Chemical Reaction Engineering-Plenary Lectures PDF

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Publication Date: July 28, 1983 | doi: 10.1021/bk-1983-0226.fw001
Chemical Reaction
EngineeringPlenary Lectures
In Chemical Reaction EngineeringPlenary Lectures; Wei, J., et al.;

ACS Symposium Series; American Chemical Society: Washington, DC, 1983.


Chemical Reaction
EngineeringPlenary Lectures
James Wei, EDITOR
Massachusetts Institute of Technology
Christos Georgakis, EDITOR

Based on the 7th

International Symposium
on Chemical Reaction Engineering
in Boston, Massachusetts,
October 4-6, 1982
ACS SYMPOSIUM SERIES
226
AMERICAN CHEMICAL SOCIETY

WASHINGTON, D.C. 1983


Library of Congress Cataloging in Publication Data

International Symposium on Chemical Reaction
Engineering
(7th: 1982: Boston, Mass.)
Chemical reaction engineeringplenary lectures.
(ACS symposium series, ISSN 0097-6156; 226)
Includes bibliographies and index.
1. Chemical engineeringCongresses. 2. Chemical
reactionsCongresses. I. W e i , James, 1930II. Georgakis, Christos, 1947. III. Series.
TP5.I67
1982a
ISBN 0-8412-0793-3
660.2'99
83-11876
Copyright 1983
American Chemical Society
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FOREWORD
The A C S S Y M P O S I U M
SERIES was founded in 1 9 7 4 to provide
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format of the Series parallels that of the continuing A D V A N C E S
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Publication Date: July 28, 1983 | doi: 10.1021/bk-1983-0226.pr001
PREFACE
IN
T H E NARROW SENSE,
CHEMICAL
REACTION ENGINEERING
(CRE)
is
concerned with the design, operation, optimization, and control of processing equipment called chemical reactors. C R E is the counterpart
to unit
operations (UO), which is concerned with processing equipment in which

no chemical reactions take place. Both chemical reaction engineering and
unit operations integrate many disciplines to attain practical engineering
goals. They differ from the engineering science subjects of kinetics, thermodynamics, fluid mechanics, and transport phenomena that seek to isolate
and analyze an individual aspect of a complex piece of machinery or to
understand and describe quantitatively the material behavior at microscopic or molecular scales.
The main difference between chemical reaction engineering and unit
operations lies in the presence or absence of chemical reactions.
Except
for purely separational processes, such as the production of oxygen from

air, the heart of any chemical process is one or more chemical reactions
that transform less valuable feed material to more valuable products. In
the case of combustion, the main products are heat and energy rather than
material products. In the case of pollution control equipment, the conversion of a harmful feed to harmless products is the main objective. Chemical
reactors lie in the heart of any chemical plant, and the unit operations
equipment serves the needs or compensates for the inadequacies of the
chemical reactors. The design of a chemical plant must start with the
chemical reactors, which usually run 10-20% of the total plant cost. When
you look over the flowchart of a process, you will find the chemical reactor
as a small unit in a very large network; yet, the design of all other equipment revolves around the chemical reactors. The optimum design of a
chemical reactor does not necessarily lead to the optimum design of a
chemical plant. The peripheral equipment of unit operations
(the tail)
usually wags the chemical reactors (the dog). A good design engineer
chooses the dog that has the smallest tail.
ix
In a comparison of the salient features, the following may be noted:
Function
Chemical Reactors
Unit Operations
Chemical reactions
Physical operations
needed to service the reactors
Individually tailored
Modular; often can be
for each reaction
ordered from catalogs
Cost
10-20% of total plant
80-90% of total plant
Performance
Highly nonlinear due to
Nearly linear

Design
kinetic dependence on
temperature and concen
trations
Intellectual
Chemists and chemical
Collaborators
engineers
Mechanical engineers
In the broader sense, chemical reaction engineering is also concerned

with the components needed for the synthesis of chemical reactors, such as
kinetics, catalysis, catalyst design, mixing, multiphase systems, fluid me
chanics and transport in fixed and fluidized beds, and solid movement
mechanics in moving and fluidized beds. Study of the maldistribution of gas
and liquid flow in trickle beds can be considered as a branch of fluid
mechanics, but this subject is very seldom studied by the major researchers
in fluid mechanics. However, it is a subject that is studied by major re
searchers in reaction engineering. O n the
other
hand, paper-making
machines would seem to be very suitable subjects for reaction engineers,

but are hardly ever studied. Polymerization reactors are enormously impor
tant in the chemical industries and are beginning to attract serious re
searchers with backgrounds in reaction engineering.
Reaction engineers form a living and changing tribe that keeps in touch
through professional meetings and journals. They share a common set of
textbooks and tools, the same vocabulary and analytical scheme to analyze
problems, and the same set of triumphant classic achievements in the past.
They agree on what are proper problems to be tackled and what are proper
standards for admissible reports and papers. In short, they form a paradigm
of their own. New people are constantly recruited by this tribe through the
process of apprenticeship and junior partnership, or by adoption into this
tribe of brilliant outsiders with brand new ideas. Whatever is accomplished
by a member of this tribe will be shared with the rest of the members and
is by definition chemical reaction engineering.

In this volume, we print the six plenary speeches given at the 7th International Symposium on Chemical Reaction Engineering at Boston. First,
the intellectual foundation of chemical reaction engineering is described by
Aris, and second, the study of alternative reactors for the methanol-togasoline process is described by Penick. These two chapters form a powerful
contrast between the academic intellectual approach and the industrial
pragmatic approach. Fluidized beds are reviewed by Rowe, and fluidizedbed combustors are reviewed by Sarofim. These two chapters are concerned
with one of the most powerful reactors, in which scale up by design engiDownloaded by ILLINOIS STATE UNIV on December 2, 2012 | http://pubs.acs.org
neers is still done with great trepidation, and one of its most important
future applications. If fluidized-bed combustors for coal are well engineered, there will be little demand for clean synthetic fuels, except for
liquid fuels for transportation. Combustion should have been one of the
most central problems in reaction engineering. Only historical events decree
that it should be a meeting ground of chemical engineers, mechanical engineers, and chemists with their own Combustion Institute and highly successful International Symposium series. It is overdue for us to build bridges
to these outstanding people. Micromixing is reviewed by Villermaux, and
polymerization reactors are reviewed by Ray. These two chapters are concerned with homogeneous phase and nearly homogeneous phase reactors
that are of growing importance. Most textbooks of reaction engineering have
rather short sections on polymerization, a subject found more often in
polymer textbooks. These reviews will go a long way toward remedying
this defect.
The plenaries serve as a powerful centralizing force among reaction
engineers, who are always in danger of moving off in their own individual
rivulets and drying out. These plenaries should be read by all students of
chemical reaction engineering, whatever their subspecialty. They augment
the basic textbooks as part of "what every educated reaction engineer
should know."
JAMES
WEI

Cambridge, MA
October 22,
1982
xi
1
Chemical Reaction Engineering as an Intellectual
Discipline

Publication Date: July 28, 1983 | doi: 10.1021/bk-1983-0226.ch001
R. ARIS
University of Minnesota, Department of Chemical Engineering and Materials
Science, Minneapolis, MN 55455
What, you are entitled to ask, do you mean by an intellectual

discipline?
Before attempting any formal answer, let me turn to
two of the traditional disciplines and try to sketch some of the
characteristics
that they may have or induce in their adepts.
I take my text from the advice given to President Gilman, the
first of the Johns Hopkins University, to start with the best
classical scholar and the best mathematician that he could find.
The latter was none other than the great James Joseph Sylvester,
retired from Woolwich since 1870 and spending his time in the
enjoyment of the classics, playing chess and versification
on the
principles of his "Laws of Verse"a pamphlet by which he set great
store. With his appointment to Hopkins at the age of 62 there came
the second flowering of his genius and with it his exploration of
the fundamental system of invariants and the syzygies of algebraic
forms.
S y l v e s t e r ' s career had not been an easy one L) . A f t e r h i s
s t u d i e s at Cambridge had been i n t e r r u p t e d by i l l n e s s he took h i s
degree i n 1837 as Second Wrangler i n the same c l a s s as George
Green. To say that he took h i s degree i s not q u i t e accurate, f o r
S y l v e s t e r , who says of himself that he was one of the f i r s t
h o l d i n g "the f a i t h i n which the founder of C h r i s t i a n i t y was
educated" t o compete f o r the mathematical t r i p o s , could not comp l e t e h i s degree without s u b s c r i b i n g t o the 39 A r t i c l e s of the
Church of E n g l a n d a s u b s c r i p t i o n he was u n w i l l i n g t o make. He
t h e r e f o r e went to T r i n i t y C o l l e g e , D u b l i n from which he received
h i s degrees i n 1841.
His Cambridge degree he d i d not r e c e i v e
u n t i l 1872, when the r e l i g i o u s b a r r i e r s had at length been
removed. I n 1890 he was given an honorary Sc.D. at the same time
as Benjamin Jowett, Henry Perry Liddon and other notables. The
P u b l i c Orator c o u l d , by then, bracket him w i t h Newton as
" S y l v e s t e r noster" i n the accolade: "Nonnulla quae Newtonus
noster, quae F r e s n e l i u s , Iacobius, Sturmius, a l i i , imperfecta
r e l i q u e r u n t , S y l v e s t e r n o s t e r , aut e l e g a n t i u s e x p l i c a v i t aut
argumentis v e r i s comprobavit." A f t e r two years at U n i v e r s i t y
C o l l e g e , he crossed the A t l a n t i c to the U n i v e r s i t y of V i r g i n i a but
0097-6156/83/0226-0001$06.00/0
1983 American Chemical Society

C H E M I C A L REACTION ENGINEERING
remained there only a matter of months ( 2 ) . Returning to England

he spent some time as an actuary f o r a l i f e insurance company, a
drudgery which might have s t i f l e d the mathematical genius of a
l e s s robust man.
During t h i s p e r i o d , however, h i s f r i e n d s h i p w i t h
Cayley matured and he took p r i v a t e p u p i l s , the most i l l u s t r i o u s of
whom was Florence N i g h t i n g a l e who went out to Crimea i n 1854, the
year of S y l v e s t e r ' s r e l e a s e from the l e g a l world. He returned to
academic l i f e as p r o f e s s o r of mathematics at Woolwich w i t h a
s a l a r y of
550, government quarters and the r i g h t of a pasturage
on Woolwich Common. He continued there u n t i l 1870 when he r e t i r e d
over what he regarded as an u n f a i r change i n the r e g u l a t i o n s and
w i t h some b i t t e r n e s s over h i s pension.
Perhaps i t was t h i s that
made him, i n coming to Johns Hopkins, request that h i s s a l a r y , the
c o n s i d e r a b l e sum of $5,000, be paid i n gold ( 3 ) . At a l l events
the move f o r the second time to America was a great success and
he found h i m s e l f able to teach mathematics w i t h great freedom and
play a l e a d i n g r o l e i n the i n t e l l e c t u a l l i f e of Baltimore s o c i e t y .
H i s colleague i n c l a s s i c s was a l s o of the g r e a t e s t d i s t i n c t i o n . C a l l e d from the same u n i v e r s i t y i n which S y l v e s t e r had
had so unhappy an experience years b e f o r e , B a s i l Lanneau
G i l d e r s l e e v e was a Southerner born and bred who served w i t h the
Confederate Army w h i l e the C i v i l War was i n progress during the
summer months i n order (as he says) "to earn the r i g h t to teach
Southern youth f o r nine months...by sharing the fortunes of t h e i r
f a t h e r s and b r o t h e r s at the f r o n t f o r three." Much l a t e r i n the
A t l a n t i c Monthly of January 1892 he s t i l l was "not c e r t a i n t h a t
a l l " readers might " a p p r e c i a t e the e n t i r e clearness of conscience
w i t h which we of the South went i n t o the war" ( 4 ) . I have not
been able to f i n d any reference to the d i r e c t i n t e r c o u r s e of these
two men, though I would t h i n k t h a t , w i t h the exception of the
q u e s t i o n of s t a t e s r i g h t s , they would have had much i n common.
I t was S y l v e s t e r s d e l i g h t to read the c l a s s i c s and G i l d e r s l e e v e
would have approved the motto which he gave the American J o u r n a l
of Mathematics which was founded at Hopkins i n 1878 and e d i t e d by
Sylvester:
1
G i l d e r s l e e v e does r e f e r to S y l v e s t e r s m e t r i c a l theory of
"phonetic syzygy" i n one of the B r i e f Mentions of the American
J o u r n a l of P h i l o l o g y , which he founded i n 1880 e a r l y i n h i s time at
Hopkins and published from there f o r many y e a r s a pleasant f o i l to
S y l v e s t e r ' s American J o u r n a l of Mathematics. G i l d e r s l e e v e was, of
course, a much younger man45 to S y l v e s t e r ' s 62when he came to
Hopkins b u t , i n c o n t r a s t to S y l v e s t e r ' s b r i e f tenure of 8 y e a r s ,
he presided over the d e s t i n y of the c l a s s i c s there f o r the next
39. During that time he e s t a b l i s h e d graduate s t u d i e s i n the
c l a s s i c a l d i s c i p l i n e s , d i r e c t i n g no l e s s than 67 d o c t o r a l d i s s e r t a t i o n s thus having a profound i n f l u e n c e on c l a s s i c a l s t u d i e s
throughout the country. I n 1901 some f o r t y - f i v e of h i s o l d p u p i l s
put together a volume of l a r g e l y p h i l o l o g i c a l s t u d i e s i n h i s

1.
ARis
Reaction Engineering as an Intellectual Discipline
honor ( 5 ) . L i k e S y l v e s t e r , he was a p r o l i f i c p u b l i s h e r on a wide

range of s u b j e c t s . S y l v e s t e r ' s " C o l l e c t e d Works" run t o 4 quarto
volumes, e d i t e d by H. F. Baker i n 1912; G i l d e r s l e e v e s papers were
as numerous though not as completely c o l l e c t e d . A volume of h i s
s t u d i e s and essays appeared i n 1890 (6) and a s e l e c t i o n of h i s
B r i e f Mentions published over the years i n the American J o u r n a l of
P h i l o l o g y was e d i t e d w i t h a b i o g r a p h i c a l sketch by h i s successor
and devoted p u p i l i n the c h a i r of Greek at Johns Hopkins ( 7 ) .
G i l d e r s l e e v e published more books than S y l v e s t e r and h i s L a t i n
grammar, r e v i s e d w i t h the cooperation of P r o f e s s o r Lodge, i s s t i l l a
standard reference book.
Both men r e j o i c e d i n an amplitude of s t y l e that betrays a
more l e i s u r e d age than ours. For example, i n a d v e r t i n g t o the
then r e c e n t l y published book e n t i t l e d "Value of the C l a s s i c s "
(Princeton U n i v e r s i t y P r e s s ) , G i l d e r s l e e v e remarks that "appended
to these impressive d e l i v e r a n c e s there i s a formidable array of
s t a t i s t i c s drawn up i n r e f u t a t i o n of those other s t a t i s t i c s that
have been used only too e f f e c t i v e l y t o s t i r up the pure minds of
b e l i e v e r s i n L a t i n and Greek. My missionary days are long overpast and s t a t i s t i c s have l o s t whatever charm they had f o r me even
i n the s y n t a c t i c a l l i n e , but the book w i l l strengthen the f e e b l e
knees of those who are a f r a i d that they w i l l have to bow thems e l v e s down i n the House of Rimmon." Compare S y l v e s t e r . He
published a paper i n the American J o u r n a l of Mathematics i n 1882
e n t i t l e d "A C o n s t r u c t i v e Theory of P a r t i t i o n s , Arranged i n Three
A c t s , and I n t e r a c t and an Exodion."
Act One i s on p a r t i t i o n s
regarded as e n t i t i e s and i s prefaced w i t h the quotation from
Twelfth-Night..."seeming
parted, but yet a union i n p a r t i t i o n . "
In a paper on the three laws of motion i n the world of u n i v e r s a l
algebra published i n 1884 he has a charming footnote i n which,
a f t e r r e f e r r i n g t o a theorem i n the t e x t , he remarks " I have not
had l e i s u r e of mind, being much occupied i n preparing f o r my
departure, t o reduce t h i s theorem t o a p o d i c t i c c e r t a i n t y . I
s t a t e i t t h e r e f o r e w i t h due reserve."
But we must t u r n from the b i o g r a p h i c a l d e t a i l s of these
g i a n t s , however f a s c i n a t i n g they may be, and ask about the
characters of t h e i r subjects as d i s c i p l i n e s . The very name
" c l a s s i c s " i s an acknowledgement of our debt t o the c u l t u r e s of
ancient Greece and Rome, f o r i n u s i n g i t we are reminding ours e l v e s that i t i s they who f i r s t recognized the c l a s s e s , o r
c a t e g o r i e s , of thought that we, f o r a l l our neglect of t h e i r
sources, s t i l l observe today. Whether we l i k e i t or not, the
f u r n i t u r e , which we bump i n t o (to borrow a metaphor from J . K.
Newman of I l l i n o i s ) i n our gropings through the room of i n t e l l e c t ,
was b u i l t and put there by the Greeks. I n our everyday and
s c i e n t i f i c language we pay hidden t r i b u t e t o the notions of
c l a s s i c a l times using words that were c o n s c i o u s l y coined t o
r e f l e c t t h e i r thought. Thus "gas" f o r the t h i r d e s t a t e of matter
has now been common f o r more than three c e n t u r i e s but goes back t o
the a l c h e m i c a l n o t i o n of the i n d w e l l i n g s p i r i t of a t h i n g , which



C H E M I C A L REACTION
ENGINEERING
Van Helmont (1577-1644) i n h i s "Ortus Medecinae" (1652) r e f e r r e d

to as " h a l i t u m i l i u m Gas v o c a v i , non longe a Chao veterum
secretum." This was charmingly t r a n s l a t e d i n Chandler's "Van
Helmont's O r a t i o n s " (1662) as: " I have c a l l e d that vapour, Gas,
being not f a r severed from the Chaos of the A u n t i e n t s . . . a f a r more
s u b t i l e or f i n e t h i n g than vapour, mist or d i s t i l l e d O y l i n e s s e s ,
although as y e t i t be many times t h i c k e r than a i r . But Gas
i t s e l f , m a t e r i a l l y taken, i s water as y e t masked w i t h the Ferment
of composed Bodies."
I f 'gas' i n the p h y s i c a l sense s t i l l bears echoes of the
formless darkness over the f a c e of the deep, the c u r r e n t l y
popular study of mathematical chaos uses the Greek work i n simple
t r a n s l i t e r a t i o n . Yet i t i s pleasant to r e f l e c t that a recent
meeting on t h i s s u b j e c t i n Los Alamos (May 1982) could be s u b t i t l e d
" EN " and thus make i r o n i c comment on the world as w e l l
as r e c a l l i n g the o r i g i n a l sense of the beauty of order inherent i n
the word . For of i t s o r i g i n a l meaningadorning or
ornamentthe only t r a c e l e f t to us i n E n g l i s h i s a s u p e r f i c i a l ,
almost m e r e t r i c i o u s , o n e c o s m e t i c . But that i t should a l s o mean
order, a 'lucidus ordo', i s n a t u r a l enough and was so t r a n s f e r r e d
by Pythagoras to the world as expressing that ordered beauty whose
a p p r e c i a t i o n i s the b a s i s f o r a l l s c i e n t i f i c n o t to say
humanisticendeavour ( 8 ) . 'Mundus' i n L a t i n f o l l o w s a p a r a l l e l
course as we see i n P l i n y ' s comment: "Quem G r a e c i nomine
ornamenti a p p e l l a v e r u n t , eum nos a p e r f e c t a absolutaque e l e g a n t i a
mundum": or C i c e r o ' s : "Hunc hac v a r i e t a t e d i s t i n c t u m bene
G r a e c i , nos lucentum mundum nominamus".
To study of the c l a s s i c s i s s u r e l y to submit to a d i s c i p l i n e
that r e j o i c e s i n the r e l a t i o n of words and ideas. I t i s not j u s t
to l u x u r i a t e i n e t y m o l o g i c a l overtones (a v i c e i n t o which I have
j u s t allowed myself to be betrayed) but to l e a r n the r e l a t i o n of
word and thought as expressed by the p r e c i s e usage of words and
t h e i r p l a c e i n the s y n t a c t i c a l s t r u c t u r e of a sentence. The act
of t r a n s l a t i o n from one language i n t o another demands t h i s hard
s t r i v i n g f o r p r e c i s i o n , and i s p a r t i c u l a r l y c a l l e d f o r t h by an
i n f l e c t e d tongue and one, such as L a t i n , where the thought i s
marshalled i n t o p r i n c i p a l and subordinate clauses. By c o n t r a s t
E n g l i s h , f o r a l l i t s m e r i t s , has a l a x and i n d i v i d u a l s t r u c t u r e ,
rambling comfortably on i n coordinated measures. I t i s almost
l i k e the c o n t r a s t you can experience by t u r n i n g aside from Watling
S t r e e t or the Fosse Way i n t o a country road or lane as you go "to
Birmingham by way of Beachy Head." The very f a m i l i a r i t y of our
n a t i v e speech and i t s c o l l o q u i a l u s e c o r r e c t and e f f e c t i v e
though t h i s b e d e n i e s i t the c u t t i n g edge needed to shape our
minds. As L i v i n g s t o n e wrote years ago "No doubt there are more
important things i n education than the study of grammar; but i t
i s not an overstatement to say that not to know Greek i s to be
ignorant of the most f l e x i b l e and s u b t l e instrument of expression
which the human mind has d e v i s e d , and not to know L a t i n i s to have
missed an admirable t r a i n i n g i n p r e c i s e and l o g i c a l thought" (11).


1.
ARis
Of the converse d i s c i p l i n e , that o f t u r n i n g E n g l i s h i n t o

L a t i n or Greek i t i s i n t e r e s t i n g t o quote the P h y s i c s master a t
Winchester.
"The t a s k " , he says, " i n v o l v e s c o n c e n t r a t i o n , c l o s e
a t t e n t i o n t o d e t a i l , and considerable l o g i c a l reasoning; there are
no short c u t s , no formulae as i n the science problem, the
reasoning i n v o l v e d cannot be avoided by mere e f f o r t of memory as
i n the w r i t i n g out of a p r o p o s i t i o n i n geometry" (12). I t has
been popular among great men from Winston C h u r c h i l l to P e t e r
Danckwerts t o deplore the hours spent on L a t i n and e x t o l t h e i r
i n s t r u c t i o n i n E n g l i s h , b u t , as I have ventured t o comment e l s e where i n reviewing " I n s i g h t s i n t o Chemical Engineering" (13),
t h e i r E n g l i s h may owe more t o the d i s c i p l i n e of the c l a s s i c s than
they a f f e c t t o admit.
But the study of the c l a s s i c s i s not merely a matter of
language however great the general b e n e f i t to our general understanding of language t h i s may a f f o r d . Language i s the entry t o
l i t e r a t u r e as l i t e r a t u r e i s the r e f l e c t i o n of the l i f e and thought
of i t s time. From t h e i r p l a c e at the root of western c i v i l i z a t i o n ,
the Greek and L a t i n c u l t u r e s have an uncanny way of a n t i c i p a t i n g
and i l l u s t r a t i n g modern p o l i t i c a l and s o c i a l problems. C l a s s i c
indeed i s Thucydides' d e s c r i p t i o n of the i n t e r n a l corrosiveness of
war and r e v o l u t i o n "Words had t o change t h e i r o r d i n a r y meaning and
to take that which was now given them...Frantic v i o l e n c e became
the a t t r i b u t e of manliness; cautious p l o t t i n g a j u s t i f i a b l e means
of s e l f - d e f e n s e . The advocate of extreme measures was always
trustworthy; h i s opponent a man to be suspected" (14). As
s o c i o l o g y or s o c i a l psychology, i t s p e n e t r a t i o n should be the
envy of the modern s o c i a l s c i e n t i s t . As l i t e r a t u r e , i t s quick
a n t i t h e s e s "breathe an almost human a l i v e n e s s " i n t o an otherwise
a b s t r a c t a n a l y s i s (15). Archaeology r e v e a l s the c i r c u m s t a n t i a l
l i f e as l i t e r a t u r e does the i n t e l l e c t u a l , and i t too has i t s own
d i s c i p l i n e s i t s sherds o f t e n to be handled as d e l i c a t e l y as
p a r t i c l e s , i t s a r t i f a c t s as l o v e l y as odes and epodes, and i t s
s i t e s as complex and i n t r i c a t e as the p l o t of a tragedy or i n t e r play of a dialogue.
T h i s , however, i s not the p l a c e to e x t o l the c l a s s i c s n o r do
they need i t w h a t I am concerned w i t h i s the f e a t u r e s of i n t e l l e c t u a l l i f e that t h e i r study c u l t i v a t e s . I n the f i r s t p l a c e ,
there i s the p h i l o l o g i c a l foundation. This necessary occupation
w i t h w o r d s t h e i r p r e c i s i o n of meaning & the exactness of the way
they are put t o g e t h e r i s fundamental t o the c a r e f u l r e c o n s t r u c t i o n
of a t e x t and i t s c r i t i c a l e v a l u a t i o n . A t r a i n i n g i n t h i s sometimes leads t o a c e r t a i n cautiousness and care i n q u o t a t i o n .
Housman gave h i s i n a u g u r a l as Kennedy P r o f e s s o r of L a t i n a t the
U n i v e r s i t y of Cambridge on 9 May 1911, but he never p u b l i s h e d i t
as was customary, f o r he was never able to V e r i f y a statement
i t contained as t o the t e x t of S h e l l e y ' s Lament of 1821' (16).
The manuscript was destroyed a f t e r h i s death but a f u r t h e r copy
found among h i s papers was published i n T.L.S. i n 1968, o m i t t i n g ,
however, the passage of S h e l l e y (and Swinburne's remarks on i t )
that he had been unable to v e r i f y (17). I t was not u n t i l a f t e r


f u r t h e r work on S h e l l e y manuscripts had j u s t i f i e d the quotation

as Housman had used i t , that John Carter published the l e c t u r e as
"The Confines of C r i t i c i s m " i n 1969 (18). I mention t h i s example
not merely because of t h i s care f o r exactness, which by some
might be thought excessive, but because Housman used i t to show
the k i n d of confusion that can a r i s e i f e x a c t i t u d e of t h i s order
i s not maintained.
Swinburne had p r a i s e d an u n m e t r i c a l l i n e i n
the commonly p r i n t e d v e r s i o n of the second stanza as "a t h i n g to
t h r i l l the v e i n s and draw t e a r s to the eyes of a l l men whose ears
were not closed against a l l harmony" by "the melodious e f f e c t of
i t s e x q u i s i t e i n e q u a l i t y . " But the l i n e that so t h r i l l e d
Swinburne's veins was a m i s p r i n t and the "sovereign sweetness" of
the stanza not S h e l l e y ' s c r a f t but some unknown compositor's
carelessness. "These, "added Housman s e v e r e l y , " are the performances of the l i t e r a r y mind when, w i t h i t s f a c i l e emotions and
i t s i n c a p a c i t y f o r s e l f - e x a m i n a t i o n , i t invades the province of
science".
I t i s only f a i r to add that having smitten the E n g l i s h tool i t e r a r y carelessness he went on to denounce the German methodisch
unimaginativeness; the one breeding the fatuousness of " t a s t e " , the
other the m e n t a l i t y of the s l a v e . Against n e i t h e r could he give
an i n f a l l i b l e a l e x i k a k o n , though he warned against that " s e r v i l i t y
shown towards the l i v i n g " that " i s . . . s o o f t e n found i n company
w i t h l a c k of due v e n e r a t i o n towards the dead" (18, p. 44).
I f the c l a s s i c s demand exactness they do not r u l e out
i m a g i n a t i o n t h e t e x t u a l c r i t i c , l i t e r a r y c r i t i c , philosopher and
a r c h a e o l o g i s t a l l need i t b u t the d i s c i p l i n e demands that t h i s
imagination should be c o n t r o l l e d by p r e c i s i o n of s c h o l a r s h i p
r a t h e r than the r a m i f i c a t i o n of fancy. To the n i c e a p p r e c i a t i o n
of language the c l a s s i c a l s c h o l a r must add a c e r t a i n copiousness
of l e a r n i n g . A very broad reading of l i t e r a t u r e , h i s t o r y and
philosophy i s p a r t of the g r a i t h of c l a s s i c a l s c h o l a r s h i p j u s t as
a wide experience of d i f f e r e n t aspects of ancient c i v i l i z a t i o n and
a keen and d i s c e r n i n g eye f o r i t s a r t i f a c t s i s needed by the
a r c h a e o l o g i s t . Indeed the c o n t r a s t that most f o r c i b l y s t r i k e s a
s c i e n t i s t i n t a l k i n g to the humanist i s the comparatively immense
amount of reading t h a t the l a t t e r must do and the recourse that
must be had to primary sources. S i r Andrew Aguecheek's lament i n
"Twelfth Night" (provoked you w i l l r e c a l l by S i r Toby's "Pourquoi")
"0 that I had but f o l l o w e d the A r t s " (19) i s a r e a l cry of the
h e a r t , f o r , save f o r the e x c e p t i o n a l l y g i f t e d , the a c q u i s i t i o n
of the v a r i e d and extensive knowledge which i s needed i n ancient
s t u d i e s i s an impossible task i f not begun i n childhood.
But l e t us t u r n to a d i s c i p l i n e which, as Hardy says, i s
"more than any other a r t or science,...a young man's game"
mathematics (20). As an i n t e l l e c t u a l d i s c i p l i n e , i t s l e a d i n g
c h a r a c t e r i s t i c s are the power of a b s t r a c t i o n , the passion f o r
elegance and the p u r s u i t of r i g o u r . I put them i n that order,
f o r , though they share these c h a r a c t e r i s t i c s i n some degree w i t h
other d i s c i p l i n e s , the power of a b s t r a c t i o n i n mathematics i s


1.
ARis
r a i s e d to a height u n a t t a i n a b l e i n any other s u b j e c t , save

perhaps music. As a r e s u l t connections can be found between
things which are very f a r from obvious.
I t was, as Whitehead
pointed out (21), an immensely important step forward i n the
h i s t o r y of thought when i t was f i r s t r e a l i z e d that there was a
commonality of some s o r t between a p a i r of twins and a brace of
pheasants. We take the concept o f number so completely f o r
granted that we tend t o f o r g e t what an achievement t h i s a b s t r a c t i o n
of concept must have been. Perhaps we can r e c a l l the i n i t i a l con
f u s i o n and u l t i m a t e d e l i g h t of r e c o g n i z i n g that the c a r d i n a l
number of a c l a s s was indeed the c l a s s of a l l c l a s s e s s i m i l a r t o
i t , or at a more lowly l e v e l our l i b e r a t i o n from and y as apples
and oranges i n our kindergarten s t r u g g l e s w i t h elementary algebra.
I t i s of course a long way from the f i v e and country senses
of the engineering world t o the t h i n a i r o f the heights that
mathematicians seem to breathe so e f f o r t l e s s l y , yet we are f o r
tunate to have had as p a r t of our t e c h n i c a l t r a i n i n g a t l e a s t a
brush w i t h some o f the s t r u c t u r e s that pervade mathematics. The
group, r i n g or f i e l d i n algebra w i t h the notions of equivalence
r e l a t i o n s , morphisms, and mappings are p a r t of our mental f u r
n i t u r e , not only i n t h e i r i n s t a n t i a t i o n s , but as a b s t r a c t e n t i t i e s
forming our powers of apprehension. I t i s thus that we p e r c e i v e
t h a t , from a purely s t o i c h e i o m e t r i c point of view, any non-singular
transformation of a set of chemical r e a c t i o n s gives an equivalent
s e t . A t the same time we are conscious of the f a c t that
stoicheiometry i s not everything and that we may have to move
beyond i t t o an aspect i n which a p a r t i c u l a r set has a p r e f e r r e d
character. Not to have perceived the equivalence i s to be l e f t i n
a confusion of c o n c r e t i o n s ; not to have perceived i t s l i m i t a t i o n s
i s to have f a i l e d to understand the nature of a b s t r a c t i o n .
I suppose the root of these notions goes back to Pythagoras
who discerned the pervasive i n f l u e n c e of number i n the order of
nature. Of course t h i s was not developed u n t i l much l a t e r when,
w i t h the understanding of the n o t i o n of f u n c t i o n , i t became
p o s s i b l e t o express p h y s i c a l laws i n mathematical form, but h i s
proof (or r a t h e r the proof which goes back to h i s school i n the
s i x t h century B.C.) of the i r r a t i o n a l i t y of the square root of two
i s c i t e d by G. H. Hardy (20) as opening up the whole realm of r e a l
numbers, making that d e f i n i t i v e step beyond the everyday common
places of i n t e g e r s and r a t i o n a l e .
I f I may, I would l i k e t o advert f o r a moment t o the recent
development of non-standard a n a l y s i s and sketch how i n f i n i t e
and i n f i n i t e s i m a l numbers can be presented.
In this I follow a
b e a u t i f u l expository a r t i c l e of Ingleton (22) though, i n my haste
s c a r c e l y doing him, or Luxemburg on whom he l e a n s , f u l l j u s t i c e .
Consider a l l i n f i n i t e sequences of r e a l numbers (^,^,,,
) and l e t two such e n t i t i e s be equivalent i f they d i f f e r only
i n a f i n i t e number of elements i . e . , X i f = x f o r a l l but
a f i n i t e number of n. From now on we can consider the e n t i t y

to be the equivalence c l a s s and representable by any of i t s members
j u s t as the r a t i o n a l 1/2 i s the c l a s s (1/2, 2/4, 3/6,..). We
1

r e t a i n the r e a l numbers as the elements (,,,)(..

f o r a l l ) and can d e f i n e a r i t h m e t i c a l operations such as
XY = ( ,, ,) X.Y = < ;|7i'* y '' >
x
ee
a n d
1/X = (1/x-^, , l / x , ) provided ^ 0 i f i t i s , ignore i t and

use 1 i n s t e a d of 1/x s i n c e t h i s can only happen a f i n i t e number
of times. These
d e f i n i t i o n s a l l o w us to comprise the
o r d i n a r y operations of the a r i t h m e t i c of r e a l s w i t h i n t h i s new
world of h y p e r r e a l s .
I f we use the u s u a l n o t a t i o n f o r the r e a l s
we can say that R, (,,,,) provides a mapping
between R* the space of h y p e r r e a l s X = (-,, ,) and the
r u l e f ( X ) = (f(x ),(x )) i s a n a t u r a l extension of the
f u n c t i o n f from R to R*.
But now we n o t i c e t h a t we have i n R* a much r i c h e r e n t i t y
than we had i n R. We have h y p e r r e a l numbers l i k e =
(1,2,3,,n,) which i s i n any sense of the word an i n f i n i t e
i n t e g e r . Yet we have not the u n d i f f e r e n t i a t e d world of aleph-zero,
i n which, you r e c a l l , ff^ = $ or K = + f f o r any f i n i t e
n

. But here Z+N = (N+l,,N+n,) and or N.Z = (,2N, ,nN )

are w e l l - d e f i n e d and g i v e (Z+N) - = Z, (Z+N) - = N, (N.Z)/N=Z
and (N.Z)/Z = N. S i m i l a r l y Z = (1,4,,n ) o r
Z = (1,4,27,, ,) a r e t r u l y " i n f i n i t e " numbers. On the
other hand 1/Z = (1,1/2,,1/n,) i s an " i n f i n i t e s i m a l " , as are
1/(Z+N), 1/Z e t c . Sums of i n f i n i t e s i m a l s are i n f i n i t e s i m a l s , as
are products of i n f i n i t e s i m a l s w i t h f i n i t e h y p e r r e a l s .
Products
of i n f i n i t e and i n f i n i t e s i m a l numbers can be f i n i t e however as can
be q u o t i e n t s of i n f i n i t e s or of i n f i n i t e s i m a l s . Two h y p e r r e a l
numbers a r e i n f i n i t e s i m a l l y c l o s e i f t h e i r d i f f e r e n c e i s
i n f i n i t e s i m a l . For example (Z+l)/Z and Z/(Z+1) are both
i n f i n i t e s i m a l l y c l o s e t o 1 though a l l three are d i s t i n c t h y p e r r e a l
numbers. I n f a c t every f i n i t e h y p e r r e a l number i s i n f i n i t e s i m a l l y
c l o s e t o a r e a l number and every r e a l number has an i n f i n i t y of
i n f i n i t e s i m a l l y c l o s e h y p e r r e a l s . The r e a l number i n f i n i t e s i m a l l y
c l o s e t o any h y p e r r e a l i s c a l l e d i t s standard p a r t , i . e . s t X =
i f (X-x) i s i n f i n i t e s i m a l .
This makes the d i s c u s s i o n of convergence r a t h e r simple. A
sequence y^ i n R i s a mapping from the space of i n t e g e r s t o R.
This can
be extended i n the non-standard r e a l s as a mapping
from the extension of t o N*, the h y p e r r e a l i n t e g e r s , i n t o R*.
Then
i s an element of a non-standard sequence i f R* and
*. We say that Y^ converges to Y i f Y = s t Y^ f o r a l l
i n f i n i t e i n t e g e r s M.
C o n t i n u i t y and d i f f e r e n t i a b i l i t y can be
s i m i l a r l y d e f i n e d , f o r example f ( a ) = s t {f(a+h) - f ( a ) } / h
f o r a l l i n f i n i t e s i m a l s h. The D i r a c d e l t a f u n c t i o n can be
defined pointwise and new approaches t o the theory of p r o b a b i l i t y
and s t o c h a s t i c d i f f e r e n t i a l equations a r e opened up. But these
are a p p l i c a t i o n s and p a r a d o x i c a l l y I have been d e s c r i b i n g the
a b s t r a c t i o n that i s the non-standard world i n very concrete terms.
This i s no p l a c e t o go back and t r y t o present i t a b s t r a c t l y , but
i t stands as an example of a recent step forward i n the path of
a b s t r a c t i o n that began two and a h a l f m i l l e n i a ago (see a l s o (23,24)) .
2
11


1.
ARis
In d e s c r i b i n g the c h a r a c t e r i s t i c s o f mathematics I put

elegance before r i g o u r , f o r so i t appears t o the mathematically
c u l t i v a t e d mind. I t i s not that s l o p p i n e s s of reasoning can be
t o l e r a t e d i n the l e a s t , but r a t h e r that r i g o u r i s a d i s c i p l i n e
learned w i t h care and p r a c t i c e d w i t h scrupulousness, whereas i t
i s the i m a g i n a t i v e leap that reaches out t o a r e s u l t and f e e l s
that i t i s r i g h t before the perhaps lengthy c o n f i r m a t i o n i s undertaken that the mathematician c h i e f l y p r i z e s . I n t h i s leap the
d r i v i n g f o r c e i s i m a g i n a t i v e rather than l o g i c a l and i t i s the
i n s t i n c t f o r beauty which i s the avenue t o t r u t h . Thus e l e g a n c e
a much deeper q u a l i t y than p r e t t i n e s s , though more r e s t r i c t e d by
context than beauty i n the l a r g e r s e n s e i s g r e a t l y valued i n
mathematical c i r c l e s . I n i t s h i g h e s t forms, mathematics has "the
s i m p l i c i t y and i n e v i t a b l e n e s s " of great a r t and, v a s t l y though he
admired him, Hardy's judgment, as a mathematician, o f the
mathematician Ramanujan was that h i s work f e l l short of t h i s " i t
would be g r e a t e r i f i t were l e s s strange" (25) was Hardy's way of
expressing i t . Yet he paid f u l l t r i b u t e to Ramanujan's "profound
and i n v i n c i b l e o r i g i n a l i t y " .
Though denying that mathematicians have c o n s c i o u s l y aimed a t
beauty r a t h e r than l o g i c , R u s s e l l (26) has w r i t t e n e l o q u e n t l y of
the a e s t h e t i c appeal of mathematics i n one of h i s e a r l y essays.
"Mathematics, r i g h t l y viewed, possesses not only
t r u t h , but supreme b e a u t y a beauty c o l d and
austere, l i k e that of s c u l p t u r e , without
appeal t o any p a r t of our weaker n a t u r e , w i t h out the gorgeous trappings of p a i n t i n g o r
music, y e t sublimely pure, and capable of a
s t e r n p e r f e c t i o n such as only the g r e a t e s t a r t
can show. The t r u e s p i r i t o f d e l i g h t , the
e x a l t a t i o n , the sense of being more than man,
which i s the touchstone of the h i g h e s t
e x c e l l e n c e , i s to be found i n mathematics as
s u r e l y as i n poetry. What i s best i n mathematics deserves not merely to be l e a r n t as a
task, but to be a s s i m i l a t e d as p a r t of d a i l y
thought, and brought again and again before the
mind w i t h ever-renewed encouragement."
But from the realm of the c l a s s i c s , so r i c h and warm w i t h
human a s s o c i a t i o n s , and the " c o l d and a u s t e r e " beauty of mathematics we must t u r n t o the banausic domain of chemical r e a c t i o n
engineering. I t was, i f I remember r i g h t l y , at one of these
meetings that P r o f e s s o r Wei (27) gave us the connection by
p o i n t i n g out that one of the o l d e s t t e c h n o l o g i c a l processes i s
the fermentation r e a c t i o n , as pure a r e a c t i v e process as we could
wish f o r r i c h and humane w h i l s t i t stayed w i t h i n our domain and
took not up w i t h d i s t i l l a t i o n p r o c e s s e s a n d r i g h t l y respected i n
the very t i t l e of our meeting. But important though the business
of wine making may be i t i s but one of many r e a c t i o n s which l i e
at the cores of the d i f f e r e n t processes o f chemical i n d u s t r y and

10
ENGINEERING
i t i s out of the experience of these that the d i s c i p l i n e of

chemical r e a c t i o n engineering has grown. I t i s a recent growth i n
a s u b j e c t of no long h i s t o r y f o r I suppose that i t i s only i n the
l a s t f i f t y years that i t has emerged as a d i s t i n g u i s h a b l e t r a i n of
thought. Damkohler's work i n the 3 0 s , Hougen's and Watson's i n
the 40's, Wilhelm's and Amundson's i n the 50's are but p o i n t s of
touch-down i n the immense s t r i d e s that have taken us onward. The
t a l e of t e x t s has lengthened decade by decade, the wen of papers
has grown year by year and I h e s i t a t e to mention any more names
for I am sure to leave out people of great s i g n i f i c a n c e . ( I have
t r i e d to survey some aspects of the h i s t o r i c a l development e l s e where (28).)
But what has emerged as c h a r a c t e r i s t i c i n t h i s development?

I would suggest f i r s t a sense of balance, then a f e e l i n g f o r
s t r u c t u r e and f i n a l l y a refinement of concept l e a d i n g to a h i g h
degree of awareness. Those are r a t h e r vague terms so l e t my t r y
to make them more p r e c i s e and then i l l u s t r a t e some aspects i n
greater d e t a i l . Under balance I t h i n k of the balance t h a t needs
to be s t r u c k between theory and p r a c t i c e on the one hand and
between the general and the p a r t i c u l a r on the other. By s t r u c t u r e
I mean the way i n which we have come to see the subject standing
on the foundation of thermodynamics, t r a n s p o r t processes and
chemical k i n e t i c s . The nature of the c o n s t r a i n t s i m p l i e d by t h i s
and the inherent s t r u c t u r e o f , f o r example, s t o i c h e i o m e t r y or mass
a c t i o n k i n e t i c s are at i s s u e here. C e r t a i n ideas have been of
great importance i n t h i s development and no p a r t of chemical e n g i neering i s r i c h e r i n dimensionless numbers; they range from the
four of Damkohler (29) or the modulus of T h i e l e (30) to the
Carberry number that B i s c h o f f (31) minted a year or two ago. I t
was e a r l y recognized that r e a c t o r s presented p e c u l i a r scale-up
problems and the height of r e a c t i o n u n i t never a t t a i n e d the popul a r i t y of the H.T.U. S i m p l i f i e d s t r u c t u r e s p l a y an important r o l e
as i n the i n s i g h t gained from Wei and P r a t e r ' s (32) monomolecular
systems and the r e s u l t i n g shape i n v a r i a n c e (33). A great
refinement of concepts has taken p l a c e over the years as, f o r
example, i n the way that we now d i s t i n g u i s h s e n s i t i v i t y , m u l t i p l i c i t y
and s t a b i l i t y (34). With the e x p l o r a t i o n of instances of these
concepts has come an awareness of the v a r i e t i e s of b e h a v i o r , the
comprehensive d e s c r i p t i o n of a l l forms of p o s s i b l e behavior of
r e a c t o r s as dynamical systems the pervasiveness of o s c i l l a t i o n and
chaos and, w i t h a l l t h i s , an exhanced a b i l i t y to f e e l a f t e r the
form of the s o l u t i o n .
Chemical r e a c t i o n engineering has been n o t a b l e f o r the
balance between experiment and theory that has marked i t from the
beginning. I t i s t r u e t h a t , save i n the r a r e i n s t a n c e of a
Shinnar at the i n d u s t r i a l - a c a d e m i c i n t e r f a c e or a Schmitz i n the
more p u r e l y academic context, t h i s blood and judgment have seldom
been "so w e l l commingled" i n one person, but there has always been
a p r o p i t i o u s i n t e r c o u r s e between those c h i e f l y concerned w i t h

1.
ARIS
11
p r a c t i c e and those pursuing the e u r i s t i c s of mathematical

modelling.
The i n g e n u i t y of the p r a c t i c i n g r e a c t i o n a r y i s always
r e f r e s h i n g : on the i n d u s t r i a l s c a l e we have the c l a s s i c a l case
of the f l u i d i z e d bed as w e l l as the s e r e n d i p i t y of the t r a n s f e r l i n e
or the i n t r i c a c y of some of the p o l y m e r i z a t i o n r e a c t o r s ; on the
research s c a l e there i s Wicke's creeping zone (35) Rony s bundle
of m i c r o f i l a m e n t s (36), Petersen's s i n g l e p e l l e t r e a c t o r (37),
Carberry's spinning basket (38) and the Berty r e a c t o r , the s t r i n g
of beads used by Hegedus and Oh (39) and Wei and Degnan's (40)
combination of c r o s s - f l o w monoliths or Schmitz' polythene bag. I t
i s a p r a c t i c a l i n g e n u i t y matched on the t h e o r e t i c a l s i d e by some
of the devices that have been used i n a n a l y s i n g r e a c t o r models.
The n o t i o n of an e f f e c t i v e n e s s f a c t o r introduced by T h i e l e ,
Amundson's e x p l o i t a t i o n o f the phase plane (34) , Gavalas' use of
the index theorem (41), the S t e i n e r symmetrization p r i n c i p l e used
by Amundson and Luss (42) and the l a t t e r ' s e x p l o i t a t i o n of the
formula f o r Gaussian quadrature (43)perhaps the p r e t t i e s t
connection ever made i n the chemical engineering l i t e r a t u r e a r e
t h e o r e t i c a l counterparts, l a r g e and s m a l l , of the c a r e f u l c r a f t
of the e x p e r i m e n t a l i s t . So perhaps a l s o the very important
i n s i g h t that Danckwerts c o n t r i b u t e d i n h i s f o r m u l a t i o n of the
residence time d i s t r i b u t i o n i s a happy f o i l t o h i s h e r o i c
ambition t o t r a c e a b l a s t furnace (44).
Faced w i t h the enormous v a r i e t y of p r a c t i c a l reactor, chemical
engineers are f o r c e d t o t h i n k of the general shape and s t r u c t u r e
of r e a c t o r a n a l y s i s i f they are to r e t a i n i t as an i n t e l l e c t u a l
d i s c i p l i n e . Wilhelm used t o speak of the "morphology" of the
subject years ago i n h i s l e c t u r e s a t P r i n c e t o n and h i s i n f l u e n c e
on t h i s s i d e of the A t l a n t i c , together w i t h that of Hougen and
Watson, was as formative on the engineering s i d e , as Amundson's
was on the t h e o r e t i c a l (45). There are many l e v e l s of s t r u c t u r e
from the r a t h e r obvious f a c t that stoicheiometry i s a manifes
t a t i o n of l i n e a r algebra t o the profound a n a l y s i s of mass a c t i o n
k i n e t i c s that Feinberg (46) has developed so f u l l y from h i s
e a r l i e r work w i t h Horn and Jackson. Wei and P r a t e r ' s (32) now
c l a s s i c treatment o f f i r s t - o r d e r r e a c t i o n s showed how the
s t r u c t u r e of l i n e a r d i f f e r e n t i a l equations leads to both theo
r e t i c a l and p r a c t i c a l i n s i g h t s i n t o k i n e t i c systems. More
r e c e n t l y Shinnar has shown how fundamental thermodynamic con
s t r a i n t s , such as the requirement that the f r e e energy decrease
along a r e a c t i o n path, g i v e shape t o the problem of understanding
a r e a c t i v e system and i n c o r p o r a t i n g i t i n t o u s e f u l design
objectives.
The i n t r o d u c t i o n of s i n g u l a r i t y theory by G o l u b i t s k y and
K e y f i t z (47) and i t s development by Luss and B a l a k o t a i a h (43,48)
i s another s t r u c t u r a l landmark. The l a t t e r show, f o r example,
that a l l the p o s s i b l e b i f u r c a t i o n diagrams can be determined f o r
c e r t a i n networks of r e a c t i o n s . They use a r e d u c t i v e scheme which
allows the system w i t h r e a c t i o n s t o be analysed by l i m i t i n g
cases i n which only r e a c t i o n s proceed at a f i n i t e r a t e and the


12
C H E M I C A L R E A C T I O N ENGINEERING
others are e i t h e r instantaneous or g l a c i a l l y slow. I t would be

i n a p p r o p r i a t e , even i f i t were n e c e s s a r i l y r e l e v a n t , to say more
on t h i s s i n c e a paper at t h i s meeting w i l l b r i n g us up to date on
t h e i r t h i n k i n g . But i t r a i s e s two p o i n t s of importance.
The
f i r s t i s the i n s t i n c t f o r comprehensiveness; the second, the
immensity of many dimensions, which I w i l l advert to at the end.
As a p r a c t i c a l device f o r making a product the chemical r e a c t o r
presents i t s e l f as a matter of design and c o n t r o l and the engineer
may be' s a t i s f i e d to o b t a i n economy i n the one and r e l i a b i l i t y i n
the other. I t i s not a q u e s t i o n of c o n s i d e r i n g a l l p o s s i b l e
r e a c t o r s but of a c h i e v i n g a working r e a c t o r that w i l l be i n t e g r a t e d
i n t o a whole p l a n t and come on stream i n time to make a p r o f i t .
As an object f o r i n t e l l e c t u a l comprehension, however, the r e a c t o r
must be regarded comprehensively, we have the r i g h t and duty to
enquire of i t s behavior f o r any, not j u s t the s o - c a l l e d
" r e a l i s t i c " , values of the parameters.
T h i s i s where such t o o l s
as s i n g u l a r i t y theory or that of catastrophes, the q u a l i t a t i v e
theory of d i f f e r e n t i a l equations or t o p o l o g i c a l methods are so
important, f o r they can, when r i g h t l y used, o f t e n g i v e comprehensive i n f o r m a t i o n . A case i n which the s t r i c t numerical
d e f i n i t i o n of regions of parameter space could be replaced by geom e t r i c a l l y d i s t i n c t p o s s i b i l i t i e s arose w i t h the competition of
two m i c r o b i o l o g i c a l populations f o r a s i n g l e n u t r i e n t i n a continuous fermentor which Arthur Humphrey and I considered a few
years ago (49). We were able to show how the r e l a t i v e d i s p o s i t i o n s of the two growth curves and the p o i n t r e p r e s e n t i n g the
d i l u t i o n r a t e and feed c o n c e n t r a t i o n could be encoded i n t o a
l a b e l which was a s s o c i a t e d w i t h a phase p o r t r a i t . Thus i t could
be s a i d that the dynamical behavior of any such system was
t o p o l o g i c a l l y e q u i v a l e n t to any other w i t h the same l a b e l .
I t i s tempting to d i g r e s s at t h i s p o i n t and enlarge on the
v i r t u e s of chemical r e a c t i o n engineering as a source of m a t e r i a l
f o r the c r a f t of f e e l i n g out a s o l u t i o n . T h i s i s as important a
technique to l e a r n and teach as i t i s enjoyable i n i t s e x e r c i s e .
However i t would take us too f a r a f i e l d and, as I have t r i e d to
expound
i t elsewhere (see Chap. 2 of 28; 50,51), I w i l l r e s i s t
the temptation even though I have a brand new example making
p r o p i t i o u s ferment i n my v i t a l s .
A f u r t h e r c h a r a c t e r i s t i c of chemical r e a c t i o n engineering i s
i t s f a c i l i t y i n r e f i n i n g concepts. I t i s a d e r i v e d c h a r a c t e r i s t i c ,
stemming from the mathematical component of the s u b j e c t , but i t
has been t y p i c a l of i t s development s i n c e the d i s t i n c t i o n between
s t a b i l i t y and s e n s i t i v i t y was f i r s t drawn (34). There have been
l a p s e s , a l a s , as i n the case of an e x p o s i t o r y paper (52) which,
to judge by the demand f o r o f f p r i n t s , proved q u i t e u s e f u l , but
which r a t e d a very low Watkins number (53), f o r i t s t i t l e was
"On the s t a b i l i t y c r i t e r i a of chemical r e a c t i o n engineering" w h i l e
i t s burden was as much the m u l t i p l i c i t y c r i t e r i a as the s t a b i l i t y
c o n d i t i o n s . But there has been a steady i n c o r p o r a t i o n of prec i s e l y defined concepts as f o r example i n the burgeoning study of



1.
ARis
13
chaos which i s evoking i n t e r e s t from mathematicians, p h y s i c i s t s

and chemists as w e l l as engineers. I n the 50's i t seemed l i k e l y
that o s c i l l a t i o n s i n r e a c t o r s would be most l i k e l y t o a r i s e when
a c o n t r o l system was added t o the r e a c t o r (54) . The n o t i o n of
m u l t i p l i c i t y c a r r i e d w i t h i t the p i c t u r e of the a s s o c i a t e d
r e g i o n of a t t r a c t i o n , an open set of i n i t i a l s t a t e s which would
l e a d t o the same steady s t a t e . Denbigh (55) had shown t h i s i n
h i s p i o n e e r i n g work using the n o t i o n of " e q u i f i n a l i t y " adumbrated
i n a b i o l o g i c a l context by Burton. But, u s i n g the newly r e v i v e d
notions of Hopf b i f u r c a t i o n , Uppal, Ray and Poore (56) were able
to show that the u n c o n t r o l l e d non-adiabatic s t i r r e d tank w i t h a
s i n g l e exothermic r e a c t i o n t h e s i m p l e s t non-isothermal s y s t e m
could e x h i b i t a wide v a r i e t y of behavior i n c l u d i n g m u l t i p l e steady
s t a t e s and l i m i t c y c l e s w i t h i n l i m i t c y c l e s . T h e i r t a l e of
p o s s i b l e modes of behavior was s c a r c e l y t o l d before a group of
Russian authors (57) augmented i t .
An important r e a l i z a t i o n that has been a t t a i n e d i n recent
years i s that the processes of a d s o r p t i o n , desorption and
rearrangement on the c a t a l y s t surface may themselves produce
m u l t i p l e r e a c t i o n r a t e s o r o s c i l l a t i o n s . Wicke (35) and h i s
colleagues found t h i s some years ago and the reviews of Sheintuch
and Schmitz (58) and Scheintuch (59) show how wide-spread the
phenomenon i s . I t i s dangerous to mention names when I am sure
to omit many important ones but those of Y a b l o n s k i i , S l i n k o and
t h e i r colleagues i n R u s s i a , Eigenberger and Hugo i n Germany,
Kenney i n England and Luss, Takoudis, Schmidt, Ray, Jensen over
here s p r i n g to mind i n a d d i t i o n to those already mentioned. The
B e l o u s o v - Z h a b o t i n s k i i r e a c t i o n has of course generated a minor
i n d u s t r y of experimental and t h e o r e t i c a l s t u d i e s , d i s s i p a t i v e
systems and l o c u s - a t o r s which i t would be rash t o rush i n t o here.
But even as the n o t i o n of p e r i o d i c s o l u t i o n s t o the n o n l i n e a r
d i f f e r e n t i a l equations of chemical r e a c t o r theory was growing
i n c r e a s i n g l y f a m i l i a r i n the '60*s and 7 0 s , there was s p r o u t i n g
beside i t the new ideas of chaos and non-periodic behavior. This
stemmed from a v a s t l y s i m p l i f i e d m e t e o r o l o g i c a l model of three
modestly n o n l i n e a r equations s t u d i e d by Lorenz (60) which e x h i b i t e d
s o l u t i o n s which were n e i t h e r p e r i o d i c nor asymptotic to p e r i o d i c
s o l u t i o n s . The p r o p e r t i e s of such s o l u t i o n s soon a t t r a c t e d
a t t e n t i o n of mathematicians and others and there i s a t h r i v i n g
i n d u s t r y t r y i n g to put order i n t o chaos a t the moment (61).
Already a t the l a s t of these symposia, Pismen (62) i n h i s
e x c e l l e n t review of k i n e t i c i n s t a b i l i t i e s was able t o g i v e
s e v e r a l references and has h i m s e l f shown how data sampling can
c o n t r i b u t e i t s meed of randomness.
I t i s c r e d i b l y h e l d that at l e a s t three equations are needed
f o r c h a o t i c behavior and i t i s not s u r p r i s i n g that i t has been
found i n the s t i r r e d tank when two r e a c t i o n s are t a k i n g p l a c e .
R b s s l e r , Varma and K a h l e r t (63) have found i t f o r consecutive
r e a c t i o n s , one exo- and the other endothermic; Lynch and others
(64) have used p a r a l l e l r e a c t i o n s ; the exothermic sequence
T

14
A->B->C has a l s o been considered by Jorgensen (65) . This l a s t i s a

system of three equations f o r u and v, the concentrations of A and
B, and w, the temperature, w i t h seven parameters:
a, the Damkhler
number f o r A-*B; 3, i t s dimensionless heat of r e a c t i o n ; , i t s
A r r h e n i u s number; , a dimensionless heat t r a n s f e r c o e f f i c i e n t ;
v, the r a t i o of a c t i v a t i o n energies of the two r e a c t i o n s ; p, the
r a t i o of the heats of r e a c t i o n ; , the r a t i o of the Damkohler
numbers. They c o n t a i n a c h a r a c t e r i s t i c n o n - l i n e a r i t y
E(w)
expiyw/(+w)}

(which reduces to expw i f *) and are:
1 - u{l+aE(w)}
=
=
auE(w) - v { l + a a E ( w ) }
-(1+K)W + a3uE(w) + $ vE (w)
Jorgensen s f i r s t endeavour was to map out the regions of

m u l t i p l i c i t y , s t a b i l i t y and i n p a r t i c u l a r the Hopf b i f u r c a t i o n
l o c i . Then t a k i n g a l l parameters except , the c o o l i n g r a t e
parameter, to be constant she v a r i e d t h i s over an i n t e r v a l
(5 < < 8) i n which there was a s i n g l e unstable steady s t a t e and
t h e r e f o r e at l e a s t one o s c i l l a t o r y s o l u t i o n , the p r i n c i p a l
o s c i l l a t i o n . There were two s u b i n t e r v a l s , (5.49,5.60) and
(6.95,7.29), w i t h i n which two i n t r i c a t e l y complex p a t t e r n s of
t r a n s i t i o n s could be seen, the p a t t e r n s being t o p o l o g i c a l m i r r o r
images of each other. The g r e a t e r p a r t of each i n t e r v a l was
occupied by a c y c l e of approximately twice the p e r i o d of the
p r i n c i p a l o s c i l l a t o r y s o l u t i o n , but then as the values of moved
outward through the l a s t f r a c t i o n s of the s u b i n t e r v a l s , cascades
of p e r i o d doublings l e d to chaos, which subsided i n t o regimes of
o s c i l l a t i o n s of s i x times the p e r i o d of the p r i n c i p a l . These
cascaded i n t o chaos, recovered as p e r i o d 10 o s c i l l a t i o n s , r e l a p s e d
and recovered as p e r i o d 8's b e f o r e t h e i r f i n a l widdershins as
fandangos f o r c h a o t i c and p e r i o d i c s o l u t i o n s .
"Morris a n t i c s " (6_6) indeed and a l l w i t h i n the f i f t h decimal
p l a c e ! "So what", says the p r a c t i c a l l y - m i n d e d engineer:
" s t u l t i t i a est enim i l l i " (6 7). But n e v e r t h e l e s s i t moves and i t
i s not so many years s i n c e Amundson's c r i t e r i a f o r s t a b i l i t y were
thought to be i d l e s o p h i s t r i e s . There may indeed be systems f o r
which some of these regions of complexity have a s i g n i f i c a n t s i z e
or are s i t u a t e d i n an otherwise d e s i r a b l e r e g i o n of parameter
space. As a branch of p r a c t i c a l engineering chemical r e a c t o r s may
be t o l e r a b l y w e l l understood without a l l the refinements of t h i s
i n t r i c a t e behavior. As an o b j e c t of i n t e l l e c t u a l study these
apparently e s o t e r i c f e a t u r e s are of great moment; they show that
the v e i n , r i c h as i t has proved to be, i s not mined out y e t .
The v a l u e of comprehensiveness makes demands t h a t open up a
question which I b e l i e v e w i l l be a l l important i n t h i s decade, the
question of how to master the daunting "espaces i n f i n i s " (68) of


1.
ARIS
15
a l a r g e number of parameters. We need theorems of great power,

such as those of Feinberg i n k i n e t i c s , that w i l l b l o c k out whole
subspaces and ensure that no e x o t i c type of behavior can hurt o r
devour there. We need ways of keeping i n the important i n t e r f a c e s
so that the boundaries of d i f f e r e n t regions do not have t o be
determined by t r i a l and e r r o r . I t i s f a i r l y easy t o see how t o
keep on the margin of s t a b i l i t y , but how can we tread the edge of
chaos? Even t h i s , however, only reduces the d i m e n s i o n a l i t y by one
or two and enormous d i f f i c u l t i e s s t i l l remain. P r a c t i c a l i t y can
sometimes come t o our a i d by c o n f i n i n g a t t e n t i o n t o subspaces
which a r e , i n some sense, o p t i m a l o r , i n some sense, s a f e . But
u l t i m a t e l y i t w i l l r e q u i r e some new i n s i g h t t o expand our
imaginations, r e v e a l i n g the power of a s u b j e c t apparently so
humdrum as chemical r e a c t i o n engineering t o charm "the wide
casements opening on the foam of k e e l l e s s seas i n f a i r y lands
f o l o r n " (69).
Literature Cited
1.
2.
3.
4.
5.
6.
7.
Baker, H. F., E d . ; "The Collected Mathematical Papers of

James Joseph Sylvester" (four volumes); Cambridge, 1912
(biographical notice in V o l . 4).
There is some confusion over the reason for Sylvester's
untimely departure from the University of V i r g i n i a .
According to . T. B e l l (Men of Mathematics) he resigned
after three months on account of the "refusal of the
University authorities to discipline a student who had
insulted him." According to Woolf "within three months
he was on his way back to England, convinced that he had
k i l l e d a student in self defensea conviction that
fortunately proved to be false". Of his experiences in
1841 H. F . Baker writes in the Biographical Notice in
Volume 4 of the Collected Mathematical Papers; "Such a
considerable change deserved a better fate than b e f e l l ;
in Virginia at this time the question of slavery was
the subject of bitter contention, and Sylvester had a
horror of slavery. The outcome was his almost immediate
return; apparently he had intervened vigorously in a
quarrel between two of his students."
Woolf, H., "An Introduction to J. J. Sylvester"; in
"Algebraic Geometry"; Igusa, J-I., E d . ; the Johns Hopkins
Centenial Lectures: Supplement to the American Journal
of Mathematics.
"The Creed of the Old South"; Atlantic Monthly Jan. 1892,
75.
"Studies in Honor of Basil L . Gildersleeve"; The Johns
Hopkins Press, Baltimore, 1902.
Gildersleeve, B. L., "Essays and StudiesEducational and
Literary"; Baltimore, 1890.
M i l l e r , C. W. E., E d . ; "Selections from the Brief Mention
of B. L . Gildersleeve"; Johns Hopkins Press, Baltimore, 1930.

