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CHEMISTRY IN THE

OIL INDUSTRY I
Chemicals in the Oil Industry

22 23 March 1983

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INSTITUTION
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Special Publication No 45

Chemicals in the Oil

Industry

The Proceedings of a Symposium Organised by the North


West Region of the Industrial Division of the Royal Society
of Chemistry

University of Manchester, 22nd-23rd March 1983

Edited by
P. H. Ogden
Akzo Chemie U K Ltd.

The Royal Society of Chemistry


Burlington House, London W1 V OBN
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Copyright 1983
The Royal Society of Chemistry

All Rights Reserved


No part of this book may be reproduced or transmitted in any form or by any
means-graphic, electronic, including photocopying, recording, taping or information
storage and retrieval systems-without written permission from the Royal Society of
Chemistry

British Library Cataloguing in Publication Data


Chemicals in the oil industry.-(Special publication/Royal
Society of Chemistry, ISSN 0260-6291; 45)
1. Petroleum industry and trade-Congresses
2. Chemicals-Congresses
I. Ogden, P. H. 11. Series
33.2'7282 HD9560.5

ISBN 0-85186-885-1

Printed in Great Britain by Henry Ling Ltd., at the Dorset Press, Dorchester, Dorset
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Introduction

The technicalities of oil production are heavily oriented towards engineering


and as a result are probably fully appreciated by only a small segment of the
chemical industry. Indeed the average practising chemist is likely to be
uninformed concerning the industries' simplest technicalities such as the
physical structure of an oil-bearing rock formation or the role of muds in
the drilling operation. Nor might he appreciate the massive scale of
operations which are required in order to reach, extract and transport crude
oil to a point of refinery. Yet, each of the processes involved in this
operation, i.e. drilling, stimulation, production and transportation is often
dependent upon the use of chemical additives.

The volume of chemical additives used may be rather small when compared with
the total quantity of oil produced, the proportion usually being expressed
as parts per million; however, it represents a considerable quantity of
chemical, frequently specialty and often expensive.

The importance of the chemical additive is particularly evident when exploration


and production occur in a hostile environmen~ such as that which confronts
operators in the North Sea. In such a location, drilling costs are extremely
high and the cost effectiveness of oil-based drilling muds in directional
drilling is obvious. Initial crude oil treatment is limited by severe space
restrictions, and the disastrous effect upon crude oil transportation caused
by corrosion or wax plugging of sub-sea pipelines can readily be understood.

On the other hand, because the use of chemicals is relatively small compared
with the volume of crude oil, production operatives, with a few exceptions,
have been unaware of the fundamental aspects of their chemical additives.
The term specialty chemical is frequently used as a misnomer for a formulated
product, such as a corrosion inhibitor ,or scale dissolver, which might be a
mixture of several active ingredients with selected solvents or surfactants
in order to allow easy application and effective transportation to the site
of operation.

If a technology gap exists between the oil producer and the chemical manufacturer,
this has been filled by the chemical service company. Such organisations combine
a kpowledge of the chemistry involved with a good understanding of oil production
technology. Their role has been extremely important but their interests
would not be served by widespread dissemination of their knowledge and it could
be argued that they sell service and expertise rather than a chemical product.

The objective of the symposium of which the proceedings follow was to draw
together representatives of the oil producing industry, the chemical service
companies, and the general chemical industry in order to describe some of the
problems associated with oil production; to define those problems which can be
solved through the use of chemical additives; the type of chemical currently

111
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favoured; the level of service required to supply such chemicals effectively
to the oil industry; the volume of chemicals used; and the financial outlay
required of the oil producer. As such, the sympOSiU1D was to be technically
informative and also to enable participants to gauge the level at which their
respective organisations might reasonably participate in the future of this
growth business.

The-North West Region of the Royal Society of Chemistry wishes to record its
gratitude to all of the contributors to these proceedings through which we
have been able to cover many of the chemical aspects of drilling, stimulation,
production and transportation. Enhanced Oil RecoverY,which is an extremely
important aspect of future oil production and is a subject which possibly
holds the highest promise for future chemical sales to the industry, will be
described in a future symposium.

In addition, the R.S.C. is grateful to Britoil and the British Petroleum


Company for their generous sponsorship of the event and for the valued support
of my fellow fuembers of the organising committee

P. Brookes, Britoil; A. Gerrard, Ciba-Geigy; R. Mitchell, B.P.;


J. Moorfield, Petrolite; A. Todd, Heriot-Watt University; and
E. Vase, Shell EXPRO.

Paul H. Ogden

Akzo Chemie U.K. Ltd.,


Littleborough,
Lancashire

IV
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Contents

Application of Chemistry to the Drilling Operation 1


By G.H. Smith
Chemicals for Water-based Drilling Fluids and Their
Temperature Limitations 11
By M.E. Hille
The Development and Application of Oil-base Muds 22
By G. Brownson and J.M. Peden
Chemical Aspects of Oilwell Cementing 42
By J. Bensted, P.E. Haynes, E. Henderson, A. Jones,
and T.B. Smallwood
The Role of Chemicals in Oil and Gas Production 61
By E.J. Vase
Chemical Demulsification of Produced Crude Oil Emulsions 73
By IhE_., Graham, A. StoakJ.JJell, and D. G. Thompson
Oily Wastewater Treatment in the Production of Crude Oil 92
By G.E. Jaakson
The Use of Ethylene-Vinyl Acetate Copolymers as Flow
Improvers and Wax Deposition Inhibitors in Waxy Crude
Oil 108
By G.W. Gilby
Water Scaling Problems in the Oil Production Industry 125
By K.S. Johnson
The Chemistry of Corrosion Inhibitors Used in Oil
Production 150
By J.A. Kelley

v
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Quaternary Ammonium Compounds: Evaluation and
Application in the Control of Sulphate-reducing
Bacteria 159
By E. Bessems and A.F. CZemmit

The Role of the Service Company in Offshore Operations 171


By G.E. Payne

The Market for Chemicals in the Oil Industry 179


By R. C. Parker

vi
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Application of Chemistry to the Drilling Operation

By G. H. Smith
BP RESEARCH CENTRE, SUNBURY-ON-THAMES, MIDDLESEX TW16 7LN, U.K.

Before considering where chemicals are applied in


the drilling operation, it will probably be profitable to
outline the mechanical processes involved in drilling a bore-
hole. Naturally in the context of this paper it will only be
possible to develop a very simplistic outline of a very
complex operation.

With the energy spotlight falling on the North Sea


in recent years many people have become familiar with the
massive structures that are designed to work miles offshore
in hostile environments. In fact once connection to the sea-
bed has been established through a 'riser' tube, drilling
from an offshore platform is essentially the same as drilling
from a land rig.

From the surface (or sea-bed) a hole, often 36" in


diameter is drilled to a depth of 50ft and a steel casing 30"
in diameter is lowered into this hole and cemented into place,
filling the entire annular space with cement slurry if possible.
At ground level a wellhead is fitted to the top of this casing
and all subsequent operations take place through the wellhead.

If troubles develop during the drilling operation,


and pressure of fluid in the formation causes the well to flow,
rams in the wellhead can be closed, even with pipe in the hole,
so that the well can be shut-in safely.

Working through the wellhead and the casing already


in the ground, the hole will be deepened to lOOO-1500ft using
a 26" bit and l8i" or 20" casing run to bottom and hung from
the wellhead. As before the annular space is filled with cement.

Drilling proceeds in stages in this manner. From


inside the l8i" casing l7~" bits extend the well to 4-5000ft
when another casing string l3i" diameter is run and cemented.
Then with l2~" bits to 8-l0000ft when 9\" casing is set and
so on down the hole using progressively smaller bits and casing
strings. Each string of casing is hung from the wellhead,
inside its predecessor and cemented into place, with the exception
that often the deepest, narrowest strings are not run back to
the surface but terminate just inside the previous string;
these short strings are termed 'liners'.

A longitudinal section through a borehole will take


the form of Fig. 1.
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2 Chemicals in the Oil Industry

50'

