation Rf = Rf *
(1 - exp (-t/t c » is often used as an empirical correlation of data and
the use of the equation rioes not necessarily imply the validity of the
Kern-Seaton assumptions. The surface integration step in crystalliza-
715
L. F. Melo el al. {eds.}, Fouling Science and Technology, 715-717.

716
tion fouling does have a strong temperature dependence.

Combined Fouling Mechanism Effects on Deposit Strength, Induction
Per iod &
and
The effect uf deposit composition on cooling water deposit
strength was introduced by presentation of the plot of strength factor t c
from the asymptotic equation Rf = Rf*(l exp(-t/t c )) versus impurity
level in CaC0 3 scale reported by Morse and Knudsen[2]. Further evidence
for the effect of impurities on deposit strength was sought. The effect
of potato addition to boiler water on boiler water scale strength
discovered decades age was mentioned by H. Muller-Steinhagen. The
weakening effect of co-deposition of particulates with scale w~s shown in
the early movies of H.T.R.I. according to Epstein. A. Pritchard
supported the view that "impurities" presumably referred to particulate
impurities since it was unlikely that different dissolved species would
reach solubility limits at the same stage and co-deposit as an impure (or
mixed), weak crystalline deposit.
L. Melo present ed some data on combined biofouling and kaolin
particulate deposition. With mixtures of kaolin deposition and
biofouling, higher Rf and significant induction periods were noted. A.
Pritchard reported that if nutrients and kaolin were well mixed
beforehand, no induction period is observed. An adsorption step
involving the kaolin may occur. H. Visser discussed the role of positive
charge effects on clay particle edges and the negative charges on the
surface. L. Melo described pH effects.
Enhanced Surfaces and Fouling
The use of turbulators to minimize chemical reaction fouling was
discussed by B. Crittenden, N. Epstein and R. Bott. Increasing the heat
transfer coefficient at the wall would tend to decrease wall temperature
and hence fouling. The impacts of turbulators on cleaning and on crevice
corrosion were mentioned. C.B. Panchal remarked that turbulators were
only one of many kinds of enhancement devices, and in fact give mild
enhancement. Could the enhancement shape be designed to reduce fouling
rather than to increase heat transfer under clean condit.fons?
The Role of Turbulent Bursts
H. Merry presented work from Birmingham on particles of 40-200 ~m
which were initially at rest on surfaces leaving the surface at an angle
of about 5° and being lif ted into the turbulent region. P. Fryer
mentioned work in early 1980's at Cambridge showing angles of 5 to 15°.
J. Visser stated that the results were just as he would predict without
invoking turbulent bursts. N. Epstein noted that the above work dealt
with single isolated particles which is different from particles embedded
in a deposit. He reiterated his argument that, in order for deposition
and removal to occur at the same time on the same overall surface, some
force over and above the average shear stress must be exerted on part of
the sur face to cause removal there while deposition was occurring on the
rest of the surface.
A Plea from Industry
P. Cousineau stated that industry needs help in identifying mechanisms
and in application of theo ries to complex fouling problems such as Bayer
proces s liquors. A. Pritchard suggested the initial attack on industrial
@ProcessEng
fouling problems could focus on what the deposit consists of, and on the
separation of mechanism into, for example, crystallization versus
particulate fouling. This information will provide guidance on key
variables for design and operation of heat exchangers.
717
Conc1uding Comments
The active discussion summarized above i11ustrates we still have a long
way to go in coping with fou1ing in coo1ing water systems. The large
co11ection of U.S. data has not yet been incorporated into a predictive
model accounting for water chemistry, and unexpected, unexp1ained, or
contradictory resu1ts, accompany a1most every report of new data.
Interpretation needs care, and workers are unhappy with existing equations
but 1itt1e new is being offered. Interactions are c1ear1y important in
coo1ing water systems, and a good start is being made in identifying
effects. Quantification is 1acking for systems where more than one
mechanism occurs. Litt1e information is available on enhanced tube
effects on fou1ing. Fundamental effects of fluid mechanics are being
shown on simp1ified model systems but need app1ication to more rea1istic
systems. Diagnosing causes and designing preventative measures remain a
problem for industry.
Acknow1edgement and Apo1ogy
This report was put together from notes taken by the chairman assis ted
by C. Tan. The author apo1ogizes for any misinterpretations, misquotes
and omissions of pertinent discussion.
References
1. Dunqi, X. and J.G. Knudsen: Heat Trans. Eng. 2, Nos. 1-2, 63-70
(1986).
2. Morse, R.W. and J.G. Knudsen: Can. J. Chem. Eng. ~, 272-278 (1977).
@ProcessEng
DEBATE FOOD PROCESSING FOULING
M. LALANDE
I.N.R.A. - Laboratoire de Genie Industriel Alimentaire

BP 39 - 59651 VILLENEUVE d'ASCQ CEDEX - FRANCE
The debate "Food processing fouling" investigated four major topics
1. EXCHANGERS
One of the most important noticed things was the design of equipment
including correct fouling. The concept of an overall fouling factor is not
sufficient and food industry needs to design exchangers taking into
account fouling as a geometrical and a dynamic factor. The second thing
pointed out was the cleaning of equipment in relation to food material
deposited. If adequacy between deposits to be cleaned and cleaning agents
has been solved in several food industries (dairy, brewery ... ) and on a
macroscopic point of view (recovery of initial heat transfer coefficientsh
in some other fieIds (meat industry, ... ) and on a microscopic point of
view (hygienic apects in terms of microorganisms remaining on heat
exchange surfaces af ter cleaning and rinsing) a lot of progress has still
to be made.
The third aspect considered the good fitting needed between a given
thermal food process and a type or geometry of the exchanger. The
conclusion was that sophisticated exchangers (as scrapped sur face
exchangers) have to be used only if necessary (in case of very high
viscous products) and/ar containing particules products. A majority
thought that use of S.C.E. is not always judicious and in some cases
single tubes and/or plate heat exchangers could be used even for viscous
products.ln food industry shell-and-tube exchangers are avoided.
The last point concerning exchangers revealed the major role that
instrumentation and control could play in monitoring fouling and cleaning
on food exchangers because of very shart fouling/cleaning cycles (less
than 24 h).
2. FOODSTUFFS
The complexity of foodstuffs (complex equilibrium) and their great
thermal sensitivity when heated (behaviour of proteins related to their

tertiary structure) imply their great ability to foul heat exchange
surfaces.Thus, the techniques of characterization af molecules as well in
bulk solutions (state of denaturation, aggregat ion , modification of
physico chemistry) as in deposits are of great interest to understand the
mechanisms of fouling by foodstuffs.
The bulk or surface reactions have not only to be considered in their
fouling involvement but also with respect to food quality (nutritive and
@ProcessEng
organoleptic) .
3. FOULING DYNAMICS AND KINETICS

A consequence of this complex physiochemistry of foodstuffs is that a
general equation does not exist yet to express fouling dynamics and
719
L. F. Melo et al. (eds.), Fouling Science and Techoology, 719-720.

720
kinetics as general laws. Nevertheless in studied cases empiri cal

equations have been set up and are of great interest as predictive models
to simulate the behaviour of exchangers with regard to fouling during
processing (optimal control) and good design of equipment (see topic 1).
4. MECHANISMS OF FOULING AND CLEANING

From the general discussion which occurred during the debate but also
from some private exchanges of information which happened during the
meeting the useful but obvious foliowing conclusions can be drawn :
- fouling and cleaning phenomena can be seen through common
physicochemical fundamentals ;
- heat exchangers can be thought as flow reactors in which chemical
reaction kinetics and interface proces ses are coupled with momentum,
heat and mass transfer
- a surface (cleaned or fouled) could be characterized in terms of its
active sites ;
- we still need to identify how the fundamental processes governing
adsorption onto surfaces are related to fouling mechanisms and
contribute, in parallel to homogeneous and heterogeneous reactions
occurring in bulk and near the interface to determine the
fouling dynamics.
Major people involved in the debate

T.R. BOTT
G. CORRIEU
N. EPSTEIN
P. FRYER
T. GOTHAM
M. LALANDE
T. MARGITTAI
M. MONTELIUS
A. PRITCHARD
R. VIDIL
J. VISSER
@ProcessEng
CLEANING OF FOULED SURFACES A DISCUSSION
Chairrran: Dr. A.M.Pritchard, Harwell Laboratory, U.K.