16
8.
9.
10.
11.
12.
13.

14.
15.
16.
17.
18.
19.
20.
21.
22.
23.
24.
25.
26.
27.
28.
29.
30.
31.
32.
33.
34.
35.
Plutarch, De Plac. Phil, i, 5.

Pliny, Hist. Nat. ii, 3.
Cicero, De Universo, 10.
Livingstone, R. W., "A Defense of Classical Education";
Macmillan: London, 1916.
Ibid. p. 223.
Aris, R., Review of "Insights into Chemical EngineeringSelected Papers of P. V. Danckwerts"; Chem. Engng. Sci.
1982, 37, 1123.
Thucydides, Peloponesian War III.82-3.
Finley, J. ., "Four Stages of Greek Thought"; p. 73.
Gow, A. S. F., "Housman, A. E. A Sketch"; Cambridge
University Press: Cambridge, 1936.
Times Literary Supplement. 9 May 1968.
Housman, A. E., "The Confines of Criticism"; Carter, J., Ed.;
Cambridge University Press: Cambridge, 1969.
Shakespeare, W., "Twelfth Night"; I, iii, 99-101.
Hardy, G. H., "A Mathematician's Apology"; Cambridge University
Press: Cambridge, 1940.
Whitehead, A. N., "Science and the Modern World"; Macmillan:
London, 1925.
Ingleton, A. W., Bull. Inst. Math. Applies. 1982, 18, 34.
Hoskins, R. F., Bull. Inst. Math. Applies. 1982, 18, 49.
Cutland, N. J., Bull. Inst. Math. Applies. 1982, 18, 52.
Hardy, G. ., "RamanujanTwelve Lectures Suggested by His
Life and Work"; Cambridge University Press: Cambridge, 1940.
Russell, B. A. W., "The Study of Mathematics" in "Philosophical
Essays"; Longmans Green: London, 1910.
Wei, J., This observation, despite its interest and
importance, seems to have escaped the public record.
Aris, R., "Reflections on Some Trends in Chemical Reaction
Engineering"; Chap. 4 of "Chemical Engineering in the
University Context"; University of Wisconsin Press:
Madison, 1982.
Damkhler, D., Einflsse
der Strmung, Diffusion und
Wrmeiiberganges
auf die Leistung von Reacktions fen,
Z. Electrochem. 1936, 42, 846; 1937, 43, 1,8; 1938, 44, 240.
Thiele,E.W.,
Ind. Eng. Chem. 1939, 31, 916.
Bischoff, . ., Ind. Eng. Chem. Fundamentals 1976, 15, 229.
Wei, J. and Prater, C. D., "The Structure and Analysis of
Complex Reaction Systems". Advances in Catalysis. Academic
Press: New York; Vol. 13.
Aris, R., "The Mathematical Theory of Diffusion and Reaction
in Permeable Catalysts"; Clarendon Press: Oxford; Vol. I,
Ch. 5.
Amundson, N. R. and Bilous, O., A.I.Ch.E. J. 1955, 1, 513.
Wicke, E., "Physical Phenomena in Catalysis and in Gas-Solid
Surface Reactions"; Proc. 1st Int. Conf. on Chem. Reac. Engng.,
Washington, 1970; American Chemical Society: Washington, D.C.,
1972.

1.
36.
37.
38.
39.

40.
41.
42.
43.
44.
45.
46.
47.
48.
49.
50.
51.
52.
53.
54.
55.
56.
57.
58.
59.
60.
ARIS
17
Rony, P. R., J. Am. Chem. Soc. 1972, 94, 8247.

Petersen, . E. and Hegedus, L. L., Ind. Eng. Chem.
Fundamentals 1972, 11, 579.
Carberry, J. J., Ind. Eng. Chem. 1964, 56, 39.
Oh, Se H., Hegedus, L. L., Baron, K. and Cavendish, J. C.,
"Carbon Monoxide Oxidation in An Integral Reactor. Transient
Response to Concentration Pulses in the Regime of Isothermal
Multiplicities";
Proc. ISCRE5 ACS Symposium Series 65,
American Chemical Society: Washington, D.C., 1978, p. 461.
Wei, J. and Degnan, T. F., "Monolithic Reactor-Heat Exchanger";
Proc. ISCRE5 ACS Symposium Series 65, American Chemical
Society: Washington, D.C., 1978, p. 83.
Gavalas, G. R., "Nonlinear Differential Equations of
Chemially Reacting Systems"; Springer-Verlag:
Heidelberg,
1968.
Amundson, N. R. and Luss, D., A.I.Ch.E. J. 1967, 13, 759.
Luss, D. and Balakotaiah, V. Chem. Engng. Sci. (to appear).
Danckwerts, P. V., "Insights into Chemical Engineering
(Selected Papers of P. V. Danckwerts)"; Pergamon Press:
Oxford, 1982.
I have touched on some aspects of this in the Wilhelm
Lecture for 1981 and in 24.
Feinberg, ., Chemical Oscillations,
Multiple Equilibria and
Reaction Network Structure
in "Dynamics and Modelling of
Reactive Systems"; Stewart, W. E., Ray, W. H. and Conley,
C. C., Eds.
Golubitsky, M. and Keyfitz, B. L., SIAM Journal Math. Anal.
1980, 11, 216.
Balakotaiah, V. and Luss, D., A.I.Ch..
J. (to appear).
Humphrey, A. E. and Aris, R., Biotech, and Bioeng. 1977, 19,
1375.
Aris, R., "Mathematical Modelling Techniques"; Pitman: London,
1978.
Aris, R., Chem. Eng. Educ. 1976, 10, 114.
Aris, R., Chem. Engng. Sci. 1969, 24, 149.
The Watkins number is a dimensionless measure of appropriate
ness in the closed interval 0 Wa 1. It was introduced
by Re in "a conversation on some aspects of mathematical
modelling"; Appl. Math. Modelling 1977, 1, 386.
Amundson, N. R. and Aris, R., Chem. Engng. Sci. 1958, 1, 122.
Denbigh, . G., Trans. Faraday Soc. 1944, 40, 352.
Uppal, ., Ray, W. H. and Poore, A. B. Chem. Engng. Sci. 1974,
29, 967.
Vaganov, D. ., Samoilenko, N. G. and Abramov, V. G., Chem.
Engng. Sci. 1978, 33, 1133.
Sheintuch, M. and Schmitz, R. ., Cat. Rev. Sci. and Eng.
1977, 15, 107.
Sheintuch, M., Kinetic Instabilities
in Catalytic Oxidation
Reactions (a review to appear).
Lorenz, . N., J. Atmos. Sci. 1963, 20, 130.

18
61.
62.
63.

64.
65.
66.
67.
68.
69.
ENGINEERING
It would be impossible to give an adequate bibliography of

the work on chaos and strange attractors, but the proceedings
of a Los Alamos Conference held in May 1982 under the title
of "Order in Chaos" will, when they appear, give a good
picture of the variety of activity.
An introductory sketch
of one aspect is given in 53.
Pismen, L. ., Chem. Engng. Sci. 1980, 35, 1950.
Rssler, O., Varma, A. and Kahlert, C. in "Modelling Chemical
Reaction Systems"; Ebert, K. and Jaeger, W., Eds., Springer
Verlag: Heidelberg, 1981.
Lynch, D. T., Rogers, T. D. and Wanke, S. ., Math. Modelling
1982, 0, 000.
Jorgensen, D. V. and Aris, R. will be in the Jan. 1983 issue
of Chem. Engng. Sci.
Bridges, R. W., "The Testament of Beauty. III"; Oxford, 1929,
1. 938.
Hieronymus, E., Vulgate version of I. Cor. 2, 14.
Pascal, B., Penses.
III, 206.
Keats, J., Ode to a Nightingale, u. 69-70. I quote Keats'
original version so that the reader may have the enjoyment
of discussing its variations from the well-known final text.
RECEIVED March 10, 1983

2
Development of the Methanol-to-Gasoline
Process
1
J. E. PENICK, W. LEE, and J. MAZIUK
Downloaded by UNIV OF ARIZONA on December 2, 2012 | http://pubs.acs.org

Mobil Research and Development Corporation, New York, N Y
10017
Mobil has developed a new process for

conversion of methanol to high quality gasoline
using a unique class of shape-selective zeolite
catalysts.
This process provides a novel route
to gasoline from either coal or natural gas via
intermediate methanol. Two reactor systems have
been devised by Mobil for this processfixed
bed and fluid bed. The f i r s t commercial
application of the fixed-bed process w i l l be i n
a 14,000 B/D (gasoline) plant based on natural
gas which w i l l be located in New Zealand. The
fluid-bed process i s being scaled up to a
100 B/D (methanol) demonstration plant located
in W. Germany. In this paper, the chemistry of
the process is reviewed and the engineering
involved i n selection, scale-up, and design of
an appropriate reactor system to produce an
acceptable product i s discussed.
M o b i l has developed a novel process f o r converting methanol
i n t o high q u a l i t y g a s o l i n e . ( 1 ) Since methanol can be made from
n a t u r a l gas o r c o a l by w e l l - e s t a b l i s h e d commercial technology,
the Methanol-to-Gasoline (MTG) process provides a unique
approach to the p r o d u c t i o n of g a s o l i n e from e i t h e r raw m a t e r i a l
as shown i n Figure 1. In the MTG process, methanol i s
q u a n t i t a t i v e l y converted to hydrocarbons and water. The
hydrocarbons are p r i m a r i l y g a s o l i n e b o i l i n g range m a t e r i a l s
s u i t a b l e f o r use as high q u a l i t y automotive f u e l .
1
Correspondence should be sent to W. Lee, Mobil Research and Development Corporation, Paulsboro, NJ 08066
0097-6156/83/0226-0019$08.50/0


Ash
Coal
Gasifier
Stearn
MTG
Process
GASOLINE
Water
Making gasoline from c o a l o r n a t u r a l gas v i a MTG.
Raw
Methanol
Water
MTG
r-*-GASOLINE
Process
F i g u r e 1.
Methanol
Process
Methanol
Process
Raw
Methanol
Synthesis
Gas
(CO + hh)
(CO + H2)
Synthesis
Gas
Steam
Reforming
Process
NATURAL G A S
Steam
Oxygen
COAL


2.
PENICK E T A L .
Methanol-to-Gasoline Process
21
The MTG process w i l l soon see i t s f i r s t commercial

a p p l i c a t i o n i n a p l a n t c u r r e n t l y being constructed f o r the New
Zealand S y n t h e t i c Fuels Corporation L i m i t e d . This p l a n t ,
scheduled f o r completion i n 1985, w i l l produce g a s o l i n e from
methanol derived from New Zealand n a t u r a l gas. I t w i l l produce
some 570,000 tonnes per year (14,000 BPSD) of unleaded g a s o l i n e
averaging 92 t o 94 research octane. This i s e q u i v a l e n t t o
about 1/3 of New Zealand's g a s o l i n e consumption. Two 2,200
tonnes-per-day methanol p l a n t s w i l l provide the feed f o r the
s i n g l e - t r a i n MTG p l a n t .
In t h i s l e c t u r e , the development of the MTG process w i l l be
reviewed. F i r s t , the unique aspects o f MTG the c a t a l y s t ,
chemistry, and i t s s p e c i a l r e a c t o r design aspects w i l l be
d i s c u s s e d . Next, the choices f o r the conversion system w i l l be
presented along w i t h the dual-pronged s t r a t e g y f o r development
of both the f i x e d - and f l u i d - b e d processes. F i n a l l y , our
f u t u r e development plans f o r t h i s general area o f technology
w i l l be h i g h l i g h t e d .
Catalyst
The ZSM-5 c a t a l y s t , the key element i n the MTG process, i s
a s h a p e - s e l e c t i v e s y n t h e t i c z e o l i t e w i t h a unique channel
s t r u c t u r e as shown i n Figure 2.(2)
This s t r u c t u r e i s
d i s t i n c t i v e l y d i f f e r e n t from the f a m i l i a r wide-pore z e o l i t e ,
f a u j a s i t e , and the narrow-pore z e o l i t e s . The l i n e s i n Figure 2
represent oxygen atoms i n a s i l i c e o u s framework. I t contains a
novel c o n f i g u r a t i o n of l i n k e d t e t r a h e d r a c o n s i s t i n g of e i g h t
five-membered r i n g s . These u n i t s j o i n through edges t o form
chains and sheets, l e a d i n g to the three dimensional s t r u c t u r e
r e p r e s e n t a t i o n shown i n the f i g u r e . I t contains two
i n t e r s e c t i n g channels: e l l i p t i c a l 10-membered r i n g s t r a i g h t
channels and s i n u s o i d a l , tortuous channels. The pore-opening
of these channels i s about 6 A and i s j u s t wide enough t o
produce hydrocarbons b o i l i n g p r i m a r i l y i n the g a s o l i n e range.
Since the mid-1970 s, more than 25 commercial p l a n t s have
been commissioned using t h i s c a t a l y s t f a m i l y . There are
c u r r e n t l y f i v e l i c e n s e d processes (other than MTG) based on the
ZSM-5 f a m i l y :
1
D i s t i l l a t e dewaxing
Xylene i s o m e r i z a t i o n
Toluene d i s p r o p o r t i o n a t i o n
Ethylbenzene
synthesis
L u b r i c a t i n g o i l dewaxing


22
ENGINEERING
Figure 2. ZSM-5 s t r u c t u r e . (Reproduced "with p e r m i s s i o n from

Ref. 2. Copyright 1978, Macmillan.)

2.
PENICK E T A L .
23
A l l o f these a p p l i c a t i o n s use fixed-bed r e a c t o r s , and, very

i m p o r t a n t l y , a l l were scaled up from bench-scale p i l o t p l a n t
data. This s u c c e s s f u l scale-up experience w i t h the ZSM-5
c a t a l y s t was an important c o n s i d e r a t i o n i n f o r m u l a t i n g the MTG
development s t r a t e g y .
Chemistry
The conversion of methanol t o hydrocarbons over ZSM-5 i s
well-represented by the f o l l o w i n g s i m p l i f i e d r e a c t i o n
network(3):
-H 0
^
^
+H 0
-H 0

2CH OH
3
CH3OCH3
> C -C
Olefins
2
Paraffins
> Aromatics
Cycloparaffins
The i n i t i a l dehydration r e a c t i o n i s s u f f i c i e n t l y f a s t t o
form an e q u i l i b r i u m mixture of methanol, dimethyl e t h e r , and
water. These oxygenates dehydrate f u r t h e r t o g i v e l i g h t
o l e f i n s . They i n t u r n polymerize and c y c l i z e t o form a v a r i e t y
of p a r a f f i n s , aromatics, and c y c l o p a r a f f i n s . The above
r e a c t i o n path i s i l l u s t r a t e d f u r t h e r by Figure 3 i n terms o f
product s e l e c t i v i t y measured i n an isothermal l a b o r a t o r y
r e a c t o r over a wide range of space v e l o c i t i e s . ( 3 )
The r a t e
l i m i t i n g step i s the conversion of oxygenates t o o l e f i n s , a
r e a c t i o n step that appears t o be a u t o c a t a l y t i c . I n the absence
of o l e f i n s , t h i s rate i s slow; but i t i s a c c e l e r a t e d as the
c o n c e n t r a t i o n of o l e f i n s i n c r e a s e s .
Under MTG c o n d i t i o n s , almost no hydrocarbons are found
higher than C ^ Q due to the shape s e l e c t i v i t y o f ZSM-5. While
higher molecular weight compounds may be formed w i t h i n the
c a t a l y s t channels, they do not escape due t o the s p a t i a l
hindrance of the c a t a l y s t s t r u c t u r e .
Reactor Design
Although the design of a r e a c t o r system f o r the MTG process
i n v o l v e s c l a s s i c a l chemical engineering p r i n c i p l e s , the unique
c a t a l y s t and r e a c t i o n mechanisms impose important design
c o n s t r a i n t s . These i n c l u d e the h i g h l y exothermic nature of the
r e a c t i o n , the need f o r e s s e n t i a l l y complete methanol conversion,
steam d e a c t i v a t i o n of the c a t a l y s t , the "band-aging" phenomena,
and durene formation.
Exotherm - The heat of r e a c t i o n i s 1740 kJ/kg of

methanol which i f u n c o n t r o l l e d would g i v e an
a d i a b a t i c temperature r i s e of about 600C.
Therefore, a p r i n c i p a l c o n s i d e r a t i o n i n designing a
r e a c t o r system i s r e a c t i o n heat management.


Wt. %
Products,
( ^ )
i l 111
1I
Olefins)
1 1 ifrQ-o-i
Olefins
1
Aromatics
PD-D-
Paraffins
(and C $ +
10
M i l l
o-o o- W a t e r
111
C2-C5
Figure 3. E f f e c t o f space v e l o c i t y a t 101 kPa and 371 C.

(Reproduced w i t h permission from Ref. 3. Copyright 1977
Academic Press.)
S p a c e Time

w
w
S
m
>
to
-

2.
PENiCK E T A L .
25
Complete Methanol Conversion - The major products

of the MTG conversion are hydrocarbons and water.
Consequently, any unconverted methanol w i l l
d i s s o l v e i n t o the water phase and be l o s t unless a
d i s t i l l a t i o n step to process the very d i l u t e water
phase i s added to the process. Thus, e s s e n t i a l l y
complete conversion of methanol i s h i g h l y p r e f e r r e d .
C a t a l y s t D e a c t i v a t i o n - Under MTG r e a c t i o n
c o n d i t i o n s , ZSM-5 c a t a l y s t undergoes two types of
aging which c o n t r i b u t e to a gradual l o s s of
c a t a l y s t a c t i v i t y . A r e v e r s i b l e l o s s r e s u l t s from
"coke" formed on the c a t a l y s t as a r e a c t i o n
byproduct.
This d e a c t i v a t i o n i s a t y p i c a l
c a t a l y t i c process design problem. What i s unusual
about the MTG process i s that a r e a c t i o n product,
steam, i s a l s o r e s p o n s i b l e f o r a gradual l o s s o f
a c t i v i t y . However, low r e a c t o r temperatures and
low p a r t i a l pressure of water w i l l minimize t h i s
aging and favor a long c a t a l y s t l i f e .
Band-Aging - E s p e c i a l l y w i t h f r e s h c a t a l y s t s , the
r e a c t i o n occurs over a r e l a t i v e l y s m a l l zone i n a
f i x e d bed. This r e a c t i o n f r o n t marches down the
c a t a l y s t bed as the coke d e p o s i t s f i r s t d e a c t i v a t e
the f r o n t part of the bed (Figure 4 ) . Use o f a
s u f f i c i e n t c a t a l y s t volume permits a fixed-bed
design i n which on-stream periods are long enough
to avoid o v e r l y frequent regeneration c y c l e s .
Durene Formation - An aromatic compound, durene ( 1 ,

2, 4, 5-tetramethylbenzene) i s produced i n the MTG
process. Durene has e x c e l l e n t research octane
blending q u a l i t y (110 RON c l e a r ) and b o i l s w i t h i n
the g a s o l i n e d i s t i l l a t i o n range (197C); however,
i t s f r e e z i n g p o i n t i s r e l a t i v e l y high a t 79C.
Based on our current designs, the g a s o l i n e d i r e c t l y
from the ZSM-5 r e a c t o r s could c o n t a i n 4 t o 7 wt%
durene. These concentrations of durene could lead
to problems w i t h s o l i d s build-up i n carburetors
during c o l d s t a r t s . While durene i s present i n
conventional g a s o l i n e , the t y p i c a l concentrations
are low enough not t o cause problems.


26
CHEMICAL
II
frft^frofr;ii^
0.1
0.2
0.3
ENGINEERING
0.4
0.5
0.6
0.7
0.8
0.9
Fractional Bed
Figure k.
bed.
REACTION
Length
Movement o f normalized temperature p r o f i l e through

2.
PENICK E T A L .
27

In the MTG process, durene i s mostly formed by

a l k y l a t i o n of lower molecular weight aromatics w i t h
methanol and/or ether. Low methanol p a r t i a l
pressures and high r e a c t i o n temperatures tend t o
reduce the durene l e v e l , presumably by reducing the
c o n c e n t r a t i o n overlap of methanol/ether w i t h the
aromatics formed. This overlap tends t o i n c r e a s e
w i t h l a r g e r c a t a l y s t p a r t i c l e s . As a consequence
the e a r l y fixed-bed development work was conducted
using 1 mm diameter extrudates.
A l l of the above f a c t o r s must be considered i n the v a r i o u s
r e a c t o r systems f o r the MTG process: fixed-bed r e a c t o r s ,
f l u i d - b e d r e a c t o r s and t u b u l a r r e a c t o r s . Figure 5a shows three
v a r i e t i e s of fixed-bed r e a c t o r s and Figure 5b i l l u s t r a t e s
heat-exchanger and f l u i d - b e d r e a c t o r v a r i a n t s .
Fixed-Bed
Systems
The major advantage of these fixed-bed systems i s that the

fixed-bed technology can be simple, and w i l l r e q u i r e minimum
scale-up s t u d i e s . As i n d i c a t e d e a r l i e r , t h i s type o f design
has been s u c c e s s f u l l y scaled-up t o commercial s i z e d i r e c t l y
from bench-scale p i l o t p l a n t data many times.
One common method f o r managing the a d i a b a t i c temperature
r i s e i n fixed-bed r e a c t o r s i s t o d i l u t e the reactant stream
w i t h a gas that would provide the mass to absorb the heat of
r e a c t i o n . L i g h t hydrocarbon r e a c t i o n products (methane,
ethane, propane) can be r e c y c l e d f o r t h i s purpose. However,
the c o s t s a s s o c i a t e d w i t h the r e c y c l e o p e r a t i o n could be
s u b s t a n t i a l i f the r e a c t i o n i s s t r o n g l y exothermic. S p e c i a l
a t t e n t i o n must be given t o reduce the r e c y c l e r a t i o .
Use of m u l t i p l e beds/reactors i n s e r i e s w i t h i n t e r c o o l i n g
or quenching i s a method which can be used t o reduce the amount
of r e c y c l e and i t s a s s o c i a t e d c o s t s . M u l t i p l e c a t a l y s t beds
reduce c o s t s by using the r e c y c l e m a t e r i a l s e v e r a l times before
i t i s separated from the r e a c t i o n products.
In Figure 6a, a multibed r e a c t i o n system i s shown f o r which
only p a r t i a l conversion i s taken across each bed; the e f f l u e n t
i s cooled before e n t e r i n g each succeeding bed such that the
e f f l u e n t from each bed does not exceed a s p e c i f i e d maximum
temperature.
The band-aging phenomena p r e v i o u s l y discussed
would complicate the development o f such an MTG process s i n c e
the c a t a l y s t appears t o age from the f r o n t t o the back. Thus,
i t might be d i f f i c u l t , e s p e c i a l l y f o r the f i r s t bed, t o
m a i n t a i n p a r t i a l conversion a t a given l e v e l f o r a reasonable
amount o f time.

28
Standard

Feed
Quench
Radial Flow
Recycle
Feed
^ ^Recycle
Feed
Recycle
Figure 5a. A d i a b a t i c r e a c t o r s .
Tubular
Isothermal
Feed
Heat
Exchange
Medium
Fluid-Bed Systems
Recycle
Heat
Exchange
Medium
Heat
Exchange
Medium
Feed
Figure 5b. Nonadiabatic r e a c t o r s .

PENICK E T A L .
MeOH
Feed ^ ^Recycle

X
r Steam
H 0'
2
Gas
Recycle
%
-C
Gas
Make
Raw
Gasoline
H0
2
Figure 6a. M u l t i b e d designs.
MeOH
Feed
I n t e r s t a g e heat removal.
Recycle^
Gasoline
Figure 6b. M u l t i b e d design.
I n t e r s t a g e feed quenching.


30
In Figure 6b, a multibed r e a c t i o n system i s shown i n which

only part of the reactant i s fed to each bed. The reactant fed
to each bed i s e s s e n t i a l l y completely converted and the
r e a c t i o n products from that conversion become part of the
temperature-moderating m a t e r i a l f o r each succeeding bed.
In
such a r e a c t i o n system the methanol feed to each succeeding bed
would be mixed w i t h aromatics made i n the preceding beds - - an
arrangement that tends to increase durene formation.
S t i l l another m u l t i - r e a c t o r approach i s to d i v i d e the MTG
r e a c t i o n i n t o two steps as shown i n Figure 7. In the f i r s t
step, methanol i s p a r t i a l l y dehydrated to form an e q u i l i b r i u m
mixture of methanol, dimethyl ether and water over a
dehydration c a t a l y s t . About 15% of the r e a c t i o n heat i s
released i n t h i s f i r s t step. In the second step, t h i s
e q u i l i b r i u m mixture i s converted to hydrocarbons and water over
ZSM-5 c a t a l y s t w i t h the concomitant release of about 85% of the
r e a c t i o n heat. Though t h i s two step approach does not have any
of the inherent complications of the p r e v i o u s l y mentioned
multibed r e a c t i o n systems, i t leaves one w i t h a s u b s t a n t i a l
amount of the r e a c t i o n heat (85%) s t i l l to be taken over one
c a t a l y s t bed. This r e q u i r e s a f a i r l y high r e c y c l e stream to
moderate the temperature r i s e over the second r e a c t o r . Such a
high r e c y c l e design would r e q u i r e c a r e f u l engineering i n order
to t r a n s f e r heat e f f i c i e n t l y from the r e a c t o r e f f l u e n t to the
r e c y c l e gas and r e a c t o r feed. However, t h i s two stage r e a c t o r
system i s the simplest of the fixed-bed systems to develop.
Fluid-Bed Reactor Systems
A r e a c t o r system which has s e v e r a l a t t r a c t i v e f e a t u r e s f o r
heat removal i s the f l u i d bed. With a f l u i d bed, the r e a c t i o n
heat can be removed by using heat exchange c o i l s i n the bed, or
c a t a l y s t can be c i r c u l a t e d to an e x t e r n a l c o o l e r f o r heat
recovery. Heat t r a n s f e r i n a f l u i d bed i s so r a p i d that the
danger of l o c a l overheating i s minimal. Furthermore, the heat
of r e a c t i o n can be recovered e f f i c i e n t l y as high pressure
steam. As expected, the f l u i d - b e d y i e l d p a t t e r n i s d i f f e r e n t
from that of the f i x e d bed; C 5 + g a s o l i n e y i e l d i s lower, but
the l i g h t o l e f i n s y i e l d s are much higher, p a r t l y because l i g h t
product gas i s not r e c y c l e d . A l k y l a t i o n of these o l e f i n s w i t h
product isobutane and blending gives an increased g a s o l i n e
y i e l d compared to that of the f i x e d bed.
Two f a c t o r s complicate the development of a f l u i d - b e d MTG
process. One i s the need to ensure the complete conversion of
methanol; the other i s to develop a f l u i d c a t a l y s t s u f f i c i e n t l y
rugged to withstand the a b r a s i v e f o r c e s inherent i n f l u i d - b e d
operation.


PENICK E T A L .
Figure T.
Two-stage fixed-bed MTG.

32
Since i n a l a r g e diameter f l u i d bed, bubbles may bypass the

c a t a l y s t , elaborate hydrodynamic s t u d i e s are required to
scale-up the r e a c t o r i n t e r n a l s to accomplish the complete
conversion of methanol. As mentioned e a r l i e r , e s s e n t i a l l y
complete conversion of methanol i s a process requirement;
otherwise, a c o s t l y d i s t i l l a t i o n step must be added to recover
unconverted methanol.
Thus, the f l u i d - b e d MTG process was assessed as being a
d e s i r a b l e but a long-term development. The scale-up would have
to proceed through s e v e r a l stages before i t would be ready f o r
commercialization.

Tubular, Heat-Exchange
Reactor Systems
Another r e a c t o r system which has s e v e r a l a t t r a c t i v e

f e a t u r e s f o r heat removal i s the t u b u l a r , heat-exchange
r e a c t o r . Good temperature c o n t r o l can be achieved i n the
t u b u l a r r e a c t o r i f the coolant approximates an i s o t h e r m a l heat
s i n k . L i g h t gas r e c y c l e can be reduced s i g n i f i c a n t l y compared
to fixed-bed systems. Tubular reactors have been used f o r
Fischer-Tropsch r e a c t i o n s and f o r s y n t h e s i s of methanol and
p h t h a l i c anhydride, f o r example.
The MTG r e a c t i o n temperature of approximately 400C
e s s e n t i a l l y precludes the use of b o i l i n g water as a coolant due
to the h i g h steam pressures i n v o l v e d . While o i l c o o l i n g might
conceivably be used, the temperatures are above the range
u s u a l l y considered p r a c t i c a l f o r such a design and l a r g e f l o w
r a t e s would be required to achieve uniform c o o l i n g . Heat
t r a n s f e r s a l t and b o i l i n g mercury are other p o s s i b i l i t i e s ; each
presents p a r t i c u l a r design c h a l l e n g e s . Of these, heat t r a n s f e r
s a l t probably represents the best compromise f o r an MTG
a p p l i c a t i o n p r i m a r i l y because the s a l t could a l s o be used to
c o n t r o l the p e r i o d i c c a t a l y s t regeneration o p e r a t i o n which
e n t a i l s temperatures of about 500C. From our viewpoint the
heat exchange r e a c t o r has the f o l l o w i n g disadvantages: (1)
m o l t e n - s a l t c o o l i n g presents s i g n i f i c a n t o p e r a t i o n a l problems,
(2) t u b u l a r r e a c t o r s g e n e r a l l y c o n t a i n l e s s c a t a l y s t per u n i t
of v e s s e l volume than other r e a c t o r types, (3) the maximum
p r a c t i c a l c a p a c i t y f o r a s i n g l e r e a c t o r i s l e s s than f o r other
types and (4) very c a r e f u l mechanical design w i l l be required
f o r a t u b u l a r r e a c t o r which can r e l i a b l y withstand both the
conversion and c a t a l y s t regeneration c y c l e s .
Strategy f o r Commercialization
Since there are many p o s s i b l e r e a c t i o n systems f o r an MTG
process, i t was necessary to focus the development e f f o r t s . In
the mid-1970 s, M o b i l decided to pursue a double-pronged
approach i n order to ensure both s h o r t - and long-term
o b j e c t i v e s . The plan was:
1

2.
PENICK E T A L .
33

NEAR-TERM P r o c e e d w i t h commercialization of a simple,

d i r e c t , and uncomplicated fixed-bed technology.
Such a development would p a r a l l e l extensive
experience i n s u c c e s s f u l commercialization of many
fixed-bed processes using s i m i l a r c a t a l y s t s and
operating c o n d i t i o n s . The f i v e l i c e n s e d processes
using ZSM-5 c a t a l y s t f a l l i n that category. The
simplest fixed-bed MTG system was the one which
employed dehydration and ZSM-5 r e a c t o r s . This
system was s t u d i e d e x t e n s i v e l y i n bench-scale
u n i t s . These s t u d i e s i n a 3 cm diameter by
30-50 cm l e n g t h r e a c t o r s were considered t o be
s u f f i c i e n t f o r scale-up.
However, i n 1978, the New Zealand government
expressed strong i n t e r e s t i n applying the MTG
technology f o r conversion of indigenous n a t u r a l gas
to h i g h - q u a l i t y g a s o l i n e . I n support of the New
Zealand e f f o r t , i t was decided t o demonstrate the
fixed-bed process i n a 4 B/D p i l o t p l a n t . Such a
demonstration t e s t could be f i t i n t o the o v e r a l l
schedule f o r the New Zealand venture and would
provide l a r g e q u a n t i t i e s of product g a s o l i n e f o r
road t e s t i n g i n cars t y p i c a l l y s o l d i n New Zealand.
LONG-TERM P r o c e e d w i t h an o r d e r l y development of the
f l u i d - b e d process, which may o f f e r an a t t r a c t i v e
a l t e r n a t i v e to the fixed-bed process f o r the f u t u r e
w i t h i t s p o s s i b l y higher g a s o l i n e y i e l d , more
e f f i c i e n t heat recovery, and economy of s c a l e .
C u r r e n t l y , a 100 B/D f l u i d - b e d p i l o t p l a n t i n
Germany i s nearing s t a r t up. This study i s a j o i n t
p r o j e c t w i t h URBK, Uhde, and M o b i l supported i n
part by the U.S. DOE and the German government.
S u c c e s s f u l completion of the 100 B/D program w i l l
be a p r e r e q u i s i t e f o r proceeding w i t h
c o m m e r c i a l i z a t i o n of the f l u i d - b e d process.
Fixed-Bed Development and Commercialization
Fixed-Bed Demonstration P l a n t . The major o b j e c t i v e of the
demonstration t e s t was t o v e r i f y the bench u n i t r e s u l t s i n a
l a r g e r p l a n t operating a t c o n d i t i o n s s i m i l a r to a commerc i a l - s i z e r e a c t o r . The l i n e a r v e l o c i t y of the reactant i s the
only v a r i a b l e which i s s i g n i f i c a n t l y d i f f e r e n t between a
bench-scale u n i t and a commercial-size r e a c t o r . The other
operating c o n d i t i o n s are normally the same f o r both r e a c t o r s .
By making the l e n g t h o f the c a t a l y s t bed i n the demonstration


34
p l a n t i d e n t i c a l to that of the proposed commercial-size

r e a c t o r , the gas v e l o c i t i e s a l s o become i d e n t i c a l , and thus a l l
the process v a r i a b l e s become i d e n t i c a l .
For a simple gas r e c y c l e system, there i s a strong
i n c e n t i v e to have the bed l e n g t h be as short as p o s s i b l e to
hold down the pressure drop and thus compression c o s t s . But as
c a t a l y s t beds get s h o r t , one has to be concerned w i t h
m a l d i s t r i b u t i o n s i n the c a t a l y s t packing and consequently i n
the flow through the bed.
I f there were regions of high flow
i n an MTG c a t a l y s t bed, unconverted methanol could breakthrough
e a r l y , r e s u l t i n g i n e i t h e r short c y c l e s or i n methanol l o s s to
the water phase. M o b i l came to the c o n c l u s i o n that w i t h a
r e a c t o r bed l e n g t h of 2.5 meters, i t could e f f e c t i v e l y load the
c a t a l y s t and ensure even d i s t r i b u t i o n of the gas i n r e a c t o r s
having l a r g e diameters.
The c a t a l y s t bed l e n g t h f o r the demonstration t e s t was set
at the l i k e l y l e n g t h f o r a commercial p l a n t . For the
demonstration u n i t , the i n t e r n a l diameter was s e l e c t e d to be
about 10 cm, which i s s i g n i f i c a n t l y l a r g e r than c a t a l y s t
p a r t i c l e s i z e to minimize w a l l e f f e c t s . In a d d i t i o n , heat
t r a n s f e r along the r e a c t o r w a l l would a l s o be n e g l i g i b l e .
The r e s u l t s of the demonstration plant are compared w i t h
those of the bench u n i t i n Table I . The two u n i t s were
operated at i d e n t i c a l c o n d i t i o n s except f o r gas v e l o c i t y .
The
product y i e l d s and s e l e c t i v i t i e s over the f i r s t c y c l e were
remarkably s i m i l a r . The a d i a b a t i c temperature r i s e and the
band aging behavior were a l s o the same. However, the
demonstration u n i t performed considerably b e t t e r w i t h respect
to c y c l e l e n g t h . T y p i c a l c y c l e s were about 50% longer.
S i m i l a r behavior of longer c y c l e lengths have been observed i n
commercial operation w i t h other ZSM-5 c a t a l y z e d processes.
In the product q u a l i t y t e s t s , p a r t i c u l a r a t t e n t i o n was
given to the e f f e c t of durene on automobile performance and
g a s o l i n e handling since i t s content i n the MTG g a s o l i n e i s the
only s i g n i f i c a n t d i f f e r e n c e from conventional g a s o l i n e s . A
t e s t f l e e t designed to simulate the New Zealand automobile
p o p u l a t i o n was used f o r the d r i v e a b i l i t y t e s t s . Figure 8
i l l u s t r a t e s the r e s u l t s of one t e s t s e r i e s conducted at -18C
ambient temperature. (4_) The data show the weight percent
durene that could be t o l e r a t e d before encountering any abnormal
d r i v e a b i l i t y c h a r a c t e r i s t i c s . A l l cars performed normally on
g a s o l i n e c o n t a i n i n g 3 wt% or l e s s durene. With 4 wt% durene,
the most c r i t i c a l car encountered a s l i g h t l y rougher-thannormal engine i d l e c o n d i t i o n . Of the 12 cars t e s t e d at -18C,
eleven had no decrease i n d r i v e a b i l i t y at 4 wt% durene, 7 were
good at 5 wt%, and 3 were good at 6 wt% durene. Much higher
durene t o l e r a n c e s were observed at higher temperatures.
To ensure that there would be no d r i v e a b i l i t y or handling
problems w i t h MTG g a s o l i n e , a t a r g e t of 2 wt% durene i n
g a s o l i n e was set as the company s p e c i f i c a t i o n , though the MTG

2.
PENICK E T A L .
Table I .
35
Scale-Up R e s u l t s of Fixed-Bed MTG

Bench Unit
4 B/D Unit

Conditions
Methanol/Water Chg. (W/W)
Conversion Reactor I n l e t
Temperature (C)
Conversion Reactor O u t l e t
Temperature (C)
Methanol Space V e l o c i t y (WHSV)
Separator Temperature (C)
Recycle R a t i o (mol/mol chg)
Pressure (kPa)
83/17
83/17
358
360
404
1.
49
9
2,163
407
1.6
52
9.2
2,156
Average F i r s t Cycle Y i e l d
(Wt%)
Hydrocarbon Products
Methane
Ethane
Ethylene
Propane
Propylene
Isobutane
n-Butane
Butnes
C 5 + Hydrocarbons
Gasoline (Wt%)
Octane, R+0
1.33
0.82
0.02
8.54
0.15
8.45
4.06
0.71
75.92
100.00
1.25
0.86
0.03
8.60
0.15
8.39
4.20
0.74
75.78
100.00
80.2
95
80.2
95

CHEMICAL REACTION
ENGINEERING

36


2.
PENICK E T A L .
37
process was producing about 5 wt% at that time. To meet t h i s

s p e c i f i c a t i o n w i t h conventional processing would have required
undercutting the g a s o l i n e product.
Consequently, an e x p l o r a t o r y program was undertaken t o see
i f t h i s s p e c i f i c a t i o n could be met by a d d i t i o n of a simple
g a s o l i n e t r e a t i n g step. I n a short time, a heavy g a s o l i n e
t r e a t i n g (HGT) technology evolved. With the HGT, durene l e v e l s
even higher than 5 wt% could be t r e a t e d down t o the 2% l e v e l .
The HGT e f f i c i e n t l y f i t s i n t o the processing scheme. The
hydrocarbon l i q u i d from the separator (shown i n Figure 9) i s
normally s t a b i l i z e d by f r a c t i o n a t i n g a t around 140 p s i g ; t h i s
pressure produces a r e l a t i v e l y hot g a s o l i n e bottoms stream.
Sending t h i s high heat content stream d i r e c t l y t o a
low-pressure g a s o l i n e s p l i t t e r a l l o w s us t o concentrate the
durene i n a small bottoms stream. Only small amounts of energy
need to be expended since the feed i s so hot and the s e p a r a t i o n
can be made w i t h l i t t l e r e f l u x .
The small amount of hydrogen required f o r the HGT can be
r e a d i l y obtained from a p o r t i o n of the methanol s y n t h e s i s purge
gas. This purge stream i s normally used as f u e l ; the f u e l
value of the hydrogen can be replaced by the small amount of
gas produced from the HGT step.
The bottom p o r t i o n of the g a s o l i n e (approximately 15% i n
the NZ design) i s processed i n a c a t a l y t i c r e a c t o r designed to
convert the durene by both i s o m e r i z a t i o n and d e a l k y l a t i o n . The
t r e a t e d heavy g a s o l i n e i s then s t a b i l i z e d and reblended w i t h
the l i g h t g a s o l i n e . Neither the f i n i s h e d g a s o l i n e volume nor
i t s octane numbers are a f f e c t e d . The minor weight l o s s from
the t r e a t i n g step i s o f f s e t by a decrease i n the s p e c i f i c
g r a v i t y of the product.
I n c o r p o r a t i o n of the HGT process has
g r e a t l y eased the durene c o n s t r a i n t o r i g i n a l l y imposed on the
MTG r e a c t o r design. I n f a c t , as a consequence o f i n c o r p o r a t i n g
HGT, we are able t o switch t o a l a r g e r c a t a l y s t p a r t i c l e s i z e ,
which makes more durene than the s m a l l e r , o r i g i n a l c a t a l y s t .
Such a change brings about l e s s r e a c t o r pressure drop, and thus
o v e r a l l , a more e f f i c i e n t p l a n t .
Commercial Fixed-Bed Plant Design. The commercial fixed-bed
MTG plant i s very s i m i l a r i n design concept t o the 4 B/D
demonstration p l a n t . A t y p i c a l design of the r e a c t i o n s e c t i o n
of a commercial p l a n t i s shown i n Figure 10. The feedstock may
be d i s t i l l e d o r crude methanol.
The feed i s vaporized by r e a c t o r e f f l u e n t heat-exchange and
enters i n t o the dehydration r e a c t o r . The dehydration r e a c t o r
e f f l u e n t i s mixed w i t h preheated r e c y c l e gas and enters the
conversion r e a c t o r s . Although Figure 10 shows f o u r p a r a l l e l o r
"swing" conversion r e a c t o r s , a l e s s e r o r g r e a t e r number of
r e a c t o r s may be used depending upon the feed rate and
regeneration frequency d e s i r e d .

38
Recycle Gas
Gas
Make
Com pressor cT]

LPG
Deethanizer

Gasoline
Stabilizer
Steam
Product
Separator
^^Steam
-Stabilized
Gasoline
Raw
Gasoline
Waste Water,
Cooled
Reactor
Effluent
Figure 9.
Fixed-bed MTG separations s e c t i o n .

DME Effluent Header
MeOH
Superheater
DME
Reactor
r
MeOH
Vaporizer
Crude
MeOH
Hot Excess
Effluent
From ZSM-5
Reactors
To Duplicate
Reactor/Effluent
Exchanger Trains
ZSM-5 Reactors
MeOH
JrlPreheater
Cooling
Water
To Separator
/ t [ \ Effluent/Recycle
\[ y
Exchanger
Cooled Effluent
From ZSM-5 Reactor
,1 1,1
Cooler
Compressed
Recycle Gas
From Separator
J-UJ
Recycle Gas Header
Figure 10. Flowsheet o f the r e a c t i o n s e c t i o n o f the fixed-bed

MTG process.


2.
PENICK E T A L .
39
We have found that to e f f i c i e n t l y recover the high heat

content i n the r e a c t o r e f f l u e n t i t i s d e s i r a b l e t o s p l i t the
stream i n t o two p a r t s . The m a j o r i t y of the e f f l u e n t from a
p a r t i c u l a r r e a c t o r i s used t o heat the r e c y c l e gas t o that
r e a c t o r . The excess hot e f f l u e n t s from a l l the r e a c t o r s are
combined and used f o r generating steam and heating the methanol
feed to the dehydration r e a c t o r . A f t e r these s e r v i c e s , the
r e a c t o r e f f l u e n t s are combined and cooled by c o o l i n g water
before e n t e r i n g the product separator.
Considerable engineering judgment and e f f o r t are needed t o
ensure that the heat recovery i s e f f i c i e n t , yet has low
pressure drop. Since a l a r g e p o r t i o n of the heat contained i n
the r e a c t o r e f f l u e n t has to be t r a n s f e r r e d back t o the c o l d
r e c y c l e gas, t h i s exchanger arrangement received our s p e c i a l
attention.
We have a l s o found i t a d v i s a b l e to vaporize the methanol
using a v a p o r - l i q u i d drum, analogous t o a steam drum. Such an
arrangement increases the loop pressure drop because the excess
hot e f f l u e n t flows through separate exchangers i n s e r i e s f o r
preheating, v a p o r i z i n g , and superheating the methanol.
However, t h i s arrangement has two advantages:
A blowdown of l i q u i d methanol can be taken i f the

crude methanol contains any s o l i d s .
As the c o n t r o l valves t o the various MTG r e a c t o r s are

adjusted, pressure waves may be transmitted t o the
methanol exchangers. I f one exchanger i s used f o r
preheating, v a p o r i z i n g and superheating the methanol
feed, the pressure waves may cause the area used f o r
v a p o r i z a t i o n to f l u c t u a t e thereby l e a d i n g t o p o t e n t i a l
i n s t a b i l i t y i n the v a p o r i z a t i o n r a t e .
Gas, l i q u i d hydrocarbon, and water phases are separated i n

the product separator. Most of the gas i s r e c y c l e d . The net
gas make and l i q u i d hydrocarbon streams are sent t o
conventional petroleum f r a c t i o n a t o r s f o r separation and
s t a b i l i z a t i o n as shown i n Figure 9.
When methanol breaks through a c a t a l y s t bed, that r e a c t o r
i s taken o f f stream and the c a t a l y s t i s regenerated by burning
o f f the deposited coke. A i r i s used as the source o f oxygen t o
burn o f f the coke and n i t r o g e n d i l u t i o n i s used t o c o n t r o l the
peak burning temperature. Most of the r e a c t o r e f f l u e n t gases
during regeneration are r e c y c l e d back to the r e a c t o r a f t e r
water i s removed.
The r e a c t i o n engineering i n the MTG plant centered on how
deep the c a t a l y s t bed had t o be t o avoid premature methanol
break-through. The d e c i s i o n that the minimum bed depth had t o
be 2.5 meters e l i m i n a t e d r a d i a l r e a c t o r s from c o n s i d e r a t i o n .

40
Fluid-Bed Development

From the small bench-scale t e s t s , the f l u i d - b e d MTG

development has proceeded to two phases of scale-up.
The
i n i t i a l scale-up was v e r t i c a l to a 4 B/D c a p a c i t y , and the
current phase i s a h o r i z o n t a l scale-up to 100 B/D c a p a c i t y .
V e r t i c a l Scale-Up of F l u i d Bed.
The f l u i d - b e d process was
f i r s t scaled up v e r t i c a l l y from the 45 cm t a l l bench-scale
r e a c t o r to the 760 cm t a l l 4 B/D r e a c t o r shown s c h e m a t i c a l l y i n
Figure 11. The 4 B/D r e a c t o r i n t e r n a l diameter was 10 cm.
The operation of t h i s 4 B/D f l u i d p i l o t plant was very
s u c c e s s f u l . E s s e n t i a l l y complete conversion of methanol was
achieved at the design c o n d i t i o n s f o r s u p e r f i c i a l gas
v e l o c i t i e s up to 0.5 m/sec. E x c e l l e n t s t a b i l i t y of the
o p e r a t i o n was demonstrated over a 75-day run. Higher g a s o l i n e
y i e l d and octane number than f o r fixed-bed processing were
v e r i f i e d (Table I I ) . A t y p i c a l temperature p r o f i l e i n the
r e a c t o r i s shown i n Figure 12. Despite the h i g h l y exothermic
nature of the r e a c t i o n and the unusually high l e n g t h - t o diameter r a t i o (greater than 75) of the r e a c t o r , a very uniform
temperature p r o f i l e was e s t a b l i s h e d . There was a complete
absence of any troublesome "hot spots". In a d d i t i o n , the
t r a n s i e n t temperature p r o f i l e s during heat-up and cool-down
were a l s o uniform and s t a b l e .
With these encouraging r e s u l t s , i t was decided to scale-up
the f l u i d - b e d process f u r t h e r . A 100 B/D f l u i d - b e d program has
been formulated to demonstrate h o r i z o n t a l scale-up.
H o r i z o n t a l Scale-Up of F l u i d Bed.
The 100 B/D p i l o t p l a n t w i l l
provide a d d i t i o n a l i n f o r m a t i o n f o r design of a commercials c a l e , f l u i d - b e d process. Key data yet to be obtained a r e :
r e a c t o r i n t e r n a l b a f f l e design to maintain complete

conversion of methanol i n a l a r g e diameter f l u i d i z e d
vessel.
c a t a l y s t a t t r i t i o n and u l t i m a t e l i f e .
A schematic diagram of the r e a c t o r system of the 100 B/D

p l a n t i s shown i n Figure 13. There are three major v e s s e l s :
r e a c t o r , regenerator, and e x t e r n a l c o o l e r . The r e a c t o r
c o n s i s t s of a dense f l u i d - b e d s e c t i o n (60 cm ID 13.2 m
height) l o c a t e d above a d i l u t e phase r i s e r . Two modes w i l l be
studied to remove r e a c t i o n heat :


(
y
OO
"I
Catalyst
Recirculation
Line
Catalyst
Storage
Vessel
Air
Regenerator
Flue G a s
Water
H2O
Tank
h B/D f l u i d - b e d p i l o t p l a n t .
Reactor10.2 c m
7.6 m
F i g u r e 11.
Vapor Feed
Liquid F e e d
Water
Tank Car
l eF ecT
Preparation
oo
Methanol
Disengager
Filter -
Gas
Liquid
Hydrocarbons
HC Prod
Tank
Separator
Off
Condenser

42
ENGINEERING
Table I I . Process Conditions and

Product Y i e l d s from MTG Processes
Fixed Bed
F l u i d Bed
83/17
83/17

Conditions
Methanol/Water Chg. (W/W)
Dehydration Reactor I n l e t
Temperature (C)
Dehydration Reactor O u t l e t
Temperature (C)
Conversion Reactor I n l e t
Temperature (C)
Conversion Reactor O u t l e t
Temperature (C)
Pressure (kPa)
Recycle R a t i o (mol/mol chg.)
Space V e l o c i t y (WHSV)
316
404
360
413
415
413
2,170
9.0
2.0
275
1.0
Y i e l d s (Wt. % of Methanol Charged)

Methanol + Ether
Hydrocarbons
Water
CO, C 0
Coke, Other
2
0.0
43.4
56.0
0.4
0.2
100.0
0.2
43.5
56.0
0.1
0.2
100.0
1.4
5.5
0.2
8.6
3.3
1.1
79.9
100.0
5.6
5.9
5.0
14.5
1.7
7.3
60.0
100.0
85.0
13.6
1.4
100.0
88.0
6.4
5.6
100.0
93
97
Hydrocarbon Product (Wt. %)

L i g h t Gas
Propane
Propylene
Isobutane
n-Butane
Butnes
C 5 + Gasoline
Gasoline ( i n c l u d i n g A l k y l a t e )
[RVP-62 kPa ( 9 p s i ) ]
LPG
Fuel Gas
Gasoline Octane (R+O)

2.
PENICK E T A L .
43
6h

Reactor
Elevation,
Meters Above
Feed Inlet
100
Figure 12.
Figure 13.
300
500
Temperature, C
700
F l u i d - b e d r e a c t o r temperature p r o f i l e .
100 B/D f l u i d - b e d MTG demonstration p l a n t .