1000'
~~~
~
I I
~ll~
I~
30"

18%"
Cement
O~
4000' l3~"

8000' 9%"

10000' 7"

FIG. 2. SCHEMATIC SECTION THROUGH A BOREHOLE

Eventually the borehole will reach target depth -


hopefully in hydrocarbon-bearing formation - and the drilling
phase of the operation is completed. If hydrocarbons are
encountered the well now enters a complicated testing and
evaluation phase to assess commercial viability.

Bits are run on the end of a hollow drill string.


This string is formed from a series of pipes 5" in diameter
and about 30ft long coupled with screw connectors. As
drilling proceeds and the bit penetrates a further 30ft
a new joint of drill pipe has to be screwed on at the surface.
The process is then resumed and new joints are constantly
being added as required.

The uppermost joint of the drill string "the Kelly",


differs from the others in having flat faces on its outer
surface. These flats mate with bushings in a rotating table
on the rig floor, so that,as power is applied to turn the
rotary table, torque is transmitted to the drill string to
turn the bit. At the same time the kelly is free to slide
down through the bushings as the bit advances.

As each connection is made the kelly has to be


removed from the string, the new joint added and the kelly
screwed back into the top of this new joint.

The whole string is supported from a travelling


block suspended in the drilling mast. When for any reason
a bit has to be pulled the whole string has to be hoisted
from the hole. It is broken out 3 joints (90ft) at a time
and racked in the derreck.

As presented above this is a very elementary outline


of the drilling process; I have not attempted to discuss the
problems that can arise when carrying out an operation that
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Application ofChemistry to the Drilling Operation 3
is taking place some two or three miles below ground with
only a 5" diameter steel tube providing contact with the
surface and where the total mass of the drill string can
exceed a million pounds.

This session is concerned more with the chemical


than with the mechanical aspects of the drilling operation.

In any drilling activity a recurring problem is


the removal of debris formed by the drill. Whereas this is
relatively simple to overcome in activities taking place on
the surface, it is more complex when the debris are generated
at the bottom of a borehole. The solution to the removal
problem is the drilling fluid or mud.

Drilling fluid is held in mud pits or storage


tanks on the rig. It is pumped down the hollow drill string
by high-capacity positive displacement pumps which are
linked to the top of the kelly by a flexible hose.

At the bottom of the string the fluid passes out


through ports in the bit, and returns up to the surface in
the annulus formed between the borehole wall and the drill
string, carrying with it the debris created by the bit. On
the surface the fluid passes over shaker screens and through
hydrocyclones where the debris are extracted and the fluid
returned to the pits to resume its cycle.

Large volumes of fluid are required to fill the


hole and surface system - 50-60000 gallons is by no means
unusual. Consequently substantial quantities of chemicals
are used in preparing and maintaining this fluid.

In addition to cuttings removal a drilling fluid


has to serve several other functions Fig. 2.
A drilling fluid should:

Seal the hole to prevent Encapsulate reactive


fluid loss particles.

Provide a conductive Prevent fluids entering


medium for logging tools the hole

Lubricate the drill string Strengthen the hole to


and bit prevent collapse

Clean the hole and bit Lift cuttings and suspend


solids

Remain stable at high


temperature

FIG. 2. FUNCTIONS OF A DRILLING FLUID


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4 Chemicals in the Oil Industry

In order to achieve these sometimes conflicting


functions a drilling mud has progressed over the years from
a simple clay/water mix prepared in a convenient pond, to a
sophisticated mixture using considerable quantities of
expensive chemicals and forming the basis of a major service
industry; extending from the prime suppliers of bulk raw
materials to the service companies providing a total package
of materials and engineering and design services.

Drilling fluids may be classified according to the


base fluid as 'Water Based' and 'Oil Based', and both will
be discussed in this session.

Water based fluids may be further classified depend-


ing upon the nature of the water used into fresh-water, sea-
water or salt-saturated systems.

To enable the fluid to carry cuttings the often


considerable distance up to the surface, a certain amount
of viscosity has to be developed. Essentially there are
two means of doing this, either by the addition of clay
(bentonite or attapulgite) or by the addition of a long-
chained water-soluble polymer (xanthan or polyacrylamide) .
In addition to viscosity however the fluid must exhibit
thixotrophy to prevent cuttings en route to the surface
falling back when for any reason circulation stops; this
is why bentonite has proved such a useful medium in the past.

Whilst a borehole is being drilled the formation


penetrated might contain fluid under pressure and it is
essential that this fluid does not enter the wellbore. In
many instances the normal hydrostatic head of the fluid
column will suffice, but there are times when the drilling
fluid weight has to be increased. This is almost invariably
achieved by the addition of finely ground barytes (barium
sulphate) to the fluid. Fluid density in excess of 2.2gm/ml
can readily be achieved in this way, and in recent years the
use of ilmenite and haematite has permitted the attainment
of even higher weights in water based fluids.

Clay and barytes are the principal bulk materials,


used in very substantial tonnages in drilling. Although
produced to meet API (American Petroleum Institute) and OCMA
(Oil Companies Materials Association - now known as Engineering
Equipment & Materials Users Association) standards 2.3 these
are essentially natural products and require very little
processing in their production.

Many other more specific chemicals are also added


to a drilling fluid to enable it to achieve its essential
functions and probably these are of more interest to this
Symposium.
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Application o/Chemistry to the Drilling Operation 5

Earlier I mentioned that viscosity could be


imparted either by the use of clay, or by a long-chained
polymer. In recent years considerable interest has been
taken in the latter technique, with the development of
the so called "no-solids" systems. This started with the
introduction a few years ago of the biopolymers, xanthan
gums and shortly afterwards of the polyacrylamides. In
addition to imparting viscosity to the system it was claimed
that these materials by "encapsulating" clay and shale particles
as they were drilled inhibited the dispersion of formation
in an aqueous medium. Potassium chloride was,frequently
added to inhibit shale hydration even further.

These polymer based systems are still used


extensively and on the whole perform very well. Some have
limitations of temperature and lack mechanical stability
and others do not perform well with electrolytes in the water,
but in the r~ght circumstances polymer fluids do an excellent
job.

Cellulosic polymers (sodium carboxymethylcellulose)


and starch are used in considerable quantity in the drilling
fluid. These are added to control the loss of the fluid phase
to the formation which tends to occur because of the pressure
exerted by the hydrostatic head of the fluid column.

Many of the formations being drilled contain


hydratable clays and shales, and there is always a tendency
for these to develop viscosity within the drilling fluid.
To some extent this can be controlled by continuous dilution
but this may be expensive if other chemicals, particularly
barytes, are being used. Frequently excess viscosity is
better controlled chemically by the use of complex phosphates
(such as sodium hydrogen pyrophosphate) or by lignites and
lignosulphonates, usually with a heavy metal substitution.
The first paper in this session will show that all of these
chemicals have temperature limitations, and to meet the
requirements of deeper, hotter holes a new series of chemical
dispersants is becoming available to the drilling fluids
engineer.

High downhole temperature is one of the main


problems confronting a mud engineer. Bentonite in suspension
flocculates and many chemicals used today degrade at the
temperatures frequently encountered in a normal borehole.
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6 Chemicals in the Oil Industry

Unless the well is being drilled in a specific


geothe~al grea, temperature gradients of between 110F (6 0 C)
and 17 F (9 C) per thousand feet of depth are normallyo
encountered so that at lSOOOft temperatures around 300 F
(lSOoC) can be anticipated, and in some areas even higher
temperatures are reported. New chemicals, the subject of
the next paper, are enabling us to extend the economic
limits of water based muds at temperature but there are
obvious constraints beyond which it will always be impractical
to use a water based mud.

When this situation is reached we have to resort


to oil based fluids with concomitant environmental and
disposal problems. Oil muds are not a recent phenomenon:
they have been is use for some twenty years but hitherto
either crude oil or diesel oil has been used as a base.

Recently oils with a low aromatic content have


been introduced to the industry and because of their
inher~ntly low toxicity these are gaining very wide
acceptance particularly in marine locations.

The use of oil muds and the various chemicals


required to produce stable emulsions, with the hole cleaning
characteristics that the mud engineer demands, is discussed
very fully in the second paper of this session. It is
interesting to comment here however that with increasing
usage of low-toxicity systems, cuttings disposal has become
less rigorously controlled by the environmental agencies
and in consequence there will probably be a reduction in
the usage of chemicals designed for use in cuttings wash
systems.

The drilling industry has a demand for large


quantities of chemicals, not usually of particularly high
quality but of ready availability. Almost invariably these
chemicals will be obtained through one of the service company
organisations who provide a total package of engineering
and chemical supply.
Such companies maintain a full inventory of
chemicals - mostly under their own brand name - and operating
companies expect, and generally receive, an immediate response
when service is required.

Certain of the commonly used chemicals, bentonite,


attapulgite and barytes, are prepared to conform to the API 2
3
and OCMA standards, and the OCMA also issue standards
covering starch, CMC and thinners.
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Application ofChemistry to the Drilling Operation 7
Other more specialised materials are purchased by
the service companies to their own specifications so that
variation in quality is sometimes apparent.

These more specialised chemicals are mostly used


in systems for specific purposes such as completion brines
and non-damaging fluids. In certain circumstances potential
hydrocarbon reservoirs may contain clays or other minerals
that would tend to hydrate if contacted by a normal drilling
fluid and possibly cause blockages within the reservoir,
whilst in other situations clays and weighting agent in the
drilling fluid might be the cause of production impairment if
they blocked reservoir pores.

Completion brines are frequently used in place of


drilling fluid under these conditions. A completion brine
is essentially solids free. Necessary weight is imparted by
a soluble ,salt, usually sodium or calcium chloride, but if
high weight is required zinc salts may be used although cost
then becomes significant. Because carrying capacity is also
required in a completion brine a suitable polymer,
hydroxyethylcellulose, may have to be added and the temperature
range of the polymer may be extended using a polyamine.

Flourosurfactants are sometimes recommended to


reduce the surface tension of a fluid and thereby prevent
water wetting of an oil reservoir.

Surface active agents are widely used in drilling


fluids to influence or control viscosity, fluid loss, emulsion
stability, wettability and drill string friction. These vary
from simple petroleum sulphonates to the high-temperature clay
stabilising agent which is a mixture of ethylene oxide adducts
of phenol and nonyl phenol.

Defoamers are not normally added unless foaming


becomes a major problem. Various chemicals are used;
tri-n-butylphosphate, aluminium stearate, higher alcohols,
polyethers etc. have all been applied in the past depending
upon the nature of the foam encountered.

I have not attempted to produce a comprehensive


catalogue of chemicals that may be used by the mud engineer
attempting to reconcile the conflicting demands made upon the
drilling fluid, but I hope that I have given an indication of
the range of materials, from the crude bulk minerals to the
sophisticated, and expensive, co-polymers, found in a modern
drilling mud.
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8 Chemicals in the Oil Industry
Turning now to the cem~nting process. The last
paper in this session will discuss in some detail the
chemistry of oil~well elements and additives. As an
introduction to this I would like to outline the mechanism
of cementing casing in a borehole.

Cement in a borehole serves three prime functions 4

1. To support and strengthen the casing string

2. To protect the casing string from corrosive


fluids

3. To prevent fluid communication between


different parts of the borehole

As illustrated at the beginning of this paper once a


section of hole has been drilled, the drill string is pulled
from the hole and an appropriate casing string is run. In
the way that drill pipe is screwed together from 30ft joints
the casing is also picked up a length at a time and screwed
together. A joint of casing is usually about 40ft long and
for example will probably weigh between 30lb and SOlb per foot
(depending on grade and wall thickness) for a string 9%" in
diameter.

The casing is slowly lowered into the hole, which


should of course be standing full of drilling fluid, until
the string almost reaches the bottom. The length of string
is tailored, by using different length joints, so that the
top joint of casing protrudes onto the drill floor. A
cementing head is attached to this upper joint and using high
pressure, quick coupling pipe, connection made to the cementing
unit normally some distance from the rig floor.

After fluid circulation has been established and the


hole cleaned up the cementing operation commences.

Before displacing any cement a 'pre-flush isl

normally pumped into the hole to act as a spacer between


the drilling fluid and the cement slurry, and to remove
mud and debris ahead of t~e cement.

Normally 300-500 gallons of pre-flush are pumped.


Often fresh water will suffice, but surfactants and/or
dispersants (acid phosphates) are sometimes added to provide
better hole cleaning.

Once the spacer fluid has been displaced the cement


slurry is prepared and pumped downhole.
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Application ofChemistry to the Drilling Operation 9

Cement from a storage silo is drawn into a


mixing hopper where it is intimately mixed with water
passing through a venturi jet in the base of the hopper.
The slurry thus formed passes to a small holding or
re-circulating tank where minor adjustments can be
made to the density.

Mixing and pumping is a continuous process.


As soon as the slurry is at the correct weight it is
pumped to the hole. As the slurry reaches the cementing
head a wiper plug is released and precedes the slurry
down the inside of the casing. This plug is circular
in section with vanes the same diameter as the inside
of the casing, and serves to wipe the casing free of mud
film and debris as it is forced downwards.

Mixing and pumping continues until a volume of


slurry equal to the volume of the annular space between
the casing and the borehole wall has been prepared. A
second plug is then inserted into the top of the casing
and the cement slurry, sandwiched between the bottom and
top plugs, is now pumped down to the bottom of the casing.
This is usually achieved by connecting the mud lines to
the cementing head and pumping mud into the casing.
Eventually the bottom plug latches into the shoe at the
bottom of the casing string and there is a momentary
increase in pump pressure, causing a diaphragm in the plug
body to rupture. The cement slurry now floods out into
the borehole and round the casing shoe to begin filling
the annulus, displacing drilling fluid and preflush ahead
of it.

As pumping continues the remaining slurry is


forced out of the casing until eventually the top plug
also reaches the shoe. This plug will not rupture and
the pressure increase indicates that displacement has been
completed, and given reasonable luck the annulus is now
full of cement slurry. Slight pressure is maintained on
the casing to prevent any leak back and after twelve hours
or so sufficient strength should have developed in the
cement to permit operations being resumed.

Again I have only attempted to develop a very


simplified outline of a very complex operation. It is
not difficult to imagine the highly specialised knowledge
that is required to produce a cement slurry that is readily
pumpable, remains pumpable for three or more hours whilst
being forced a couple of miles down steel pipe, is subjected
to very high temperatures and pressures, and returned to the
surface and yet will have developed sufficient strength after
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10 Chemicals in the Oil Industry

8 or 12 hours to permit drilling to resume.

The mud engineer and the cementation engineer


both need a good working knowledge of the chemistry of
their products, and both depend upon the chemical industry
extending the range of materials available to them, as
drilling operations become progressively more complex and
more costly. Happily the chemical industry has never let
them down; solutions have been found as rapidly as problems
have arisen.

ACKNOWLEDGEMENT

The author wishes to thank the British Petroleum


plc for permission to publish this paper.

REFERENCES

1. Gray, G.R., Darley, H.C.H., Rogers, W.F.


Composition and Properties of Oil Well Drilling
Fluids, Fourth Edition, Gulf Publishing Co.

2. API Specification for Oil Well Drilling Fluid


Materials API Specification l3A Ninth Edition
American Petroleum Institute. Washington DC.

3. OCMA Specifications for Salt Water Clay (DFCP-l),


Low Viscosity CMC (DFCP-2), Barytes (DFCP-3),
Bentonite (DFCP-4), Starch (DFCP-S), High Viscosity
CMC (DFCP17) and Torcian and Lignosulphonate
Thinners (DFCP-8). October 1973
Oil Companies Materials Association
Hayden & Son Ltd.

4. Smith, Dwight K.
Cementing. SPE Monograph Volume 4
Second printing. Society of Petroleum Engineers of AIME.
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Chemicals for Water- based Drilling Fluids and Their


Temperature Limitations

By M. E. Hille
HOECHST AG., D-6230 FRANKFURT-AM-MAIN, WEST GERMANY

In drilling for petroleum and natural gas the drilling mud is an


important parameter. It is intended to ensure that the target
depth is reached in the shortest possible time.

Efficient drilling muds have been developed in the past for many
different geological formations through which wells had to be
drilled. l ,2

Approximately 90% of them are water-based drilling muds. In the


course of its relatively short history drilling mud technology
has been repeatedly confronted with development tasks which
presented themselves mainly because drilling had to be done at
ever greater depths and through formations that had not previously
been encountered. So long as drilling was carried out in
relatively shallow depths, drilling muds made of clay suspensions
were adequate; these were either diluted as required with water
or fluidized with polyphosphates or quebracho.

With increasing well depth, and particularly when drilling through


electrolyte-releasing formations such as gypsum or salt formations,
these drilling muds become too unstable and they have to be
continuously replenished.

One soon learnt to master this problem by introducing colloids


into drilling mud technology. The most widely used protective
colloids used for stabilization of drilling muds nowadays are as
follows:

starch and starch derivatives


cellulose ethers such as CMC, HEC, CMHEC
biopolymers
acrylate/acrylamide polymers
vinyl sulfonate/vinylamide polymers
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12 Chemicals in the Oil Industry

In addition to the stabilizing action imparted by these protective


colloids to drilling muds they also regulate the flow properties
and water loss very specifically. The water loss is generally
measured according to the API method, but increasing importance
is being attached to the HT/HP water loss which characterizes the
real infiltration rate better under borehole conditions. The
protective colloids for wauer-based drilling muds are water-soluble
polymers with a certain critical molecular weight.

Water-based drilling muds, depending on the additives used, can


be employed up to certain borehole temperatures. Thus the
effectiveness of starch and starch derivatives declines markedly
in drilling muds at 100 - 120 C. As from these temperatures
the consumption of these substances increases considerably because
reconditioning of the drilling mud to control the necessary
properties has -to take place at ever shorter intervals.

In the case of carboxymethyl celluloses this temperature interval


is approximately 130 - 160 C. This applies also to hydroxyethyl
celluloses and carboxymethylhydroxyethyl celluloses.

During recent years biopolymers have been widely introduced into


drilling mud technology. They give to the water-based drilling
muds very good rheological properties and they are not susceptible
to bivalent ions. There are various types, the best of which
possess the thermostability of cellulose ethers.

No sharply defined temperature limit, but only temperature interval,


can be stated for the decline of the effectiveness of different
polymer types, because this is not the same in different drilling
mud systems and the individual functions of the polymers decline
within different temperature intervals; this is explained with
the aid of the example of CMC. The viscosity of a drilling mud
conditioned with high viscosity CMC, for example, declines
noticeably above 100 c, although the water loss hardly shows a
reduction. As from approximately 135 c the HT/HP water loss
increases noticeably, and rapidly as from 150 c, whilst the API
water loss and the stability of the flow properties only deteriorate
significantly at a further 20C above this temperature. These
data relate to water-based salt-saturated drilling muds.

Practically, it has to be decided from case to case when the


polymer bases will be changed. The reason for it may be, for
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Chemicals for Water-based Drilling Fluids 13

example, to strong rising reconditioning rates, high technical


difficulties as a result of a too thick filter cake under
formation conditions or possible formation damage due to high
HT/HP water loss.

Besides polymers, thinning agents are widely used in drilling muds:

Type of thinning agent application limit


Polyphosphates 60 - 80 c
Quebracho 100 - 120 c
Lignosulfonates 140 - 170 c
Huminates/Lignites up to over 200 c
Styrene sulfonate/maleic acid
anhydride polymers up to over 200 c
For the above mentioned temperature limits the same as for the
polymers is valid. There are intervals which only specify the
approximate upper limits by which the temperatures are the
limitant factor for their use. Below these intervals there are
numerous other reasons which are determining for the application
of another mud system.

The most important thinning agents are the lignosulfonates and


lignites.

These additives are dispersants which stabilize drilling muds on~y

to a limited extent against electrolytes and elevated temperatures.


In freshwater drilling muds practically free from electrolytes
the reconditioning rates increase rapidly already at temperatures
over 100 C. This high-temperature jelling can be kept low up to
over 200 c with copolymers of styrene sulfonate and maleic
anhydride. 3

However, the water loss is unsatisfactory in freshwater drilling


rnuds and generally increases significantly within a short time in
saltwater thinning agent rnuds with rising temperature. It is
then only possible to keep the water loss low by the additional
use of the protective colloids mentioned above.

Naturally products from both additive groups, polymers and thinners,


are frequently used over the above mentioned limits. This is
possible without big disadvantages when the mud circulates, because
the mud stream operates like a cooling device for the well and dis-
places the isotherm downwards. The experience of numerous wells
shows, however, that often difficulties appear during standstill
r t u P
14 Chemicals in the Oil Industry

periods when the bottom hole temperatures stabilize. The


additives become inactive and thereby the viscosity and the HT/HP
water loss increase considerably. The fixation of the drill
string is retarded and becomes complicated and the well logging
tools do not reach the bottom. The high HT/HP water loss leads
to pipe sticking, the initial pumping pressures increase and the
recovered mud from the bottom hole has to be reconditioned or
partically rejected. 4 Furthermore, particularly detrimental
will be the decomposition of mud chemicals during the drilling
of the formations.

The high HT/HP water loss often leads to formation damage which
decreases ~he production rates. High gelled muds are frequently
the cause of deficient cementation. Particularly at high mud
densities, the cement sludges will not completely displace the
mud and the cement will build preferential flow channels in the
highly viscous mud of the annulus. By this means the hydrocarbon-
bearing formations will not be entirely sealed and, especially
at high formation pressures and differential pressure, the gas
will flow to other porous layers through the annulus.

The application of mud additives above their stability limits is


mostly uneconomical: at least during the drilling of the
formations, a qualitative good mud should be used.

Generally the costs of the damage produced by an unstable mud are


substantially higher than a thermostable mud system.

The largest gap in drilling mud technology until now has been
the lack of highly effective additives for conditioning saltwater-
containing drilling muds which are exposed to high temperatures
during drilling at great depths. 5

However, it has to be relatively considered, because an improvement


of the present available thinners for very high temperatures may
be also economical.

Acrylatejacrylamide and vinylsulfonate/vinylarnide were until now


practically the only copolymers of importance for conditioning
water-based drilling muds as from about 150 c to over 200 C.
Copolymers of the acrylate/acrylamide type, which have been used
in drilling rouds for over 30 years, have only found limited
application. The reason is the sensitivity of these products
even to relatively low concentrations of calcium ions which very
r t u P
Chemicals for Water-based Drilling Fluids 15
often cannot be excluded in practice, for example, in the form of
gypsum or cement.

Table 1 shows the laboratory tests which demonstrate the


sensitivity of the polymers of the acrylate/acrylamide type to
calcium ions. In freshwater-based drilling muds these additives
are effective under normal conditions and also at 200 C. However,
if the drilling mud contains gypsum and thus calcium ions due to
the solubility of gypsum, the polymers of the acrylate/acrylamide
type provide good results under normal conditions, but on account
of exposure to heat lose their effectiveness.

The reason is increasing saponification of the acrylamide groups


according to the following formula:

H H H H H H H H
I I I I H2 0 I f I ,
(-c - c-) (-C - C-) ( - c - c-) (-c-c-)
I I n I I m I f n I I m
H C=O H C=O H C=O H C=O
I
6-Na+ NH
2
o,- Na + b-NH+
4

The additional carboxyl groups formed on the carbon atom chain


increase the sensitivity to calcium. Higher pH values and temper-
atures accelerate this saponification process. If higher concen-
trations of calcium ions are present in a drilling mud, such as
may occur on account of the influx of brine, the low concentration
of the original carboxyl groups in the polymer is sufficient to
precipitate these ions and to render them ineffective as drilling
muds.

When using copolymers of the acrylate/acrylamide type in practice


one endeavours to keep the calcium ion content low by means of an
excess of soda or alkali. However, these drilling muds are
strongly alkaline, a fact which makes it difficult to control the
flow properties and may lead to obstructions in oil-bearing
formations and gas-bearing formations. At high pH values and
elevated temperatures the solubility of the pay zone material
is occasionally considerable. The pay zone material
dissolves in the alkaline filtrate during drilling and is
precipitated when the pH drops on further penetration of the
filtrate into the formation; th~s occurs at the start of production
at the latest. This may result in a considerable reduction of the
0'.

Table 1

Under normal conditions After Ageing

r
15 h at 200C

I 11 III I II III

1 L Water 1 L Water 1 L Water


40 g Bentonite 40 g Bentonite 40 g Bentonite
10 g Additive 250 g NaC1 100 g NaC1

t
10 g CaS0 4 100 g caC1
2
10 g Additive 20 g Additive

u
Additive Water losses according to API in cm

Acry1ate/acry1amide 9.0 8.8 100 9.2 46 100


mg approx. 3 x 10 6 (J
~
~
~

P
~'
Viny1su1fonate/viny1- 8.5 9.0 4.8 8.8 10.4 5.5 ~
r;;--
amide
5'
mg approx. 0.8-1.0 x 10 6 So
~

~
~
~
~
~
V:J

~
r t u P
Chemicals for Water-based Drilling Fluids 17

recovery rate of oil or gas. A further disadvantage of the


acrylate/acrylamide polymers is that they precipitate in acid
solutions such as are used in the acidization of pay zones which
in turn may lead to fu~ther plugging.

For the stated reasons these products have only found limited
acceptance as additives in drilling mud systems for deep wells.
They inhibit swelling clays very well and are therefore used in
the formulation of drilling muds in which the calcium concentration
has to be kept low.

These are, foreKample, drilling muds based on KC1. 6 ,7 In concen-


tration as low as approximately 0.1%, acrylate/acrylamide polymers
have a good inhibitory effect on swelling clays in thinning type
drilling muds based on lignosulfonates and/or lignites.

Copolymers based on vinylsulfonate/vinylamide do not possess these


disadvantages. They tolerate calcium ions up to saturation point,
that is to say, they stabilize drilling muds also if there is an
influx of calcium and magnesium salt brines.

With partially saponified polyacrylamides, the existing and the


later formed carboxyl groups by saponification are the reason for
the sensitivity limits to calcium ions. Polymers of the type
vinylsulfonate with vinylamide have negative sulfo-groups which
are insensitive against calcium ions. During saponification of
the amide groups, which is a function of the pH and temperature,
secondary amine groups are built in the polymer chain, which are
also not affected by calcium ions.
R H
I I
C=C H H
I I H20 I I
B N-R ---~ c=c + R COOH
I
r=O
R
I
H
I
,
N- R

This saponification takes place with technical velocities over 120


c, also in neutral range. Besides, the very weak basic amide
groups will be converted to weak basic secondary amine groups. For
the performance of these polymers, those basic groups are very
significant. They adsorb on the lattice sites on the surface of
the clay and thereby reduce the adsorption of the cations of the
r t u P
18 Chemicals in the Oil Industry

water phase, such as calcium, magnesium, sodium and potassium.

Also at increasing concentrations of electrolytes, the cations


cannot displace the polymers in the clay surface, reducing
significantly the negative charge of the clay particles. The
reduction of the charges of the clay particles caused by the
adsorption of cations on the free lattice sites will be compen-
sated by the negative sulfo-groups of the polymer. In order to
reach the optimal mud quality, the polymers of vinylsulfonates
and vinylamides must have determined molecular weights and
specified ratios between the cationic and anionic groups. The
whole polymer has to have negative charge surplus, and a high
ratio of vinylamide will lead to a drilling mud with high viscos-
ities. Owing to their high molecular weights of approximately
6
1 - 2 x 10 , those polymers inhibit the swelling of the clay.
With the vinylsulfonate/vinylamide polymers conditioned muds it is
possible to minimize the environmental problems in comparison to
water-based chrome-containing thinner muds or oil-based muds.
Their clay and solids content can be kept low, which results in
higher penetration rates and lower energy consumption for the
circulation.

Polymers of the vinylsulfonate/vinylamide type make it possible


nowadays to drill safely to depths of over 200 c with water-
based drilling muds. In this case the HT/HP water loss can be
kept low in order to cause no damage to the pay zone and avoid
difficulties in drilling, also at all the electrolyte concentrat-
ions occurring in drilling muds. Influxes can be controlled
relatively well with the aid of these drilling muds. Influx of
water of brines into the drilling muds practically causes only
dilution which can be corrected easily. Through their action as
protective colloids, polymers of the vinylsulfonate/vinylamide
type prevent considerable deviation of the drilling mud properties
initially set, such as flow properties and water loss, in the
case of influx of brines with high concentrations of bivalent ions
such as calcium and magnesium. Influx of crude oil into the
drilling mud is homogeneously emulsified and gas that is entrained
can be separated relatively safely and then flared.

The properties of drilling muds conditioned with polymers of the


vinylsulfonatejvinylamide type have been proved in practical
application with the aid of the following examples.
r t u P
Chemicals for Water-based Drilling Fluids 19

Table 2 shows the result of measurements on a field mud condit-


ioned with CMC/CMHEC. The API water losses were acceptable, but
the technical difficulties met with in drilling were found to
have been due to the high HT/HP water losses. By means of 1%
polymer it was possible at 150 c
and 35 bar, after ageing for
3
15 hours at 150 c, to reduce the water loss to about 10 cm ,
3
whereas it had previously been 62.0 cm .

Table 3 demonstrates the drilling mud data of a non-damaging


drilling mud based on chalk for the solids content, with about
2.6% polymer. I Despite the low gel values the chalk remained well-
dispersed also above ground whilst the solid cuttings were separ-
ated practi~ally completely in the settling tank. This drilling
mud was introduced into the circulation of a bore-hole with a
temperature at the bottom of about 160 c and was found to be
extremely stable during the subsequent drilling operation.

Table 4 shows the means of the slightly saline drilling mud (NaCl
7-8%, ca++ 2000 to 6000 ppm) of a deep bore-hole with a final
depth of about 5600 m and a temperature of 195 c at the bottom.
At a depth of about 4900 m this drilling mud has been changed from
a CMC conditioning to polymer. The planned final depth was
safely reached after unproblematical drilling, with only small
drilling mud replenishments being required.

These three practical examples show the manifold application


possibilities of the vinylsulfonate/vinylamide polymer types and