Rapporteur: Dr. P.J.Freyer, Cambridge Univers ity, U.K.
Chairrran's Introduction
This conference has been devoted so far almast entirely to fouling.Howe-
ver, in may cases it is not possible to stop fouling, and in practical tenns
getting rid of deposits may be even more important than knowing how they we-
re formed in the first place. Despite this the process of cleaning is in ge-
neral very poorly understood. One small exception is the removal of milk de-
posits, but even there the paper by Lalande (IoN.R.A., France) on milk fou-
ling and cleaning showed a lack of agreement about the kinetics of the clea-
ning process.
Cleaning methods can be divided into tw::> types:
(1) brute force methods, such as high pressure jets, lances, drills,and
chemicals that are usually very toxie and corrosive; for these virtually no
scientific analysis of the proces ses has been made.
(2) mild mechanical methods, sueh as the use of brushes ans balls; some
experimental data is available on the efficiency of these methods.
A more detailed analysis of cleaning processes would be wall worth whi-
le,and should leas to lower costs and less hazard. Lund and Sandu have pro-
posed a parallel between fouling and chemical cleaning processes:
FOULING CLEANING
Induction Surface Conditioning
Transport of material Transport of cleaning chemicals
to be deposited to surface of deposit
Attaehment Penetration of deposit by chemieals
Ageing Interaction with deposit do break it up
Removal Removal in solution or suspension
This suggests that the considerable progress that has been made in
modelling the processes that occur during fouling might be repeated if the
same approach were used to model the processes involved in cleaning.
T.B.Margittai (T.B.M.Technologies, U.S.A.); This is a systematic approach to

the problem; from a practical point of view fouling and cleaning are mirror
processes . We need to learn how to get rid of fouling, but we must minimise
it first. Then there is less to remove . If the geometry of an exchanger cau-
ses it to foul slower, there is a longer time between cleanings and also a
shorter cleaning time, as is the case for the exchanger described in my pa-
per. We also never know where in the exchanger the deposi t fonns: if there
@ProcessEng
is 50 per cent occlusion of the surface this could mean that all the surface
is half fouled, or that half of it is completely fouled, and the other half
clean. Once there is any clean area, the chemical cleaner runs through that
elean surface and does not clean the fouled area. Ageing complicates this:
an aged deposit is much more difficult to remove. Cleaning-in-place is a way
of life, a statistical hope that the unit is clean.Every so often it must be
721
L. F. Melo et al. (eds.). Fouling Science and Technology, 721-726.

722
opened up, but we don 't wanto to do it very often. Units that natur':llly foul
slowly are guicly cleaned. Scrape surface heat exchangers are sornetlITeS used
to reduce the effects of fouling, but although they foul slowly they are ex-
pensive and very very difficult to clean and complex to dismantle.
Pritchard : Control of flow distribution is important in both fouling and

cleaning, but difficult. We may aim for the perfect clean, but we don't
al ways get it.
D.Zudkevitch (Columbia U., U.S.A.) : There is a basic difference between

cleaning and fouling : the former is done by people, the latter is a fact
of nature.
LDowney (Bath U., U.K.) : If surfaces didn't get fouled, there would be
no need to clean them. People in industry are more interested in how to
clean surfaces than in how they foul.
Zudkevitch : Sometimes you can't prevent fouling, but you have to clean.
In the tar industry there is only a smal l annua l consumption of
anthracene ; more is found in reboilers than can be used in 50 years.
There is much more stuck on surfaces. This =sts money : about 35 per cent
of material in railway cars stays in the bottom, so shipping creosote is
an expensive business.
Margittai : Can we use a chemical surface treatment to mlnlmise fouling ?

For example teflon sur face coatings reject fouling and are easy to clean.
Zudkevitch : Not on my pan r
J.Visser (Unilever Research, Netherlands) : You have an old pan. But if

the sur face coat breaks we have the problem back again. If we can avoid
fouling we don't need cleaning. This should be possible, but not today.
Pritchard : This suggests that surface conditioning is a useful approach

to the problem. To return to my earlier suggestion, is it accepted that
cleaning is the opposite to fouling ?
Zudkevitch: No. Prevention is the opposite. Cleaning is for the squaws,

prevention is for the engineers.
Visser : We should try to prevent fouling, perhaps by use of van der Waals
forces as suggested in my paper. But every contaminant is different. Each
problem requires its own solution, and for all cases the surfaee must be
modified. The system has therefore to be analysed to see if it is possibIe
to predict its surfaee behaviour. We should recall that dolphins dont get
fouled in the sea. Maybe nature has some solutions that can help us. I
have plants in my garden that do not get wetted : why ? Maybe because of
roughness, surfaee temperature ? Perhaps we could manufacture a non-
wetting pipe.
@ProcessEng
Zudkevitch But would you get good heat transfer? I had some experience
with teflon exchangers : they had a high resistance to heat transfer.
Visser : As Professor Zudkevi tch says, there are other aspects of non-
fouling surfaces such as poor heat transfer. We should therefore go for
723
sur face treatrnents rather than different materials such as stainless steel
and titanium.
Pritchard : One example af a non-fouling surface is a polymer impregnated

with a hydrocarbon oil that is used to make underwater labels for offshore
oil platforms. The oil exuded an to the surface maintains a low surface
energy, and doesn't get covered by marine fouling. The same approach has
been tried for marine paints, but there is sometimes trouble in keeping
the paint stuck to the ship.
Margittai : Ducks have glands that produce oil that stops water from
penetrating their feathers.
Zudkevitch : Both af these are isothermal systems.
Margittai : Peaches and prunes have littIe hairs that stop them getting
wetted, but this solution would make heat transfer difficult.
Pritchard : There shouldn't be a heat transfer problem: all that is

needed is a ccating ane molecule thick, but that layer must be maintained.
One needs a heat exchanger with 'glands' that secrete an antifouling
compound.
J.Chenoweth (Heat Transfer Research Incorporated, U.S.A.) : We talk af

fouling in general, but there are many different sorts, particularly in
the petroleum industry. We are a lang way from preventing fouling. We can
mitigate i t, but if we have fouling we have to clean.
Zudkevitch : In the petroleum industries they live with fouling, they

don't really complain. An exchanger an a refinery reaches an asymptotic
level af fouling and stays there until the next shutdown : people have
learned to ccpe. The economics are also important in determining when you
shut dawn. In milk processing cleaning is crucial, but for many other
processes there is no problem, and they jXlt up with the fouling.
A.J.Karabelas (Thessaloniki U., Greece) : I return to a point made

yesterday : most fouling literature uses a single fouling factor Rf . It is
like having an illness and only taking one's temperature. If we are to
establish connections between fouling and cleaning we need more
information: the thickness af a deposit, its cohesion, the mass flux.
This is a much bette r basis an which to collect fouling data: much af
what is in the literature is incomplete.
C.B.Panchal (Arganne National Laboratory, U.S.A.) : This is an important

point. For a time we have been going off track. We must character ise
fouling. We are not going to avoid it, but we may keep it dawn to an
acceptable level. If we have to remove it we must know its mechanical and
chemical properties, e.g. How much chlorine is needed 7 What effect will
the cleaning reagents have 7 Will the deposit break up 7 Will it swell 7
In our laboratory we are looking at in situ cleaning. Cleaning-in-place is
@ProcessEng
becoming increasingly popular since you don't have to open up the heat
exchanger. For the big OTEC heat exchangers we have to characterise the
problem.
Pritchard Deposit analyses are aften presented in terms af percentages

724
of elements and sometimes of compounds, obtained for example by x-ray

diffraction. VirtuaIly no data is ever presented for porosity, and yet it
can be very important if boiling occurs and corrosive environments are
developed in the pores. Porous deposits should also offer ea sier access to
the cleaning chemicals. Porosity is not very easy to measure, but the
effort should be made. Two more points: (1) I remember Jerry Taborek
saying that in some cases i f people had looked at the thickness of deposit
implied by the Rf value they had used for their heat exchanger, there
would have been no room left for the fluid to flow through it. (2) How far
is there a future in controlling the physical and chemical properties of a
deposit to make it easier to remave ?
Zudkevitch : Whether or not cleaning is carried out depends on the value

of the product relative to manpower costs. A plant manager decides how
long he can run between cleaning on this basis. If the product is worth a
few cent s per pound he'll keep going, but at $25 per pound he will clean
more frequently. There is no general answer to this question.
Pritchard : We certainly need to look at the economics of cleaning. Would

it be true to say that in many cases cleaning is quick, and it is carried
out without too much thought for the consequences e.g. loss of metal by
corrosion from the cleaning fluid ?
H.Muller-Steinhagen (Karlsruhe U., F.R.Germany) : We seem to be assuming