44
c i r c u l a t i o n of c a t a l y s t through an e x t e r n a l c a t a l y s t
c o o l e r , and
i n t e r n a l heat exchange pipes immersed i n the dense bed

reactor.
To m a i n t a i n a constant c a t a l y s t a c t i v i t y i n the r e a c t o r , a
small f r a c t i o n of "coked" c a t a l y s t w i l l be c o n t i n u o u s l y
regenerated and returned to the r e a c t o r .
The mechanical design b a s i s of the 100 B/D u n i t has been
v e r i f i e d on a f u l l - s c a l e Cold Flow Model (CFM). This
non-reacting model proved very u s e f u l f o r o p t i m i z i n g b a f f l e
design and c a t a l y s t c i r c u l a t i o n s t r a t e g i e s . S e v e r a l d i f f e r e n t
b a f f l e designs h o r i z o n t a l and v e r t i c a l arrangements
(Figure 14) have been t e s t e d i n the CFM using s e v e r a l
experimental techniques: gas t r a c e r , capacitance probes, bed
expansion a n a l y s i s , and v i s u a l o b s e r v a t i o n . Integrated
residence time behavior of the bed and q u a n t i t a t i v e , l o c a l
g a s / s o l i d s d i s t r i b u t i o n and bubble s i z e d i s t r i b u t i o n were
measured.
Experimental r e s u l t s i n d i c a t e that h o r i z o n t a l b a f f l e s are
e f f e c t i v e i n breaking bubbles. In the t u r b u l e n t f l u i d i z a t i o n
regime, h o r i z o n t a l b a f f l i n g provides a l s o the e f f e c t of s t a g i n g
the f l u i d bed and l i m i t i n g the formation of gross c i r c u l a t i o n
p a t t e r n s w i t h i n the bed. Thus, h o r i z o n t a l b a f f l e s were
s e l e c t e d f o r i n s t a l l a t i o n i n the p i l o t p l a n t . The b a f f l e
design was optimized to ensure s u f f i c i e n t c a t a l y s t f l u x through
the b a f f l e d s e c t i o n . An o v e r l y r e s t r i c t i v e design can cause a
marked d e n s i t y gradient i n the bed, w i t h most of the c a t a l y s t
accumulating above the top b a f f l e s e c t i o n . The f i n a l b a f f l e
design chosen f o r the 100 B/D p i l o t p l a n t d i d not e x h i b i t t h i s
c a t a l y s t segregation phenomenon.
We b e l i e v e that the 100 B/D p l a n t represents the f i n a l
development step before a commercial-size r e a c t o r can be
designed w i t h confidence.
Future Development
The fixed-bed MTG process designed f o r New Zealand
represents a simple but h i g h l y r e l i a b l e design concept.
The
development of the HGT, which r e l a x e s the durene c o n s t r a i n t ,
opens the process v a r i a b l e window c o n s i d e r a b l y . For example,
i f the r e c y c l e r a t i o i s reduced from 9:1 to 7:1, the s i z e of
the r e c y c l e c i r c u i t i s reduced and i t becomes more e f f i c i e n t ,
l e a d i n g to reductions of about 30% i n heat t r a n s f e r area and
compressor horsepower. However, the octane of the g a s o l i n e
product i s reduced by about one number. S e v e r a l more advanced
fixed-bed process arrangements which reduce processing c o s t s
without reducing octane are being considered and subjected to
p r e l i m i n a r y screening t e s t s .


PENiCK E T A L .
Figure Ik.
Examples o f f l u i d - b e d r e a c t o r i n t e r n a l b a f f l e s .


46
CHEMICAL
REACTION
ENGINEERING
The f l u i d - b e d process being developed i n the 100 B/D p i l o t

plant has good p o t e n t i a l f o r becoming an important part of our
f u t u r e technology. I t has inherent p o t e n t i a l advantages over
the fixed-bed process as mentioned e a r l i e r . I t i s b a s i c a l l y
f l e x i b l e f o r easy a d a p t a t i o n t o petrochemicals production and
b e t t e r c o n t r o l of the a u t o c a t a l y t i c r e a c t i o n .
We are l o o k i n g a t c a t a l y s t m o d i f i c a t i o n s both f o r improved
y i e l d / o c t a n e c h a r a c t e r i s t i c s and f o r improved steam s t a b i l i t y .
I t has been our experience that new, improved c a t a l y s t s are an
i n t e g r a l part of r e a c t i o n engineering. To keep processes v i t a l
and c o m p e t i t i v e , i t i s necessary t o c o n t i n u a l l y look f o r
improved c a t a l y s t s .
In a d d i t i o n t o the production o f g a s o l i n e , the prospects
look promising f o r manufacturing d i e s e l f u e l s and chemicals
using r e l a t e d technology. R e f e r r i n g back t o Figure 3, which
shows the r e a c t i o n steps i n v o l v e d i n methanol conversion t o
hydrocarbons, we observe that l i g h t o l e f i n s form f i r s t as
intermediate products. As the r e a c t i o n proceeds, the l i g h t
o l e f i n s react f u r t h e r t o form i s o p a r a f f i n s and aromatics. I n
the g a s o l i n e production mode, we are operating a t the f a r r i g h t
where the g a s o l i n e components dominate.
By m o d i f i c a t i o n of c a t a l y s t and/or process c o n d i t i o n s , one
can operate where the s e l e c t i v i t y t o l i g h t o l e f i n s i s h i g h .
We have learned to i n c r e a s e the ethylene y i e l d to about 30 wt%
of hydrocarbon, f o r i n s t a n c e . This process i s perhaps the most
promising new route f o r the production of ethylene from
s y n t h e s i s gas.
In our e x p l o r a t o r y s t u d i e s , we have now found good leads
f o r y i e l d i n g as much as 75-80% C 2 - C 4 o l e f i n product, which
i n t u r n can be converted to good q u a l i t y d i s t i l l a t e . ( _ 5 > 6 ) We
can now consider the co-production of g a s o l i n e and d i s t i l l a t e
from methanol as shown i n Figure 15. Engineering and
development s t u d i e s are i n the i n i t i a l phases of e v a l u a t i n g
such concepts.
The z e o l i t e - c a t a l y z e d methanol conversion technology,
whether the d e s i r e d product i s g a s o l i n e , d i e s e l , j e t f u e l o r
ethylene f o r petrochemicals, w i l l provide new o p p o r t u n i t i e s f o r
s y n f u e l s i n the coming decades.


2.
PENICK E T A L .
47
Ethylene for Chemicals
Methanol
Methanol
To
Olefins
r,Pr,c =
Olefins
4
MTG
371-427C
172-2068 kPa
Gasoline
MOGD
Distillate
204-316C
3447-5516 kPa
F i g u r e 15.
P r o d u c t i o n o f e t h y l e n e , g a s o l i n e , and d i s t i l l a t e
methanol.
American Chemical
Society Library
1155 16th St., N.W.
In Chemical Reaction
EngineeringPlenary
Lectures; Wei, J., et al.;
Washington,
D.C. 20036
from
48
Literature Cited
1. Meisel, S. L., McCullough, J. P., Lechthaler, C. ., and
Weisz, P. B., CHEMTECH, 1976, 6, 86-9.
2. Kokotailo, G. T., Lawton, S. L., Olson, D. ., and Meier,
W. ., Nature, 1978, 272, 437-8.
3. Chang, C. D., and Silvestri,
A. J., J. Catal., 1977, 47,
249-59.
4. Fitch, F. B., and Lee, W., "Methanol-to-Gasoline, An
Alternative Route to High Quality Gasoline," presented at
the International Pacific Conference on Automotive
Engineering, Honolulu, Hawaii, Nov., 1981.
5. Garwood, W. E., "Conversion of C -C
Olefins to Higher
Olefins Over Synthetic Zeolite ZSM-5," presented at Am.
Chem. Soc. Mtg., Las Vegas, Nevada, March, 1982.
6. Meisel, S. L. and Weisz, P. B., "Hydrocarbon Conversion and
Synthesis Over ZSM-5 Catalysts", presented at Advances in
Catalytic Chemistry II Symposium, Salt Lake City, Utah,
May, 1982.
2

ENGINEERING
RECEIVED March 10,
10
1983

3
Fluidized-Bed Reactors
P. N . ROWE

University College London, Department of Chemical and Biochemical

Engineering, Torrington Place, London WC1E 7JE, England
This Plenary Lecture surveys the place of

fluidised beds within the field of chemical reaction
engineering and describes some developments and
changes of interest over the last decade. It
concludes by suggesting the direction basic research
should take in the future.
The previous s i x I n t e r n a t i o n a l Symposia on CRE have

included 56 plenary l e c t u r e s three of which were devoted exc l u s i v e l y to f l u i d i s e d bed r e a c t o r s and a f u r t h e r two were subs t a n t i a l l y concerned w i t h them (1-5). This i s a l e v e l of
i n t e r e s t equalled only by the general subject of o p t i m i s a t i o n ,
s t a b i l i t y and c o n t r o l and exceeded only be plenary l e c t u r e s
concerned w i t h k i n e t i c s ( j u s t exceeded; there were s i x ) . Here we
are w i t h yet another t a s t e of t h i s f a s c i n a t i n g , i n t r i g u i n g ,
c h a l l e n g i n g , i n t e r e s t - f u l l , promising and v e r s a t i l e form of
chemical r e a c t o r . There i s a l o t of j u i c e yet l e f t i n such a
succulent subject although i t becomes i n c r e a s i n g l y d i f f i c u l t to
t r e a t w i t h o r i g i n a l i t y a t o p i c that has been mouthed by so many.
Two years ago we were t r e a t e d to a n o s t a l g i c account of the
coming of age of chemical r e a c t i o n engineering by P r o f e s s o r
L e v e n s p i e l who dated i t s b i r t h as 1957 and i t s p o s s i b l e conception as 1947 (6). U n c h a r a c t e r i s t i c a l l y Octave seems to have overlooked Denbigh's c l a s s i c a l paper (7) submitted i n 1943 i n which
Denbigh described and defined the continuous f l o w t u b u l a r r e a c t o r
and the 'continuous flow s t i r r e d tank r e a c t o r f o r each of which
he showed how to c a l c u l a t e both y i e l d and s i z e of r e a c t o r needed
f o r given orders of r e a c t i o n and r e q u i r e d production r a t e s . He
a l s o showed how s e l e c t i v i t y would depend on the order of competing r e a c t i o n s . This and Danckwerts c l a s s i c a l paper on residence
time d i s t r i b u t i o n s (8) submitted i n 1952, l a i d most o f the founda t i o n s on which chemical r e a c t i o n engineering has since b u i l t .
I t i s an i n t e r e s t i n g experience to re-read these papers,
e s p e c i a l l y Denbigh's. I t i s q u i t e a long paper (22 pages, he
1
0097-6156/83/0226-0049$06.00/0


50
would never get away w i t h that l e n g t h today) and gives an imp r e s s i o n of being r a t h e r tedious and t a k i n g a long time to come
to the p o i n t . This i s a poignant reminder of how deeply we have
accepted h i s ideas and now take f o r granted t h i s imaginative and
f r u i t f u l approach. The heart of h i s i d e a i s the b e a u t i f u l l y
l o g i c a l combination of b a s i c laws of chemistry w i t h simple
models of how the r e a c t a n t s come i n t o contact w i t h each other.
The PFR and CSTR are r e a d i l y imagined and widely a p p l i c a b l e
d e s c r i p t i o n s of how r e a l l a r g e s c a l e r e a c t o r s a c t u a l l y behave.
These models of the patterns of r e a c t a n t c o n t a c t i n g form the
b a s i s f o r much of present day chemical r e a c t i o n engineering.
The reason f o r me reminding you of these foundations i s to
draw a t t e n t i o n to the s c a r c i t y of f u r t h e r models beyond these two
b a s i c types. The bubbling gas f l u i d i s e d bed i s one of the very
few a d d i t i o n a l models a l b e i t a much more complicated one and
n e c e s s a r i l y more l i m i t e d i n a p p l i c a t i o n . This i s why i t i s such
a f a s c i n a t i n g subject to chemical r e a c t i o n engineers.
To r e t u r n f o r a moment to the t r a d i t i o n a l models, they have
been expanded, elaborated upon and mixed i n a l l p o s s i b l e (and
some impossible) proportions and, w i t h the w i l l i n g a i d of modern
computational methods, developed to a l e v e l of complexity that i s
i n some cases out of touch w i t h r e a l i t y and c e r t a i n l y no longer
p h y s i c a l l y imaginable but t h i s process of p a r a l y s i s by a n a l y s i s
i s the f a t e of many o r i g i n a l l y simple i d e a s . F o r t u n a t e l y f l u i d i s e d bed r e a c t o r models are s t i l l reasonably c l o s e l y r e l a t e d to
what a c t u a l l y happens and by and l a r g e the models can s t i l l be
imagined as p h y s i c a l r e a l i t i e s .
At t h i s stage I should f o r the b e n e f i t of those l e s s f a m i l i a r
w i t h f l u i d i s e d beds spend a few minutes d e s c r i b i n g the p r i n c i p a l
features that govern t h e i r behaviour as r e a c t o r s ( 9 ) . A l l
powders bubble when f l u i d i s e d by gas at v e l o c i t i e s i n excess of a
minimum value and look r a t h e r as i n F i g u r e 1 which i s a photograph of a two-dimensional bed sandwiched between glass p l a t e s .
I t i s the bubbles that cause p a r t i c l e mixing and b r i n g about the
h i g h heat t r a n s f e r r a t e s that can occur between the bed and w a l l s
or immersed s u r f a c e s . They are r e s p o n s i b l e f o r the high degree of
u n i f o r m i t y , e s p e c i a l l y of temperature and p a r t i c l e composition,
w i t h i n the bed and without them the system would behave more or
l e s s as a packed bed.
Bubbling leads immediately to the concept of two phases w i t h
p a r t of the gas f l o w i n g i n t e r s t i t i a l l y amongst c l o s e l y spaced
p a r t i c l e s and the r e s t f l o w i n g i n the form of bubbles. The i n t e r s t i t i a l f l o w remains constant at the minimum f l u i d i s a t i o n value
although f i n e powders may expand a l i t t l e and permit a r a t h e r
l a r g e r flow. The bubble flow i s t h e r e f o r e e a s i l y evaluated from
Q
and the f a c t that
Qi
=
Qmf.


ROWE
Figure 1. Bubbles i n a two-dimensional f l u i d i z e d bed.


52
ENGINEERING
The bubbles coalesce r e a d i l y so that they may be small and

numerous at the bottom and large and few at the top w h i l s t maint a i n i n g s u b s t a n t i a l l y constant flow. Average bubble s i z e i n creases w i t h height as i n d i c a t e d i n F i g u r e 2. These simple f a c t s
a l l o w an immediate c o n s i d e r a t i o n of r e a c t o r v e s s e l s i z i n g (10).
P r o d u c t i o n requirements w i l l determine the r e a c t a n t gas feed r a t e
and bed diameter f i x e s v e l o c i t y and thence the bubbling r a t e .
Heat t r a n s f e r c o n s i d e r a t i o n s and blower c a p a c i t y are l i k e l y to
set l i m i t s to the bed height or aspect r a t i o and bed diameter
must accommodate the bubbles. What would be a bubble i n a l a r g e
r e a c t o r at a given height and v e l o c i t y would be a s l u g i n a
narrow one as Figure 3 i n d i c a t e s . The slugging bed g e n e r a l l y
gives b e t t e r g a s / s o l i d c o n t a c t i n g but must be modelled d i f f e r e n t l y from the bubbling bed and r e q u i r e s greater free-board. In the
past p i l o t p l a n t s have operated i n the slugging regime and
reduced performance was experienced when s c a l i n g up simply by
i n c r e a s i n g diameter but no one should make that mistake today.
P a r t i c l e mixing i s caused by the bubbles, p a r t l y be shear
displacement or d r i f t but a l s o by the bulk t r a n s p o r t of p a r t i c l e s i n the bubble wake. Bubbles may a l s o cause segregation i f
there are d i f f e r e n t kinds of p a r t i c l e s present. U n l i k e other
kinds of mixers, segregation i s i n s e n s i t i v e to p a r t i c l e s i z e
d i f f e r e n c e but p a r t i c u l a r l y s e n s i t i v e to d e n s i t y d i f f e r e n c e . I n
a b i n a r y system of p a r t i c l e s segregation increases approximately
as p a r t i c l e d e n s i t y r a t i o to the power 5/2 but w i t h p a r t i c l e s i z e
r a t i o only to the power 1/5 (11). This can cause problems i n ,
f o r example, c o a l combustion where char has a markedly lower
d e n s i t y than ash and a l s o i n some ore r e d u c t i o n processes using
coke.
Chemical r e a c t o r models i n v a r i a b l y s t a r t from the two-phase
theory (12). The i n t e r s t i t i a l f l o w i s assumed to be i n good and
continuous contact w i t h s o l i d s w h i l s t some by-passing occurs i n
the bubble phase. There i s , however, very l i t t l e a x i a l or r a d i a l
mixing of the gas. There may be some exchange between the two
phases and F i g u r e 4 d e p i c t s t h i s k i n d of model.
A major reason f o r by-passing i n the bubble phase i s the
formation of clouds or s p h e r i c a l v o r t i c e s centred on the bubbles,
a s i t u a t i o n that occurs when bubbles r i s e f a s t e r than i n t e r s t i t i a l gas which i s commonly the case. Gas i s o b l i g e d to f l o w
upwards through the bubble because of pressure d i f f e r e n c e but as
i t r e - e n t e r s the dense phase ahead i t i s caught i n a stream of
p a r t i c l e s f l o w i n g downwards r e l a t i v e to the bubble and, when the
f l o w i s f a s t enough, i t i s trapped and dragged downwards u n t i l
pressure d i f f e r e n c e pushes i t back i n t o the bubble. This i s
i l l u s t r a t e d i n Figure 5. Only that p o r t i o n of the cloud or
v o r t e x that extends beyond the bubble i s i n contact w i t h p a r t i c l e s
andtherefore able to r e a c t . In many r e a l i s t i c s i t u a t i o n s t h i s
p r o p o r t i o n can be very s m a l l . At any i n s t a n t only t h i s proport i o n of the t o t a l cloud i s r e a c t i n g so that the e f f e c t i v e r a t e
constant i s reduced. The whole i s c i r c u l a t i n g as a v o r t e x w i t h

3.
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53

g'4
increasing gas flow
<=> |
tut
Figure 2. Bubbles s i z e increases w i t h bed height and flow r a t e .
Figure 3. A bubble i n a l a r g e bed becomes a s l u g i n a s m a l l one.

54

interstitial
"
exchange
phase
Figure h.
ENGINEERING
bubble
phase
B a s i c two-phase bubble model.
particle
flow
induced
Figure 5
clouds.
gas circulation
P a r t i c l e flow induces gas c i r c u l a t i o n and so forms


3.
ROWE
55
upward v e l o c i t y through the empty space of the bubble of s i m i l a r

magnitude to minimum f l u i d i s a t i o n v e l o c i t y . With f i n e p a r t i c l e s
t h i s i s small so that l i t t l e c i r c u l a t i o n occurs during the r e s i dence time of a bubble i n the bed. This i s the very s i t u a t i o n
where the cloud cannot penetrate f a r i n t o the dense phase so the
o v e r a l l e f f e c t i s poor c o n t a c t i n g o f bubble phase gas w i t h p a r t icles.
Severe by-passing i n the bubble phase and very poor gas
mixing can make the f l u i d i s e d bed an extremely poor chemical
r e a c t o r but a t l e a s t the major reasons f o r t h i s are now understood. The prospects o f success f o r a given process can be
judged a t an e a r l y stage and design can minimize by-passing
u s u a l l y by choosing p a r t i c l e s i z e a p p r o p r i a t e l y .
What development and progress has occurred during the l a s t
ten years or so? Experience has accumulated and a number of
f l u i d i s e d bed processes are operated s u c c e s s f u l l y . I n d u s t r i a l
companies are r e l u c t a n t to d i s c l o s e too many d e t a i l s o f a successf u l and p r o d u c t i v e r e a c t o r but I have seen beds as l a r g e as 17 m
i n diameter very uniformly and s t a b l y f l u i d i s e d which could be
shut down and r e - s t a r t e d without t r o u b l e .
During the l a s t decade much i n t e r e s t has centred on the
behaviour of l a r g e p a r t i c l e s (diameters i n m i l l i m e t e r s r a t h e r
than microns) as r e q u i r e d i n f l u i d i s e d c o a l combustion. The
t o p i c has generated two l a r g e conferences r e c e n t l y i n the U.K.
alone (13, 14) and many more i n the U.S.A. This i s the subject
of the next Plenary Lecture so I w i l l only mention some f e a t u r e s
b r i e f l y . Large p a r t i c l e s are necessary i n t h i s a p p l i c a t i o n
because high f l o w r a t e s are r e q u i r e d since the f l u i d i s i n g a i r i s
a l s o combustion a i r and a high i n t e n s i t y of heat generation i s
aimed f o r . I n order f u l l y t o convert oxygen to C O 2 , c o a l conce n t r a t i o n i n the bed i s low (a few percent) and most of i t i s ash
or a chosen r e f r a c t o r y granular m a t e r i a l such as sand. Limestone
may be a d d i t i o n a l l y included to adsorb S O 2 . These p a r t i c l e s must
be f a i r l y l a r g e t o avoid e l u t r i a t i o n . Furthermore, the bed i s
shallow to minimise the pressure drop the fans are r e q u i r e d to
overcome. There i s l i k e l y t o be a l o t o f heat exchanger surface
w i t h i n the bed. Of course, gas v e l o c i t y and hence the need f o r
l a r g e p a r t i c l e s can be reduced by i n c r e a s i n g absolute pressure.
These c o n d i t i o n s have not been widely studied i n the l a b o r a t o r y because of the obvious d i f f i c u l t i e s of p r o v i d i n g high a i r
v e l o c i t i e s (a few meters/sec) on a s c a l e that i s l a r g e compared
w i t h the s i z e of the p a r t i c l e s . C e r t a i n l y i n t e r s t i t i a l gas f l o w
w i l l f a r exceed bubble r i s e v e l o c i t y and there i s no p o s s i b i l i t y
of cloud formation as shown i n Figure 5. Instead gas w i l l f l o w
s t r a i g h t through the bubbles and the o v e r a l l p a t t e r n w i l l approximate to plug flow. Because o f the l a r g e d i f f e r e n c e i n d e n s i t y
between c o a l char and other bed m a t e r i a l the former w i l l tend to
f l o a t . This i s a c o m p l i c a t i o n imposed upon what would otherwise
be a w e l l mixed p a r t i c l e bed. E f f i c i e n t in-bed combustion
r e q u i r e s uniform d i s p e r s i o n of c o a l but the process of p a r t i c l e


56
ENGINEERING
segregation i s q u i t e w e l l understood (15) and the system can be

designed to be reasonably uniform under operating c o n d i t i o n s .
S a t i s f a c t o r y models e x i s t f o r p r e d i c t i o n of combustor performance
although there i s some d i f f i c u l t y i n c o r r e c t l y e s t i m a t i n g the
temperature of a burning c o a l p a r t i c l e . The major design problems are of the broadly mechanical k i n d such as c o a l feeding and
i n i t i a l d i s t r i b u t i o n , heat exchanger design and ash removal.
At the other end of the spectrum there i s c o n t i n u i n g
i n t e r e s t i n the behaviour of f i n e p a r t i c l e s (approximately l e s s
than 100 ym) because c a t a l y s t powders are g e n e r a l l y i n t h i s range.
F l u i d bed c r a c k i n g c a t a l y s t i s the best known example. Geldart
(16) made an important c o n t r i b u t i o n when he proposed a c l a s s i f i c a t i o n of powders and l a b e l l e d t h i s f i n e m a t e r i a l Type A.
The
c h a r a c t e r i s t i c f e a t u r e of them i s that they expand u n i f o r m l y at
v e l o c i t i e s not g r e a t l y i n excess of U f as i l l u s t r a t e d i n F i g u r e
6. Only at some higher v e l o c i t y , U ^ do they begin to bubble.
Values of U b/U can be as high as 3 or 4 and the bed volume can
double i n extreme cases before bubbling begins.
I f the dense phase expands t h i s immediately a f f e c t s the
r e a c t o r model because more gas w i l l then flow v i a the favourable
i n t e r s t i t i a l phase. Most models r e a d i l y a l l o w f o r t h i s change
given that the t r u e d i v i s i o n of f l o w can be p r e d i c t e d . Unh a p p i l y i t has so f a r only been p o s s i b l e to measure t h i s d i v i s i o n
experimentally at f a i r l y low flow r a t e s , w e l l below those
employed i n commercial r e a c t o r s . C e r t a i n l y at v e l o c i t i e s up to
about 15 cm/s much more gas flows i n t e r s t i t i a l l y through Geldart
type A powders than minimum f l u i d i s a t i o n f l o w (17).
I n d u s t r i a l r e a c t o r s g e n e r a l l y operate a t very high v e l o c i t i e s
(of order 1 m/s) much i n excess of t e r m i n a l f a l l i n g v e l o c i t y f o r
at l e a s t the f i n e s t powder f r a c t i o n s . Powder i s c o n t i n u a l l y
e l u t r i a t e d and returned to the bed v i a cyclones. Under these
c o n d i t i o n s there i s disagreement as to whether or not bubbles
r e t a i n t h e i r i d e n t i t y and such beds have been described as
" t u r b u l e n t " or " f a s t f l u i d i s e d " . What l i t t l e evidence there i s
supports the continued existence of bubbles but now i n a much
d i s t u r b e d or heterogeneous dense phase and w i t h a l e s s d e f i n i t e
shape. U n t i l more i s known about t h i s p h y s i c a l s i t u a t i o n i t i s
not easy to see how the bubbling bed r e a c t o r models should be
modified c o r r e c t l y to d e s c r i b e t h i s f l o w regime.
I t i s too simple to assume that average p a r t i c l e s i z e i s an
adequate index of powder type i n G e l d a r t s c l a s s i f i c a t i o n .
C e r t a i n l y type A powders depend s t r o n g l y on d i s t r i b u t i o n of s i z e
and p a r t i c u l a r l y on the p r o p o r t i o n at the lowest end of the range.
There i s p l e n t y of i n d u s t r i a l experience to support t h i s view and
p l a n t operators u s u a l l y acknowledge the importance of m a i n t a i n i n g
a c e r t a i n p r o p o r t i o n of f i n e s i n the r e a c t o r . W h i l s t the v i t a l
r o l e of the f i n e s f r a c t i o n has been recognised i t i s a d i f f i c u l t
dependence to study s y t e m a t i c a l l y .
The two-phase bubbling bed model i s capable of many minor
adjustments and has given numerous academics a l o t of fun p l a y i n g
m

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3.

57

58
v a r i a t i o n s on the b a s i c tune. There are more models than data

against which to t e s t them and s u i t a b l e data f o r t h i s purpose are
not e a s i l y obtained. Whatever the model chosen i t i s commonly
observed that the r e a c t i o n r a t e i s unusually h i g h i n the bottom
few centimeters of the bed and t h i s i s o f t e n r e f e r r e d to as the
distributor effect.
The d i s t r i b u t o r p l a t e i n a f u l l s c a l e r e a c t o r i s u s u a l l y
d r i l l e d w i t h a number of holes s e v e r a l m i l l i m e t e r s i n diameter
and the gas v e l o c i t y through these i s h i g h (tens of m/s). I t i s
easy to imagine that t h i s produces a spout or j e t of gas above
which a stream of bubbles occurs. Powder could be entrained i n t o
the j e t as i n a spouted bed and i t has been imagined that t h i s
p o t e n t i a l l y good g a s / s o l i d s c o n t a c t i n g arrangement i s r e s p o n s i b l e
for a h i g h r a t e of chemical conversion (18).
Although a t t r a c t i v e t h i s model i s q u i t e wrong simply
because gas does not form a j e t above the d i s t r i b u t i o n o r i f i c e
but enters the bed i n the form of bubbles j u s t as, f o r example,
a i r blown i n t o water (19) - F i g u r e 7. Here I must pause to
emphasise the importance of i d e n t i f y i n g c o r r e c t l y the mechanism
by which events occur which can o n l y be done by s u i t a b l e e x p e r i mental o b s e r v a t i o n .
The evidence comes from X-ray cin photographs taken at 50
frames/s w i t h an exposure time of 1 ms which c o n d i t i o n s a l l o w the
very r a p i d events to be c l e a r l y followed. As Figure 8 shows, the
bubble forms as a near p e r f e c t sphere above the h o l e , detaches
and r i s e s and w i t h i n a very short d i s t a n c e , assumes i t s c h a r a c t e r i s t i c shape w i t h an indented base as the wake forms. E s s e n t i a l l y the same bubbling occurs i f the hole i s covered with a
bubble cap, i f gas enters downwards through a pipe b u r i e d i n the
bed or i f gas enters h o r i z o n t a l l y through a hole i n the w a l l . In
t h i s l a s t case there i s no observable l a t e r a l p e n e t r a t i o n and
bubbles r i s e v e r t i c a l l y from the o r i f i c e . This mode of entry has
been observed at gas v e l o c i t i e s up to 70 m/s and through holes as
l a r g e as 16 mm diameter. A l l t h i s has been seen w i t h a v a r i e t y
of p a r t i c l e s but not very l a r g e ones ( d measured i n mm) where
there i s reason to t h i n k behaviour may be d i f f e r e n t .
One reason f o r the p e r s i s t e n c e of a wrong concept of how gas
enters i s the f a c t that i t does so d i f f e r e n t l y i n a two-dimensiona l f l u i d i s e d bed, an arrangement chosen because of the ease of
o b s e r v a t i o n . In t h i s case i t i s q u i t e p o s s i b l e to e s t a b l i s h a
permanent j e t s t a b i l i s e d by the w a l l s . In a narrow slab bed
p a r t i c l e s can only flow towards the hole over a r e s t r i c t e d r e g i o n
and cannot always move f a s t enough to c l o s e the hole p e r i o d i c a l l y .
There i s no such d i f f i c u l t y when p a r t i c l e s can approach w i t h i n
the f u l l 360. P o s s i b l y a j e t could be e s t a b l i s h e d i n a c y l i n d r i c a l bed by e r e c t i n g s u i t a b l e b a f f l e s to hinder p a r t i c l e f l o w
but t h i s would have to be a d e l i b e r a t e arrangement.
I would l i k e to spend a few minutes over t h i s d e t a i l because
i t leads to a simple and s a t i s f y i n g model f o r chemical r e a c t i o n
i n the d i s t r i b u t o r zone. When an i n s o l u b l e gas enters a l i q u i d
p


3.
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59
i t i s no s u r p r i s e that bubbles form because of the i n c o m p a t i b i l i - *

ty of the two phases. Furthermore bubble s i z e and frequency must
be equivalent t o the gas flow r a t e . When gas enters a f l u i d i s e d
bed the phases are not incompatible because gas may form bubbles,
f l o w i n t e r s t i t i a l l y o r t r a n s f e r between the two. I t i s a f a c t of
observation that a t the moment o f detachment bubble s i z e and
frequency accounts f o r only about h a l f the o r i f i c e gas flow.
About two bubble diameters higher they have grown i n s i z e and now
account f o r a l l the flow. Frequency i s e s s e n t i a l l y independent
of f l o w r a t e and constant a t about 8/s.
U n l i k e formation i n a l i q u i d the boundary of a f l u i d i s e d bed
bubble can only expand by gas f l o w i n g across i t to produce the
drag f o r c e that w i l l cause the p a r t i c l e s to move a p p r o p r i a t e l y .
During the time that a bubble grows to the s i z e shown i n F i g u r e 9
the gas that produced i t has advanced t o f i l l the volume i n d i c a t ed by the outer broken l i n e . The annular r e g i o n above and around
the bubble now contains an excess of gas and so the powder v o i d age must increase. This i s unstable and as the bubble detaches
and r i s e s through the expanded dense phase the powder r e l a x e s and
and r e t u r n s the excess gas t o the bubble. This appears t o be
completed by the time i t has r i s e n about one diameter (of order
1/10 second) and t h e r e a f t e r i s of constant volume u n t i l i t coalesces .
Considering now the consequences f o r chemical r e a c t i o n , much
of the reactant gas that u l t i m a t e l y forms a bubble w i l l f i r s t
enter the i n t e r s t i t i a l phase and enjoy a b r i e f moment of i n t i m a t e
contact w i t h the p a r t i c l e s . L a t e r i t may form a cloud as i n
F i g u r e 5 w i t h l i m i t e d access t o p a r t i c l e s . Hence the high
r e a c t i o n r a t e s a s s o c i a t e d w i t h the process of bubble formation
and l i m i t e d to the bottom l a y e r of the bed of thickness up to
twice the i n i t i a l bubble diameter - a few centimeters a t most.
As yet there i s no f l u i d dynamic model that describes i n
q u a n t i t a t i v e d e t a i l the bubble formation process but i t i s b a r e l y
necessary f o r a r e a c t i o n engineering model. I t i s adequate to
assume that e n t e r i n g reactant gas passes i n plug f l o w through the
bottom l a y e r of p a r t i c l e s , say, one i n i t i a l bubble diameter deep
and t h e r e a f t e r forms bubbles.
I n i t i a l bubble diameter i s r e a d i l y
estimated from the known flow through the o r i f i c e and the f a c t
that frequency i s about 8/s. Above t h i s d i s t r i b u t o r l a y e r the
two-phase bubble model can be a p p l i e d .
The other end c o n d i t i o n where the bubbling bed model i s
i n a p p r o p r i a t e i s above the bed where there may be r e a c t i o n i n the
f r e e board r e g i o n . With f i n e powders where there i s appreciable
e l u t r i a t i o n gas and p a r t i c l e s may remain i n contact w i t h f u r t h e r
opportunity f o r r e a c t i o n . This s i t u a t i o n has not a t t r a c t e d the
a t t e n t i o n of many modellers but a t l e a s t one model p r e d i c t s that
considerable r e a c t i o n can continue under c e r t a i n circumstances
(20).
The l a s t area I wish to mention i s the e f f e c t on f l u i d i s a t i o n of changing temperature and pressure. Not very much funda-


60
CHEMICAL REACTION
F i g u r e 7 Gas enters the bed as a

stream o f bubbles.
ENGINEERING
ski
1
|
F i g u r e 8. x-Ray photograph o f bubble

formation at an o r i f i c e .
Figure 9 Gas flow causes the bubble

boundary t o expand.

3.
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61
mental work has been reported on the former (21, 22) but there i s
i n c r e a s i n g i n t e r e s t i n the l a t t e r (23-29). I t i s becoming f a i r l y
c l e a r that when compared a t the same s u p e r f i c i a l gas v e l o c i t y ,
bubble s i z e decreases as pressure i n c r e a s e s . The reason f o r t h i s
seems t o be that p r o p o r t i o n a t e l y more gas flows i n t e r s t i t i a l l y as
pressure increases and bubbles are smaller because the reduced
f l o w gives l e s s opportunity f o r growth by coalescence. Powders
that normally behave as Geldart type ( i . e . U f = U ^ ) become
type A a t q u i t e modest increases i n pressure. This i s good news
from a chemical r e a c t i o n engineering point of view and the
bubbling bed models continue to apply and only r e q u i r e the
changed d i v i s i o n of flow to be q u a n t i f i e d .
At pressures greater than about 80 bar some i n t e r e s t i n g
hydrodynamic changes occur. Bubbles begin to l o s e t h e i r i d e n t i t y
and a t q u i t e low gas v e l o c i t i e s the bed takes on the general
appearance of a " t u r b u l e n t " o r " f a s t f l u i d i s e d bed". This again
i s advantageous f o r r e a c t i o n engineering but few processes w i l l
be r e q u i r e d t o operate a t such high pressures.
I t u r n f i n a l l y to consider the d i r e c t i o n f u t u r e b a s i c
research should take. I t i s fundamental to the s t a t e o f f l u i d i s a t i o n that p a r t i c l e s are supported by the drag of f l o w i n g gas.
This f o r c e depends not only on the gas p r o p e r t i e s and v e l o c i t y
but a l s o on the p a r t i c l e spacing and arrangement. I n s p i t e of
the i n t e r e s t of f l u i d dynamicists
l i t t l e i s known about the
r e l a t i o n s h i p between p e r m e a b i l i t y , voidage and the flow c o n d i t
ions and yet i t i s t h i s that decides the d i v i s i o n of gas between
the phases w i t h important consequences f o r chemical r e a c t i o n . I t
i s evident that p a r t i c l e s i z e and s i z e d i s t r i b u t i o n are f a c t o r s
determining p e r m e a b i l i t y and that " f i n e s " are important i n t h i s
respect but i t i s d i f f i c u l t to understand why change of absolute
pressure should change voidage and p e r m e a b i l i t y .
Understanding
these things could g r e a t l y improve our a b i l i t y t o engineer f l u i d
i s e d bed chemical r e a c t o r s and t h i s should be a major object of
b a s i c research.
However deep our knowledge of the mechanism of f l u i d i s a t i o n
i t i s s a l u t a r y to pause and consider the freedom of choice a
chemical r e a c t i o n engineer w i l l have. Leaving aside d e t a i l s o f
mechanical design such as the d i s t r i b u t o r , b a f f l e s , heat exchang
ers and m a t e r i a l s of c o n s t r u c t i o n , the v a r i a b l e s are very l i m i t e d .
Gas d e n s i t y and v i s c o s i t y and p a r t i c l e d e n s i t y w i l l be determined
by chemistry and thermodynamics and the only major v a r i a b l e s
remaining are gas v e l o c i t y , bed height and p a r t i c l e s i z e and s i z e
d i s t r i b u t i o n . The f i r s t two are l a r g e l y f i x e d by production r a t e
and simple engineering c o n s i d e r a t i o n s and p a r t i c l e s i z e i s about
the only t h i n g l e f t to choose. I f we knew more about how to make
t h i s choice our designs might be much improved.


62
CHEMC
IAL REACTO
IN ENGN
IEERN
IG
L i s t of Symbols
cL
bubble diameter
JD
r e a c t o r diameter
bed height
volumetric flow
Q_.
bubble f l o w r a t e
r a t e i n t o the bed

Q.
i n t e r s t i t i a l flow rate
minimum f l u i d i s a t i o n flow r a t e
U ^
minimum bubbling flow v e l o c i t y
U ^
minimum f l u i d i s a t i o n flow v e l o c i t y
Literature Cited
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
Pyle, D.L. Advances in Chemistry Series 109, 1972, 106.

Rowe, P.N. Proc. 2nd ISCRE; Elsevier: Amsterdam, 1972, A9.
van Swaaij, W.P.M. Advances in Chemistry Series 72, 1978,
193.
Rudolph, P.F.H. Proc. 4th ISCRE 2; Dechema: Frankfurt, 1976,
537.
Kunii, D. Chem. Eng. Science 1980, 35, 1887.
Levenspiel, O. Chem. Eng. Science 1980, 35, 1821.
Denbigh, K.G. Trans. Faraday Soc. 1944, 40, 352.
Danckwerts, P.V. Chem. Eng. Science 1953, 2, 1.
Davidson, J.F.; Harrison, D. (Editor) "Fluidisation";
Academic Press: New York, 1971, 121 et seq.
Rowe, P.N. Chemistry & Industry No. 12 1978, 424.
Rowe, P . N . : Nienow, A.W.; Agbim, A . J . Trans. I. Chem. 1972,
50, 324.
Kunii, D.; Levenspiel, O. "Fluidisation Engineering"; John
Wiley: New York, 1969.
"Fluidised Combustion" 1975, London: Institute of Fuel,
Symp. Series N o . l .
"Fluidised Combustion - systems and applications" 1980,
London: Inst. of Energy, Symp. Series No.4.
Nienow, A.W.; Rowe, P.N.; Cheung, L . Y . - L . Powder Tech'y
1978, 89.
Geldart, D. Powder Tech'y 1973, 7, 285.
Rowe, P.N.; Yates, J . G . ; Santoro, L. Chem. Eng. Science
1978, 133.

3.
18.
19.
20.
21.
22.
23.

24.
25.
26.
27.
28.
29.
ROWE
63
Zenz, F.A. "Fluidisation"; P i r i e , J . M . , E d . ; I. Chem. E .

Symp. Series No.30, 1968, 136.
Rowe, P.N.; MacGillivray, H . J . ; Cheesman, D . J . Trans. I.
Chem. E. 1979, 57, 194.
Yates, J . G . ; Rowe, P.N. Trans. I. Chem. E . 1977, 55, 137.
B o t t e r i l l , J . S . M . ; Yeoman, Y. "Fluidization"; Grace, J . R . ;
Matsen, J . M . , Eds.; Plenum Press: New York, 1980, 93.
Desai, .; Kikukawa, H . ; Pulsifer, A.H. Powder Tech'y 1977,
16, 143.
Harrison, D.; Davidson, J.F.; de Kock, J.W. Trans. I. Chem.
E. 1961, 39, 201.
C l i f t , R.; Grace, J . R . ; Weber, M.E. Ind. Eng. Chem. Fund.
1974, 135, 45.
Carvalho, J . R . F . Guedes de; Harrison, D. Inst, of Fuel Symp.
Series No.1; 1975, B1.
Varadi, T . ; Grace, J.R. "Fluidisation"; C.U.P.: 1978, 55.
Carvalho, J . R . F . Guedes de; King, D . F . ; Harrison, D.: i b i d .
59.
Subzwari, M.P.; C l i f t , R.; Pyle, D . L . : i b i d . 50.
Rowe, P.N.; MacGillivray, H . J . Inst, of Energy Symp. Series
4, 1980, IV, 1.
RECEIVED April 27,
1983

4
Fluidized-Bed Coal Combustion: Controlling
Parameters
A D E L F. SAROFIM
Downloaded by CORNELL UNIV on December 2, 2012 | http://pubs.acs.org

Massachusetts Institute of Technology, Department of Chemical Engineering,

Cambridge, MA 02139
The factors controlling the performance of atmospheric-pressure fluidized-bed combustors (AFBC's) are
illustrated by order-of-magnitude calculations of the
design and operating variables for a hypothetical
100 MW boiler. Bed height, bed cross-sectional area,
immersed heat-transfer surface area, sorbent feed
size and rate, bed temperature, fluidizing velocity
and coal feed size are selected by consideration of
the fluids mechanics, heat transfer, and kinetics of
the governing gas-solid reactions. The fluid mechanics and heat transfer in AFBC's are shown to be
differ distinctly from those in more traditional
fluidized bed reactors.
t
F l u i d i z e d bed combustion provides one option f o r u t i l i z i n g

some of our l a r g e c o a l reserves f o r purposes of energy generation.
I t s advantages over a l t e r n a t i v e methods o f d i r e c t c o a l u t i l i z a t i o n , e.g., suspension f i r i n g of p u l v e r i z e d c o a l and the burning
of lump c o a l on s t o k e r s , i s that i t i s able to handle coals o f
w i d e l y v a r y i n g composition, i n c l u d i n g low-grade coals w i t h high
ash content, and i t provides a c a p a b i l i t y of in-bed s u l f u r
capture.
The development of the technology of AFBC's has been pursued
v i g o r o u s l y s i n c e the e a r l y s i x t i e s . Small (<3MW) u n i t s are i n
commercial s e r v i c e i n both the United Kingdom (1) and the People's
Republic of China, w i t h over 200 u n i t s i n use i n the l a t t e r , some
w i t h over 40,000 hours o f o p e r a t i o n a l experience (2). Larger
demonstration u n i t s (>20MW) have been constructed and operated
(1, 2_, _3 ). At present s e v e r a l firms o f f e r designs of AFBC's f o r
i n d u s t r i a l steam generation, and the development of atmosphericpressure and p r e s s u r i z e d f l u i d i z e d - b e d combustors f o r c e n t r a l s t a t i o n e l e c t r i c - p o w e r generation i s being pursued at a p i l o t s c a l e l e v e l (4_, 5). Consideration i n t h i s paper w i l l be r e s t r i c t ed to u n i t s operated at atmospheric pressure (AFBC's) s i n c e these
are o f greater current commercial i n t e r e s t .
0097-615 6/83/0226-0065$10.00/0
66
F l u i d i z e d - b e d combustors are complex chemical r e a c t o r s , a

f a c t often overlooked because t h e i r primary purpose i s t o generate
steam and e l e c t r i c i t y . The r e a c t i o n s of importance i n f l u i d i z e d
beds i n c l u d e those r e l a t i n g to c o a l combustion,
c o a l -> char + v o l a t i l e s ( i n c l u d i n g NH^ +
v o l a t i l e + 0 + C0 + H 0 '
2C + 0 + 2C0
+ NO + S 0
C + C0 + 2C0
CO + 1/2 0 > C0
2
H S)
2

to s u l f u r capture,
CaC0
CaO +
CaS0
S0 +
CaS0
+ CaO
S0 >
+ 1/2
1/2 0
+ 1/2
2
+ C0
CaS0
0 + CaS0
-> S 0
0 -> CaS0
2
and to n i t r i c oxide formation
and d e s t r u c t i o n ,
2NH + 3/2 0 -> 2N0 + 3/2 H 0

NH + NO + 1/4 0 -> N + 3/2 H 0
NO + C > 1/2 N + CO
3
N 0
C 0
1 / 2
^
2
2
NO + CaS0 + CaS0 + 1/2
3
From t h i s p a r t i a l l i s t i n g one can f i n d r e a c t i o n s belonging to many

of the important c l a s s e s of homogeneous and heterogeneous reactions .
The performance of a f l u i d i z e d bed combustor i s s t r o n g l y
i n f l u e n c e d by the f l u i d mechanics and heat t r a n s f e r i n the bed,
c o n s i d e r a t i o n of which must be part of any attempt to r e a l i s t i c a l l y model bed performance.
The f l u i d mechanics and heat
t r a n s f e r i n an AFBC must, however, be d i s t i n g u i s h e d from those i n
f l u i d i z e d c a t a l y t i c r e a c t o r s such as f l u i d i z e d c a t a l y t i c crackers
(FCCs) because the p a r t i c l e s i z e i n an AFBC, t y p i c a l l y about 1 mm
i n diameter, i s more than an order of magnitude l a r g e r than that
u t i l i z e d i n FCC s, t y p i c a l l y about 50 jJm. The consequences of
t h i s d i f f e r e n c e i n p a r t i c l e s i z e i s i l l u s t r a t e d i n Table 1.
P a r t i c l e Reynolds number i n an FCC i s much s m a l l e r than u n i t y so
that viscous forces dominate whereas f o r an AFBC the p a r t i c l e
Reynolds number i s of order u n i t y and the e f f e c t of i n e r t i a l
forces become n o t i c e a b l e . Minimum v e l o c i t y of f l u i d i z a t i o n ( f )
i n an FCC i s so low that the b u b b l e - r i s e v e l o c i t y exceeds the
gas v e l o c i t y i n the dense phase (u f/c ) over a bed's depth; the
FCC s operate i n the s o - c a l l e d f a s t bubble regime to be e l a b o r a t ed on l a t e r . By contrast- the b u b b l e - r i s e v e l o c i t y i n an AFBC may
be slower or f a s t e r than the gas-phase v e l o c i t y i n the emulsion
f

4.
Fluidized-Bed Coal Combustion
SAROFiM
67
Table I .
D i f f e r e n c e s i n F l u i d i z a t i o n and Heat Transfer o f AFBC's
and F l u i d i z e d C a t a l y t i c Reactors (e.g. FCC s)
T
FCC
AFBC

particle(s)
heating
phase, l e a d i n g t o operation i n e i t h e r the slow or f a s t bubble

regime. F i n a l l y the c h a r a c t e r i s t i c h e a t i n g time of p a r t i c l e s i n
an FCC i s s m a l l r e l a t i v e t o the residence time o f s o l i d s near a
tube surface and the heat t r a n s f e r r a t e i s then c o n t r o l l e d by the
p e n e t r a t i o n o f a thermal waves i n t o the s o l i d s as f i r s t proposed
by M i c k l e y and Fairbanks ( 6 ) . For an AFBC, the c h a r a c t e r i s t i c
h e a t i n g times are long compared t o the p a r t i c l e residence time a t
the w a l l and the p a r t i c l e s can be t r e a t e d as being a t the b u l k
temperature f o r purposes o f heat t r a n s f e r c a l c u l a t i o n s (7).
The paper w i l l consider the parameters c o n t r o l l i n g the design
and operation of an AFBC, shown s c h e m a t i c a l l y i n Figure 1 . The
questions to be addressed are what are the f a c t o r s t h a t guide the
s e l e c t i o n of bed h e i g h t , freeboard h e i g h t , c o a l feed l o c a t i o n ,
immersed h e a t - t r a n s f e r s u r f a c e s , sorbent s i z e and feed r a t e , c o a l
feed s i z e , bed temperature and f l u i d i z i n g v e l o c i t y . In order t o
help focus the d i s c u s s i o n , order-of-magnitude c a l c u l a t i o n s w i l l
be performed f o r the conceptual design of a b o i l e r designed t o
produce 1 0 0 MW of steam a t 644 K, f i r e d w i t h a c o a l of elemental
composition C H Q ^ S O Q
N Q . 0 3 OQ
( 2)Q.07
8
value
of 2 9 , 1 0 0 kJ/kg* and ten percent ash by weight. The b o i l e r w i l l
be operated w i t h 2 0 percent excess a i r .
Q
Pressure Drop Across Bed (Bed Height S e l e c t i o n )

The bed height i s determined by c o n s i d e r a t i o n of the work
r e q u i r e d t o overcome the pressure drop across the bed and d i s t r i b
utor p l a t e . The pressure drop across the bed i s simply the weight
of the bed.
= P g ( l - e ) h
s
(1)
where and h are the v o i d f r a c t i o n and height of the unexpanded

bed, and p i s the d e n s i t y o f the bed s o l i d s . The a d d i t i o n a l
pressure drop across the d i s t r i b u t o r p l a t e w i l l here be taken t o
be one t h i r d that across the bed. The fan work, and a i r flow r a t e
g


CHEMICAL
SPENT
SORBENT
REACTION
ENGINEERING
COAL
Figure 1. Schematic o f atmospheric pressure f l u i d i z e d bed

combustor.

4.
SAROFiM
69
i s the product o f the v o l u m e t r i c a i r flow r a t e and the pressure

drop, may be expressed as an e q u i v a l e n t amount of f u e l , given
the v o l u m e t r i c a i r requirement v per mass o f f u e l . The f r a c t i o n
of the f u e l flow rate m needed t o supply the energy t o d r i v e the
fans i s r e a d i l y shown to be
a
3 (-AH )n n
c
v>
where -^ i s the heat o f combustion,

the fan e f f i c i e n c y , and
r) the e f f i c i e n c y o f conversion of thermal t o e l e c t r i c a l energy.
For r e a l i s t i c values o f the c o e f f i c i e n t s : p = 2400 Kg/m ,e= 0.5,
t ) = 0.3, n = 0.6, v = 24.5 m /Kg c o a l , s
e

-: = 0.028 h
*F
(3)
where the bed height h i s i n meters. The unexpanded bed height

needs to be kept low i n order to minimize pumping energy l o s s e s ,
and a value of about 0.7 m i s o f t e n s e l e c t e d to keep the energy
l o s s f o r fan power t o 2 percent o f the f u e l ' s h e a t i n g value. A
consequence of t h i s c o n s t r a i n t on maximum bed height i s that
f l u i d i z e d bed c r o s s - s e c t i o n a l area i s p r o p o r t i o n a l to the c a p a c i t y
of a b o i l e r , r e s u l t i n g i n bed widths much l a r g e r than bed depth
f o r l a r g e r u n i t s ; t h i s can pose problems o f ensuring uniform f u e l
d i s t r i b u t i o n over the bed, as w i l l be discussed l a t e r . Inasmuch
as the fan power l o s s i s p r o p o r t i o n a l t o the v o l u m e t r i c a i r
requirement v ^ per u n i t mass of f u e l (Eq. 2 ) , the bed height cor
responding t o a given -/- i s p r o p o r t i o n a l to pressure so that
p r e s s u r i z e d FBC's may be operated w i t h deep beds and much s m a l l e r
c r o s s - s e c t i o n a l areas than AFBC's.
S u l f u r Capture
( S e l e c t i o n o f Bed Temperature and P a r t i c l e S i z e )
The s u l f u r sorbent that has r e c e i v e d the most a t t e n t i o n i s

limestone because o f i t s widespread a v a i l a b i l i t y and low cost.
Unfortunately the conversion o f limestone to calcium s u l f a t e
r e s u l t s i n a v o l u m e t r i c i n c r e a s e , and i t can be r e a d i l y shown (<3)
that f o r p a r t i c l e s that do not permit v o l u m e t r i c expansion on
r e a c t i o n the maximum conversion a t t a i n a b l e i s about 59 percent
(the value i s dependent on the s p e c i f i c volumes of reactant and
product). This c o n s t r a i n t can be avoided by use of dolomite,
s i n c e the MgO i s not s u l f a t e d and the v o i d volume produced by the
decomposition of MgCO^ and CaCO^ i s s u f f i c i e n t t o permit complete
calcium u t i l i z a t i o n , but a t the expense of an added weight o f
sorbent and added energy requirement f o r c a l c i n a t i o n . The above
conclusions f o l l o w from c o n s i d e r a t i o n o f the s t o i c h i o m e t r i c r e l a
tions :

70
CaC0
S0
CaC0 .MgC0
3
2
3
1/2
S0
1/2
CaSO. +
4
0
C0
= -325 kj/mole
+ Mg0.CaS0
2C0
(4)
= - 2 1 0 kJ/mole
(5)
The r a t e constant f o r s u l f a t i o n of a limestone i s shown as a

f u n c t i o n of the f r a c t i o n a l s u l f a t i o n m of calcium, f o r s e v e r a l
p a r t i c l e s s i z e s , i n Figure 2 , taken from the measurements of
F i e l d e s and Davidson (9). The rate of s u l f a t i o n i s seen to de
crease w i t h extent of s u l f a t i o n approaching zero at a maximum
s u l f a t i o n m Both the r a t e constant K at a given s u l f a t i o n and
oo
the maximum s u l f a t i o n m decrease w i t h i n c r e a s i n g p a r t i c l e s i z e ;

the data may be c o r r e l a t e d by one curve when p l o t t e d versus
m/m^,
a c o r r e l a t i o n which has proved u s e f u l i n developing models of
s u l f u r capture f o r AFBC s (10).
The maximum s u l f a t i o n observed i s c o n s i d e r a b l y s m a l l e r than
the t h e o r e t i c a l l i m i t of 59 percent. This o b s e r v a t i o n , together
w i t h the decrease i n r a t e constant K w i t h extent of s u l f a t i o n ,
can be e x p l a i n e d by models which assume that the r e a c t i o n i s
retarded by a product l a y e r of CaSO^ of low p o r o s i t y through
which the SO2 must d i f f u s e i n order to reach the unreacted CaO.
Such a hypothesis has formed the b a s i s f o r the development of
s e v e r a l models to q u a n t i t a t i v e l y f i t s u l f a t i o n data, of which the
g r a i n model ( 1 1 , 1 2 ) and the pore-plugging model (13, 14) are the
most n o t a b l e .
In the g r a i n model, i t i s assumed that the CaO c o n s i s t s of
s p h e r i c a l grains of uniform s i z e d i s t r i b u t e d i n a porous matrix.
The r a t e of r e a c t i o n i s c o n t r o l l e d by the d i f f u s i o n of S 0 through
the porous m a t r i x and the product CaSO^ l a y e r formed on each g r a i n
(11).
Allowance can be made f o r a f i n i t e rate of the C a 0 / S 0
r e a c t i o n ( 1 2 ) . The models have been found to d e s c r i b e experiment a l data f o r many limestones (13) by a d j u s t i n g the constants i n
the model, most n o t a b l y the d i f f u s i v i t y through the product l a y e r .
In the pore-plugging model the c a l c i n e d limestone i s assumed
to c o n s i s t of calcium oxide p e r f o r a t e d by c y l i n d r i c a l holes of
uniform diameter. The S 0 d i f f u s e s through the pore and the product CaSO^ to unreacted CaO.
Because of the increase i n volume
on r e a c t i o n , the pore diameter decreases w i t h a maximum decrease
at the opening where the d i f f u s i o n path i s s h o r t e s t . As a consequence the r e a c t i o n r a t e f a l l s to very low values as the pore
mouth plugs. The model has been developed without (14) and w i t h
(15) allowance f o r a k i n e t i c r e s i s t a n c e due to the C a 0 / S 0
r e a c t i o n . As w i t h the g r a i n model, the pore-mouth plugging model
can adequately describe the decrease i n r e a c t i o n r a t e w i t h i n c r e a s i n g extent of r e a c t i o n and w i t h decreasing p a r t i c l e s i z e by
appropriate adjustment of the d i f f i s u v i t y through the product
layer.
The r e a c t i o n of S 0 w i t h c a l c i n e d limestone i s found to be
f i r s t order w i t h respect to S 0 but the dependence on 0 concent r a t i o n i s more complicated. F i e l d e s et a l . (16) have observed



4.
SAROFiM
m/m oo
Figure 2 . Rate constant f o r the r e a c t i o n o f S O 2 w i t h c a l c i n e d
limestone as a f u n c t i o n o f m, the f r a c t i o n a l s u l f a t i o n , and
m/m , the f r a c t i o n a l s u l f a t i o n normalized w i t h i t s asymptotic
value (9.).