the field experience largely confirms the laboratory findings.

The very special advantage of these products is that, independently


of the electrolyte content, the HT/HP water loss can be kept low
at temperatures up to over 200 c, i.e. at 15 cm 3 and below. This
makes it possible to drill through oil-bearing pay zones and
particularly gas-bearing pay zones without causing damage and to
minimize the permeability reduction caused by the drilling mud,
in order to obtain maximum production.

The results mentioned were obtained with Hostadrill 2825


vinylsulfonatejvinylamide polymer. If very high concentrations
of bivalent ions of calcium or magnesium, which may go right up to
saturation, are employed, Hostadrill 3118 is more effective.

Registered trademark
r t u P
20 Chemicals in the Oil Industry
Table 2

Before ageing After ageing


15 h at 150 C

3 4.8
API water loss (cm ) 3.8
3 62.0
HT/HP water loss (cm ) 44.4
35 bar/150C

Field mud plus 1% polymer VS/VA


3 1.8 2.0
API water loss (cm )
3
HT/HP water loss (cm ) 12.0 10.2
35 bar/l500C

Field mud: 3
Chalk, approx, 200 g KCl/l, density 1.40 g/cm
conditioned with CMC and CMHEC and plus 1% polymer
VS/VA

Table 3

Density 3
g/cm 1.46
Marsh 59/48
WV API 2.4
Filter cake 0.5
WV HT/HP 22.0
pH 7
at 50C at 90C
SV cp 28.5 20
PV cp 26 18
2
FL Ibs/lOO ft 5 4
10" gel 1.5 2.5
10' gel 1.5 3

3
Drilling mud: per 1 m water: 30 kg bentonite, 338 kg NaCl, 640
kg chalk, 35 kg polymer, 0.8 kg defoamer
HT/HP water 10ss/35 bar/150c
r t u P
Chemicals for Water-based Drilling Fluids 21

Drilling mud means of a bore-hole with 5600 m final depth;


temperature at bottom 195 0 C

Density g/cm 3 1. 6 - 1. 66
Marsh sec 45 - 50
3
WV API cm 5 - 8
WV HT/HP 3
cm approx. 20
0
25 bar, 160 C
Filter cake mm 0.5 - 0.6
pH 9 - 10
SV cp 40 - 50
PV cp 30 - 40
Yield point 2
lbs/100 ft 5 - 15
10" gel 6 - 10
10' gel 18 - 30

Drilling mud: Bentonite heavy spar, NaCl 7-8%, Ca++ 2000 - 6000
ppm, approx. 1% VS/VA polymer plus a little CMC

References
1
G.R. Gray, H.C.H. Darley, and W.F. Rogers, 'Composition and
Properties of Oil Well Drilling Fluids', Fourth Edition, Gulf
Publishing Co., Houston, Texas, 1980.
2
K.H. Grodde, 'Bohrspulung und Zementschlamme in der Tiefbohr-
technik', Verlag Otto Vieth, Hamburg, 1963.
3
W.G. Chesser, and D.P. Enright, J. Petrol. Technol., June,
1980, 950 - 956.
4
C.E. Chadwick, Oil and Gas J. Oct. 1981, 251 - 257.
5 P. Simpson, World Oil, April 1967, 135 - 139.
6
D.E. O'Brien and M.E. Chenevert, J. Petrol Technol., Sept.
1973," 1089 - 1100.
7
R.K. Clark, R.F. Scheuermann, H. Rath, and H. van Laar,
J. Petrol. Technol., June 1976, 719 - 727.
r t u P
The Development and Application of Oil- base Muds

By G. Brownson and J. M. Peden


DEPARTMENT OF PETROLEUM ENGINEERING, HERIOT-WATT UNIVERSITY,
EDINBURGH EHl lHX, U.K.

Introduction

The onset of World War 11 dramatically increased the

demand for petroleum products. As deeper wells were drilled,

it was found that water based muds were often not performing

satisfactorily and more attention had to be paid to the drilling

fluid used.

A conventional water based mud consists of the

following components:

(1) A clay which provides filter cake and suspension


properties.

(2) A polymer which provides suspension and fluid


loss characteristics.

(3) Speciality chemicals to:

(a) reduce corrosion


(b) absorb dangerous gases CO , H S
2 2
(c) eliminate foam
(d) reduce torque
(e) inhibit clays
(f) kill bacteria.

(4) Minerals such as barite and iron oxide to


control density.

(5) Plugging materials to control lost


circulation.
r t u P
The Development and Application ofOil-base Muds 23

The continuous phase is of course water often

saturated with salts to prevent wash Guts when drilling through

salt sections. Economics usually dictate that the polymer is

naturally occurring, e.g. starch, guar gum, XC polymer,

alginates, or solubilised from a natural base CMC, CMHEC (base

cellulose) .

I. Advantages and Disadvantages of Water Base Muds

A. Advantages of Water Base Muds


(1)- 110\'7 cost
(2) Non-polluting, ease of disposal.
(3) Treatments can be effective in a single
circulation.
(4) The conductive nature of the continuous
phase allows resistivity and SP logs
to be run.

B. Disadvantages of Water Based Muds in Order of


Importance

(1) Temperature Instability

At high temperatures the polymer chain breaks at


its weakest link and the viscosifying and fluid loss
properties are lost. If gel strength is also lost
and circulation stops, barite settling and stuck
pipe can occur. Much of the research into water
based muds is into producing a high temperature
stable polymer.

(2) Formation Damage

Where water swelling clays are present, fluid


invasion can cause the formation to become less
permeable to the reservoir fluid.

(3) Chemical Instability

(a) Clays
Swelling clays entering the mud system can
give excessive viscosities and high fluid
losses (permeable filter cake and wrong
polymer/clay ratio) which ultimately leads
to hole erosion and collapse.
r t u P
24 Chemicals in the Oil Industry

Formation waters often contain high


concentrations of ca 2 +/Mg 2 + which reduce
the thermal stability of starch and CMCS.
Water is conductive and hence a corrosive
medium. Scaling can also be serious under
certain conditions.

If the continuous phase (water) is replaced by another liquid

(oil) and the colloidal dispersed fluid loss additive (polymer)

is replaceq by an alternative (emulsified water, colloidal

asphalt or bentone) it is possible to develop a drilling fluid

which overcomes some of the above problems.

Miller 1, in 1951, discussed the advantages of oil

base muds.

11. Advantages and Disadvantages of Oil Base Muds

A. Advantages of Oil Base Muds

(1) Excellent fluid loss control at high


temperatures. Oil base mud
formulations can have API HT/HP
(350 0 F/500 psi) fluid loss values of
0.5 ml. This results in a very thin
filter cake.

(2) The continuous phase (filtrate) is oil so


even if it enters the formation, damage
should be less.
(3) Corrosion and scaling problems are minimal.

(4) The local fluid loss and high lubricity mean


that stuck pipe problems are infrequent.
(5) Once the components that make up the mud
have reacted together and it has aged, it
can be stored in tanks for long periods.
One little known application of oil base
muds is as a ships ballast material.
For such applications the mud can be
weighted up with PbO to give densities of
3
3.5 - 4.0 g/ce .
r t u P
The Development and Application ofOil-base Muds 25

(6) Correctly formulated muds do not disturb


shales. Shales adsorb water in two ways:

(a) By surface adsorption

(b) By osmosis (because of high ionic


concentration).

Oil muds,having oil as a continuous phase, stop surface

water-adsorption by making them oil-wet. By maintaining higher

salinity in the water phase (by adding CaCl 2 ), oil muds not only

prevent osmotic migration of water but also can dehydrate shale

by reverse osmotic migration. Thus, water-sensitive shales

remain stable. The layer of emulsifier at the interface acts as

a semi-permeable membrane, and, provided the vapour pressure of

the aqueous phase is less than the vapour pressure of the

formation water, transfer from the emulsion fluid to the shale

will not occur. This frequently requires the aqueous vapour

pressure of the drilling fluid to be less than that of a

saturated sodium chloride solution and often it is desirable to

saturate the aqueous phase of the drilling fluid with calcium

chloride. Where formations are particularly water sensitive

solutions containing ZnBr , ZnCl , LiBr and LiCl can be used.


2 2
B. Disadvantages of Oil Base Muds

(1) Cost

Oil base muds are much more expensive than


water based muds. The major costs are
the oil phase base, normally diesel oil,
and the emulsifiers used.

(2) Drilling Fluid Disposal

The aromatics in diesel oil are carcinogenic


and cuttings and mud disposal pose real
problems. A number of methods have been
tested none of which are considered totally
satisfactory2 The used mud itself is
usually sold back to the mud company.
r t u P
26 Chemicals in the Oil Industry
(a) Incineration

Expensive wi th problems of air pollution.

(b) Microorganism Processing

Theoretically possible.

(c) Distillation, Liquid Extraction and


Chemical Treatment

Distillation in an electric kiln. The


kiln and heating costs are high and
problems occur with blocked filters.
Chemical fixation converts the heavy
metals present into inert silicates
or hydrous oxides by reacting the
drilling fluid with a mixture of sodium/
potassium silicate and portland cement.
The process works with fluids containing
17
up to 20% oil .

(d) Burial

Where local regulations permit the cuttings


are washed with a suitable solvent.
13
Mondshine recommends a wash with a fluid
mixture of alcohols, acetates and glycols
and subsequently burial.

(e) Reuse as a Filler for Roads

One company in Europe claims,to have a


process to use the cuttings as a filler
for roads.

(3) Handling Difficulties

Due to the dirty slippery nature of oil


muds the working conditions on the rig
floor are difficult.

(4) ~2S Solubility Under Pressure

Gas solubility in oil is far greater than


in water; as a result dangerous levels of
gas may be carried undetected up the hole
in a mud column and released unexpectedly
at the surface 3 .
r t u P
The Development and Application ofOil-base Muds 27

(5) Permeability Reduction in Gas Reservoirs

In gas sands containing water, an oil mud


may do more damage than a water base mud
due to trapped water reducing the gas
permeability. Mud companies claim the oil
is vaporised during production.

(6) Damage caused by Emulsifer Contamination


in Filtrate

(a) Oil with emulsifiers can change the


wettability of the rock.

(b) Emulsifiers can cause emulsion blockage


in the presence of formation water.

From the above brief discussion it can be seen that it

is very difficult to generalise on the optimum mud formulation

until all the reservoir parameters have been taken into

consideration.

Ill. Historical Development of Oil Base Muds

The first patent was issued in 1923 to SwanS who

suggested a solution of asphalt in benzene. Moore and Cannon 6

(1936) patented an oil base drilling fluid in which the weighting


7
material was oil wet. Van campen (1940) used a peptising agent

consisting of a higher carboxylic acid and an amine soap. Miller

(1940-50) in a series of patents used a composition based on


9
blown asphalt, calcium oxide and naphthenic acid. Fischer

used the soaps of "disproportionated" rosin (dihydroabietic and


10
dehydroabietic acids). Fischer also patented an electrically

conductive drilling fluid using uranium nitrate.


11
Lummus (1957) patented an oil base drilling fluid

consisting of an oil base, fatty acid residue containing poly-

basic acid having at least 12 carbon atoms per acid radical, an

alkali metal base, a strong oxidising agent such as sodium

dichromate, lecithin and calcium chloride.


r t u P
28 Chemicals in the Oil Industry

Wilson 12 , (1963), used blown asphalt, diesel oil and

an anionic surface active material from the group consisting of

alkyl aryl sulfonic acid and alkyl aryl sulfonates.

The early oil base muds were difficult to maintain if

their water content exceeded 10% - 15%; this led to research

into muds with a water content of greater than 50% whilst main-

taining oil as the external phase. These muds are known as

inverts. Before discussing oil mud formulations it is worthwhile

briefly d~scussing the basic theory of emulsions.

IV Basic Emulsion Theory


A surfactant is a molecule containing both polar and

non-polar parts (amphiphilic). These molecules sit at inter-

faces because the polar portion is attracted to the polar medium

and the non-polar to the non-polar medium. Surfactants are

classified as anionic, cationic, non-ionic or amphoteric

according to the charge carried by the surface-active part of

the molecule.

Anionic

Sodium stearate - +
CH 3 (CH 2 ) 16 COO Na
Sodium oleate CH 3 (CH 2 ) 7CH = CH (CH 2 ) 7
COO-Na+
- +
Sodium dodecyl sulphate CH3(CH2)11S04 Na
- +
Sodium dodecyl benzene sulphonate CH 3 (CH 2 ) 11C6H4S0sNa

Cationic

Dodecylamine hydrochloride
+
CH 3 (CH 2 ) 11 NH 3 Cl
Hexadecyltrimethylammonium bromide
+
CH3(CH2)15N(CH3)3Br
Trimethyl dodecyl ammonium chloride
+
C12H25N(CH3)3Cl
r t u P
The Development and Application of Oil-base Muds 29

N-alkyl trimethylene diamine chloride

H H H H H
2+

I I I I I
R N C C C N -H Cl Cl -
I I I I I
H
H H H H

Non-ionic

Polyethylene oxides

Spans (sorbitan esters)

Tweens (polyoxyethylene sorbitan esters)

Phenol 3D-mol ethylene oxide (DMS)

C6 HS 0 -- (CH 2 -- CH 2 -- O)30H
Amphoteric
+ (CH ) 2
3
Dodecyl betaine C H N
12 25 ----- CH CO-
2 2

Alkali metal soaps favour O/W emulsions whilst heavy

metal soaps favour W/O emulsions. The type of emulsion which

forms depends on the balance between the hydrophilic and lipo-

philic properties of the emulsifier. Alkali metal soaps favour

O/W emulsions because they arernorehydrophilic than lipophilic

whereas the reverse holds for heavy metal soaps.


13
HLB VALUES are an empirical scale which indicate how

an emulsifier will behave.

Applications Dispersibility in Water

3-6 W/O emulsions 1-4 Nil

7-9 Wetting agents 3-6 Poor

8-15 O/W emulsions 6-8 Unstable milky dispersion

13-15 Detergent 8-10 Stable milky dispersion

15-18 Solubiliser 10-13 Translucent dispersion/soln

13- Clear solution


r t u P
30 Chemicals in the Oil Industry
The interfacial tension between oil and water is

about 50 dynes/cm, so they separate to minimise interfacial

area. An emulsifier lowers the interfacial tension 10

dynes/cm) and forms a protective skin round the droplets. An

O/W emulsion can be broken by adding a small amount of a W/O

emulsifier, and vice versa.

Particles can stabilise emulsions when they are

partly oil wet and partly water wet - contact angle = 90 0

This is the principle behind the use of asphalt as a filter

cake material in water based muds. The asphalt is mixed

together with a mineral, fused and then ground up. The particles

of mineral partly coated with asphalt can now be water wet in

the mud system.

Most emulsions become unstable at high temperatures

as a result of changes in solubility of the emulsifiers in one

or other of the phases,thus altering its distribution and

affecting the interface. Since emulsifiers are organic compounds

it is difficult to find effective emulsifiers above 600 0 F.

Oil Wetting Agent

If the attractive force between oil molecules and

some solid surface is not sufficient to overcome the surface

tension of oil, oil does not wet the surface.

Since most metal and mineral surfaces are negatively

charged,cationic surfactants are oil wetting agents. N-alkyl-

trimethylene diamine chloride is a typical example.


14
Lecithin is used to oil-wet barite. The positively

polarised nitrogen is attracted to the barite surface leaving

the hydrocarbon tail to dissolve in the oil phase.

Oil Dispersible Bentonite (Bentones)

Bentonites can be made to swell and disperse in oil by


r t u P
The Development and Application o/Oil-base Muds 31

14
replacing the alkali metal cations with an onium salt , e.g.
16
(C14H29NH3)+Cl-. White claims that better results are obtained

when the bentone is mixed with finely divided particles of

glyceryl tri-12-hydroxystearate and an amide wax.

Onium salts can also be used to make lignites oil

dispersing.

Other Filter Cake Materials for Oil Base Muds

The mechanism by which fluid loss is reduced appears

to be adsorpt~on of the continuous phase which produces swelling.

The swollen particle is thus more compressible and the filter

cake becomes more and more impermeable as the differential


16
pressure across it is increased. Browning et al patented an

oil adsorbing vinyl toluene-acrylate copolymer as a fluid loss

control material for oil base muds.

v. Drilling Fluid Formulations

Considerable skill and experience is needed to

formulate a drilling fluid composition. This should be followed

by a series of empirical tests with added drill solids which

are representative of the formation being drilled. Two

formulations will be discussed which illustrate the application

of oil muds.

(1) An Oil Base Mud

A true oil base mud does not require water to


function yet it can function with water 18 .
Filter cake and rheology are controlled using
a special air blown asphalt. A non-ionic
surfactant is introduced to act as a wetting
agent to oil-wet solids present. An emulsifier
emulsifies water present and calcium hydroxide
adsorbs CO 2 or H S contaminants.
2
Blown asphalt can only be used in a narrow cut
of oil. (Aniline point 140 SOF). If the
aromatic content is too low, the asphalt
r t u P
32 Chemicals in the Oil Industry

flocculates giving an adverse effect on


viscosity. If the aromatic content is too
high the asphalt may be dissolved by the other
components giving a black filtrate (possibly
formation damaging).
The soap class of materials such as calcium
stearate soaps and heavy metal rosinates are
satisfactory at low and moderate temperatures
but go into undesirable solution at high
temperatures. Their use is generally limited
to temperatures of less than 300 0 F.
In oil muds the relatively weak hydrogen bonding
forces between the asphaltenes are readily broken
by heating, so that viscosity and gels tend to be
substantially reduced by temperature rises. To
obtain satisfactory gels the blown asphalt must
have a reasonably high penetration and a high
MP (260-280 0 F)19. The addition of small
quantities of metal oxides (iron, titanium,
manganese, molybdenum, tungsten, lead, etc.)
20
also reduces filtration rates . A good oil base
0
mud can tolerate about 540 F without degradation.

(2) An Invert Mud


An invert emulsion must have water in the interior
phase. Modified clays and sometimes lignite are
used in their formulation to provide rheological
and fluid loss characteristics. The oil wetting
is achieved using a cationic surfactant,usually
quaternary amines. The surfactant must be
compatible with the quaternary amine and so is
usually also a quaternary amine. This surfactant
also replaces the clay oil-wetting agent which
degrades with time and temperature.
18
Bauman and Methven observed a high temperature
0
gellation problem at 410 F which may occur from
thermal degradation of the organophilic clays.
High molecular weight alkaline metal soaps are
used for emulsifying the water in the oil and to
improve rheological parameters and even filtration
21 22
loss in some systems . Sharmur et a1 replaced
r t u P
The Development and Application ofOil-base Muds 33
the soap by a sulphonated bitumen. Aluminium
stearate improved the gels after hot rolling.
Tests were carried out at 140 0 C. A high-
temperature emulsifier for invert muds is claimed
to be a mixture of oleyl amide and dimerised
oleic acid 25 The dimerised oleic acid functions
to impart thixotropic properties.

VI Recent Developments in Oil Base Muds

Oil base muds have traditionally had two drawbacks;

these are slow drilling rate and pollution. These problems have

been partial-Iy solved with relaxed fluid loss muds and "clean

oil" muds.

Relaxed Fluid Loss Muds

Simpson 23 showed that a low viscosity invert oil

base mud with bentone for gels gave a much improved drilling

rate. Desired characteristics would be:

(1) low viscosity for continuous oil phase

(2) low concentration of emulsified solids

(3) low concentration of dissolved solids.

A low colloid oil base mud, API HT/HP 41 ccs, gave

a 40% faster drilling rate in carbonate rock than a conventional

invert oil base mud using a rock bit. It was found that,

provided sufficient CaC1 was present in the water phase, the


2
low colloid oil base mud was just as effective as the high

salinity conventional invert oil base mud in preventing shale

hydration.
24
According to O'Brien et aI, relaxing filtration

control provided drilling rates in shale/lime sequences equal

to or better than those attained by water based muds. Further-

more the filtrate from the HT/HP for an oil mud gives a

misleadingly high result because:


r t u P
34 Chemicals in the Oil Industry
(1) The high pressures downhole gives a higher
oil viscosity and slower fluid loss.

(2) The HT/HP filter press models cake filtration


with no allowance for internal filter cake.

Only where filtrate losses are large in highly

permeable formations does it seem more economical to drill with

a high colloid oil mud.

"Clean Oil" Muds

It has long been known that oils other than diesel

could be used as a drilling fluid. Lack of pollution controls

and economics dictated until recently the use of diesel oil.

The UK Department of Energy laid down the following guidelines

relating to the use of low toxicity oil muds.

(1) Toxicity tests must have been carried out on the


base oil and/or mud formulation to the
satisfaction of the Ministry of Agriculture and
Fisheries (MAFF) and Department of Agriculture and
Fisheries for Scotland (DAFS).
(2) No whole mud shall be discharged.

(3) Adequate screen area should be available to cope


with the volumes of cuttings anticipated.

(4) Representative samples of the cuttings discharged


shall be taken each shift and analysed for oil
content. The results shall be submitted to the
DoE on completion of the well.

(5) The depth of hole drilled and the hole diameter


shall be reported for the period between each
sample.

(6) If this mud is to be used on the large diameter


(17~") hole,cuttings from the shale shakers
should have an oil content which does not exceed
16g of oil per 100g of dry solid averaged over
the whole drilling period.
r t u P
The Development and Application of Oil-base Muds 35
(7) Samples of mud and/or cuttings shall be supplied on
request to the DoE.

(8) Special consultation with MAFF and DAFS shall take


place if it is proposed to use these muds within
30 miles of the UK coast.

Toxicity Tests on Clean Oil

Toxicity tests consist of recording the drilling

fluid concentration in sea water to kill 50% of fauna, and by

recording the drilling fluid concentration in sea water to

reduce by 50% the growth of phytoplancton.

Typical fauna used in a test are:

Anguilla Anguilla
Littorima Littorea
Mythilus Edulis
Scrubicularia Plana
Palaemon SP
Artemia Salina
Phaeodacrylum Tricornutum
Dunaliella Tertiolacta.

Biodegradability tests consist of recording the

percentage of biodegradability of mud in sea water after a

period of time.

If the drilling fluid at concentrations of 1000 ppm

is non-toxic to fauna and the mud is as biodegradable as a

water-based system this is regarded as acceptable. With flcl ean "

oil muds the cuttings may be discharged directly into the sea.

The oil used is a special refinery product,with the

aromatic fraction removed of a food grade quality. It is less

destructive to rubber components than diesel. Mud companies

claim the "clean fl oil retained on the cuttings is much less

than from the diesel oil base mud (being less polar, clean oil
gives less adhesion).
r t u P
36 Chemicals in the Oil Industry

However the cost of a clean oil mud is 2-3 times

that of a normal oil base mud and where lost circulation occurs

costs can soar to a prohibitive level.

The other chemicals in the " c l ean " oil mud are

typical chemicals to make an invert mud.

VII. Future Requirements

To assess this one must first consider the various

fluid constituents and properties required with an oil base mud.

Secondly_one must then consider the way in which we assess fluid

performance and properties.

(1) Flu~d properties and Constituents

(a) Base Fluid

One obvious question is why aren't natural


vegetable oils used as the oil base. The
prices of crude vegetable oils in US $/lb
26
are :
Coconut oil NY 0.26
Coconut oil Pacific 0.235
Corn oil Midwest 0.26
Cottonseed oil Valley 0.19
Linseed oil 0.28
Peanut oil 0.30
Soyabean oil 0.18
Rape seed oil 0.18 (approx.)
Unfortunately, fats and oils are esters of the
trihydric alcohol glycerol and one would
expect that, under the conditions of high
temperature and pressure encountered in an oil-
base mud system, they would hydrolyse back to
free fatty acids or their salts and glycerol.
Soyabean and rape seed oils appear to be the
cheapest of the naturally occurring oils.
If a natural cheap clean oil exists this would
have great value as a drilling fluid.
r t u P
The Development and Application ofOil-base Muds 37
(b) Filter Cake Material

Some improvement in the grades of asphalts


available are possible. Ideally the asphalt
0 0
should have a high MP (250 C - 300 C), swell
and adsorb oil and be available in gelling
and non-gelling forms. The asphalt should be
available in "stick" form for ease of grinding.

Some research into high MP non-polluting waxes


(natural and synthetic) that swell in oil and
give good filter cake material would be of
value. Ideally the wax should dissolve slowly
in the crude oil so that when the well comes
on production any damage done to the formation
is removed.

(c) Emulsifiers and Wetting Agents

More research is needed into emulsifiers and


oil wetting agents that are stable at high
temperatures. At present no adequate
completion fluid exists for geothermal wells
0
(800 p). The emulsifier should be a solid so
that it can be blended into a sack material,
non-ionic so that it is stable to ca 2 +/Mg 2 +
0
and ideally temperature stable to 800 P.

Usually, the emulsifier is temperature degraded


by the "bridge" breaking which links the hydro-
philic and lipophilic parts of the molecule.
Work at present is underway into looking for
temperature stable bridges.

A sulfonyl derivative of diethanolamine has been


patented recently which seems to be stable to
600 0 p27; the bridge is stabilised by
hyperconjugation.

~.. ~CH2CH20H
C12H25~S - N~
CH CH 0H
2 2
The emulsifier should also be non-toxic and
biodegradable.
r t u P
38 Chemicals in the Oil Industry

(d) Gelling Agents


0
At temperatures above 450 F bentones undergo
degradation and are unsatisfactory. Asphalts
give a slow drilling rate. Work is needed into
improving agents to provide suspension properties
at high temperatures. Bentonite in water seems
to have no temperature limitations; it is also
a naturally occurring inorganic polymer.
Theoretically it should be possible to control
fluid loss with filter cake alone; some effort
should be made into producing a drilling fluid
with inorganic chemicals alone.

(e) Additives to Remove CO 2 and H2~

Better additives are needed to adsorb CO and


2
H S (which usually occur together). If ~
2
H S is detected chemicals such as diethanol-
2
amine should be added to remove it, otherwise
reactions will occur between the steel casing
and drill pipe. This can lead to the disastrous
situation of hydrogen embrittlement and casing
failure.

(2) Testing

The equipment needed to test drilling fluids at high


temperatures and pressures is becoming increasingly
complicated and expensive. Dynamic fluid loss is
still not properly understood and no standard is
available. Better standards for evaluating torque,
lubricity, drag are also needed. Standards for
abrasion are under review. The Universities have an
important role to play in carrying out independent
tests on oil field chemicals and acting as a link
between the oil and chemical industries.

Better methods of analysis for emulsifiers are


also important to understand fully the mechanisms
involved and reduce costly overtreatments.

Finally, more work is needed into the mechanisms


governing pollution by drilling fluids, how much
damage is done to the sea bed by physical smothering
r t u P
The Development and Application of Oil-base Muds 39

of marine life by drill cuttings, how long does


it take adsorbed oil to diffuse away from the
cuttings into the surrounding waters?

REFERENCES

1. G. Miller, 3rd World Pet. Congress, Sect 11, The Hague, 1951.

2. L. E. Nesbitt, J. A. Sanders, J. Pet. Tech., 1981, 2377.

3. T. B. O'Brien, World Oil, 1981, 83.

4. R. Matherly, J. Pet. Tech., 1981, 1389.

5. J. C. Swan, US 1,455,010, Method of Drilling Wells.

6. T. V~ Moore, G. E. Cannon, US 2,055,666, Weighted Oil


Base Fluid.

7. P. van Campen, US 2,217,926, Non Aqueous Drilling Fluids.

8. G. Miller, US 2,316,967, Oil Base Drilling Fluid and


Method of Regenerating the Same.

US 2,316,968, Oil Base Drilling Fluid

US 2,356,776, Composition for Preparation of Oil


Base Drilling Fluid

US 2,475,713, Oil Base Drilling Fluid and Mixing


Oil for Same

9. P. Fischer, US 2,542,019, Drilling Fluids

US 225,054, Treatment of Oil Base Drilling Fluids

US 2,573,959, Drilling Fluids

US 2,573,960, Drilling Fluid Concentrates

US 2,573,961, Low Resistance Drilling Fluids

US 2,612,471, Oil Base Drilling Fluids

US 2,617,767, Oil Base Drilling Fluids

10. P. Fischer, US 2,696,468, Conductive Oil Base Drilling Fluid

US 2,717,239, Electrically Conductive Oil Base


Drilling Fluid

US 2,721,841, Conductive Drilling Fluids

US 2,739,120, Electrically Conductive Drilling Fluids

US 3,111,491, Electrically Conductive Drilling Fluids

US 2,793,187, Conductive Oil Base Fluids


r t u P
40 Chemicals in the Oil Industry
11. J. L. Lumrnus, US 2,793,996, Oil Base Drilling Fluids.

12. D. L. Wilson, US 3,099,624, Oil Base Drilling Fluid


and Method of Use.

13. D. J. Shaw, Introduction to Colloid and Surface Chemistry,


Butterworth, 237.

14. J. P. Simpson, J. C. Cowan, A. E. Beasley, J. Pet. Tech.,


1961, 1177-1183.
15. E. A. Hauser, USP 2,531,427.

16. R. W. White, A. Franco, USP 3,977,894.

17. W. C. Browning, B. G. Chesser, J.L. Wood, USP 3,738,934.

18. N. E._Methven, R. Bauman, Petroleum and Petrochemical


Int'ernational, 1973, 13, ~, 50.
19. G. Miller, USP, 3,622,513, 1971.

20. R. E. McGlothlin, J. C. Bagget, R. L. Schultz, USP


3,658,701.

21. G. R. Gray, S. Grioni, J. Pet. Tech., 21 (3), 261.

22. S. M. Sharma, K. K. Girdhar and R. M. Mathur, Bul. ONGC,


1978, ~ , 65-72.
23. J. P. Simpson, J. Pet. Tech., 1979, 643-650.

24. T. B. O'Brien, J. P. Stinson and F. Brownson, World Oil,


(Aug 1977, March 1978), 75.
25. Halliburton Company British Patent 1,467,841.

26. Chemical Marketing Report, March 1, 1982.

27. Private Communication C. Scoggins, 11.


r t u P
The Development and Application ofOil-base Muds 41

APPENDIX

Molecular Formulae

Oils

Lecithin

It consists of glycerol combined with two fatty acid

radicals, phosphoric acid and choline.

Choline is:

H COOCR
2 , Lecithin
H COOCR'
I ~o
H2CO - p,---O-CH2CH2~(CH3) 30H -
OH

Castor oil is the triglyceride of ricinoleic acid.

Ricinoleic acid is 12-hydroxy - 9 - octadecenoic acid

CH 3 (CH 2 ) SCH (OH) CH 2CH = CH (CH 2 ) 7C0 2H


Fatty Acids

Lauric acid CH3(CH2)10C02H

Stearic acid CH 3 (CH 2 ) 16C02H

Oleic acid CH3(CH2)7CH=CH(CH2)7C02H


Waxes

Amide Wax

H" /HSA
N- (CH) - N
/ 2n '"
R H

n is from 2 - 18

HSA is the acyl radical of 12-hydroxy stearic acid.

R is hydrogen or HSA.
r t u P
Chemical Aspects of Oilwell Cementing

By l. Bensted, P. E. Haynes, E. Henderson, A. lanes and


T. B. Smallwood
BLUE CIRCLE INDUSTRIES PLC, LONDON ROAD, GREENHITHE, KENT DA9 9JQ, U.K.

Abstract

Oilwell cementing is described from a chemical viewpoint.


Standards and 'classification systems used for oilwell cements are
discussed. A brief survey of hydration is given, including those aspects
linked with the strength development that follows setting. The main
types of chemical materials added to oilwell cements are considered.
These include accelerators, retarders, friction reducers, lightweight
additives, densifiers, lost circulation controllers and strength
regression inhibitors. Reasons for making such additions are considered.

Portland cements, upon which oilwell cements are normally based,


are composed of four principal clinker mineral phases - tricalcium
silicate, dicalcium silicate, tricalcium aluminate and a calcium alumino-
ferrite of more variable composition - to which some gypsum CaS042H20 (or
its derivatives like hemihydrate CaS04\H20 or natural anhydrite CaS04)
has been incorporated during manufacture to regulate the setting
process. Where sulphate-resistance is required, the level of tricalcium
aluminate must be reduced, since this phase is the most susceptible to
sulphate attack. The rate of reaction of these mineral phases rises with
increasing temperature and so therefore does the rate of setting and
hardening of a cement paste, as hydration products are formed between the
clinker grains. In very severe conditions, set retarders such as calcium
lignosulphonate are employed and, for the specially high temperatures and
pressures and the extended pumpability times required in oilwell
cementing grouts, the contents of the most reactive phases must be
limited. This requires the manufacture of a special oilwell cement
clinker.

An account of some observations of the early hydration behaviour


of a Class G oilwell cement and the effects of retardation upon the
hydration is given.
r t u P
Chemical Aspects of Oi/well Cementing 43

Standards for Oilwell Cement

There are two principal standards for oilwell cement in use in


the world, the American Petroleum Institute (API) Spec 10 1 and the
USSR Standard GOST 1581-78 2 Different classification systems for
oilwell cements are used ~n the two Standards.

The USSR Standard defines two basic grades of oilwell cement, one
for "cold" wells and the other for "hot" wells. The tests on cement must
be made at 22 2C and 75 3C. For improving the properties of oilwell
cements for both "cold" and "hot" wells, GOST 1581-78 permits up to 15%
active and up to 10% inert mineral additives provided that they be
ground. In addition some special oilwell cements are produced under
various technical specifications, e.g. sulphate-
resistant types. Initial set for the "cold" well cements must be not
less than 2 hours and for the "hot" well cements not less than 1.75
hours. The retardation of the setting times of the "hot" well cements is
effected largely by the use of clinker low in alumina. The "hot" well
c~ment is designed for utilising at a temperature of about 75C. Oilwell
cements with 3-4% tricalcium aluminate content are produced both for
"hot" and "cold" wells.

The API Standard, which is widely used in many countries


including the U.K., specifies nine classes of oilwell cements for use at
different well depths (see Table 1). Oilwell cement is defined by the
API(l) for Classes A-H as the product obtained by grinding clinker,
consisting essentially of hydraulic calcium silicates, to which no
additions other than set-modifying agents have been interground or
blended during manufacture. Class J cement is defined as the product
which conforms to performance specifications shown in the applicable
physical requirements of the API Standard. A suitable set-modifying agent
is defined as one which has no deleterious effect on the durability of
the hardened cement and causes no retrogression in strength. Well
cements include any class of cement defined above and may also include
optional additives to obtain necessary performance. No specifications
are written for blends of well cement and optional additives. Certain
optional additives are covered by these specifications.

The API have collected considerable data about well conditions


from borehole logs and have used it to produce "average" conditions for
given depths. These average conditions have been arranged into testing
schedules for running standard specification tests 1. In the tests
the "static" bottom hole temperature (BRT) is the temperature achieved
when the log is left in the hole for a length of time and approximates to
the actual stratum temperature. The "circulating" BRT is the temperature
attained at the bottom by drilling mud circulating down through the pipe
and returning to the surface - it is lower because it does not come to
equilibrium with the ground temperature. The cement at the bottom of the
hole during circulation will be subjected to a pressure equal to the pump-
ing pressure plus the hydrostatic head of mud or slurry in the hole, and
hence total pressure also increases with depth of hole. For example, if
the fluid h~8 a density of 100 Ib.jcu.ft., it will exert a pressure of
695 lb.f/in. for each 1000 ft. depth.
r t u P
44 Chemicals in the Oil Industry

TABLE 1

API CLASSES OF OILWELL CEMENTS

Class Typical use