that all cleaning is done by chemicals and that mechanical cleaning is a
waste of time. In one case of cleaning a power plant the chemical clean
cost $12,500 i a mechanical clean only cost $2,000 and left the heat
transfer surface much cleaner.
Chenoweth: More mechanical devices are becoming available for on-line

cleaning. Conco have developed a 300 p.s.i. airgun that fires small pigs
through the fluid in tubes to clean them at regular intervals, every 7-8
minutes. A pressure gauge can be added to tell whether they have got stuck
or passed through. The pigs are collected at the other end and recycled,
so that 10,000 can be fired through in 24 hours. Another device called
Turbotal is a twisted metal ribbon that is inserted into the tube and held
on a bearing at the ends. It is rotated by the fluid flow and fits very
closely inside of the tube. It increases the heat transfer and the
pressure drop, and is claimed greatly to reduce the fouling : times
between cleaning of up to 9 months have been reported. A loose coiled wire
(Spiralelf), fixed at both ends of the tube, which moves back and forth as
the fluid flows past, is available and has been used successfully in the
petroleum industry. Brush cleaning systems have usually used nylon

brushes, but are naw being made in stainless steel and titanium by Water
Services in the U.S.A. Many bal l cleaning systems have used high pressure
to force the balls through the pump. An alternative system floods a low
pres sure system with balls intermittently, giving a much higher
probabili ty of getting all the tubes cleaned. The balls don't go through
the pump, and this increases their life by 95 per cent.
@ProcessEng
Zudkevitch How do you clean a coil insert ?
Chenoweth Perhaps by secondary flow? By uncoiling it ? The coils were

tailored for particular heat exchangers, so may not be useful everywhere.
725
Panchal : What Chenoweth says reinforces my view that we must characterise

the deposit. We cannot assess whether these cleaning devices will work if
we dont know the mechanical properties of the deposit. If the deposit is
hard and crystalline, for example, or if there are stagnant points, they
are not likely to work.
Margittai : This sounds wonderful for the future, but we have to run the
heat exchanger today and tomorrow. Will the characterisation of the
mechanical properties of the deposit be useful now to keep the plant
working ? We have to proceed slowly.
Pritchard : There is one comment nobody so far has made: do cleaning

methods work ? Corrieu and Lalande in their papers have described cleaning
monitoring techniques. Are cleaning monitors needed more generaIly ?
Zudkevitch : Again it all depends on the value of the product. You

wouldn't clean a coal tar plant, but you would clean a vitamin one.
Pritchard : True, but how do you judge the performance of one cleaning
technique against another ?
T.R.Bott (Birmingham U., U.K.) : Perhaps by measuring pressure drop?
Zudkevitch : By telephoning around ?
Pritchard : Is that right ?
Zudkevi tch : It is true for smal l oompanies.
Pritchard : Maybe we need an expert system for cleaning.
H.Merry (National Engineering Laboratory, U.K.) With horizontal

exchangers i t is difficul t to tell whether they are clean, because the
tubes bow and one gets gas blanketing during acid cleaning. Maybe it would
be better to mount them vertically or at a small angle to the horizontal.
Zudkevitch : In the petroleum industry the furnace tubes in large plants

are vertical and one can look through them : i t is done.
Pritchard : This reflects an earlier comment about designing plant to be

cleaned.
Chenoweth : Do you really want chemical cleaning all the time? It is

expensive. with regard to the geometry of heat exchangers they are usually
horizontal because it is easier to take the heads off. Having a slight
tilt is a good idea, but difficult to arrange.
Pritchard : Maybe we need another practical fouling factor. We aIready

have the original clean Rf and the fouled Rf , but perhaps we should
include an attainable value for the exchanger af ter cleaning. There might
@ProcessEng
be different values corresponding to different cleaning treatments and

then one could assess the different costs of cleaning against the added
capital cost of providing the extra surface for less effective but cheaper
treatments.
726
G.Corrieu (Institut National de Recherches Agronomiques, France) : In the

food industry we have no choice : we have to clean for sterilisation. In
milk processing there is much deposit, but in other cases such as
breweries there is very littie and only regular sterilisation is required.
M.Lalande (Institut National de Recherches Agronomiques, France) : The

purity of the product is so important in the food industry that you cannot
disinfect without cleaning.
Margittai : Wherever you have an unconventional deposit, such as fibres in

orange juice that lodge in the heat exchanger, you must cl ean , whether you
require steril ity or not.
N.Epstein (U. of British Columbia, Canada) : You must clean if fouling

affects production. In some cases this is for the long term economics, as
I showed in an earlier paper that covers falling rate processes such as
fouling in evaporators. If one assumes that the aim is to maximise
production the time between cleaning can be related to the cost.
Visser: This is not the point. The heat exchanger we found the other day
had a very heavy deposit. Surely it should have been cleaned long before,
when there was only a thin deposit. Passage of an air-water mixture should
have removed the deposit.
Pritchard : The deposit was on the shell side, maybe it wasn't so

important.
Zudkevitch : The exchanger was about to foul up completely. There were

probably many af them, and ane fouled exchanger wasn't important. If it
had been the only exchanger the fouling would have been noticed earlier.
Chenoweth : I t was badly designed. One finds in refineries that when you
measure the overall effect of fouling, you only notice it when all the
exchangers are fouled up.
P.J.Fryer (Cambridge U., U.K.) : As I showed in my paper, fouling of heat

exchanger networks tha't are robust, Le. tolerant to fouling, may only be
noticed when it is tao late to avoid major cleaning.
Zudkevitch: In the real world we have networks of pipes, and we often

have no idea what is flowing through them.
Chainnan' s Sunmary
My original suggestion that cleaning is more important than fouling has

not been well received. However, a number of valuable points have come out
af the discussion :
(l) Prevention. of fouling is bettenthanhaving to cure/clean it.
(2) On-l ine cl'eaning deserves more attention and new techniques. are
becoming available.
( 3) Cl eaning is determined mainl y by economics.
@ProcessEng
(4) Much more attention needs to be gi ven to characterising deposi ts,

particularly their porosity, so that the hest method can be used to
remove them.
(5) It would be useful to have values; Qf fouling resistances that
referred to the degree af cleanliness achieved after cleaning.
CHEMICAL REACTION FOULING DEBATE
BARRY CRITTENDEN (CHAIRMAN) AND IMELDA DOWNEY (SECRETARY)

UNIVERSITY OF BATH
BATH BA2 7AY
UNIT ED KINGDOM
l. INTRODUCTION
Traditionally, fouling problems have been generaIly classified accord-
ing to the mechanism which governs the mode of deposition. However,
chemical changes or physico-chemical surface effects occur in the majority
of fouling situations found throughout the broadest spectrum of industries,
for example, in
(a) deposition via hydrocarbon degradation
(b) deposition via in situ corrosion
(c) deposition from foodstuffs (particularly dairy products)
(d) gas-side fouling (combustion + inorganic reactions)
(e) bio-fouling (microbiological + biochemical reactions)
(f) crystallisation (physico-chemical surface changes)
(g) particulate fouling (surface effects)
In each case very strong dependencies of fouling rates on temperature
are observed. Since all these mechanisms can be unified by the folIowing
simple schematic:
reaction aging
transportation ~ +
+
adhesion
-- removal
the Chairman posed the general question: does a compartmentalised approach
restriet creative thinkingin particular aspects of fouling, such as
chemical reaction fouling?
Inevitably the ranges of process conditions, typ.es of equipment and
mechanisms involved lead ,to a very complex situation for the comparison of
results, ideas, theoriesand models. For example, in chemical reaction
fouling,temperatures can range from ambient to more than lOOOOC. Feed-
stocks may be pure chemicals or extremely complex mixtures in liquid or
vapour (gas) phase. The equipment may primarily be a heat exchanger, for
example in the crude distillation unit ofan oil refinery, or a chemical
reactor, for example a steam cracking furnace. Reactions may be homo-
geneous or heterogeneous" catalytic or non-catalytic. Heat transfer
surfaces may be treated or coated. Data may be obtained from well
control led laboratory experiments in which there may be problems of
scale-down, or from industri al observations in which theremay be
@ProcessEng
problems of accuracy and control. Overall fouling rates may be governed

by the rates of chemical or physical steps and deposit removal mechanisms
are uncertain.
It may be this 'complexity and the seemingly opposite effects or
situations .which occur throughout industry that have led to very specific
727
L. F. Melo et al. (eds), 'Fouling Science and Technology, 727-729.