71
72
t h a t the maximum s u l f a t i o n m
of a v a r i e t y of limestones
00
decreased
w i t h i n c r e a s i n g oxygen c o n c e n t r a t i o n . They a t t r i b u t e d t h i s decrease t o an i n c r e a s e i n SO^ concentration w i t h i n c r e a s i n g oxygen;

s i n c e the rate of r e a c t i o n of SO,, w i t h CaO i s high the SO- w i l l
react p r e f e r e n t i a l l y a t the moutn of a pore and l e a d to the pore
plugging.
The maximum s u l f a t i o n m i s expected t o pass through a peak
as temperature i s i n c r e a s e d s i n c e , f o r the l e v e l s o f S 0 and 0
found i n combustion products, CaSO^ decomposes a t temperature i n
excess o f 1500 K. The maximum observed, however, i s at lower
temperatures.
The maximum s u l f a t i o n m i s reported as o c c u r i n g
around 1120 (17, 18). This provides the b a s i s f o r the current
s e l e c t i o n of optimum bed temperature.
The e x p l a n a t i o n f o r the
peaking i n s u l f u r capture a t temperatures below that at which
CaSO^ decomposes has not been d e f i n i t e l y e s t a b l i s h e d . A p l a u s i b l e
argument f o r the decrease i n r e a c t i v i t y w i t h i n c r e a s i n g tempera
ture i s that s i n t e r i n g o f grains i s a c c e l e r a t e d a t higher tempera
tures and that the maximum s u l f a t i o n t h e r e f o r e decreases as a
consequence of the increased g r a i n s i z e . Examples of the i n c r e a s e
i n g r a i n s i z e (19) and the decrease i n maximum s u l f a t i o n (9) w i t h
i n c r e a s i n g temperature are shown i n Figure 3.
In order to p r e d i c t emissions from AFBC s i t i s necessary t o
couple a model of the s u l f u r capture of i n d i v i d u a l p a r t i c l e s i n t o
a system's model which takes i n t o account the S 0 formation, r e
moval, and t r a n s p o r t . Because the s i n g l e p a r t i c l e behavior i s so
complex, most such models (10, 20, 21, 22) use s i m p l i f i e d , u s u a l l y
e m p i r i c a l , f i t s o f s i n g l e p a r t i c l e behavior determined, f o r
example, from thermogravimetric a n a l y s i s .
The optimum c o n d i t i o n s needed to achieve the d e s i r e d s u l f u r
capture e f f i c i e n c y (90 percent) i s dependent on sorbent type, c o a l
type, and f l u i d i z e d bed design. Representative c o n d i t i o n s are a
bed temperature of 1116 K, a sorbent p a r t i c l e of 1 mm, and a Ca/S
r a t i o of about 3. The bed temperature s e l e c t i o n i s based on the
admittedly shaky evidence that t h i s i s where the maximum s u l f a t i o n
peaks. The p a r t i c l e s i z e s e l e c t i o n i s a compromise between a
d e s i r e t o use high gas v e l o c i t i e s and the observed decrease i n
s u l f a t i o n w i t h i n c r e a s i n g s i z e (Figure 2). The Ca/S r a t i o cor
responds t o a maximum s u l f a t i o n of about 0.3. For these condi
t i o n s the mass feed r a t e of a limestone sorbent i s 0.345 that of
the c o a l feed and the flow r a t e of the p a r t i a l l y s u l f a t e d spent
sorbent i s 0.235 the c o a l feed r a t e .
C l e a r l y there i s an i n c e n t i v e f o r reducing the amount of
sorbent. Promising areas f o r research are on reducing g r a i n s i z e
by minimizing g r a i n growth (23, 24), i n c r e a s i n g limestone u t i l i z a
t i o n through p a r t i a l h y d r a t i o n (25) and the development o f r e
generative sorbents (26).
2

F l u i d Mechanics (Determination of Bed C r o s s - s e c t i o n a l Area and

Flow Regime
The f l u i d i z i n g v e l o c i t y i n a bed i s bounded by the minimum
fluidizing velocity u
and the t e r m i n a l v e l o c i t y u (27). The


4.
SAROFiM
1050
1100
1150
73
1200
Temperature (K)
Figure 3. E f f e c t o f bed temperature on g r a i n s i z e and asymptotic

f r a c t i o n a l s u l f a t i o n o f limestone. Data from Refs. 9 and 19.


74
CHEMICAL REACTION
ENGINEERING
c o r r e l a t i o n s f o r the bounding curves are given i n Figure 4 where

the dimensional coordinates are f o r the c o n d i t i o n s i n an AFBC
(using a s p h e r i c i t y f a c t o r = 0.6). At low v e l o c i t i e s the slopes
approach two as would be expected f o r v i s c o u s flow, and a t the
h i g h e r v e l o c i t i e s at which i n e r t i a l forces are dominant, the
slopes approach 0.5. For FBC's, the p a r t i c l e s i z e s are about
1.0 mm. From F i g u r e 4, t h i s s i z e i s found t o correspond t o a
minimum f l u i d i z i n g v e l o c i t y of 0.4m/s, the approximate t r a n s i t i o n
p o i n t to the regime i n which i n e r t i a l forces b e g i n to become
appreciable.
From a viewpoint of m i n i m i z i n g the c r o s s - s e c t i o n a l area of a
bed, i t i s d e s i r a b l e t o operate a t as h i g h a v e l o c i t y above the
minimum f l u i d i z i n g v e l o c i t y as i s p r a c t i c a l . The upper l i m i t on
f l u i d i z i n g v e l o c i t y i s imposed i n part by the i n c r e a s e i n amount
of e l u t r i a t e d m a t e r i a l w i t h i n c r e a s i n g v e l o c i t y . E l u t r i a t i o n
r a t e s i n c r e a s e approximately i n p r o p o r t i o n to the e x p o n e n t i a l of
the r a t i o u /u^_ of the f l u i d i z i n g to t e r m i n a l v e l o c i t y , a c c o r d i n g
to one of tfie a v a i l a b l e e m p i r i c a l c o r r e l a t i o n s (28). From c o n s i
d e r a t i o n o f the t r a d e - o f f s between decreased bed c r o s s - s e c t i o n and
i n c r e a s e d e l u t r i a t i o n r a t e s a v e l o c i t y o f about 2 m/s i s o f t e n
s e l e c t e d as the nominal o p e r a t i n g v e l o c i t y i n AFBC s. At t h i s
v e l o c i t y , p a r t i c l e s w i t h diameters below 350 ym once e n t r a i n e d
from the bed w i l l be c a r r i e d over t o the p a r t i c u l a t e c o l l e c t i o n
devices s i n c e t h e i r t e r m i n a l v e l o c i t i e s w i l l be exceeded by the
f l u i d i z i n g v e l o c i t y , as may be seen from F i g u r e 4.
Once the f l u i d i z i n g v e l o c i t y i s s e l e c t e d , the bed c r o s s s e c t i o n area i s f i x e d , b e i n g given by the v o l u m e t r i c f l o w r a t e
r e q u i r e d f o r combustion m v d i v i d e d by the f l u i d i z i n g v e l o c i t y
U . For our t e s t case o f 100 MW ^hernial output, the c r o s s s e c t i o n a l area o f the bed i s 87 m . The approximate c r o s s s e c t i o n a l area of AFBC s may be estimated by n o t i n g that the
v e l o c i t y c o n s t r a i n t of 2 m/s corresponds approximately t o 1.1 MW
thermal output per square meter of bed area.
The b u b b l i n g behavior o f a bed i s a l s o determined by the
f l u i d i z i n g v e l o c i t y u . According t o the two-phase theory o f
f l u i d i z a t i o n (29), the excess v e l o c i t y over that r e q u i r e d f o r
minimum f l u i d i z a t i o n passes through the bed i n bubbles, which
provides a u s e f u l , although o v e r s i m p l i f i e d (30, 31) view of bubble
flow.
The gas flow through the bubbles depends on whether the bub
b l e r i s e v e l o c i t y , 0.7l/gd^ (29) i s slow or f a s t r e l a t i v e t o the
gas v e l o c i t y i n the emulsion phase ( u f / e f ) . When the bubble
r i s e v e l o c i t y exceeds the emulsion v e l o c i t y , the bubbles are s a i d
to be f a s t o r clouded and the gas c i r c u l a t e s through a cloud s u r
rounding the bubble as shown s c h e m a t i c a l l y i n F i g u r e 5 (adapted
from Ref. 32). When the emulsion v e l o c i t y i s f a s t r e l a t i v e t o
the bubble r i s e v e l o c i t y the bubbles are s a i d to be slow or c l o u d
l e s s and the emulsion gas uses the bubble as a by-pass (see Figure
5). The t r a n s i t i o n from slow t o f a s t bubble depends upon the
1

4.
SAROFiM
75

dp (/im)
Figure h. C o r r e l a t i o n s f o r the minimum f l u i d i z i n g v e l o c i t y u ^

and p a r t i c l e t e r m i n a l v e l o c i t y u, as a f u n c t i o n o f p a r t i c l e s i z e .


76
ENGINEERING
d (m)
B
Figure 5. The dependence o f the t r a n s i t i o n from the slow t o f a s t

bubble regime on bubble diameter d^ and minimum f l u i d i z a t i o n
velocity u

4.
SAROFiM
77
minimum f l u i d i z i n g v e l o c i t y and the bubble diameter d^, which may

be estimated from the simple r e l a t i o n developed from the theory
f o r bubble growth due t o coalescence by Darton e t a l . ( 3 3 ) .
d
= 0.54
(u -u
o
m f
(h + 4 / T )
2 / 5
4 / 5
/g
(6)
1 / 5
where A i s the area o f d i s t r i b u t o r p l a t e per o r i f i c e and h i s the

height o f the bubble above the p l a t e . For u = 2 m/s and
u
= 0.4 m/s and a bubble-cap p l a t e w i t h A = 2.5 10" m , the
bubbles i n c r e a s e i n diameter from a value of 0.079 m a t the d i s
t r i b u t o r p l a t e t o a value of 1 m a t the top o f the bed (1 m).
The bubble diameter at which the bubble v e l o c i t y , 0.71/gdb,
equals the emulsion v e l o c i t y , u ^ / ^ ,
0.13m, and i s the value
encountered a t a height o f 0.1m above the d i s t r i b u t i o n p l a t e . The
bubbles are, t h e r e f o r e , expected t o s t a r t i n the slow o r c l o u d l e s s
bubble regime but a c c e l e r a t e i n t o the f r e e bubble regime a t an
e l e v a t i o n o f 0.1m. As the bed p a r t i c l e diameter i n c r e a s e s , u f
increases and the f r a c t i o n of the bed that i s i n the slow bubble
mode w i l l i n c r e a s e . Whereas FCC's operate p r i m a r i l y i n the f a s t
bubble regime AFBC s operate i n the t r a n s i t i o n of the f a s t t o
slow bubble regimes.
The bubble motion w i l l a l s o determine the s o l i d c i r c u l a t i o n
i n the bed, as a consequence o f the entrainment o f s o l i d s i n the
bubble wake. For an assumed r a t i o of wake t o bubble volume, the
v o l u m e t r i c c i r c u l a t i o n r a t e of s o l i d s per u n i t c r o s s - s e c t i o n a l
area of bed i s equal t o ( u - u f ) a . The s o l i d c i r c u l a t i o n time i s
then equal to h/(u - 1 1 ^ ) 0 1 .
For the values U = 2m/s, u^f = 0.4m/s,
h = lm, and a reasonable value f o r o f 0.1 to 0.2 (34), the s o l i d
c i r c u l a t i o n time i s found to be about 3 t o 6 seconds which i s slow
enough compared t o limestone r e a c t i o n times (see above) o r char
burnout times (see below) that the bed s o l i d s can be t r e a t e d as
being well-mixed.
Whether the gas can be t r e a t e d as being well-mixed o r i n p l u g
flow depends upon the v e l o c i t y o f the downward f l o w i n g s o l i d s
r e l a t i v e t o the minimum f l u i d i z i n g v e l o c i t y (34). I f we n e g l e c t
temporarily the c r o s s - s e c t i o n o f the bed occupied by the bubbles
and the a s s o c i a t e d s o l i d s moving upwards, the v e l o c i t y o f the
s o l i d s f l o w i n g downwards i s then determined by t h e i r v o l u m e t r i c
flow r a t e per u n i t c r o s s - s e c t i o n a l area o r a i ^ - u ^ ) . When t h i s
v e l o c i t y exceeds the i n s t e r t i t i a l gas v e l o c i t y o f f/ f*
8
i s r e c i r c u l a t e d w i t h the s o l i d s . The simple c r i t e r i a f o r gas r e
c i r c u l a t i o n , developed i n a more general form by K u n i i and
L e v e n s p i e l ( 3 4 ) , i s then
Q
m f

i s
-U2->l __
u ^
.
mf
mf
T N E
(7)
For values of o f 0.1 t o 0.2 and e

= 0.5 we f i n d that the
t r a n s i t i o n from a p l u g flow t o well-mixed gas occurs a t a value of
m f

78
CHEMICAL REACTION
ENGINEERING
u / u f i n the range of 10 to 20, and once again we f i n d a d i f f e r

ence between the regime of operation of an FCC which operate w i t h
U Q / U J J J ^ >20 and AFBC which t y p i c a l l y operate w i t h u / t ^ f below the
transition point.
An other important e f f e c t of bubbles i s to cause the bed to
expand. The bed expansion i s a consequence of the bubble h o l d up
i n the bed and can be c a l c u l a t e d from the bubble flow r a t e and the
bubble r i s e v e l o c i t y (29, 34). For the considions here, a bubble
v o i d f r a c t i o n of 0.3 i s assumed, corresponding to an expanded bed
h e i g h t of about lm. From the expanded bed h e i g h t , bed c r o s s s e c t i o n a l a r e a , and sorbent feed r a t e , i t can be r e a d i l y shown
that the mean residence time of the limestone i n the bed i s about
20 hours.
0

Heat Transfer ( S e l e c t i o n of Tube Area)

The heat t r a n s f e r to the immersed tubes i s by a combination
of r a d i a t i o n , convection from gases f l o w i n g past the tube, and
t r a n s f e r from p a r t i c l e s i n the v i c i n i t y of the tube s u r f a c e .
Since the p a r t i c l e residence time near the tube w a l l s i s s m a l l
r e l a t i v e to t h e i r thermal r e l a x a t i o n times (see Table 1 ) , the
temperature of the p a r t i c l e s near the w a l l does not depart ap
p r e c i a b l y from the mean bed temperature. The heat t r a n s f e r coef
f i c i e n t from the p a r t i c l e s i s then governed by conduction across
the gap s e p a r a t i n g the p a r t i c l e s from the w a l l . The sum of the
conductive and convective f l u x e s can be c a l c u l a t e d from the
expression derived by Decker and Glicksman (7_) :
^
- [12 + 0.05
(1 + 2 0 ) ( ^ d p ) P r ]
(8)
where 6 i s the bed v o i d volume. The above e x p r e s s i o n i s f o r a

tube surface i n the emulsion phase, w i t h the f i r s t term represent
ing the conduction from the p a r t i c l e s and the second the augmenta
t i o n of the f l u x by convection. The r a d i a t i v e heat t r a n s f e r
c o n t r i b u t i o n can be adequately approximated by the f l u x between
two i n f i n i t e p a r a l l e l gray p l a t e s
4
h
( T
b - V
- /, I l/ - 1
b
w
<>
where i s the tube w a l l e m m i s i v i t y , and ^ i s the e f f e c t i v e emm i s s i v i t y of a plane formed by the s p h e r i c a l p a r t i c l e s . The con
t r i b u t i o n s to the heat t r a n s f e r by the above mechanisms i s shown
i n Figure 6. As p a r t i c l e diameter increases the conduction con
t r i b u t i o n given by the f i r s t term i n Eq. 8 f a l l s r a p i d l y but
compensation i s provided by the i n c r e a s e d convection c o n t r i b u t i o n
given by the second term, so that the t o t a l passes through a
minimum. The e f f e c t i v e heat t r a n s f e r c o e f f i c i e n t to the tubes
w i l l be s l i g h t l y lower than that given by Equations 8 and 9, since


4.
SAROFiM
Figure 6. C o n t r i b u t i o n s o f the convective and r a d i a t i v e

t i o n s t o heat t r a n s f e r on p a r t i c l e diameter.

79
contribu-

80
CHEMICAL REACTION ENGINEERING
the tubes w i l l be s h i e l d e d p e r i o d i c a l l y from contact w i t h the

dense phase by bubbles.
The area of the tubes immersed i n the bed i s then determined
from energy balances on the FBC (Figure 7). An energy i n p u t w i t h
the c o a l of 111 MW i s needed to provide the d e s i r e d thermal output
of 100 MW and the l o s s e s o f 9.8 MW w i t h the stack gases ( f o r an
exhaust temperature of 450 K) and 1.3 MW w i t h the spent bed solids
(assuming no recovery of the s e n s i b l e h e a t ) . Given a r e c y c l e o f
13 MW t o the bed as a i r preheat, 73 MW must be e x t r a c t e d by c o i l s
immersed i n the bed i n order t o maintain the bed temperature a t
1116 K. The tube area needed t o achieve t h i s i s 515 m^, provided
for example by s i x rows o f 50 mm O.D. tubes w i t h a h o r i z o n t a l
p i t c h o f 150 mm and a v e r t i c a l p i t c h o f 125 mm.
C o n t r o l o f bed temperature provides some s p e c i a l challenges.
As the load i s v a r i e d , e i t h e r the heat t r a n s f e r c o e f f i c i e n t o r
immersed tube area must be v a r i e d correspondingly. This may be
achieved over a moderate load change by v a r y i n g the area o f tubes
immersed i n the bed by v a r y i n g the h e i g h t o f the bed.
Carbon Combustion E f f i c i e n c y ( S e l e c t i o n o f Coal Feed Diameter)
The p r i n c i p a l l o s s o f combustible from the bed i s by l o s s of
unburned carbon e i t h e r e l u t r i a t e d from the bed o r withdrawn w i t h
the bed s o l i d s . In order t o evaluate the carbon l o s s e s i t i s
d e s i r a b l e t o consider a balance on the carbon i n the bed (34). To
s i m p l i f y the a n a l y s i s we w i l l f i r s t approximate c o a l as carbon.
The governing population balance f o r the carbon i n the bed i s :
. W
F (R) =
o o
= W K(R)p(R)
input
s o l i d s withdrawal
d[p(R)R]
c
dR
net shrinkage
out o f s i z e range
where
F
F^
K(R)
p(R)
p (R)
R
R
W
W
Q
=
=
=
=
=
=
=
=
=
elutriation
3W p(R)R
c
(10)
R
growth w i t h i n
s i z e range
c o a l feed, kg/s
s o l i d s withdrawal r a t e , kg/s
e l u t r i a t i o n constant f o r p a r t i c l e s o f s i z e R, s"
f r a c t i o n of mass of c o a l i n s i z e range R t o R + dR,
p(R) f o r feed stream, m~l
p a r t i c l e radius, m
r a t e o f change o f p a r t i c l e r a d i u s , m/s
carbon l o a d i n g , kg
t o t a l s o l i d s i n bed, kg
For the s p e c i a l case o f a feed o f constant s i z e R-^, i . e .

p ( R ) = (R-R^), f o r n e g l i g i b l e l o s s o f carbon by e l u t r i a t i o n and
Q

4.
SAROFiM
81
23.2 MW

Qc*27.2 S
MW
50.4 MW
t
III MW
QF
Q =73 C MW
^
-T =644
6
1.3 MW
BED SOLIDS
I3MW 589K
298
AIR
PREHEAT
9.8 MW
= 515 m
h(T -Tw>
B
_ L . o
0.125 m
T'b
Figure Energy balance on a h y p o t h e t i c a l 100 MW^ b o i l e r and t h e

in-bed heat t r a n s f e r area r e q u i r e d t o m a i n t a i n the bed temperature
at 1116 K, e.g., 6 rows o f 50 mm O.D. tube w i t h a h o r i z o n t a l p i t c h
of 150 mm and a v e r t i c a l p i t c h o f 125 mm.

82
w i t h the s o l i d s withdrawn from the bed [K(R) = ? = 0 ] , and f o r a

d i f f u s i o n l i m i t e d carbon burning to C O 2 (R = -6ShPC^yQ /p R, where
V i s the oxygen d i f f u s i v i t y , C the t o t a l molar gas c o n c e n t r a t i o n ,
p the carbon d e n s i t y , and y
the oxygen mole f r a c t i o n ) , Eq. 10
can be solved f o r the p a r t i c l e s i z e d i s t r i b u t i o n (R) and the
carbon l o a d i n g . The s o l u t i o n s are
c
and
P

o l
-*-
= ShPC^
where t ^ i s the burning
2
( 1 2 )
- f Vb
time of p a r t i c l e s of
i n i t i a l radius
R-^.
The carbon l o a d i n g i s found to be p r o p o r t i o n a l to coal feed

rate and p a r t i c l e burning time. I t i s a v a r i a b l e of major impor
tance because i t determines the carbon l o s s from the bed and a l s o
has an important impact on the emissions of n i t r o g e n oxides.
Estimates of the carbon l o a d i n g can be obtained by e v a l u a t i n g t ^
from the r e l a t i o n f o r a s h r i n k i n g sphere model of a d i f f u s i o n l i m i t e d o x i d a t i o n of carbon. I t i s r e a d i l y shown t h a t , f o r
p a r t i c l e s of density p and i n i t i a l diameter
c
48ShPC
( 1 3 )
p
where Sh i s the Sherwood Number, V the oxygen d i f f u s i v i t y , and C

the oxygen concentration i n the emulsion phase.
Although some controversy e x i s t s on the c o r r e l a t i o n of
Sherwood Number a p p l i c a b l e to f l u i d i z e d beds, w e l l - d e f i n e d combus
t i o n experiments support the use of the Ranz and M a r s h a l l (35) or
F r o s s l i n g (36) c o r r e l a t i o n w i t h an approximate c o r r e c t i o n of e f
to allow f o r the o b s t r u c t i o n to d i f f u s i o n by the i n e r t p a r t i c l e s
surrounding the burning char p a r t i c l e s (37). Thus
p
Sh * [2 +0.6
Re
1 / 2
Sc
1 / 3
(14)
The oxygen concentration C w i l l depend upon the excess a i r ,

expressed as a f r a c t i o n of the s t o i c h i o m e t r i c a i r , and the f l u i d
mechanics. Assuming that n e g l i g i b l e amounts of oxygen by-pass
the bed i n bubbles, the oxygen concentration C i n the bed can be
r e l a t e d to the i n l e t oxygen concentration C and excess a i r by
p

4.
SAROFiM
83
f o r a w e l l - s t i r r e d emulsion gas, and
( 1 6 )
(l+e)n(l+l/e)
f o r p l u g flow. With char p a r t i c l e s 1mm i n diameter, an excess a i r

e of 0.2, a bed temperature o f 1116 K, and e f of 0.5, the burning
times are 185 seconds f o r a w e l l - s t i r r e d gas, and 67 seconds f o r
plug flow, The lower times are more p e r t i n e n t t o AFBC s i n which
the gas i s approximately i n p l u g flow. The carbon l o a d i n g i n the
bed i s then determined by s u b s t i t u t i n g the c o a l feed r a t e
(3.83 Kg/s f o r 111 MW thermal i n p u t ) and burning time i n t o Eq. 12.
A carbon l o a d i n g o f 103 Kg i s obtained f o r the case o f p l u g f l o w
i n the gase phase. The f r a c t i o n o f the t o t a l bed weight which i s
i n the form o f carbon i s s m a l l . S u b s t i t u t i n g i n t o
m

W
=
9
Ahp (l- )
s
(17)
K / J
the p r e v i o u s l y determined values of h = 0.7 m, A = 87 m and the

density of limestone ( p = 2400 Kg/m^), we f i n d that the carbon
accounts f o r only 0.14 percent o f the t o t a l bed weight.
With carbon l o a d i n g determined, one i s i n a p o s i t i o n t o
evaluate the carbon l o s s from the bed. The three p r i n c i p a l
sources are carbon withdrawn from the bed w i t h spent s o l i d s ,
e l u t r i a t i o n o f carbon that has burned down t o an e l u t r i a b l e s i z e
range, and the e l u t r i a t i o n o f f i n e s produced by a t t r i t i o n .
The f r a c t i o n m /m-p o f the carbon feed l o s s w i t h spent solids
i s determined by the rate m o f spent s o l i d w i t h d r a w a l , and the
f r a c t i o n (W /W ) of the bed s o l i d s i n the form o f carbon:
s
m
m W
c,s _ s ^
( 1 8 )
The f r a c t i o n m /m l o s t by e l u t r i a t i o n i s determined by the

e l u t r i a t i o n r a t e constant K ( R ) , the p a r t i c l e s i z e d i s t r i b u t i o n
p(R) of carbon i n the bed, and the carbon l o a d i n g W (Eq. 10). A
f i r s t approximation f o r t h i s l o s s may be obtained by assuming that
that p a r t i c l e s of feed diameter d^ s h r i n k t o an e l u t r i a b l e s i z e d
approximately 300 ym from Figure 4, and are then blown out of the
bed. For t h i s simple model
c e
= (~) * (0.3 * 2.7 10

i
(19)
Another source o f e l u t r i a t e d carbon are the f i n e s produced by

the a t t r i t i o n of the carbon surface by a b r a s i o n . This mechanism
f o r a t t r i t i o n has been s t u d i e d by M a s s i m i l l a and coworkers (38-41).

84
ENGINEERING
They f i n d that the r a t e of a t t r i t i o n i s p r o p o r t i o n a l to the energy

d i s s i p a t i o n r a t e i n the bed, which i s p r o p o r t i o n a l to u - u ^ f , and
that i t i s much higher during o x i d a t i o n than p y r o l y s i s . They
p o s t u l a t e that a s p e r i t i e s are produced on the surface of the char
during combustion and that these are abraded by c o l l i s i o n s w i t h
the bed s o l i d s . The r a t e of the carbon surface r e g r e s s i o n due to
a t t r i t i o n i s approximately given by
Q
(20)
where k i s about 3.5x10"^. The r a t e of feed carbon l o s s due to

the e l u t r i a t i o n of a t t r i t e d carbon i s then given by
d /2
3p(R)Wk ( u - u
c a mf)
n
3k (u -u -)
a mf .
(21)
For the c o n d i t i o n s we have s e l e c t e d , m /m.p equals 1.1x10

The above c a l c u l a t i o n s show a carbon l o s s of about 4 percent
of the c o a l feed, p r i m a r i l y as f i n e s produced by carbon a t t r i t i o n
or by the shrinkage of the c o a l feed. As c o a l p a r t i c l e feed s i z e
increases the a t t r i t t e d carbon increases (note t ^ i n Eq. 21 i s
p r o p o r t i o n a l to d^) but the e l u t r i a t e d carbon (Eq. 19) decreases.
Carbon l o s s e s can t h e r e f o r e be minimized by the j u d i c i o u s choice
of c o a l feed s i z e . The s i m p l i f i e d model presented above y i e l d s
the f o l l o w i n g expression f o r the optimum s i z e :
c
1/4
3
( i>opt
48ShPCp(d*)
k (u -u ,)
c a mf
(22)
For the t e s t case, being considered, the optimum c o a l feed s i z e

given by Eq. 22 i s 1.6mm. C l e a r l y , the optimum depends upon
o p e r a t i n g c o n d i t i o n s , and a l s o on the model assumptions.
The f i n e s e l u t r i a t e d from the bed are u s u a l l y captured i n a
cyclone and r e c y c l e d to the bed, so that high combustion e f
f i c i e n c i e s are achievable w i t h AFBC's. B e t t e r understanding of
the residence time of f i n e s i n a bed i s needed i n order to deter
mine the r e c y c l e r a t e .
The above s i m p l i f i e d a n a l y s i s was intended to provide a f e e l
f o r the r e l a t i v e importance of the processes that govern carbon
l o a d i n g , and t h e r e f o r e carbon combustion e f f i c i e n c y . More com
p l e t e treatments of AFBC s are a v a i l a b l e which consider the
d e t a i l e d population balance equations f o r the char p a r t i c l e s
coupled w i t h an oxygen balance (41-50). These treatments have
given r e s u l t s which p a r a l l e l observations on o p e r a t i n g AFBC*s but
1

4.
85
SAROFiM
are q u a l i f i e d by u n c e r t a i n t i e s i n the flow models and mass t r a n s f e r

models which are used t o c a l c u l a t e the t r a n s f e r o f oxygen t o the
dense phase and by d i f f e r e n c e s i n assumptions concerning the comb u s t i o n of the char.
The refinements that can be made t o the model f o r c o a l char
o x i d a t i o n are seemingly endless (51), A few o f these w i l l be
discussed b r i e f l y .
Dominant Oxidant. Carbon g a s i f i c a t i o n i n f l u i d i z e d bed
combustors can occur by both the C O 2 / C and the O 2 / C r e a c t i o n s :

C0
(1
+ C=
- |)
(23)
2C0
+ C = xCO
(1 - x ) C 0
(24)
Avedasian and Davidson (37) i n t h e i r p i o n e e r i n g work on the

modelling of char o x i d a t i o n i n f l u i d i z e d beds assumed a t w o - f i l m
model f o r char o x i d a t i o n , i n which C O 2 reacts w i t h carbon a t the
surface t o form CO w i t h the CO b e i n g o x i d i z e d i n a d i f f u s i o n flame
enveloping the p a r t i c l e . L a t e r s t u d i e s (52) showed that the C O 2 / C
r e a c t i o n was too slow a t f l u i d i z e d bed temperatures t o c o n t r i b u t e
s i g n i f i c a n t l y t o the carbon g a s i f i c a t i o n r a t e . The primary product o f the C / O 2 r e a c t i o n i s b e l i e v e d to be CO, based on molecu l a r beam s t u d i e s on graphite (53). CO i s then converted t o
C O 2 as i t d i f f u s e s from the p a r t i c l e surface. A g e n e r a l i z e d
treatment of the carbon o x i d a t i o n r e a c t i o n s a l l o w i n g f o r the two
g a s i f i c a t i o n r e a c t i o n s , Eqs. 23 and 24, and the carbon monoxide
o x i d a t i o n i n the boundary l a y e r has been presented by Amundson and
coworkers (54-58).
E x t e r n a l D i f f u s i o n vs. Chemical K i n e t i c s . As expected, the
rate of carbon o x i d a t i o n i s determined by the combination o f
e x t e r n a l d i f f u s i o n and the k i n e t i c s o f the carbon o x i d a t i o n .
E a r l y c a l c u l a t i o n s by Borghi e t a l (59) determined the c o n t r i b u t i o n s of k i n e t i c s and e x t e r n a l d i f f u s i o n as a f u n c t i o n of bed
temperature, p a r t i c l e s i z e , and oxygen concentrations.
These show
that f o r p a r t i c l e s o f 1 mm diameter 1116 K, c o n d i t i o n s t y p i c a l o f
commercial p r a c t i c e , the d i f f u s i o n and k i n e t i c r e s i s t a n c e s are of
equal importance. Experimental support f o r these p r e d i c t i o n s i s
provided by Ross and Davidson (60, 61).
Reaction Order. Studies o f the r e a c t i o n o f oxygen w i t h carbon a t temperatures o f i n t e r e s t f o r AFBC's suggest that i t i s near
zero order i n oxygen (62). Most models have been based on an assumed f i r s t order r e a c t i o n but they can be r e a d i l y m o d i f i e d t o
accommodate the more r e a l i s t i c lower r e a c t i o n order (63, 64). The
c o r r e c t i o n f o r order o f r e a c t i o n w i l l be most important f o r the
p r e d i c t i o n of the combustion of r e c y c l e d f i n e s which are i n the
s i z e range i n which chemical k i n e t i c s dominate and f o r p r e d i c t i n g
the performance o f p r e s s u r i z e d f l u i d i z e d beds.


86
Pore S t r u c t u r e . The chars produced from coals are h i g h l y

porous, w i t h i n t e r n a l surface areas of 100 to 1000 m^/g, and pore
r a d i i ranging from nanometer to micron i n s i z e . Models of
i n c r e a s i n g s o p h i s t i c a t i o n have been developed to describe the
r e a c t i o n i n porous chars (65-71) which a l l o w f o r d i f f u s i o n and
chemical r e a c t i o n , pore s i z e d i s t r i b u t i o n , and v a r i a t i o n i n pore
s i z e w i t h i n c r e a s i n g extent of r e a c t i o n . The added refinements are
not needed f o r purposes of c a l c u l a t i n g char burnout times f o r
most of the carbon i n AFBC's, since the e x t e r n a l r e s i s t a n c e
c o n s t i t u t e s a s i g n i f i c a n t f r a c t i o n of the t o t a l r e s i s t a n c e .
Use
of such models are, however, d e s i r a b l e when examining d e t a i l s of
secondary r e a c t i o n s such as those that i n f l u e n c e p o l l u t a n t forma
t i o n which occur w i t h i n the pores, or i n e v a l u a t i n g the e f f e c t of
pore s t r u c t u r e on a t t r i t i o n and fragmentation r a t e s .
P a r t i c l e Temperature Overshoot. The temperature of the burn
ing char p a r t i c l e s w i l l run h o t t e r than that of the bed by amounts
that depend upon p a r t i c l e s i z e , r e a c t i v i t y , bed temperature. I t i s
determined i n p a r t by the heat r e l e a s e d at the p a r t i c l e surface
due to r e a c t i o n and i n part to the a d d i t i o n a l heat released by
carbon monoxide o x i d a t i o n near the p a r t i c l e surface (54-58).
Measurements f o r 1.8 to 3.2 m i l l i m e t e r s i z e coke p a r t i c l e s burning
i n a f l u i d i z e d band of sand at 1173 increased from the bed temp
erature at low oxygen concentrations to values 150 to 200 above
the bed temperature f o r oxygen concentrations approaching that of
a i r (72). E s t i m a t i o n of t h i s temperature r i s e i s important f o r
purposes of e v a l u a t i n g the NO/C r e a c t i o n and a l s o f o r p r e d i c t i o n
of the burnout times of f i n e s .
Carbon Monoxide Oxidation. A n a l y s i s of the carbon monoxide
o x i d a t i o n i n the boundary l a y e r of a char p a r t i c l e shows the pos
s i b i l i t y f o r the existence of m u l t i p l e steady s t a t e s (54-58).
The
importance of these at AFBC c o n d i t i o n s i s u n c e r t a i n . From the
theory one can a l s o c a l c u l a t e that CO w i l l burn near the surface
of a p a r t i c l e f o r l a r g e p a r t i c l e s but w i l l react outside the
boundary l a y e r f o r s m a l l p a r t i c l e s , i n q u a l i t a t i v e agreement w i t h
experimental observations.
Q u a n t i t a t i v e agreement w i t h theory
would not be expected, s i n c e the t h e o r e t i c a l c a l c u l a t i o n s , are
based on the use of g l o b a l k i n e t i c s f o r CO o x i d a t i o n . Hydroxyl
r a d i c a l s are the p r i n c i p a l oxidant f o r carbon monoxide and i t can
be shown (73) that t h e i r concentration i s lowered by r a d i c a l r e
combination on surfaces w i t h i n a f l u i d i z e d bed.
I t i s therefore
expected that the CO o x i d a t i o n rates i n the dense phase of f l u i d
i z e d beds w i l l be suppressed to l e v e l s considerably below those
i n the bubble phase. This expectation i s supported by s t u d i e s of
combustion of propane i n f l u i d i z e d beds, where i t was observed
that i g n i t i o n and combustion took place p r i m a r i l y i n the bubble
phase (74). More a t t e n t i o n needs to be given to the e f f e c t of bed
s o l i d s on gas phase r e a c t i o n s occuring i n f l u i d i z e d r e a c t o r s .

4.
SAROFiM
87
A s h - D i f f u s i o n C o n t r o l . A U.S. c o a l contains on the average

about 10 percent by weight of m i n e r a l c o n s t i t u e n t s . These y i e l d
an ash during combustion which tends t o accumulate on the surface
of the receding char. Since AFBC s operate below the f u s i o n temperature of ash, the ash e i t h e r f l a k e s o f f as the carbon surface
recedes or forms a h i g h l y porous, l o o s e l y - s i n t e r e d , f r i a b l e cage
about the char. In p r i n c i p l e , the ash l a y e r should r e t a r d the
r a t e of char combustion (34) but the experimental evidence t o date
suggests that i t s e f f e c t i s s m a l l i n determining o v e r - a l l burning
r a t e s . I t may, however, i n f l u e n c e the l a t t e r stages of combustion
and the achievement of h i g h carbon burnout.

P a r t i c l e Fragmentation. An added complication i n the modell i n g of c o a l combustion i s provided by the d e v o l a t i l i z a t i o n step,

which determines the y i e l d of the char, i t s p o r o s i t y , p a r t i c l e
s i z e , and p a r t i c l e number. M a s s i m i l l a and coworkers (41) have
measured the c o a l fragments produced during p y r o l y s i s . I n d i r e c t
evidence f o r fragmentation of various chars during combustion was
a l s o provided by Campbell and Davidson (75) who a t t r i b u t e d the
d e v i a t i o n of the p a r t i c l e s i z e d i s t r i b u t i o n during the combustion
of char p a r t i c l e s of uniform i n i t i a l s i z e from the p r e d i c t e d s i z e
d i s t r i b u t i o n given by Eq. 11 as b e i n g due t o fragmentation.
Although a complete model f o r s i n g l e p a r t i c l e burning requires
d e t a i l e d i n f o r m a t i o n on p h y s i c a l parameters, such as pore s t r u c t u r e
and chemical parameters, such as i n t r i n s i c r e a c t i v i t i e s o f char/
oxygen, the near dominance o f the e x t e r n a l d i f f u s i o n r e s u l t s i n
good agreement being obtained between the p r e d i c t i o n s o f burning
times obtained using r e l a t i v e l y simple models and experimental
r e s u l t s . The d e t a i l e d models w i l l prove u s e f u l i n r e s o l v i n g
i s s u e s that cannot be addressed by simpler models, such as the
importance of h i g h i n t e r n a l CO concentrations on the augmentation
of the reduction of NO by char, on the e f f e c t o f e v o l v i n g pore
s t r u c t u r e on a t t r i t i o n and fragmentation, and on where CO
combustion occurs.
V o l a t i l e E v o l u t i o n (Coal Feed L o c a t i o n )
Most models o f f l u i d i z e d - b e d combustors have been developed
for chars on cokes w i t h n e g l i g i b l e v o l a t i l e content o r , i f address i n g c o a l s , have t r e a t e d the v o l a t i l e e v o l u t i o n as being e i t h e r
instantaneous o r uniformly d i s t r i b u t e d throughout the f l u i d i z e d
bed. The c o a l d e v o l a t i l i z a t i o n step i s , however^ of major
importance t o the operation o f AFBC s s i n c e the c o a l must be d i s t r i b u t e d throughout a bed i n a manner that ensures t h a t the
v o l a t i l e s w i l l have access t o s u f f i c i e n t a i r f o r t h e i r complete
oxidation.
I f the v o l a t i l e r e l e a s e r a t e i s slow r e l a t i v e t o the rate of
s o l i d c i r c u l a t i o n , the assumption of uniform v o l a t i l e r e l e a s e
would be j u s t i f i e d . Estimates of the v o l a t i l e r e l e a s e r a t e may be
obtained from the e x t e n s i v e l i t e r a t u r e on c o a l p y r o l y s i s (76).
T


88
Using the data of Howard and coworkers (77) Borghi et a l (59) have
modeled the v o l a t i l e r e l e a s e rate f o r AFBC c o n d i t i o n s . Their pred i c t i o n f o r both the duration of a v o l a t i l e flame and the subsequent char burnout times have been confirmed by the experimental
measurements of Andrei (78). Sample r e s u l t s are shown i n Figure
8, which presents the c a l c u l a t e d ( s o l i d l i n e ) and measured (data
p o i n t s ) weight l o s s of
3 m i l l i m e t e r p a r t i c l e s burned i n 5 percent oxygen stream i n a f l u i d i z e d bed maintained a t 1173 K.
The
i n i t i a l steep drop i n weight i s due to v o l a t i l e e v o l u t i o n , and i t
i s followed by the slower char burnout stage. T h i r t y percent of
the weight of coal i s l o s t i n a p e r i o d of a l i t t l e under 4 seconds
for the 3 mm p a r t i c l e . For 1 mm p a r t i c l e s the time f o r d e v o l a t i l i z a t i o n i s under 1 second. These times can be compared w i t h the
estimates of the s o l i d c i r c u l a t i o n time of 3 to 6 seconds obtained
above. The v o l a t i l e r e l e a s e time i s therefore comparable to the
s o l i d c i r c u l a t i o n time and n e i t h e r the model of instantaneous or
distributed v o l a t i l e release i s v a l i d .
Park et a l (42) recognized the importance of modeling the
v o l a t i l e release i n AFBC s and developed a plume model based on
the instantaneous r e l e a s e of v o l a t i l e s and l a t e r a l d i f f u s i o n using
a d i f f u s i v i t y based on t r a c e r d i s p e r s i o n . Their model succeeded
i n showing the major importance of l a t e r a l d i f f u s i o n w i t h i n AFBC*s
i n determining feed p o i n t l o c a t i o n . Stubingdon and Davidson (79)
however showed that the combustion of hydrocarbons, which are a
v a l i d surrogate f o r c o a l v o l a t i l e s , i s governed by molecular d i f f u s i o n which i s considerably lower than the r a d i a l d i f f u s i o n
obtained from t r a c e r s t u d i e s .
(The t r a c e r s t u d i e s apparently
provide a measure of the meandering of a laminar stream without
mixing at the molecular l e v e l needed f o r r e a c t i o n ) . The mechanism
for r a d i a l d i s p e r s i o n i s due to
s o l i d and not gas d i f f u s i o n .
A s l i g h t v a r i a n t on the plume model of Park et a l (42) i s shown
i n F i g . 9. Coal p a r t i c l e s i n j e c t e d a t the bottom of the bed are
convected upward and d i f f u s e r a d i a l l y as a consequence of bubble
motion. V o l a t i l e s w i l l be r e l e a s e d at a decaying r a t e f o r s e v e r a l
seconds, depending upon p a r t i c l e s i z e and bed temperature. The
radius r of the c r o s s - s e c t i o n over which the v o l a t i l e s are r e leased i s determined by the s o l i d d i f f u s i v i t y P .
To a f i r s t
approximation
1
r = ifuZt
(25)
The c o r r e l a t i o n proposed by K u n i i and L e v e n s p i e l (34) w i l l be here

used to obtain an estimate f o r f}
3
(26)
The mechanism of s o l i d d i s p e r s i o n i s complex and p o o r l y understood so that Eq. 26 represents only a f i r s t approximation. For


4.
SAROFiM
89
Figure 8. Time-resolved values o f the f r a c t i o n a l weight r e t e n t i o n

o f c o a l p a r t i c l e s i n i t i a l l y 3 mm i n diameter burned i n a f l u i d i z e d
bed at 1173 and an oxygen c o n c e n t r a t i o n o f 5 percent. S o l i d
l i n e c a l c u l a t e d from t h e o r y , data p o i n t s experimental.
F i g u r e 9 Schematic e l e v a t i o n and p l a n views o f v o l a t i l e plume

formed by c o a l i n j e c t e d at base o f bed.

90
a v o i d volume of 0,3, a mean bubble diameter of 0.5, the value

of Vs = 0.03 m^/s.
The time f o r the bubble to r i s e to the surface
we have p r e v i o u s l y shown to be of the order of 1.5 to 3 second.
Consequently r - 0.4 to 0.6 m.
The spacing of c o a l feed p o i n t s (Figure 9) should be such
that the a i r f l o w i n g i n the c r o s s - s e c t i o n r^ of the v o l a t i l e
plume should be s u f f i c i e n t to o x i d i z e the v o l a t i l e s . The f r a c t i o n
f of the s t o i c h i o m e t r i c a i r requirement needed to consume the
v o l a t i l e s w i l l depend upon the v o l a t i l e y i e l d and composition (76,
79 80). A t y p i c a l value f o r f i s about 0.4.
A f r a c t i o n f of
about 0.1 of the s t o i c h i o m e t r i c a i r i s used to t r a n s p o r t the c o a l .
The oxygen requirements of the v o l a t i l e s i s then s a t i s f i e d when
v

2 f -f
Trr _ y a
2~
1+e
(27)
For the values s e l e c t e d above i s 1.4 to 2.1 m.

This estimate
agrees w i t h current commercial p r a c t i c e of spacing feed p o i n t s
at i n t e r v a l s of 1 to 3 m. For our t e s t case, t h i s corresponds to
one c o a l feed p o i n t f o r every 1.8 to 4 MW, or approximately 25 to
55 feed p o i n t s . The requirement f o r a l a r g e number of feedpoints
i s one of the shortcomings of AFBC s. Methods of overcoming the
problem of m u l t i p l e feed p o i n t s i n c l u d e the use of a spreaders t o k e r to d i s t r i b u t e the c o a l evenly over the surface of the bed
or the promotion of l a t e r a l mixing by r e c i r c u l a t i n g bed s o l i d s .
1
Emissions of Nitrogen Oxides (Staging of A i r A d d i t i o n )

1
One of the advantages of AFBC s i s that t h e i r emissions of

n i t r o g e n oxides can be c o n s i d e r a b l y lower than corresponding
values from p u l v e r i z e d c o a l f i r e d b o i l e r s . The n i t r o g e n oxides
are produced p r i m a r i l y by the o x i d a t i o n of n i t r o g e n o r g a n i c a l l y
bound i n the c o a l (82, 83). Rapid conversion of the f u e l bound
n i t r o g e n occurs near the d i s t r i b u t o r place w i t h peak l e v e l s of
1000 ppm NO and higher being observed.
The NO concentration then
decays as a consequence of both heterogeneous and homogeneous
reactions.
AFBC's operate i n the temperature regime i n which ammonia
reacts s e l e c t i v e l y w i t h NO i n the presence of oxygen (84):
NH
+ NO + 1/4
=
2
+
2
3 / 2
28>
( *
Ammonia i s evolved w i t h the c o a l v o l a t i l e s and may be t h e r e f o r e

p a r t i a l l y r e s p o n s i b l e f o r the reduction of NO that occurs i n
AFBC's. Because of the i n h i b i t i o n of f r e e r a d i c a l r e a c t i o n s w i t h
i n the bed t h i s r e a c t i o n i s expected to be most important i n bub
b l e s and i n the s o l i d disengaging height above the bed.
This
importance of the NII3/NO r e a c t i o n and i t s p a r t i a l suppression by
bed s o l i d s has been demonstrated by the i n j e c t i o n of N H 3 i n t o

4.
SAROFiM
91
d i f f e r e n t p o s i t i o n s w i t h i n a f l u i d i z e d bed combustor (85). These

experiments showed that the NO r e d u c t i o n was most e f f e c t i v e when
the ammonia was i n j e c t e d d i r e c t l y above the bed.
Several heterogeneous r e a c t i o n s c o n t r i b u t e t o the r e d u c t i o n
of NO i n AFBC's. Carbon w i l l reduce NO d i r e c t l y :
(1 - )NO + C = 1/2 N
+ xCO + ( l - x ) C 0
(29)
The r a t e o f the r e a c t i o n (86-90) i s about two orders of magnitude

slower than the O2/C r e a c t i o n , c o n s i s t e n t w i t h the greater
strength o f the NO bond than that i n 0 . The C0/C0 r a t i o i n the
products of the r e a c t i o n increases w i t h i n c r e a s i n g temperature
(86, 87). At low temperatures (850 ) , a s t a b l e chemisorbed
oxygen compled (86) forms and i n h i b i t s the r e a c t i o n . At AFBC
temperatures, however, i t has been observed that the r e a c t i o n i s
a c c e l e r a t e d i n the presence o f oxygen (91). This l a t t e r r e s u l t
may be a consequence o f the increase i n the CO concentration w i t h
i n a char p a r t i c l e as the 0 concentration i s r a i s e d . Because the
O2/C r e a c t i o n i s so much f a s t e r than the NO/C o r the carbon
c a t a l y z e d CO/NO r e a c t i o n (86, 91), the s i t u a t i o n e x i s t s i n which
the e f f e c t i v e n e s s f a c t o r f o r the O2/C r e a c t i o n i s s m a l l and l i t t l e
O 2 p e n e t r a t i o n i n t o char occurs a t a time when the e f f e c t i v e n e s s
f a c t o r f o r the NO reduction r e a c t i o n s are near u n i t y . A d d i t i o n a l
NO reduction r e a c t i o n s that may occur are the CO/NO r e a c t i o n
c a t a l y z e d by bed s o l i d s (90 - 92) and the reduction of NO by
s u l f i t e - c o n t a i n i n g , p a r t i a l l y s u l f a t e d limestone (93).

CaS0 + NO = CaS0 + 1/2 N

3
(30)
A complete modeling of NO formation i n AFBC s i s a formidable

task, depending upon the knowledge of the (1) d e v o l a t i l i z a t i o n
chemistry and k i n e t i c s of f u e l n i t r o g e n which determines the
d i s t r i b u t i o n of n i t r o g e n between char n i t r o g e n , ammonia, and other
s p e c i e s , ( i i ) the k i n e t i c s o f formation o f NO by the o x i d a t i o n of
the products o f d e v o l a t i l i z a t i o n , ( i i i ) the k i n e t i c s of reduction
of NO by NH , C, CO, and CaS0 . In order t o solve f o r the NO
concentration one needs t o a l s o determine the concentration of
C, CO, and CaSO^ i n the bed and f o r the temperature overshoot by
the carbon. Because o f the many chemical r e a c t i o n s i n v o l v e d , and
the a d d i t i o n a l complexity introduced by the f l u i d mechanics,
models of NO formation i n beds are only p a r t i a l . Several have
been developed which adequately c o r r e l a t e a v a i l a b l e experimental
data (94-98) but t h e i r p r e d i c t i v e c a p a b i l i t y i s yet to be proven.
The understanding o f the dominant mechanism f o r NO formation and
r e d u c t i o n can, however, guide the s e l e c t i o n of appropriate c o n t r o l
s t r a t e g y . For example, the NO reduction by char can be a c c e l e r
ated by i n c r e a s i n g the carbon l o a d i n g i n the bed by s t a g i n g the
a i r a d d i t i o n (99-100). But s t a g i n g the oxygen w i l l increase the
carbon l o a d i n g and correspondingly the formation o f carbon f i n e s ,
so that the reduction i n NO may be a t the expense of an increase
i n carbon l o s s o r an increase i n r e c y c l e of t i n e s .
3

92
ENGINEERING
Freeboard Reactions (Determination of Freeboard Height)

A height of three to four meters above the bed i s r e q u i r e d
to a l l o w s o l i d s e n t r a i n e d by the bubble wakes i n t o the freeboard
to r e t u r n to the bed s u r f a c e . The i n i t i a l v e l o c i t y of the s o l i d s
that splash i n t o the freeboard i s 4 to 8 times the bubble r i s e
v e l o c i t y (100) and the freeboard height i s determined by the
k i n e t i c energy of the l a r g e r p a r t i c l e s f o r which drag forces are
r e l a t i v e l y unimportant. For a bubble r i s e v e l o c i t y of 3.2 m/s
(estimated from u - u f + 0.7l/gd^ (29) and a bubble diameter of
0.5 m), the maximum h e i g h t obtained by a p a r t i c l e w i t h an i n i t i a l
v e l o c i t y s i x times the bubble r i s e v e l o c i t y i s 4.3 m, a t y p i c a l
h e i g h t s e l e c t e d f o r the freeboard.
The s o l i d concentration i n the freeboard i s s u f f i c i e n t l y h i g h
to c o n t r i b u t e s i g n i f i c a n t l y to the r e a c t i o n s occuring i n AFBC's.
Reactions of p a r t i c u l a r importance are those between NO and char,
the burnout of carbon monoxide, and the combustion of the r e c y c l e d
f i n e s . Space i s not a v a i l a b l e to cover the s u b j e c t adequately
and the reader i s r e f e r r e d to s e l e c t e d l i t e r a t u r e on the subject
(101-104). I t i s of i n t e r e s t to n o t e , however, that the e l u t r i a t i o n r a t e of l a r g e r p a r t i c l e s has been found to be g r e a t l y
augmented by the concentration of f i n e s (103) i n a bed, so that
the r e c y c l e of f i n e s may i n f l u e n c e bed behavior i n an unobvious
manner.

Impact of Immersed Tubes on Flow Regimes

In the above attempt to provide an order-of-magnitude e s t i mate of the f a c t o r s c o n t r o l l i n g the design and operation of AFBC s
gross approximations were made, p a r t i c u l a r l y i n e s t i m a t i n g some
of the flow and mixing parameters. A number of the c o r r e l a t i o n s
used were derived from the l i t e r a t u r e on b u b b l i n g beds of f i n e
p a r t i c l e s . I t must be emphasized that the flow regimes i n beds
of coarse p a r t i c l e s d i f f e r from those i n beds of f i n e p a r t i c l e s
(105, 106) and that t h i s must be taken i n t o c o n s i d e r a t i o n i n the
s e l e c t i o n of the most r e l e v a n t models.
The e a r l y s t u d i e s of flow i n coarse p a r t i c l e systems was f o r
beds without immersed tubes (107, 108). More recent s t u d i e s have
shown that the f l u i d mechanics and gas and s o l i d mixing can be
considerably i n f l u e n c e d by the presence of tubes i n the bed (109114).
The e f f e c t of tubes i n the bed i s t o decrease the pressure
f l u c t u a t i o n s , presumably due to a r e d u c t i o n i n the s i z e of the
bubbles. The net consequence of t h i s would be to i n c r e a s e the
importance of the slow or c l o u d l e s s bubble regime (see Figure 4 ) .
The data of F i t z g e r a l d , L e v e n s p i e l and co-workers (109) show that
the impact of tubes i s to reduce the d i s p e r s i o n of gas due to the
meandering of a t r a c e r gas plume but to increase the d i f f u s i o n
due to t u r b u l e n t mixing. This augmentation of mixing by the tubes
should be taken i n t o account i n the modeling of v o l a t i l e combustion.
T

4.
SAROFiM
93
Although general treatments o f the flow i n f l u i d i z e d beds o f

coarse p a r t i c l e s , i n view of the d i f f i c u l t y o f the problem, w i l l
only evolve s l o w l y , there have been some promising developments.
These i n c l u d e the success achieved i n c o r r e l a t i n g heat t r a n s f e r
data (7_, 113, 114) and the development o f s c a l i n g parameters t h a t
permit the use o f c o l d flow models t o study many of the c h a r a c t e r
i s t i c s o f AFBC s (114,115),
1
Concluding Comments
The above c o n s i d e r a t i o n o f the f a c t o r s that govern the
design and operation o f the f i r s t generation of AFBC s provide
an a p p r e c i a t i o n f o r the parameters t h a t c o n s t r a i n t h e i r perform
ance. There i s c l e a r l y opportunity f o r improvement, p a r t i c u l a r l y
w i t h respect t o reducing the amounts o f sorbent used f o r s u l f u r
capture, reducing the number of c o a l feed p o i n t s , reducing the
l o s s o f carbon f i n e s , and changing heat l o a d without v a r y i n g bed
temperature. A number o f f l u i d i z e d bed combustors o f advanced
design have been developed o r are under i n v e s t i g a t i o n . These
i n c l u d e f a s t f l u i d i z e d beds, p r e s s u r i z e d beds, m u l t i - s t a g e beds,
c i r c u l a t i n g beds, and r o t a t i n g beds. The f a s t - f l u i d i z e d r e
c i r c u l a t i n g bed i s f u r t h e s t developed of those advanced concepts,
and has already been commercialized.
From a fundamental standpoint, the order o f magnitude e s t i
mates of many o f the parameters i n the bed was intended t o
i n d i c a t e which processes were important.
There i s c l e a r l y a need
f o r a b e t t e r understanding o f the processes that govern ( i ) par
t i c l e c i r c u l a t i o n and e l u t r i a t i o n i n l a r g e p a r t i c l e systems,
( i i ) g r a i n growth f o r purposes o f improving stone u t i l i z a t i o n ,
( i i i ) the generation and burnout o f f i n e carbon p a r t i c l e s .
An attempt was made i n the p r e s e n t a t i o n t o show the complex
i n t e r a c t i o n between the d i f f e r e n t processes occuring i n the bed.
For example, sorbent u t i l i z a t i o n may a f f e c t N 0 through the
formation o f CaSO^ and bed pressure drop through the dependence of
s o l i d d e n s i t y on extent of s u l f a t i o n ; carbon burning times deter
mine the carbon l o a d i n g i n the bed which i n turn governs both
the amount of f i n e char p a r t i c l e generation and the r e d u c t i o n of
NO; the carbon f i n e s i n f l u e n c e the e l u t r i a t i o n r a t e s of coarser
p a r t i c l e s ; the carbon monoxide i n f l u e n c e s the carbon p a r t i c l e
temperature overshoot and a l s o p a r t i c i p a t e s i n the surface c a t a
l y z e d r e d u c t i o n o f NO. Such i n t e r a c t i o n s add t o the challenges
of modeling t h i s c l a s s o f chemical r e a c t o r s .