A Surface to 6000 ft where special properties are not


required. Ordinary type Portland cement only (ASTM
Type 1, BS12 Ordinary Portland cement).

B Surface to 6000 ft where conditions require moderate


or high resistance to sulphates.

C Surface to 6000 ft where high early strength development


is required. Ordinary type or moderate or high sulphate
resistant types.

D For depths between 6000 and 10,000 ft under conditions


of moderately high temperatures and pressures. Moderate
or high sulphate resistant types.

E For depths between 10,000 and 14,000 ft under conditions


of high temperatures and pressures. Moderate or high
sulphate resistant types.

F For depths between 10,000 and 16,000 ft under conditIons


of extremely high temperatures and pressures. MOderate
or high sulphate resistant types.

G and H Surface to 8000 ft as manufactured or can be used with


accelerators or retarders to cover a wide range of well
depths. Class H was introduced for us~ in higher teMp-
erature holes than Class G cement.
Moderate or high sulphate resistant types (the HSR
specification for H is only tentative).

Both classes are defined as basic cements in which no


additives other than calcium sulphate or water or both
shall be interground or blended with the clinker during
manufacture. Class H differs from Class G typically in
being coarser ground cement.

J For depths between 12,000 and 16,000 ft as manufactured


where extremely high temperatures and pressures exist
or can be used with accelerators or retarders to cover
a wider range of well depths. No additions other than
calcium sulphate or water or both shall be interground
or blended with the clinker during manufacture. This is
not a true Portland cement, being based largely on a
dicalcium silicate composition.
r t u P
Chemical Aspects ofOi/well Cementing 45

Manufacture of oilwell cements

The normal raw materials and processes are used to make both the
Class A (ordinary type) or other classes of moderate or high sulphate
resisting clinkers of Portland cement which form the basis of oilwell
cements, and which comply, with the chemical requirements. The compound
composition will of course vary within the set limits depending on the
targets set by the manufacturer bearing in mind the materials and plant
available to him, and also the route which gives him the best control of
his quality. Oilwell cements are used in geothermal wells for both oil
and gas extraction.

Testing of oilwell cements

Normal analytical procedures, whether classical gravimetric or


modern instrumental, are satisfactory for controlling the chemistry of the
products, while standard methods of determining soundness and fineness
are well known.

The cementing properties however, require specialised apparatus


for testing compressive strength and thickening time under conditions
simulating those found in a well.

The API accumulated much data on temperature and pressure


conditions at various depths in many wells. Using this data approximate
simulations of average conditions were worked out for testing purposes,
and generally applied to the minimum and maximum conditions for use of a
given class of cement; for example a retarded Class D cement would be
expected to comply with tests simulating 6000 ft and also 10 000 ft
conditions, the range of depths at which this cement would be used.

Cement slurries

The cements are used in the form of aqueous slurries made by


injecting cement into a fast moving stream of water.

The specimen for test is therefore made in the laboratory in a


specified high speed blender to the appropriate density. The required
water/cement ratios are given in API Spec 10 thus:

TABLE 2
REQUIRED WATER/CEMENT RATIOS

Cement class W/C ratio (US gals water per 94 lb sack


of cement)
A, B 0.46 5.19
C 0.56 6.32
D,E,F,H 0.38 4.29
G 0.44 4.97
J As recommended by manufacturer
r t u P
46 Chemicals in the Oil Industry
Strength tests

The slurry as prepared is poured into 2 inch cube moulds in a


specified way, and the moulds are then subjected to a regime of curing
appropriate to the simulated well temperature conditions. For shallow
well tests simple water bath curing at atmospheric pressure and lOOF
(38C) is used. For other tests, the bottom hole static temperature is
obtained by adjusting the heating rate over a four hour period and
maintaining this until about 45 minutes before the end of the test
period. In all cases the cubes are cooled to 80F (27C) before
determining the compressive strength in an appropriate hydraulic testing
machine.

In these tests the maximum pressure applied during curing is


3000 Ib/in 2 and not the bottom hole total pressure. This follows from
work which showed that increasing the curing pressure from atmospheric to
about 2000 Ibs/in 2 increased the compressive strength appreciably but
applied pressures higher than 2000 Ibs/in 2 had little further effect.

Thickening time

This term is applied to the change of viscosity with time after a


cement has been slurried with water, and hence has an important bearing
on the time for which a cement slurry remains in a pumpable state. The
viscosity is measured in Bearden units of consistence (Bc) so called in
honour of the late Bill Bearden who had served for many years as chairman
of the Cement Committee of the API.

Fig. 1 shows a typical curve shape of viscosity against time


which indicates the ideal low viscosity (easy pumpability over a period
of time suitable for placing the cement slurry in the annulus, followed
by a steep curve corresponding to the slurry stiffening prior to final
hardening)

100

Thickening
Time

Time

Figure 1
TYPICAL CURVE SHAPE FOR THICKENING TIME
r t u P
Chemical Aspects ofOi/well Cementing 47

Operating conditions

The API testing schedules mentioned above can of course be


adapted for actual down hole conditions found in a well, but rather more
is required to ensure that an oilwell cement can be successfully used for
cementing the hole. The borehole will not of course run through perfect
strata. There will be layers of varying mechanical strength, some hard,
some friable, some subject to sloughing, the permeability will vary and
indeed some strata will be fissured to a greater or lesser extent. These
faults will be observed by the experienced drilling team and measures
will be taken to ensure that a good cementing job will be carried out.
These include the use of various additives.

Additives

As with ordinary cements for construction jobs the chemical


reactions occurring during hydration of oilwell cement can be modified by
the use of additives such as calcium chloride, lignosulphonates etc.

Lignosulphates are by-products from the paper pulp industry.


They are impure materials, variable in composition, whose complete
structures are not precisely known. Lignosulphonates are polymeric,
based upon substituted phenylpropane units containing -OH, -C02H, -OCH3
and -S03H groupings. These polymers have typical average molecular
weights of -20,000 - 30,000 in a typical distribution range -300-
100,000. They are not linear but take the form of spherical microgels
with charges predominating on the outside of the spheroids - the internal
carboxyl and sulphonate groups are non-ionised. Lignosulphonates tend to
be only 20-30% ionised. Calcium and sodium lignosulphonates are the most
frequently encountered commercial forms. They contain sugar impurities
~1-30%, mostly pentoses 3. Bacteria can feed on the sugar content and
in so doing can degrade the lignosulphonates, which thereby lose their
desirable properties like retardability. Under these conditions the
effective active life of lignosulphonates may not be very long.
For this reason lignosulphonates are either treated with anti-bacterial
formulations, or suitably modified to minimise the sugar content and then
treated with a suitable bactericide, so as to extend active life
indefinitely.

For given well conditions a service company will normally


recommend and supply the cement and proportions of additives to produce a
satisfactory cementing job. Most service companies have their own "brand
names" for such materials which are commonly of similar composition for
similar use. Over the years improvements have occurred to produce the
required cement slurry properties and to extend the range of use as depth
and temperature have increased.

a) Accelerators

Accelerators are normally used in cementing shallow holes or


surface casings at low temperatures where thickening time would
be long and strength low. It is generally accepted that a
strength of about 500 psi is needed to support a casing and the
r t u P
48 Chemicals in the Oil Industry

use of accelerators allows this to be achieved in a comparatively


short time, possibly in 4 hours. The thickening time could be
approximately halved but, since pumping times for such shallow
holes are short, this does not matter.

The most commonly used accelerator is calcium chloride CaC12;


a dosage of 2% by weight on cement would be satisfactory in most
cases. Sodium chloride NaC1 in doses of about 2 to 4% is also
used but large doses retard. Sea water is thus also an
accelerator and since in offshore work the cement slurry is
usually made with sea water, this must be taken into account in
designing the mix. Sometimes a mixture of cement and hemi-
hydrate plaster is used for producing short thickening time and
rapid strength development.

b) Retarders

Retarder.s are required to lengthen the thickening time.

These are already present in manufactured retarded cements API


classes D, E and F, being added at the cement plant in quantities
adjusted to give thickening times greater than the API minimum
for the given class of cement.
Current practice however is to use basic oi1wel1 cements (Class G
and Class H) and a retarding additive sufficient to cope with the
particular well conditions in holes deeper than about 8000 ft.

The most frequently used retarder is probably a calcium 1igno-


sulphonate which is generally satisfactory for cementing to
12 OOO to 14,000 ft. However, some 1ignosulphonates modified
j

with other organic cOlnpounds such as hydroxycarboxylic acids are


used for higher-temperature conditions. Other organic substances
such as gums and starches have been used. One of the most
effective for high-temperature work is carboxymethyl
hydroxyethyl cellulose. Amongst inorganic retarders,
borax Na2B40710H20 and sodium chloride NaCl (high
concentrations) have been employed 4.

As stated above high concentration (> 20% by weight of cement) of


sodium chloride will retard oilwel1 cements and will also reduce
strength. It is sometimes necessary in drilling through salt
beds to pre-saturate the cement slurry with salt to prevent
formation salt being dissolved into the slurry.

c) Friction reducers

These are dispersants which improve the flow properties of the


slurry by breaking up cement agglomerates and freeing the water
for its proper function. They produce lower-viscosity slurries
and allow turbulent flow conditions to be reached at lower pump
pressures. Substances used as dispersants include ligno-
sulphonates, salt and polymers such as acrylamides and
naphthalene condensation products.
r t u P
Chemical Aspects ofOi/well Cementing 49

d) Lightweight additives

In cases where lower-density cement slurries are required, some


reduction can be brought about by increasing the water content.
However, if too much water is added separation will occur. The
materials added to produce lower-density slurries allow the
addition of greater amounts of water without segregation and,
having relative densities less than that of cement, reduce the
density of the solid phase as well.

The most frequently used material is bentonite (specifications


for which are given in API Spec 10). An approximate formulation
is Al5/3M81/3[(OH)2/Si4010]173Na1/3(H20)4. A sodium
bentonite, often called "gel", was used in the early days to
decrease weight and increase the volume of cement slurry since
it absorbs water and swells. Depending on requirements anything
from 2% to 12% (by weight of cement) can be used. For each 1%
added, the-water can be increased by about 5.3% and slurry
densities of 12-13 lb per US gallon can be achieved yielding an
extra 60% of volume of slurry. Higher additions of bentonite may
be used, but only if dispersants are used to reduce the viscosity
of these high gel slurries. Salt is also sometimes used in these
slurries.

Diatomaceous earth Si02 x H20 and attapulgite, approximate


formulation (Mg,Al)2 [OH/Si4010]2H20, behave similarly but may cost
more. Their only advantage may be that their viscosities are
lower than those of bentonite slurries.

Other materials used are gilsonite, a naturally occurring


asphaltite consisting of high molecular weight hydrocarbons, or
expanded perlite, a volcanic siliceous glass (though the latter
is less stable mechanically when used in high pressure areas),
pulverised fuel ash (pfa), anhydrous sodium metasil~ate Na2Si03,
crushed coal and a special calcined shale - cement

e) Densifying additives

These are required where high formation pressures are encount-


ered, so that blowout of the cement slurry might be prevented.
High-density materials such as barite BaS04 and haematite Fe203
are the commonest densifying additives. They do not generally
appear to have a significant effect on the cement properties.
Sand Si02 may also be used.

f) Lost circulation control additives

Strata that are highly porous or fissured give rise to "lost


circulation", i.e. the cement slurry is lost into the strata
instead of circulating to the surface. This can be overcome by
using a low density slurry (to reduce pressure on a weak zone)
and adding materials which may be blocky granules (walnut shells,
gilsonite, crushed coal, expanded and semi-expanded perlite) that
r t u P
50 Chemicals in the Oil Industry

form bridges and lamellated materials like cellophane flakes that


form flake type mats 4. The bridges or mats are of sufficiently
large particle sizes to cover the fissures and build up a layer
of cement to seal the thief zone. Fibrous materials like nylon
fibres are effective in drilling fluid for sealing large
openings, but are not normally employed in oilwell cementing
because of the tendency to plug surface and downhole cementing
equipment. Also, most other fibrous materials contain organic
compounds which can seriously retard cement thickening time.

g) Strength r~gression inhibitors - pozzolan or silica flour

A pozzolan is defined 1 as a siliceous or siliceous and


alwninous material which in itself possesses little or no
cementitious value, but will, in finely-divided form and in the
presence of moisture, chemically react with calcium hydroxide at
ordinary temperatures to form compounds possessing cementitious
properties. Glassy volcanic material and diatomaceous earth
Si02 x H20 are examples of natural pozzolans, whilst pfa is an
example of an artificial pozzolan.

At temperatures above about 230-250F (-110-120C), Portland


cements suffer from regression of strength, i.e. instead of
the usual increase in strength with time, loss of strength and
also of permeability occurs due to the formation of large
crystals of a -dicalcium silicate hydrate Ca2 (HSi04)OH. This
phenomenon is at least partly prevented by the addition of active
silica from pozzolan or silica flour, for example, which will
react with lime released by the change in crystalline form of the
calcium silicate hydrates that causes the loss in strength.
Additions of, say,-35% silica flour (Si02) prevent formation of
a - dicalcium silicate hydrate at these temperatures and give a
CaO/SiOZ ratio of ~0.8, which is favourable for the formation
of tobermorite Ca6(H2Si6018)4H20, a good strong binder, that
has a smaller crystal size.

Class J cement, which can be employed to depths of 16 000 feet


without containing retarders, does not need additions of silica
flour.

General

One of the requirements for oilwel1 cements is that they should


be compatible with the additives likely to be used for modifying their
properties for given conditions. The service companies therefore tend to
work beyond the API Spec 10 for cement properties, and require cements
that show consistent properties from batch to batch, so that their job of
formulating satisfactory mixtures of cement and additives is thereby made
easier.

Hydration Behaviour

The essential criterion for oi1we1l cementing is that the slurry


of cement and water should remain capable of being pumped down to its
r t u P
Chemical Aspects of Oi/well Cementing 51

required position before stiffening takes place.

Oilwell cements are normally based upon Portland cement


compositions, which comprise four principal clinker mineral phases -
trica1cium silicate Ca3SiOS, dica1cium silicate Ca2Si04, trica1cium
a1uminate CaJA!206 and a calcium a1uminoferrite of more variable
composition approximately Ca2A1FeOs - to which some gypsum CaS042H20 (or
its derivatives like hemihydrate CaS04~H20 or natural anhydrite CaS04)
has been incorporated during manufacture to regulate the setting
process. Where sulphate-resistance is required, the level of tricalcium
a1uminate must be reduced, since this phase is the most susceptible to
sulphate attack 5 . The detailed hydration of ordinary and su1phate-
resisting Portland cements has been described 6 . Strength is obtained
principally from the reaction of the silicate phases to form calcium
silicate hydrate. Trica1cium silicate is the main cementing phase, with
dica1cium silicate (normally in the B-form) reacting at a much slower
rate to form similar hydration products. Early strength is largely
obtained from~trica1cium silicate, but at later ages (e.g. 28 days and
beyond) the contribution from B-dicalcium silicate becomes very
important.

At surface temperatures or just above, the silicates react with


water to form an amorphous calcium silicate hydrate, which can be
represented approximately as follows:

Ca3SiOs + 6 H20 ~ Ca3Si2073H20 + 3 Ca(OH)2

Ca2Si04 + 4 H2 0 ---) Ca3Si2073H20 + Ca(OH)2

These reactions are not of the dissolution and precipitation type, but
occur topochemica11y at the silicate surfaces. The equations are only
approximate, because the calcium silicate hydrate formed, known as
C-S-H(I), is in reality a very poorly crystalline non-stoichiometric
material consisting principally of dimeric units at first, but
subsequently slowly polYmerising after a few days to give higher linear
units like pentamer and thence octamer with the passing of time.

Up to NIOOC the hydration products from the tri- and B-dicalcium


silicate phases do not differ essentially from those formed at ambient
temperature, although there may be some differences in morphology and
microstructure. No changes in the mechanism of hydration have been
reported in the temperature range from ambient to 90C, but more
polysilicate hydrate in relation to dimer was found in calcium silicate
hydrate pastes at 65C than at 25C 7. The hydration of B-dicalcium
silicate is accelerated in relation to that of tricalcium silicate at
elevated temperatures, which may be related to the increased solubility
of silica and decreased solubility of calcium hydroxide under these
condi tions 8

Different products are formed when Portland cements are hydrated


under geothermal conditions, where high temperatures and pressures
exist. Hydrated aluminate and a1uminoferrite phases have not generally
been observed under these conditions, so presumably the Al 3+, Fe3+ and
S04 2 - ions have become incorporated in the calcium silicate hydrate
r t u P
52 Chemicals in the Oil Industry
phase(s). The calcium silicate hydrates formed under such conditions
range from X-ray amorphous t~_y~ghlY crystalline phases. A number of
studies have been reported

Oilwell cements are normally used with-35% of strength


regression inhibitor, e.g. silica flour, to prevent formation of a-
dicalcium silicate hydrate Ca2(HSi04)OH, a dense orthorhombic phase which
is deleterious to strength and permeability. Under these conditions
tobermorite Ca5(H2Si601a)4H20 is the first crystalline phase to form.
Formation of tobermorite is associated with good strength and
permeability. Above about 150C it will transform to xonotlite
Ca6Si6017(OH)2 and gyrolite Caa(Si4010)(OH)4-6H20. Gyrolite will
subsequently transform at,., 250C to truscottite Ca7(Si4010)(Sia019)-
(OH)4H20. The temperatures in deep wells can easily reach~400C and
truscottite and xonotlite have been detected. At higher temperatures
truscottite decomposes and a residue containing quartz may remain.
Xonotlite and gyrolite generally have good strength and moderate
permeability. -Truscottite has a lower permeability than xonotlite.

It should be remembered that conditions in oilwells are far from


ideal 14. Geothermal waters are rarely fresh and their dynamic nature
probably precludes equilibrium conditions. Geothermal zones are
inherently porous or highly fractured. Extenders and other additives are
all likely to affect cementitious behaviour to a greater or lesser
degree. Such widespread variations mean that standard conditions for
equilibrium transformations do not exist. Accordingly, the actual
products formed in a given oilwell will depend on the precise conditions
pertaining in that particular oilwell and may include calcium silicate
hydrates and related mineral compositions of different types from the
aforementioned.

Mechanism of Retardation

Until fairly recently it was thought that retarders of cement


hydration, which commonly contain -OH, -C02H groups or both, functioned
by adsorption onto the surfaces of the cement particles to form
monolayers and thus physically impede hydration. However, examination
of the hydrated systems in the presence of retarders has shown that
whilst hydration of the tri- and dicalcium silicate phases is indeed
retarded, the hydration of the tricalcium aluminate and tetracalcium
aluminoferrite phases to form ettringite is enhanced, often substantially
so. Clearly, the idea of an all-embracing monolayer physically thwarting
hydration can no longer be entertained. Where adsorption takes place, as
with lignosulphonates, there is clearly a selective element involved in
the process, which has the effect of accelerating early aluminate and
aluminoferrite hydration. The precise mechanism is not to date clearly
understood and requires further investigation.

In the less deep wells, where the normal hydration products


calcium silicate hydrate C-S-H(I) and ettringite are formed during
hydration, a possible mechanism involves the following.

It appears that when the clinker silicate phases (primarily


tricalcium silicate, or alite) begin to hydrate, the calcium ions react
preferentially to form ettringite, rather than assisting with the initial
r t u P
Chemical Aspects of Oilwell Cementing 53
formation of C-S-H. This results in the transient formation of amorphous
hydrated silica at the clinker silicate surfaces. These latter surfaces,
particularly alite, are still reacting, but are not initially forming
C-S-H in quantities comparable to those being formed in the absence of
retarders like sugars and lignosulphonates. Scanning electron microscopy
shows no evidence for the existence of "skin" barriers. Indeed, a
protectionist barrier is inconceivable because more, not less, ettringite
is formed during early hydration. It is possible that the retarder could
locally reduce the pH in the vicinity of exposed alite particles in
particular. As a result of this, calcium ions at the alite surfaces
would be caused to migrate to aluminate (and, to a lesser degree, to
aluminoferrite) phase surfaces and preferentially react there to form
ettringite. There would thus be a relative deficiency of calcium ions at
the alite surfaces, as a result of which C-S-H formation there would be
impeded.

Therefore, when retardation and retarders are spoken of, it is


necessary to b~ precise concerning the meaning. Retardation refers to
the effect upon setting or thickening of the cement and not necessarily
to particular chemical reactions that take place during cementation.

Investigation of the Early Hydration Chemistry in Schedule 5 Thickening


Tests

a) Background

An examination of the early hydration behaviour of a Class G


oi1well cement subjected to API Schedule 5 treatment 1 was
carried out under standard and retarded conditions. This
investigation was undertaken in order to understand more fully
the nature of the oilwe1l cement hydration process.

API Schedule 5 for thickening time is for casing cementing down


to a depth of 8000 feet. The final temperature reached is
125F (52C). The mixing water (distilled water) is 44%. For
retarded cements tested under Schedule 5 conditions, no gelation
should occur and the retarding effect at a given retarder dosage
should be approximately constant from batch to batch.

b) Experimental Part

API Schedule 5 thickening time experiments (1) were undertaken


using a production Class G oilwel1 cement a) alone, b) with 0.3%
of a commercial calcium lignosulphonate retarder, c) with 0.4% of
this retarder. Thickening time curves were drawn (Figure 2).
The tests were repeated to appropriate inflection points and the
actual thickening times on the thickening time curves. The test
runs to each of these stages were immediately followed by
stopping the hydration by acetone drying in a glove box under an
atmosphere of nitrogen gas to prevent aeration of the relatively
small partially hydrated samples obtained 17 . This meant
that(i) for the cement without retarder, hydration proceeded to
20, 60 and 103 minutes respectively; (ii) for the cement with
0.3% retarder, hydration was stopped at 90, 130 and 142 minutes
respectively; (iii) for the cement with 0.4% retarder, the
r t u P
54 Chemicals in the Oil Industry

Figure 2 THICKENING TIME CURVES

103 142 222


100

90

80

70

u 60
CO

~ 50
Vl
0
u
Vl
> 40

30

20

10

o 50 100 150 200 250


Time (minutes)
r t u P
Chemical Aspects of Oilwell Cementing 55
corresponding times at which hydration was stopped were 160, 200
and 222 minutes respectively. After drying out with acetone, the
samples were all stored in a desiccator over silica gel.

These partially hydrated cement specimens were examined by a


variety of experimental techniques - IR, XRD, SEM, TG and DSC. IR
(Figure 3) was performed on a Perkin-Elmer 577 infrared spectro-
photometer over the wavenumber range 200-4000cm- 1 using KBr
discs, XRD with a Philips' X-ray diffractometer, SEM with an IS1
DS 130 scanning electron microscope, TG with a Stanton's TR-02
thermobalance and DSC using a Setaram differential scanning
calorimeter.

c) Results and Discussion

The unhydrated cement contained alite, belite, ferrite and a


little aluminate as well as calcium sulphate and some calcium
hydroxide. A large part of the calcium sulphate was in the form
of hemihydrate CaS04~H20 as a consequence of some dehydration of
gypsum by the grinding of the clinker with gypsum during the
manufacturing process:

+ 1\ H20
The presence of some calcium hydroxide was due to the
moisturisation of some of the free lime content of the clinker:

CaO + H20 ~ Ca(OH)2

c)(i) Unretarded Cement

For the unretarded cement, after 20 minutes of Schedule 5


hydration, some gypsum was observed, which would have formed from
hydration of the hemihydrate:

Some ettringite was also formed. This would have arisen by


reaction of the ferrite phase and calcium hydroxide and also of
the small quantities of aluminate phase present with calcium
sulphate and water. Simplified chemical equations to represent
these chemical reactions are given thus:

Ca2(Al,Fe)05 + Ca(OH)2 + 3 {CaS042H20} + 25 H20 ~

Ca6[(A1,Fe)(OH)6]2(S04)326H20

Ca3Al206 + 3 {CaS042H20) + 26 H20 -+ Ca6[Al(OH)6]2(S04) 326H20

Because of the impure nature of the phases and the fact that
Al(II1) readily enters into solid solution with Fe(III), it is
not possible in practice to apportion how much ettringite arises
from the ferrite phase and how much arises from the a1uminate
phase. Small amounts of calcium hydroxide, as present in the
unhydrated cement, were also observed here. No calcium silicate
r t u P
56 Chemicals in the Oil Industry

ricu re ,
Infrared Spectra ot (1) tJ~ratecl Cl... G Oil..11 C...Il't, (2) Ceaent
B7d.ratecl UDretard" to !hick.aiae Tt. of 10' JIIillut , (3) Ce.ent Hyd-
rated with 0 Retarder to Thick.Bin '1'i_ ot 222 JIIillutell

0....::

w
u
z
~
~
z
<C(

i
4000 3500 3000 2700 1800 1600 1400 1200 1000 800 600 LOO 200

WAVENUMBER Icm- 1 )

2
.~

~
z
~
~
<C(

i i i i i i i i I
4000 3500 3000 2700 1800 1600 1400 1200 1000 800 600 LOO 200

WAVENUMBER (cm-I)

3
~

i i i I , i
4000 3500 3000 2700 1800 1600 1400 1200 1000 800

WAVENUMBER (cm -1 )
r t u P
Chemical Aspects ofOilwell Cementing 57

hydrate was observed.

At 60 minutes hydration the gypsum content had decreased and the


ettringite had increased compared with 20 minutes hydration. No
calcium silicate hydrate was observed and there was no further
perceptible rise in the quantity of calcium hydroxide present.

At the thickening time of 103 minutes, similar quantities of


gypsum as at 60 minutes hydration were found to be present.
Ettringite had significantly increased. Calcium silicate hydrate
C-S-H(I) was detected as was some additional calcium hydroxide
from the onset of significant hydration of the silicate phases
(principally alite):

c)(ii) 0.3% calcium lignosulphonate retarder

At 90 minutes hydration very small quantities of gypsum were


observed. The quantities of ettringite present were greater than
for the unretarded cement at its thickening time. Calcium
hydroxide was found in similar amounts to those contained in the
unhydrated cement and no calcium silicate hydrate was detected.
The lignosulphonate affects the thickening behaviour by
functioning as a dispersant or friction reducer, as well as a
retarder, as a result of which the development of thickening is
less than for the unretarded system.

After 130 minutes hydration the quantities of gypsum present were


still very small. Ettringite had increased in amount. Calcium
hydroxide was still present in similar quantities and again no
calcium silicate hydrate could be detected.

At the thickening time of 142 minutes small quantities of calcium


silicate hydrate C-S-H(I) became apparent along with some extra
calcium hydroxide from alite phase hydration. Ettringite was
present in similar quantities to those observed at 130 minutes.
Gypsum was no longer detected, suggesting that at least some of
the sulphate ions were entering into solid solution with silicate
ions in C-S-H(I).

c)(iii) 0.4% calcium lignosulphonate retarder

At 160 minutes hydration larger quantities of ettringite were


found than at the thickening time for the Class G cement with
0.3% retarder. Gypsum was not detected, presumably because of
its rapid consumption to form ettringite. Calcium hydroxide was
present in similar quantities to those found in the unhydrated
cement. No calcium silicate hydrate was experienced.

After 200 minutes hydration ettringite had slightly increased


over that present at 160 minutes. Neither gypsum nor calcium
silicate hydrate were recorded, and similar quantities of calcium
hydroxide to those found at 160 minutes and in the unhydrated
cement were apparent.
r t u P
58 Chemicals "in the Oil Industry

At the thickening time of 222 minutes, quantities of ettringite


had increased somewhat over those present at 200 minutes, but
likewise no dihydrate gypsum was detected. Calcium silicate
hydrate C-S-H(I) was just detected along with some calcium
hydroxide from alite hydration by S~~. More ~ttrin~ite was found
here than h.t the thickeninp- time with O. 3~cJ retarder present.
c)(iv) General Points

These results are of interest in that they show the thickening


times in the API Schedule 5 to be associated with the onset of
significant calcium silicate hydrate C-S-H(I) formation and not so
directly with the levels of ettringite formed. In the presence
of the calcium lignosulphonate retarder formation of ettringite
is accelerated and that of calcium silicate hydrate C-S-H(I)
retarded. Hence retarder response is likely to be influenced
much more by the extent of silicate phase hydration than by the
extent of aluminoferrite and aluminate phase hydration. The
viscosity changes appear to be linked more to morphological
changes than to direct chemical reactions increasing the
quantities of products formed. The ettringite formed is more
disordered in its structure than the synthetic variety because of
the effects of impurities contained in solid solution in the
phase. Thickening time seems to be more sensitive to C-S-H(I)
formation in the presence of more ettringite in retarded systems.
In the API Schedule 5 testing the temperature rises to 52C.
From the phases detected during hydration, the rise in
temperature to 52C is insufficient to decompose the ettringite
formed and to allow the formation of any crystalline calcium
silicate hydrates - only the very poorly crystalline C-S-H(I) is
encountered at the actual thickening time. The hydration
behaviour of oilwell cement during Schedule 5 thickening is
similar to that encountered during the normal setting 18 of
Portland (and especially of sulphate-resisting Portland) cement,
where the onset of normal setting is due primarily to the
formation of significant quantities of C-S-H(I) which immobilise
the water present - ettringite plays only a secondary role in
this respect. The main difference from normal setting at ambient
temperature is the temperature effect. As a result, during
Schedule 5 hydration the various chemical reactions are
accelerated because of the higher temperatures (rising to 52C)
encountered.

d) Conclusion

Hydration of a production Clas~ G oilwell cement under both un-


retarded and retarded conditions by API Schedule 5 to the
respective thickening times has shown some similarities with
normal setting behaviour at ambient temperature, except that the
processes are speeded up because of the temperature rise.
However, from the published work on geothermal samples 9-16,19
where crystalline calcium silicate hydrates of various types and
their derivatives are commonly encountered, it is clear that once
the cement casing has been pumped into position, hydrothermal
changes take place with the passage of time. Such changes result
in the development of crystalline calcium silicate hydrates and
the decomposition of ettringite, whose constituents become
r t u P
Chemical Aspects ofOi/well Cementing 59
incorporated into the silicate phases. Consequently the
chemistry of early hydration of Class G oilwell cement as in API
Schedule 5 is s~mply the initial process prior to the occurrence
of hydrothermal reactions, particularly as the wells become
deeper, at later stages.

Acknowledgement

The authors wish to thank Blue Circle Industries PLC for


permission to publish this work.

TABLE 3

CHEMICAL ANALYSIS OF CLASS G CEMENT

!PI Limit

~ !
CS 64.7 48 min - 65 max
3
Cs 7.0
2
CA 2.1 3
3
C AF
4 14.0
C4 AF + 2 x C A 18.2 24
3
K0 0.25
2
Na 0 0.16
2
Na 0 equivalent 0.32 0.75
2
MgO 0.7 6.0

53 1.9
Loss on Ignition 0 9
0

Insoluble Residue 0.30


r t u P
60 Chemicals in the Oil Industry
References

1. API Specification for Materials and Testing for Well Cements.


API Spec 10, First Edition, January 1982. American Petroleum
Institute, Washington D.C., 1982.
2. USSR Standard GOST 1581-78: Portland Cement for Oi1we11s.
Moscow, 1978.
3. M.R. Rixom: "Chemical Admixtures for Concrete" E & F Spon Ltd.,
London, 1978. p.6.
4. G.O. Suman Jr. and R.C. E11is: World Oil 1977, 185, 48.
5. J.Bensted: World Cement Tech. 1981, 12, 178.
6. S.N. Ghosh: "Advances in Cement Technology". Pergamon Press,
Oxford, 1982.
7. H.F.W. Tay10r and D.M. Roy: 7th lnt. Cong. Chem. Cement, Paris,
1980. Principal Reports. Editions Septima, Paris p.II-2/1.
8. J.P. Ska1ny and J.F. Young: lnt. Congr. Chem. Cement, Paris,
1980, Vo1.1. Principal Reports. Editions Septima, Paris,p.ll-1/3.
9. A.I. Bu1atov and D.F. Novohatsky: 6th Int.Congr. Chem. Cement,
Moscow, 1974, Vol. Ill. Stroyizdat, Moscow, 1976, p.243.
10. V.S. Danyushevsky and T.I. Rataychak: 6th lnt. Congr.
Chem. Cement, Moscow, 1974. Vol. Ill, pp.248-251. Stroyizdat,
Moscow.1976.
11. G.L. Ka10usek and S.Y. Chaw: Soc. Petr. Eng. J. 1976, No.12, 307.
12. A. Nakamura, T. Amaya, K. Kobayashi and M. Tsuji: Cement Assoc.
Japan - Rev. 32nd Gen. Meeting - Technical Session 1978, p.75.