728
research being undertaken. This poses the questions:

(al will chemical reaction fouling remain a process-specific
problem? or
(bl is it possibIe to unify the approach and perhaps apply ideas
and techniques from one specific are a or category of fouling
to another?
2. DISCUSSION
Most chemical reaction fouling rates increase as expected with increas-
ing surfaee temperature , but mechanistic changes, both physical and
chemical, are complicating factors. At least two such changes have been
identified in this Advanced Study Institute. Firstly, there appears to be
a marked drop in the fouling rate at or close to the transition from
5
liquid to vapour at the heat tr~sfer surface. For hydroca bons the
change occurs around 300 to 350 C. Secondly, at around 600 c, there is a
change in the type of carbon formation from whisker-growth to homogeneous
gas phase deposition. It is interesting to note that the description of
the deposits found at very high temperatures, namely soot, is also some-
times used for the deposits formed from liquid hydrocarbons at relatively
low temperatures.
It is also interesting to note that some chemical impurities are
deleterious across the entire temperature range, for example oxygen and
olefins. However, others such as sulphur and copper are beneficial in
high temperature gas phase applications but are particularly deleterious
in low temperature liquid phase systems. The very detailed and meticu-
lous work which is reported at this Advanced Study Institute on catalyst
fouling and carbon growth has led to significant advances being made in
the understanding of high temperature process problems. The Chairman
therefore tabled the folIowing questions as a basis for discussion:
(al What ean be learnt from the work at high temperatures to help
solve the problems at low temperatures?
(bl Are heat exchangers operating at low temperatures likely to
aet as catalytic reactors?
(cl Is it possibIe to study the initial stages of growth or
attachment in heat exchangers?
(dl Is it possibIe to develop fouling probes for low temperature
hydrocarbon work in industry?
(el Can control of feedstocks and opera ting conditions be used
effectively in order to alleviate fouling problems?
The laboratory techniques which have been used for high temperature
gas phase studies, such as electron microscopy and microbalance reactors,
have been attempted on small cells and the fouling of oils has been filmed.
This work is embryonic. Work on the fouling of lubricating oil in motor

engines, in particular on the catalytic effect of the metal, has been
carried out using the microbalance technique. Viscosity is a limiting
factor, and the forces and turbulence in the oil lead to loss of sensi-
tivity, thereby precluding the use of such equipment on-line. Neverthe-
less, it may be possibIe to use small samples of the heat exchanger
fluid and to treat them batchwise.
@ProcessEng
Any possibility of unifying the approach to reaction fouling should

come from a basic understanding of the fundamentals. To do this, systems
in which the chemical reactions involved are reasonably well understood,
such as styrene polymerisation, need to be studied. However, research
with such model chemical systems ean create uncertainties in realism.
Laboratory.work has also been carried out using synthetic and crude oils
729
in order to simulate fouling in refinery heat exchangers, but these

experiments often do not yield deposits of the same chemical composition,
structure and morphology as those found in the fieid. The consequential
difficulties in interpretation arise from the need to scale-down hydro-
carbon systems for laboratory use and the need to accelerate the fouling
experiments. Plant data often suffers from poor accuracy. In addition,
there may be inadequate instrumentation for a detailed study of fouling
on-site. It was suggested that it may be possibie to use tracer s in the
field and to study how these were included in the deposits.
The compromising of experiments is unfortunately necessary in indust-
rial plants. Naturaily there is a certain amount of resistance from
plant/refinery management and operators. Hence any specialist field
equipment should not intrude in the work environment and must be intrin-
sically safe. There is much scope for the development of portable
fouling probes, of the kind described by both the National Engineering
Laboratory and Heat Transfer Research Incorporated, for refinery and
chemical plant service.
3. CONCLUSION
Much scientific effort has been directed at the fundamentals of carbon
growth from gases at high temperature. Very littie, if any, attention
has been paid to the attachment, growth and removal of deposits from
liquid hydrocarbons. Apart from chemical analyses, very littie is also
known about the structure of such de~Jsits. Future studies, both
laboratory and fieid, should therefore include:
(al nature of reactions occurring at, or close to, the surface
(bl physical properties of the deposit-fluid-surface interface
(cl aging of deposits
(dl characterisation of the mechanical, thermal and chemical
properties of the deposits.
The unique and complex chemical structure of many hydrocarbon streams
implies that such studies may have to be carried out on a broad range of
feedstocks, temperatures, flow rates, etc.
@ProcessEng
DEBATE ON GAS-SIDE FOULING
J DISDALE
NATIONAL ENGINEERING LABORATORY, EAST KILBRIDE, GLASGOW
To open the debate, it was suggested that the main priori ty for gas-side
fouling research should be to provide methods for predicting Rf in prac-
tical situations, and, to provide a focal point for the discussions, the
NEL project with this aim was reviewed as an example of one approach to the
problem. Participants were then asked to comment on the project's aims and
methods to help define the priori ties in this area.
The NEL approach was based on the view that the mass accumulation was the
key unknown and the main source of uncertainty for the calculation or
prediction of Rf ; the other parameters, the effective density and conduc-
tivity of the deposits, could often be estimated with sufficient accuracy
for many engineering applications from some knowledge of the deposit
materials, or indeed measured independently. Most gas-side applications,
however, involved several deposition, collection, and possibly removal
mechanisms, and many were also controlled to some degree by chemical
factors such as corrosion or reaction fouling. For higher temperature work
particle residence time and radiative heat transfer could also influence
the mechanisms. To cope with such a collection of simultaneous processes,
the NEL approach was based on the experimental measurement of mass
accumulation using robust probes of simple cylindrical geometry. The mass
data so obtained were used to identify the relevant mechanisms and develop
analytic models based on these and on the chemical and physical analyses of
gas streams and deposits.
The analytical problem was hampered by the lack of an accepted general

method or system of equations in mass collection efficiency, to cope with
the concurrentaction of several processes, each of which, in the case of
particulates, might also require an individual sticking probability. The
current NEL approach was based on a modification of the equation for

summation of efficiencies given by Whitmore and Meissen 1 • This was used in
effect to convert the mass data to a single effective sticking probability
for the environment, with measurements covering as wide a range of surface
and gas stream conditions as possible. The influence of particle size
distribution was alsoirtcluded, but the 'need here was for a robust and
simple method to measure distributions at high temperatures in industrial
@ProcessEng
environments.
The results of thi s methodology were illustrated for diesel exhausts and
impaction fouling in incinerator plant, where less sophisticated modelling
had produced successful predictions from mass probe data. The chemical
background to the current study, fouling from pulverised coal combustion,
731
L. P. Melo el al. (eds.), Pouling Science and Technology, 731-733.

732
and some pilot measurements in incinerator exhausts had been presented in

earlier papers 2 ,3 and typical deposit patterns were illustrated. Future
work on fouling from combustion of refuse-derived fuel was planned.
There was general agreement that the development of prediction methods to

give realistic values for Rf should have a high priority, and the merit of
direct measurement of Rf as opposed to the analysis of its constituent
variables was discussed. The general view was that both approaches would
be useful in different circumstances. While direct Rf measurements would
be cheaper and possibly better when carried out and applied in a specific
plant, the mass-conductivity-density approach would provide a deeper
insight, and have a wider range of potential application. The latter
would, therefore, be more appropriate for the most costly types of fouling,
where the advantages to be gained were large. The view was also expressed
that measurement of effective density and conductivity of the deposits
could be more important than had been suggested, as both could be difficult
to estimate, especially for porous or irregular materials.
The use of probes was considered to be the leading issue for gas-side
fouling, especially in the US where Jet Propulsion Laboratory was believed
to be developing a double probe system to measure mass accumulation and
heat flux simultaneously. This type of approach would have the advantage
that the effective conductivity of the deposits would be measured at the
stream conditions, together with the mass accumulation rates. While the
present NEL probes provided some data on heat flux from temperature
measurements in the probe coolant, the heat-transfer area was small and it
was difficult to obtain sufficient precision to produce reliable values,
though developments were in progress. Further developments in this
direction were indentified as being important.
There was also some discussion on how fully developed analytic models
might be used for design and related activities, in particular how they
could help to select the best geometry for a particular situation, choose
between gas flow inside or outside a tube system or calculate the effects
on fins. While such models would clearly have limitations in the range of
conditions over which they could be applied they provided the only alter-
native at present to full-scale tests or guesswork based on experience.
The fact that they were based on measured data from the environments
concerned and made suitable use of any available theory, helped to de fine
the limitations. Provided the geometries considered, and the other
environmental variables, fell within these limitations, then the models
would provide a useful tool for improvement and optimisation of design or
operation. However, extremely complex geometries (such as multiply baffled
exchangers with sinuous or variable passages) produced a very wide range of