Legend of Symbols
bed c r o s s e c t i o n a l area, m
spacing between c o a l feed p o i n t s , ra
Cp
i n l e t oxygen c o n c e n t r a t i o n , mole/m
average oxygen concentration i n emulsion phase, mole/m
Continued on next page

94
Legend o f SymbolsContinued

t o t a l gas-phase molal c o n c e n t r a t i o n mole/m
d^
bubble diameter, m
d^
i n i t i a l diameter of char p a r t i c l e , m
dp
bed p a r t i c l e diameter, m
d*
diameter of p a r t i c l e s w i t h t e r m i n a l v e l o c i t y lower than

fluidizing velocity, m
gas-phase d i f f u s i v i t y , m /s
2
d i f f u s i o n c o e f f i c i e n t s f o r s o l i d s i n emulsion phase, m /s
V
V
excess a i r , f r a c t i o n of s t o i c h i o m e t r i c
f r a c t i o n of s t o i c h i o m e t r i c
coal feed
oxygen requirement to completely combust the v o l a t i l e s ,

f r a c t i o n o f s t o i c h i o m e t r i c a i r requirement
F^
a i r requirement
a i r used as c a r r i e r gas f o r
c o a l feed r a t e , Kg/s
s o l i d s withdrawal r a t e , Kg/s
2
grativational acceleration,
m/s
height of bed, m
convective heat t r a n s f e r c o e f f i c i e n t i n Equation 8, W/(m )(C)
2
h^
r a d i a t i v e heat t r a n s f e r coefficient,W/(m )(C)
-^
k
K(R)
heat of combustion, J/Kg

c o e f f i c i e n t of a t t r i t i o n defined by Equation 20, dimension
less
e l u t r i a t i o n constant f o r p a r t i c l e s of s i z e R, s
r a t e constant f o r the S0 /Ca0 r e a c t i o n ,
2
o
cm/s
f r a c t i o n of calcium converted t o the s u l f a t e
m^
value of m approached a s y m p t o t i c a l l y a t l o n g times
rate of carbon l o s s from the bed, Kg/s. S u b s c r i p t s s, e,

and a r e f e r t o l o s s w i t h s o l i d s w i t h d r a w a l , by e l u t r i a t i o n ,
and by a t t r i t i o n r e s p e c t i v e l y

4.
SAROFiM
95
m
c o a l feed r a t e , Kg/s
c o a l feed r a t e needed t o supply power f o r a i r fans, Kg/s
r a t e of s o l i d s withdrawal from bed, Kg/s
p(R)
f r a c t i o n o f mass of c o a l i n s i z e range R t o R + dR, m ^~

(R) p(R) f o r c o a l feed stream, m ^

2
pressure drop across bed, N/m
radius of v o l a t i l e plume, m
p a r t i c l e radius, m
R^
p a r t i c l e r a d i u s o f monodisperse feed, m
Re
Reynolds number based on v e l o c i t y
r a t e of change of p a r t i c l e r a d i u s , m/s
Sc
Schmidt number
Sh
t
t
Sherwood number
residence time, s
p a r t i c l e burnout time, s
absolute temperature, K. S u b s c r i p t s b, w r e f e r t o bed and
tube w a l l temperature, r e s p e c t i v e l y
u^
bubble r i s e v e l o c i t y , m/s
u
U
u
m
i n
emulsion phase
minimum f l u i d i z i n g v e l o c i t y , m/s
mr
f l u i d i z i n g v e l o c i t y , m/s
p a r t i c l e t e r m i n a l v e l o c i t y , m/s
3
v o l u m e t r i c a i r supply per u n i t mass o f c o a l , m /Kg

carbon mass i n the bed. Kg
c
W
t o t a l mass o f the bed, Kg
^2
mole f r a c t i o n of oxygen
r a t i o of wake to bubble volume
f r a c t i o n of bed volume occupied by bubbles

96
CHEMICAL
REACTION
ENGINEERING
bed v o i d f r a c t i o n
mf
v o i
d f r a c t i o n a t minimum f l u i d i z i n g v e l o c i t y
f r a c t i o n a l e f f i c i e n c y o f conversion of thermal t o e l e c t r i c a l
energy
fan e f f i c i e n c y
3
carbon d e n s i t y , Kg/m
3

bed s o l i d d e n s i t y , Kg/m
s
2
4
Stefan-Boltzmann constant, W/(m )(K )
c h a r a c t e r i s t i c h e a t i n g time o f p a r t i c l e s , s
Acknowledgments
The above overview has drawn on background developed as p a r t
of an i n t e r d i s c i p l i n a r y program on f l u i d i z e d bed combustion a t MIT
funded by DOE, w i t h p a r t i a l support from Stone and Webster E n g i
n e e r i n g Corp, The authors i s indebted t o h i s students and c o l
leagues f o r h i s education on many aspects o f the problem especially
to Janos M. Beer, C h r i s t o s Georgakis, and Leon R. Glicksman whose
views are r e f l e c t e d , a l b e i t through a g l a s s d a r k l y , i n the paper.
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Borghi, G.G.; Sarofim, A . F . ; Ber, J.M. AIChE 10th Annual
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Ross, I . B . ; Davidson, J . F . Trans I Chem 1979, 57, 215.
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Froberg, R.W.; Essenhigh, R. Seventeenth Symposium (Inter
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Calleja, G . ; Sarofim, A . F . ; Georgakis, C. Chem. Eng. S c i .
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Gavalas, G.R. AIChE J 1980, 26,
577-536.
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1982, 21, 1-12.
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Fifteenth Symposium (International) on Combustion 1975,
pp 1303-1316.
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Solomon, P.R.; Colket, M.B. Ibid pp 131-140.
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Schoffstoll,
C.B. Argonne National Laboratory Annual Report
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Fifteenth Symposium (International) on Combustion 1975,
pp 1149-1155.
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Hampartsoumian, E.; Gibbs, B.M. Nineteenth Symposium (Inter
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Levy, J.M.; Chan, L.K.; Sarofim, A.F.; Ber, J.M. Eighteen
Symposium (International) on Combustion 1981, pp 111-120.
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1980, 20, 293-244.
Kunii, D.; Wu, K.T.; Furasawa, T. Chem. Eng. Sci. 1980, 35,
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de Soete, G.G.; Revue Gnrale de Thermique, 1980, 19, 545.
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1982, 196, 347-357.
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Fluidized-Bed Coal Combustion Processes" ASME Winter Ann.
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x

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94.
Horio, M.; Mori S.; Muchi, I. Proc. 5th FBC Conference

1977, II, PP 605-623.
95. Pereira, F.J.; Ber, J.M., 2nd European Symposium on
Combustion 1975, 339.
96. Ber, J.M.; Sarofim, A.F.; Lee, Y.Y. J. Inst. Energy
1981, 54, 38-47.
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Fluidized Bed Combustion 1980, III, pp 773-783.
98. Walsh, P.M.; Chaung, T.Z.; Dutta, .; Ber, J.M.; Sarofim,
A.F. Nineteenth Symposium (International) on Combustion,
1983, pp 1281-1289.
99. Gibbs, B.M.; Pereira, F.J.; Ber, J.M. Sixteenth
Symposium (International) on Combustion 1977, pp 461-472.
100. George, S.E.; Grace, J.R. AIChE Symposium Series 1978, 176
(74), 67-74.
101. Wen, C.Y.; Chen, L.H. AIChE J. 1982, 28, 117-128.
102. Yates, J.G.; Rowe, P.N. Trans. Inst. Chem. Engrs. 1977, 55,
137-142.
103. Geldart, D.; Cullinan, J.; Georghiades, S.; Gilvray, D.;
Pope, D.J. Trans. I Chem. E 1979, 57, 269-275.
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Conf. on Fluidized Bed Combustion 1982, II, 1054.
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1978, 24, 543-546.
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R.E. Trans. Inst. Chem. Eng.
1971, 49, 70-79.
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T.J.;
Levenspiel, O. "Fluidization", Grace, J.R.; Matsen, J.M.,
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74, 54
111. Fitzgerald, T.J.; Catipovic, N.; and Jovanovic, G.
Proceeding of Fifth International Conference on Fluidized
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RECEIVED May 2,
1983

5
Current Problems in Polymerization Reaction
Engineering
W. HARMON R A Y

University of Wisconsin, Department of Chemical Engineering, Madison, WI 53706
Polymerization reaction engineering is an important area in the process industry with many diverse
and challenging design problems. In this survey, an
introduction to some of the key design d i f f i c u l t i e s
is followed by several specific examples i l l u s t r a t ing some of the intriguing and exotic phenomena
arising routinely in polymerization reactors. A
survey of the recent literature indicates a strong
upsurge of interest in these problems.
C u r r e n t l y some 200 b i l l i o n l b s (~100 m i l l i o n m e t r i c tons) per

year of s y n t h e t i c polymers a r e produced i n the world i n a wide
v a r i e t y of p o l y m e r i z a t i o n r e a c t o r s . The world c a p a c i t y and
expected r a t e of growth of the 10 l a r g e s t volume polymers i s shown
i n Table I . The u l t i m a t e use of these products ranges from
s y n t h e t i c c l o t h i n g t o l a t e x p a i n t s . The t o t a l world sales of the
raw polymer i s now approaching $100 b i l l i o n / y e a r and the s a l e s of
the f i n a l product a f t e r p r o c e s s i n g , molding, compounding, e t c . i s
many times t h i s f i g u r e . Thus the f i e l d of p o l y m e r i z a t i o n r e a c t i o n
engineering i s of s i g n i f i c a n t economic importance.
Up u n t i l a decade or two ago, polymers were l a r g e l y s p e c i a l i t y
m a t e r i a l s , manufactured i n batch r e a c t o r s from f a i t h f u l l y f o l l o w e d
r e c i p e s scaled up from the chemists beaker. However, w i t h the
growth of demand and increased p r i c e competition ( p a r t i c u l a r l y
f o r h i g h volume commodity polymers), more e f f i c i e n t p o l y m e r i z a t i o n
methods have been r e q u i r e d . Manufacturers of h i g h volume polymers
are now moving t o fewer product l i n e s , more uniform product and
the use of continuous r e a c t o r s . S i m i l a r l y , producers of
r e l a t i v e l y low volume, h i g h q u a l i t y (and value) polymers are f i n d ing that t h e i r c o m p e t i t i v e edge comes from a deeper understanding
of the r e l a t i o n s h i p between p o l y m e r i z a t i o n c o n d i t i o n s and product
quality.
Although t h i s change from t r a d i t i o n a l p o l y m e r i z a t i o n methods
r e q u i r e s a much b e t t e r understanding of the p h y s i c a l and chemical
0097-6156/83/0226-0101$09.25/0
102
Table I. World Capacity and Expected Growth of Largest Volume

P l a s t i c s (1_)
Rank
Capacity, millions

1980s 1981
Resin
Mid-1980s
of l b per yr.
1981
Change
P o l y e t h y l e n e , low-density
38,047
31,702
20.0%
Polyvinyl chloride
35,339
32,430
8.9
Polyethylene, high-density
22,895
18,071
26.7
Polypropylene
17,809
15,631
13.9
Polystyrene
17,626
16,491
6.9
10
P o l y e t h y l e n e , l i n e a r low-density
8,081
2,669
202.8
Acrylonitrile-butadiene-styrene
4,662
4,374
6.6
Isocyanates
4,270
3,634
17.4
Polyols*
4,255
4,246
0.2
10
Unsaturated
3,538
3,516
0.6
Other
TOTAL
polyesters
8,006
7,359
164,528
140,123
8.8
17.4%
a Used as i n d i c a t o r s f o r d e r i v a t i v e polyurethanes.
b includes a c r y l i c s ,
amino r e s i n s , c e l l u l o s i c s , f l u o r o p o l y m e r s , p h e n o l i c s , p o l y a c e t a l s ,
p o l y c a r b o n a t e s , polyphenylene o x i d e , s t y r e n e - a c r y l o n i t r i l e .
phenomena i n the polymerizing medium, (and t h i s r e q u i r e s the

s e r v i c e s of more w e l l - t r a i n e d p o l y m e r i z a t i o n r e a c t o r engineers),
the economic b e n e f i t s from such improved engineering can be
enormous. As only one example, new processes f o r l i n e a r lowdensity polyethylene (such as the continuous f l u i d i z e d bed process
of Union Carbide (2_)) present a t t r a c t i v e a l t e r n a t i v e s to the t r a d i t i o n a l high pressure processes. These new processes can operate
at 300-1000 p s i g rather than the t r a d i t i o n a l 30,000-50,000 p s i g
and thus can reduce the plant c a p i t a l expenditure by 50% and
energy consumption by 25%. This type of new low density p o l y ethylene process i s making s i g n i f i c a n t progress against the o l d e r ,
more w e l l e s t a b l i s h e d technology. Because polymerization r e a c t i o n
engineering i s a r e l a t i v e l y new f i e l d , i t seems probable that many
other t r a d i t i o n a l polymerization processes can be comparably
improved through the a p p l i c a t i o n of polymerization r e a c t i o n
engineering.
In preparing t h i s review of p o l y m e r i z a t i o n r e a c t i o n
engineering the author i s f o r t u n a t e that there have been so many
books and survey a r t i c l e s to appear i n the l i t e r a t u r e r e c e n t l y
( c f . Table II). These, taken together, provide good d e t a i l e d
coverage of the e s s e n t i a l s of the f i e l d ; t h e r e f o r e , extensive
delegation of d e t a i l w i l l be made to these surveys. Foremost

5.
RAY
103
Polymerization Reaction Engineering
Table I I . Some Recent Books and Survey A r t i c l e s on


Author(s)
T o
Reference
i c
Keane (1972)
Ray (1972)
K e i i (1972)
A l b r i g h t (1974)
Min and Ray (1974)
Gerrens (1976)
Bouton and Chappelear
(1976)
S i n g l e Phase P o l y m e r i z a t i o n
Mathematical M o d e l l i n g
Ziegler-Natta Polymerization
Polymerization Processes (Monograph)
Emulsion P o l y m e r i z a t i o n
P o l y m e r i z a t i o n Reactions and Reactors
Continuous Reactors (ed. volume)
Piirma
and Gardon
(1976)
Ray and Laurence (1977)
Poehlein and Dougherty
(1977)
Schildknecht and S k e i s t
(1977)
Henderson and Bouton
(1979)
Boor
(1979)
Gerrens (1980, 1981,
1982 )
Odian (1981)
Ray (19 81)
Bassett and Hamielec
(1982)
Piirma (1982)
E l - A a s s e r and
Vanderhoff
(1982)
Sebastian and
Biesenberger
Quirk (1983)
(ed. volume)
3
4
5
6
7
8
9
10
P o l y m e r i z a t i o n Reaction Engineering
Continuous Emulsion P o l y m e r i z a t i o n
11
12
P o l y m e r i z a t i o n Processes
13
P o l y m e r i z a t i o n Reactors
(ed. values)
(ed. volume)
14
O l e f i n Polymerization
P o l y m e r i z a t i o n Technology
15
16-18
Polymerization Kinetics
P o l y m e r i z a t i o n Reactor Dynamics
Emulsion P o l y m e r i z a t i o n (ed. volume)
19
20
21
22
23
(ed. volume)
(ed. volume)
P o l y m e r i z a t i o n Engineering
24
Ziegler-Natta Polymerization
25
(1983)
among these a r e the recent reviews of Gerrens beginning w i t h h i s

outstanding plenary l e c t u r e of the 1976 ISCRE meeting ( 8 ) . This
has been updated and expanded i n the recent chapter on polymerizat i o n technology (16) which has n e a r l y 500 r e f e r e n c e s . Just
r e c e n t l y Gerrens has summarized t h i s review i n a superb d i s c u s s i o n
of p o l y m e r i z a t i o n r e a c t o r s (17,18) . The novice j u s t beginning
work i n t h i s area, as w e l l as the experienced p o l y m e r i z a t i o n
r e a c t i o n engineer, w i l l both f i n d Gerrens surveys p r o f i t a b l e
reading.
In t h i s paper, we s h a l l f i r s t provide a broad brush
p e r s p e c t i v e of the f i e l d and then focus on some i n t e r e s t i n g unsolved problems which a r e the subject of current research.
1
P o l y m e r i z a t i o n K i n e t i c s and Reactor
Design
Much has been w r i t t e n about p o l y m e r i z a t i o n k i n e t i c s and the

e s s e n t i a l steps a r e shown i n Table I I I f o r the three p r i n c i p a l
types of mechanisms ( f r e e r a d i c a l , i o n i c and c o o r d i n a t i o n , and

104
Table I I I .
Major Classes of Polymerization Reactions
Monomer Addition:
A.
Free Radical
* 2R
1
\
kd
R
+ M
initiation
1
+ M
7~+ +1
*P
P
+A
P^g^tion
+M
f
^
M
^t^**
chain transfer
+ M^ disproportionate )
m ^
Vtermination
k
tc
" M_.
combination
(sometimes chain branching reactions also occur)

Ionic (anionic, cationic, coordination)
I
initiation
+ M
* n+l
propagation
(sometimes chain transfer or termination mechanisms also occur)

H.
Polymer Coupling (polycondensation, crosslinkLng)

P
m 1 n4m
propagation
condensation p o l y m e r i z a t i o n ) . However, there i s not comprehensive

understanding of the k i n e t i c s . o f even these simple polymerizations,
p a r t i c u l a r l y w i t h heterogeneous systems. The reader should cons u l t the surveys of Table I I f o r a d i s c u s s i o n of the remaining
i n t e r e s t i n g problems i n k i n e t i c s .
As important as k i n e t i c mechanism are the phase changes that
occur i n p o l y m e r i z a t i o n . Only a small f r a c t i o n of polymerizat i o n s are c a r r i e d out only i n one phase; thus thermodynamics,
heat and mass t r a n s f e r , and the k i n e t i c s of the phase change
i t s e l f a l l play a r o l e i n determining the p r o p e r t i e s of the
product polymer. Table IV i n d i c a t e s the p r i n c i p a l types of
k i n e t i c mechanisms and r e a c t i o n media which a r i s e i n polymerizat i o n r e a c t o r s . Each of these c l a s s e s of systems has i t s own
p e c u l i a r problems so that p o l y m e r i z a t i o n r e a c t o r design can o f t e n
be much more c h a l l e n g i n g than the design of r e a c t o r s f o r short
chain molecules.
To i l l u s t r a t e some of the c h a l l e n g i n g problems of polymeriza-


medium
2.
Suspension
c. P r e c i p i t a t i o n
( b u l k and
solution)
b.
Heterogeneous
a. E m u l s i o n
1. H o m o g e n e o u s
( b u l k and s o l u t i o n )
Reaction
K I N E T I C MECHANISMS AND
radical
Vinyl
(PVC)
polymers
V i n y l polymers
( S t y r e n e , PVC)
V i n y l polymers
( S t y r e n e , PVC)
V i n y l polymers
(Styrene,
LDPE)
Free
P o l y a m i d es
(Nylon
interfac i a l
poly . )
Polyesters,
Polyamides
(PET,
Nylon)
Polyethers
(Ethylene
ox i d e)
Polyacetals
(formaldehyde)
Vinyls
(iso-butylene-buty1
rubber)
Condensation
mechanism
Polyolef ins
with
insoluble
catalyst
( L i q u i d and
gas p h a s e
processes f o r
HDPE, L L D P E ,
polypropylene)
Polyolefins
with
soluble
catalyst
(ethylenepropylene
copolymers)
Coord i n a t i o n
Catalysis
I N P O L Y M E R I Z A T I O N REACTORS
Ionic
Kinetic
REACTION MEDIA EMPLOYED
TABLE IV


106
CHEMICAL
REACTION
ENGINEERING
t i o n r e a c t o r design, l e t us l i s t some of the issues which must be

faced:
1. K i n e t i c s and Phase Behavior - Table IV represents a
s i m p l i f i e d p i c t u r e of the s i t u a t i o n ; however, some
polymerizations go through s e v e r a l phase changes i n the
course of the r e a c t i o n . For example, i n the bulk polymeri z a t i o n of PVC, the r e a c t i o n medium begins as a low
v i s c o s i t y l i q u i d , progresses to a s l u r r y (the PVC polymer,
which i s i n s o l u b l e i n the monomer, p r e c i p i t a t e s ) , becomes
a paste as the monomer disappears and f i n i s h e s as a s o l i d
powder. As might be expected, modelling the k i n e t i c s of
the r e a c t i o n i n such a s i t u a t i o n i s not a simple exercise.
2. M a t e r i a l Mixing and Conveying - With such a v a r i e t y of
morphologies, there can be serious n o n - i d e a l i t i e s i n
micromixing and macromixing, p a r t i c u l a r l y at high conv e r s i o n s . Often a large amount of mechanical energy i s
required f o r mixing and conveying.
Sometimes, s t i c k i n g
and f o u l i n g of the r e a c t o r surfaces by polymer i s a
d i f f i c u l t design problem.
3. Heat Removal - Most polymerizations r e l e a s e l a r g e
amounts of heat as monomer i s converted to polymer ( c f .
Table V). In a d d i t i o n , the mechanical energy required
f o r mixing may be converted to heat under h i g h l y viscous
c o n d i t i o n s . Removal of t h i s heat i s o f t e n d i f f i c u l t
f o r high conversion p o l y m e r i z a t i o n because of high
v i s c o s i t y , heat t r a n s f e r surface f o u l i n g , and change of
phase during r e a c t i o n . In many i n d u s t r i a l s i t u a t i o n s ,
d i s a s t r o u s r e a c t o r runaway i s an ever present p o t e n t i a l
hazard because of these heat removal d i f f i c u l t i e s .
This presents a great challenge to the process c o n t r o l
engineer as w e l l as to the r e a c t o r designer.
TABLE V
HEATS OF POLYMERIZATION FOR SOME COMMON MONOMERS
cal/mole at
25C
Ethylene
Propylene
Butadiene
Styrene
Vinyl chloride
Vinylidene chloride
V i n y l acetate
Methyl a c r y l a t e
Methyl methacrylate
Acrylonitrile
Formaldehyde
-21.2
-19.5
-17.6
-16.7
-22.9
-18.0
-21.2
-18.5
-13.2
-18.4
- 7.4


5. RAY
107
4. Q u a l i t y of Polymer Product - Product q u a l i t y i s a

much more complex i s s u e i n p o l y m e r i z a t i o n than i n
more conventional short chain r e a c t i o n s . Because the
molecular a r c h i t e c t u r e of the polymer i s so s e n s i t i v e
to r e a c t o r operating c o n d i t i o n s , upsets i n feed
c o n d i t i o n s , mixing, r e a c t o r temperature, e t c . can
a l t e r c r i t i c a l molecular p r o p e r t i e s such as molecular
weight d i s t r i b u t i o n , polymer composition d i s t r i b u t i o n ,
chain sequence d i s t r i b u t i o n , degree of chain branching,
and s t e r e o r e g u l a r i t y . I n a d d i t i o n , the morphological
form of the polymer i s o f t e n a key q u a l i t y v a r i a b l e .
For example, the p a r t i c l e s i z e d i s t r i b u t i o n i n emulsion,
suspension, and p r e c i p i t a t i o n p o l y m e r i z a t i o n can be
a c r u c i a l product s p e c i f i c a t i o n . One of the greatest
d i f f i c u l t i e s i n a c h i e v i n g q u a l i t y c o n t r o l of the polymer
product i s that the a c t u a l customer s p e c i f i c a t i o n s may
be i n terms of non-molecular parameters such as t e n s i l e
s t r e n g t h , crack r e s i s t a n c e , temperature s t a b i l i t y , c o l o r
or c l a r i t y , a b s o r p t i o n c a p a c i t y f o r p l a s t i c i z e r , e t c .
The q u a n t i t a t i v e r e l a t i o n s h i p between these product
q u a l i t y parameters and r e a c t o r operating c o n d i t i o n s
may be the l e a s t understood area of p o l y m e r i z a t i o n
r e a c t i o n engineering. Table VI summarizes both types
of q u a l i t y c o n t r o l measures. Because of the l a c k of
o n - l i n e measurements f o r most of these product q u a l i t y
v a r i a b l e s (molecular or otherwise), c o n t r o l of polymeri z a t i o n r e a c t o r s i s a s p e c i a l challenge.
In subsequent s e c t i o n s , examples w i l l be used t o i l l u s t r a t e some

of the design c o n s i d e r a t i o n s l i s t e d here.
Although a number of the surveys l i s t e d i n Table I I (e.g.;
6,11,13,16-18) provide a treatment of p o l y m e r i z a t i o n r e a c t o r s
and processes i n i n d u s t r i a l use, Gerrens has provided an outstanding summary of t h i s i n f o r m a t i o n i n h i s recent survey (18).
Table V I I , taken from Gerrens review provides an i n d i c a t i o n o f the
v a r i e t y of r e a c t o r c o n f i g u r a t i o n s found i n i n d u s t r i a l p r a c t i c e .
Because the s t a t e of the l i t e r a t u r e through 1980 i s so w e l l
covered by the surveys l i s t e d i n Table I I , only very recent work
on p o l y m e r i z a t i o n r e a c t i o n engineering w i l l be provided here as a
supplement. This i s c a t e g o r i z e d by t o p i c i n Table V I I I . This
l a r g e amount of l i t e r a t u r e (which i s not exhaustive) over the
l a s t 18 months i s i n d i c a t i v e of the recent e x p l o s i o n of i n t e r e s t
i n these problems.
T

Table VI. Some Measures of Polymer Product Q u a l i t y

END USE PROPERTIES
Flow P r o p e r t i e s
( F i l m Blowing,
Molding, e t c . )
Strength
S t r e s s Crack
Resistance

Color, C l a r i t y
MOLECULAR ARCHITECTURE
Average M o l e c u l a r
Weight and Molecular
Weight D i s t r i b u t i o n
(or Melt Index,
Viscosity, etc.)
MW
Polymer Composition
and Composition
Distribution
nlOO
Melting P o i n t
Corrosion
Resistance
Abrasion
Resistance
Chain Sequence
Distribution
Degree of Chain
Branching
Density
-A-A-B-A-A-A-B-Ba.
Linear:
I II !! I
-c-c-c-c-c-c-
I IIII I
Impact Resistance
b.
Temperature
Stability
Branched :
-C-C-C-C-C-C-
Swellability
P l a s t i c i z e r Uptake
Spray Drying
Characteristics
Coating and
Adhesion P r o p e r t i e s
Stereoregularity
(Tacticity)
a.
Isotactic:
-C-C-C-C-C-C-C-
A
b.
Syndiotactic:
A
-c-c-c-c-c-
I
A
c.
I
A
Atactic:
A
-c-c-c-c-c-c-c-
Average P a r t i c l e
Size D i s t r i b u t i o n
Size
P a r t i a l P o r o s i t y and
Surface Area


38
37
36
ho 39
Fluidized bed
Continuous stirred tank
(Double) Loop
35
Rotating ring disc
3k
CO
33
32
31
30
Stirred tank cascade
Table V I I .
Stirred tank + tower
29
28
Tower or tower cascade
27
26
25
Extruder
2k
23
Mixer + conveyor
22
21
Continuous tube
18
Continuous tube with distri- 9

buted bead
w
19
2-Component mixer + mold

20
16
Batch stirred tank + autoclave

with gate paddle nuscer
17
15
Batch stirred tank + filter press

Ik
<u
13
BR
Piston
12
Semibatch
11
10
Practice.
Precipitation
polymerization
Solid-phase polycondensation
Interfacial polycondensation
Solution or melt-polycondensation
p. y

Emulsion polymerization
Solution polymerization
Precipitation
polymeri zation
Bead polymerization
<
JJ
Solution polymerization
Polymerization reactions
Reactor C o n f i g u r a t i o n s Found i n I n d u s t r i a l

Batch stirred tank
110

Table V I I I .
Some Very Recent Work i n Polymerization Reaction

Engineering
Topic
Principal Research Groups
References
Gel or Trommsdorf Effect
Hamielec, Ito, O'Driscoll,

Sundberg, T i r r e l l
(26-48)
Biesenberger, Johnson, T i r r e l l
(49-60)
(61-94)
Polycondensation
Gajewski, Gupta, Kaneko, Kumar,

Mashelkar, Rafler
Olefin Polymerization with

Coordination Catalysts
Bohm, Brockneier, Hogan, Keii,

Pino, Ray, Reichert, Zakharov
(95-124)
Kinetics of High Pressure

(Low Density) Ethylene
Polymerization
Ehrlich, Jovanovich, Loft,

Yamamoto
(125-135)
CSTR for Polymerization
Chen, Fan, Meira, Ray
(136-147)
Tubular Polymerization
Reactors
Janssen, Joosten, Middleman,

Nigam, Ottino, Ray
(148-166, 246)
Reaction Injection Molding

(RIM)
Gogos, Kamal, Macosko, Ottino,

Throne, T i r r e l l
(167-184)
Process Dynamics, Optimization,

and Control
Chen, Johnson, Laurence, MacGregor, (20, 50-54,

Ray, T i r r e l l
l3"5"-l39~,~T42-143,
4T-I4T, 8T-2uD
Suspension Polymerization
Reichert
(206-217)
Emulsion Polymerization
Bassett, Brooks, Guillot,

Hamielec, Kiparissides, Nomura,
Piirma, Ray, Sundberg, Ugelstad,
Vanderhoff
(21-23_, 160,
201-205,
TTff-TBT)
in Free Radical Polymerization

Copolymerization

5.
RAY
Some Current
111
Research Problems
To provide an i l l u s t r a t i o n of some of the challenges of

polymerization r e a c t i o n engineering, we s h a l l discuss here a few
i n t r i g u i n g but p r a c t i c a l l y important research problems which a r i s e
i n the design of polymerization r e a c t o r s . These examples r e f l e c t
the author s own i n t e r e s t and are s e l e c t e d from research p r o j e c t s
c u r r e n t l y underway at the U n i v e r s i t y of Wisconsin.

S o l u t i o n Polymerization i n a CSTR. Although many polymerizat i o n reactors i n use by industry have the residence time d i s t r i bution of a CSTR, they may not, at f i r s t glance, have the
appearance of a CSTR ( c f . Figure 1). Nevertheless, CSTR models,
perhaps with some allowance f o r imperfect micromixing, are
s u c c e s s f u l l y employed to d e s c r i b e these r e a c t o r s . Thus the
behavior of the CSTR i s of great p r a c t i c a l i n t e r e s t .
Recent studies of CSTR s f o r bulk or s o l u t i o n f r e e r a d i c a l
polymerization i n d i c a t e the p o s s i b i l i t y of m u l t i p l e steady s t a t e s
(e.g.; 20,137-139,145-147). The f a c t that t h i s occurs should not
be s u r p r i s i n g given the l a r g e heat e v o l u t i o n and d i f f i c u l t heat
t r a n s f e r c h a r a c t e r i s t i c of polymerization r e a c t o r s . However,
there are dramatic new t w i s t s to these phenomena even i n simple
s o l u t i o n polymerization.
For example, a u t o c a t a l y t i c k i n e t i c s
lead to the existence of m u l t i p l e steady states even under
isothermal reactor c o n d i t i o n s . Figure 2 (taken from (145))
i l l u s t r a t e s t h i s f o r the case of methyl methacrylate
polymerizat i o n i n e t h y l acetate solvent c a r r i e d out at the b o i l i n g point
of the r e a c t i n g l i q u i d . Note that the model p r e d i c t i o n s and the
steady s t a t e experiments agree that there i s i g n i t i o n to a
high conversion, inoperable, steady s t a t e at a c e r t a i n
residence time f o r solvent f r a c t i o n s l e s s than ~40%.
The upper
steady s t a t e i s inoperable due to the extremely high v i s c o s i t i e s
at such high conversions.
In the laboratory, i g n i t i o n which was
allowed to proceed to t h i s upper steady s t a t e r e s u l t e d i n a
reactor f i l l e d with s o l i d polymer. The p r a c t i c a l consequence
of t h i s f o r the i n d u s t r i a l r e a c t o r i s that even with p e r f e c t
temperature c o n t r o l (an u n l i k e l y event a f t e r i g n i t i o n has
occurred), the r e a c t o r w i l l i g n i t e i n t o a "runaway" c o n d i t i o n f o r
c e r t a i n combinations of solvent concentration and r e a c t o r
residence time. I f only temperature measurements are being
taken, the operator would not be aware of the runaway u n t i l the
a g i t a t o r motor blew a fuse, or the g r e a t l y increased r a t e of
r e a c t i o n exceeded the c o o l i n g system capacity and caused a sharp
increase i n temperature and pressure i n the r e a c t o r .
1


112
[1
El
m
m
m
flf
m
m
Stirred tank cascade
Tower cascade
11 1
Ring disc
Stirred tank-tower
combination
Polymer
Catalyst
solvent .
Catalyst
ethylene Polymer
powder
Gaseous monomer
Monomer Catalyst
CSTR
(Double) Loop
Fluidized bed ("gas phase")
F i g u r e 1. Continuous s t i r r e d tank r e a c t o r types i n use by

i n d u s t r y (l8).


I.Oj
20
30
20
J
40
I
60
L
80
40
100
50
I I I I j
RESIDENCE TIME (MIN.)
10
(3
20
30
40
50
F i g u r e 2. Isothermal p o l y m e r i z a t i o n o f
methyl methacrylate i n a CSTR (1U5).
a. P r e d i c t e d steady-state monomer conver
s i o n v s . r e a c t o r residence time f o r t h e
s o l u t i o n p o l y m e r i z a t i o n o f MMA. i n e t h y l
acetate a t 86 C. b. Steady-state and
dynamic experiments f o r the i s o t h e r m a l s o l u
t i o n p o l y m e r i z a t i o n o f MMA i n e t h y l acetate
( s o l v e n t f r a c t i o n 0 ) () steady s t a t e s ,
Co) non-steady s t a t e s , c. Steady-state con
v e r s i o n v s . CSTR residence time f o r s o l v e n t
f r a c t i o n o f 50%.
10
B O U N D S -J"*
1.0 r
E X P E C T E D ERROR

S'
S'
>

114
In r e a l i t y , there i s l i m i t e d heat removal capacity f o r

i n d u s t r i a l r e a c t o r s , so that heat e v o l u t i o n due to r e a c t i o n i s an
a d d i t i o n a l source of a u t o c a t a l y t i c behavior.
Including these
temperature e f f e c t s produces even more i n t e r e s t i n g types of
m u l t i p l e steady s t a t e behavior.
Figure 3 (taken from (147))
i l l u s t r a t e s the types of steady s t a t e behavior which a r i s e f o r
methyl methacrylate polymerization when the solvent volume
f r a c t i o n i s high enough that isothermal m u l t i p l i c i t y i s not
p o s s i b l e and high conversion steady s t a t e s are f e a s i b l e
operating c o n d i t i o n s f o r the CSTR. Note that high conversions
can be achieved at long residence times ( l a r g e r e a c t o r s ) on the
S-shaped m u l t i p l i c i t y branch or a l t e r n a t i v e l y at short residence
times (small reactors) on the i s o l a t e d branch. The i s o l a t e d
branch has the advantage that high conversion polymerization may
be c a r r i e d out with a reactor only 10% the s i z e required f o r the
same conversion on the continuous branch of steady s t a t e s .
However, these i s o l a t e d steady s t a t e s r e q u i r e s p e c i a l start-up
procedures and r e l i a b l e c o n t r o l systems to prevent e x t i n c t i o n
of the r e a c t i o n . These model p r e d i c t i o n s have been v e r i f i e d by
experiment f o r the polymerization of methyl methacrylate and
f o r the polymerization of v i n y l acetate (147).
Figure 4 (taken
from (147)) provides a d e t a i l e d comparison of model p r e d i c t i o n
and experiment f o r v i n y l acetate polymerization.
Note that
e x t i n c t i o n i s indeed observed at both ends of the i s o l a .
Emulsion Polymerization i n a CSTR. Emulsion polymerization
i s u s u a l l y c a r r i e d out i s o t h e r m a l l y i n batch or continuous
s t i r r e d tank r e a c t o r s . Temperature c o n t r o l i s much e a s i e r than
f o r bulk or s o l u t i o n polymerization because the small (~.5
ym)
polymer p a r t i c l e s , which are the locus of r e a c t i o n , are suspended
i n a continuous aqueous medium as shown i n Figure 5.
This
complex, multiphase r e a c t o r a l s o shows m u l t i p l e steady states
under isothermal c o n d i t i o n s . Gerrens and coworkers at BASF seem
to be the f i r s t to report these phenomena both computationally
and experimentally.
Figure 6 (taken from r e f . (253)) p l o t s the
a u t o c a t a l y t i c behavior of the r e a c t i o n r a t e f o r styrene polymeri
z a t i o n vs. monomer conversion i n the r e a c t o r . The i n t e r s e c t i o n
of R
with
^ f ^
s a t i s f i e s the m a t e r i a l balance and
determines
the r e a c t o r steady s t a t e s . These m u l t i p l i c i t i e s occur f o r any

polymerization having the Trommsdorf e f f e c t . For example, m u l t i
p l i c i t i e s f o r methyl methacrylate polymerization, found by
Schork, et a l . (204), are shown i n Figure 7 where experimental
steady s t a t e measurements are compared with model p r e d i c t i o n s .
It i s c l e a r that the reactor designer would need to consider t h i s
isothermal m u l t i p l i c i t y i n s e l e c t i n g the d e s i r e d reactor
operating c o n d i t i o n s .
Another exotic feature of emulsion polymerization i n a CSTR
i s that sustained o s c i l l a t i o n s are f r e q u e n t l y observed i n


5.
RAY
115
8.888
45
688
758
98
1858
188.8
R 58.8
fi
U
R
.
1858
RESIDENCE TIME
Figure 3. E f f e c t o f feed temperature on steady-state o p e r a t i o n
f o r MMA p o l y m e r i z a t i o n (lV7_) Base case,
23 C
21 C
; and T = 25 c
.
U

116

8.5H
I I I '0|
25
I I I ! [ 1 1 I 1 j I 1
58
75
I > I I
j I I I I
125
158
188
&QvÔ
rj^^
58 H
-J_
I I I j I I I I [ I I 1 I j I I I I I j I I I I
25
50
75
108
125
150
RESIOENCE TIME ( M I N )
Figure U. A comparison o f the steady-state v i n y l acetate model
and experimental data (1U7). T~ = 20 C; T = 25 C;
= 0.50;
I = O.OUlT m o l e / l i t . 0 - s t a b l e steady s t a t e ; and 0 - unstable
transient.
Q

5.
RAY
111
Monomer
H2O

Emulsifier
Initiator
Polymerizing
Emulsion
Figure 5 A continuous
reactor.
s t i r r e d tank emulstion p o l y m e r i z a t i o n


118
ENGINEERING
() S t y r o i / g Latex
K)0
80
&0
40
20
% Conversion
Figure 6. M u l t i p l e steady s t a t e s i n the emulsion p o l y m e r i z a t i o n o f

styrene i n a CSTR. (Reproduced w i t h permission from Ref. 253.
Copyright 1971, V e r l a g Chemie, GMBH.)

5. RAY
119

100-1
1 0
2 0
3 0
Residence Time
4 0
5 0
6 0
(min)
Figure 7. Isothermal m u l t i p l i c i t y f o r the emulsion p o l y m e r i z a t i o n

of methyl methacrylate i n a CSTR '(20h). [ s ] = [ i ]_ = 0.03
moles/L-water; o,x - experimental steady s t a t e s ; a n d * - t h e o r e t i c a l steady s t a t e s .

120
CHEMICAL
REACTION
ENGINEERING

i n d u s t r i a l p r a c t i c e ( c f . (20,253,254) f o r a d i s c u s s i o n of t h i s ) .
Experimental r e s u l t s from our l a b o r a t o r y (201,202) shown i n
Figure 8 provide only one example of t h i s troublesome problem.
There i s great i n t e r e s t i n developing a q u a n t i t a t i v e understanding of the fundamental nature of these o s c i l l a t i o n s so that
reactor design c r i t e r i a f o r a v o i d i n g them can be developed.
Recent developments by Rawlings (255) would seem to provide a
f i r s t step i n t h i s d i r e c t i o n .
S o l i d - C a t a l y z e d O l e f i n P o l y m e r i z a t i o n . A t h i r d area where
extremely c h a l l e n g i n g p o l y m e r i z a t i o n r e a c t i o n engineering
problems a r i s e i s i n t r a n s i t i o n - m e t a l c a t a l y z e d polymerization
of o l e f i n s such as ethylene, propylene and t h e i r copolymers.
There i s great controversy at present over issues such as ( i )
which f a c t o r s c o n t r o l the molecular weight d i s t r i b u t i o n and
t a c t i c i t y , ( i i ) what causes the d e c l i n e i n c a t a l y s t a c t i v i t y
observed i n these r e a c t o r s , and ( i i i ) what p h y s i c a l phenomena
are o c c u r r i n g i n the pores and on the c a t a l y s t s u r f a c e .
Unambiguous measurements are few, so t h e o r i e s abound. For example,
o l e f i n p o l y m e r i z a t i o n with a Z i e g l e r - N a t t a type c a t a l y s t y i e l d s
narrow molecular weight d i s t r i b u t i o n s when the system i s
homogeneous and very broad molecular weight d i s t r i b u t i o n s when
the p o l y m e r i z a t i o n becomes heterogeneous.
Has the nature of the
c a t a l y s t changed so that some s i t e s are producing short chains
while other s i t e s produce long chains? Or, has the increased
heat and mass t r a n s f e r r e s i s t a n c e of the heterogeneous polymeriz a t i o n produced the great nonuniformity i n polymer chain length?
To produce some answers to these and other questions requires
a combination of mathematical modelling and d i a g n o s t i c experimentation.
There i s some concensus that the p h y s i c a l p i c t u r e
i n s i d e the growing polymer p a r t i c l e i s as f o l l o w s . For
heterogeneous c a t a l y t i c systems polymerization occurs on the
c a t a l y s t s u r f a c e producing polymer chains which f i l l the pores
and grow out from the a c t i v e s u r f a c e . The c a t a l y s t p a r t i c l e
f r a c t u r e s i n t o t i n y fragments as the pores are ruptured by
growing polymer. Monomer, which must d i f f u s e to the c a t a l y s t
surface to be c a t a l y t i c a l l y i n s e r t e d i n t o the polymer chain, sees
an i n c r e a s i n g path f o r d i f f u s i o n as p o l y m e r i z a t i o n progresses
and the c a t a l y s t fragments become more and more encapsulated by
polymer. C l e a r l y t h i s i s a very complex p h y s i c a l s i t u a t i o n and
simple models are not adequate to represent a l l the important
phenomena. Therefore a number of r a t h e r complex models f o r the
c a t a l y s t p a r t i c l e have been developed and t e s t e d computationally
with r e a l i s t i c parameters f o r heat and mass t r a n s f e r as w e l l as
k i n e t i c s . F i g u r e 9 i l l u s t r a t e s some of these models while
Figure 10 (taken from (256)) shows the p r e d i c t e d propylene
monomer c o n c e n t r a t i o n p r o f i l e to be expected i n a polypropylene
polymer p a r t i c l e over a 4 hour period i n a s l u r r y batch r e a c t o r .
Figure 11 i n d i c a t e s the corresponding molecular weight d i s t r i b u t i o n to be expected.
As described i n d e t a i l elsewhere (121,122,
124,256,257), these extensive modelling s t u d i e s show that

5.
RAY
Continuous p o l y m e r i z a t i o n ,
Run 15, R e c i p e 8,
Example o f o s c i l l a t o r y b e h a v i o r
[ S ] - 0 . 0 2 mo l e s / l - w a t e
[I]
- 0.01 mo l e s / l - w a t <

121
in
CSTR,
<3
r i i i
""
300
400
5 00
300
40
500
1 1 1
1 1 1 1
00
rf
f i l l
00
1 1 1 1
SO
'300
300
90
I I I I I
600
7O0
MINUTES
Figure 8. CSTR emulsion p o l y m e r i z a t i o n o f methyl methacrylate.

Residence time =
min., temperature = hO C (201).
S = 0.02
moles/ -water; I =0.01 moles/ -water.

122
CHEMICAL
REACTION
ENGINEERING

S C M
P C M
F M
M Q
GROWTH
Figure 9. Schematic i l l u s t r a t i o n o f p a r t i c l e d i s i n t e g r a t i o n and
the p o s t u l a t e d morphological models; SCM ( s o l i d core model),
PCM (polymeric core model), PFM (polymeric flow model), and
MGM ( m u l t i g r a i n model).


5.
RAY
5-
123
5
Y
I
R
ft
IHE, HOURS
IHE/ HOURS
Figure 1 1 . M u l t i g r a i n model p r e d i c t i o n s f o r propylene polymeriza

t i o n i n a semibatch r e a c t o r : Q = M^/M , r a t e = gm polymer/gm c a t . - h r ,
y i e l d = gm polymer/gm-catalyst.
n

124
CHEMICAL
REACTION
ENGINEERING

( i ) mass t r a n s f e r r e s i s t a n c e can e x p l a i n at l e a s t some of

the observed broadening i n MWD f o r ethylene and
propylene polymerization,
( i i ) P a r t i c l e overheating can occur e a r l y i n the polymeriza
t i o n , f o r small p a r t i c l e s , and lead to s t i c k i n g and
agglomeration problems e s p e c i a l l y f o r gas phase
processes.
( i i i ) D e t a i l e d q u a n t i t a t i v e matching of molecular weight
d i s t r i b u t i o n data requires even more complex
mathematical models.
However, much remains to be done, both experimentally and
t h e o r e t i c a l l y , before there w i l l be a comprehensive understanding
of t r a n s i t i o n - m e t a l c a t a l y z e d o l e f i n polymerization.
Concluding Remarks
As may be evident from the few examples above, polymerization
r e a c t i o n engineering i s a f a s c i n a t i n g d i s c i p l i n e , r i c h with
d i v e r s e and c h a l l e n g i n g design problems. C u r r e n t l y there i s
considerable research and development a c t i v i t y i n t h i s area i n
i n d u s t r i a l l a b o r a t o r i e s and there e x i s t s a high demand (even i n
these times) f o r Ph.D. graduates with polymerization r e a c t i o n
engineering e x p e r t i s e . However, as yet there i s not a commensu
r a t e l e v e l of i n s t r u c t i o n and research i n the u n i v e r s i t y . Thus
we i n the u n i v e r s i t y should i n c l u d e more from t h i s area i n our
teaching. S i m i l a r l y , government and industry could do more to
provide the resources necessary t o support u n i v e r s i t y research
and stimulate the number of Ph.D. graduates i n t h i s important
area of chemical r e a c t i o n engineering.
Acknowledgments
The author i s indebted to the N a t i o n a l Science Foundation
and t o the Mobil O i l Foundation f o r research support.
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Cutter, L. .; Drexler, T. D. 182nd ACS Meeting N.Y. 1981,
200.
Harwood, H. J.; Dworak, .; Nyeu, T. K. L.; Tong, S.-N.
182nd ACS Meeting N.Y. 1981, 220.
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Hulme, J. M.; Thibodeau, W. E. ISA 1980, 39.
Trathnigg, B. Makromol. Chem. 1980, 181, 1979.
Gusika, P. L.; Zhizhin, V. G. PMM USSR 1981, 44, 495.
Blanks, R. F.; Meyer, J. .; Grulke, E. A. Poly. Eng. Sci.
1981, 21, 1055.
Wu, G. . .; Denton, L. .; Laurence, R. L. Poly. Eng.
Sci. 1982, 22, 1.
Meira, G. R.; Johnson, A. F. Poly. Eng. Sci. 1981, 21 415.
Rao, . B.; Mhaskar, R. D. Polymer 1981, 22, 1593.
Hwu, M. C.; Foster, R. D. CEP July 1982, 62.
Zamani, H.; Daroux, M.; Gregge, J. L.; Bordet, J. 2nd
Schork, F. J.; Ray, W. H. ACS Sym. Series 1981, 162, 505.
Schork, F. J.; Ray, W. H. J. Appl. Poly. Sci. 1983, 28,
in press.
Schork, F. J.; Chu, G. C.; Ray, W. H. 1980 Annual A.I.Ch.E.
Meeting Chicago.
Schork, F. J.; Rawlings, J. B.; Ray, W. H. 1981 Annual
A.I.Ch.E. Meeting New Orleans.
Kiparissides,
C.; MacGregor, J. F.; Hamielec, A. E.
Can. J. Chem. Eng. 1980, 58, 48, 56, 65.
Allsopp, M. W. Pure & Appl. Chem. 1981, 53, 449.
Yang, C. M.; Hamann, H. C. J. Appl. Poly. Sci. 1980, 25,
2555.
Hatate, Y.; Ikeura, T.; Shinonome, M.; Kondo, K.;
Nakashio, F. J. Chem. Eng. Japan 1981, 14, 38.
Lin, C.-C.; Wang, Y.-F. J. Appl. Poly. Sci. 1981, 26,
3909.
Schrder,
R.; Piotrowski, B. Chem.-Ing.-Tech. 1981, 53,
748.
Cameron, J. B.; Lundeen, A. J.; McCulley, J. H., Jr.;
Schwab, P. A. 181st ACS Meeting Atlanta 1981.
Moritz, H.-U.; Reichert, . H. Chem.-Ing. Tech. 1981, 53,
386.
Langner, F.; Reichert, . H. Chem.-Ing.-Tech. 1981, 52,
747.
Langner, F.; Moritz, H.-U.; Reichert, . H. Ger. Chem.
Eng. 1979, 2, 329.
Moritz, H.-U.; Langner, F.; Reichert, . H. Ger. Chem.
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132
ENGINEERING

216.
217.
Baade, W.; Reichert, . H. Chem.-Ing.-Tech. 1981, 53, 472.

Langner, F.; Moritz, H.-U.; Reichert, . H. Chem. Eng.
Sci. 1980, 35, 519.
218. Brooks, B. W. J.C.S. Faraday I 1980, 76, 1599.
219. Guillot, J. Makromol. Chem. Rapid Commun. 1980, 1, 697.
220. Kiparissides, C.; MacGregor, J. F.; Hamielec, A. E.
A.I.Ch.E. J. 1981, 27, 13.
221. Nomura, M.; Harada, M. J. Appl. Poly. Sci. 1981, 26., 17.
222. Ranee, D. G.; Zichy, E. L. Pure & Appl. Chem. 1981, 53,
377.
223. Tseng, C. M.; El-Aasser, M. S.; Vanderhoff, J. W. ACS
Meeting N.Y. 1981.
224. Ugelstad, J.; Mork, P. C.; Hansen, F. K. Pure & Appl. Chem.
1981, 53, 323.
225. Oldshue, J. Y.; Mechler, D. O.; Grinnell, D. W. CEP May
1982, 68.
226. Bataille, P.; Van, B. T.; Pham, Q. B. J. Poly. Sci. Poly.
Chem. 1982, 20, 795.
227. Cauley, D. .; Thompson, R. W. J. Appl. Poly. Sci. 1982,
27, 363.
228. Piirma, I.; Chang, M. J. Poly. Sci. Poly. Chem. 1982, 20,
489.
229. Almog, Y.; Levy, M. J. Poly. Sci. Poly. Chem. 1982, 20,
417.
230. Brooks, B. W.; Makanjuola, B. O. Polymer 1982, 23, 77.
231. Ham, G. E. J. Macromol. Sci.-Chem. 1982, A17, 369.
232. James, D. R.; Sundberg, D. C. J. Poly. Sci. Poly. Chem.
1980, 18, 903.
233. Sundberg, D. C.; Hsieh, J. Y.; Soh, S. K.; Baldus, R. F.
ACS Symp. Ser. No. 165 1981, 327.
234. Dautzenberg, H.; Goebel, H.-H.; Koch, H.; Jaeger, W.;
Linow, K.-J.; Purz, H. J.; Reinisch, G.; Schneider, H. J.;
Richter, I.; Wolf, J. Acta Poly. 1980, 31, 335.
235. Friedman, . M. J. Poly. Sci. Poly. Phys. 1980, 18, 1771.
236. Piirma, I.; Chen, S.-R. J. Coll. Interface Sci. 1980, 74,
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1979, 18, 272.
238. Kiparissides, C.; Ponnuswamy, S. R. Chem. Eng. Commun.
1981, 10, 283.
239. Nomura, M.; Harada, M. ACS Symp. Ser. No. 165 1981, 121.
240. Nomura, M.; Kubo, M.; Kujita, K. Mem. Fac. Eng. Fukui
Univ. 1981, 29, 167.
241. Nomura, M.; Yamamoto, K.; Horie, I.; Fujita, K. J. Appl.
Poly. Sci., in press.
242. Kawaguchi, H.; Sugi, Y.; Ohtsuka, Y. ACS Symp. Ser. No.
165 1981, 145.
243. Bassett, D. R.; Hoy, K. L. ACS Symp. Ser. No. 165 1981,
371.