13. D.M. Roy, F.L. White, C.A. Langton and M.W. Grutzeck: AlME
lnt. Symp. Oilfield and Geotherma1 Chem. Houston, Texas, 1979,
p.153.
14. C.A. Langton, E.L. White, M.W. Grutzeck and D.M. Roy: 7th
lnt. Congr. Chem. Cement, Paris, 1980. Vol. Ill. Communications
(cont.) Editions Septima, Paris,p.V/145.
15. K. Luke, H.F.W. Tay10r and G.L. Ka1ousek: Cement Concrete
Res. 1981, .!.!., 197.
16. E.B. Nelson, L.H. Ei1ers and G.L. Ka1ousek: Cement Concrete
Res. 1981, 11, 371.
17. J:'""Bensted and S.P. Varma: Cement Tech. 1974,2., 440.
18. J. Bensted: Silicates lnd. 1980, 45, 115.
19. L.D. Wake1ey, B.E. Scheetz, M.W. Grutzeck and D.M. Roy:
Cement Concrete Res. 1981, .!.!., 131.
r t u P
The Role of Chemicals in Oil and Gas Production

By E. J. Vase
SHELL U.K. EXPLORATION AND PRODUCTION, 1 ALTENS FARM ROAD, ABERDEEN, U.K.

Introduction

A production platform in the North sea will have some or all of the
following, depeming whether it is producing gas as most are in the
southern North Sea, or producing crude oil as in the northern
operations area:-

A. Oil or gas producing wells,


B. Water injection wells, and/or
C. Gas inj ection wells,
D. Crude oil comitioning plant,
E. Gas comitioning plant,
F. Water filtration plant,
G. Gas and/or water injection facilities,
H. Effluent comitioning plant.
I. In addition there are domestic areas, plus administration
offices, communications and a helicopter landing area with
aircraft refuelling ability, maintenance workshops, stores,
sickbay etc. These installations are communities of between
200 to 400 men with all the logistical problems of life
support in a desert of water.

Shell U. K. Exploration and Production (Shell Expro for short) operates


the Auk, Brent, Cormorant, Nor th Connorant, Dunl in am Fulmar Nor th Sea
oilfields, and substantial parts of the Leman and Indefatigable
southern gas fields, on behalf of Shell, Esso and other partners.

Figure 1 shows fields some 150 kms N. E. of Shetland which are


linked to the Brent System for oil export am the Far North Liquids and
Associated Gas System (FIAG for gas exp:>rt. Shell Expro operates
this complex networ k to serve both Shell/Esse fields and those of other
operators.
r t u P
62 Chemicals in the Oil Industry

SHELL Operated
and Associated
Oil and Gas
SuJtom
Systems
N.North Sea

Orkney

~~
~O

c===J Oil
c===J Gas
DD Proposed
"' Mossmorran Gas
~raefoot Bay

Figure 1
r t u P
The Role ofChemicals in Oil and Gas Production 63

'!he purpose of this paper is to deseribe the process plant on a typical


North Sea oil prcx1uction platform and indicate where chanicals are
often used to assist in winning oil ani gas ani their transfer to
shore. '!he mode of operation and use of chanicals outlined in this
paper is based on the Shell/Esso Brent field. '!he use of chanicals by
the many other operators will differ but we all face snnilar problems
and these differences will not be very great.

Platform Processes

Table 1 shows the design capacity of Brent Bravo production


platfoDn which is fairly typical for the Northern North Sea.

Table 1 BRENT B PLATFORM FACILITIES

DESIGN CAPACITY

CRUDE OIL/GAS SEPARATlrn 160,000 bid of oil


320 million sef/d of gas

CRUDE OIL S'IDRAGE 950,000 bls

EXPORT CAPACITY 275,000 bid

GAS CCMPRESSICN 190 million scf/d

G.2\S PROCESSING 285 million sef/d

WATER INJOCTlrn 350,000 bid

DRILLING 38 well coniuctors

Reservoir Depth 9,500 feet

PCNlER GENERATICN 62.6 Mega watt

UTILILTIES: WATER MAKERS


CHEMICAL PLMPS
INSTRLMENI' AIR
HEATING AND VENrlIATION
FIRE PlMPS

IN ADDITION BRENT B IS THE MAIN EXFORT STATION FOR BREm' ~S AND

GAS LlQUIOS
r t u P
64 Chemicals in the Oil Industry

160,000 barrels per day will provide adequate daily feedstock for an
average sized refinery.

62.6 Mega Watt would light a small town. '!he four Brent Platforms
produce and use electrical power equivalent to the needs of a city the
size of Aberdeen.

285 million standard cubic feet is sufficient gas per day to provide
2,800 houses with gas for one year.

When crude oil is produced it contains large proportions of dissolved


gas which ha~ to be separated and treated separately to:

(a) Produce a low vapour pressure (safe for handling) crooe oil.
(b) Provide gas for energy used on the platform, if required.
(c) Provide gas for gas injection or gas sales, if required.

In most North Sea oil bearing formations the oil is in contact with
large reservoirs of water (known as formation water) and as the oil is
produced it is replaced in the oil bearing zone by this formation
water. Eventually this water is produced with the crude oil: therefore
all producing platforms are provided with the means to separate this
water fran the crude.

Figure 2 depicts a typical process train on a Brent platform.


There are usually two such trains. Crude oil from the well manifold is
separated by passing through four separators each maintained at
progressively lower pressure and temperature until crude leaving the
last separator has a low vapour pressure and can be safely stored until
exported. Oil fran the wells is a mixture of liquid hydrocarbons and
dissolved gas and nearly always in association with water. '!his water
is often an emulsion which can be difficult to break.

Chemicals used at this stage are a danulsifier, a carbonate scale


inhibitor and a sulphate scale inhibitor, all injected at the well
manifold or before the well choke. Wi th certain crooes wax deposition
can be a problem at various stages in the process calling for the use
of wax crystal modifier.
~
~
BRENT PLATFORM PROCESS ~
~
~
TO GAS PIPEL INE ~
(140 BARS) OR
GLY.
GAS INJECTION
Q
~
WELLS (415 BARS) ~
(=:;'

r
6,OOOlbs/m.2
~
FUEL SYSTEM r;;--
5'
~
~
;:::
~
Cl

t
~
V:J
~
~
~
:;::
~
cs'
;:::

u
150,000
bbl/D
~CRUDE

P
+ NGL

METHANE ETHANE PROPANE BUTANE


FROM WELL 65% 17-20% 5-10 % 2-8%
MANIFOLD
35% OF GAS

Figure 2
0'1
VI
r t u P
66 Chemicals in the Oil Industry

On the Brent platfonns, water will drop out in the storage cells prior
to export to the Sullom Voe Oil Terminal, but on most other platforms
water is separated in the various stages of separation at the same time
as gas stabilisation takes place. This is called three phase
sepa~ation. (See Figure 3). f.t:>st producing platfonns in the Brent
System are able to export "dead" 8-11 lbs vap:>ur pressure crude or add
natural gas liquids to the crude before export to produce a gas rich
crude with vap:>ur pressures of between 40 to 150 psi. On the Shell
platfonns this is achieved by contacting snaIl portions of "decrl" crlrle
with natural gas liquids and reinjecting this rich crude into the main
crude stream leaving the platfonn. '1b obtain these natural gas liquids
the gases from the separator train are canpressed contacted with the
crude oil sidestream, cooled and allowed to separate again into rich
crude and the more volatile gas fraction. '!he gas separated at this
stage is contacted with Glycol to ranove water and then is either
reinjected into the producing reservoir or exported to shore. Other
North sea operators control vapour pressure by pressure control of the
last stage separator. Other operators inject NGLs directly into the
exported crude oil.

Chemicals used are corrosion inhibitor continually injected before the


first cooler and batch corrosion protection of the gas export line.

Figure 4 is the flow scheme of a typical water injection system


used by Shell in their North Sea operation. Gas and water injection
into the oil bearing zone is a method of maintaining reservoir pressure
or at least minimising the reduction of pressure. In the North sea,
sea water is deaerated by vacuum and oxygen scavenger chemicals,
filtered by screens and/or diatanaceous earth filters before injection
into the reservoir. '!he quality of water required by the various
operators can range from almost untreated water to a very severe
specification dependent on the porosity of the rock into which the
water is injected. For most of the Shell operation water with 95 per
cent of all particles greater than tYJO micron diameter ranooed and an
oxygen content of five parts in one billion. is specified. On sane
platfonns injection water is filtered through deep sand bed units in
which case polyelectrolytes and ferric chloride are used to assist
filtration.
r t u P
The Role ofChemicals in Oil and Gas Production 67

r------------ ------~--.-----

::fa:: ::i~ .... :1:

~~ ~i
o~

~!
~~
~3
",Cl:
...
~~
~

"'""a; 2~
0'1
00

OIATOYACE~
EARni

r
HOPPER
OVEReOARO
PUMP

t
SEA WATER
PUMPS

u
SEA
WATER
INTAKES

OXVGEN
SCAVENGING
F"LOWLlNES
TO WEu..5
Q
~
PUMP & TANI(
3

P
OVERBOARD
DUMP INJEC TION PUt.lPS (:;"
~
c;;--
s"
S-
~
OEAERATOR (~ANSFER) PUMPS
g
SEA WATER INTAKE DEAE RATION TRANSFER FIL TRATION INJECTION ~
~
~
~

Figure 4 ~
r t u P
The Role ofChemicals in Oil and Gas Production 69

Table 2 shows the typical analysis of the various formation


waters, and sea water. As can be seen there is a high scaling
potential when sea water is mixed with these formation waters. '!his
can affect operation in two ways, precipitation of bar ium sulphate at
the interface causing loss of injectivity due to formation zone
blockage and to scale deposition in the production facilities when this
mixture is eventually produced along wi th crude oil. Chemicals
required for this system are scale inhibitors at both the injection
point and at the production facilities and of course oxygen scavenger
to reduce corrosion of the injection well equipment.

Dumped Production Water

Water produced with crude can be separated whilst stored in the storage
cells, but same installations separate water in the separation train.
In either case oil- contaminated water (100 to 1,000 ppn) has to be
processed to reduce any oil contamination to the level required by law
(about 40 to 50 ppm). Two systems are used, parallel plate
interceptors and gas flotation uni ts. In both these systems
polyelectrolytes can be used to improve performance.

Movement of Gas and 0 il by P ipel ine

The line used to transfer crude oil fran the Brent field to the
Shetlands is 160 kilanetres long and the gas pipeline to the St Fergus
gas plant is 450 kilanetres in length. Studies are being performed to
evaluate if corrosion is a problem in the oil line and at present it is
not yet being treated except two sections of line (Brent Alpha to Brent
Bravo and Brent Delta to Brent Charlie) which have corrosion inhibitor
continuously injected. Consideration is being made how best to treat
the very long gas line against sweet (carbon dioxide) corrosion, and we
are also prepar ing a procedure should sour (hydrogen sulphide)
corrosion manifest itself. Continuous injection of inihibitors could
be very, very expensive; therefore we are exper imenting with viscous
slugs, or gels impregnated with inhibitor. How effective such a
technique will be remains to be established.

Biocide Treatment

There has been some manifestation of sulphate reducing bacteria in


parts of these structures where water can accunulate and became
-.J
o
Table 2 REPRESENrATIVE WATER ANALYSES

1- ---.------------,---------1---------1---------.------, , , , ,- 1
1 1 1 1 1 1 1 1 1 1 1 1
:Field : AUK : BRENr : BRENr : FORrIES :INDEFATIGABLE: LEMAN : LEMAN : 'lliISTLE : SPA : SPA :
1 I I I I I I I I I I I
1 1 1 1 I 1 1 1 1 1 1 1

r
: Formation :RCYI'LIEGEND : MIDDLE : IiliER :PALEOCENE : RCJrLIEGEND : RCTLIEGEND: ZECHSTElli : MIDDLE : WATER : WATER :
: : :JURASSIC :JURASSIC : : : : :JURASSIC: AUK : BRENr :
:Well : 30/16-3 :211/29-3 :211/29-3 : 21/10-5 : 48/18-3 I 49/26-4 : 49/26-5 :211/19-1: : :
I I I 1 I I I I I I I
~
1
:
1
:
1
:
1
::
1 1
::
1 1
:-"--:---:
1 1 1
:pH : 6.3 : 6.6 : 6.6 : 7.2 : 6.8 4. 7 : 4.4 : 7.0 : 7.9: 8.1:
I I I 1 I I I I I I I
1 1 1 1 1 1 1 1 1 I I
:Ion concns(mg/l) : : : : : : : : : :

t
1 1 I 1 1 I I I I I I
1 + 1 1 1 1 I I 1 1 1 I
:Na : 40,500: 9,600: 8,100: 33,000: : : 8,290: 11,000: 12,000:
: : : : : : )77,940 )75,250: )35,270: : : :
:K+ : 580: 170 : 180: 2, 700 : ) ) :) : 240: 400: 450:
I 1 I I I 1 I I I I I I
1 ++ 1 I I I 1 1 1 1 1 1 I
:Ca : 5,700 I 260 : 480: 3,950: 11,822: 12,770: 57,740: 292: 495: 346:

u
I I I I I I I I I I I
1 ++ I 1 1 I 1 1 1 I 1
:M3
I
:
I
900 65 55 :
I
500 :
1
4,093:
I
2,910:
I
41,290:
I
59 : 1,335:
I I
13.6:
I

:Ba+
I

I
:
I

I
N.A. 39
1
39 :
I
1
210 :
I
N.A.:
I

I
N.A.
1
:
I
N.A.:
1

I
I
54 :
I
1
- :
I
- :
1

I
1 ++ I 1 1 1 I 1 1 1 1
:Fe
I
:
I
69 73 6. 0 :
1
170 :
I
N. A.:
I
N. A. :
I
N. A.:
I
O. 2:
I
O. 05:
I
O. 02 :
I
Q
~

P
1 _ I 1 I 1 1 1 1 1 1
~
:Cl : 74,000 14,400 13,472: 58,500: 146,763: 146,830: 276,900: 12,800: 20,000: 20,500: ;::;.
I I I I I I I I I I I $:::l
1 _ 1 1 1 1 1 1 1 1 1 1
~
:HC03 : 150: 1,400 433 : 450 : 43 : 21: N.A.: 1,190: 95: 73:
I 1 I I I I I I I I I 5
1 _ 1 1 1 1 I 1 1 1 1 1
:00
I 3 :
I
Nil:
I
Nil Nil:
I
Nil:
I
Nil:
I
Nil :
I
Nil :
I
N.A.:
I
Nil:
I
17:
I
So
~

~
1 _ 1 1 1 1 1 1 1 1 1 1
:s04
I I
: 650 :
I
33 21 :
I
<10 :
I
461 :
I
570 :
I
80 :
I
11 : 2,760 : 2,820 :
I I I ~
1 _I 1 1 1 I 1 1 1 1_1 ~

~
V:l

~
r t u P
The Role ofChemicals in Oil and Gas Production 71

anaerobic. However our main concern has been the possibility of these
microbes becaning active in the oil bearing rocks by being injected
wi th the injection water. Q.lr microbiologists have advised against
attempting to treat the injection water and we have accepted their
advice. Biocides are used but in small dosage for particular
applications, such as a well closed in for several weeks at a time.
The policy of whether to use biocide to protect a reservoir when
pressure maintenance is through water injection varies widely in the
North Sea fron nil use through batch treatment to possibly continuous
injection.

Policy depends on whether or not bacteria can survive and reproduce


under prevailing reservoir pressure/temperature.

The Need for Chemicals in the Future

Proouction will continue well into the next century even if no more
fields are discovered. As plant ages corrosion problems certainly are
not reduced. Seawater breakthrough will steadily increase with
sulphate scaling problems increasing in proportion. Carbonate scaling
and wax deposition will certainly continue during the lifetime of these
fields and hydrogen sulphide generation downhole is a possibility
lurking in the background. As larger quantities of water are produced
as fields age descaling chemicals consumption will increase in
proportion.

The whole area of enhanced oil recovery other than gas and water
injection is an uncharted area. Enhanced oil recovery with respect to
the North Sea is still very firmly with the E & P research laboratories
and any likely applications are a long way away.

Tb summarise finally, chemicals are required for:-

(1) Demulsification.
(2) Carbonate scale inhibition.
(3) Sulphate scale inhibition.
(4) Sweet and sour corrosion inhibition.
(5) Defoamers.
(6) Oxygen scaveng ing .
r t u P
72 Chemicals in the Oil Industry
(7) Biocide treating.
(8) Wax inhibition.
(9) Wax solvents.
(10) Sulphate scale removers.
(11) Deoiling chemicals.
r t u P
Chemical Demulsification of Produced Crude Oil Emulsions

By D. E. Graham, A. Stockwell and D. G. Thompson


BP RESEARCH CENTRE, SUNBURY-ON-THAMES, MIDDLESEX TWl6 7LN, U.K.

Abstract

During the production of crude oils, formation water (and,


under conditions of water breakthrough, injection water)
may also be coproduced. The high fluid temperatures,
indigenous crude oil surfactants and turbulence experienced
at the wellhead chokes and valves all contribute to produce
a finely dispersed emulsion of water droplets-in-crude
oil. The indigenous crude oil surfactants adsorb at the
water droplet interface giving rise to an interfacial
'skin' which has rheological properties capable of inducing
droplet stability.

To aid coalescence of the emulsified water droplets,


demulsifier surfactants are injected into the produced crude
oil emulsion. These surfactants act to displace indigenous
crude oil surfactants, thereby reducing the interfacial
water-crude oil tension, and so causing weaknesses in the
interfacial skin' and consequently coalescence of the
I

water droplets.
r t u P
74 Chemicals in the Oil Industry

The surfactant activity of the demu1sifier is dependent on


the bulk phase behaviour of the chemical when dispersed in
the crude oil emulsions. This behaviour can be monitored
by determining the demu1sifier surface pressure isotherms
for adsorption at the crude oil-water interface. Further,
demu1sifier adsorption is dictated by the bulk physical
properties of the demulsifier particularly with respect to
the effect of diluents on the demulsifier efficacy. These
properties are described and discussed.

Direct consequencies of the bulk and interfacial physicochemical


parameters on predicting realistic field conditions for
treating p~oduced fluids can be realised when using laboratory
techniques. The importance of thermally treating the crude
oil to reproduce wellhead conditions within the oil and the
consequences upon wax behaviour and emulsion stability are
demonstrated.

Introduction

There is an increasing number of crude oil fields that are


now producing both crude oil and water. The water which is
coproduced with the crude oil can result either from the
aquifer layer in the reservoir, from the injected water for
secondary or tertiary recovery stages or from both sources.
It is generally believed, although not proven, that during
fluid flow up the field drillstem and riser the two fluids
are likely to remain as essentially discrete phases.
However, at the wellhead chokes and valves where there is
significant turbulence, shearing and pressure drops, the two
liquid phases become mixed giving rise to a water-in-crude
oil emulsion. The indigenous surfactants of the crude oil
give rise to an interfacial skin around the dispersed water
droplets which in turn gives rise to stable emulsions.
These interfacial films have been studied l - 4 to identify
r t u P
Chemical Demulsification ofProduced Crude Oil Emulsions 75

the specific physicochemical parameter which can best be


correlated with emulsion stability; to date, there is no
single unique parameter that can be completely correlated
toe mu 1s ion s tab i 1 i t Y4,

There is a number of commercial and operating reasons


why it is advantageous to remove this emulsified water
from the c r ude 0 i 1. It i sex pen si vet 0 t ran s p 0 r tin bot h
tankers and pipelines; the water contains salts which
can poison downstream refinery catalysts as well as enhance
corrosion of overhead distillation columns, pipework and
pumps; and the emulsion has a higher bulk viscosity than
the dry crude oil and this can give rise to increased
pressure gradients in pipeline transportation resulting in
slower flow rates or a greater number of, or more powerful,
feed pumps.

One readily used procedure for separating the water from


the produced crude oil is by chemical addition; such chemicals
are surface active agents which act to enhance emulsion
instability and are so called demulsifiers. This paper
will discuss the surface active behaviour of a selected
demulsifier and identify how its efficacy can be enhanced
by changing its bulk physicochemical behaviour. Moreover,
the enhancement is demonstrated both at the molecular level
using interfacial adsorption isotherm behaviour, at the
laboratory level using simulated emulsions and at the pilot
scale level using a dehydrating rig. In addition, since the
experiments are carried out often in an environment away
from the production site using crude oil that is aged, it
is important that the oil be thermally treated to recapture
most of its "production" physical properties. Thi s important
concept is demonstrated for a North Sea crude oil in terms
r t u P
76 Chemicals in the Oil Industry

of controlling wax behaviour (ie crystal growth) within the


crude oil and consequently emulsion stability and reproducibility.
The latter is crucial when selecting demulsifiers for oil
field use.

Materials

Cru~. The crude oil used throughout this study was


obtained from one ofjthe BP operated fields in the North
Sea. The oil was allowed to stand at atmospheric pressure
for at least a day uefore being transported by road to the
Sunbury Research Centre. Consequently, the oil used in the
experimenfs was at least three to four days old and at
atmospheric pressure but was obtained in about 10 barrel
quantities so that sufficient experiments could be carried
out on the same crude oil sample batch. The barrels were
heated and thoroughly shaken befor~ taking samples for
laboratory experiments. The oil used in the model rig
experiments was recirculated continually throughout the rig
runs.

Water. The water in the laboratory emulsion studies was


double distilled; simulated field formation water for the
emulsions was prepared using AnalaR salts, wherever
possible.

Demulsifier. The demulsifiers used in this study were


commercially available mat2rials supplied by Service
Companies to the Oil Industry. The chemical compositions are
not completely known but on the other hand the demulsifiers
are knawn to consist of more than one surface active species.
The demulsifiers are designated simply as A and B throughout
this text. The former (A) comprises a blend of ethoxylated
propoxylated adducts (mw ca 2000) together with a cationic
r t u P
Chemical Demulsification ofProduced Crude Oil Emulsions 77

fatty acid (mw ~ 800); the latter (B) is mainly an ethoxylated


phenolic resin of molecular weight 1600. The chemicals were
selected as suitable for treating this particular North
Sea crude oil after e~aluating simulated emulsions made in
the laboratory and identifying the optimum demulsifiers
from a range of chemicals supplied by many Chemical Company
suppl i ers.

Methods

Thermal micro~copy. An Olympus BH microscope was used in


conjunction with a Mettler FP5 control unit and FP 52
microfurnace. A trinocular head with eyepiece, camera and
photocell/recorder attachments allowed simultaneous visual
and photographic records to be made while thermograms were
recorded. The thermograms provided the only objective
discrimination between wax and other (insoluble) crystalline
matter.

Wax crystals in crude oil were observed at a magnification


of 100X using transmitted polarised light. The crude oil
sample thickness was maintained at 50 micron by use of a
sealed cell consisting of two perspex sheets, one 1.6 mm
thick (the 'slide l
the other 0.3 mm thick (the 'coverslip'),
),

separated by a 50 micron thick nickel washer. The thicker


perspex sheet was drilled and tapped to permit filling,
cleaning and re-use of the cell.

Crude oil pretreatment. Pressure-tight stainless steel


vessels (vol. ~ 700 ml) were used to reduce to a minimum any
11 ight end' loss from the crude oil. These vessel s were
filled to near capacity to reduce the risk of oxidation of
the crude oil. The oil sample was then placed in an air
oven at 40, 60 or 80C and left for three hours prior to
controlled cooling to ambient temperature. Two extreme cooling
rates were used; rapid (10 Co min- 1 ) and slow (0.1 Co min- 1 ).
r t u P
78 Chemicals in the Oil Industry

In the following text and plates these heating and cooling


rates will be abbreviated in the following manner: 80/S
means heat the oil sample to 80C, hold for three hours
and then cool to room temperature slowly (0.1 Co min- 1 );
40/R means heat the oil sample to 40C, hold for three
hours and then cool to room temperature rapidly
(10 Co min- 1 ).

Laboratory bottle tests. These experiments were carried


out as described e1sewhere 5 with the emulsions being prepared
and resolved at 40C. In the present work, 20 ppm demu1sifier
A was intected into the prepared emulsions. The demu1sifier
was used as supplied to the laboratory and consisted of
a 50% by vol. active ingredient in solvent.

Results and Discussion

Thermal behaviour of crude oils. The thermomicrograph for


the specific North Sea crude oil used in this study is
given in Plate 1; the wax content and size distribution
are typical of those observed with other North Sea crude oils.

PLATE 1: NORTH SEA CRUDE OIL AS RECEIVED

100 MICRON ~

MAGNIFICATION SIMILAR FOR PLATES 2 - 7


r t u P
Chemical Demulsification ofProduced Crude Oil Emulsions 79

The wax crystals can be seen as the bright specks being


approximately 10 micron in diameter. However, when the
sample of oil is heated in a bomb to 80C and then cooled
the wax morphology depends on the relative rate of cooling.
For example, Plate 2 shows wax crystals in a crude oil
sample which was cooled slowly and Plate 3 shows those
in a sample which was cooled rapidly.

PLATE 2: 80S PLATE 3: 80R

Clearly the slowly cooled sample contains a considerably


greater amount of wax in larger aggregates than the rapidly
cooled sample. The same observation can be made when
heating the crude oil sample to 60C and cooling, although
on this occasion the difference is not as noticeable as
when heating the sample to 8GoC (see Plates 4 and 5).
r t u P
80 Chemicals in the Oil Industry

PLATE 4: 60S PLATE 5: 60R

Again the slowly cooled sample had a greater amount of crystalline


wax and also larger wax crystals/aggregates than the rapidly
cooled sample. Following on with this trend, when the oil
sample is heated to 40C then there is only a marginal
difference between the quantity and size of wax crystals
following both slow and rapid cooling rates (Plates 6 and 7,
respectively). The fact that there is negl igible difference
between the two cooling rates at 40C is hardly surprising
bearing in mind (i) the original sample had been maintained
at some 22C (room temperature) prior to heating, (ii) the
temperature at which all crystalline wax is in solution is
! 50C (depending on the exact heating rate) and (iii) the
wax thermal behaviour is greatly dependent on previous
r t u P
Chemical Demulsification ofProduced Crude Oil Emulsions 81

thermal history (ie whether wax is in the form of large


aggregates (Plate 2) or small particulates (Plate 6)).

PLATE 6: 40S PLATE 7: 40R

The connotations of these observations on crude oil samples


are that the size and the number (or amount) of wax present
in crystall ine form will significantly depend on the thermal
history of the crude oil samples and also on the pretreatment
cei 1 i ng temperatures and cool i ng rates. Thermal.hi story
will then have a consequential effect on the emulsion stability.
It is generally observed that emulsion stability becomes
significantly greater when wax crystallites are present in
crude oil and significantly reduced when these crystallites
are dissolved. To this end, therefore, when selecting
chemical demulsifiers for treating produced crude oils it
r t u P
82 Chemicals in the Oil Industry

is important to beneficiate the waxes and to return the oil


sample wax content to a state approaching that perti~ent to
the production state of the oil. In the next section the
effect of oil sample thermal treatment is correlated with
emulsion stability.

Effect of thermal behaviour on emulsion stability. Simulated


emulsions of the North Sea crude oil were prepared at 40C
and resolved at 40C using the commercial demulsifier, A.
The crude oil had previously been pretreated to 80C, 60C
and 40C and samples were cooled slowly and rapidly to give
a variety of crystalline wax morphologies as discussed above.
These oil samples were then used to prepare emulsions which
were then resolved by chemical injection and the separated
water level measured after 24 hours at 40C. The comparative
emulsion stability is given in the histogram (Figure 1)
for the s pe cif i c c r ude 0 i 1 p r;~ t rea t men t s

It is clear from Figure 1 that crude oil pretreated to 40C


before emulsifying and chemically resolving is, within
experimental error, largely unaffected by the rate of oil
cooling; both rapid and slow cooling give rise to similar
emulsion resolution. However both pretreatments afforded
sl ight1y more unstable oil than the s tandard sample which
II
ll

received no thermal pretreatment. The similarity between


the emulsion resolution histograms for 40C thermal
pretreatment tends to follow from the similarity of the wax
morphology shown in Plates 6 and 7.
r t u P
Chemical Demulsification ofProduced Crude Oil Emulsions 83

100

80

60
~

s-
O)
-+->
ItS
3
-0
40
0)
-+->
ItS
s-
ItS
c-
O)
(/)
20

o80R 60R 40R - 40S 60S 80S


FIGURE 1 THE INFLUENCE OF CRUDE OIL THERMAL PRETREATMENT ON THE
WATER SEPARATION AFTER 24 HOURS FROM A 20% WATER-IN-NORTH
SEA CRUDE OIL EMULSION

On the other hand, the ease of emulsion resolution


is significantly different for oil samples preheated to
80C prior to cooling and emulsifying. In fact, slowly
cooled oil samples were almost totally resolved by the
demulsifier A whereas the rapidly cooled samples were very
stable and were only marginally resolved by the same chemical
demulsifier. This observation again correlated well with
the Plates 2 and 3. The slowly cooled sample gave rise to
large wax aggregates which were too large to stabilise the
r t u P
84 Chemicals in the Oil Industry

(approximately 10 micron diameter) droplets of the dispersed


water phase. The rapidly cooled sample gave rise to an
increased number of smaller wax crystallites which are now
capable of stablising the emulsion. It is proposed that this
stability arises via adherence of wax particles at the
oilwater interface increasing the interfacial rheology.

The resolution of emulsions with crude oil pretreated at


60C is intermediate between those samples treated at 40C
and 80C; see Figure 1. The correlation of emulsion
stability with wax crystallite appearance, as per Plates 4
and 5, is~in line with that correlation observed at 80C
only of reduced magnitudes.

100 --
80

CtQ. 60
~
Q)
+J
to
3:
-0
"CV 40
+J
's"..
tU
0-
Q)
I---
V>

20
~ -

o
80R 80S 80R 80S 80R
FIGURE 2 THE INFLUENCE OF CONSECUTIVE CRUDE OIL THERMAL PRETREATMENTS
ON THE WATER SEPARATION AFTER 24 HOURS FROM A 20% WATER-
IN-NORTH SEA CRUDE OIL EMULSION
r t u P
Chemical Demulsification ofProduced Crude Oil Emulsions 85

By way of demonstrating the repeatability of the oil


treatment on emulsion stability, Figure 2 contains repeat
emulsion resolution curves using oil samples which were
preheated to 80C before being cooled initially rapidly,
then slowly, then rapidly, slowly and finally rapidly again.
At each occasion, 20% water-in-oil emulsions were prepared
and resolved by chemical injection of demulsifier A
at 40C. The repeatability was extremely good and
compares well with the similar data obtained using a
different oil consignment shown in Figure 1.

Two important ~oints to be drawn from these data are firstly


that the progressive heating and cooling of crude oil
samples do not cause any physical or chemical change in
the oil such as loss of light ends or oxidation which
could then in turn affect the emulsion stability ratings.
Secondly, because the alternate emulsion stabilities are
reproducible, the thermal behaviour of the waxes in the
oil is completely reversible. This reversibility lends
credence to the view that thermally ~edting the oil to
80C will tend to revert the oil sample towards the state
that it was in at the wellhead. It is then further postulated
that the production thermal history has been destroyed and
the oil can then be thermally manipulated to mimic any
production phenomena. This would further support the fact
that some confidence can be given to non-site reproducibility
of demulsifier evaluation programmes using oil which has
been pretreated to destroy the thermal history and then
cooled in a manner similar to the site conditions.

Demulsifier adsorption behaviour. Most, if not all, chemical


demulsifiers are diluted in a solvent phase (often typically
40-60% by volume) to reduce the surfactant viscosity and so
improve the chemical handling ability. However, it has
r t u P
86 Chemicals in the Oil Industry

been demonstrated 5 ,6 that the interfacial behaviour of


demulsifiers can be significantly effected by the solvent phase
in which they are diluted. The significant factor which
arises from the previous stud y6 is that the interfacial
tension adsorption isotherm shows that demulsifier B, the
nonionic ethoxylated phenolic resin, can have an enhanced
surface activity when diluted in the solvent, xylene. At
the concentration of only 0.2 ppm the demulsifier B will
have attained a maximum reduction in the oil-water interfacial
tension. In other solvents such as methanol, propanol or
toluene the interfacial activity is only partially enhanced
in comparison with the chemical as supplied. In the same
paper 6 , light scattering data supported the proposal that
the demulsifier is readily solvated in the xylene giving
almost complete molecular solubility. However, the same
chemical is more (irreversibly) aggregated in the other
solvents thereby having a reduced surface activity.

Relative n-A curves for crude oil-water interface

A relative measure of the interfacial film1s n-A curve can


be obtained by allowing the interface to establish steady
conditions of film tension and then compressing that film.
Since the exact number of surface active species indigenous
to the crude oil is unknown it is not possible to give an
accurate value for A, the area per surface active molecule.
Hence, it is only possible to quote A/A o , the relative
area reduction for the whole interfacial film where A is
that area existing during compression and Ao is the initial
uncompressed film area. The n-A/A o can be considered a
relative n-A curve. Such a curve for the North Sea
crude oil-distilled water film is shown in Figure 3 along
with similar curves for demulsifier B diluted in different
solvents as a 1 per cent solution and then injected into the
crude oil prior to compression.
r t u P
Chemical Demulsi,fication ofProduced Crude Oil Emulsions 87

16

12 ,,
,
-1
'\
1r/mN m
8

o
o 0.2 0.4 0.6 0.8 1.0

A/A
o
FIGURE 3 CRUDE OIL-DISTILLED WATER RELATIVE COMPRESSION CURVES IN
ABSENCE (-----) AND PRESENCE OF DEMULSIFIER B DILUTED AS
1% SOLUTION IN PROPANOL( .... ) METHANOL (-----) AND
XYLENE ( - - -) AND ADDED TO THE OIL AT 0.2 ppm

The n-A curve observed for the specific North Sea crude
oil is similar to those curves obtained for a range of
other North Sea and Middle East crude oils as provided
elsewhere 3 ; subtle differences do exist which can be
related to relaxation rates within the adsorbed interfacial
film and the relative speed of compression. Addition of
demulsifier B to the crude oil interfacial film prior to
compression generally results in a reduction of the change
in n for a given compression but the reduction is clearly
r t u P
88 Chemicals in the Oil Industry

dependent on the nature of the solvent in which B is diluted.


The changes observed with propanol are barely outside
experimental reproducibility but the compression observed
with demu1sifier B in xylene is significantly reduced compared
with the crude oil film alone.

The rheologica1 properties of crude oil-water films have


been correlated with emulsion stability by a number of
workers l - 4 Shear properties have generally, but not
without exception, been well correlated to emulsion stability
although recently4 attempts have been made to evaluate
dilatation~l properties. It can be deduced from the data
presented in Figure 3 that the pseudostatic dilatational
properties of the specific crude oil film (the pseudostatic
modulus is directly proportional to the negative slope of
the n-A/A o curve) are much reduced when demulsifier B
is added in xylene and so it is anticipated that this
could have significant effects on the stability of the
water-in-crude oil emulsions. From the data obtained in
Figure 3, it would be predicted that demulsifier B in
xylene would destabilise the emulsions to a greater extent
than that in methanol, and in return, in propanol. Moreover,
it is possible to demonstrate physically the skin developed
at the crude oil-water interface by making a hanging oil
drop-in-water and then shrinking the droplet. The interfacial
skin so produced remains as a wrinkled phenomenon. But,
in the presence of demulsifier B this skin is difficult to
produce and indeed it is impossible when the demulsifier
is added to the oil in xylene. Hence, it is perhaps worth
recalling how the demulsifer efficacy can be improved by
diluting in the xylene solvent.

Laboratory and model rig emulsion stabilities. Previous


results 6 obtained with laboratory produced water-in-North
Sea crude oil emulsions have highlighted the practical