flow conditi.ons, which were in practice difficult to cover adequately using
a cylindrical probe. In these specialised cases, full-scale testing was
the only reliable alternative, but there was no reason in principle why a
similar experimental technique combined with appropriate analysis could not
provide viable solutions for application in refining, combustion and many
other industries.
@ProcessEng
The broad conclusions which may be drawn from the debate were:
l Allowances for fouling should be made at a very early stage in the

design process, and consequently the provision of a background education in
733
fouling for designers was seen as an important issue. In this context

attempts should be made to differentiate uncertainties associated with
accepted design procedures from those arising exclusively from fouling.
These measures would help to avoid the selection of arbitrary solutions
which often make fouling problems worse.
2 The produetion and interpretation of data from probes was felt to be a

key issue. Since the most significant and costly fouling problems often
occurred in extremely complex fouling environments, there was a clear need
for reliable experimental data to improve our understanding of these at
both the practical and theoreticaI leveIs. Interpretation of bulk data
from a plant, where effects were averaged over a wide range of physical and
chemical conditions was difficult or impossible, so the use of probe
techniques to determine Rf seemed to be the most appropriate route. In
addition, it was extremely difficult to reproduce the more complex exhaust
environments on a laboratory scale, so measurements of real exhausts were
essential.
3 In industrial exhausts the range of data required to improve our

knowledge of fouling was very large, and would include for example mass
accumulation rates, deposit and gas stream physical and chemical
properties, particulate distribution and properties, stream velocities, and
gas stream and substrate temperatures. There was, therefore, also a need
for robust instrumentation and techniques to measure these variables on
industrial sites. To aid interpretation of the data an acceptable and
usable theoreticaI framework was also needed to cope with the simultaneous
action of several mechanisms.
REFERENCES
1. Whitmore pJ and Meisen, A: Estimation of Thermo- and Diffusiophoretic

Particle Deposition. Can. J. Chem. Eng., Vol. 55, pp.279-285, 1977.
2 Howarth J and Bott TR: High Temperature Fouling: the Nature of

Deposits. NATO ASI. Advances in Fouling Science and Technology, Alvor,
Portugal 1987.
3 Tsados A and BOTT TR: High Temperature Gas-side Fouling Case Study.
NATO ASI. Advances in Fouling Science and Technology, Alvor, Portugal
1987.
@ProcessEng
Index
abrasive material 329 aromatic hydrocarbons 320

absorption oil coolers 318 ash 317, 681
aeeelerated test 326 asphaltenes 317, 320, 327
aeeumulation 214 asymptotic 318
aeeuraey 727 asymptotic fouling 22
aeetylaeetonates 321 asymptotic fouling resistance 308, 323
aeid deposition probes 67, 73 attachment 17,150,728
aeid detergent 584 attraetion 564
aequisition of scientific data 326 Auger spectra 337
activation energies 318 auto-retardation mechanisms 21
aetive magnesia 413 autoexhaust catalyst 363
additive 320 autoxidation 293, 297, 299, 301, 302, 320, 321
adhesion 173, 181,228,308,727 aviation 322
adhesion eoeffieient 176 aviation kerosene 318
adhesion forces 179, 183, 184, 186, 197 avoiding fouling 637
adhesion in flowing systems 135
adhesion in microbial fouling 234 back pressure problem 4
adhesion of baeteria 228 bacteria 207
adhesive strengths 135 bacterial adhesion 99, 125
aerobes 209 baffle cuts 481
aging 727, 729 ball or brush c1eaning systems 34
air 317, 320, 328 barnaclcs 207
air-conditioning 37 beta-Iactoglubine 95
air -eoolcd heat exchangcrs 466 biochemical reactions 727
algae 207 biocides 233,591
algal control 597 biofilm 207
alkali 413 biofilm aceumulation 214
alkali chlorides 698 biofilm aeeumulation models 218
alkali injection 317 biofilm dctaehment 217
aluminum alloys 246 biofilm dcvclopment and growth 216
amensalism 209 biofilm formation 230
ammonium bisulphate 363 biofilm growth models 217
amorphous calcium phosphatc 96 biofouling 125,207,223,233,241,727
anaerobes 209 biological fouling 125,207,591,639
anaerobic bacteria 602 biological growth 637
anal ysis 523 biological origin 125
analyticai modeIling of scale formation 649 biological rate proces ses 214
ankerite 685 blowdown 35
annular test seClion 50 boilers 35, 68, 262, 285
annuli 326 boiling conditions 255

anti-corrosion 328 Boudouard reaetion 414
anti-drag agent 111 boundary layer 325
anti-oxidation 328 Brownian diffusion 166
antifoulant ehemicals 326, 329 Brownian motion 113, 192
alllifoulants 10, 309, 328 bursting 165
antifouling 32
antifouling equipmcnt 33 CaC03,673
@ProcessEng
antifouling paints 234 CAEM 376

antipolymerant additives 328 calcitc 685
antiscalants 38 calcium binders 113
aragonite 685 calcium bridging 93
argon 282 calcium carbon atc solubility 649
735
736
calcium phosphate 36 clean mechanically 479

calcium scaling 649 clcaning 4, 315, 575, 721
calorimeters 208 clcaning dynamics 559
capital expenditure 31 cleaning mechanisms and kinelics 564
carbide intermediate 378 clcaning of heat exchange sur[accs 557
carbon deposition 369, 425, 430 clcaning procedures 473
carbon filaments 432, 433 cleanliness 585
carbon formalion 337, 351, 369, 407, 432, 433, 728 cleanliness factors 477
carbon gasification 337, 369 cloud point lemperature 275
carbon growth 728 CO 2-re[onning 417
carbon limits 408 coal-[ired 679
carbon tetrailuoride 283 coal-fired power stations 35
carbonates 660, 685 coat the heat transfer sur face s 328
carbonization o[ construetion materials 421 cobalt 40,373
carbonyles 352 cohesion 723
carburization 433 cohesion tests 173
carburized 426 cohesive slrcngths 135
casein 94 coil426
casein micelIes 93 coilcd wire test seclion 54
catal ysc 30 l coke 297, 307, 317, 369,425,426,432
catalyst [ouling 351, 728 coke fouling 391
catalysts 293, 294 coke oven cooling syslem 60 l
catalytic 727 coker 318
catalylic carbons 371, 392,432 coking 35, 297, 309, 370,433
catalytic Cf<lCking 365 coking-decoking 432, 433
catalytic filament growlh 391 collection e[[iciency 194
catal Ytic louling 345 colloid chemislry 125
catalytic reactors 728 colloidal panicle deposition 16
caustic injection 327 colloidal particles 98
CDU exchangers 318 combined fouling mechanism effects 716
cell adhesion 125 combustion 727
ccll concentralion and lype 217 commensalism 209
ccll growlh and multiplicalion 217 commercial fouling monilors 58
cell maintenance 217 compacl heat exchangers 465
cement industry 35 compaclion of biofilm 223
central healing systems 208 composilion 208, 294, 315, 319, 325
chain branching 320 computer 498,500,515,520
characterisation 729 conclenseclthiophenes 320
chemical additi ves 328 condenscrs 32, 468
chemical analyses 703 condilioning film 129
chemical bonds 130 conduclivily 643, 644
chcmical changes 727 conscrvation o[ encrgy 3
chemical cleaning 38,329,470,721 contact angle measuremCnlS 99
chcmical composition 210, 729 control 518, 520, 524, 727

chemical equilibria 254 control of reaction fouling 327
chemical industry 293, 321 control proces variables 327
chcmical mechanisms 297 control-mcthod 243
chemical rcaction fouling 17,293,297,315,327, controlled combuslion 329
333, 727 convcctive mechanisms 293
chemical rcaction fouling models 303 convective or di[[usive mechanism 306
@ProcessEng
chemical reactions 293 cooling 37

chcmical reactor 727 cooling condensers 262
chemical soaking 329 cooling tower fans 37
chlorides 325 cooling towcr waler scaling 649
chlorination 243 cooling towers 42, 208, 646
chlor ine 34 eooling water fouling 486, 715
circulalion 329 cooling water trealmcnt 637
737
copper 321, 728 deposition from flue gases 69