5. R A Y
133
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Symp. Ser. No. 165 1981, 389.
245. Guyot, .; Guillot, J.; Pichot, C.; Guerrero, L. R.
ACS Symp. Ser. No. 165 1981, 415.
246. Patterson, I.; Rollin, A. L.; Estaque, L.; Bataille, P.
A.I.Ch.E. Meeting Chicago 1980.
247. Guillot, J. Makromol. Chem. Rapid Commun. 1980, 1, 697.
248. Ohtsuka, Y.; Kawaguchi, H.; Sugi, Y. J. Appl. Poly. Sci.
1981, 26, 1637.
249. Chonde, Y.; Krieger, I. M. J. Appl. Poly. Sci. 1981, 26,
1819.
250. Snuparek, J., Jr.; Kaspar, K. J. Appl. Poly. Sci. 1981,
26, 4081.
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1981, 26, 1327.
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43, 693-98.
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(submitted for publication).
RECEIVED April 26, 1983

6
Mixing in Chemical Reactors
JACQUES V I L L E R M A U X

Institut National Polytechnique de Lorraine, Laboratoire des Sciences du Gnie

Chimique, CNRS-ENSIC, Nancy, France
Recent progress in the understanding and modelling

of mixing phenomena in chemical reactors is reviewed. The following items are discussed: characterization of the degree of mixing, Eulerian
approach to turbulence theory with application to
modelling combustion, macromixing and residence time
distributions, phenomenological models for mixing
earliness i n the age space, mechanism of micromixing i n physical space and segregation phenomena
at the microscopic l e v e l , mixing in stirred tanks
and static mixers. An example is presented of the
application to continuous free radical polymerization. It is concluded that a comprehensive and
predictive theory for micromixing should not be
sought through turbulence theory alone, but rather
in phenomenological interaction models, whose parameters could be interpreted on a fundamental basis
by this theory.
Contacting reactants and subsequent mixing of r e a c t i n g species
i s one of the major features c o n t r o l l i n g the behaviour of chemical
r e a c t o r s . In s p i t e of recent advances, a u n i f i e d theory p r o v i d i n g
the engineer with general r u l e s a p p l i c a b l e to any case of competit i o n between mixing and chemical r e a c t i o n i s s t i l l l a c k i n g . However, d i r e c t i o n s i n which such a theory should be sought are now
i n view. The aim o f t h i s chapter i s t o review recent and s i g n i f i cant c o n t r i b u t i o n s which may l e a d t o such a general treatment.
Of course, the f i e l d of mixing i n chemical engineering i s immense. Therefore, t h i s review w i l l be r e s t r i c t e d , with perhaps a
few exceptions, to those phenomena where mixing and chemical reactions are c l o s e l y l i n k e d . The purely p h y s i c a l aspects of mixing
won't be considered, although t h i s important operation also poses
unsolved problems to i n d u s t r y .
That mixing i n chemical r e a c t o r s i s a subject of very a c t i v e
research i s a t t e s t e d by the recent p u b l i c a t i o n of s e v e r a l review
0097-615 6/ 8 3/0226-013 5 $ 13,80/ 0

136
ENGINEERING
papers, which appeared a few years ago or while the present was i n
p r e p a r a t i o n (J_-6) .
Instead o f d u p l i c a t i n g these reviews and r a t h e r than present
i n g an exhaustive l i t e r a t u r e survey, I have chosen t o emphasize
the points which seem the most c r i t i c a l and c o n t r o v e r s i a l , or
those where s i g n i f i c a n t progress has been made i n recent years,
and to give personal views on these s u b j e c t s . In doing so, I ac
cept the r i s k that t h i s review may appear p a r t i a l or incomplete to
those authors whose (sometimes e x c e l l e n t ) papers w i l l be l e f t out.
That mixing i n chemical reactors i s also a problem of v i t a l
importance to i n d u s t r y appears i n some, too r a r e , papers d e s c r i b
i n g the e f f e c t of a g i t a t i o n on y i e l d i n p i l o t p l a n t reactors (7.)
or the d i f f i c u l t i e s of conserving a good s e l e c t i v i t y when s c a l i n g
up a mixing device to the commercial s c a l e (8).
I t i s a p i t y that
p r o p r i e t a r y requirements r e s t r a i n the p u b l i c a t i o n of such indus
t r i a l case s t u d i e s , whose a n a l y s i s would be o f the g r e a t e s t i n t e r
est t o t h e o r i c i a n s o f mixing. But t h i s i s a general problem i n
Chemical Reaction Engineering. Nevertheless, i t i s encouraging to
see i n d u s t r i a l p a r t i c i p a n t s attending meetings and g i v i n g t h e i r
o p i n i o n about the relevance of research topics and about what
should be done to improve our knowledge i n the f i e l d (9,10). This
should prevent "too many academics pursuing too many non-problems"
(Jl).
The l a s t point that should be o u t l i n e d i n t h i s i n t r o d u c t i o n
i s that mixing i n chemical reactors r e a l l y c o n s t i t u t e s an o r i g i n a l
chapter of Chemical Reaction Engineering. Since the p i o n e e r i n g
work of Danckwerts ( 12) , Zwietering (13) and others, i t i s c l e a r
that chemical r e a c t i o n engineering c o n s t i t u t e s a s c i e n t i f i c d i s c i
p l i n e with i t s own methods. The RTD and the segregation concepts
f o r i n s t a n c e , have completely renewed the d e s c r i p t i o n of the beha
v i o u r of r e a c t i n g mixtures i n r e a c t o r s . I am convinced that f u t u r e
progress can be expected i n pursuing novel concepts rather than i n
more s o p h i s t i c a t e d combinations of chemical k i n e t i c s and f l u i d me
chanics. Of course t h i s doesn't mean that we must neglect the con
t r i b u t i o n of the l a t t e r d i s c i p l i n e , as w i l l be seen below.
D e f i n i t i o n and c h a r a c t e r i z a t i o n of the degree of mixing
A d e f i n i t i o n of mixing i s proposed i n many papers and t e x t
books (14, 15, 16, 2),
and t h i s point w i l l not be discussed here.
Several c r i t e r i a are used f o r a q u a n t i t a t i v e c h a r a c t e r i z a t i o n of
the " q u a l i t y of mixing". These have been r e c a l l e d by Hiby (17). In
a non-uniform mixture, l e t p(C) be the l o c a l c o n c e n t r a t i o n d i s t r i
b u t i o n of a species. p(C) may be c h a r a c t e r i z e d by i t s mean C, its_
variance
and the average value AC of the d e v i a t i o n AC = |C - C|
from the mean. From these q u a n t i t i e s , s e v e r a l c r i t e r i a may be de
f i n e d (17), namely 6 = AC/C, 6
= A C / C and = /C. Another
critrium i s = AC/AC , where AC
i s the value o f Sc before mix
i n g (or at the reactorinlet).
Smarting from two_streams o f ( r e
duced) c o n c e n t r a t i o n 0 and 1, then AC = 2 C ( l - C).
The
m a x
max

6.
VILLERMAUX
137
I n t e n s i t y of Segregation d e f i n e d by Danckwerts
is
I = ^/
= o / C ( l - C) , but / = / bas a l s o been used. I f
two species A and are mixed, the d e f i n i t i o n of I becomes 02)
*s
"~ A BÂo*^Bo* R e l a t i o n s h i p s between a l l these i n d i c e s are
obvious. Their common property i s that the s m a l l e r they are, the
b e t t e r the q u a l i t y of the mixture. The corresponding degrees of
homogeneity may a l s o be defined as 1 - , 1 - 6 , 1 - / J , e t c . . .
Mixing times are the times r e q u i r e d f o r 6, or , or I to
f a l l from t h e i r i n i t i a l value (before m i x i n g ) , down to some pres
c r i b e d small value ( f o r instance 0.05
or 0 . 0 1 ) . We s h a l l see that
i n Lagrangian coordinates, - /(do /dt) i s a l s o a mixing time.
The e s t i m a t i o n of mixing times i n s t i r r e d tanks w i l l be discussed
i n a further Section.
The s c a l e of segregation gives i n f o r m a t i o n on the s i z e of se
gregated regions. Let c(x) and c(x+r) be the f l u c t u a t i n g concen
t r a t i o n s at p o i n t s and x+r (c = C - C), then the a u t o c o r r e l a t i o n
f u n c t i o n of c o n c e n t r a t i o n i s (2):g (r) = c(x) c ( x + r ) / o .
The s c a l e of segregation i s then defined as :
2

8 s ( r ) dr
In turbulence theory, t h i s i s a l s o known as the c o n c e n t r a t i o n mac r o s c a l e , which plays an important r o l e i n the i n t e r p r e t a t i o n of

micromixing phenomena.
A f i r s t remark about these mixing i n d i c e s i s that a c e r t a i n
confusion p r e v a i l s i n the l i t e r a t u r e owing to the m u l t i p l i c i t y of
d e f i n i t i o n s . I t would be d e s i r a b l e to adopt one s i n g l e measure f o r
the degree of mixing (and/or homogeneity), based f o r instance on
the reduced variance of the c o n c e n t r a t i o n d i s t r i b u t i o n .
A second remark i s that an experimentally measured degree of
mixing depends on the s p a t i a l r e s o l u t i o n of the probe used f o r mea
s u r i n g " p o i n t " values of the concentration.
In l i q u i d s , the most commonly used methods are e l e c t r i c a l
c o n d u c t i v i t y (18, 19), l i g h t a b s o r p t i o n , fluorescence (30) and che
m i c a l methods based on the c o l o r change of an i n d i c a t o r under the
i n f l u e n c e of an instantaneous r e a c t i o n (21, 22). The s p a t i a l r e s o
l u t i o n of p h y s i c a l methods ( o p t i c a l , e l e c t r i c a l microprobes) i s
about 100 ym (19) so that these are w e l l s u i t e d to macromixing
s t u d i e s but cannot compete w i t h chemical methods f o r the study of
mixing at the molecular s c a l e . An o r i g i n a l method based on the con
tinuous i n j e c t i o n of r a d i o a c t i v e t r a c e r s i n an i n d u s t r i a l mixer
has a l s o been proposed (23). In gases, c o n c e n t r a t i o n f l u c t u a t i o n s
have been measured using a c a t a l y t i c wire
(24).
The d e f i n i t i o n s of the degree of mixing presented above aim
at a l o c a l c h a r a c t e r i z a t i o n of the mixture homogeneity i n the phy
s i c a l space. There a l s o e x i s t more i n d i r e c t mixing i n d i c e s . The
segregation index J of Danckwerts (12) i s one of the most famous
ones. I t a p p l i e s to continuous r e a c t o r s and r e l i e s upon the v a r i
ance of age : J = Var a /Var a,where a i s the age of a molecule,
p


138
dp the mean age at " p o i n t " and Var denotes the variance of the
d i s t r i b u t i o n s over a l l " p o i n t s " or a l l molecules i n the r e a c t o r .
J = 1 i n a t o t a l l y segregated mixture ( a l l the ages are the same
w i t h i n a " p o i n t " = ) and J takes a minimum value depending on
the residence time d i s t r i b u t i o n when mixing e a r l i n e s s i s at a mi
nimum. J i s s t i l l a very popular q u a n t i t y i n the l i t e r a t u r e where
i t i s used by many authors to compare t h e i r micromixing models.
However I t h i n k that w h i l s t i t c o n s t i t u t e s some u s e f u l reference
for mixing e a r l i n e s s , i t i s of l i t t l e i n t e r e s t f o r the design of
chemical r e a c t o r s as i t cannot be measured d i r e c t l y nor be used
for a s t r a i g h t f o r w a r d c a l c u l a t i o n of chemical conversion.
Another i n d i r e c t mixing index was proposed by Ogawa et a l .
(25, 26), based on i n f o r m a t i o n theory and on the e s t i m a t i o n of the
"entropy" of a mixture. This "entropy" i s defined from the t r a c e r
d i s t r i b u t i o n among zones i n the r e a c t o r as = - V?
In p^,
where V* i s the reduced volume of zone i and p i t h e i = l
" p r o b a b i l i t y " of occurence of the t r a c e r i n zone i (see reference
(25) f o r more d e t a i l s ) . As mixing proceeds, the degree of homoge
n e i t y of the mixture i s defined as = H/H^, where H^ i s the f i n a l
entropy of the homogeneous mixture. This method was used to study
the mixing r a t e i n s t i r r e d v e s s e l s . M was p l o t t e d as a f u n c t i o n of
time from a record of the concentrations at v a r i o u s places i n the
v e s s e l . This allowed a comparison of e f f i c i e n c y of d i f f e r e n t a g i
t a t o r s (26). As an i n t e r e s t i n g g e n e r a l i z a t i o n , the macromixing ho
mogeneity i n a continuous r e a c t o r having a RTD E ( t ) may be defined
as (25) : M = - J " E ( t ) In E ( t ) dt,from which i t i s seen that M= 0
i n a plug flow r e a c t o r and M = 1 i n a continuous s t i r r e d r e a c t o r .
E u l e r i a n approach: M i x i n g and
Turbulence
Turbulence theory provides a c l a s s i c a l approach to mixing

phenomena. This i s a n a t u r a l way f o r mechanical engineers and spe
c i a l i s t s of combustion, who are very f a m i l i a r w i t h the methods of
f l u i d mechanics. However, when complex chemical r e a c t i o n s are i n
volved, the use of the formalism of turbulence alone seems to lead
to a deadlock, as has been pointed out by s e v e r a l authors. An ex
c e l l e n t p r e s e n t a t i o n of the s t a t e of the a r t can be found i n the
recent l i t e r a t u r e e s p e c i a l l y by Brodkey (16, _2, 27) and P a t t e r s o n
(3). These reviews r e v e a l no major breakthrough, and only slow
progress on a d i f f i c u l t road.
As the r e s u l t s of turbulence theory are sometimes used i n c o r
r e c t l y i n the l i t e r a t u r e , i t seems h e l p f u l to r e c a l l (Table I) the
p r i n c i p a l q u a n t i t i e s c h a r a c t e r i z i n g v e l o c i t y and c o n c e n t r a t i o n
f l u c t u a t i o n s , based on the assumption of homogeneous i s o t r o p i c
turbulence. Most of them can be deduced from s p e c t r a l measurements.
I f the techniques f o r determining v e l o c i t y f l u c t u a t i o n s p e c t r a are
w e l l e s t a b l i s h e d (hot wire anemometer, l a s e r - d o p p l e r anemometer...)
r e l i a b l e methods f o r monitoring c o n c e n t r a t i o n f l u c t u a t i o n s are l e s s
known. I n t e r e s t i n g data were r e c e n t l y obtained by using l o c a l conductometry microprobes i n t e r f a c e d w i t h a high g a i n , f a s t response

6.
viLLERMAUX
conductimeter (28, 29, 30), but there are s t i l l problems of space

and time r e s o l u t i o n (19) and new methods should be developed f o r
the determination of concentration f l u c t u a t i o n s s p e c t r a i n chemi
c a l r e a c t o r s . I t i s c l e a r from Table I that there are two p a r a l l e l
f a m i l i e s of c h a r a c t e r i s t i c s p e r t a i n i n g to v e l o c i t y f l u c t u a t i o n s on
one hand and to c o n c e n t r a t i o n f l u c t u a t i o n s on the other hand. This
d i s t i n c t i o n i s not always made i n the l i t e r a t u r e , some authors
using f o r instance v e l o c i t y macro or m i c r o s c a l e s , (which are b e t t e r
known) i n place of c o n c e n t r a t i o n s c a l e s . I t must a l s o be r e c a l l e d
that d i f f e r e n t length and time s c a l e s have very p r e c i s e meanings
and should not be used at random on the s i n g l e b a s i s o f dimension
a l a n a l y s i s . The macroscales L and L c h a r a c t e r i z e l a r g e i n i t i a l
eddies, whose s i z e i s g e n e r a l l y comparable to that of the i m p e l l e r
i n s t i r r e d tanks, or that of the i n l e t tubes i n tubular r e a c t o r s .
Taylor and C o r r s i n microscales Xf and A are those of the maximum
of d i s s i p a t i o n e i t h e r of the turbulent k i n e t i c energy, or of the
segregation. In t h i s respect, the C o r r s i n microscale X and the
a s s o c i a t e d time constant T play an important r o l e . The c l a s s i c a l
treatment of C o r r s i n , widely used i n the l i t e r a t u r e on mixing,
y i e l d s the f o l l o w i n g expressions :
f

139
1/3
2/3
(3-1)
f o r gases
Se
1/3
2/3
il
1/2
In Sc
for liquids
(3-2)
In l i q u i d s , the second term of (3-2) i s o f t e n n e g l i g i b l e and

T ifc 2 ( L 7 ) / .
The problem i s to estimate the turbulent energy d i s s i p a t i o n
per u n i t mass from macroscopic data. For i n s t a n c e , i n s t i r r e d
tanks, i t i s not obvious that a l l the power d i s s i p a t e d at the
shaft contributes to and s e v e r a l authors (2_, 3J_, 32) have been
led
to introduce an unknown " e f f i c i e n c y " such that = /pV.
An a d d i t i o n a l d i f f i c u l t y i s that i s not uniform w i t h i n the tank
volume and may vary by a f a c t o r 10 from one place to the other.
(See S e c t i o n on s t i r r e d tanks).
In order to estimate
T , Patterson (3) proposed a s s i m i l a t i n g
:e Tc,
L
to L and found ( ^ / ) / * = (Lf/)'
(^/)
= q/
A t y p i c a l value f o r
i n an i n d u s t r i a l s t i r r e d tank i s a few
m i l l i m e t e r s (19).
The smallest s i z e f o r turbulent eddies i s given by the
Kolmogorov microscale ^. Energy loss below t h i s s i z e only occurs
v i a viscous d i s s i p a t i o n . Here a l s o , s e v e r a l s c a l e s have been i n t r o
duced i n the framework of turbulence theory, depending whether ve
l o c i t y or concentration f l u c t u a t i o n s are considered, namely , ,
and X (see Table I ) . In l i q u i d s , i s t y p i c a l l y between 10 and
100 urn. The Kolmogorov microscale i s f r e q u e n t l y used i n the i n 1
1 / 3


constant
dissipation
time
Kolmogorov m i c r o s c a l e
Viscous
Taylor
.2
A l l directions
Taylor microscale
Spectra
energy d i s s i p a t i o n
= 10
rt
dt
= (
3
2
...2
~,2
/)
10
3/2
dt
dk,
f
lOv
,1/2
B a t c h e l o r m i c r o s c a l e _
)dk
E(k.)dk.
1
1
E(k,)
k, E ( k
dk,
E(k,)
E(k.)
direction
<*L ,
@bv
1/2
1 M
(5)/)
/
s i
microscale
-/
time c o n s t a n t
dissipation
intensity
microscale
/)
Se
Corrsin
Small
Corrsin
Corrsin
Segregation
Segregation
-1
"
E (k)
s
dr
dk
dk
2
'
s
12<
dk
E (k)
dk
,2
de
dt
(Corrsin)
g(r)
/ V >
E(k)
de*
dt
5)
1
,2
= 2
(&^/)^
12$c'
c'
E (k)
g(r)
c(x) c(x+r)
,2
(c )
Concentration C = C + c
Homogeneous I s o t r o p i c Turbulence
du'
dt
u(x+r)
,2
f ( r ) dr
E(Q)
,
,2
30 v u'
= 30
u'
E ( k ) , One
/2
u(x)
(uV
=f
energy o f t u r b u l e n t motion
Turbulent
Kinetic
f(r)
autocorrelation
Macroscale
u' =
U - U + u
Mean square f l u c t u a t i o n
Velocity
Table I .

w
m
W
25
>
>
PI
4^
6.
VILLERMAUX
141
t e r p r e t a t i o n of micromixing phenomena, as w i l l be discussed i n a

later section.
The general equations f o r chemical r e a c t i o n i n a turbulent
medium are easy to w r i t e , i f not to solve (2). I n a d d i t i o n t o tho
se f o r v e l o c i t i e s (U = U + u_)_and concentrations (Cj = Cj + C j ) ,
balance equations f o r q = A u ^ the segregation ( ? , and the d i s s i
pations and can be w r i t t e n (3). Whatever the shape of the
r e a c t o r under c o n s i d e r a t i o n ( u s u a l l y a tube or a s t i r r e d tank),
the s o l u t i o n of these equations poses d i f f i c u l t problems of c l o
sure, as u u, C J , C j , and a l s o C ^ C J , c?Cj ... i n the r e a c t i o n
terms have to be evaluated. The s i t u a t i o n i s even more complicated
when the temperature and the density of the r e a c t i n g mixture are
a l s o f l u c t u a t i n g . P a r t i a l s o l u t i o n s to t h i s problem have been proposed. I n the case of instantaneous r e a c t i o n s ( t ^ << T ) the "eq u i l i b r i u m assumption" a p p l i e s : the mixed reactants are immediat e l y converted and the apparent r a t e of r e a c t i o n i s simply that of
the decrease of segregation, w i t h C o r r s i n s time constant T . For
i n s t a n c e , w i t h a s t o i c h i o m e t r i c p r o p o r t i o n of r e a c t a n t s , the extent of r e a c t i o n X i s given by 1 - / ( 2 ) , a simple r e s u l t which
can a l s o be found by a p p l i c a t i o n of the IEM model (see (33)).
Another c l o s u r e approximation r e l i e s on the use of higher o r
der moments, but t h i s i s almost a deadlock as f o r only two reac
t i n g components, a 13-equation model i s required ! ( 3 ) .
A more f r u i t f u l s o l u t i o n to the c l o s u r e problem i s provided by
the use of p r o b a b i l i t y d e n s i t y functions f o r the f l u c t u a t i n g com
ponents. Various shapes (spiked, square wave, gaussian d i s t r i b u
t i o n s ) have been s u c c e s s f u l l y t r i e d 0 3 ) .
Among experimental studies of chemical r e a c t i o n s i n turbulent
media, f a s t r e a c t i o n s i n tubular reactors w i t h m u l t i j e t i n j e c t i o n
of reactants are very popular, since the f i r s t experiments of Mao
and Toor (34) and V a s s i l i a t o s and Toor (35). Their data have been
(and are s t i l l ) e x t e n s i v e l y e x p l o i t e d f o r t e s t i n g t h e o r e t i c a l mo
d e l s , although one may ask i f homogeneous i s o t r o p i c turbulence was
p e r f e c t l y c o n t r o l l e d i n these experiments. I n order to r u l e out
t h i s o b j e c t i o n , a new s e r i e s of experiments was r e c e n t l y performed
by Bennani e t a l . (_28, 29_, 30, 36) i n a 0.29 m i . d . tube e l i m i n a
t i n g the i n f l u e n c e of boundary l a y e r s . Turbulence was created by a
g r i d and c a r e f u l l y c o n t r o l l e d by v e l o c i t y f l u c t u a t i o n measurements.
Previous studies (2) had confirmed that the decrease of I w i t h a
non-reacting species (passive s c a l a r ) obeys C o r r s i n s equation :
9

dl
(3-3)
dt
where T i s given by (3-2). I n t h i s case, Bennani e t a l . (28)

found
/g~ , ( - z )~0.60
j spectrum decreasing as kj-5/3^
Let us now consider the case of a moderately f a s t second o r
der r e a c t i o n A + -> products, r = k2 C^Cg. The chemical product
t i o n term i n v o l v e s the c o r r e l a t i o n c^c^ :
s

142
- ~
- " 2
(C
' B
A B
I t i s found e x p e r i m e n t a l l y that c^cg < 0. Mc Kelvey et a l . (37)

have shown that c^cg can be c a l c u l a t e d when the segregation I of
a non-reacting species was known, i n s e t t i n g
g

A B
(3-5)
C
Ao* Bo
This i s very encouraging because i t i n d i c a t e s that C o r r s i n ' s

time constant T i s a b a s i c q u a n t i t y a l l o w i n g the p r e d i c t i o n of
the segregation both i n the absence and i n the presence of chemi
c a l r e a c t i o n s . Bennani et a l . have brought a d d i t i o n a l i n f o r m a t i o n
i n studying c o n c e n t r a t i o n f l u c t u a t i o n s i n t h e i r tube, i n the pre
sence of a chemical r e a c t i o n : the a l k a l i n e h y d r o l y s i s of methyl
formate (29). The sodium hydroxyde c o n c e n t r a t i o n C was monitored
by f a s t conductimetry. c^ was found to f i r s t increase then to de
crease as "~^6 w h i l e i t s spectrum e x h i b i t e d an unexpected decay
i n k f . Using a c l o s u r e w i t h a gaussian p r o b a b i l i t y d e n s i t y func
t i o n , they showed (30) that p h y s i c a l mixing ( 1 / T ) and chemistry
act i n an a d d i t i v e manner i n the decay of segregation. This sup
p o r t s lumped models of the IEM type (see S e c t i o n on phenomenologi
c a l models below), where these two processes are uncoupled. In ad
d i t i o n , Bennani et a l . (36) were able to p r e d i c t the value of the
c o r r e l a t i o n c^cfi < 0 from t h e i r experiments w i t h a passive t r a c e r .
This confirms T o o r s hypothesis according to which the i n f l u e n c e
of turbulence on a chemical r e a c t i o n w i t h unmixed reactants can be
determined from the s o l e knowledge of the segregation decay of a
non r e a c t i n g species i n the same c o n d i t i o n s .
We have seen that the formalism of turbulence theory (when
used alone) l e d to p r a c t i c a l l y unmanageable equations. Some au
thors have t r i e d to avoid the c l o s u r e problem by i n t r o d u c i n g phenomenological parameters. As an example, Berker et a l . (38) attemp
ted to model uc^ and ucg i n a tubular r e a c t o r w i t h a t r a n s v e r s a l
d i s p e r s i o n c o e f f i c i e n t . A more general c o n c l u s i o n of the above r e
s u l t s i s that C o r r s i n s theory and T o o r s hypothesis provide the
framework f o r a simple model where turbulence causes mass t r a n s f e r
w i t h a time s c a l e T ^ (Lg/)
, whereas chemical r e a c t i o n s would
simply be superimposed to t h i s mass t r a n s f e r . This l e d s e v e r a l au
thors to simulate segregation decrease v i a a coalescence-dispersion
(C-D) process, whose frequency only depends on the l o c a l value
of L and . Thus Canon et a l . (39) s u c c e s s f u l l y i n t e r p r e t e d
V a s s i l i a t o s and T o o r s experiments by a C-D model where the f l u i d
was d i v i d e d i n t o small c e l l s undergoing p e r i o d i c and random coal e s c e n c e - r e d i s p e r s i o n s , w i t h the frequency , the r e a c t i o n going
on between each coalescence. Canon (39) and P a t t e r s o n (3) f i t t e d
the experimental data w i t h the expression = 1333(/|) ' (the
s

6.
viLLERMAUX
143
numerical c o e f f i c i e n t should be used w i t h some p r e c a u t i o n , as the

r e s u l t i s not e x a c t l y expressed i n t h i s way i n the o r i g i n a l paper).
This i s the b a s i s f o r a f a m i l y of C-D models, which w i l l be d i s
cussed f u r t h e r .
In p a r t i c u l a r , mixing i n a s t i r r e d tank can
be, represented by a set o f s m a l l c e l l s connected by s p e c i f i e d f l o w r a t e s , i n which mixing occurs v i a a C-D process whose frequency i s
given by the expression above (HDM model (40)).
According to these models, the t u r b u l e n t f i e l d f o r chemical
r e a c t i o n i s determined once L and are known a t any p o s i t i o n i n
the r e a c t o r . This leads to i n t e r e s t i n g scale-up c r i t e r i a i n s t i r
red r e a c t o r s (2) : the mixing c h a r a c t e r i s t i c s are the same i f
/Lg i s kept constant. As ^^P/pV and V ^ L , the power input
should be p r o p o r t i o n a l to L L . This may be as high as
i f one
assumes that L ^ L. The e m p i r i c a l exponent a c t u a l l y l i e s i n b e t
ween 3 and 5.
Thus, a f t e r s t a r t i n g from the ambitious and general formula
t i o n provided by the E u l e r i a n equations of turbulence theory, most
authors have been l e d to introduce s i m p l i f y i n g assumptions and
c l o s u r e hypotheses which g r a d u a l l y brought them nearer to the
Lagrangian approach and i t s phenomenological c o e f f i c i e n t s , as w i l l
be discussed i n the next Sections. This does not mean that turbu
lence theory i s useless i n t h i s matter : i t provides the p h y s i c a l
i n t e r p r e t a t i o n of the phenomenological c o e f f i c i e n t s and may y i e l d
t h e i r value as a f u n c t i o n of experimental parameters. I n a d d i t i o n ,
the c o n s i d e r a t i o n o f the s i g n of c o n c e n t r a t i o n c o r r e l a t i o n s y i e l d s
u s e f u l r u l e s to determine the e f f e c t of segregation on s e l e c t i v i t y
(41).
In t h i s S e c t i o n devoted to turbulence and chemical r e a c t i o n ,
recent work on what has been c a l l e d "chemical turbulence" must a l
so be mentioned. This work i s e s s e n t i a l l y experimental and has
been c a r r i e d out w i t h the famous "Belousov-Zhabotinsky" r e a c t i o n .
Decreasing the space time i n a CSTR, some authors (42) have obser
ved a t r a n s i t i o n from p e r i o d i c to c h a o t i c c o n c e n t r a t i o n f l u c t u a
t i o n s . They c l a i m that t h i s i s a purely chemical phenomenon which
has nothing to do w i t h any c o u p l i n g between d i f f u s i o n and r e a c t i o n .
This c o n c l u s i o n should be checked by designing experiments where
mixing c o n d i t i o n s and p h y s i c a l u n i f o r m i t y of the mixture are to be
c a r e f u l l y c o n t r o l l e d . I n any case, the Belousov Zhabotinsky reac
t i o n , once i t s k i n e t i c mechanism i s e n t i r e l y e l u c i d a t e d and w e l l
accepted, should be an i n t e r e s t i n g t o o l f o r the study of micromix i n g i n l a b o r a t o r y r e a c t o r s , owing to i t s s e n s i t i v i t y to concentra
t i o n gradients (43).
In c o n c l u s i o n to t h i s S e c t i o n devoted to the turbulence
approach to mixing the main p o i n t s are :
- Need f o r more data on s p e c t r a E of c o n c e n t r a t i o n f l u c t u a
tions .
-Improvement of the techniques f o r monitoring l o c a l i n s t a n t a
neous concentrations down to the viscous d i s s i p a t i o n microscale
(e.g. s p a t i a l and time r e s o l u t i o n o f c o n d u c t i v i t y probes), develop
ment of new techniques (e.g. o p t i c a l , r a d i o a c t i v e t r a c e r methods).
s


144
ENGINEERING
- C l e a r d i s t i n c t i o n between macromixing e f f e c t s (large s c a l e

motions due to average v e l o c i t i e s ) and micromixing e f f e c t s ( t u r b u
lent fluctuations).
- Check f o r homogeneous i s o t r o p i c turbulence i n t e s t e x p e r i
ments ( i n f l u e n c e of boundary l a y e r s , p e r t u r b a t i o n s c l o s e to impel
lers) .
- Need f o r more t h e o r e t i c a l or experimental i n f o r m a t i o n on
the " e f f i c i e n c y " of u t i l i z a t i o n of macroscopic d i s s i p a t e d power
at the molecular s c a l e ().
- C o r r s i n s theory and i t s c h a r a c t e r i s t i c s time constant
^ ^ /
c o n s t i t u t e s a sound b a s i s f o r r e p r e s e n t i n g segregation
i n t u r b u l e n t r e a c t i n g media. This supports the Lagrangian approach
to mixing phenomena (e.g. coalescence, d i s p e r s i o n w i t h ^
\/T ).
1

Turbulence and combustion

This domain i s t r a d i t i o n a l l y at the f r o n t i e r of Chemical Reac
t i o n Engineering, and although being the subject of a c t i v e research
won't be reviewed i n d e t a i l here. However, i t represents an impor
tant f i e l d of a p p l i c a t i o n f o r the theory of chemical r e a c t i o n s i n
turbulent media w i t h the a d d i t i o n a l d i f f i c u l t y that the k i n e t i c
schemes i n v o l v e d are o f t e n complex (e.g. f r e e r a d i c a l r e a c t i o n s )
and that temperature and d e n s i t y f l u c t u a t i o n s have to be taken i n
to account. A major problem i s the p r e d i c t i o n of the formation of
p o l l u t a n t s l i k e CO, NO, N0 (44-47). C l a s s i c a l treatments using
turbulence theory are a v a i l a b l e (48, 49, 50). I t i s i n t e r e s t i n g to
n o t i c e that authors faced w i t h the c l o s u r e problem have indepen
dently imagined models of the Lagrangian type where i n t e r a c t i o n
between t u r b u l e n t eddies i s accounted f o r by an apparent mass
t r a n s f e r between each eddy and i t s average environment (See
Spalding and h i s EBU model (50). This i s e x a c t l y the same approach
as i n the IEM model developed i n Chemical engineering. Here a l s o ,
most authors recognize that the rigorous c l o s u r e problem comes to
a deadlock (46) and plead f o r simple models (51) a l l o w i n g e a s i e r
p r e d i c t i o n s (52). I t i s very encouraging to see that the chemical
engineering approach r e l y i n g on the RTD concept and d e s c r i b i n g mi
c r o s c o p i c mixing v i a C-D processes accounts w e l l f o r the produc
t i o n of p o l l u t a n t s , i g n i t i o n phenomena and s t a b i l i t y of combustors
(53, 54). This should be an i n c e n t i v e f o r chemical r e a c t i o n e n g i
neers to develop t h e i r o r i g i n a l methods and to apply them i n neigh
bouring f i e l d s , i n cooperation w i t h the s p e c i a l i s t s of these d i s
c i p l i n e s who may e n r i c h them w i t h t h e i r own experience.
X
Macromixing and Residence Time D i s t r i b u t i o n s
(RTD)
The RTD concept i s now w e l l e s t a b l i s h e d and w i d e l y used f o r

d e s i g n i n g , scaling-up and o p t i m i z i n g chemical r e a c t o r s . This sub
j e c t was r e c e n t l y reviewed by Nauman (J_). Most c l a s s i c a l textbooks
(55) mainly deal w i t h the simple case of steady s t a t e incompres
s i b l e f l o w , s i n g l e i n l e t and o u t l e t , and p u r e l y convective motion

6.
145
viLLERMAUX
of the f l u i d across the i n l e t / o u t l e t s e c t i o n s . A u s e f u l represen

t a t i o n of t h i s s i t u a t i o n i s the "Bundle of P a r a l l e l Tubes" (BPT)
model ( f i g u r e 1) where the r e a c t o r volume i s reorganised i n the
form of a bundle of small tubes of i n c r e a s i n g l e n g t h , equal to the
residence time t . The f l u i d flows a t constant v e l o c i t y (the par
t i c l e s o f the same age are on the same v e r t i c a l l i n e ) and the e l e
mentary f l o w r a t e dQ i n each tube i s such that dQ = E ( t ) d t . The
locus of the tubes extremity then p i c t u r e s the f a m i l i a r F ( t ) cur
ve. This model i s introduced because i t has i n t e r e s t i n g p r o p e r t i e s
(56) and provides a concrete p i c t u r e of the RTD so that a frequent
use of t h i s r e p r e s e n t a t i o n w i l l be made i n the next S e c t i o n s .
Recent work has attempted to g e n e r a l i z e RTD theory to l e s s
r e s t r i c t i v e assumptions, so that i t might apply to more r e a l i s t i c
s i t u a t i o n s encountered i n p r a c t i c e . The type of flow and the ope
r a t i n g c o n d i t i o n s of the r e a c t o r are given i n Table I I below, t o
gether w i t h the corresponding references :
s

Table I I : G e n e r a l i z a t i o n of the RTD theory

Classical
assumption
Generalization
Reference
steady
transient, periodical
(0(56)
Volume
constant
variable, periodical
ly variable
(0(56)
(58) (59)
Density
constant
variable
(0(56)
convective
dispersive
(0(57)
Flow regime
Inlet/Outlet
Number of
Inlets/Outlets
1/1
Semi-batch r e a c t o r
2/1
n/n
1/0 ,
2/0 *
( 0 ( 5 6 ) (60)
(61)(62)(1)
(56)
RTD problems' i n v a r i a b l e regimes can be d e a l t w i t h as s p e c i a l

cases o f the p o p u l a t i o n balance method (56).
Let ipdadV be the number of p a r t i c l e s i n volume dV w i t h i n the
age i n t e r v a l a, a + da. The t o t a l number of p a r t i c l e s i n the reac
tor i s = j ifjdadV and obeys the w e l l known p o p u l a t i o n b a l a n
ce equation
a
| f + V.C*5> + ? = 0
at
The
(5-1)
l o c a l age d i s t r i b u t i o n f u n c t i o n i s defined as f = /. f i s


146
ENGINEERING
Figure 1. The BPT (bundle o f p a r a l l e l tubes) model. The f l o w r a t e i n a tube w i t h residence time between t and t
^
dQ = E ( t )dt . The f l u i d flows i n the tubes at constant v e l o c i t y .
A l l p a r t i c l e s on a v e r t i c a l have the same age. The h e i g h t o f the
p i l e i s Q. The l o c u s o f tube e x t r e m i t i e s i s a p i c t u r e o f F-curve
ts
E(t) d t ) . Olson and Stout a l s o make use o f such a model
/
i n t h e i r review (177).
s

6.
viLLERMAUX
147
normalized and could be the impulse response to an i n j e c t i o n o f

t r a c e r a t the i n l e t . L e t f_ be the average value o f f over the r e
a c t o r volume and f and f
be the f l u x averages over the i n l e t
and o u t l e t s e c t i o n s r e s p e c t i v e l y . Then f = I ( a , t ) i s the i n s t a n
taneous i n t e r n a l age d i s t r i b u t i o n (IAD), f ^ = (a) and
f
= E ( t , t ) i s the instantaneous RTD. From ( 5 - 1 ) , i t i s easy t o
show by averaging that
n
o u t
o u t

The corresponding moment equation i s

1
\ a. o u t n,out
V
^
d"t
}+
( 5
"
3 )
where
i s the n^ti order moment of E ( t , t ) and that o f
I(a,t).
These equations a l l o w v a r i o u s s p e c i a l cases t o be t r e a t e d .
This l i n k s the n ^ order moment of the RTD to the n-l*-* order mo
ment of the IAD.
The IAD I ( a , t ) i n a chemical r e a c t o r i s s p e c i a l l y i n t e r e s t i n g
and i t does not seem that s u f f i c i e n t a t t e n t i o n has been p a i d t o
the p o s s i b i l i t i e s o f f e r e d by t h i s f u n c t i o n . For i n s t a n c e , l e t us
consider a semi-batch r e a c t o r , and l e t Q(t) be the feed f l o w r a t e
of an incompressible f l u i d . The instantaneous f l u i d volume i s
V = J Q i t ^ d t ' , from which the IAD i s w r i t t e n I ( a , t ) = Q(t-a)/V.
I ( a , t ) can be used to c a l c u l a t e the chemical conversion i n d i f f e
rent segregation s t a t e s . Consider a species of c o n c e n t r a t i o n C
produced w i t h the r a t e n t . I f the mixture i s assumed to be w e l l mi
xed a t the molecular s c a l e , one obtains the f a m i l i a r mass balance
equation
s
QC
in
+&V =
(VC)
(5-4)
whereas i f the f l u i d i s t o t a l l y segregated, C v a r i e s i n each par

t i c l e as C-Q(a, t) (batch conversion) such that :
_ = & ,
a = 0, C - C . ( t - a )
B
(5-5)
The average c o n c e n t r a t i o n i n the r e a c t o r i s then given by

C(t) =
C_(a,t) I ( a , t ) da
y
(5-6)
JD
The conversion i n p a r t i a l l y segregated f l u i d can be c a l c u l a

ted i n a s i m i l a r manner, f o r i n s t a n c e by using the IEM model (see
next S e c t i o n and (56)). The IAD approach can a l s o be g e n e r a l i z e d
to the case o f s e v e r a l f f l f f l ^
ÎCA
Society Library
1155 16th St. N. W.
In Chemical ReactionWashington,
EngineeringPlenary
D.C.Lectures;
20036Wei, J., et al.;
148
Nauman (J_) has proposed an i n t e r e s t i n g treatment of RTD i n

unsteady-state r e a c t o r s . Two washout f u n c t i o n s are defined :
W (t ,t) = 1 - F - , f r a c t i o n o f m a t e r i a l e n t e r i n g a t time t
which w i l l remain i n the r e a c t o r f o r a d u r a t i o n greater than t ,
and W
(t ,t) = 1 -F
, f r a c t i o n of m a t e r i a l l e a v i n g a t time t
which remained i n the r e a c t o r f o r a d u r a t i o n g r e a t e r than t . From
tfiese f u n c t i o n s , two RTD can be defined, namely E ^ = i / s
out ^ o u t ^
^- ^
all
c l a s s i c a l p r o p e r t i e s of steady
s t a t e RTD except that they vary w i t h time. I n p a r t i c u l a r , chemical
conversion can be c a l c u l a t e d i n the two l i m i t s o f mixing e a r l i n e s s
(see next S e c t i o n ) . For minimal mixedness :
n
out
o u t
9 F
wn
n a v e
9 t

C _(t) =
out
C f t , C. ( t - t )1
( t ,t) dt
B [s' m
s J out s'
s
v
(5-7)
and f o r maximal mixedness :

, . - C tt -] H
W
(A,t)
SC
3
c
t o
o n t
(., )
t
Qut
o u t
( t ) = C(X = 0,t)
which i s a g e n e r a l i z e d form of Zwietering's equation.

Thanks to t h i s formalism, p e r i o d i c regimes can be d e a l t w i t h
( e s t i m a t i o n of average conversion). The case of an unsteady CSTR
has been e s p e c i a l l y studied (J_) . Mixing e f f e c t s i n variable-volume
chemical reactors were considered by Roth e t a l . (58). I n t h e i r
model, the volume of a semi-batch r e a c t o r i s v a r i e d p e r i o d i c a l l y
(at constant f l o w r a t e Q) between V and V . The f i l l i n g and empty
ing stages are separated by a p u r e l y batch p e r i o d . The model de
pends on two parameters, namely = V / V and Og = t b a t c h ^ t o t a l *
The authors show that t h i s p e r i o d i c operation i s equivalent to
that i n a continuous r e a c t o r whose degree of macromixing can be
v a r i e d between that of a plug flow r e a c t o r and that of a CSTR.
In steady s t a t e continuous r e a c t o r s , an important case en
countered i n p r a c t i c e i s that of mixtures w i t h v a r i a b l e d e n s i t y .
The general p o p u l a t i o n balance equations presented above t h e o r e t i
c a l l y give the s o l u t i o n to the problem i f the RTD approach i s r e
tained f o r c a l c u l a t i n g chemical conversion. However, there e x i s t
simpler treatments a p p l i c a b l e to s p e c i a l cases. Nauman (J_) propo
sed a s o l u t i o n v a l i d f o r segregated mixtures whose density only
depends on an a x i a l coordinate i n the r e a c t o r . He used a v a r i a n t
of the Bundle of P a r a l l e l Tubes model i n which a l l the tubes have
the same length but d i f f e r e n t f l o w i n g v e l o c i t i e s . V i l l e r m a u x (56)
extended the well-known tanks i n s e r i e s model to the case where
the flowrate Q i s v a r i a b l e from tank to tank, according to an ex
pansion f a c t o r
= Q^/Qi^. I f the expansion i s ignored, the ex
p l o i t a t i o n of a RTD experiment leads to an apparent number of tanks
0


6.
viLLERMAUX
149
i n s e r i e s l a r g e r than the a c t u a l one. I t would be i n t e r e s t i n g to

see whether t h i s apparent number can be used to o b t a i n an a p p r o x i
mate value of the conversion.
The case of r e a c t o r s w i t h two i n l e t s was considered more than
ten years ago by Treleaven and Tobgy ( 6 0 ) . The BPT model allows an
i n t e r e s t i n g r e p r e s e n t a t i o n of the flow i n these r e a c t o r s ( 5 6 ) ( f i gure 2 ) . This w i l l be u s e f u l when micromixing phenomena w i l l be
d e a l t w i t h (next S e c t i o n ) .
A somewhat academic problem a l s o seems to have found i t s so
l u t i o n i n the work of Nauman (57) who showed that RTD i n systems
governed by the d i s p e r s i o n equation could be defined as i n c l o s e d
systems provided the time spent by the t r a c e r outside the r e a c t o r
owing to d i f f u s i o n be excluded from the count.
The l a s t item deserving emphasis i n t h i s s e c t i o n i s the pro
mising concept of " g e n e r a l i z e d r e a c t i o n time" (J_) (56). Consider a
chemical r e a c t i o n w i t h r a t e equation r = k F(C-) and assume that
k i s a l o c a l l y v a r i a b l e parameter owing t o s p a t i a l d i s t r i b u t i o n s
of e x t e r n a l p o r o s i t y e ( c a t a l y t i c r e a c t i o n ) , temperature, e t c . . .
and l e t k be the average value of k over the whole r e a c t o r . D e f i
ning the l o c a l parameter h = k/k, i t i s p o s s i b l e to introduce a
g e n e r a l i z e d r e a c t i o n time t ^ such that d t ^ = h dt , where h i s the
l o c a l value of k/k along the tube of the BPT model ( f i g u r e 1 ) . The
value of t ^ f o r a p a r t i c u l a r tube (residence time t ) i s t = <h> t
where <h> i s the average value of h along the tube a x i s . Now consi
d e r i n g a l l the tubes, there e x i s t s a " r e a c t i o n time d i s t r i b u t i o n "
JCitO s i m i l a r to the RTD E ( t ) . The conversion along the tube can
be c a l c u l a t e d according t o
e
S s r
o f :
k F
< j>
c
( 5
9 )
and the o v e r a l l extent of r e a c t i o n (under the assumption of m i n i

mal mixedness) i s
X = J" X( )%( )
t i
(5-10)
t i
This g e n e r a l i z e s the well-known equation e s t a b l i s h e d i n the case

of RTDs. N o t i c e t h a t t = t .
For homogeneous i s o t h e r m a l r e a c t o r s , h 1 and f ^ ( t ^ ) i s the
RTD. For i s o t h e r m a l heterogeneous r e a c t o r s , h = (1 - ^/ and
7^(tj_) i s the contact-time d i s t r i b u t i o n (CTD) introduced by Nauman
and C o l l i n g e ( 1 ) . I n the case of non-isothermal r e a c t o r s ,
h = k ( T ) / k ( T ) , andj(t) i s a "thermal time d i s t r i b u t i o n " .
U n f o r t u n a t e l y , i f there e x i s t experimental methods f o r measu
r i n g the RTD and the CTD by means of t r a c e r t e s t s , nothing has
been p u b l i s h e d about the experimental determination of the l a t t e r
d i s t r i b u t i o n . At present, t h i s l i m i t s the p o t e n t i a l a p p l i c a t i o n s
of such an approach.
This b r i e f review on RTDs would be incomplete without a few
g


150
ENGINEERING
Figure 2. E x t e n s i o n o f the BPT model t o the case o f a r e a c t o r

having two i n l e t s (two unmixed feedstreams o f r e s p e c t i v e f l o w r a t e s
Q- and Q^). The p i c t u r e shows how t o b u i l d the o v e r a l l RTD from
those o f each separate feedstream by a s s o c i a t i n g tubes having the
same residence time.


6.
VILLERMAUX
151
words on experimental techniques. Tracer methods are now r o u t i n e l y

u t i l i z e d i n i n d u s t r y and i n l a b o r a t o r i e s . Bourne e t a l . (63) desc r i b e d a r e v e r s i b l e photochromic t r a c e r f o r RTD measurements i n
h i g h l y viscous l i q u i d s . Conochie and Gray (64) developed a s p e c t r o photometer f o r the study of mixing i n a channel s i m u l a t i n g a metall u r g i c a l r e a c t o r . I n t e r e s t i n g v i s u a l i s a t i o n techniques were a l s o
devised by Q u r a i s h i and Fahidy (65) who induced the change of col o r of an i n d i c a t o r a t a surface by e l e c t r o l y s i s and by C a s t e l l a n a
et a l . (66) who s t u d i e d mixing i n r e a c t o r v e s s e l s by means of a
gamma camera and a Technetium 99 t r a c e r . There i s s t i l l a need f o r
a good t r a c e r f o r p a r t i c u l a t e s o l i d s . Magnetic t r a c e r s should be
developed f o r t h i s purpose (9).
In c o n c l u s i o n to t h i s s e c t i o n , research i n the RTD area i s
always a c t i v e and the i n i t i a l concepts of Danckwerts are g r a d u a l l y
being completed and extended. The p o p u l a t i o n balance approach provides a t h e o r e t i c a l framework f o r t h i s g e n e r a l i z a t i o n . However, i n
s p i t e of the e f f o r t s of s e v e r a l authors, simple procedures, easy
to use by p r a c t i t i o n e r s , would s t i l l be welcome i n the f i e l d of
unsteady s t a t e systems ( v a r i a b l e volumes and flow r a t e s ) , m u l t i p l e
i n l e t / o u t l e t r e a c t o r s , v a r i a b l e d e n s i t y mixtures, systems i n which
the mass-flowrate i s not conserved, e t c . . . On the other hand, the
promising " g e n e r a l i z e d r e a c t i o n time d i s t r i b u t i o n " approach could
be developed i f s u i t a b l e experimental methods were a v a i l a b l e f o r
i t s determination.
Mixing e a r l i n e s s i n the age domain ; phenomenological
models
The RTD (one or two i n l e t s ) c h a r a c t e r i z e s macromixing, but i t

i s w e l l known that t h i s i s not s u f f i c i e n t to describe the whole
mixing process i n the r e a c t o r . A d d i t i o n a l i n f o r m a t i o n i s r e q u i r e d
and two questions must be answered : how are p a r t i c l e s of d i f f e rent ages mixed and brought i n t o c o n t a c t , t a k i n g i n t o account the
RTD c o n s t r a i n t ? This i s the problem of "mixing e a r l i n e s s " , the
subject of t h i s S e c t i o n . Once p a r t i c l e s having the same l i f e expectancy (or r e s i d u a l l i f e t i m e ) are c l o s e t o each o t h e r , what i s the
degree of mixing between molecules contained i n these p a r t i c l e s ?
This i s the problem of "segregation", discussed i n the next Sect i o n . I t must be c l e a r l y s p e c i f i e d that these two problems are d i s t i n c t and independent, a p o i n t which does not seem to be obvious
i n the mind of a l l authors. I n other words a f l u i d i n a s t a t e of
maximum mixedness may w e l l remain segregated i f microscopic i n t e r a c t i o n between p a r t i c l e s i s u n e f f e c t i v e . I n a continuous r e a c t o r ,
the f l u i d i s i n a s t a t e of Minimum Mixedness (Min Mix) i f mixing
between p a r t i c l e s occurs a t the l a t e s t moment : Neighbouring part i c l e s have the same age. Conversely the f l u i d i s i n a s t a t e of
Maximum Mixedness(Max Mix) i f p a r t i c l e s of d i f f e r e n t ages are m i xed as soon as they enter the r e a c t o r , mixing occurs a t the earl i e s t moment and neighbouring p a r t i c l e s have the same l i f e expectancy. P h y s i c a l mixing among p a r t i c l e s i s c h a r a c t e r i z e d by a d i f f e r e n t n o t i o n : the s t a t e of segregation which may l i e between two


152
CHEMICAL
REACTION
ENGINEERING
extreme s i t u a t i o n s : the " m a c r o f l u i d " , where no p h y s i c a l mixing a t

a l l takes place between p a r t i c l e s , and the " m i c r o f l u i d " , which i s
i n t i m a t e l y mixed on the molecular s c a l e . There i s an ambiguity
between these two notions i n the l i t e r a t u r e because many authors
make the i m p l i c i t assumption that once the f l u i d i s mixed i n the
age domain, i t behaves l i k e a m i c r o f l u i d i . e . minimum mixedness i s
confused w i t h s e g r e g a t i o n and maximum mixedness w i t h molecular
mixing.
I n what f o l l o w s , i t may happen that we accept t h i s assumption
i n order to e x p l a i n t h e i r treatments but we must keep i n mind that
t h i s i s not necessary.
We may now r e c a l l the fundamental equations f o r c a l c u l a t i n g
chemical conversion i n the l i m i t i n g s t a t e s of Min Mix and Max Mix.
The BPT model provides a convenient p i c t u r e of the two s i t u a t i o n s
( f i g u r e 3 ) . I f the bundle i s arranged i n such a way that the p a r t i
c l e s of same r e s i d u a l l i f e t i m e are s i t u a t e d on the same v e r t i c a l
l i n e , then minimal mixedness corresponds to a p e r f e c t i n s u l a t i o n
between tubes and the conversion f o r a s i n g l e r e a c t i o n i s w r i t t e n
Cj =
C
0
( c
j B
E ( a )
- r ^
- & . ( C .
da
C.
j ,B
"
C.
jo
Conversely, i f the p a r t i c l e s on a same v e r t i c a l l i n e are r e a l l y

mixed, then maximum mixedness i s achieved. I n a d d i t i o n , i f the
f l u i d i s w e l l micromixed, then, Z w i e t e r i n g s equation a p p l i e s :
T
- i
- V
to be i n t e g r a t e d from = to = 0. The problem of modeling i n

termediate mixing s t a t e s has been and i s s t i l l the subject of many
t h e o r e t i c a l i n v e s t i g a t i o n s . Equations ( 6 - 1 ) and (6-2) are w r i t t e n
at steady s t a t e . Chen (67) has shown how to g e n e r a l i z e them to
unsteady regimes by using the p o p u l a t i o n balance formalism. An ex
c e l l e n t review of a l l the models proposed f o r r e p r e s e n t i n g impremixed feedstreams r e a c t o r s was published by R i t c h i e and Tobgy ( 6 ) .
I t i s u s e f u l to t r y to s e t some order i n t h i s host of models.
For t h i s purpose, the r e p r e s e n t a t i o n proposed by Spencer, Leshaw
et a l . (68) i s h e l p f u l . I t i s e s s e n t i a l l y a two-environment model
i n which the assumption c i t e d above: Min. Mix. = m a c r o f l u i d and
Max. Mix. = m i c r o f l u i d i s i m p l i c i t l y made. Along the a x i s o f a
s m a l l tube o f the BPT model, the f l u i d g r a d u a l l y passes from a Min.
Mix. s t a t e t o a Max. Mix. s t a t e (Figure k). The residence time i n
t h i s p a r t i c u l a r tube l i e s i n the range t , t + d t and the flowr a t e i s dQ = Q E ( t ) d t . The flow t r a n s f e r r e d from t h e E n t e r i n g
Environment (E.E.) t o t h e Leaving Environment (L.E.) i n the i n t e r v a l
g


6.
viLLERMAUX
153
Figure 3. The two l i m i t i n g cases f o r mixing e a r l i n e s s . L e f t ,

Min. Mix.: p a r t i c l e s having the same age are c l o s e together (on
the same v e r t i c a l ) ; r i g h t , Max. Mix.: p a r t i c l e s having the same
l i f e expectancy are c l o s e together (on the same v e r t i c a l ) .
ts+dts ts
+dX
DISCHARGE
yzQ t<0
Figure k. tyodel o f Spencer and Leshaw (68). Along the a x i s o f a

tube o f the BPT model, the f l u i d g r a d u a l l y passes from a Min. Mix.
E.E. (unshaded) t o a Max. Mix. L.E. (shaded). M i x i n g i s c h a r a c t e r
i z e d by the f u n c t i o n (, t ) such t h a t over dX, d Q = h(X,t )dXdQ (a).
A l l the Max. Mix. f l u i d having the same l i f e expectancy can be
c o l l e c t e d (b) i n a s i n g l e zone w i t h f l o w r a t e QMax ( c ) . This zone
may a l s o be considered as an "accumulator" (dimensionless volume v)
t r a n s i t i n g along the time a x i s and r e c e i v i n g the Max. Mix. f l u i d
before being discharged a t time t = 0 ( d ) .
2

154
ENGINEERING
i s : d^Q = Q A ( X , t ) d X d t
where A ( X , t ) i s a mixing f u n c t i o n
which can a l s o be expressed from the RTD by i n t r o d u c i n g h ( X , t ) :
A ( X , t ) = h ( X , t ) E ( t ) . For a given l i f e expectancy , the f r a c
t i o n of f l u i d i n the Min.Mix. s t a t e i s s and the complementary
f r a c t i o n 1 - s i s i n the Max.Mix. s t a t e . From (6-4) and f i g u r e 4,
s(X,t ) = s(0,t ) + j
h(X,t )dX (6-3)
where one may have
s ( t , t ) 1 (tube inet) and s ( 0 , t ) 0 (tube O u t l e t ) . s ( X , t ) ,
also w r i t t e n s(X,a) i s known as the "segregation f u n c t i o n "
although, as the above remark i n d i c a t e s , "segregation of ages"
would be b e t t e r . In our p a r t i c u l a r tube, the flowrate of the Max.
Mix. f l u i d i s d Q
= Q g(X)dX with g(X) = } A ( X , t ) d t =
J~ h ( X , t ) E ( t ) d t . In the whole r e a c t o r , the Max.Mix flowrate i s
thence Q
= J " g(X')
dX .
This t r a n s f e r between two environments can a l s o be described
as a Lagrangian process where a small band of volume
d^Max
^Max ^ moves with a constant v e l o c i t y along the X axis i n
the d i r e c t i o n of decreasing X. Spencer et a l . (68) consider t h i s
volume as an "accumulator" whose dimensionless volume was d e f i
ned by
s
M a x

m a x
f
A (-z, - t ) dz
z
(6-4)
i s the accumulator volume at time t < 0.

The accumulator entered the r e a c t o r at time < 0 (- < - t ) .
It leaves the r e a c t o r and discharges at time t = 0. This Lagran
gian formulation i s very i n t e r e s t i n g as i t allows the representa
t i o n of t r a n s i e n t regimes by a succession of accumulators which
are g r a d u a l l y f i l l e d during t h e i r t r a n s i t i n the r e a c t o r and are
discharged when they leave i t . The conversion i s then given by the
f o l l o w i n g equation :
dC.
I
dt
A(-z,-t)
i,B
C ( z ) , t-z
k
C. dz +31
(6-5)
C j ^ Is the f a m i l i a r batch expression and the equation has to be

i n t e g r a t e d from t = - (vCj > 0) up to t = 0,
Most "micromixing models" published i n recent years can be
compared on the base of t h e i r "segregation" f u n c t i o n . As t h e i r
a b s t r a c t mathematical character may render the o r i g i n a l p u b l i c a
tions d i f f i c u l t to understand to n o n - s p e c i a l i s t s , I have t r i e d to
i l l u s t r a t e t h e i r p r i n c i p l e i n a more concrete manner by represen
t i n g both the two environments i n the BPT model and the r e l a t e d
segregation functions i n the (,) space (Figures 4 and 5). The
reader w i l l recognize well-known models o f "intermediate micromixing."
He w i l l a l s o agree that one can e a s i l y imagine an almost
endless set of models of t h i s kind by varying the shape of the sf u n c t i o n without r e a l l y b r i n g i n g i n anything new.
Once we know how the f l u i d i s t r a n s f e r r e d from the E n t e r i n g


6. viLLERMAUX
155
to the Leaving Environment, there remains the need to s p e c i f y the

mechanism of i n t e r a c t i o n between p a r t i c l e s having the same l i f e
expectancy i n the L.E. T h i s i s the problem of so c a l l e d segrega
t i o n decay. A f i r s t way to represent t h i s i n t e r a c t i o n i s to assume
that p a r t i c l e s w i t h the same undergo random coalescence-disper
sions (C-D) w i t h frequency . Chemical r e a c t i o n s , i f any, occur
w i t h i n the p a r t i c l e s between two coalescences. A t each coalescence,
the molecules i n the p a r t i c l e s are mixed up and the composition i s
thus averaged before d i s p e r s i o n . I n a continuous r e a c t o r w i t h
space time , the corresponding parameter i s I = , r e p r e s e n t i n g
the average number of coalescences per p a r t i c l e during i t s stay i n
the r e a c t o r . The random-coalescence process i s g e n e r a l l y simulated
by a Monte-Carlo method. This method was f i r s t used by Spielman
and L e v e n s p i e l (82) and then e x t e n s i v e l y e x p l o i t e d by Kattan and
A d l e r (83) and R i t c h i e and Tobgy (77).
In a second k i n d of model, the i n t e r a c t i o n i s represented v i a
a d e t e r m i n i s t i c process. Each p a r t i c l e i s assumed to exchange mat
ter w i t h an average environment made up of a l l p a r t i c l e s having
the same l i f e expectancy. For i n s t a n c e , the IEM Model ( I n t e r a c t i o n
by Exchange w i t h the Mean), was i n i t i a l l y developed f o r represen
t i n g micromixing i n s t i r r e d r e a c t o r s (33, 32). However, i t can ea
s i l y be extended to any RTD (84). The b a s i c equation f o r conver
s i o n of a species i n the L.E. i s w r i t t e n
c.(A) - c . ( x , t )
ac.
3a
1
where C.() =
j
1 - F(X)
w
(6-6)
m
C.(X,t) E ( t ) dt
j
b
S
b
(6-7)
The c h a r a c t e r i s t i c parameter i s the micromixing time t ( N.B. :

t = + ).
In a t h i r d f a m i l y of models, i n t e r a c t i o n between p a r t i c l e s i s
assumed to occur by molecular d i f f u s i o n , e i t h e r between a p a r t i c l e
and i t s average environment (81, 109) or between two s p e c i f i e d c a
tegories of p a r t i c l e s (79). This p o i n t w i l l be examined w i t h more
d e t a i l i n the next S e c t i o n .
The case of r e a c t o r s w i t h two unmixed feedstreams i s e s p e c i a l
l y i n t e r e s t i n g ( 6 ) , because more r e a l i s t i c f o r a p p l i c a t i o n s . I t
has been thoroughly i n v e s t i g a t e d i n a s e r i e s of papers by r e s e a r
chers of Exeter U n i v e r s i t y (UK). The BPT model o f f e r s a convenient
p i c t u r e of the r e a c t o r where both feed streams have t h e i r own RTD
and the two bundles are placed side by s i d e i n such a manner that
p a r t i c l e s w i t h the same l i f e expectancy are s i t u a t e d as usual on
the same v e r t i c a l l i n e ( f i g u r e 6). I n a f i r s t paper (60), a d i s
t i n c t i o n i s made between age mixedness and species mixedness : Ma
ximum age and species mixedness i s achieved i f p a r t i c l e s w i t h the
same l i f e expectancy are mixed. A more r e s t r i c t i v e case i s that
where p a r t i c l e s are able to mix only i f they have both the same
m

156

SU.a)
Figure 5. Models, a, general case. F l u i d flows from l e f t t o

r i g h t a t constant v e l o c i t y and i s t r a n s f e r r e d from the E.E. (un
shaded tubes, Min. Mix.) t o the L.E. (shaded area, Max. M i x . ) . I n
the s(,a) space, a p a r t i c l e having a given residence time t de
s c r i b e s a t r a j e c t o r y between the plane = 0 and the plane = 0;
b, * model o f Spencer e t a l . (68_) . Each p a r t i c l e stays i n the E.E.
f o r a d u r a t i o n p r o p o r t i o n a l t o i t s residence time; c , r d model o f
Spencer e t a l . (68), which i s a l s o the s e r i e s model o f Weinstein
and A d l e r (69). Each p a r t i c l e stays f o r a constant time
i n the
E.E., provided t > r ^ ; d, p a r a l l e l model o f Weinstein and A d l e r
(69). A l l p a r t i c l e s w i t h t < r s t a y i n the E.E.
The other ones
are immediately t r a n s f e r r e d i n the L.E.
g


6.
VILLERMAUX
157
Figure 5 Models, e, model o f V i l l e r m a u x and Z o u l a l i a n (TO) F o r

each residence time, a given f r a c t i o n o f the p a r t i c l e s s t a y i n the
E.E. and the r e s t i s immediately t r a n s f e r r e d i n the L.E. The segreg a t i o n f u n c t i o n s o n l y depends on t . On the f i g u r e , s = e x p ( - K t )
but other f u n c t i o n s may be proposed; f , i n V i l l e r m a u x and Z o u l a l i a n s
model (T0_) (when s only depends on t ) , an a l t e r n a t i v e representat i o n i s p o s s i b l e where a l l the tubes o f the E.E. and a l l those o f
the L.E. have been p i l e d up t o g e t h e r ; g, model o f Ng and R i p p i n (72)
I t i s somewhat s i m i l a r t o the preceding one, except t h a t s only depends on the age, s = exp(- Ra) For r e p r e s e n t i n g the r e d u c t i o n o f
s i z e o f e n t e r i n g p a r t i c l e s i n an unmixed feedstream r e a c t o r , P l a s a r i
et a l . (71) have used a model o f t h i s k i n d where s = ( l - a / t ^ ) ; h ,
model o f Valderrama and Gordon (73. - J) . This i s a two-parameter
model (p,w) d e r i v e d from the one on F i g u r e 5c.
s


158
Q.
Figure 6. M i x i n g i n a flow r e a c t o r w i t h two unmixed feedstreams

(60). L e f t , Maximum age, maximum species mixedness; middle,
minimum age, maximum species mixedness (mixing i n t h i s case can
a l s o be assumed t o occur by molecular d i f f u s i o n between two tubes
having the same
and
(79)); and r i g h t , mixing between p a r t i c l e s
o f t h e same l i f e expectancy by a random-coalescence process (77.)