importance of the effect of improving surface activity of
r t u P
Chemical Demulsification ofProduced Crude Oil Emulsions 89

demulsifier B by diluting in specific solvents. Diluting


the nonionic ethoxylated phenolic resin chemical in xylene
tends to give better solubility in the crude oil and so
improve its abil ity to enhance emul sion i nstabil ity. In
addition to this improved emulsion resolution 6 ,it is
also possible to control the rate of water separation from
an emulsion by judicial selection of the solvent phase as
shown elsewhere 5 Consequently, the potential to control
demulsifier efficacy, by selecting the solvent in which
the active ingredient is diluted, is open to exploitation.

In addition to~he laboratory results obtained with simulated


water-in-crude oil emulsions, experiments have b2en carried
out on the model dehydrating rig to evaluate the emulsion
resolution under conditions more closely resembling those
in production. As though to confirm those data obtained in
the laboratory, the data on the rig 7 exactly confirmed that
demulsifier B diluted in xylene had increased efficacy over
that dissolved only in the solvent as supplied. In fact,
the latter resolved 10% simulated production water-in-crude
oil emulsions to a level of only approximately 8 ~ 2% residual
water content whereas the demulsifier B diluted in xylene
as a 4% solution resolved the identical emulsion immediately
to 0.25 ~ 0.2% residual water. This important concept has
significant advantages for offshore production.

Conclusions

There are two important findings fro~ this and other related
studies.

Firstly, the crude oil samples received in laboratories


for demulsifier evaluation should be thermally treated to
destroy the production-transport thermal history which the
r t u P
90 Chemicals in the Oil Industry

crude oil remembers through its crystalline wax morphology.


Providing the crude oil samples are thermally treated, then
reliable and reproducible emulsion behaviour can be obtained
by which chemical demulsifier evaluations can be routinely
and reliably carried out under simulated production thermal
conditions.

Secondly, the demulsifier concentrate is generally too


viscous to handle neat and so a solvent is added to improve
handling. However, a careful selection of solvent can
significantly improve the surface activity of the demulsifier;
it is proP9sed that the correct solvent is one which allows
the demulsifier to dissolve totally without irreversible
aggregation.

The consequences of this selection of a solvent are improved


surface activity and emulsion resolution efficiency.

Acknowledgements

The authors wish to thank Jane Bell for preparation of


the typescript and The British Petroleum Company plc for
giving permission to publish this paper.

References

1. J. Reisberg and T.M. Doscher, Prod. Monthly, 1956, ~,

43.

2. J.E. Strassner, J. Petrol. Technol., 1968,~, 203.

3. T.J. Jones, E.l. Neustadter and K.P. Whittingham,


Canadian Pet. Tech., 1978, ll, 100.
r t u P
Chemical Demulsification ofProduced Crude Oil Emulsions 91
4. E.l. Neustadter, K.P. Whittingham and D.E. Graham, In
"Surface Phenomena in Enhanced Oil Recovery", edited
by Denesh O. Shah, Plenum Publishing Corp., 1981,
pp 307-326.

5. D.E. Graham, E.l. Neustadter, A. Stockwell, K.P. Whittingham


and R.J.R. Cairns, In "Surface Active Agents", SCI publication
1979, p127.

6.' D.E. Graham and A. Stockwell, European Offshore Petroleum


Conference~ london, 1981, p453.

7. A. Stockwell, D.E. Graham and R.J.R. Cairns, Oceanology


International 80, 1980, Section F, 9.
r t u P
Oily Wastewater Treatment in the Production of Crude Oil

By G. E. Jackson
PETROLITE LIMITED, BIRCHILL ROAD, KIRKBY INDUSTRIAL ESTATE, LIVERPOOL L33 7TD,
U.K.

Increasingly more stringent environmental regulations on the


quality of water discharged to rivers and the sea offshore have
created increased interest in oil-water separation processes,
and in ways of chemically enhancing these processes.
Oily wastewater arises in a number of ways in the production
of crude oil. The major sources of wastewater include:
produced water which contains residual oil and oil derived
chemicals, after separation from the oil. The quantity of
this produced water increases as the reservoir is depleted and
water invades the formation, particularly when water injection
is used for pressure maintenance. Other sources of wastewater
include: displacement water from oil storage systems, which
may contain emulsions which accumulate at the oil-water
interface in the storage tanks; tanker ballast water;
operational discharges from rainfall run off; oily wastes
and slops from drilling operations. Before the oil-contaminated
wastewater can be discharged or re-injected for pressure
maintenance, the oil and suspended solids must be removed.
The concentration to which oil and solids in the water have
to be reduced depends on local conditions but data suggest 1
that average oil concentrations of 30-40ppm are achievable
with available technology offshore. This level can be
considerably reduced in land based operations where secondary
biological treatment can be used to reduce further the oil and
organic loading of an effluent.
r t u P
Oily Wastewater Treatment in the Production ofCrude Oil 93
Contamination of water in the production of crude oil
frequently leads to intimate mixtures or emulsions of
dispersed oil, finely divided solids, dissolved organic material,
and water. These mixtures can be extremely difficult to
separate. Entrained oil may be present in the wastestream
in a variety of forms. Free oil may be present as large
d r 0 p 1 e t s, Le. par tic 1 e s >1 5 0 ~m d i a met er. The sed r 0 p 1 e t s are
normally easily separated by gravity. Smaller droplets
of 'dispersed' oil mayor may not coalesce and be separable
by gravity. As the oil droplets decrease further in size,
to the range of 1-5~m diameter, they become 'stabilised' or
'emulsified~ and cannot be readily separated by conventional
gravitational separation processes. Generally, emulsified
oils need a more sophisticated process, together with some
chemical treatment, in order to separate and remove the oil
contaminant. Finally, soluble oil or dissolved organic
material which is not present as discrete particles is very
difficult to remove without chemical treatment and may increase
the stability of the emulsified oil in some cases.
Emulsion Formation and Stability
Co-production of oil, gas, and water in the presence of
surfactants leads to the formation of two types of emulsion:
water in oil or 'regular' emulsions, and oil in water or
'reverse' emulsions.
In a reverse emulsion, the oil is broken up into very small
particles or droplets which are dispersed in water, the external
phase. This can happen in production systems by shearing the
fluids in a pump, in a choke, in a production separator etc.
Dispersing the oil in this way leads to a tremendous increase
in the interfacial energy of 'the system.
If the two immiscible liquids concerned were pure, the
emulsion produced would be extremely unstable thermodynamically
relative to the two bulk phases separated by a minimum area
of interface. This is why two immiscible liquids when pure
do not form emulsions, and an emulsifying agent has to be present.
r t u P
94 Chemicals in the Oil Industry
At the interface between the oil particles and water there
is always an unequal distribution of charges between the two
phases. This causes one side of the interface to acquire a
net charge of a particular sign giving rise to a potential
across the interface which is known as the 'electrical double
layer'.
The emulsifying agents or surfactants act by absorbing
at the interface as an oriented interfacial film, hence
stabilising the dispersed particles whether it be a liquid/
liquid or liquid/solid dispersion.
These emulsifying agents act by:
a) redDcing ~ow,the interfacial tension between the
oil and water:
So, for a fixed amount of mixing energy W ergs given to the
system
W = ('tow) (Aow)
any reduction in 'tow will lead to a corresponding increase
in Aow, the interfacial area. This increase in Aow is achieved
by creating a large number of smaller particles. La an
emulsion
b) decreasing the rate of coalescence of the dispersed
particles by forming a mechanical, steric; and/or
electrical barriers around them. These barriers inhibit
close approach of the particles.
The resistance of the dispersed oil particles to coalescence
is a measure of the 'stability' of the emulsion, and is
determined by:
i) the physical nature of the interfacial surfactant
film.
ii) the presence of a charge on the dispersed phase
droplets or particles, which constitutes an electrical
barrier to the close approach of the particles.
ill) the viscosity of the continuous phase, water.
iv) the oil particle size distribution.
r t u P
Oily Wastewater Treatment inthe Production ofCrude Oil 95
Emulsifying agents found in oil-water reverse emulsions tend
to be anionic and non-ionic surfactants, e~. sodium and potassium
soaps, sodium naphthenates, cresylates and sodium and potassium
sulphides. These are often only water soluble at neutral or
alkaline pH, and in such cases pH adjustment may be used to
reduce emulsion stability and improve oil removal efficiencies.
Apart from surfactants which may derive from the crude
oil itself, very finely dispersed solid particles may also act
to stabilise o/w emulsions. These can originate from a
number of sources such a silts, clays, fine particles of
limestone or sands from the formation, any insoluble inorganic
mate r i a 1 e.g. i r 0 n sui phi d e, s c ale 0 r cor r 0 s ion pro d u c t s wh i c h
may precipitate from the aqueous phase.
A further source of potential o/w emulsifying agents
are the other chemicals being used in the production system
and includes: regular demulsifiers, scale and corrosion
in h i bit 0 r s, s c a v en g er s, b i 0 cid e s, pro d u c t s fro m a cid i sin g
operations, chemicals used for tertiary recovery programmes.
The ability of these chemicals to create a reverse emulsion
varies widely and may not pose a problem at normal usage
levels. However, overtreatment, batch treatments, or squeeze
treatment programmes can lead to severe problems when
excesses of the chemicals are present in the wastewater stream.
In most cases it is necessary to use a reverse demulsifier
to destabilise the dispersed oil droplets, increase their
size and hence increase the efficiency of the physical
separation processes used to de-oil the water.
Oil Removal Methods
The optimum process or combinatian of processes for a
particular oily wastewater depends on a number of factors t
Le. oil droplet size distribution, oil concentration, gravity
of oil, level of suspended solids, presence of surfactants etc.
The optimum process will produce the required effluent water
quality at the lowest capital operating and maintenance cost.
A brief description of these individual unit processes
follows.
r t u P
96 Chemicals in the Oil Industry
Gravity Separation
Primary treatment or equalisation of oily wastes is generally
by gravitation. This is the most efficient and economical
way to remove large quantities of free oil, and is usually
achieved by equalisation tanks fitted with oil skimming
facilities. Although gravity separation is effective in
removing free and some dispersed oil it will not remove
soluble oils and most emulsions. The performance of a
gravity separator is governed by:
a) The Stokes Rising Velocity of the individual droplets
of free oil.
This is a tunction of temperature and density difference
between oil and water.
b) The hydraulic loading of the unit.
The API Separator is designed to remove oil droplets of
150~m diameter or larger. 2
Tne parallel plate separator has also been used for
primary de-oiling] This is basically a large number of
shallow separators stacked on top of each other operating
in parallel. As the wastewater flows between the plates the
oil floats to the under-surface of the plates, coalesces,
and finally rises to the top of the tank where it is skimmed.
The plates establish laminar flow through the plate pack and
drastically reduce the distance that oil droplets must rise
in order to be skimmed. Plate separators are generally
designed for removal of 60~m diameter oil droplets.
The performance of gravity separators may be enhanced
by promoting agglomeration and/or coalescence of oil droplets,
which increases the Stokes rising velocity of the oil droplets.
This may be achieved by pH adjustment and/or the use of
reverse demulsifiers.
A very important factor in the design and operation of
gravity separation systems is the efficient removal of any
suspended solids which settle out and form an oil-wet sludge.
Air flotation
The two main types of flotation process used for de-oiling
water differ in the way in which the gas (usually air) is
r t u P
Oily Wastewater Treatment in the Production ofCrude Oil 97
introduced to the system. Both rely on the interaction of
bubbles with the dispersed oil droplets in order to increase
their rising velocity.4
Induced Air Flotation I.A.F.
In I.A.F. air or gas is drawn into the liquid by an eductor-
rotor and is sheared into bubbles (10 2 -10 3
micron diameter).
The main oil removal mechanism is via oil droplet/air bubble
interaction. This process may be considerably enhanced by
the use of an appropriate organic polyelectrolyte flotation
reagent. Inorganic coagulants are generally unsuitable for
this process due to the violent stirring action of the rotors
which tends _to redisperse the rather fragile flocs formed
when using salts.
Dissolved Air Flotation D.A.F.
In D.A.F., the whole of the wastewater stream, or part of it,
is saturated with a gas,usually air under pressure. The air
in excess of atmosphenc saturation is precipitated by pressure
release in a flotation chamber. Bubbles generated in this
manner are much smaller than for I.A.F. 30-150 ~m.

Once again, the air bubble/oil droplet interaction is


very important in determining the efficiency of the process,
and this may be increased dramatically by the addition of an
appropriate organic polyelectrolyte flotation aid. This
acts to destabilise emulsified oil, and improve bubble/droplet
interaction. When organic polyelectrolytes are used alone,
the floated-skimmed oil may be recycled to the primary
treatment unit. If inorganic salts are used as coagulants,
large volumes of oily sludge tend to be generated. This
seriously reduces the ability to ,recover the skimmed oil, and
can create a disposa~ problem.
The size and weight of D.A.F. units preclude their use
in offshore applications.
Filtration Systems
Filtration Systems have been applied to the separation of free
and emulsified oil from wastewater streams 5. Filter media
of sand, anthracite, plastics, graphite, etc., have all been
used with varying success.
r t u P
98 Chemicals in the Oil Industry
Granular media filtration is more appropriate for solids
removal from wastewater, though its use in de-oiling is
claimed to be efficient. 6

Oil removal is proposed to be by separation of the oil


and solids in the upper layers of the filter bed followed
by enhanced coalescence of the solids-free oil droplets.
The coalesced oil tends to remain floating in the upper part
of the bed until the filter is back-washed. Addition of
polyelectrolytes has been shown to improve the performance
of this process significantly.
A number of other processes have been used with varying
success for~de-oiling wastewater and include: ultrafiltration,
coalescers and centrifugation. However, these are not applicable
for handling large volumes of water.
Chemical Enhancement of Oil-Water Separation Processes
Chemicals are frequently used to enhance the physical separation
processes described above. Since the most common type of
emulsifying surfactant found in reverse emulsions are anionic
and non-ionic it is not surprising that cationic polyelectrolytes,
or blends of these with inorganic salts, are found to be
extremely effective in destabilising emulsions and improving
process efllciency.
The mechanism of action of these chemicals is proposed
to be: adsorption at the interface followed by charge
neutralisation and/or interparticle bridging. This destabilises
the colloidal particles and allows their agglomeration or
flocculation and subsequent separation from the bulk phase.
Inorganic Coagulants
Metal salts which are used as coagulants include zinc,
aluminium, and iron salts. In water these hydrolyse to form
insoluble hydroxides. These precipitated hydroxides provide
the charges needed to neutralise the charge on the colloidal
particles, and form flocs which enmesh the particles.
These metal salts are particularly sensitive to changes in
pH and alkalinity. The flocs which they form tend to be easily
re-dispersed, and tend to generate large volumes of sludge
which may cause a disposal problem.
r t u P
Oily Wastewater Treatment in the Production ofCrude Oil 99
Organic Polyelectrolytes
The use of metal salts has declined over recent years with
the advent of water-soluble organic polymers. These are long-
chain macromolecules made by linking together synthetic
monomers, some of which carry electrical charge or contain
groups which can be ionised.
The important characteristics which govern the effectiveness
of these polyelectrolytes are:
i . the mol e cuI a r we i g h t Le.
J c ha i n 1 en g t h
ii . ch a r get y pe, Le. non - ion i c, ani 0 n i c, 0 rea t ion i c
i i i. c h a r g e den sit YJ i.e. ch a r g e per un i t we i g h t 0 f poly mer
The m09t widely used non-ionic polymers are polyamides
which vary in molecular weight from 10 6 _ 30x10 6 .
e.g.

polyacrylamide

Anionic polymers carry a negative charge, an example being


the co-polymer

acrylamide acrylate salt


The functional group providing the negative charge centre is
the carboxylate anion which at normal pH ranges is the
predominant form. The ratio (x/y) will determine the charge
density on the polymer chain.
There is a large variety of cationic polyelectrolytes
available commercially, ago Polyamines, polyquaternaries,
polydiallyldimethylammonium chloride, co-polymers of
acrylamide, and dimethyl aminomethyl methacrylate etc.
An example of a cationic polymer is the condensation
product of an amine with epichlorhydrin.
r t u P
100 Chemicals in the Oil Industry

e-g.
-7-(CH 1
H N-'CH 'NH
)n- N
H
-r H
tCH1 )n-.l.-
H N-(CHJ- NH ____
2 \ ~n n

The charge on the polymer chain is carried on the nitrogen atoms


which mayor may not be protonated depending on the pH,

R,+
"N - Hl.
RI
amine amine salt
These polyamines may be further reacted to form quaternary
ammonium ~alts which are permanently charged,i~. in a
quaternised polymer the charge density is independent of pH.
e.g.
R
1

R2 -
'+
N-
I
R3 Cl

R
4
These polymers are available in a number of physical forms,
the low to medium molecular weight usually as solutions, but
as the molecular weight is increased the viscosity of the
polymer solution increases and for these it is normal to
use an emulsion or dispersion polymer. Solid polymers are
available commercially but not widely used in the oil-field.
Effect of Charge Density on Polymer Performance
In an effort better to understand the mechanism of emulsion
destabilisation, a study was made of the effect of charge
density on the performance of polyelectrolytes in a number
of wastewater treatment processes.
The polymers used were a series of polyquaternary
ammonium compounds (C23,C35,C55 and C ) quaternised to
76
varying degrees in order to vary the charge density on the
polymers. The charge density or mole % quaternised was 23,
35, 55, and 76 mole % respectively and the molecular weight
was essentially constant at rV10 6

Zeta Potential Studies


The Zeta potential of colloidal silica was measured using a
r t u P
Oily Wastewater Treatment in the Production a/Crude Oil 101

1
100mgl- dispersion of 1 .11J.m particles in deionised water
buffered at pH 8 with ammonium chloride. Measurements were
made as a function of polyelectrolyte dose for each of the
four polymers.
60
A-
t 40
C7~ C
S8
/& EJ--
zeta
20 ;JJ ~
Potent al
- &. G
I-~//~'----,'/-----'--,--,../-...-..-.-....,----"-
. (iJr J!
mv
o

-20 <if/ 0.2 / '

0
0.3

Dose polymer ppm


0,4

--+

-40 11 ~ 0/
- 60
~ Figure

The results are shown in Figure 1. The dose of polymer required


to neutralise the charge on the particles decreased as the
charge on the polymer increased,up to 50%. At 50%, further
increase in the charge density does not produce any further
appreciable decrease in the dose of polymer required for
charge neutralisation.
Adsorption Studies
Size-graded silica sand, 70-80 mesh D.S. sieve, was thoroughly
washed, filtered, dried and its specific surface area measured
using the BET method.
Equilibrium adsorption isotherms were measured for C
23
and C on silica sand after contacting the polymer solutions
76
for 24 hours. Equilibrium polymer concentrations were determined
using DV adsorption spectrophotometry at 270 nm.
The equilibrium adsorption density of the low charge
density polymer, C , was much greater than for C , and was
23 76
found to increase as the ionic strength of the polymer solution
r t u P
102 Chemicals in the Oil Industry
increased. Using the adsorption density, the specific surface
area of the sand, and the molecular weight of the polymer,
the effective surface area of the sand covered per polymer
molecule was calculated. At low ionic strength this gave
1 . 6 x1 06 A2 for C and 4.5x10 5 A2 for C .
76 23
Induced Air Flotation Studies
A laboratory scale induced air flotation unit was used to
study the effect of polymer structure on IAF de-oiling of
a synthetic emulsion of oil in water. The unit consists of
a 3 litre bowl in which there is immersed a variable speed
rotor. The vacuum created by the impellers of the rotor pulls
air down a standpipe, where it is sheared through a diffuser
into small bubbles which float to the surface. Blank runs
were carried on the emulsion without polymers.

I
90
CV

1 80

70

Residual
60
Oil
and
Grease 50

ppm
40

30

20

10

10 20 30 40

Dose polymer ppm


r t u P
Oily Wastewater Treatment in the Production ofCrude Oil 103

The flocculated oil which floated to the surface was


skimmed for 3 minutes. The oil and grease level in the
underflow was measured by Freon extraction and I.R. absorbance
measurement at 3.4~m. Runs were made with the oily water
treated with C , C and C at various doses. The oil
23 33 i6
removal efficiency was measured at each dose and the results
are shown in Figure 2.
The most highly charged polymer C gave the lowest
76
residual oil level at the lowest dose, 7-8ppm. C
33
optimised at 15ppm and the lowest charge density polymer
needed 25ppm to optimise its performance. The form of the
performance curves also varied as the charge density decreased.
The curve f6r C was very deep and the performance curves
76
became shallower as the charge density reduced to 23 mole%.
Sedimentation Studies
The conventional stirred jar tests for sedimentation of solids
was carried out on turbid river water. One litre samples were
dosed with polymers, rapid mixed for 30 seconds, slow mixed for
1 minute and allowed to settle for 30 minutes. The supernatant
was then sampled and the turbidity measured using a Hach
Turbidimeter; results are shown in Figure 3.

60

r 50 C
33
Turbidity
NTU
40

C,23

30

20

S 10 lS 20 2S

Dose ppm -----.


r t u P
104 Chemicals in the Oil Industry

The results closely parallel the Zeta Potential measurements.


As the charge density increased the minimum of the performance
curve moved to lower dose of polymer: C ~20ppm, C N15ppm
23 33
with C and C giving almost the same performance with a
58 76
minimum of ~ 1 Oppm. As the charge densi ty increased, the
treatment range decreased.
Filtration Studies
A pilot scale upflow filter containing silica sand was used
to filter turbid river water at a flow rate of 7.0gpm/ft 2

The differential pressure across the filter and the residual


turbidity in the effluent were monitored. At the end of each
run the sand media was thoroughly back washed and cleaned
by air scouring and flushing twice. Polymers were i~ected

as 1% solutions immediately upstream of the filters.


Data for C and C are shown in Figures 4 and 5.
76 23

-1
g
/16.0m l
100

10.6mgl- 1
f 80
/
EJ/ ..J

~
Turbidity
NTU

60

Px10psi

40

10.6mgl- 1

20

2 3 4 s
Time hours -..
r t u P
Oily Wastewater Treatment in the Production ofCrude Oil 105
The criteria used to evaluate filter performance were:-
a) Rapid reduction of effluent turbidity to 1NTU, and
maintenance of this quality for the length of the filter
cycle.
b) The differen tial pressure across the bed, /::;. P, should
not increase rapidly i~. maximise filter cycle time.
Without chemical addition the turbidity removal was
maximum 10-20%. Addition of 10ppm of C gave good performance
76
for about 2 hours at which point 'breakthrough' occurred.
Increasing the dose to 16ppm gave good quality water for almost
six hours at which time the ~P limit of 6psig was reached and
the run terminated.
The other polymers were all tested under the same conditions
and at the same dose of 16mgl- 1 .
-1
47mgl

100
16mgl- 1

t 80
16mgl- 1
Turbidity
NTU
60

Px10psi

40

0

20 0 ~~
/,O~ ~O 0
~ooo-

1 2 345 6 7 8

Time hours -----.


r t u P
106 Chemicals in the Oil Industry
Dosing C at 16ppm, Figure 5, never achieved the desired
23
effluent quality, and the rate of head loss development was
very slow. Increasing the dose to 47mgl- 1 to give an
equivalent cationic charge dose gave adequate performance
for almost two hours. At this point breakthrough occurred
and the effluent quality deteriorated rapidly. The rate of
head loss development increased rapidly on increasing the
polymer dose to 47mgl- 1 .
Treatment with C at 16~pm only gave good performance
33
for 2~ hours. Normalising the dose on a charge density basis
gave good performance in terms of solids removal but gave
a much faster rate of head loss development.
Dosing at 16ppm gave almost equivalent performance to
that of C with a slightly reduced cycle time. Increasing
76
the dose of C to normalise the charge dose improved the solids
58
removal but once again increased the rate that ~p increased, and
hence decreased the cycle time.
Discussion
Equilibrium adsorption densities and calculated values of the
relative surfaces of polymers C and C on silica sand
23 76
correlate well with the rates of the doses required to
neutralise the surface charge on colloidal particles. Zeta
pot e n t i a 1 d a t a in d i cat e t hat a 1 i mi tin g v a 1 u e ex i s t s, ab 0 v e
which increasing the charge density on the polymer further
does not produce a proportionate ability to neutralise particle
charge.
If the mechanism of action of the polymer in the applications
examined is primarily adsorption followed by a charge
neutralisation, then the data indicate that the more highly
charged the polymer, the lower the dose required to optimise
the polymer performance. Also, the greater would be the
tendency of the polymer to 'overtreat' since if the polymer
had higher than this limiting value of charge density, the
'excess' charge per polymer chain will tend to re-stabilise
the dispersed particles if more than the optimum dose is
applied.
r t u P
Oily Wastewater Treatment in the Production ofCrude Oil 107

In all the applications studied it was found that, the


higher the charge density,the more effective the polymer is.
Further,for flocculation and induced air flotation the
highest charge density polymer tends to have a much narrower
treatment range,L~ a greater tendency to 'overtreat'.
In the case of filtration where the removal mechanism
for particles is proposed to be a two-step process, transport
of the particle to the media surface followed by attachment
via the polymer, the results indicate that the attachment
step required a minimum critical charge density on the polymer
before the deposited solids can withstand the high hydraulic
shear within the filter-bed.
Summary
The processes described above for treating oily wastewater can
all be enhanced by the addition of an appropriate chemical.
Selection of a chemical treatment programme and optimisation
of the process can be achieved by use of laboratory tests
followed by full scale plant trials. These should be closely
supervised and monitored.
The data presented on polyelectrolytes illustrates the
importance of charge density as one parameter which determines
their efficiency in various water treatment processes.

References

1. D.O.E. Pollution Paper No. 6, H.M.S.O., 1976.


2. Manual on Disposal of Refinery Wastes, Volume on
Liquid Wastes, Chapter 5, American Petroleum
Institute, Washington DC, 1975.
3. G.J. Iggleden, Chemistry and Industry
November 1978, 826.
4. R.J. Churchill and K.J. Tacchi, Water 1977,
AIChE Symposium Series 178, ~, 1978, 290.
5. G.E. Jackson, Crit. Rev. in Environmental Control,
1980, 2-.Q., 339, and 1 980 ~, 1.
6. R.A. Boze, C.C. Tyrie, R.K. Hummel, SPE Publication
7813, presented Production Operations Symposium
of SPE, Oklahoma City, February 1979.
r t u P
The Use of Ethylene-Vinyl Acetate Copolymers as Flow
Improvers and Wax Deposition Inhibitors in Waxy Crude
Oil
By G. W. Gilby
IMPERIAL CHEMICAL INDUSTRIES PLC, WELWYN GARDEN CITY, HERTFORDSHIRE, U.K.

Introduction

The majority of crude oils, if not all, contain a proportion of petroleum


waxes. The concentration, structure and molecular weight ranges of these
waxes vary considerably from one crude oil source to another, and, since
their boiling points also differ certain waxes occur, and indeed
concentrate, in different distillate fractions. The tendency of the
waxes to precipitate and crystallise as the oil cools during production,
transportation, storage or even subsequent use gives rise to a variety
of problems such as poor flow or in extreme cases gelation,
sedimentation, deposition on pipe and storage vessel walls, filter
blockages etc. These problems arewegl known within the industry and
have been widely reported elsewhere 1-

Control of Paraffin Wax Related Problems

Complete elimination of problems related to crystallisation of paraffins


during crude oil production by the obvious method of heating pipelines,
storage vessels etc is clearly not often economically viable. However
a variety of other techniques for the control of such problems do exist
so that at least they become manageable and the wax, and therefore the
problem, is transferred to downstream operations and/or products where
they may perhaps be more conveniently handled. Examples of these
alternati e techniques have been listed more comprehensively
2
elsewhere ,7 but include:-

(a) Dilution with low wax content crude stock or light distillates.

(b) Controlled thermal conditioning to take advantage of the natural


pour point depressing effect of resins etc which may be present in
the oil.

(c) Pigging of pipelines. This largely re-disperses deposits on


pipeline walls although some d~posit may be carried through the pipe
ahead of the pig.

(d) The addition of solutions of oil-soluble surfactants such as


polyolesters or amine ethoxylates. These possibly act partly as
dispersants for the wax crystals keeping them in suspension and
partly by modifying the surface characteristics of, for example, the
pipe wall as a result of which the wax crystals show less tendency
to adhere.
r t u P
The Use ofEthylene- Vinyl Acetate Copolymers 109
(e) The use of wax crystal modifiers. A variety of different additives,
usually polymeric, have been shown to modify the wax crystal size
and regularity which results in a reduced tendency to interlock and
form a gel and hence lowers the pour point of the oil, ie they act
as pour point depressants. Materials which act in this way include
polyalkyl acrylates and methacrylates, low molecular weight
polyethylene waxes, certain aromatic-paraffin wax condensation
products and ethylene-vinyl acetate copolymers.

The preferred technique, or indeed combination of techniques, for


treating any crude oil will depend on a great many factors and it is
beyond the scope of this paper to discuss these. Suffice it to say
therefore that economics are paramount and these can be dramatically
influenced by such factors as location, climatic conditions, topography,
availability of materials and energy and also the efficiency of the
response of the particular crude oil to the various available techniques
or chemical treatments. This paper is concerned with the use of
ethylene-vinyl ac~tate (EVA) copolymers as wax crystal modifiers and, in
particular, the s'tructural and other factors which can influence the
selection of the preferred EVA copolymer for any particular oil.

Petroleum Waxes and Mechanism of Crystal Modification

Types of Wax. The waxes occurring in crude oils are very complex
mixtures of normal paraffins, branched or isoparaffins and cylcoparaffins
or naphthenes. These are simply illustrated in Figure 1. Although of
little practical relevance to the oil production situation where
precipitation and crystallisation is complex, it helps in the general
understanding if the basic characteristics of the two main categories of
wax extracted from crude oils are compared. These are listed in Table 1
and Figure 2 shows crystallisation exotherms measured by differential
scanning calorimetry (DSC) on some typical commercially available refined
paraffin and microcrystalline waxes. The individual base lines of these
curves, in this and all other similar figures showing DSC exotherms in
this paper, have, been staggered to minimise confusion of one curve with
another. Similar crystallisation exotherms on waxy crude oil samples
where, at the commencement of the test, the waxes are in solution show
that crystallisation is delayed to a lower temperature and the
temperature range over which crystallisation occurs is very much broader.
This is of course to be expected. In practice the crystallisation
process is considerably influenced by many factors including shear and
thermal history and although observation of these exotherms provides some
information it is of limited practical use.

Wax Crystal Structure. In some circumstances close packed hexagonal or


triclinic lattices can be found but by far the most common paraffin wax
crystal lattice is orthorhombic, each chain having the fully extended
zigzag configuration. The ideal crystalline form is as thin rhombic
plates although long needles also form during crystallisation from crude
oil. Microcrystalline waxes also form thin plate-like crystals although,
as their name implies, their size is much smaller due to the steric
hindrance of the side branches and cyclic groups restricting crystal
growth. These smaller crystals show much less tendency to interlock and
form a three dimensional network compared with the normal paraffins and
the problems associated with wax in crude oil production and
transportation are more usually, but not necessarily always, associated
with the larger crystal formations resulting from normal paraffins.
r t u P
110 Chemicals in the Oil Industry
CHJ CHJ CH J CHI C~ CHJ CHz CH J CtIz CH~

\/\/\/\/\/\/\/\/\/
C~ C~ C~ C~ C~ C~ C~ C~ c~

NORMAL PARAFFIN

c~ c~ c~ c~ c~ c~ ,~ c~ c~

/\/\/\/\/\/\/\/\/\
c~ c~ c~ c~ c~ c~ c~ c~ ~ c~

\
CHz
ISOPARAFFIN /
CHJ

CYCLOPARAFFIN

Figure Typical formulae of petroleum waxes

Table 1

Typical Composition and Properties of Commercially Available Paraffin and


Microcrystalline Waxes.

Paraffin Waxes Microcrystalline


Waxes

Normal paraffins (%) 80-95 0-15


Branched paraffins (%) 2-15 15-30
Cycloparaffins (%) 2-8 65-75

Melting point range (OC) 50-65 60-90


Average molecular weight 350-430 500-800
range
Typical carbon number range 18-36 30-60
Crystallinity range (%) 80-90 50-65
r t u P
The Use ofEthylene- Vinyl Acetate Copolymers 111

PARAFFIN WAX(M.PNTapprox.6SC)
PARAFFIN WAX
(M.PNT approx. SOC)

MICROCRYSTALLINE WAX
(M.PNT approx. 5SC)
MICROCRYSTALLINE WAX
(M.PNT approx. 8S-C)

t
dH
dt

1
Scale [- 2 m cal sec

Coating

80 60 40 20 o -20
Temperature (OCl

Figure 2 Crystallisation exotherms of different refined petroleum waxes


r t u P
112 Chemicals in the Oil Industry
Mechanism of Crystal Modification. An important common feature of the
wax crystal modifiers mentioned above is that they all include within
their structure crystallisable polymethylene segments identical with the
basic paraffin wax chains. This is illustrated in Figure 3 for ethylene