corrosion 36, 241, 261, 294, 297, 315, 317, 324, 326, deposition from olefins 343
328,592,637,701,727 deposition model 512
eorrosion effeets 213 deposition of hardness salts 261
eorrosion fouling 17,21,244,293,294,324,620 deposition of metals 354
eorrosion fouling models 302 deposition of organic erystals 275
eorrosion fouling rates 325 deposition probes 67, 71
eorrosion inhibition 309 deposition rates 323
eorrosion produets 251 deposition of siliea 653
eorrosion reaetion 302 dcsalination plants 262
cos ting 474 dcsalters 317, 328, 329
eosts 31, 504, 520, 521, 523, 524 design 470, 495,500,507,511,514,520,524
counter rotating vOrliees 165 design ehanges 534
eraeking 293, 297, 298, 318, 321,425 design eonditions 489
eraeking fumaee 322 design of heat exehangers for fouling conditions 477
critieal 136 dctergeney 328
eritieal surfaee shear stresses 136 dewpoints 36
eritical surfaee tension 131,224 diatoms 133, 207
critieal thiekness 216 diene synthesis 299
emde assay 327 differential pressure 576
emde distallation 34 difficulty of cleaning 478
emde distillation units 309, 315, 327, 727 diffusion (Brownian motion) 215
emde oil preheat exehangers 327 diffusion 144,334
erude oil storage tanks 328 diffusion eoeffieient 352
erude oils 315, 322, 327, 728 diffusion of carbon 345, 377
emde unit 329 diffusion/eonveetion 302
erudes 318, 329 dipole interaetions 130
eryogenie liquids 281 direet-contact apparatus 437
erystal deposition 25 l dispersant 328
crystal growth 19, 256 dispersion forces 126
erystal struetures 256 dissolution 303
crystallisation 252, 275, 727 dissolvcd oxygen 320
erystallisation fouling 16,251,280 dissulphides 320
erystallisation models 257 distributed parameter 505
cylindrieal tube test section 52 distributed parameter modelling 505
DLVO-theory 91, 92,126
dairy fluids 94 dolomite 685
dairy industry 575 double-pipe heat exchanger 464
deaetivation 369 down hole heat exehangers 669
death 217 downswccps 215
deeoking 433 drag 215
decontamination 41 drainage 215
dehydrogenation 298, 364 droplcts 391,430
delay period 15 dust 352

(deNO) 361 dynamie behaviour 309
deoxigenation 320, 325 dynamie resiIience 503
dcoxygenerataed fuels 317 dynamie response 518
dcposit 317,363,729
dcposit analysis 57 carly stages of bio[ouling 135
deposit composition 716 economies 31, 723, 724
@ProcessEng
deposit formation from glue gases 68 eddy diffusion 192,215

deposit morphology 317 effeet of dissolved oxygen 347
deposit removal 303 effeet of wall temperature 347
deposit removal meehanisms 727 effeets of biofoulding 213
deposit roughness 321 elTeets of eorrosion 4
deposition 22,125,207,230,727,731 effeets of ions 134
dcposition flux 176, 178,560 eleetrieal double layer interaction forces 152
738
electrical double layers 126 fluid dynamic forces 215

electrical sur[ace charges 228 fluid flow effects 213
elcctricity generation 36 fluid pH 228
electro-chemical reactions 294, 325, 621 fluid treutment plans 482
electrode potential 294 fluidised bed heat exchanger 41
electromagnetic flowmeter 579 f1uxing 201
c1ectron microscopy 335, 728 f1y-ash 35
electropolishcd 41 food industry 293
elcctrostatic doublc-Iuyer forces 88, 91, 180 food processing 315
electrostatic forces 126 food processing equipment 262
elcmental analyses 210 food processing fouling 719
cncapsulation 375 foodsluffs 727
energy consumption 315 [orced draft 466
energy management 309 foulant 293
cnhaced tubing 41 foulant precursors 293, 302, 328
enhanced heat transfer sur[aces 481 [ouling 31,125,391,504,575,637
enhanced surfaces 716 fouling allowance 482
ensemble control 382, 417 fouling and cleaning of exchanglOrs 557
enzyme ll9 fouling and design 8
E-NTU method for heat exchanger analysis 449 fouling and plant operation IO
equivalent sand roughness 211 fouling by milk and dairy produet 557, 558
erosion 303 fouling by suspensions of kaolin and magnetite 173
evaporative cooling towers 467 fouling dynamics 559
evaporator fouling 487 fouling factor 723,725
expert system 474, 637, 641 fouling from hydrocarbons 333
extracellular material 209 fouling from light hydrocarbons 333
extracellular polymer [onnation 134 fouling in heat exchanger nClworks 529
extracellular polymers 133 fouling mechanisms 5, 230
fouling models 15,293,511
factors affecting biofilm devclopmcnt and uccumula- fouling of catalysls 369
tion 217 fouling of geOlhcrmal cnergy 649
falling rate 318 fouling of heal cxchanger networks SIl
falling rute fouling 19 fouling probes 67, 702, 728
Fanning friclion factor 211 fouling ralCS 307, 308, 318, 327, 727
fault tree analysis 642 fouling resislances 32, 477
feedslocks 327 fouling tendencies 326
feedwater healer 468 fouling tests 173
fibrous carbon 371 free energy barrier 128
filamentary-like struclures 317 free radicaI scuvengers 328
filamenlous carbon 369, 371,433 frictional resistance 211
filaments 391, 426 [u el costs 31
film coefficient 78 fuel oils 321
film densities 228 fucls 322
film theories of heat and mass 303 fungi 208
filter beds 208 fumaces 201, 315, 334

filters 326 fused particlcs 689
Fimbriae 132
financial penaltics 315 gas 322
finned tubes 20 l gus holders 208
Flagella 132 gus oils 308, 318, 322, 323
l1exibilily 503, 504, 520 gus-side fouling 35, 67, 727, 731
@ProcessEng
flow 209 gas-side fouling moniloring equipment 67

flow qua lit y 283 gasification 425, 432, 433
flow ratc 307, 308, 315, 321, 322, 323, 325, 327 gasoline 322
flow velocity 217 geOlhermal brine loop 657
flue gas 686, 703 geOlhermal fluid 669
flue gas cleaning 360 geOlhermal fouling 649, 659
739
geothermal plants 262 imfulfillcd opportunities 31

globular 426 impaet of fouling on design 437
gravitational forces 87 impact of fouling on heat transfer 453
growth 125,207,728 impaet of fouling on pressure drop 456
growth on excisting nuclei 265 impaction 147
growth process 623 in situ cleaning 723
ineineration 681, 70 l
Hamal::er coefficient 89 induccd draft 466
Hamaker constant 180 induetion 256
hardness 325, 644 induction or initiation period 5
hardness salts 261, 271 induetion step 165
heat exchanger design 452 inert gas blankctting 328
heat cxchanger networks 495, 497, 531 inertia 215
heatexchangers 33, 62,208, 315,323, 328,437,463, inertia regime 145
511 incrtial impaction 70 l
heat flux 283 inhibitor chemieals 328
heat flux meters 67 inhibitor protective films 638
heat flux probes 72 inilial impaction 192
heat recovery 3 inorganie 191,327
heat transfer 31, 293 inorganic eontent 328, 329
heat transfer eoefficient 323 inorganic ions 217
heat transfer effects 213 inorganie rcactions 727
heat transfer film 307 inorganic sealc 591
heat transfer properties 212 inorganic suspended particles 229
heat transfer resistance 212 installation 33
heat transfer software 309 interaction free encrgy 128
heated wire apparatus 626 interactions 133, 717
heterogeneous 727 intraparticle fouling 352, 358
heterogeneous nucleation 255, 265, 267 ion bonding 107
high temperature fouling 345, 679 ion bric!ging 100
high vclocity liquid jets 329 ion exchange 265
higher hydrocarbons 412 ionising radiations 41
hold-fast 133 iron 373
homogeneous 727 iron saIts 324
homogeneous gas phase deposition 728 irreversible adhesion 126
homogeneous nuclcation 255, 264 isoclewie point 115
honey-comb design 361 isothcrrnal particle transport 143
hot spots 408
hot tubes 408 jet fucl318, 319, 320, 329
hot wires 326 jet fucl stabilily 315
humidity 107
hydrocarbon 303, 728 kaolonite 685
hydrocarbon composition 319 Kem model 176
hyclrocarbon degradation 727 kerosene 319,322

hydrocarbon fouling 321 kerosene vaporiser 318
hydrocarbon streams 293 kineties 306, 308, 322, 575
hydrocarbons 299,315,320,321,326,728 kineties of earbon c!eposition 337
hydrodcsulphurization 354
hydrodynamic force 112 labonltory simulation 326
hydrogen sulphic!e 417 lamella465
@ProcessEng
hydroc!ynamic mClhods 329 laminar bounclary layer 98