6.
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159
l i f e expectancy and the same age (Minimum age, Maximum species

mixedness). Mixing i s simulated by Monte-Carlo method (random coa
lescence) (77)
This t h e o r e t i c a l work i s supported by an e x p e r i
mental study where a r e a c t o r was f e d with two unmixed feedstreams
having d i f f e r e n t RTD (85).
Chemical r e a c t i o n measurements are r e
p o r t e d (86), and i t i s shown that a s i n g l e i n t e r a c t i o n parameter
I = accounts f o r chemical conversion when the s t o i e c h i o m e t r i c
r a t i o and the Damkohler number (kC x) are v a r i e d . The l a s t paper
of the s e r i e s (79) compares the merits of a r e a c t i o n / d i f f u s i o n mo
del and of the C-D model. I t i s concluded that C-D provides a bet
ter c o r r e l a t i o n of experimental r e s u l t s . The models presented on
f i g u r e 5 can e a s i l y be extended to the case of two separate feedstreams by j o i n i n g the corresponding E n t e r i n g and Leaving E n v i r o n
ments side by side ( f i g u r e 7). For i n s t a n c e , a three environment
model has been proposed by R i t c h i e and Tobgy (87) (Two E.E. and
one L.E.) with the segregation f u n c t i o n s(a) = exp(-R a). A gene
r a l i z a t i o n to four environments (Two E.E. and two L.E.) was s t u
died by Mehta and T a r b e l l (88). A Three-Environment model where
the segregation f u n c t i o n only depends on t was published by
R i t c h i e (78). In t h i s case, the r e p r e s e n t a t i o n of f i g u r e s 5-6 i s
v a l i d . The model depends on three parameters : two i n t e r a c t i o n mo

d u l i Ig and I
f o r the E.E. and the L.E. r e s p e c t i v e l y , and the
"segregation parameter R x [s = e x p ( - R t ) ] . The reader w i l l
understand that with a l i t t l e imagination an almost endless s u i t e
of models of t h i s k i n d can be conceived.
In the models c i t e d above, i n t e r a c t i o n between the e n v i r o n
ments from the two feedstreams was modelled by a C-D mechanism.
The IEM Model can also be used f o r t h i s purpose. Equation (6-6)
s t i l l holds but the mean value Cj(A) at a given l i f e expectancy
must comprise both feedstreams 1 and 2 :
L
11
l - FM
FAX)
C j l
( A , t ) a, E
s
l (
t )
s
dt
(6-8)
C (X,t ) a
j 2
E ( t ) dt
2
with a = Q /(Q + Q ) , ^ ( ) = a
E ( t ) d t and s i m i l a r d e f i
n i t i o n s f o r feestream 2.
I now come to a very important observation. We have seen that
i n t e r a c t i o n between the environments (or between the p a r t i c l e s
themselves i f t h i s i s assumed equivalent to segregation decay)
could be represented by d i f f e r e n t one parameter models, e.g.
- The C-D model, parameter I =
- The IEM model, parameter T / t
- The Models of Ng and R i p p i n , parameter R T
- The Shrinking-Aggregate Model (71), parameter /te
Numerical simulations and t h e o r e t i c a l arguments (based on con

c e n t r a t i o n variance or chemical conversion) l e a d to the very i n t e r ]


160
E.E.1
E.E.2
Qi
Figure 7. Top, extension o f Spencer and Leshaw's model t o the case

of a r e a c t o r having two i n l e t s (unmixed feedstreams). I n the
general case, there are four environments (two e n t e r i n g , two
l e a v i n g ) . Bottom, when the segregation f u n c t i o n o n l y depends on
residence time, t h i s r e p r e s e n t a t i o n i s a l s o v a l i d (78). Three
environment model w i t h three parameters R
s = exp(-R t ^ ) ,
1^ ( i n t e r a c t i o n modulus i n the l e a v i n g environment), 1^ ( i n t e r
a c t i o n modulus i n the e n t e r i n g environment, assumption o f Figure
6, m i d d l e ) .

6.
VILLERMAUX
161
e s t i n g r e s u l t that they y i e l d approximately equivalent r e s u l t s i f

the f o l l o w i n g r e l a t i o n s h i p between the parameters i s e s t a b l i s h e d
(33, 78) :
Let us give three examples f o r t h i s equivalence i n comparing

the C-D and the IEM models. Figure 8 shows the conversion f o r an
instantaneous r e a c t i o n i n a CSTR f e d with unmixed feedstreams i n
s t o i c h i o m e t r i c amounts (33). On Figure 9 the y i e l d of intermedi
ate product R i n a system o f consecutive competing r e a c t i o n s A+B-+R
R+B*S i s p l o t t e d against the conversion o f i n a CSTR with un
mixed feedstreams (33, 80). Figure 10 compares r e s u l t s obtained f o r
a second-order r e a c t i o n i n a r e a c t o r with unmixed feedstreams
having d i f f e r e n t RTDs (equivalent t o 2 and 6 tanks i n s e r i e s ) by
Treleaven and Tobgy (77) to a s i m u l a t i o n by the IEM model using
equations (6-6) and (6-8)(84). In a l l the cases, a s a t i s f a c t o r y
agreement i s observed between the p r e d i c t i o n s of both models. Of
course, t h i s would be less good f o r small values of the i n t e r a c t i o n
parameters (see f i g u r e 8), when the p a r t i c l e s undergo s t a t i s t i c a l
l y very few coalescences during t h e i r t r a n s i t i n the r e a c t o r . We
can conclude from t h i s that a l l these phenomenological models are
approximately equivalent, and that the choice i n favor of one or
the other i s o f t e n more a matter of computational convenience than
of p h y s i c a l relevance. Other models i n the l i t e r a t u r e are based on
systems with r e c y c l e loops, as f o r instance i n reference (89)
where the f l u i d flows i n a plug flow reactor with d i s t r i b u t e d l a
t e r a l o u t l e t and r e c y c l i n g at a given age. Dudukovic (90) has
shown that these r e c y c l e models are not recommended f o r represent
i n g intermediate micromixing as i t i s d i f f i c u l t to r e t a i n the same
RTD w h i l s t varying the r e c y c l e r a t i o . However, i n using t h i s model
and others, he found (91, 92) that the number of m u l t i p l e steady
states could depend on the degree of segregation i n chemical reac
tors where some forms of Langmuir-Hinshelwood r e a c t i o n s were c a r
r i e d out. For each model, some authors s t i l l evaluate Danckwert's
degree of segregation J and t r y to l i n k i t to the segregation i n
t e n s i t y (93, 94) but we have seen above that t h i s i s rather an
academic e x e r c i s e .

The l a s t point that w i l l be discussed i n t h i s s e c t i o n i s con

cerned with i d e n t i f i c a t i o n o f micromixing by using r e a c t i v e
tracers.
I t i s known that the spread of an i n e r t t r a c e r during i t s
t r a n s i t i n the reactor can only y i e l d information on macromixing
(unless concentration f l u c t u a t i o n s are measured as explained
above).
However, owing to i t s s e n s i t i v i t y to mixing h i s t o r y ,
the conversion of a r e a c t i v e t r a c e r may allow i d e n t i f i c a t i o n of
intermediate micromixing s t a t e s . For instance, P a r i n i and H a r r i s
(95) proposed to determine the r e l a t i v e p o s i t i o n of mixing zones
i n models having the same RTD by studying the conversion i n a pulse


162
ENGINEERING
Figure 8. Equivalence between the C-D model and the IEM model.
Instantaneous r e a c t i o n between two unmixed feedstreams o f A and
i n s t o i c h i o m e t r i c amount i n a CSTR (33).
Figure 9
Equivalence between the C-D model and the IEM model.

i
Consecutive competing second-order r e a c t i o n s A +
R,
k
R + B
* S . Unmixed feedstreams o f A and i n a CSTR. C
=
C , k2/k =0.5.
The y i e l d o f R i s p l o t t e d against the conver
s i o n o f ( 80_, 33).
k
Bo


6.
VILLERMAUX
2 3 4 5
10
163
20 30 50
Figure 10. Equivalence between the C-D model and t h e IEM model.
Reactor w i t h two i n l e t s having d i f f e r e n t RTDs e q u i v a l e n t t o t h a t
o f 2 and 6 tanks i n s e r i e s , r e s p e c t i v e l y . Unmixed feedstreams o f
A and (equal f l o w r a t e s ) , second-order r e a c t i o n , C^ =8
A
^
e l e a v e n and Tobgy (77) f o r ?he C-D model.
k C
T r


164
ENGINEERING
of r e a c t i v e t r a c e r . A s i m i l a r study was made by Wood and Hop (96).

More r e c e n t l y , Spencer e t a l . proposed and i n t e r e s t i n g method to
determine mixing e a r l i n e s s by using two r e a c t i v e t r a c e r s A and
(68). When the f l u i d i s c l o s e to Min.Mix. (* % 0 or
large i n
the models of f i g u r e s 5.2 and 5.3), the best d i s c r i m i n a t i o n i s ob
tained when A and are i n j e c t e d i n the form of two sharp pulses
separated by a short i n t e r v a l . When the f l u i d i s c l o s e to Max.Mix.
(* % 1,
0) the recommended i n j e c t i o n shape i s a square pulse
c o n t a i n i n g both A and B. The conversion i n the o u t l e t pulse i s then
s t r o n g l y dependent on micromixing. An experimental i l l u s t r a t i o n of
the method i s given i n the next paper by Spencer and Lunt (97).
The r e a c t i v e t r a c e r s were p - n i t r o p h e n y l acetate and sodium hydrox
ide which undergo a second-order r e a c t i o n t o produce p-nitropheny l a t e , an o p t i c a l l y d e t e c t a b l e product. I n a p o o r l y mixed CSTR,
segregation was found to i n c r e a s e w i t h v i s c o s i t y but the i n t e r p r e
t a t i o n o f the experiments i s d i f f i c u l t owing to an i l l - d e f i n e d RTD.
The c o n c l u s i o n to t h i s S e c t i o n i s c l e a r : there are now enough
phenomenological models i n the l i t e r a t u r e f o r r e p r e s e n t i n g i n t e r
mediate micromixing (mixing e a r l i n e s s ) i n flow r e a c t o r s . Most of
them are more or l e s s e q u i v a l e n t . Instead of imagining more and
more s o p h i s t i c a t e d mathematical ways to pass from the E n t e r i n g to
the Leaving Environment, i t would be a d v i s a b l e to c o l l e c t more ex
perimental data on r e a l r e a c t o r s (the r e a c t i v e t r a c e r method i s
e s p e c i a l l y promising i n t h i s way) and to t r y to c o r r e l a t e the value
of the micromixing parameters to physicochemical p r o p e r t i e s of the
mixture and o p e r a t i n g c h a r a c t e r i s t i c s of the r e a c t o r . This leads
us d i r e c t l y to the next S e c t i o n .
Segregation and mixing at the microscopic l e v e l : mechanism of mi
cromixing i n the p h y s i c a l space.
In t h i s s e c t i o n , t h e fundamental mechanism o f i n t e r a c t i o n be
tween f l u i d p a r t i c l e s w i l l be d i s c u s s e d . U n t i l now, the term "par
t i c l e " has not been a c c u r a t e l y d e f i n e d . As w e l l a Danckwer^s
"point", i t may denote a f l u i d b l o b , clump or aggregate of any
shape (sphere, c y l i n d e r , s l a b , lamina) a group of molecules, or
more g e n e r a l l y any segregated region of the f l u i d which the mixing
process has to destroy and d i s p e r s e i n order to achieve mixing at
the molecular s c a l e (or a t l e a s t a t a s c a l e where chemical reac
t i o n s can o c c u r ) . This S e c t i o n w i l l thus be devoted to a Lagrangian
approach to the problem already discussed i n E u l e r i a n coordinates
The aim i s to give a p h y s i c a l d e s c r i p t i o n amenable to q u a n t i t a t i v e
p r e d i c t i o n of segregation decay, r e l y i n g on experimental parame
ters .
Simultaneously, such a comprehensive d e s c r i p t i o n should pro
v i d e a p h y s i c a l i n t e r p r e t a t i o n f o r the phenomenological parameters
of the models depicted i n the preceding S e c t i o n .
In my o p i n i o n , the soundest b a s i s f o r t h i s d e s c r i p t i o n was
p u b l i s h e d by Beek and M i l l e r t h i r t e e n years ago (98). According to
t h e i r own words, three stages may be d i s t i n g u i s h e d i n the mixing
process :

6.
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165

1. D i s t r i b u t i o n o f one f l u i d through the other and u n i f o r m i z a t i o n of average composition without decreasing l o c a l concentra
tion variations.
2. Reduction of s i z e of the regions of uniform composition
and increase of contact between regions of d i f f e r e n t composition.
3. Mixing by molecular d i f f u s i o n .
Stage 1 i s c l e a r l y macromixing. Let us review the models pro
posed f o r the l a s t two processes (32).
P u r e l y convective mixing. An important c o n t r i b u t i o n t o the
s o l u t i o n of t h i s problem was given by O t t i n o , Ranz and coworkers
(99-106) i n the l a s t three years. However, the a b s t r a c t c h a r a c t e r
o f the mathematical formalism used i n these papers might d i s c o u r
age p r a c t i t i o n e r s who are not very f a m i l i a r w i t h t e n s o r a n a l y s i s ,
although the u n d e r l y i n g concepts are f i n a l l y r a t h e r simple. The
theory considers only convective mixing under the i n f l u e n c e of the
v e l o c i t y f i e l d . D i f f u s i o n i s f u r t h e r superimposed on to the p a t t e r n
created by convection. The main i d e a i s that once the v e l o c i t y
f i e l d i n s i d e the r e a c t o r i s known, i t i s p o s s i b l e t o p r e d i c t the
deformation of any m a t e r i a l p o r t i o n of f l u i d as a f u n c t i o n of the
Lagrangian time attached to t h i s element. Two q u a n t i t i e s are of
s p e c i a l i n t e r e s t : the m a t e r i a l time r a t e of change of l i n e a r
s t r e t c h , and that of area s t r e t c h . Let L = V.lf =
.1 be the v e l o
c i t y g r a d i e n t . From t h i s , we may d e f i n e the ^
i
s t r e t c h i n g tensor D = (1/2)(L + L ) and the v o r t i c i t y tensor
Q = (1/2)(L - L ) . The fundamental r e l a t i o n s h i p s e s t a b l i s h e d by
O t t i n o , Ranz e t a l . (99^, 101, 103, 105) are then f o r the r a t e of
change o f l i n e a r s t r e t c h (/)
and area s t r e t c h ( ?), respec
tively:
x
= D :
/ = V.U - D : n n
(7-1)
A few words of e x p l a n a t i o n are not useless i n order to understand

t h i s formalism. As a consequence of m i x i n g , the medium i s assumed
to have a l a m e l l a r s t r u c t u r e and n i s a u n i t v e c t o r which remains
normal to the m a t e r i a l s l i c e s undergoing deformations i n the v e l o
c i t y f i e l d , n n denotes a dyadic product (the dyadic product of
v e c t o r s a and b i s the tensor a^bj) and I) : n n denotes the s c a l a r
product of the two tensors (the s c a l a r product of tensors T^ = T^j
and W = W x i s the s c a l a r q u a n t i t y : W = Wj^). Assume
that we s t a r t w i t h two m i s c i b l e f l u i d s A
i J and (having f o r
instance d i f f e r e n t c o l o r s ) . Upon mixing, we o b t a i n a l a m e l l a r mar
b l e d s t r u c t u r e c h a r a c t e r i z e d by a s t r i a t i o n thickness 6 and a spe
c i f i c " i n t e r f a c i a l " area a . I f the f l u i d i s i n c o m p r e s s i b l e ,
a = 1. Then,by a p p l i c a t i o n o f (7-1)
k
/a = - / = - D : n n

(7-2)
This equation can be i n t e g r a t e d i n p a r t i c u l a r v e l o c i t y f i e l d s to

166
ENGINEERING
y i e l d the v a r i a t i o n of the s t r i a t i o n thickness as a f u n c t i o n of

time (see below). In a newtonian f l u i d , i t can be shown that (99,
105) :
D : ^ (D : D )
1 / 2
= ( /2)
1 / 2
(7-3)
where i s the viscous d i s s i p a t i o n per u n i t mass. I f we d e f i n e a

s t r e t c h i n g time tg as tg = -/, (7-3) imposes a lower bound
tg ^ (2/)'/^. (7-3) a l s o allows a l o c a l e f f i c i e n c y to be defined
as :

->- -D : n
->
D :
( = D)
( /2)
1 / 2
the l a t t e r being v a l i d f o r newtonian f l u i d s o n l y . The average v a l

ue o f e over the whole r e a c t o r volume leads t o the o v e r a l l e f f i
ciency " e f f " of the mixing process t e l l i n g us how the viscous d i s
s i p a t i o n i s u t i l i z e d to promote the t h i n n i n g of the laminae (107,
102, 103, 105). Let us give three examples (the reader may t r y to
f i n d these r e s u l t s by a p p l i c a t i o n o f ( 7 - 2 ) ) .
1) Shear flow ( U = Gy, U = 0, U = 0, laminae i n i t i a l l y nor
mal to Ox) (99, 104) :
x
= , Uy = - ay, U
1 / 2
(7-5)
= 0, laminae i n i
exp(- at)
(7-6)
3) S t r e t c h i n g at constant v e l o c i t y (
= 0)
= - G t / ( 1 + G t ) and = 6 (1 + G t ) "
2) Stagnation flow ( U
t i a l l y normal to Oy) (104)
= G / ( l + Gt), U
= - G/(l + Gt) and = (1 + G t ) "
= 0,
(7-7)
This k i n d of s t r e t c h i n g occurs f o r instance i n " t a f f y p u l l " . I f the

sheet i s f o l d e d up a f t e r a given s t r e t c h i n g d u r a t i o n t and the
r e s u l t i n g sheet i s streched up again, then the number of f o l d s i s
2 ' o and = 2"" ' o. In a l l these processes, e f f i c i e n t mixing
i s achieved when the laminae are p e r i o d i c a l l y r e o r i e n t e d w i t h r e
spect t o the d i r e c t i o n o f s t r e t c h i n g (101). This remark i s a l s o im
portant i n the design of s t a t i c mixers.
Q
E r o s i v e (or d i s p e r s i v e ) Mixing. O t t i n o s treatment assumes

continuous motion, namely connectedness of m a t e r i a l s u r f a c e s , and
hence c o n s e r v a t i o n of t o p o l o g i c a l features (105). Conversely, one
may t h i n k of a mixing process t h a t would g r a d u a l l y p u l l o f f s m a l l
er fragments from the segregated clumps by t u r b u l e n t f r i c t i o n at
t h e i r e x t e r n a l surface. This i s the b a s i s f o r the " S h r i n k i n g Aggre-

6.
VILLERMAUX
167
gate" (SA) Model of P l a s a r i et a l . (71). The p e e l i n g - o f f process

i s c h a r a c t e r i z e d by a mass t r a n s f e r c o e f f i c i e n t h which i s assumed
to be expressed by the Calderbank-Moo Young c o r r e l a t i o n , a p p l i c a
ble to small p a r t i c l e s immersed i n t u r b u l e n t media :
hl/<Sb = 0.13 l(e/v ) /^
Sc
, I i s the diameter of the s h r i n k i n g
aggregate. For s p h e r i c a l shape, t h i s leads to a l i n e a r s i z e de
crease as a f u n c t i o n of age : & = Z (\ - ct/t ) with the characte
r i s t i c e r o s i o n time-constant
3
1 / 3
^- ^
e

I/O

= 726W
-1/3
S

276^
/"7 Q\
,
%
i n l i q u i d s (Se ^ 1000).
i s the f a m i l i a r Kolmogorov m i c r o s c a l e
(see above).
The dependence of t on experimental parameters
i s thus t ^ t
<)-2/3
problems remain to be s o l ved : How to estimate the i n i t i a l s i z e Z of the aggregates ? Is i t
p r o p o r t i o n a l to the i n i t i a l v e l o c i t y U of the f l u i d as i t has been
assumed i n s t i r r e d r e a c t o r s (71) ? What i s the expression of the
energy d i s s i p a t i o n r a t e ? As already pointed out, i t seems necessary to introduce e f f i c i e n c i e s j and 2 f o r the u t i l i z a t i o n of mecha
n i c a l energy and k i n e t i c energy d i s s i p a t i o n r e s p e c t i v e l y (71, 108)
= j ] + 2 2 * These are questions f o r f u r t h e r research.
e
Coalescence-Dispersion Mixing. This process has already been

mentioned i n the preceding S e c t i o n s . The p a r t i c l e s merge at random
with the average frequency . A f t e r mixing, two new p a r t i c l e s are
instantaneously produced by breaking up of the coalesced complex.
The c h a r a c t e r i s t i c time constant i s t^p = /. This i s mainly a
phenomenological parameter. In turbulent media, i t i s g e n e r a l l y
accepted that t^p i s p r o p o r t i o n a l to C o r r s i n s time constant T
(See above).
1
Mixing by molecular d i f f u s i o n .
This i s the u l t i m a t e and f i
n a l l y the only process r e a l l y able to mix the components of a f l u i d
to the molecular s c a l e . The time constant f o r t h i s process i s the
d i f f u s i o n time tp = \/<&. y i s a shape f a c t o r and L i s the r a t i o
of the volume to the e x t e r n a l surface area of the p a r t i c l e . For
instance l e t us consider v a r i o u s shapes : slabs (thickness 2 R , case
of l a m e l l a r s t r u c t u r e with s t r i a t i o n thickness 6 = 2 R ) , long cy
l i n d e r s (diameter 2 R , case of filamentous s t r u c t u r e ) , and spheres
(diameter 2 R , case of s p h e r i c a l aggregates).
I t can be.shown (110) that
2
= {HH
'
(p 0(
+
P +
3)&
where = 0 f o r s l a b s , = 1 f o r c y l i n d e r s and = 2 f o r spheres.

The p a r t i c l e then approximately behaves as a f i r s t order dynamic
system o f time constant t ^ with respect to mass t r a n s f e r .
The prob
lem, when molecular d i f f u s i o n i s r e t a i n e d as the mixing mechanism

168
i s to choose the adequate length s c a l e (or 2R). Should (or 2R)

be i d e n t i f i e d w i t h the s t r i a t i o n thickness 6 or w i t h one
of the viscous d i s s i p a t i o n microscales of Table I (Kolmogorov
= ( / ) , Batchelor = ( ^ / ) , Corrsin X = (grVc) / )
or w i t h C o r r s i n s m i c r o s c a l e f o r segregation d i s s i p a t i o n
( = 24) ( L / )
? This may depend on the mechanism l e a d i n g
to the u l t i m a t e stage of molecular mixing. An experimental clue
f o r the choice of the r e l e v a n t microscale i s the i n f l u e n c e of v i s c o s i t y which intervenes i n a d i f f e r e n t manner i n t h e i r expression.
This p o i n t i s s t i l l open to d i s c u s s i o n . Some authors f i n d a marked
i n f l u e n c e of v i s c o s i t y and i n c l i n e towards the choice of =
(111-116). Others f i n d almost no i n f l u e n c e of v i s c o s i t y and con
clude i n favour of A (2, 30, JJJ7, 118, 39, 109, 7_1_, J08, 32).
However, i t i s not q u i t e sure that a l l the experiments reported i n
the l i t e r a t u r e are f r e e from spurious e f f e c t s (macromixing, e a r l y
stages of convective or e r o s i v e mixing, e t c . . . ) . Rigorous e x p e r i
ments, i n p e r f e c t l y w e l l defined c o n d i t i o n s should be devised to
s e t t l e t h i s problem.
As the r a t e of energy d i s s i p a t i o n per u n i t mass f i g u r e s i n
a l l the expressions f o r the m i c r o s c a l e s , the problem of i t s spa
t i a l r e p a r t i t i o n and of the conversion e f f i c i e n c y of the macrosco
p i c d i s s i p a t i o n i s a l s o posed here. I n order to give a few orders
of magnitude, the approximate values of some microscales and time
constants i n t y p i c a l c o n d i t i o n s are reported i n Table I I I .
3
1 / 4
1 / 4
1 / 3

Table I I I
Experimental parameters : = 10
ms
,3=10
/> =
T
t
3/2
1/2
/(3> )
=2
= /2
|/)
1 / 3
= (2/)
Case 2 : = 10 Watts
kg""
L = 0.1 m
(small r e a c t o r )
32 ym
70 ym
18 ym
1 6 ym
1 s
0.3 s
\l = <2>/)
1/2
0.2 s
0.9 s
1/2
, Sc = 10
Case 1 : = 1 Watt
kg
L = 0.3 m
(large r e a c t o r )
s
Kolmogorov
Corrsin
A
ms
0.45 10" s
1.4 10~" s
5
3.5 10" s
I t i s concluded from t h i s Table that X and X l i e between 10

and 100 ym, and that X^/tf) and x have the same order of magnitude
between 0.1 and 1 second. Other processes ate much f a s t e r .
v

6.
VILLERMAUX
169
M i x i n g and chemical r e a c t i o n . We must now d i s c u s s the cou

p l i n g between the mixing processes and chemical r e a c t i o n s . Simula
t i o n s v i a the IEM model or the C-D model have a l r e a d y been p r e s e n t
ed i n the preceding s e c t i o n . The key parameter i s the r a t i o o f
some c h a r a c t e r i s t i c r e a c t i o n time (e.g. t = 1/k CQ "" f o r an n
order r e a c t i o n ) to the micromixing time t (or t ^ - p ) . When t ^ / t
i s s m a l l , the chemical r e a c t i o n i s f a s t e r than mixing and micro
s c o p i c c o n c e n t r a t i o n g r a d i e n t s appear: the f l u i d becomes segregat
ed. Conversely, when t ^ / t i s l a r g e , the f l u i d may be considered
as w e l l micromixed from the viewpoint of the chemical r e a c t i o n (98) .
Several authors have s t u d i e d the competition between chemical
r e a c t i o n s and molecular d i f f u s i o n i n f l u i d p a r t i c l e s . In s t i r r e d
r e a c t o r s , Nauman (81) introduced a s e g r e g a t i o n number
^Seg
** /(^3) ) , which compares the d i f f u s i o n time w i t h the
space time. A major c o n t r i b u t i o n to t h i s problem was brought by
Rys, Bourne and t h e i r group at the E.T.H. o f Z u r i c h . They developed
a model (the MIRE model) e s s e n t i a l l y adapted t o ^ p r e d i c t the ^
y i e l d of consecutive competing r e a c t i o n s A +
R, R + __?.> S
i n s t i r r e d r e a c t o r s (119, 120). The p a r t i c l e s are assumed to be
s p h e r i c a l (radius R) and the equations f o r r e a c t i o n / d i f f u s i o n are
s o l v e d i n v a r i o u s cases: V e r s i o n I : P a r t i c l e s i n i t i a l l y c o n t a i n
i n g A immersed i n pure (A i s not allowed t o d i f f u s e w i t h i n the
p a r t i c l e , other species a r e ) . V e r s i o n I I : symmetrical case (par
t i c l e of n o n - d i f f u s i n g immersed i n A). The parameters are two
Thiele c r i t e r i a
= k B R / D * t / t , = A / B and = V /V .
The model p r e d i c t s the y i e l d o f S : X = 2S/(2 S + R) a t the end
of the r e a c t i o n (when a l l i s consumed). I t was developed f o r
batch and semi-batch r e a c t o r s (119, 120), and l a t e r extended to
continuous s t i r r e d r e a c t o r s v i a a somewhat complicated procedure
(121-112). Some c r i t i c i s m may be adressed, to the MIRE-model, i n
s p i t e o f i t s great i n t e r e s t : a r b i t r a r y choice o f s p h e r i c a l shape,
a s s i m i l a t i o n of R to h a l f the Kolmogorov m i c r o s c a l e (which i s not
obvious as we have seen above) and above a l l , assumption that the
i n i t i a l r e a c t a n t i n the p a r t i c l e cannot d i f f u s e o u t s i d e , which
creates an unwanted dissymmetry between A and when V^ = V-Q.
The r e a c t i o n / d i f f u s i o n c o m p e t i t i o n can a l s o be simulated by
the IEM-Model. I t s u f f i c e s to set t = t = yL /J. The equivalence
w i t h the MIRE-model w i l l be discussed below.
More s o p h i s t i c a t e d mechanisms may be considered, where chemi
c a l r e a c t i o n takes place during v a r i o u s stages of Beek and M i l l e r ,
or a combination of these :
- E r o s i v e mixing f o l l o w e d by r e a c t i o n : Two unmixed r e a c t a n t s
come i n t o contact i n a CSTR by e r o s i o n of f r e s h aggregates. The
e r o s i o n product i s e i t h e r a m i c r o f l u i d (71) or small segregated
p a r t i c l e s of mixed reactants undergoing f u r t h e r i n t e r a c t i o n by mo
l e c u l a r d i f f u s i o n (108).
- S t r e t c h i n g of p a r t i c l e s and simultaneous r e a c t i o n .
For r e p r e s e n t i n g r e a c t i o n and d i f f u s i o n i n s t r e t c h i n g l a m e l l a r
s t r u c t u r e s , O t t i n o and Ranz (101) introduced a "warped time" t
defined by :
11
t n

R i

170

= /
Jo
JL^
H t < )
or =S>
dt
ENGINEERING
(7-10)
where the r a t e of change of the s t r i a t i o n thickness i s given by

( 7 - 2 ) . The equations f o r r e a c t i o n / d i f f u s i o n are then e a s i e r to
solve i n Lagrangian coordinates. In the same way Bourne, Angst et
a l . ( 1 2 2 , 1 1 4 ) extended t h e i r MIRE-Model by assuming that the s i z e
of the p a r t i c l e s decreases according to ( 7 - 5 ) . This would mean
that a r e d u c t i o n of the s t r i a t i o n thickness below the Kolmogorov
m i c r o s c a l e i s conceivable. Reaction and d i f f u s i o n i n d i s t o r t i n g
s t r u c t u r e s were a l s o s t u d i e d by Palepu et a l . ( 3 1 ) and Spalding
( 1 2 3 ) . The I.E.M. Model accounts f o r such deformations i n assuming
that the micromixing time i s a s p e c i f i e d f u n c t i o n of the p a r t i c l e
age
(32).
We may now complete the l i s t of equivalences c i t e d i n ( 6 - 9 )
by a new one between the d r o p l e t - d i f f u s i o n model of Nauman ( 8 1 ) or
the MIRE-model of Rys, Bourne et a l . ( 1 1 9 - 1 2 0 ) , and the IEM Model.
The c o n d i t i o n f o r equivalence i s t = t ^ , where tp i s given by
( 7 - 9 ) . The IEM-Model i s a lumped v e r s i o n of the d i s t r i b u t e d para
meter r e a c t i o n / d i f f u s i o n model. Numerical s i m u l a t i o n s prove that
r e p l a c i n g c o n c e n t r a t i o n p r o f i l e s by average values does not change
the o v e r a l l conversion and y i e l d i n the p a r t i c l e very much, even
f o r " s t i f f systems" of f a s t r e a c t i o n s . Figures 11 and 12 are exam
p l e s of such equivalences. Therefore, my o p i n i o n i s that i n most
a p p l i c a t i o n s , a simple lumped parameter model may be used i n place
of s o p h i s t i c a t e d d i s t r i b u t e d models. This saves much computer time
and the d i f f e r e n c e i n the r e s u l t s i s not greater than f o r instance
that induced by a change i n the a r b i t r a r y assumptions concerning
the p a r t i c l e shape.
The s i m u l a t i o n s v i a the IEM model revealed an i n t e r e s t i n g
property. A p a r t i a l l y segregated f l u i d may be considered as a mix
ture of m a c r o f l u i d ( f r a c t i o n 3) and m i c r o f l u i d ( f r a c t i o n 1 - 3 ) .
I t comes out that the r a t i o (1 - )/(3 i s always c l o s e to that of two
c h a r a c t e r i s t i c times ( 3 2 ) . In the case of e r o s i v e mixing of two
reactants i n a CSTR (1 - ft/S % x / t % 4 /t .
In the case of r e a c t i o n and d i f f u s i o n or premixed r e a c t a n t s
i n a CSTR ( f i g u r e 1 3 ) : ( 1 - 3 ) / 3 D % ^ ^ *
interesting
r u l e of thumb f o r r a p i d e s t i m a t i o n of the extent of segregation.
m
T h i s
i s
a n
I d e n t i f i c a t i o n of segregation by chemical methods. P a r t i a l

segregation can be s t u d i e d through i t s i n f l u e n c e on the conversion
and y i e l d of chemical r e a c t i o n s . For i n s t a n c e , l e t us denote by
X
and Xmicro the l i m i t i n g extents of r e a c t i o n one would ob
serve i n a w e l l macromixed r e a c t o r . I f the r e a c t o r i s p a r t i a l l y
segregated : X = ^,- + (1 - 3) XmicroThis a l s o holds f o r the y i e l d of an intermediate product and
i s the b a s i s f o r the determination of 3 or conversely, f o r the pre
d i c t i o n of X ( 3 2 ) . Fast consecutive-competing r e a c t i o n s A + B LL>R,
R+B
_JL> S (kj >> k ) are e s p e c i a l l y i n t e r e s t i n g : i f a small
amount of i s mixed i n t o an excess o f A, R i s formed and immedim a c r o


6.
VILLERMAUX
Figure 11.
and the IEM
reaction i n
for perfect
second-order
111
Equivalence between the d r o p l e t d i f f u s i o n model (81)

model f o r a zero-order r e a c t i o n and a second-order
a CSTR. The Damkohler numbers are such t h a t f = 0.5
micromixing. The agreement i s e x c e l l e n t f o r the
r e a c t i o n , more approximate f o r the zero-order one.


172
Figure 12. Equivalence between the r e a c t i o n / d i f f u s i o n model and

the IEM model f o r second-order consecutive competing r e a c t i o n s
k
l
&2
A +
R, R +
S. The curves represent t h e average con
c e n t r a t i o n s v s . (reduced) time i n a s p h e r i c a l p a r t i c l e immersed
i n a bath o f constant composition (C^ 0.105, C = 0 ) . I n i t i a l
concentrations i n the p a r t i c l e : C
= 0, CBO = 1> R
0
k C g R / ^ = 2 f o r A and R. cannot d i f f u s e w i t h i n the p a r t i c l e
(S> = 0 ) . k-^/k^ = 10. F- represents the t o t a l production o f R
(equivalent c o n c e n t r a t i o n i n the p a r t i c l e ) . B a s i s f o r the e q u i
valence t . - t . = 0 L / j ; = 3/5, L = R/3 (sphere). The
agreement i s s a t i s f a c t o r y . I n much " s t i f f e r " c o n d i t i o n s
(k^> > k ) , the agreement i s always good f o r the o v e r a l l produc
t i o n o f R, even i f the i n d i v i d u a l c o n c e n t r a t i o n p r o f i l e s become
different.
=
///
f
t /t
R
0.1
10
Figure 13. M i c r o f l u i d / m a c r o f l u i d volume r a t i o v s . r e a c t i o n / d i f f u s i o n

time r a t i o . Key t o curves: 1 t o If, s i m u l a t i o n w i t h the IEM model,
t = t p ; 1 t o 3, second-order r e a c t i o n k CAo = 2 ( l ) , 5 ( 2 ) , 10(3);
U, second-order consecutive competing r e a c t i o n s
= 0- , k-,/kp =
2, t ^ = l / k ^ C ^ ; 5, r e a c t i o n and d i f f u s i o n i n a s l a b (See Rer. 3 2 . ) .
m

6.
VILLERMAUX
173
a t e l y converted to S at the contact of i f the f l u i d i s segregated.

Therefore, X i s some kind of segregation index : X
i
< X < 1,
and = ( X - X ,
) / ( l " * ,micro)
The method was e x t e n s i v e l y e x p l o i t e d by Bourne and coworkers,
who enumerated the q u a l i t i e s of a good r e a c t i o n f o r i n d u s t r i a l
tests ( 124) (t-R % t , d i s t r i b u t i o n of products depending on segre
gation, i r r e v e r s i b l e r e a c t i o n , known mechanism, easy a n a l y s i s and
regeneration, safe and inexpensive chemicals). Unfortunately, the
r e a c t i o n s proposed to-date do not f u l f i l l a l l these requirements :
Azo-coupling (119,137), n i t r a t i o n of aromatic hydrocarbons (125),
bromation of r e s o r c i n (124) , bromation of 1-3-5
trimethoxybenzene
( 126). Some of them e x h i b i t complex pH e f f e c t s (124, 127, 111),
but a l s o a good s e n s i t i v i t y t o s e g r e g a t i o n . For i n s t a n c e , the
amount o f 2-U dibromoresorcin i n the di-isomer may vary from 30%
to 60 % when the a g i t a t i o n speed passes from 0 to 360 r.p.m. (124).
A new r e a c t i o n i s proposed i n t h i s Symposium by Barthole et a l .
(128) : the p r e c i p i t a t i o n of baryum s u l f a t e complexed by EDTA i n
a l k a l i n e medium under the i n f l u e n c e of an a c i d . I t has many of the
advantages c i t e d above, but the r e a c t i o n i s not s t r i c t l y i n s t a n t a
neous and thus dependent on macromixing. Fluorescence methods may
also be employed (20). In a recent s e r i e s of papers (129, 112, 113,
114), Bourne and coworkers presented a thorough i n v e s t i g a t i o n of
segregation i n s t i r r e d reactors (2.5 and 63 dm ) with various i n l e t
p o s i t i o n s . As a t e s t r e a c t i o n they used the coupling of 1-naphtol
(A) with d i a z o t i s e d s u l p h a n i l i c a c i d (B). They succeeded i n apply
ing the MIRE-Model provided that the p a r t i c l e s i z e 2R be 2 to 9
times smaller than the Kolmogorov m i c r o s c a l e . The agreement was
improved by assuming s t r e t c h i n g of p a r t i c l e s : 6 = ( 1 + t / t ) /
where t = 2 ( v / ) ' (122, 114). They showed that the best mixing
conditions were achieved with i n l e t tubes placed j u s t beneath the
turbine. They concluded from t h e i r i n t e r p r e t a t i o n ,
r e l y i n g on the
Kolmogorov microscale, that the scale up of the state of segrega
t i o n requires keeping and thus N d^ constant. The i n t e r p r e t a t i o n
of these b e a u t i f u l experiments should be discussed with much care,
taking i n t o account p o s s i b l e macromixing e f f e c t s (comparison of
r e a c t i o n time and c i r c u l a t i o n time t ) , i n t e r v e n t i o n of d i f f e r e n t
mixing processes (of stage 2) preceding the d i f f u s i o n a l one,and
the s p a t i a l d i s t r i b u t i o n of i n the tank.
Beside consecutive-competing r e a c t i o n s , instantaneous (gener
a l l y acid-base) r e a c t i o n s are a l s o used as an i n d i c a t o r of segre
gation, e s p e c i a l l y i n m u l t i j e t tubular r e a c t o r s . O t t i n o (102) de
duced the r e l a t i o n s h i p t ^ ( t ) between "warped" and r e a l time from
the comparison between experimental conversion X(t) along the axis
of a tube and the t h e o r e t i c a l expression X ( t ) . a was then c a l c u
lated by (7-10) and the e f f i c i e n c y e f f ( t ) by :
(l/a )da /dt = eff(t)(D : D )
. e f f ( t ) was found to decrease as
a f u n c t i o n of t with 6 = 1/a of the order of 10 ym. In the same
paper, the average e f f i c i e n c y " e f f " was estimated i n a s t i r r e d
reactor, " e f f " was found to decrease from 20-30 % f o r t < 0.25 s to
1-10 % l a t e r , but here a l s o , macromixing e f f e c t s ( c i r c u l a t i o n
0
m i c r o

1 / 2

- 1
174
time ?) cannot be excluded. Bourne et a l . (116) a l s o performed ex

periments w i t h NaOH/HCl mixing behind a Sulzer s t a t i c mixer i n a
tube, was estimated by U(Ap/)/p and the i n f l u e n c e of the v i s c o
s i t y was e s p e c i a l l y s t u d i e d , and found to be n o t i c e a b l e . Assuming
a d i f f u s i o n a l mechanism f o r mixing, these authors conclude that
C o r r s i n s micromixing time T cannot e x p l a i n t h e i r observations
and that the i n f l u e n c e of v i s c o s i t y suggests a d i f f u s i o n time ba
sed on Kolmogorov m i c r o s c a l e . The same c o n c l u s i o n was drawn from
experiments i n s t i r r e d tanks, where the IEM-model seemed unable to
account f o r a l l experimental data. This i s i n c o n t r a d i c t i o n w i t h
the r e s u l t s of Pohorecki and Baldyga (117) who a l s o studied the
r e a c t i o n of NaOH and HCl c o n t r o l l e d by mixing i n a tube. They found
that the IEM-model was a p p l i c a b l e w i t h t = 2 ^ ( L ^ / e ) ' where
L was equal to the diameter of the i n j e c t i o n tube, was deduced
from the assumption of i s o t r o p i c homogeneous turbulence.
This problem of mixing w i t h chemical r e a c t i o n has drawn the
a t t e n t i o n of many authors i n the l a s t few years. Takao et a l . ( 130)
studied the a l k a l i n e h y d r o l y s i s of c h l o r o a c e t a t e i n a batch s t i r
red r e a c t o r ( t ^ % t ) ; t h e i r r e s u l t s , obtained on the b a s i s of the
IEM model, can probably be explained by macromixing ( t ^ t ^ 1/N).
Miyawaki et a l . (118) s t u d i e d the r e a c t i o n of C O 2 + N H 3 and
C O 2 + OH" i n m u l t i j e t tubes and i n s t i r r e d r e a c t o r s . In tubes, the
data are compatible w i t h the IEM model (X = 1 - e x p ( - t / t ) ) w i t h
t ^ C o r r s i n s T , whereas i n s t i r r e d tanks conversion i s probably
c o n t r o l l e d by r e c i r c u l a t i o n ( t ^ 1/N) as i n reference (130).
Murakami et a l . (131) developed a model e q u i v a l e n t to the IEM model
for i n t e r p r e t i n g mixing i n batch s t i r r e d r e a c t o r s (1 and 50 t) both
w i t h a non r e a c t i v e t r a c e r and i n the presence of three r e a c t i o n s
of d i f f e r e n t r a p i d i t y . They found that N t could be c o r r e l a t e d as
a f u n c t i o n of the a g i t a t i o n Reynolds number Nd /v and a Damkohler
number. Costa and L o d i (136) a s s i m i l a t e d the IEM mixing time t to
(v/) ' w i t h a c o r r e c t i o n depending on the Schmidt number, but
without any experimental support. Hanley and C a l l (132) suggested
e x p l o i t i n g c o n c e n t r a t i o n f l u c t u a t i o n s at the o u t l e t of a CSTR to
c a l c u l a t e micromixing parameters. Ghodsizadeh and A d l e r (133) pro
posed an i n t e r e s t i n g method based on d i l a t o m e t r y to f o l l o w the
course of an acid-base r e a c t i o n i n a batch r e a c t o r . Bhatt and
Z i e g l e r ( 134) determined the m a c r o f l u i d f r a c t i o n i n a CSTR by t a
k i n g i n t o account the n o n - i d e a l i t y of the segregated phase RTD and
by assuming i n t e r a c t i o n by r e a c t i o n and d i f f u s i o n . Bryant (135)
considered the case of zero order r e a c t i o n i n fermenters by assu
ming d i f f u s i o n a l l i m i t a t i o n s i n p a r t i c l e s having the Kolmogorov
s i z e Palepu et a l . (31) used the "warped -time method d e s c r i
bed i n (102) to estimate the s t r i a t i o n thickness 6 as a f u n c t i o n
of time i n a m u l t i j e t tube and i n a s t i r r e d r e a c t o r . A f t e r an i n i
t i a l decrease, i t seems that 6 tends to X but there i s s t i l l some
strange behaviour (climb of 6 before s t a b i l i z a t i o n ) and the pro
blem of the e f f i c i e n c y i n the c a l c u l a t i o n of i s a l s o posed. From
t h e i r own experiments (109, 71, 108), V i l l e r m a u x and coworkers
suggest (32) that depending on experimental c o n d i t i o n s , and chemi1


6.
VILLERMAUX
175
c a l r e a c t i o n s , there are s e v e r a l mixing mechanisms f o r stages 2

and 3 of Beek and M i l l e r o c c u r i n g simultaneously and i n t e r a c t i n g
w i t h chemical processes. This might e x p l a i n the d i s c r e p a n c i e s ob
served between authors w i l l i n g to i n t e r p r e t t h e i r experiments by
one s i n g l e mechanism.
Conclusion. There are s t i l l u n c e r t a i n t i e s i n the f i n a l i n t e r
p r e t a t i o n of mixing and chemical r e a c t i o n a t the molecular l e v e l .
The IEM model seems to provide a simple b a s i s f o r r e p r e s e n t i n g i n
t e r a c t i o n between p a r t i c l e s , even by molecular d i f f u s i o n . The pro
blem i s to decide what i s hidden behind the micromixing time t ?
C o r r s i n s time constant T (32) ? A d i f f u s i o n constant based on
Kolmogorov microscale (113, 114) ? F u r t h e r research should be de
veloped i n the f o l l o w i n g d i r e c t i o n s :
- Search f o r r e l i a b l e t e s t r e a c t i o n s obeying the c r i t e r i a
s t a t e d i n reference ( 124). These r e a c t i o n s should be usable i n i n
d u s t r i a l r e a c t o r s and perhaps be l e s s " s t i f f than those proposed
by Bourne and coworkers.
- Design of experiments where hydrodynamic c o n d i t i o n s are per
f e c t l y c o n t r o l l e d : small s t i r r e d r e a c t o r s w i t h high power input
(no macromixing e f f e c t s , c i r c u l a t i o n time t << t , no s p a t i a l va
r i a t i o n of ), m u l t i j e t t u b u l a r r e a c t o r s w i t h a diameter l a r g e
enough f o r pure homogeneous i s o t r o p i c turbulence to be achieved.
- C l e a r d i s t i n c t i o n between the mechanisms p e r t a i n i n g to suc
c e s s i v e o r simultaneous stages of m i x i n g .
- Once the above requirements are f u l f i l l e d , a systematic stu
dy of the i n f l u e n c e of v i s c o s i t y and power d i s s i p a t i o n should
be made.
1

1 1
The S t i r r e d Tank
A review on mixing i n chemical r e a c t o r s would be incomplete
without an account of recent progress i n the understanding of the
working of s t i r r e d tanks, which remain the b a s i c devices f o r indus
t r i a l mixing.
I n t e r n a l c i r c u l a t i o n p a t t e r n s and turbulence. Sasakura e t
a l . (138) and Rachez e t a l . (139) i n v e s t i g a t e d i n t e r n a l age d i s t r i
butions by means of t r a c e r s and proposed r e p r e s e n t a t i v e models o f
the c i r c u l a t i o n p a t t e r n . Bryant and coworkers (135, 140, 141) and
Reuss s t u d i e d more s p e c i f i c a l l y c i r c u l a t i o n times i n l a r g e s t i r r e d
tanks by using r a d i o f l o w - f o l l o w e r s (aiming a t a p p l i c a t i o n s f o r
fermenters > 0.5 m ). They showed that c i r c u l a t i o n times t were
log-normally d i s t r i b u t e d :
3
f(t )
c
exp
/2-ot
the mean value t
In t -
c
/2
c
and n a t u r a l variance s being given by
z

176
ENGINEERING
= exp(y + / 2 ) and s = ( t ^ ) ( e x p - 1). I f i s the height

of l i q u i d i n the tank, they found t ^ H/(Nd ) and s ^ H ' / ( N d ) .
They also studied the terminal mixing time 0 , required f o r redu
cing c o n c e n t r a t i o n gradients down to a s p e c i f i e d l e v e l by m u l t i p l e
r e c i r c u l a t i o n s . They found 6 /"tf^ = A + B( s / t ) , s / t > 0.8, so
that 0 ^ H ^_ /(Nd ) when A i s small. The power input i s thus
% (Nd) (V/t ).
Many c o r r e l a t i o n s f o r mixing time (see above) have been
proposed i n the l i t e r a t u r e (142). One of the most comprehensive
treatments of t h i s problem was published by Khang and L e v e n s p i e l
(143), on the b a s i s of a r e c y c l e model. 6 i s defined as the time
constant f o r the exponential decrease of pseudo-periodic o s c i l l a
tions a f t e r a pulse i n j e c t i o n of t r a c e r i n a batch s t i r r e d reactor.
When Re > 10 , they obtain f o r turbines :
3

(8-2)
= 0.9 % 1.5 P/(pN d )
(8-3)
e (d/d ) *
m
= 0.5 % 0.1 p/(pN d )
and f o r p r o p e l l e r s
N0
(d/d )
C o r r e l a t i o n s f o r jet-mixing can be found i n (157).

Experimental data on mixing times may be used to estimate the
o v e r a l l e f f i c i e n c y f o r batch mixing of viscous f l u i d s , according
to the method proposed by Ottino et a l . (107).
In a d d i t i o n to these macromixing c h a r a c t e r i s t i c s , many au
thors have determined turbulence parameters and t h e i r s p a t i a l d i s
t r i b u t i o n w i t h i n the tank volume by measuring v e l o c i t y and concen
t r a t i o n fluctuations(144-147, 19, 158) . In a t y p i c a l i n v e s t i g a t i o n
(19) concerning a s e m i - i n d u s t r i a l tank (0.15 m ) and aqueous me
dium, the f o l l o w i n g s p a t i a l v a r i a t i o n s were found : u = 5 to 30 %
of TrNd, L f = 4 to 150 mm, Xf = 1 to 5 mm, / = 0.2 to 2.5,
c'/C = 2 to 10 10"" ( f o r eddies > 100 ym). This shows that a
s t i r r e d tank i s f a r from being the homogeneous and uniform system
assumed i n many academic papers.
3
C e l l models. In order to p r e d i c t chemical conversion i n s t i r

red tanks, P a t t e r s o n and coworkers (3, _39, 40) d i v i d e d the tank
volume i n t o 30 mixing segments connected by s p e c i f i e d flowrates
Q^j % Nd . The turbulence l e v e l i n each segment i s c h a r a c t e r i z e d
by L (^ d ) and (^ d ) (HDM model). Mann and coworkers (148,149)
also studied a model where c e l l s (or segments) are connected accor
ding to the average flow p a t t e r n . Commutation according to a spe
c i f i e d p r o b a b i l i t y at each c e l l ' s o u t l e t allows a s t o c h a s t i c path
to be simulatedj f o r instance f o r a flow f o l l o w e r . They thus ob
tained c i r c u l a t i o n time d i s t r i b u t i o n s very s i m i l a r to experimental
ones (135, 140, 141).
3
Multiphase s t i r r e d tanks. This item w i l l be reviewed only ve

ry b r i e f l y as the subject was r e c e n t l y covered i n e x c e l l e n t and

6.
VILLERMAUX
177
quasi-exhaustive surveys by J o s h i e t a l . f o r g a s - l i q u i d r e a c t o r s
(150) and T a v l a r i d e s and Stamatoudis f o r l i q u i d - l i q u i d r e a c t o r s
05, 40 . J o s h i e t a l . gave a thorough comparison of c o r r e l a t i o n s
for N0 . This product seems to increase w i t h the gas-flowrate.
L i t t l e i s yet known about the s t a t e of mixing of the dispersed gas
and on the i n f l u e n c e of s o l i d i n suspension.
T a v l a r i d e s presents a s o p h i s t i c a t e d model f o r r e p r e s e n t i n g
coalescence and breakage of d r o p l e t s i n l i q u i d - l i q u i d d i s p e r s i o n s .
The model r e l i e s on the p o p u l a t i o n balance equation and s t i l l r e
q u i r e s the adjustment of 6 parameters. The s o l u t i o n of such equa
t i o n s i s d i f f i c u l t and r e q u i r e s the use of Monte-Carlo methods
(151) . The e f f e c t of coalescence and break-up of d r o p l e t s on the
y i e l d of chemical r e a c t i o n s was s t u d i e d by V i l l e r m a u x (33). M i c r o mixing e f f e c t s may occur even i n batch r e a c t o r s i f there i s a drop
s i z e d i s t r i b u t i o n and mass-transfer c o n t r o l . Although p r a c t i c a l
r u l e s f o r the design and scale-up of l i q u i d - l i q u i d r e a c t o r s are
a v a i l a b l e as Oldshue showed i n the case of a l k y l a t i o n ( 152), many
problems remain unsolved (.5) : mass t r a n s f e r e f f e c t s , high hold-up
f r a c t i o n s (> 20 % ) , l a r g e d e n s i t y d i f f e r e n c e s , high v i s c o s i t i e s ,
i n f l u e n c e of s u r f a c t a n t s .