vinyl acetate copolymers. These polymethylene se~ents can crystallise
within the polymer network itself to give crystalline regions or
crystallites, as they ~re sometimes known, and it has been shown, at
least for polyethylene and ethylene-vinyl acetate copolymers, that the
lattice form is also orthorhombic, ie identical with that most common in
paraffin waxes. This common crystal structure between polymer and wax
clearly plays an important role in the mechanism by which the growth of
the paraffin wax crystal is modified. Although not studied by the author
it can reasonably be assumed that the other wax crystal modifiers
mentioned above which contain polymethylene segments also exhibit the
same orthorhombic crystal form.

, I
I CH, CHz CH, CH, C:i z CHz C~
i l \ / \ 1 \ / \/\1\/1\
,CHz CHz CH, CH, CH, CHz CH, I
I I
I I
C~ C~ C~ C~ C~ C~ C~ C~ c~ C~ C~ c~ c~
/ \ / \ 1 ) / \ / '-I \./ \ / \ / \ / ~ / \ / \ / \
CH CKz iCH, CH, CHz CHz CH, CH, CHz I CH, CH, CH
/ I I /
o'
C~ C~ C~ C~ C~ C~ C~
I
C~ 0
\ C=1 /\/\/\/\/\/\/\/~
: CH, c~ CH, CH, CH, CH, C~ I
\
C:0
/
C~
J
I
I /
C~
I I
AMORPHOUS: CRYSTALLINE REGIONS : AMORPHOUS
REGION , J REGION

Figure 3 Close packing of the po1yethy1ene parts of the chain enabling


crystallisation and the disruptive effect of vinyl acetate groups

The exact way in which crystal modifiers operate is not absolutely clear
but it is a~most certainly a combination of different mechanisms
involving both nucleation and either co-crystallisation or absorption.
In order to achieve any effect the additive must be in solution in the
crude oil at a temperature at which at least some proportion and
preferably the major part of the offending waxes are also in solution.
As the oil cools the waxes and the additives crystallise out within the
same temperature range. Nucleation of crystals by crystallisable
polymethylene segments of the polymer is believed to lead, to the
formation of a large number of wax crystals. The growth of these
crystals is then subsequently arrested by the incorporation into the
lattice of further polymethylene segments of the additive whose bulky
substituent groups prevent further incorporation of molecules of the
paraffin. It also seems likely that the polymethy1ene segments of the
additive actually build onto the wax crystal as a result of nucleation by
the wax crystal itself. In order to achieve the maximum affect on wax
crystal growth it is desirable that molecules of the modifying additive
continue to precipitate from the crude oil throughout the whole period
during which the wax is also precipitating. To achieve this it is
sometimes useful to use blends of additives having slightly different
r t u P
The Use ofEthylene- Vinyl Acetate Copolymers 113

solubility characteristics. Melt crystallisation exotherms of the active


ingredients of two commercially available crude oil flow improvers of
different chemical types are shown in Figure 4 - that based on ethylene-
vinyl acetate copolYmer confirming the use of the blending technique.

POLY METHACRYLATE

EVA COPOLYMER BLEND

dHt
dt

Scale L
[
1m cal sec
-1

Cooling

Ba 60 40 20. 0 -20
Temperature ee)
Figure 4 Commercial pour point depressants- crystallisation exotherrns
r t u P
114 Chemicals in the Oil Industry

Structure and Properties of Ethylene-Vinyl Acetate Copolymers

General. The range of properties available from ethylene-vinyl acetate


copolymers is exceptionally wide and this has led to large scale usage
in many different industries. In the treatment of crude oil the
relevance of crystallisation and solution characteristics has already
been mentioned and discussion of structure/property relationships here
will be largely restricted to those having an influence on these
properties. It also follows that products which are either non-
crystalline or largely insoluble in oils are of doubtful interest and
will limit the range of EVA copolymers suitable for crude oil treatment.
The main structural features of EVA copolymers which have an influence on
their properties are:-

comonomer ratio (or, as more usually expressed, vinyl acetate content)


average molecular weight
short chain branching
long chain b;ranching
molecular weight distribution
distribution of vinyl acetate groups

A more detailed discussion of the influence of each of these on general


properties may be found e1sewhere 10 For crude oil treatment only the
first four of these need be considered since it is these that have the
main influence on their crystallisation and solution characteristics.
The fifth, molecular weight distribution has, for practical purposes,
almost no effect on either of these properties. Although the sixth,
distribution of vinyl acetate groups, would be expected to have some
effect, in fact, the polymerisation of ethylene with vinyl acetate
proceeds in such a completely random manner that it is not easy to
exercise control over this aspect of their structure. This means that
statistically, EVA copolymers of the same vinyl acetate content have more
or less the same distribution of vinyl-acetate groups within their
structure. Hence this may also be ignored for the purposes of this
paper.

Comonomer Ratio or Vinyl Acetate Content. This is one of the two most
important factors which control all the properties of ethylene-vinyl
acetate copolymers, the other being average molecular weight which is,
of course, discussed below. As vinyl acetate content increases, three
important trends can be identified. Firstly degree of crystallinity is
reduced, secondly polarity of the polymer increases and thirdly, at very
high levels of vinyl acetate, chain stiffness is increased by steric
hindrance. However, as far as crude oil treatment is concerned, it is
the first of these that is of most importance. The relationship between
crystallinity and vinyl acetate content of EVA copolymers is shown in
Figure 5. Crystallisation exotherms measured by differential scanning
ca10rimetry on EVA copolymers having different vinyl acetate contents are
shown in Figure 6. It is interesting to note that the peaks of these
exotherms span the range for petroleum waxes. From the foregoing
discussions on wax control it follows that this ability to control
polymer crystallinity, and indirectly the temperature range over which
crystallisation occurs, by altering vinyl acetate content is of
considerable significance. It is of equal importance that this reduction
in crystallinity is, not surprisingly, accompanied by a corresponding
increase in solubility due to the increased amorphous content of the
r t u P
The Use ofEthylene- Vinyl Acetate Copolymers 115

o 10 20 30 40 50
VINYL ACETATE CONTENT~)
Figure Relationship between vinyl acetate content and degree of
crystallinity for EVA copolymers

copolymer. This is illustrated in Table 2 by comparing the pour point of


5% solutions of various EVA copolymers in toluene. The reasons for
choosing this method of comparing solubility will become clear later in
this paper.

Table 2

Pour Point of Solutions of 5% of Different EVA Copolymers in Toluene.

EVA Copolymer Characteristics

Pour Point
Vinyl Acetate MFI Hydrocarbon Branches per (OC)
Content 1000 Carbon Atoms
(% by weight)

24 20 7 7
33 25 6 2

28 6 6 9
28 400 9 2

28 400 9 2
28 400 19 -5
r t u P
116 Chemicals in the Oil Industry

18%VA

12.S%VA

dHl
dt

-1
Scale - 1 m cat sec
[

Cooling

80 60 40 20 0 -20
Temperature C

Figure 6 Effect of VA content on crystallisation exotherms of EVA


copolymers

EVA copolymers containing less than about 15% of vinyl acetate by weight
tend to be comparatively insoluble unless their molecular weight is also
very low and these latter products are comparatively costly. For this
reason EVA copolymers containing from about 18-40% vinyl acetate are of
most interest in crude oil treatment and in fact products containing from
25-40% VA are the most commonly used.
r t u P
The Use ofEthylene- Vinyl Acetate Copolymers 117

Average Molecular Weight. As with vinyl acetate content, average


molecular weight has a very considerable influence on many of the
properties of EVA copolymers. However, degree of crystallinity is an
exception to this, there being no significant difference between EVA
copolymers of widely differing molecular weight provided vinyl acetate
content and other structural features such as chain branching are
identical. Molecular weight does however, as would be expected, have a
significant influence on solubility characteristics: the higher the
molecular weight, the poorer its solubility in oils and other organic
solvents. This is also illustrated by means of solution pour point in
Table 2. Products having number average molecular weights in the range
10,000 to 30,000 appear to be of most interest in crude oil.

Figures for molecular weight are in fact rarely quoted for polymeric
materials and for EVA copolymers it is standard international practice
to follow the melt flow rate or melt flow index (MFI) procedure of
classification using International Standards Organisation Test Method
ISO R292. This is a ram extrusion viscosity measurement carried out
under standardised conditions which gives a value which is inversely
related to molecular weight. This method of describing the molecular
weight of EVA copolymers will be adopted in this paper. Table 3 shows
the approximate relationship between MFI and number average molecular
weight.

Table 3

Relationship Between MFI and Approximate Number Average Molecular Weight


of EVA Copolymers.

MFI Approximate Number


Average Molecular Weight (Mn)

2 32,000
20 24,000
200 19,000
400 13,000

Short and Long Chain Branching. The influence of hydrocarbon chain


branches on the properties of EVA copolymers is, as might be expected by
comparison with isoparaffin and cyc10paraffin waxes, largely associated
with their disruption of the crystallisation process. The main
hydrocarbon branches in EVA copolymers are alkyl and the disruption
increases with number of carbon atoms up to about six. Chains longer
than this can themselves become part of the crystalline network and are
those defined as long chain branches. Although these long chain branches
do have an influence on some properties of EVA copolymers other than
crystallisation, these effects are in fact irrelevant to the present
subject. In addition short chain branches generally outnumber long chain
branches by some 20-25 to 1 and hence, for the purposes of this paper, it
is not necessary to distinguish between long and short chain branches.
r t u P
118 Chemicals in the Oil Industry
The most common side chains found in EVA copolymers are methyl, resulting
from the frequent use of propylene as chain transfer agent, and butyl,
produced by intramolecular chain transfer. Other chain lengths such as
ethyl are also found. A useful quantitative comparison of the influence
of chain branch length or other substituent group on crystallinity has
been given by Salyer and Kenyon l l . This compares the disruptive
effect of these various branches in terms of the number of main chain
carbon atoms on each side of the branch point over which crystallisation
is prevented. For methyl branches this is 3, for butyl 4 and for acetoxy
groups resulting from the copolYmerised vinyl acetate it is also 4. It
can readily be seen from this that the influence of including an
additional side branch is far greater than increasing the length of an
existing branch and hence for the purposes of this paper it is sufficient
to consider only number of branches and not to distinguish their
individual lengths. The influence of chain branching on crystallinity is
illustrated in Figure 7 in which crystallisation exotherms of two EVA
copolYmers, having identical vinyl acetate contents and molecular weights
(MFIs), but differing in total number of side chains are compared. The
area of each exotherm approximates to the amount of crystallised polymer.
This difference in degree of crystallinity is of course also reflected
by a difference in solubility characteristics and this is again shown in
terms of effect on pour point of 5% solutions in toluene in Table 2.

19 Chain Branches
9 Chain Branches

dHt
dt
Scale [= 1 m cal. sec'
VA Content 28 %
MFI 400

80 60 40 20 0 -20
Temoerature (OC)

Figure Effect of hydrocarbon chain branching on crystallisation


exotherms of EVA copolymers
r t u P
The Use ofEthylene- Vinyl Acetate Copolymers 119

Simple Laboratory Tests for Initial Screening of EVA Copolymers as Wax


Control Additives

No single laboratory test is capable of determining the best wax control


additive for a particular crude oil. Indeed, because of many complex
interactions, different crude oil compositions and different oil field
production conditions, laboratory tests can only be used for initial
screening. Final selection of the most cost effective additive must
depend on the results of pilot plant experiments and actual field trials.
Nevertheless such laboratory tests do provide a useful pre-selection
guide such that additives unlikely to give useful effects may be
eliminated and only those shQWi~ginitial promise are evaluated at the
much more costly pilot"or production stages.

Pour Point. This is an internationally known test method which, as its


name implies, relates to the temperature at which the oil is just
pourahle. Several different pour point values can be quoted for anyone
oil sample, eg mifiimum pour point, maximum pour point, etc. These
differences result from different heat treatment or pre-conditioning of
the oil sample and other procedural differences such as cooling rate and
temperature of addition of any additive. Ouite clearly such differences
can dramatically influence the crystallisation behaviour of the waxes and
additives and as a consequence widely differing pour point figures can
be obtained on the same oil sample.

The basic procedures for pour point determination are described in


international specifications and need not be detailed here. The results
quoted in this paper have been determined in accordance with these
procedures except that the oil samples have been conditioned at, and
additive doping has taken place at, a temperature approximating to that
of the crude oil at the well head. By using this procedure an indication
whether or not the additive is effective over the temperature range
encountered in production is obtained. Indeed actual experience has
confirmed the value of this procedure in initial screening programmes
using EVA copolymers.

Viscosity and Yield Stress. The viscosity of the crude oil during its
passage through a pipeline for example is clearly important. In
particular, throughput rates and energy consumption, and therefore
production costs, are obviously directly related to it. Laboratory
dynamic viscosity measurements give valuable information on this.
However, in many situations, arguably it is the yield stress of the oil
in the event of solidification (or gelation) which is of most
importance, since it is this which governs the ability to restart flow
after a production stoppage. For the purposes of. this paper emphasis has
therefore been placed on this aspect.

There are several techniques available for determining yield stress using
rotational viscometers or miniature pipelines but these tend to suffer
from certain disadvantages. In particular, the equipment is usually
comparatively expensive. There is also a risk of obtaining false
readings due to unseen contraction of the oil away from a critical
surface and further the time required to obtain statistically sound
results can be very lengthy.
r t u P
120 Chemicals in the Oil Industry

A very simple test which overcomes these limitations involves the use
of glass tubes say 100-200 mm long by 10 mm internal diameter. In this
test several samples, usually not less than 10, of each crude oil are
conditioned, cooled and sheared as appropriate above the pour point. The
glass tubes, sealed with a cork at one end, are then filled to a length
of approximately 100 mm with the crude oil. Cooling and conditioning is
then continued, obviously without shear, as required. Typically this may
involve cooling from about 35C to 4C over a period of several hours
followed by storage for 72 hours at this temperature before conducting
the test. The yield stress is simply measured by applying air pressure
to one end of the tube and recording on a manometer the pressure at which
the gelled slug of oil starts to flow. By testing a large number of
samples it is possible to eliminate obviously erroneous results. Ouite
clearly this test is far removed from actual operational conditions but
nevertheless it has again proved of value in the initial screening of EVA
copolymers as oil flow improvers.

Wax Deposition Tests. No ~tndard wax deposition test exists although


several have been reported ' The equipment used in the wgrk reported
in this paper is similar to that used by Mendell and Jessen but has
been somewhat modified particularly with respect to control and
instrumentation. Figure 8 shows a schematic diagram of this apparatus.
With this equipment the oil product may be circulated through the
deposition cell under variable, but closely controlled, conditions of
time, temperature, flow rate and shear rate and the deposit on the cell
wall collected and weighed. The percentage reduction in deposit compared
with untreated samples of oil can be calculated using the following
relationship:

Stirrer Deposition cell


Chiller/Heat
Exchange
Cooling Jacket Unit

OilFlow-'

Oil
Reservoir

Coolant Flow

Thermostatically
Controlled Bath +- Drain Cock
Peristaltic
Pump

Figure 8 Schematic diagram of wax deposition test equipment


r t u P
The Use ofEthylene- Vinyl Acetate Copolymers 121

W - W
% Reduction = __u t x 100
Wu

where Wu is the weight of deposit from the untreated crude oil

and Wt is the weight of deposit from the treated crude oil

Results of Laboratory Screening Tests on a Variety of


Crude Oil Samples

Results of a number of pour point, yield stress and deposition tests


using different crude oils are presented in Tables 4 and 5. Study of
these, and many other results not presented here, together with some
knowledge of experience in the field, has led to the following
conclusions:

Simple laboratory tests of the type described in this paper are very
useful for initial screening of EVA copolymers for use as crude oil
flow improvers or wax deposition inhibitors.

Different crude oils react differently to different EVA copolymers and


it is often necessary to provide a special formulation for a
particular crude oil.

3 EVA copolymers having low levels of hydrocarbon chain branching are


usually more effective than EVA copolymers of similar vinyl acetate
content and average molecular weight (MFI) but containing higher
levels of hydrocarbon branches.

Field Experience

Published information on the use of EVA copolymers in crude oil


production is sparse. This is perhaps one result of the patent
situation briefly mentioned below. EVA copolymers are nevertheless in
use in various parts of the world for both flow improvement and the
inhibition of wax deposition. It is therefore considered to be of
interest to provide some information on one situation where an EVA
copolymer has been in use successfully, without problems for several
years.

The oilfield in question is located in Eastern Europe and the crude oil
has a pour point of l8-20C. This oil is required to be pumped through
a subterranean pipeline 70 kilometres in length. Winter soil
temperatures are 4c and the operator specifies a maximum pour point of
OC during winter to give a reasonable margin of safety. Laboratory pour
point tests showed that the addition of 100 ppm of EVA copolymer
containing 28% of vinyl acetate and having an MFI of 400 readily met this
requirement. In this case copolymers with a high level of chain
branching were selected since the copolymer solution, in a mixed aromatic
solvent, is pumped through a small diameter pipe 2.5 kilometres in length
and it therefore also needs to exhibit a low pour point. This solution
is added to the crude oil in a mixing tank which collects the output from
several wells. In practice the dosage rate of the active ingredient is
varied depending on the climatic conditions and is typically 20 ppm
during the summer and 100 ppm in winter. Throughout several years
operation no flow problems have been encountered either during rer.ular
production or on re-starting after stoppages.
r t u P
122 Chemicals in the 0 it Industry
Table 4 Effect of Different EVA Copolymers on the Pour Point of
Various Crude Oils

1 J 1
1 EVA Copolymer Characteristics 1 1
1 1 Addition 1 Pour Point
1 1 Rate of 1 (OC)
1 VA Content MFI Hydrocarbon 1 EVA to 1
1 % branches per 1 oil (ppm) I
1 1000 carbon 1 1
1 atoms 1 1
1 1 I
I 1
I Untreated Crude Oil 1 30
I 1
I 24 20 7 I 100 8
1,- 24 20 11 1 100 14
1 1
1 24 400 10 1 100 12
1 24 400 16 1 100 18
1 24 400 24 1 100 20
1 I
1 1
I 28 400 9 1 100 9
1 28 400 19 1 100 20
1 1
1 1
1 Untreated Crude Oil 1 8
1 1
1 24 20 7 1 25 1
I 28 400 9 1 25 -18
1 28 5 6 1 25 below -25
1 1
I 33 25 4.5 1 25 -23
1 33 45 8.5 1 25 -13
1 1
1 1
1 Untreated Crude Oil 1 -1
1 I
1 28 400 9 I 25 -26
1 28 400 19 1 25 -16
I 1
I 24 400 10 1 25 -22
1 24 400 16 1 25 -10
1 1
I I
1 Untreated Crude Oil I 21
I I
I 18 2 6 I 200 11
I 18 25 8 1 200 22
1 I
I 28 400 9 I 200 25
1 I
Table 5 Effect of Different EVA Copolymers on Pour Point, Yield Stress and Wax Deposition ~
of Various Crude Oils. ~

s:
~

EVA Copolymer Characteristics ~


I
EVA
I
I Pour Point
I
I Yield Stress
I
I Reduction
I g,
I ;:::s-.
(OC) ~
Copolymer I I (N/m2) I in I ~
VA Content I MP! I Hydrocarbon I Addition I I I Deposition I ;::

r
% 1 I branches per I Rate I I I (%) I 7
1000 carbon I (ppm) I I I I :s;::
atoms I 1 I I I ~
~
~
~
Untreated Crude Oil I - I 30 I 250 I - I E;-
I I I I I ~
24 20 I 7 100 I 8 35 40 I (J

t
I 1 1 1
.g
\:)
28 1 5 I 6 1 100 1 11 I 30 I 55 I ~
~
28 I 400 I 9 I 100 I 9 I 25 I 50 I ~
"""'I:
~
28 I 400 I 19 I 100 I 20 I 55 I 25
28 I 400 1 21 I 100 I 21 I 70 1 20

u
I I I I I I
33 I 25 I 5 I 100 I 15 I 45 1 -
I I I I I I
40 I 50 I 6 I 100 I 26 I 85 I 35
I 1
1 1
- -

P
Untreated Crude Oil 1 I 8 I
I 1 1 1
28 I 400 1 9 I 100 1 Below -25 I - I 80
I 1 I I
1 I
Untreated Crude Oil I - 1 -1
I I I 1
28 I 5 1 6 I 100 1 Below -25 1 - I 75
I 1 I I I
28 I 400 I 9 I 100 I Below -25 1 - 1 85
N
w
r t u P
124 Chemicals in the Oil Industry

Future Development

The use of EVA copolymers in crude oil is currently covered by patents


in many, but far from all, countries and this may have restricted their
exploitation in some circumstances. However, the earliest patents in
this field were filed many years ago and will expire within the next few
years in most countries. When considered within the time scale of oil
discovery to actual production this unexpired period is not long. It is
expected that this will stimulate efforts to develop the use of EVA
copolYmers in the field on a much wider scale. Indeed an increasing
awareness of the future potential for EVA copolymers can already be
detected, not only when used alone but also in conjunction with other
additives, where their combined use can give improved performance. All in
all an exciting prospect for a fascinating area of modern oil industry
technology.

Acknowledg_ement

The author gratefully acknowledges the helpful comments and information


provided by several colleagues and the permission of ICI (Petrochemicals
and Plastics Division) to publish this paper.

References

C A Bilderback and L A McDougall, J Pet Tech 1969, ~, 1151.

2 A Uhde and G Kopp, J Inst Pet, 1971, 1I, 63.

3 R C Price, J Inst Pet, 1971, ~, 106.

4 M Brod, B C Deane and F Rossi, J Inst Pet, 1971, 1I, 110.

5 J L Mendell and F W Jessen, J Can Pet Tech, 1972, 11(2), 60.

6 P B Smith and R M J Ramsden, Proc Eur Offshore Pet Conf, London 1978,
283.

W Smith, Oil Gas J, 1979, 12, Ill.

8 P A Bern, V Withers and R J R Cairns, Proc Eur Offshore Pet Conf,


London 1980, 571.

9 C W Bunn, Trans Farad Soc, 1939, ~, 482.

10 G W Gilby, Developments in Rubber Technology -3, Applied Science


Publishers, London, 1982, Chapter 4, p.101.

11 I 0 Salyer and A S Kenyon, J Poly Sci, 1971, ~, 3083.


r t u P
Water Scaling Problems in the Oil Production Industry

By K. S. Johnson
OILFIELD CHEMICAL SERVICES, 430 CLIFTON ROAD, ABERDEEN AB2 2EJ, U.K.

Types of scali'ng compounds found in oilfield production systems


are discussed with particular reference to physical environment
effects on scaling probability.
General calculation methods for predicting scaling tendency are
mentioned together with the static scale precipitation tests and the
relatively new dynamic capillary tube pressure drop increase or
blocking test.
Generic chemical types that are used as scale inhibitors are listed
and reviewed and the mechanism by which they act is touched on.
Areas of oilfield systems where scaling may create operational problems
and application usage of scale inhibitors to prevent scaling in these
systems are discussed.

Water is utilised in oilfield systems in water injection (secondary


recovery) to maintain reservoir pressure and to create a driving
force towards the production wells.
It is also produced along with crude oil as part of the IItotal
produced fluids". Initially it is present as formation water;
later, where secondary recovery ;s practised, water associated with
cru de oi 1 wi 11 be a mi xture of forma tion wa ter and returned i njecti on
water. Where practicable and certainly in all offshore oilfield
installations where water injection is carried out, the water used
will be seawater.
The chemistry of many of the waters encountered in oilfield operations
is such that low solubility compounds are present and under certain
conditions may precipitate out and form scale build up.
r t u P
126 Chemicals in the Oil Industry

The chemical composition of seawater varies in different parts of


the world. As an example, are given in TABLE 1 typical major
components chemical analysis of North Sea and Arabian Gulf seawaters.
It may be seen that seawater contains tons that in combination
could give rise to compounds known ~o have low so~ubility.
In the case of North Sea seawater this would be 1tmi'ted to Calcium
Carbonate (by the initial decomposition of bicarbonate). Other
ionic combinations (e.g. calcium sulphate, barium sulphate and
strontium sulphate) of low solubility are nevertheless nQt in
sufficient concentration to give rise to precipitation and hence
possible scaling.

TABLE
---------1

!y~!~~~_~~~Q~_~Q~~Q~~~I~_~~~tj!~~h_~~~~Y~!~_E.QB-~Q~I~_~~~

~~g_~8~~!~~_~kE_~~I~8

North... Sea
---_.~ --- ~r~,~!~,!2_ ~l f

Sodium (Na) 11000 13700


Potassium (K) 460
Calcium (Ca) 476 576
Magnesium (Mg) 1440 1670
Barium (Ba) 0.1 NIt
Strontium (Sr) 7 NIL
Iron (Fe) 0.05 NIL

Chloride (Cl) 19900 24500


Sul phate (50 4) 2725 3400
Carbonate (C0 ) NIL NIL
3
Bicarbonate ( HC0 ) 145 159
3
Hydroxyl (OH) 1~IL NIL
Total Dissolved Salts 35000 44000
pH 7.8 7.8

All data as mg/l except pH.


r t u P
Water Scaling Problems in the Oil Production Industry 127

It should be noted however that the fact that a chemical compound


is precipitated from solution under a particular prevailing set of
conditions does not automatically imply that it will form a scale~
i.e. it will deposit as a hard solid on the walls of pipework,
heat exchanger surfaces, valves and vessels etc. However, in
many cases where precipitation does take place, scaling occurs and
in consideration of water systems in oilfield operations it is
always prudent to consider scaling possibility seriously since
not to do so could be very costly, both in the replacement of
scaled up equipment or in the downtime involved in carrying out a
descaling operation.

Produced waters may be totally formation water (i.e. water that is


present within the rock formation), or may be a combination of
formation water and seawater which has been injected into the
formation via an injection well.
The poi nt in a well's 1i fe where injected seawater is fi'r'st found
with produced formation water is called "seawater breakthrough".
The time from start up of seawater injection to when water analysis
indicates that seawater has made it through the formation to a
production well will depend primarily on the reservoir geology and
. the rate of water injection; the time period can range from a
matter of months to several years.
Formation waters vary very considerably in chemical composition
even over limited areas. As an example, four produced water
analyses from areas of the North Sea are given in TABLE 2. It is
considered for each example that seawater breakthrough has not yet
occurred.
It may be seen that considerable variation in individual ionic
species concentrations and total dissolved solids can occur.
Examples 2 and 3 are analyses of produced waters from wells in
the same field, in fact wells on the same production platform.
It can be readily seen that ionic combination may suggest the
possibility of calcium carbonate scaling. Although barium and
strontium are present there is no sulphate (except for water (4)
which has 11 mg/l) and hence 110 possibility of barium or strontium
sulphate precipitation.
The picture may change markedly when seawater breakthrough occurs.
Seawater contains the order of 2725 mg/l of sulphate ion. Hence
with only a small percentage seawater breakthrough there is the
possibility of particularly barium sulphate precipitation. In
general where a water has both barium and strontium content,
despite the fact that strontium is considerably more soluble than
barium, if there is sufficient sulphate ion present and scaling
occurs then analysis of the scale will reveal principally barium
sulphate but some strontium. Strontium co-precipitates with
barium sulphate even at sub-solubility levels.
r t u P
128 Chemicals in the Oil Industry

TABLE 2
----------

2 3 4

Sodium (Na) 17280 9330 8370 29370


Potassium (K) 580 198 200 372
Calcium (Ca) 2890 460 240 2808
Magnesium (Mg) 310 56 52 504
Barium (Bat 5 42 43 252
Stronti urn (Sr) 195 40 46 574
I ron (Fe) 19 0.1 0.1
Chloride (Cl) 31950 14320 13000 52360
Su1 pha te (S04) NIL NIL NIL 11
Carbona te (C0 ) NIL NIL NIL NIL
3
Bicarbonate (HC0 3) 312 980 1100 496
Hydroxyl (OH) NIL NIL NIL NIL
Approx Total
Dissolved Sales 53541 25926 23051 86747

pH 6.74* 7.76* 8.2*


NOTE:

1. pH values at atmospheric pressure.


2. All data as mg/l except pH.
3. Waters 2 and 3 are from individual wells on the same productton
platform.

An example of seawater breakthrough may be seen in TABLE 3 where


the effect on formation water 4 (TABLE 2) from increasing percentage
seawater composition is calculated. It can be seen that at
approximately 6% seawat~r composition, the amount of sulphate
supplied in the seawater will be sufficient to satisfy the
stiochiometry of the reaction to produce barium sulphate. It can
also be seen that there is a mixed waters (formation + seawater)
ratio above which sulphate content is always in excess. With
increasing seawater breakthrough the actual quantity of barium and
strontium per unit of produced water volume decreases and hence the
potential rate of scale build up will also decrease.
r t u P
Water Scaling Problems in the Oil Production Industry 129

TABU:
---------3

Formation Water/Seawater Percentage Mixes mg/1


Analytical 100% 100%
I.-ormation Sea-
Parameters 95/5 90/10
Water 85/15 80/20 75/25 water

Barium 252 239 227 214 202 189 NIL


Strontium 574 546 517 489 461 432 7
Sulphate 11 147 282 418 544 689 2725

Stoichiometric
Ratio Ba: S04
(theoreti ca1=
1:0.7) 1:0.04 1:0.61 1: 1.24 1: 1.95 1:2.7 1:3.64 -

Excess S04 2-
after reacti on
with Barium (i.e.
available for Sr) NIL NIL 123 268 403 537 -
Stoichiometric
Ratio Sr:S04
(theoreti ca1 =
1: 1.09) - - 1:0.24 1:0.55 1:0.87 1: 1.24 -
-
NOTES:
1. There is sufficient sulphate ion for complete barium precipitation at 6%
seawater breakthrough.
2. There is sufficient sulphate ion to satisfy the stoichiometry of barium and
strontium at approx. 20% seawater breakthrough.
3. The ionic strength of the formation water is 1.56. Hence solubilities of
both barium and strontium will be higher than theoretical for a given
tempera ture.
r t u P
130 Chemicals in the Oil Industry

Mixed waters will also change the probability of calcium carbonate


deposition. TABLE 4 shows the effect of seawater breakthrough on
formation water (1) in TABLE 2.
The Langalier Scaling Index (see later for details) ha~ been calculated
for the pure waters and various combinations of their mixtures; the
temperature at which the index becomes positive (i.e. scaling may be
predicted) is also calculated.
GRAPH 1 shows these calculated data diagramatica11y.
It can be seen that at the temperature considered (85 0 C), which is
the bottom hole temperature (BHT) for the well in question, that both
individual waters would be predicted "scaling". The combination waters,
in every case, have a higher scaling index indicating relative
probability and severity of scaling. The worst case is when a 50/50
waters mix exists.
I~~k~ 1
~EE~~I_QE_~~~~~I~~_~~~~~I~8Q~~_Q~_~_EQ~~I!Q~_~~I~~:~~h~!~~_~~~~Q~~I~_Q~~Q~!I!Q~

Analytical SEAWATER/FORMATION \~ATER MIXTURES mg/l


Parameter
Re 1ated to 1OO~~ 100%
Scaling ormation 75/25 60/40 50/50 40/60 25/75 Sea-
Tendency Water \'.Jater

pH 6.74 7.02 7.19 7.3 7.41 7.58 7.86

Sodium 17280 15960 15168 14640 14112 13320 12000

Calcium 2890 2282 1918 1675 1432 1067 460

Magnesium 310 582 746 855 964 1127 1400

Barium 5 3.78 3.04 2.55 2.08 1.32 0.1

Strontium 195 148 120 100.7 81.8 53.6 6.4


Chloride 31950 28882 27042 25815 24588 22748 19680
Carbonate NIL NIL NIL NIL NIL NIL NIL
Bi carbonate 312 269 243 226 209 183 140
Sulphate NIL 662 1060 1325 1590 1987 2650

Scaling Index by !
Stiff Davis Extr
of Langalier
method +1.65 +1.80 +1.83 +2.13 + 1.88 +1.86 +1.68
Temp above
which SI +VE 30 0 C 23 0 C 23 C 23 0 C 20 0 C 20 0 C 280 C
r t u P
Water Scaling Problems in the Oil Production Industry 131

!
+-----+----+----+---+-----t------;.--.,...-O+-----+--
I ~ I i
: ~: 1 I'
I ' cfil (;\3'-
I o:~ I i
~. -_.:- -~._~ -.-- ~_.. ---1-- -------I J -- -,- ",f
i 5 ~JS:! I I I
I
I ''ll 9 2.lI
\'
\
I

I I'
!
i' I
I
"'I
I
"
~-----l-}----- -'-.~ '\ t-_' 'r--~-t--:---l-/!--+--'------'---4'-'--
l---.~-l--::--: 1-~--1~1 .1;/
', Jji 2~ I "i \}-l-/j
I \
~---+----i------+----+-'
----t----+------1o-~--!---
i ,! I I.
I 1,0 ~c."> ~ ,p 411' 50 -'P ..~ ~c
i l l !
~ 10

---.----- --- --_._-.,.------ ---+-- ..


I
I
I
~- ~

,-----1---'--
I
r t u P
132 Chemicals in the Oil Industry
0
From the scaling index calculated at 85 C is also determined the
temperature at wh~ch the waters first become scaling. The minimum
temperature is 28 C, that of seawater alone. It may be deduced
therefore that 3n a downhole situation where the temperature rgnge
will be from 85 C (bottom hole temperature) reducing to say 60 C
as the surface separation equipment scaling could be expected
throughout the system.
It is also in~eresting to note that,since seawater has a positive
index from 28 C,for seawater used in water injection systems
there is the possibility of carbonate scale ~mere water is used,
for heat exchange/cooling purposes, prior to injection into the
formation.

Knowledge of simple solution chemistry has been assumed but factors


that influence solubility of scaling salts may not be widely known
and therefore are briefly reviewed.
Key factors that may influence scaling probability in oilfield systems
are:
tempera ture
pressure
pH value
total ionic strength of the solution containing the scaling ions.

TABLE 5 lists the common scaling species and the physical conditions
that influence scale formation.

As mentioned earlier, since few waters contain carbonate ion the


potential for scaling comes from the initial decomposition of
bicarbonate by the reaction.
Ca(HC0 3)2 ~ CaC0 3 + CO 2 i +H 20.
The solubility of calcium carbonate in pure water is 53.0 mg/l (25 0 C)
In the presence of carbon dioxide the pH is lowered and the solubility
of calcium carbonate increases. Conversely if the carbon dioxide
concentration is reduced (e~. in a reducing pressure situation as ;n
a produced water passing through a well choke valve or a separator
vessel, or by injection seawater being deoxygenated by a vacuum
stripping tower) then the solubility of calcium carbonate decreases.
The effect of C02 partial pressure on the solUbility of calcium
carbonate for a range of temperatures is shown in GRAPH 2.
r t u P
Water Scaling Problems in the Oil Production Industry 133

TABLE
---------5