hydroperoxic!e 299 laminar sub-layer 321, 327
hydrolreating 34 Langelier index 260, 263
hydroxy apati le 101 Langelier saturalion index 650
hypoehlorite 34 lift 215
light 209
illile 685 linear 318
740
linear fouling 16 microbiological control 592

linearisation 513 microorganisms 207, 242
liquid bridging 93 microprocessor syslem 579
liquid fouling monitoring equipment 49 migration 375
liquid hydrogen 281 milk 94,251,575
liquid jet 322 milk derivatives 560
liquid side 620 milk fouling 721
LMTD method for heat exchanger analysis 446 milk fouling dynamic 559
Ion g-range forces 126 milk processing 725
loss in throughput 315 milkslone 94
loss of production 31 mineral fouling 561
low rank coal 695 mineral maller 685
mineral sealing 637
macrobial fouling 207 minimum lemperalure driving force 0.T min 498, 499,
macromolccules 129 525
magnetic suspension 178 mitigating lechniques 327
mainlenance 315 miligalion ol' fouling 7
maintenance costs 31 mixed kaolin-magnetite suspension 178
marine biofouling 241 mixing ol' diffcrent erude types 327
marine corrosion 241 mobile larry layer 307
marine fouling 38, 208 model for fouling of HDS catalysl 356
mass accumulation probes 67, 68 modelof corrosion fouling 623
mass accumulation tesls 705 modelling 505
mass probe 731 modeIling fouling 504
mass transfer 321, 327 models 207, 293, 512, 514
mass transfer coefficienls 307 moniloring 640
mass transfer effecls 324 moniloring fouling 77
mass transport 215 moniloring methods 638
maximum energy recovery (MER) 497, 498, 500, monolayer 214
502,503,522 morphology 729
mecllanieal clcaning 329, 724 motilily 132, 215
mechanieal resisUlnce 184 mouIds 207
mcehanical resistance of deposit 185 moulh 208
meehanieal slrcngth of lhe deposit 178 multipass and crossl1ow heal exehangers 448
mechanism of cryslJ!llisation 276 multiple tube test sections 53
mcehanism of crystallisation fouling 256 munieipal waste ineineration 679
mcchanisms 293, 298, 727 mulualism 209
meehanisms of fouling and cleaning 720
mechanisms of fouling by milk eomponents 560 n-hexadecane 319
mechanisms of sealing 264 N 319
metal ehlorides 321 naphtha reboilers 318
metal co-ordination 328 naphtha vaporisers 317
metal deactivalors 329 naphthene 320, 321
metal dusting 421, 433 nature of rcaclions 729

metal surfaees 391 nature of lhe deposi t 7
metallurgy 327, 638 network inleraetions 536
methane 283 nelworks 309
miero-organisms 125 neutralisation 328
mierobail auae' .cnt at lhe surfaee 216 neulralism 209
mierobalanee 335, 343, 373, 425 nickel 373
@ProcessEng
mierobalance reaelors 728 nickcl-copper system 419

microbial adhesion 125 nitrifying bacteria 602
mierobial biofilms 208 nitrogen 282
microbial fouling 125,207 nitrogen compounds 321, 328
microbial interaetion 209 non-catalytic 727
mierobiological 727 non-isothermal parlic1e transport 148
microbiological aspecLs 131, 208 non-oxidizing bioeides 234, 595
741
nonionics 118 particulate material 328

normal solubility salts 253 passivation 297
nuclcation 254, 337 passive films 325
nucleation in grain boundarics 345 passive response 516, 520, 533
nucleation sites 324 percent oversurface 477
nu trient concentration 229 petrochcmical industry 293, 327
nutrients 209 pH 209, 325
physical proper ties 729
occ urrence 207 physical transport 214
ocean thermal energy con version 213 physieo-ehemical aspccts 210
ocean thermal energy con version plant 34 physico-chcmical aspects of microbial adhcsion 125
octopus carbon 382, 420 physico-chemical interactions 214
oi1321,327 physico-chemical surfaee changes 727
oil fractions 320 physico-chemical surface e[feets 727
oil platforms 38 Pili 132
oil produetion equipment 262 pilot-seale fumace 68,70
oil refineries 309, 727 pine h 495, 498, 499, 500, 502, 503, 517
oil refinery heat exchangers 315 pinch method 511
oilwells 40 Pinheiro model 176
olefins 320, 728 pipelines 208
on-line clcaning 10,491 plagioclase feldspars 695
on-line fouling sensor 575 plant geometry 706
on-line measurements 559 plate 669
operability 503, 511 plate heat exchanger 576, 578
operability package 309 plme heat exchanger fouling 487
operational and design strategies 309 plate-and-frame heat exchanger 464
optical devices 67 plate-fin 41
optimal1caning 585 plate-like structures 317
optimal temperature driving force 507 poison 369
optimismion 507 polarisation 296
optimum 521 polymer bridging 133
optimum clcaning cyclcs 309 polymer !ayer 242
organ ic conditioning film 214 polymeric material 209
organic content 329 polymerisation 293, 297,301,302
organic deposits 591 polymerisation of styrene 322, 323
organic peroxides 320 polymerisation rcactors 315
organisms 125,207 polymers 210
overall heat transfer coefficient 212 pore mouth poisoning 351
overdesign 530 pore volume distribution 353
overvicw of rcaction fouling 294 porosity 723, 724
oxides 669 potential energy ofinteraction 126,181
oxidizing biocides 233, 593 pour point temperature 275
oxygen 209,282,299,302,317,319,321,325,327, powdered coatings 328
328, 728 prccipiullion fouling 252, 638

oxygen scavengers 328 precursor diffusion 308
predation 209
paraffins 320, 321 predicative models 302, 309
parameters a[fecting the cleaning kinetics 567 preheat cxchangcr trains 309
parasitism 209 preheat exchangers 317, 329
particle bonding 692 pressure 294, 315, 321, 327
@ProcessEng
particle diffusion 192,701 pressure drop 50, 358

particle flux 216 pressure transmitters 579
particle removal 112 pretreatrnent of water 265
particle transport 177 prevention of solids agglomeration 327
particulate concentration 702 prevention of solids formation 327
particulate fouling 143, 153, 173, 176,516,517,638, preventive and remedial actions 327
727 primary cncrgy minimum 131
742
principle of equilibrated gas 413 removal of foulant 306

probe684 removal of solid deposits 327
process control strategies 309 removal proces s 624
process design 495 repulsion 564
process plant 33 research unit 49
process synlhesis 495 resiiience 503, 504, 520, 525
produet formation 217 resiiience analysis 516
properties 208 resins 317, 320
properties of the deposit 725 reverse osmosis 266
Prosthecae 132 rcverse osmosis plant 262
protective film 63 reversible adhesion 126
protective scales 325 Reynolds number III
protozoa 208 Rf values 212
pulverised fuel-firing 681 ring-shapcd pellets 358
pump motors 37 rippling motion 211
pure and blended hydrocarbons 320 robustness 511, 516, 517, 518, 520, 524, 525
purging 328 rolling-up mechanism 119
pyridines 321 rotating cylinder 98
pyrocondensation 299 rotating cylinder apparatus 174, 182
pyrolysis 334, 425 rotating disc 97
pyrolylic carbons 432, 433 rotating disc contactor 208
pyrolytic fouling 345 rust preventatives 329
pyrrolcs 321 Ryznar index 260, 264
Ryznar stability index 650
quartz 685
quasi-steady state assumplion 309 S 319
safety 31
radial-flow growlh chambcrs 135 saturation lemperalure 253
rate expressions 217 sawtooth fouling 25
rating 470 scak 251, 669
re-entrainment 153 scale formation 35
reaction 302, 727 scale inhibitors 266
reaction fouling 293,302,326,516,517,731 science 207
reaction fouling in heat cxchangers 347 scientific models 326
rcaction fouling model 512 scouring 217
reaction kinetics 81, 302, 306 scraped-surface heat exchanger 466
reaction of aggregation 564 Seaton mod cl 176
reaction zone 293 seawater 62
reacti ve organic species 315 seaweed 207
reboilcr fouling 487 secondary energy 37
reboilers 315, 322,468 secondary minimum 131
rceuperators 437 sedimentation 215
reentrainment 217 selection 470
refineries 34 seleetion of heat exehangers 463

refinery heat exehangers 326 selective catalytic reduction 361
refinery streams 322 selective metallurgy 328
refinery units 324 sensitivity 5ll, 513, 514, 523, 524
reforming 34 sensitivity analysis 515, 524
refrigeration equipment 37 sensilivity coefficients 514
refuse incineration 696, 702 sensitivity lab les 503, 523, 532, 533
regeneration 363, 384, 421 shear action 307
@ProcessEng
regenerators 35, 437 shear forces 6, 135,217