Conclusion : areas f o r f u t u r e research. Mixing i n s t i r r e d

reactors i s no longer the e m p i r i c a l o p e r a t i o n i t used to be,
("mostly a r t and very l i t t l e s c i e n c e " (153). For i n s t a n c e , Oldshue
summarized u s e f u l r u l e s f o r the scale-up of fermenters (153). How
ever, s e v e r a l current problems are s t i l l w a i t i n g s o l u t i o n . These
were reviewed i n an e x c e l l e n t paper by Kipke (154). Future r e
search should be d i r e c t e d towards
- Turbulent phenomena
- Large volumes ( s p a t i a l unhomogeneities)
- Multiphase systems ( g a s - l i q u i d , l i q u i d - s o l i d , l i q u i d - l i q u i d ,
gas-liquid-solid)
- Non newtonien media, rheology problems (155, 156)
- Search f o r s i m p l i f i e d models and new concepts
- Less dimensional a n a l y s i s
Less c l a s s i c a l devices : s t a t i c mixers
S t a t i c mixers have been e s s e n t i a l l y developed s i n c e 1970.
About 30 types of these devices are known (159). Their e f f e c t i v e
ness can be c h a r a c t e r i z e d i n two ways : by__the r e d u c t i o n of /C
(See above) along the mixer a x i s (159), /C = a exp(-mz/d ) or by
the increase of s t r i a t i o n number produced by passing through m i
xing elements (160) :
/ = b .
For i n s t a n c e , w i t h the Hi-Mixer (161), 6 /6 = 4 . A f a c t o r of
5 i s easy to o b t a i n f o r m w i t h respect to an empty tube, at the ex
pense of a corresponding increase i n pressure-drop. A comparison
between the e x i s t i n g types of s t a t i c mixers (162) shows that most
of them have an e q u i v a l e n t e f f e c t i v e n e s s . The case of Sulzer-Mixers
has been e s p e c i a l l y s t u d i e d (163), i n c l u d i n g use w i t h gases (164).
t

178
Mixing i n s t a t i c mixers considered as chemical r e a c t o r s was

e s s e n t i a l l y s t u d i e d by Nauman ( 165, 166). This author proposed a
model which c o n s i s t s of a t u b u l a r r e a c t o r comprising zones i n
laminar flow ( p a r a b o l i c v e l o c i t y p r o f i l e ) . Mixing between each
zone i s achieved accross a plane by a permutation of the r a d i a l po
s i t i o n of f l u i d p a r t i c l e s ( r j ^ ^), i n t h i s way the f l o w r a t e
i s kept unchanged . Several cases are considered : complete mixing
(permutation at random), complete flow i n v e r s i o n ( r 2 = 1 ~ \>
W2 = 1 " Wj), p a r t i a l i n v e r s i o n . I n the f i r s t case, = 0 c o r r e s
ponds to a CSTR and
to a plug-flow r e a c t o r . I t i s shown that
the best chemical conversion i s obtained w i t h complete flow i n v e r
s i o n . The RTD i n a Kenics mixer comprising 8 elements could be r e
presented by t h i s model w i t h = 3 and complete mixing. S t a t i c mi
xers could be used as chemical r e a c t o r s f o r s p e c i f i c a p p l i c a t i o n s
(reactants having large v i s c o s i t y d i f f e r e n c e s , p o l y m e r i z a t i o n s ) but
the published data are s t i l l very scarce and a d d i t i o n a l informa
t i o n i s r e q u i r e d f o r assessing these p o s s i b i l i t i e s .
Beside s t a t i c mixers, there are p r a c t i c a l l y no a l t e r n a t i v e s
to the " u b i q u i t o u s " s t i r r e d tank, i f one excepts loop r e a c t o r s
(167) and the somewhat s p e c i a l back-flow mixer ( 168). Imagining en
t i r e l y new p r i n c i p l e s f o r mixing r e a c t a n t s i s a challenge f o r f u
ture researchers. F i r s t estimations show that an "informed" mixing
system, working as a Maxwell demon would be much more e f f e c t i v e
than our present devices (169).

Mixing of S o l i d s . This p o i n t i s a c t u a l l y very important but

deserves a s p e c i a l review, and w i l l not be t r e a t e d i n t h i s paper.
The reader w i l l f i n d the s t a t e of the a r t and a l i t e r a t u r e survey
i n three e x c e l l e n t papers (170, 171, 172).
An example of the importance of mixing e f f e c t s i n chemical
reactors : continuous f r e e r a d i c a l p o l y m e r i z a t i o n . One might now
ask the question : are segregation e f f e c t s r e a l l y important i n
p r a c t i c e or i s micromixing "a s o l u t i o n i n search of a problem"
(173), a mere i n t e l l e c t u a l e x e r c i s e f o r academics who are short of
o r i g i n a l PhD subjects ?
I t i s true that micromixing e f f e c t s can g e n e r a l l y be neglec
ted i n the design of r e a c t o r s f o r simple and slow r e a c t i o n s . How
ever, as has been pointed out i n the preceding Sections i n the
case of f a s t r e a c t i o n s w i t h unmixed r e a c t a n t s , chemical conversion
could be e n t i r e l y c o n t r o l l e d by mixing, and induce dramatic v a r i a
t i o n s i n the d i s t r i b u t i o n of products. The p r a c t i c a l examples of
combustion and r e a c t i o n s i n l i q u i d suspension are e s p e c i a l l y i l l u
minating i n t h i s respect.
Another area where micromixing plays a c a r d i n a l r o l e i s con
tinuous p o l y m e r i z a t i o n .
The subject i s t r e a t e d elsewhere i n t h i s Symposium, and was
reviewed by Nauman ( 173) and Gerrens ( 174) a few years ago. There
fore a thorough d i s c u s s i o n of mixing e f f e c t s i n polymer r e a c t o r s
would go beyond the scope of t h i s paper. I t i s l i k e l y that s i g n i -

6.
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179
f i c a n t progress has been made s i n c e these reviews, but they are d i f

f i c u l t to assess because of a lack of published data. Two examples
w i l l show the importance o f micromixing e f f e c t s on the s t r u c t u r a l
c h a r a c t e r i s t i c s of polymers ( 175). The f i r s t example i s a simula
t i o n o f f r e e r a d i c a l p o l y m e r i z a t i o n i n a CSTR. The r e t a i n e d k i n e
t i c scheme i s
kd,f
A
> 2R
k
R + M
*> R
k
Initiation
Propagation
t P
R +
> + R
Transfer to Polymer

k
R + R
-> +
Termination ( D i s p o r p o r t i o n a t i o n )
F i g u r e 14 shows a p l o t of the D i s p e r s i o n Index DI = M /M

wersus the conversion X of the monomer f o r segregated flow (S; and
w e l l micromixed flow (M). The dramatic i n f l u e n c e of segregation
can be n o t i c e d a t high conversion, e s p e c i a l l y w i t h t r a n s f e r to po
lymer. Moreover, an i n t e r e s t i n g e f f e c t i s observed w i t h d i l u t e d
and slow i n i t i a t o r s , namely an i n v e r s i o n of the r e l a t i v e p o s i t i o n
of S and M curves when the t r a n s f e r constant k p i s increased.
This doesn't happen w i t h concentrated and f a s t i n i t i a t o r . The se
cond example i s an experimental one (176). Continuous polymeriza
t i o n of styrene was c a r r i e d out i n a CSTR and i n cyclohexane s o l u
t i o n i n order to keep the v i s c o s i t y low and constant. The D i s p e r
s i o n Index was measured as a f u n c t i o n of space time and a g i t a t i o n
speed. L i m i t i n g curves f o r segregated flow (S) and w e l l micromixed
flow (M) were c a l c u l a t e d from batch experiments. C l e a r evidence
for segregation e f f e c t s can be seen on f i g u r e 15 which shows that
p e r f e c t micromixing may be very d i f f i c u l t to achieve, even w i t h
strong a g i t a t i o n and low v i s c o s i t y .
Besides these l a b o r a t o r y experiments, the a n a l y s i s of indus
t r i a l r e a c t o r s may a l s o r e v e a l segregation e f f e c t s , as f o r instance
i n r e a c t o r s f o r f r e e r a d i c a l p o l y m e r i z a t i o n of ethylene where the
i n i t i a t o r feedstream i s l i k e l y to be mixed by an e r o s i v e process
( 175) . P o l y m e r i z a t i o n and polycondensation r e a c t o r s o f f e r s an es
p e c i a l l y i n t e r e s t i n g f i e l d f o r f u t u r e a p p l i c a t i o n s of micromixing.
w
General c o n c l u s i o n
The end of t h i s survey leaves us w i t h the f e e l i n g that r e
search on mixing i n chemical r e a c t o r s i s a very l i v e l y area, where
problems have been attacked from s e v e r a l d i r e c t i o n s (turbulence
theory, RTD and mixing e a r l i n e s s , segregation and micromixing . . . ) .
I f the major concepts have been i d e n t i f i e d , there i s s t i l l a need
f o r a u n i f i e d theory a l l o w i n g a - p r i o r i p r e d i c t i o n s from the s o l e
knowledge of physicochemical p r o p e r t i e s and operating parameters,
even i f encouraging progress has been made i n t h i s d i r e c t i o n .
Without r e p e a t i n g the conclusions drawn at the end of each


180
Q2
, Q6 , 0.8
04
,X
Figure ih.
Free r a d i c a l p o l y m e r i z a t i o n i n a CSTR. D i s p e r s i o n
Index DI v s . conversion X.
S - segregated flow, M = w e l l - m i c r O mixed flow, I = l i n e a r p o l y m e r i z a t i o n k = 5 x L mol"- * h
k
= 1,5 x 10
L mol" h " , k = 0.033 1' , f = 0.5, A = 3 x 10"
mol L
, S =7.12
mol L"" ( s o l v e n t ) , M = 3.56 mol L " .
Curves
2 t o U:
T r a n s f e r t o polymer. 2 : k p = 3-5 x 1 0 mol L " h
,
3 : k
= 1.05 x I0h
I T m o l " h " , k : k p = 1.05 10 L
mol"
h"* , A = 3 x 10
mol L " , k = 0.33 h "
(other parameters un
changed) .
1
t p
3.0i
DI
S
2-5
'~
s'
. /
^ '
/
__/ N-100
RPM
(o)N-300
x)
" " J ^ N-1800

3
N.2700
N-3600
/ ^
^-----*
L -
HOURS
Figure 15.
E f f e c t of segregation on p o l y m e r i z a t i o n of styrene
i n cyclohexane s o l u t i o n . Standard CSTR with h b a f f l e s and a
6-blade t u r b i n e , V = 670 cm , = 75 C.
D i s p e r s i o n Index DI
vs. space time. Influence o f a g i t a t i o n speed. Curves S (segre
gated flow) and M (we11-micromixed flow) c a l c u l a t e d from batch
experiments^ I n i t i a t o r : PERKADOX l 6 , A = 0.033 mol I T ,
k
= 5 x 10" s " , f = 0.85; M = 6.65 mol L " , S = 2.22 mol I T .
3


6.
VILLERMAUX
181
S e c t i o n , we may t r y to summarize the s i t u a t i o n as f o l l o w s : R e s i

dence time d i s t r i b u t i o n s are now a w e l l e s t a b l i s h e d t o o l but pro
gress i s s t i l l d e s i r a b l e f o r m u l t i p l e i n l e t / o u t l e t systems, un
steady s t a t e operations, f l u i d s w i t h t i m e - v a r i a b l e p r o p e r t i e s and
inhomogeneous r e a c t i n g media. More a t t e n t i o n should be paid to i n
t e r n a l age d i s t r i b u t i o n s and r e l a t e d q u a n t i t i e s such as c i r c u l a
t i o n time d i s t r i b u t i o n s i n s t i r r e d tanks. I n continuous r e a c t o r s ,
models f o r mixing e a r l i n e s s d e s c r i b i n g the t r a n s f e r between Ente
r i n g and Leaving Environments are superabundant. Further r e d u c t i o n
of segregation by i n t e r a c t i o n between f l u i d p a r t i c l e s can be conve
n i e n t l y represented by simple models (exchange w i t h the mean,
c o a l e s c e n c e - d i s p e r s i o n ) , but s e v e r a l stages f o r mixing, each w i t h
t h e i r own time constants should be considered, p o s s i b l y i n s e r i e s
or i n p a r a l l e l . There i s s t i l l a problem as to the u l t i m a t e stage
of mixing by molecular d i f f u s i o n where i t i s not c l e a r whether the
mixing time i s t = T ^ (Lg/) ' or t = ^ /Jb. C a r e f u l l y
designed experiments (no macromixing e f f e c t s , p e r f e c t l y defined
hydrodynamic p a t t e r n s ) and new chemical t e s t r e a c t i o n s would be
welcome i n t h i s respect. The method of " c h a r a c t e r i s t i c times" i s
e s p e c i a l l y h e l p f u l f o r determining which processes are c o n t r o l l i n g .
These are f o r instance the space time f o r a continuous r e a c t o r ;
a c h a r a c t e r i s t i c time f o r i n t e r n a l macromixing p a t t e r n , e.g. the
c i r c u l a t i o n time t i n a s t i r r e d tank ; one or s e v e r a l r e a c t i o n
times, e.g. t = 1/kC^" ; and one or s e v e r a l micromixing times t ,
e.g. t (erosion) or t ^ / ^ , or t _ = l/ or
^ (v/) ' ,
or T ^ (Lg/)^' . Comparison between a l l these times allows the
determination of the mixing regime, sometimes q u a n t i t a t i v e l y . I t
was thus e s t a b l i s h e d that the m i c r o f l u i d / m a c r o f l u i d volume r a t i o
was n e a r l y equal to t ^ / t p . Another c h a r a c t e r i s t i c of current r e
search i s a gradual and f o r t u n a t e merging between the E u l e r i a n
approach of F l u i d Mechanics and the Lagrangian approach of Chemi
cal Engineering. Measurement of c o n c e n t r a t i o n f l u c t u a t i o n s should
be developed, both i n presence and i n absence of chemical reac
tions i n order to o b t a i n r e l i a b l e s p e c t r a l data. However, the f i
nal s o l u t i o n to micromixing problems should not be sought i n t u r
bulence theory alone, but r a t h e r i n phenomenological i n t e r a c t i o n
models, whose parameters could have a fundamental i n t e r p r e t a t i o n
by t h i s theory.
This i s the wish of most i n d u s t r i a l s : "In g e n e r a l , i n d u s t r y
would plead f o r l e s s s o p h i s t i c a t e d mathematical models and more
phenomenological models g i v i n g us more understanding of what's
going on i n the tank" (10). Among other recommendations (9, _K), 27,
154), there i s a general agreement f o r encouraging research on
large volume r e a c t o r s , g a s - l i q u i d - s o l i d systems and mixing of non
newtonian f l u i d s . New ideas on e n t i r e l y novel mixing p r i n c i p l e s
and equipments would a l s o be welcome. But above a l l , theory w i l l
progress i n a d i r e c t i o n u s e f u l to p r a c t i t i o n e r s i f more experimen
t a l data on r e a l i s t i c i n d u s t r i a l s i t u a t i o n s are a v a i l a b l e to r e
searchers .
1

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138. Sasakura, T.; Kato, Y.; Yamamuro, S.; Ohi, N. Internat. Chem.
Eng. 1980, 20, 251-258
139. Rachez, D.; David, R.; Villermaux, J. Entropie, 1981, N 101,
72, 32-39
140. Bryant, J.; Sadeghzadeh, S. Proceed. Third Europ. Conf. on
Mixing, April 4-6th 1979, York, BHRA Fluid Eng. paper F3, 325
141. Bryant, J.; Sadeghzadeh, S. Proceed. Fourth Europ. Conf. on
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ENGINEERING
144. Okamoto, Y.; Nishikawa, M.; Hashimoto, K. Int. Chem. Eng.

1981, 21, 88-94
145. Van der Molen, K.; Van Maanen, H.R.E. Chem. Eng. Sci. 1978,
33, 1161-68
146. Nishikawa, M.; Okamoto, Y.; Hashimoto, K.; Nagata, S. J.
Chem. Eng. Japan 1976,6,489-494
147. Fort, I.; Placek, J.; Kartky, J.; Durdil, J.; Drbohlav, J.
Collect. Czechoslov. Chem. Comm. 1974,39,1810-1822
148. Mann, R.; Mavros, P.P.; Middleton, J.C. Trans. I. Chem. Eng.
1981, 59, 271-278
149. Mann, R.; Mavros, P. Proceedings of the Fourth Europ. Conf.
on Mixing, April 27-29, 1982, BHRA Fluid Eng. Paper B3, 35-47
150. Joshi, J.B.; Pandit, A.B.; Sharma, M.M. Chem. Eng. Sci. 1982,
37, 813-844
151. Rod, V.; Misek, T. Trans. Inst. Chem. Eng. 1982, 60, 48-53
152. Oldshue, J.Y. A.C.S. Symp. Series, 1977, 55, 224-241
153. Oldshue, J.Y. Chemtech. September 1981, 554-561
154. Kipke, K. Chem. Ing. Tech. 1982, 54, 416-425
155. Quraishi, A.Q.; Mashelkar, R.A.; Ulbrecht, J.J. AIChE Journal
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156. Ulbrecht, J.J.; Sema Baykara; Z.; Chem. Eng. Commun. 1981, 10
165
157. Lane A.G.C.; Rice, P. Trans. I. Chem. E. 1982, 60, 171-176
158. Okamoto, Y.; Nishikawa, N.; Hashimoto, K. Int. J. Chem. Eng.
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159. Pahl, M.H.; Muschelknautz, E. Int. Chem. Eng. 1982, 22, 197
160. Boss, J.; Czastkiewicz, W. Int. Chem. Eng. 1982, 22, 362-367
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162. Henzler, H.J. Chem. Ing. Tech. 1979,51,1-8
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RECEIVED April 15, 1983


Publication Date: July 28, 1983 | doi: 10.1021/bk-1983-0226.ix001
INDEX
Accumulator volume, mixing

theory
154
A c r y l o n i t r i l e , heats of
polymerization
1061
AeryIon i t r ile-butadienestyrene polymer, world
capacity and expected
growth
1021
A c t i v a t i o n energy in s t i r r e d
tank r e a c t o r
14
Adiabatic r e a c t o r s
28f
Age d i s t r i b u t i o n , instantaneous
i n t e r n a l , population balance
method
147-48
Age domain, mixing
earliness
151-63
Aging, band, methanol-togasoline process
25-27
A i r a d d i t i o n and nitrogen
oxide emission
90-92
Air flow r a t e in atmospheric
pressure f l u i d i z e d bed
combustor
67-69
A l k y l a t e , product y i e l d s from
methanol-to-gasoline
processes
42t
Amides, polymerization
mechanism
105t
Anionic polymerization
reactions
103-7
Area, f l u i d i z e d bed combustor
cross-sectional
69,72-78
distributor plate
77
tube
78-80
Aromatics, methanol conversion
products
23
Ash d i f f u s i o n c o n t r o l in
atmospheric pressure f l u i d
bed combustor
87
Atmospheric pressure f l u i d bed
combustor
bed height and pressure
drop
67-69
bed temperature
69-73
carbon combustion
efficiency
80-87
Atmospheric pressure f l u i d bed

combusterConti nued
c o n t r o l l i n g parameters
65-93
flow regimes and immersed
tubes
92-93
f l u i d mechanics and flow
regime
72-78
p a r t i c l e s i z e and s u l f u r
capture
69-73
v o l a t i l e evolution
87-92
A t t r i t i o n r a t e , carbon
combustion e f f i c i e n c y . . . 83-85
Autocatalytic kinetics,
s o l u t i o n polymerization
in a continuous flow
s t i r r e d tank r e a c t o r . . . 110-14
A u t o c o r r e l a t i o n , homogeneous
i s o t r o p i c turbulence
138-41
Background, h i s t o r i c a l survey
of mathematics
1-15
Baffles
f l u i d bed r e a c t o r , design.... 40f
f u l l - s c a l e cold flow model
design
44
Band-aging in methanol-togasol ine process
25-27
Batch s t i r r e d tank,
polymerization r e a c t i o n s . . . 109t
Batchelor microscale,
homogeneous i s o t r o p i c
turbulence
138-41
Bead polymerization
109t
BedSee also F l u i d bed
Bed, in f l u i d bed r e a c t o r
c r o s s - s e c t i o n a l area
68,72-78
density of s o l i d s
67-69
height
50-55, 67-69
length and gas r e c y c l e
system
34
temperature
69-73
weight
67-69
Belousov-Zhabotinsky
r e a c t i o n in continuous
flow s t i r r e d tank r e a c t o r . . 143
B i f u r c a t i o n , Hopf
13-14
B i f u r c a t i o n diagrams
11-12
189
190
CHEMICAL REACTION

Bubbles in f l u i d bed reactor

diameter
50-55,75-77
rise velocity
66-67,74-78,92
Bundle o f p a r a l l e l tubes
model
145-57
Butadiene, heats of
polymerization
106t
Butad iene-acryIon i t r i l e - s t y r e n e
polymer, world capacity and
expected growth
1021
-Butane and butnes, f i r s t
c y c l e y i e l d , scaled-up
f i x e d bed r e a c t o r
35t,42t
C
Calcium carbonateSee Limestone
Calcium s u l f a t e , conversion of
limestone
69-73
CaIderbank-Moo-Young
c o r r e l a t i o n f o r small
p a r t i c l e s immersed in
turbulent media
167
Carbon combustion e f f i c i e n c y
in atmospheric pressure
f l u i d bed combustor
80-87
Carbon dioxide and monoxide,
product y i e l d s from
processes
42t
Cascade, s t i r r e d tank
polymerization r e a c t i o n s . . . 109t
Catalysis
s o l i d polymerization,
olefin
120-24
s o l u t i o n polymerization
k i n e t i c s in a continuous
flow s t i r r e d tank
reactor
110-14
Catalyst
c i r c u l a t i o n , f u l l - s c a l e cold
flow model
44
cracking, f l u i d bed
56
for propylene
polymerization
120-24
z e o l i t e , shape-selective, f o r
process
19-23
C a t a l y s t bed length in
commercial plant
34
C a t a l y s t d e a c t i v a t i o n in
process
25-27
C a t a l y t i c reactors
durene conversion
37
f l u i d i z a t i o n and heat
transfer
67
ENGINEERING
C a t i o n i c polymerization
reactions
103-7
C e l l models, mixing theory
176
Chain t r a n s f e r in
polymerization r e a c t i o n s . . 103-7
Chaotic behavior
13
Chemical r e a c t i o n and
mixing
169-70
Chemical r e a c t o r s S e e Reactors
Circulation
of c a t a l y s t f o r f u l l - s c a l e
cold flow model
44
in s t i r r e d tanks, i n t e r n a l
pattern
176-77
Closure problem
141
Coal
19
Coal combustion
reactions
66,87-90
r e a c t o r s , f l u i d bed
55-56
atmospheric pressure
controlling
parameters
65-93
feed diameter s e l e c t i o n . . . 80-87
feed l o c a t i o n
87-90
f l u i d mechanics
66,72-78
heat t r a n s f e r
66,78-87
Coal-to-gasoline v i a
methanol
20f
Coalescence-dispersion
process
142
Coalescence-dispersion process,
random model, mixing
theory
156-64
Coke formation in methanolto-gasoline conversion 25-27,42t
Cold flow model, f u l l - s c a l e ,
b a f f l e design and c a t a l y s t
circulation
44
Combination termination in
polymerization r e a c t i o n s . . 103-7
Combustion, c o a l , using f l u i d bed
c o n t r o l l i n g parameters.. 65-93
bed c r o s s - s e c t i o n a l
area and flow regime.... 72-78
drop
67-69
bed temperature
69-73
carbon combustion
efficiency
80-87
f l u i d mechanics
72-78
heat of r e a c t i o n
69
immersed tubes and flow
regimes
92-93
particle size
69-73
reactions
66
reactors
55-56


INDEX
191
Combustion, c o a l , using f l u i d
bedContinued
s u l f u r capture
69-73
volatile evolution
87-90
Commercialization
of methanolto-gasol ine process
32-44
of, polymerization r e a c t o r s . . . 109t
Concentration
oxygen, and carbon combustion
efficiency
82-83
propylene, p r o f i l e s in the
m u l t i g r a i n model f o r
c a t a l y t i c polymerization
120-24
solvent, in polymerization
reactions
110-15
Concentration d i s t r i b u t i o n
136
Concentration f l u c t u a t i o n s ,
turbulence theory
138-40
Concentration macroscale
137
Condensation polymerization... 103-7
Conductive f l u x e s and heat
t r a n s f e r in atmospheric
pressure f l u i d bed
combustor
78-80
Configuration of z e o l i t e
c a t a l y s t f o r methanolto-gasol ine process
21-23
Constructive theory of
p a r t i t i o n s , Sylvester
3
Continuous fermentor
12
Continuous flow reactor
steady s t a t e , mixtures with
v a r i a b l e density
148-49
s t i r r e d tank
49
Belousov-Zhabotinsky
reaction
143
polymerization r e a c t i o n s . . 109t
emulsion
114-20
free r a d i c a l
178-79
isothermal, of methyl
methacrylate
113f
solution
110-14
Continuous f r e e r a d i c a l
polymerization, mixing
theory
178-79
Convective f l u x e s , heat
t r a n s f e r , atmospheric
combustor
78-80
Convective mixing
165-66
Convergence and i n f i n i t e s i m a l
numbers
8
Conversion, steady-state
monomer, vs. reactor
residence time in s o l u t i o n
polymerization
113f
Conversion of energy, thermal

to e l e c t r i c a l , e f f i c i e n c y
in atmospheric pressure
69
Conversion r e a c t i o n
of limestone to calcium
carbonate
69-73
of methanol to hydrocarbons. 23-25
Conversion reactor o u t l e t and
i n l e t temperature,
scaled-up f i x e d bed
reactor
35ti,42t
Coolant f o r tubular r e a c t o r s . . . 32
Cooling
in f i x e d bed reactor
27
in s t i r r e d tank r e a c t o r
14
Coordination polymerization
reactions...
103-7
Copolymers, ethylene-propylene,
polymerization mechanism.. 105t
Core model, polymerization.... 122f
Corrsin equation
141-41
C o r r s i n microscale,
turbulence
138-41
Cost, r e c y c l e operation in
f i x e d bed reactors
27
Cracking c a t a l y s t in f l u i d
bed
56
Cross!inking in polymerization
reactions
103-7
Cross-sectional area of f l u i d
bed
69,72-78
CSTRSee Continuous flow
recTor, s t i r r e d tank
Cyclohexane s o l u t i o n , e f f e c t
of segregation on polymeri z a t i o n of styrene
178-79
C y c l o p a r a f f i n s , methanol
conversion products
23
D
Damkohler numbers
mixing models
170f
for s t i r r e d tank r e a c t o r
14
Danckwert segregation
index
136-38,161
Deactivation, c a t a l y s t ,
process
25-27
Dealkylation of durene
37
Deethanizer
38f
Degree of homogeneity, mixing
theory
137
Dehydration r e a c t i o n ,
process
23


192
CHEMICAL REACTION
Dehydration r e a c t o r
commercial f i x e d bed plant
design
37-39
in methanol-to-gasoline
processes, product
yields
42t
Density
of atmospheric pressure
f l u i d bed combustors.... 67-93
of b a f f l e s
f o r f u l l - s c a l e cold flow
mode1.................... 44
f o r f l u i d i z e d bed r e a c t o r . . 4 0 f
of bed s o l i d s in atmospheric
combustor
67-69
of continuous flow s t i r r e d
tank emulsion
polymerization r e a c t o r . . . 117f
of dehydration r e a c t o r
37-39
of f i x e d bed r e a c t o r s . . . . 27,37-39
of methanol-to-gasoline
reactor
23-32
of multibed r e a c t o r
29f
of polymer r e a c t o r
103-7
probability functions
141-42
and residence time
d i s t r i b u t i o n theory
145t
and steady-state
continuous r e a c t o r s . . . . 148-49
of v a r i a b l e s in f l u i d i z e d
bed r e a c t o r
62
Diameter
of bubbles in atmospheric
combustor
75-77
of coal feed in atmospheric
combustor, s e l e c t i o n . . . . 80-87
of p a r t i c l e s
in f l u i d bed r e a c t o r s
55
in f l u i d bed r e a c t o r s ,
convective and r a d i a t i v e
c o n t r i b u t i o n s to heat
transfer
78
of pores in s u l f a t i o n of
limestone
70-73
D i f f e r e n t i a l equations in
chemical r e a c t o r theory.... 13
Diffusion
of ash, c o n t r o l i n
87
e x t e r n a l , vs. k i n e t i c s in
carbon combustion
85
molecular, in mixing
166-69
of oxygen and carbon
ENGINEERING
Dimethyl ether formation in

process
23-25
Dirac d e l t a f u n c t i o n
8
D i s i n t e g r a t i o n of p a r t i c l e s
and postulated morphological
models f o r polymerization.... 122f
Dispersion
index f o r polymerization... 178-80
s o l i d , mechanism in coal
combustion
88-90
Dispersive mixing
166-67
D i s p r o p o r t i o n a t e in
polymerization
103-7,178-80
D i s s i p a t i o n of energy
and carbon combustion
efficiency
83-85
and homogeneous i s o t r o p i c
turbulence
138-41
D i s t i l l a t i o n range,
gasoline
25-27
Distribution function
instantaneous internal and
l o c a l age, population
balance method
145,147-48
r e a c t i o n time, mixing
theory
149
Distributor plate
in an atmospheric pressure
77
in a f u l l - s c a l e r e a c t o r
58
Dolomite, s u l f u r capture
69-73
D r o p l e t - d i f f u s i o n model,
mixing theory
170-71
Durene formation in methanolto-gasol ine
process
25-27,34,36f,37
E a r l i n e s s mixing in the age

domain
151-64
E f f i c i e n c y in an atmospheric
pressure f l u i d bed combustor
of carbon combustion
80-87
of energy conversion,
thermal to e l e c t r i c a l . . . . 69
of fans...................... 69
E l e c t r i c a l energy from thermal
energy, e f f i c i e n c y of
conversion in an
bed combustor
69
E l u t r i a t i o n constant f o r
p a r t i c l e s and carbon
combustion e f f i c i e n c y
80-82

193

INDEX
Emmissions of nitrogen oxides,

from an atmospheric pressure f l u i d bed combustor.. 90-92
Emissivity, tube w a l l , and
heat t r a n s f e r in an
bed combustor
78-80
Emulsion phase, atmospheric
combustors vs. f l u i d
c a t a l y t i c crackers
66-67
Emulsion polymerization in a
continuous flow s t i r r e d
tank r e a c t o r
105t, 114-21
Emulsion v e l o c i t y in an
bed combustor
77
Energy
a c t i v a t i o n , s t i r r e d tank
reactor
14
conversion, thermal to
e l e c t r i c a l , in an
69
dissipation
carbon combustion
efficiency
83-85
molecular d i s p e r s i o n
167
turbulent, homogeneous
isotropic
turbulence
138-41
Entering environment, mixing
theory
151-64
Entropy of a mixture
138
Erosive mixing
166-67
Ethane, in a scaled-up f i x e d
bed r e a c t o r
35t,42t
Ether, y i e l d in methanol-togasol ine processes
42t
Ethylene
heats of polymerization
106t
production from methanol
40f
y i e l d in a scaled-up
35t,42t
Ethylene oxide, polymerization
mechanism
105t
Ethylene-propylene copolymers,
polymerization mechanism... 105t
E u l e r i a n approach t o mixing
and turbulence
138-44
Exotherm, methanol-to-gasoline
process
23-24
Exothermic r e a c t i o n , unc o n t r o l l e d nonadiabatic
s t i r r e d tank r e a c t o r
13-14
Expansion type A powders in a
f l u i d bed r e a c t o r
57f
Extruder, polymerization
reactions
109t
Fans f o r an atmospheric pressure

f l u i d bed combustor.
69
Feed diameter, c o a l , f o r an
bed combustor
80-87
Feedstreams
See a l s o I n l e t ( s )
in the bundle of p a r a l l e l
tubes model
150-57
mixing.....
158f
Fermentor, continuous
12
Fixed bed r e a c t o r s f o r
conversion
27-30,33-39
Flow
in a d i a b a t i c r e a c t o r s . . . . . 28f,29f
in carbon combustion
84-85
in a f l u i d bed r e a c t o r
50-62
in a f l u i d bed r e a c t o r a t
f l u i d mechanics
72-78
and immersed tubes
92-93
mixing with two unmixed
feedstreams
158f
polymerization
122f
and residence time
145t
Flow r a t e
135-80
in bundle of p a r a l l e l tubes
model
145-46
in a f l u i d bed r e a c t o r of
a i r and f u e l . . . . . . 50-55,67-69
Fluctuation
mean square and homogeneous
i s o t r o p i c turbulence... 138-41
probability density
f u n c t i o n s . . . . . . . . . . . . . . 141-42
F l u i d bed r e a c t o r s
49-62
b a f f l e s , design.....
40f
bubble models
50-62
catalyst
56
c a t a l y t i c d i f f e r e n c e s in
f l u i d i z a t i o n and heat
transfer
6
coal combustion
55-56
coal combustion a t
drop
67-69
bed temperature
66-73


194
CHEMICAL REACTION
F l u i d bed r e a c t o r s
Continued
carbon combustion
efficiency
80-87
c o n t r o l l i n g parameters.... 65-93
flow regimes and immersed
tubes
92-93
f l u i d mechanics
66,72-78
heat t r a n s f e r
66,78-87
particle size
69-73
s u l f u r capture
69-73
volatile evolution
87-90
for methanol-to-gasoline
process
28f,30-32,40-44
p i l o t plant scale-up
40-43
F l u i d mechanics, determination
of bed c r o s s - s e c t i o n a l
area and flow regime in
bed combustor
72-78
F l u i d p a r t i c l e s , mechanism o f
interaction
164-75
F l u i d i z a t i o n and heat t r a n s f e r
d i f f e r e n c e s of atmospheric
combustors and f l u i d
catalytic reactors
67
F l u i d i z a t i o n v e l o c i t y in f l u i d
bed r e a c t o r s
52-56,72-78
Fluxes, conductive and
convective, heat t r a n s f e r
78-80
Formaldehyde, heats of
polymerization
106t
Formation
of bubbles in f l u i d bed
reactor, x-ray
photograph
58-60
of durene in methanol-togasol ine process
25-27
of n i t r i c oxide in coal
combustion
66
Formation k i n e t i c s o f
process
23-25
Fragmentation of p a r t i c l e s in
an atmospheric pressure
87
Free r a d i c a l polymerization
mixing theory
178-79
reactions
103-7
Freeboard r e a c t i o n s in an
bed combustor
92
Fuel flow r a t e in an
bed combustor
69
ENGINEERING
Gas
l i g h t , methanol-to-gasoline
processes
42t
n a t u r a l , conversion to
gasoline v i a methanol.... 20f
Gas phase
alchemy
3-4
c i r c u l a t i o n , f l u i d i z e d bed
reactor
50-62
Corrsin microscale, mixing
theory
139-41
flow, atmospheric pressure
74-78
mixing, atmospheric
combustor
77-78
r e c y c l e system and bed
length
34
v e l o c i t y , atmospheric
combustors vs. f l u i d i z e d
66-67
v e l o c i t y , f l u i d bed
reactors
52,55-56
G a s i f i c a t i o n , carbon, in f l u i d
bed combustors
85
Gasoline
manufacture from methanol... 19-46
treating
37,38f
y i e l d in scaled-up f i x e d bed
reactor
35t,42t
G i l d e r s l e e v e , B a s i l Lanneau.... 2-3
Grain model, calcium oxide.... 70-72
H
Heat exchange
in c a t a l y t i c r e a c t o r s
67
in tubular r e a c t o r s in a
process
32
Heat of r e a c t i o n
combustion, atmospheric
combustor
69
conversion, limestone to
calcium s u l f a t e
69-73
polymerization
106t
in a s t i r r e d tank r e a c t o r . . . . 14
Heat removal, polymerization
reactions
106
Heat sink, isothermal, tubular
reactors
32
Heat t r a n s f e r
f l u i d bed combustor.. 67,78-80

195

INDEX
Heat t r a n s f e r C o n t i n u e d
f l u i d bed combustor vs.
fluidized catalytic
reactors
67
in a f l u i d bed
30
in nonadiabatic r e a c t o r s . . 28f,29f
in a s t i r r e d tank reactor.... 14
Heavy gasoline t r e a t i n g
technology
37,38f
Height
bed
and bubble s i z e in a f l u i d
bed r e a c t o r
50-55
and pressure drop in an
f l u i d bed combustor... 67-69
freeboard, in an atmospheric
combustor
92
Heterogeneous media,
polymerization
105t
Heterogeneous r e a c t o r s ,
isothermal
149
H i s t o r i c a l survey of
mathematics
1-15
Homogeneity degree, mixing
theory
137
Homogeneous isothermal
reactors
149
Homogeneous i s o t r o p i c
turbulence
138-40
Homogeneous media,
polymerization
105t
Hopf b i f u r c a t i o n
13-14
Horizontal scale-up of f l u i d
bed r e a c t o r s
40-42
Hydrocarbons
conversion r e a c t i o n of
methanol
23-25
y i e l d in scaled-up f i x e d
bed reactor
35t,42t
Hyperreal numbers
8
I
Immersed tubes and flow
regimes in an atmospheric
combustor
92-93
Indices
mixing
136-44
segregation, Danckwerts.... 136-38
IndustrySee Commercialization
Inert t r a c e r and mixing
161-64
I n f i n i t e and i n f i n i t e s i m a l
numbers
7-8
I n i t i a t i o n of polymerization
reactions
103-7,177-79
Inlet(s)
number and mixing
149
temperature
f i x e d bed reactor
35t,42t
product y i e l d s from
processes
42t
residence time d i s t r i b u t i o n
theory
145t
Instantaneous i n t e r n a l age
d i s t r i b u t i o n , population
balance method
147-48
Integers, hyperreal
8
I n t e n s i t y of segregation,
definition
136-37,140t
I n t e r a c t i o n by exchange with
the mean model.... 156-64,169-71
Interaction of p a r t i c l e s ,
models
156-75
I n t e r f a c i a l polycondensation... 109t
Internal age d i s t r i b u t i o n ,
instantaneous, population
balance method
147-48
Internal b a f f l e s , design in
40f
Internal c i r c u l a t i o n patterns
in s t i r r e d tanks
175-76
Ionic polymerization
reactions
103-7
Isobutane, f i r s t c y c l e y i e l d
in a scaled-up f i x e d bed
reactor
35t,42t
Isocyanates, world c a p a c i t y
and expected growth
102t
Isomerization of durene
37
Isothermal heat sink, tubular
reactors...................
32
Isothermal heterogeneous and
homogeneous r e a c t o r s
149
Isothermal polymerization
of methyl methacrylate in a
tank r e a c t o r , m u l t i p l i c i t y . . . . 113f,114,118f,121f
reactor conditions
Ill
Isothermal, non-, uncontrolled
nonadiabatic s t i r r e d tank
reactor with a s i n g l e
exothermic r e a c t i o n
13-14
I s o t r o p i c homogeneous
turbulence
138-40


196
CHEMICAL REACTION
K i n e t i c energy of turbulent
motion, homogeneous
138-41
Kinetics
of carbon combustion
85
process
23-25
of mixing
169-71
of polymerization.,.. 103-7,178-80
of s u l f a t i o n of limestone... 69-73
Kolmogorov microscale,
turbulence
138-41
L
Lagrangian approach and mixing
theory
164-75
Leaving environment and mixing
theory
151-64
Length of bed and gas r e c y c l e
system.
34
Light gas, product y i e l d s from
processes
42t
Limestone
reduction of nitrogen oxide.. 91
as sorbent in atmospheric
combustor
69-73
L i q u i d phase and C o r r s i n
microscale f o r mixing
theory
139-41
Local age d i s t r i b u t i o n
function
145,147
L o c i , Hopf b i f u r c a t i o n
14
M
Macroscale
turbulence
138-41
mixing and residence time
distributions
144-51
Magnesium limestone,
sulfation
69-73
Mass t r a n s f e r models f o r
carbon combustion
84-85
Mathematics, h i s t o r i c a l
survey
1-15
Maximum mixedness, d e f i n i t i o n . . . 151
Mean square f l u c t u a t i o n ,
turbulence
138-41
ENGINEERING
Mechanics, f l u i d , i n
f l u i d i z e d bed combustor... 72-78
Mechanisms
coal combustion
66
i n t e r a c t i o n , micromixing in
the p h y s i c a l space
164-75
process
23-25
in polymerization r e a c t o r s ,
kinetics
105t
of s o l i d d i s p e r s i o n , coal
combustion
88-90
s u l f a t i o n of limestone
69-73
Media, r e a c t i o n , employed in
polymerization r e a c t o r s . . . . 105t
Melt polycondensation
109t
Methane, f i r s t c y c l e y i e l d ,
reactor
35t,42t
Methanol-to-gasoline process
reactor design
23-32
scale-up and
commercialization
32-44
space v e l o c i t y , in a
reactor
35t,42t
zeolite catalysts
19-23
Methyl a c r y l a t e , heats of
polymerization
106t
Methyl methacrylate
106t
isothermal polymerization in
a continuous flow
s t i r r e d tank
reactor
113f,114,118
M e t r i c a l theory of "phonetic
syzygy," S y l v e s t e r
2
Microscale, mixing
phenomena
137,164-75
Minimum mixedness, d e f i n i t i o n . . 151
Mixing
135-81
d e f i n i t i o n and
c h a r a c t e r i z a t i o n of
degree
136-38
e a r l i n e s s in the age
domain
151-64
entropy
138
Eulerian approach
138-44
52
of gas in an atmospheric
combustor
77-78
macro-, and residence time
distributions
144-51
by molecular d i f f u s i o n
167-70


INDEX
197
Mi xi n g Continued
for polymerization
reactions
106
and segregation at the
microscopic level
164-75
static
176-78
in s t i r r e d tank r e a c t o r s . . . 175-77
times
137
Molecular d i f f u s i o n , mixing.. 167-70
Molten s a l t c o o l i n g
32
Moment equation, population
balance method
147-48
Monomers
106t
linkage
109t
Monte Carlo method, mixing
theory
156-59
Morphological models and
particle disintegration,
polymerization
122f
Motion, turbulent, k i n e t i c
energy and homogeneous
138-41
Multibed designs
29f
M u l t i g r a i n model,
polymerization
122f
M u l t i p l i c i t y , multiphase
s t i r r e d tank reactor.. 14,175-76
Natural gas and natural

gas-to-gasoline v i a
methanol
Newtonian f l u i d s , mixing
theory...
NG and Rippin model
N i t r i c oxide formation, coal
combustion
Nitrogen oxide emissions,
Nonadiabatic reactors
Nonadiabatic s t i r r e d tank
r e a c t o r , uncontrolled,
with a s i n g l e exothermic
r e a c t i o n , non isothermal
system
Numbers, hyperreal, i n f i n i t e ,
and i n f i n i t e s i m a l
Nylon, polymerization
mechanism
OctaneContinued
reactor
35t,42t
O l e f i n polymerization,
solid-catalyzed
120-24
Operating conditions of
reactor and residence time
1451
Oscillatory solution, stirred
tank r e a c t o r
14
Outlet
dehydration r e a c t o r
42t
theory
145t
temperature, in a scaled-up
35t,42t
Oxidant, dominant, carbon
combustion
85
Oxidation of bound nitrogen in
coal
90-92
Oxygen
atom c o n f i g u r a t i o n in a
s i l i c e o u s framework,
zeolite catalyst
21-22
concentration and
d i f f u s i v i t y , carbon
19,20f
165-66
153-64
66
90-92
28f
13-14
7-8
105t
0
Octane
blending q u a l i t y , durene.... 25-27
P a r a f f i n s , methanol conversion
products
23
P a r a l l e l model of Weinstein
and Adler
154f
Particles
definition
163
diameter
55,69-73,78-80
flow in f l u i d bed r e a c t o r . . . 50-62
fragmentation in atmospheric
combustor
87
heating in atmospheric
combustors vs. f l u i d i z e d
66-67
mixing in f l u i d bed
reactors
52
models
of i n t e r a c t i o n
156-64
of polymerization,
disintegration
122f
Partitions, constructive
theory, Sylvester
3
Phase behavior
c o m p a t i b i l i t y in f l u i d bed
reactor
59-62


198
CHEMICAL REACTION
Phase behavi o r C o n t i nued

and polymerization r e a c t i o n
kinetics
106
Phonetic syzygy, Sylvester's
metrical theory
2
P h y s i c a l space and mechanism
of micromixing
164-75
Plants
f i x e d bed r e a c t o r s
33
f l u i d bed r e a c t o r s
41f,43f
P l a s t i c s , world c a p a c i t y and
expected growth
102t
Polymerization r e a c t i o n s
classes
104t
condensation
103-7
continuous f r e e r a d i c a l ,
mixing theory
178-79
core model
122f
emulsion, in a continuous
flow s t i r r e d tank
reactor
114-20
engineering
101-24
heat of r e a c t i o n
106t
isothermal, of methyl
methacrylate in a
tank r e a c t o r
113f
k i n e t i c s and mechanisms
103-7
r e a c t o r design
103-7,117f
solid-catalyzed olefin
120-24
s o l u t i o n , in a continuous
s t i r r e d tank r e a c t o r . . . 110-14
Polymers, world c a p a c i t y and
expected growth
102t
Population balance method
in residence time
145-48
Pore s i z e of z e o l i t e c a t a l y s t
process
21-23
Pore-plugging model f o r
s u l f a t i o n of limestone.... 70-73
Powders, type A, expansion in
57f
P r e c i p i t a t i o n polymerization
105t,109t
Pressure
atmospheric, in f l u i d bed
coal combustion,
c o n t r o l l i n g parameters
65-93
in f i x e d bed r e a c t o r ,
scaled-up
35t,42t
in f l u i d bed
reactors
55,60-62,67-69
Probability density functions
f o r the f l u c t u a t i n g
components
141-42
ENGINEERING
Product q u a l i t y of polymer.... 107-8

Propagation, polymerization
reactions
103-7,177-79
Propane, y i e l d in scaled-up
35t,42t
Propylene
polymerization
concentration p r o f i l e s i n
the m u l t i g r a i n model
for a high a c t i v i t y
catalyst
120-24
heats of r e a c t i o n
106t
reactor
35t,42t
P y r o l y s i s of coal
87-90
Q
Quenching
in a d i a b a t i c r e a c t o r s
in f i x e d bed r e a c t o r s
28f,29f
27
Radial flow in a d i a b a t i c
reactors
28f,29f
Random coalescence-dispersion
model, mixing theory
156-64
Rate of a t t r i t i o n and carbon
83-85
Rate of c o o l i n g in a s t i r r e d
tank r e a c t o r
14
Rate of flow
See a l s o Flow r a t e
67-69
tubes model
145-46
50-55
Rate of heat t r a n s f e r ,
bed combustors vs.
fluidized catalytic
crackers
66-67
Rate of r e a c t i o n
b i f u r c a t i o n diagrams
11-12
carbon g a s i f i c a t i o n
85
reduction of nitrogen oxide.. 91
s u l f a t i o n of limestone
70-73
Rate of s o l i d ( s ) withdrawal and
carbon combustion
efficiency
80-82
Reactant mixing
135-80
Reaction, exothermic, s i n g l e ,
uncontrolled nonadiabatic
s t i r r e d tank r e a c t o r ,
nonisothermal system
13-14


INDEX
199
Reaction/diffus ion model,

mixing theory
158
Reaction h e a t S e e Heat of
reaction
Reaction media employed in
polymerization r e a c t o r s . . . . 105t
Reaction order, carbon
combustion
85
Reaction time d i s t r i b u t i o n ,
mixing theory
149
Reactor, f i x e d bed,
process
27-30,33-39
Reactor, f l u i d bed,
process
28f,30-32,40-44
Reactor temperature, polymerization
110-15
Reactors
adiabatic
28f
c a t a l y t i c , durene
conversion
37
continuous flow s t i r r e d tank
Be1ousov/Zhabotinsky
reaction
143
design f o r emulsion
polymerization
117f
dehydration
37-39
d e s i g n S e e Design
distributor plate,
full-scale
58
f o r emulsion polymerization.. 117f
f i x e d bed, f o r methanol-togasol ine process.... 27-30,33-39
f l u i d bed.
49-62
b a f f l e s , design
40f
bubble models
50-62
f o r coal combustion at
65
f o r methanol-to-gasoline
process
28f,30-32,40-44
isothermal
149
mixing
135-81
nonadiabatic
28f
semibatch, and residence
time d i s t r i b u t i o n
theory
145t
steady-state c o n d i t i o n s ,
mixtures with v a r i a b l e
density
148-49
s t i r r e d tank, uncontrolled
nonadiabatic
nonisothermal
13-14
tubular
32,141-43
two-inlet
156-64
Real numbers, i n f i n i t e
sequences
7-8
Recycle operation
and bed length
34
in f i x e d bed r e a c t o r s . . 27,35t,42t
Reduction of nitrogen oxide... 91-92
Residence time d i s t r i b u t i o n s
and macromixing
144-51
Reynolds number, p a r t i c l e
66
R u s s e l l , Bertrand
9
S
S a l t , molten, c o o l i n g
32
Scale-up
See a l s o Commercialization
of f i x e d bed r e a c t o r s
27
of f l u i d bed r e a c t o r s ,
h o r i z o n t a l and
vertical
40-42
process
32-44
of polymerization r e a c t o r s . . . 109t
Segregation
by chemical methods,
identification
170-75
index, Danckwerts
136-38,161
intens i t y , def in i t ion..136-37,140t
and mixing at the
microscopic l e v e l
164-75
and polymerization of
styrene in cyclohexane
solution
178-80
Semibatch r e a c t o r
m u l t i g r a i n model p r e d i c t i o n s
for propylene
polymerization
120-24
polymerization r e a c t i o n s
109t
theory
145t
Separations i n f i x e d bed
process
38f
Separator temperature in
reactor
35t,42t
Shape, molecular, and mixing
theory
167-70
Shape-selective z e o l i t e
catalysts for a
process
19-23
Sherwood number and carbon
82-83
Shrinking aggregate model 159,166-67
S i l i c e o u s framework, oxygen
atoms in z e o l i t e
catalyst
21-22
S i n g u l a r i t y theory
11-12


200
CHEMICAL REACTION
Size
bubble, in f l u i d bed
reactor
50
coal feed, f o r optimum
carbon combustion
efficiency
84-85
p a r t i c l e , in an atmospheric
combustor
66-73
pore
70
Solid(s)
bed, density, atmospheric
combustor
67-69
d i s p e r s i o n mechanism f o r
coal combustion.
88-90
mixing
178
o l e f i n polymerization
catalysis
120-24
polycondensation
109t
withdrawal rate and carbon
S o l u b i l i t y and polymerization
reactions
106
Solution polymerization in a
tank r e a c t o r
110-14
Solvent concentration in
polymerization
110-15
Spectra and homogeneous
138-41
Spencer and Leshaw model...153f,158f
S t a b i l i t y regions in a s t i r r e d
tank reactor
14
State of matter, gas, and
alchemy
3-4
S t a t i c mixers
176-78
Steady state conditions i n
continuous s t i r r e d tank
reactors
14,110-14,148-49
Steam d e a c t i v a t i o n of the
c a t a l y s t in methanol
conversion
23
S t i r r e d tank reactors
13-14
and mixing theory
175-77
multiphase
176-78
f o r polymerization
reactions
109t,117f
turbulent k i n e t i c energy
and segregation
dissipation
139-41
Structure of a z e o l i t e
c a t a l y s t f o r a methanolto-gasol ine process
21-23
Styrene
emulsion polymerization in a
tank reactor
117f
ENGINEERING
Sty r e n e C o n t i nued
106t
segregation e f f e c t on
polymerization
179-80
Styrene-acry Ion i t r i l e butadiene polymer, world
c a p a c i t y and expected
growth
102t
S u l f a t i o n and s u l f u r capture
f l u i d i z e d bed
combustor
66,69-73
Surface of r e a c t o r s , and
polymerization r e a c t i o n s . . . 106
Suspension in polymerization... 105t
S y l v e s t e r , James Joseph,
metrical theory
1-3
Tank reactor
See a l s o S t i r r e d tank
reactors
uncontrolled nonadiabatic
nonisothermal system
reaction
13-14
Taylor microscale, homogeneous
138-41
Temperature
bed in an atmospheric
combustor
69-73
o u t l e t and i n l e t , product
y i e l d s from
processes
42t
reactor
and f l u i d i z a t i o n
60-62
process
26f,43f
polymerization
110-15
tubular, c o n t r o l . . . .
32
Terminal v e l o c i t y in an
bed combustor
72-78
Termination,
polymerization
103-7,178-80
1,2,4,5-Tetramethylbenzene
formation, methanol-togasol ine process
25-27
Theory of p a r t i t i o n s ,
constructive, Sylvester....
3
Thermal to e l e c t r i c a l energy,
e f f i c i e n c y of conversion,
f l u i d i z e d bed combustor.... 69
Thermal time d i s t r i b u t i o n
149

201

INDEX
Three-envronment model,
mixing theory
159
Time constant, C o r r s i n ,
Taylor, and viscous
d i s s i p a t i o n , homogeneous
138-41
Time d i s t r i b u t i o n s , residence,
and macromixing
144-51
Times of mixing
137
Tower and s t i r r e d tank
cascade, polymerization
reactions
109t
Tracer, i n e r t , and mixing.... 160-63
Transfer of heat in an
Transfer models
mass, and carbon
combustion
84-85
po lymer i z a t ion
178-80
Transversal d i s p e r s i o n
c o e f f i c i e n t , tubular
reactors
142
Trommsdorf e f f e c t
114
Tube(s)
area s e l e c t i o n f o r an
78-80
bundle of p a r a l l e l , model.. 145-57
e x t r e m i t i e s , locus
146f
immersed, and flow regimes,
92-93
Tubular r e a c t o r s
32,141-43
Turbulence
E u l e r i a n approach
137-44
s t i r r e d tanks
175-76
Two-phase bubble model
53-58
Two-stage f i x e d bed r e a c t o r s . . . . 3If
U
Uncontrolled nonadiabatic
s t i r r e d tank r e a c t o r
reaction
Unsaturated p o l y e s t e r s , world
c a p a c i t y and expected
growth
Veloci t y C o n t i n u e d
of emulsion, in an
77
f l u c t u a t i o n s , and turbulence
theory
- 138-40
of f l u i d i z a t i o n . 52-56, 66-67,72-78
gradient, and mixing theory.. 164
methanol, in a scaled-up
35t,42t
V e r t i c a l scale-up of f l u i d
bed r e a c t o r s
40-42
Villermaux and Z o u l a l i a n
model
154f
V i n y l polymers, polymerization
mechanism
105t,106t,115t
Viscous d i s s i p a t i o n ,
turbulence
138-41
V o l a t i l e e v o l u t i o n in an
bed combustor
87-92
Volume and residence time
145t
Volume, accumulator, and
mixing theory
154
Volumetric expansion, s u l f u r
capture
69-73
Volumetric f l o w r a t e ,
69,72-78
W
Water
formation in a methanol-togasol ine process
23-25
y i e l d in a scaled-up f i x e d
bed r e a c t o r
35t,42t
Weight of bed in an
Weinstein and Adler p a r a l l e l
model
154f
13-14
102t
Valderrama and Gordon model

154f
Velocity
bubble, freeboard r e a c t i o n s . . 92
tubes model
145-46
x-Ray photograph of bubble

formation in a f l u i d bed
reactor
58-60
Y
Y i e l d s of products from
processes

42t
CHEMICAL REACTION
202
ENGINEERING
Zwietering equation and

mixing theory

Z e o l i t e c a t a l y s t s , shapes e l e c t i v e , in a methanolto-gasoline process...... 19-23
Jacket design by Kathleen Schaner

Indexing and production by Florence Edwards and Paula Brard
Elements typeset by Service Composition Co., Baltimore, MD
Printed and bound by Maple Press Co., York, PA

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Downloaded by FORDHAM UNIV on December 2, 2012 | http://pubs.acs.org

In Chemical Reaction EngineeringPlenary Lectures; Wei, J., et al.;

Downloaded by FORDHAM UNIV on December 2, 2012 | http://pubs.acs.org

In Chemical Reaction EngineeringPlenary Lectures; Wei, J., et al.;

Massachusetts Institute of Technology

Christos Georgakis, EDITOR

Based on the 7th

ACS SYMPOSIUM SERIES

AMERICAN CHEMICAL SOCIETY

In Chemical Reaction EngineeringPlenary Lectures; Wei, J., et al.;

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In Chemical Reaction EngineeringPlenary Lectures; Wei, J., et al.;

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ACS Symposium Series

Davis L . Temple, Jr.

In Chemical Reaction EngineeringPlenary Lectures; Wei, J., et al.;

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SERIES was founded in 1 9 7 4 to provide

a medium for publishing symposia quickly in book form. The

reports of research are acceptable since symposia may

embrace both types of presentation.

In Chemical Reaction EngineeringPlenary Lectures; Wei, J., et al.;

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operations (UO), which is concerned with processing equipment in which

for purely separational processes, such as the production of oxygen from

In a comparison of the salient features, the following may be noted:

Modular; often can be

for each reaction

ordered from catalogs

10-20% of total plant

80-90% of total plant

Highly nonlinear due to

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Chemists and chemical

In the broader sense, chemical reaction engineering is also concerned

machines would seem to be very suitable subjects for reaction engineers,

In Chemical Reaction EngineeringPlenary Lectures; Wei, J., et al.;

Massachusetts Institute of Technology

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What, you are entitled to ask, do you mean by an intellectual

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remained there only a matter of months ( 2 ) . Returning to England

In Chemical Reaction EngineeringPlenary Lectures; Wei, J., et al.;

Reaction Engineering as an Intellectual Discipline

honor ( 5 ) . L i k e S y l v e s t e r , he was a p r o l i f i c p u b l i s h e r on a wide

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In Chemical Reaction EngineeringPlenary Lectures; Wei, J., et al.;

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Van Helmont (1577-1644) i n h i s "Ortus Medecinae" (1652) r e f e r r e d

In Chemical Reaction EngineeringPlenary Lectures; Wei, J., et al.;

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Reaction Engineering as an Intellectual Discipline

Of the converse d i s c i p l i n e , that o f t u r n i n g E n g l i s h i n t o

In Chemical Reaction EngineeringPlenary Lectures; Wei, J., et al.;

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f u r t h e r work on S h e l l e y manuscripts had j u s t i f i e d the quotation

In Chemical Reaction EngineeringPlenary Lectures; Wei, J., et al.;

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Reaction Engineering as an Intellectual Discipline

r a i s e d to a height u n a t t a i n a b l e i n any other s u b j e c t , save