re1ease 307, 308 shear stress 136, 217, 307, 323
reliability 39 shen and exchangers 315
removal22, 302, 307, 308, 309, 727, 731 shen and lube 669
removal flux 176 shen-and-tube heat exchangers 467, 478
removal of deposits 294 shellside fouling research unit 54
743
ships' hulls 208 stopping disk1nce 195

short-range forces 130 storage 319,321
shut-downs 39 stripping 328
siderite 685 slructure 729
silica scaling 649 Slructure and com position of deposits 561
silica solubility 649 structure of the deposit 223
silicates 669 styrene in kerosene 307
silicum compound s 352 styrene polymerisation 728
sillica polymerization 654 styrene solution polymerisation 318
simulator 309 sublayer boundary 165
sinter 683 submicron deposit 684
site blockage 351 subslrate 217
slag 683 substratum 208
slag viscosity 690 sulphate-rcducing bacteria 40
slagging 679 sulphates 325
slime 133,208 sul ph ides 320, 669, 685
sloughing 217 sulphur320, 321, 327, 328, 728
sludge 328 sulphur passivated rcforming 417
smal! tubes 326 sulphuric acid converters 358
sOllium aluminosilicatc scalcs 77, 80 superheatcrs 692
sodium triphosphate 116 supcrsaturation 81, 252, 276
solid conk1minants 315 surface 125,208
solid deposits 369 surface area 32
solidification 282 surfacc bound biocidcs 233, 235
solidification fouling 275 surface carbon 371, 432
solubility product 262,650 surface charactcristics 224
solvation forces 130 surface condcnsers 63, 469
soot371,432,728 surface condition 279
soot-like 317 surface conditioning 721, 722
sOOlblowing 36 surface effects 727
spalling 303 surface forces 152
SPARG principle 416 surfaee nuclcation 345
specialised allachment slructures 131 surface phenomena cffccts 173
specific fouling models 309 surface roughness 147,224
specifications 470 surface tcmperature 323, 327
spiral heat exchangers 464 surface tension 90
stability 321 surface-frec energy approach to mierobial adhcsion
Stalks 132 131
standard eleclrode potential 294 suspcndcd solid s 591
static resiiience 503, 517 synergenie effeets 185
steady state activity of carbon 409 syncrgism 347
steam cracking fumace 315, 727 synthesis 321, 497, 503
steam raising plant 681 synthesis reaetions 299
stcam rcfonning 353, 405

steam-air decoking 329 T.L.E.426
stcam-cracker 426 tarry deposits 317
steamcracking 425 tars 425, 432
steric forces 126 TEMA fouling resisk1nces 486
steric hindrance 93 tcmperature 209,279,294,308,315,318,325,327,
sterilizer 578 727
sticking probability 150,216,731 temperature driving force 507
@ProcessEng
sticking sk1ge 165 temperature-programmcd surfacc reaetion techniquc

Stiff and Davis index 264 378
stirred k1nk heat exchanger 465 tenaeity 329
stirred k1nks 326 test section geomelries 49
stochastic model 165 thermal eonductivities 212, 491, 674
Stokes-Einstein equation 97 thermal cracking 408
744
thermal cracking of n-octane 322 vapour phase thermal 318

thermal decomposition 321 varnish-like structurcs 317
thermal denaturation of bcta-lactoglobulin 563 velocity 242, 278, 321, 327
thermal diffusion 192, 701 visbrcaker 318
thermall y cracked feedstocks 319 visbreaking 34
thermoelectric effect 150 viscoclastic 211
thermogravimetric methods 335 viscous layer 108
thermophoresis 149, 192,215 viscous sublayer 211
thermosetting 328 void fraction 358
thickness of the fouling layer 491
thio Is 320 wall shear effects 55
threshold 517 wall shear stress 121
through nickel 375 wall temperature 50
time 309 wastewater treatment 208
time between cleanings 478 water deionisers 208
time-course of biofilm development218 water treatment chemicals 38
titanium 242 water washing 327
titanium alloy 321 water weeds 207
tower 37 water-cooled hcat exchangers 637
trace level constituents 315 waxy deposits 317
trace metal contaminants 319 wet meters 208
trace quantities 319 whey proteins 101
tracers 729 whisker407
transfer 308 whisker carbon 371
transfer-line heat exchanger 425 \ • isker -growth 728
transient temperature measurement test section 52 Wilson plot 56
transition from liquid to vapour 728 work function 106
transition metals 373 X-ray diffraction 335
transport of oxygen 302 X-rays photoclectron microscopy 337
transport of particIcs 176
transport to the surface 215 yeasts 207
transportation of bacteria 125
triboclcctric forces 93 zeolite catalyst 363
trickling filter 208 zeta potential s 99,175, 180, 185
tropical seawater 241
tube diameter 323
tube inserts 328
tube surfaee condition 81
tube wall temperature 406
tubular heat exchangers 670
turbines 36
turbulence 111
turbulent bursts 7, 716
turbulent flow 98, 109,215
ultra high temperature 575

uncerwinties at thc time of design 489
unsaturated hydrocarbons 328
utility industry 293
@ProcessEng
van der Waals force 94, 126, 152, 180

vanadium 354
vaporisation 315, 321, 327
vapour diffusion 196, 70 I
vapour phase coking 323
vapour phase pyrolysis of naphtha and light gas oil
322

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Process Engineering Channel

Fouling Science and Technology

A Series presenting the results af activities sponsored by the NA TO Science Committee,

The Series is published by an international board of publishers in conjunction with

A Life Sciences Plenum Publishing Corporation

C Mathematical Kluwer Academic Publishers

F Computer and Systems Sciences Springer-Verlag

Series E: Applied Sciences - VoL 145

Kluwer Academic Publishers

Published in cooperation with NATO Scientific Affairs Division

Library of Congress Cataloging in Publication Data

1. Heat exeha~gers--Foul Ing. 2. Foul Ing. l. Melo, L. F. (Luis

ISBN-13: 978-94-010-7766-8 e-ISBN-13: 978-94-009-2813-8

Published by Kluwer Academic Publishers,

Kluwer Academic Publishers incorporates the publishing programmes of

Sold and distributed in the U.S.A. and Canada

In all other countries, sold and distributed

P.O. Box 322, 3300 AH Dordrecht, The Netherlands.

All Rights Reserved

Softcover reprint of the hardcover 1st edition 1988

held in Hotel D. Joao II, Alvor, Algarve

Luis F. Melo (Director)

CHAPTER 1. FUNDAMENT ALS AND ECONOMICS

. General Fouling Problems

. General Thermal Fouling Models

The Economics of Fouling

CHAPTER 2. MONITORING EQUIPMENT

Liquid Fouling Monitoring Equipment

Gas-Side Fouling Monitoring Equipment

Monitoring Fouling using a Novel Technique

Adhesi.on and Removal of Particles - I

Adhesion and Removal of Particles - II

Aspects of Cell Adhesion

CHAPTER 4. P AR TICULATE FOULING

Particulate Fouling of Heat Transfer Surfaces:

Stochastic Model for the Induction Step on

Fouling by Aqueous Suspensions of Kaolin and

• Gas Side Fouling

CHAPTER 5. BIOLOGICAL FOULING

• Biological Fouling: Basic Science and Models

• Surface Bound Biocides - A Novel Possibility

• Experimental Investigation of Marine Biofouling

CHAPTER 6. CRYSTALLISATION FOULING

• Crystallisation Fouling - Basic Science and

• Basic Science and Models of Reaction F ouling

• Chemical Reaction Fouling of Heat Exchangers

• Fouling from Light Hydrocarbons on Metal

• Fouling of Catalysts: Industrial Examples

• The Fouling of Catalysts by Deposition of

Droplets and Filaments: on the Fouling of

Carbon Limits in Steam Reforming

CHAPTER 8. DESIGN AND OPERAnON OF HEAT EXCHANGERS

Basic Relationships for Heat Exchangers and

. Selection of Heat Exchangers

. General Design of Heat Exchangers for

Basic Concepts in Heat Exchanger Network

The Fouling of Heat Exchanger Networks

Compensating tor Fouling in Heat Exchanger

CHAPTER 9. FOOD PROCESSING FOULING

Fouling by Milk and Dairy Product and Cleaning

. On-Line Measurement of Fouling and Cleaning of

G. Corrieu, M. Lalande and F. Ferret 57 5

CHAPTER 10. FOULING IN INDUSTRIAL WATER SYSTEMS

. Case Study-Clean-up of a Coke Oven Cooling