~~~Q~_~~~~!~_~~~~!~~_!~_Q!~E!~~g_~Y~I~~~_~!I~_!~Eh~~~~!~

E~Y~!~~~_E~~IQ~~

Calcium Carbonate Partial pressure CO 2 ,


Temperature.
Total Dissolved Solids.
Calcium Sulphat
as gypsum, hemi hydrate,
anhydrite Temperature.
Total Dissolved Solids.
Pressure.

Barium Sulphate Temperature.


Total Dissolved Solids.
Pressure.

Strontium Sulphate Tempera tu re.


Total Dissolved Solids.

GRAPH
---------2
EFFECT OF COz PARTIAL P(~ESSURE ON THE
SOLUBILITY Of CALCIUM CA.ROONATF.

120

100 -

00-

(,0
c~
PHESSURE
(BAR) 40-

20

--~i ----y----.,.------.-,-...---,-.~
1000 I~OO 2000 2~OO 3000 3500
SOLUBILITY OF CoCO~
(mo ILlTHE)
r t u P
134 Chemicals in the Oil Industry

An example of the effect of pressure change deposition is shown


in PLATE 1. The photograph shows scale deposition in a well
flow line. In this case there was at least an indication that
scale deposition could occur but none had been found downhole.
The high pressure drop accross the Christmas tree valve systems
was sufficient to "seed out" crystals of scaling species and the
immediate downstream flow line rapidly scaled up.
Temperature also has a marked effect on the solubility of calcium
carbonate. Contrary to conventional solubility behaviour. the
solubility of calcium carbonate decreases with increased temperature.
GRAPH 3 illustrates this effect at a fixed partial pressure of C02
in pu re wa ter .
Total disso1veu salts of the water containing the calcium carbonate
is also an important factor. Up to a TDS of approx 200,000 mgil
the higher the level of dissolved salts (excluding of course Ca 2+
or C03-2- /HC03-) the greater the solubility of calcium carbonate.
Above this TDS level no further enhanced solubility is observed.

PLATE 1 Photograph of Scale Deposition in Crude Flow L tne

Calcium sulphate (gypsum) scale may be found in some oilfield waters.


The reaction is simply
Ca 2+ + S042- ~ CaS0 4

Solubility in distilled water is given as 2080 mg/l (25 0 C). The


actual calcium sulphate molecular structure is dependent on temperature;
up to 40 0 C it is Ca S04 2H20, solubility increasing with increased
temperature. From 40 0 C to 1100C water of crystallisation is driven
off to form the hemihydrate and anhydrous salt.
r t u P
Water Scaling Problems in the Oil Production Industry 135

----------l
SOLUBILITY OF CaC03 AT I BAR
COl PARTIAL PRESSURE IN PURE WATER

1250

1000

750

SO~~~~1TY
(m~/I )
500

250

O~--"I--,--r-i
-'-~---r----.--~_--.
20 40 C:O 80 100
TEMPERATURE. QC

Over this range, solubility decreases with increased temperature. It


is therefore important to be aware of the operational temperature range
and whether the water is undergoing an upward or downward temperature
change.
The type of scale formed is generally hard and difficult to remove
once laid down. Simple inhibited acid treatment may be used for
calcium carbonate but passivation occurs when calcium sulphate removal
is attempted using mineral acids alone. It is generally necessary to
pre-treat with a "converter" (ammonium carbonate - to produce calcium
carbonate) before acid treatment.
Carbon dioxide partial pressure is not a factor in the precipitation
of calcium sulphate. The only real effect of a high C02 environment
is to hold calcium carbonate in solution thus leaving more calcium ions
free to combine as calcium sulphate.

Presence of dissolved solids TDS (other than Ca 2+ and 5042- ions),


increases calcium sulphate solubility as with calcium carbonate up
to a TDS of approximately 150,000 mg/1. Above this dissolved salts
va lue the solubi 1i ty of cal cium sul phate decreases.
GRAPH 4 shows the solubility of calcium sulphate at a range of salt
(NaCl) solution concentrations. The graph holds for temperatures
between 0 - 900C.
Increased pressure is found to increase solubility. There are
however at present no complete data on this effect. At very high
pres su res the effect is reversed and a decr'ease in sol ubi 1i ty occu rs.
r t u P
136 Chemicals in the Oil Industry

SOLUBILITY OF GYPSUM IN Noel BRINES


FROM ooe - 90C

8000

LEGEND
TEMP C
o 05
5
p 10
6 25
35
50
70
90

o~----..----r- i I
50 100 ,~o 200 250 300
NoCI CONCENTRATION
'--
(om/l) -1

Barium sulphate is one of the most insoluble compounds formed in


oilfield water systems. The reaction to form barium sulphate ;s
simply

Solubility in distilled water is quoted as 2.3 mg/l (25 0 C).


Solubility increases with temperature in the pure water and also in
brine solutions. For example the solubility of barium sulphate is
quoted at 2.3 mg/l at 250C and 3.9 mg/l at 95 0 C. For barium sulphate
in 5~ brine solution the figures are 20 mg/l and 42 mg/l respectively
for the two temperatures considered.
The converse is equally true; hence for waters at well bottom containing
barium and sulphate ions in solution as the temperature and pressure
decrease up the tUbing string and through the surface separation system,
precipitation of barium sulphate may occur.
The effect of temperature and ionic strength on the solubility of
barium sulphate is shown in GRAPH 5.
Pressure also increases solubility of barium sulphate; however, as
yet there are no pUblished data.
r t u P
Water Scaling Problems in the Oil Production Industry 137

,..-.------------_._--_._---_ _---- ..

SOLUBILITY OF BaS04 IN Noel SOLUTIONS

OOS04
SOLUBILITY
(moll)

o ----or-----_.,-.
L - ...
10
-------r.30
20
----~i-
40
IONIC STRENGTH

It can be seen that for say a mixed water containing barium and sulphate
ions that scaling may occur if the separate ionic concentrations are
above the values as defined by the key physical conditions. Hence
if barium is known to be present in the formation water and seawater
breakthrough has taken place then the probability of scale deposition
somewhere in the system should not be ignored. Failure to find
barium in the analysis of a produced water sample taken at the surface
facility in a water known to contain some barium must suggest that
precipitation has already taken place and the scale has already been
deposited downhole.

Strontium may under conditions~of high sulphate level precipitate


as strontium sulphate. The actual quoted solubility of SrS04 is
150 mg/l in pure water solution, up to an ionic strength of
approximately 1.3; the solubility increases to 750 mg/l after
which there is no appreciable increase. This effect is shown in
GRAPH 6.
Generally strontium sulphate scale is not found alone but in
combination with barium sulphate. Strontium sulphate is known to
co-precipitate with barium sulphate even under sub-solubility
conditions.
There is some increase in strontium sulphate solubility with
temperature rise although not as pronounced as with barium.
Pressure would seem to have no effect.
r t u P
138 Chenlicals in the Oil Industry

-------------------------_._---_._---
SOLUBILITY OF SrSO" IN No Cl SOLUTIONS t~T 25C

500

SrSO" 400
SOLUBILITY
(mQ/I) 300

200

100

------,-------,------T--- , -r
05 10 15 2-0 2-5
L- . . ...
IONIC STRENGTH . _ . . _ . _ . _ _. _ -

g~~~!'!!1i!}~~iQ!}_Qf_~rQ~~~i!l~~_Qf_~~l~_EQr'E~~iQ~_~~_~~l~~!~~iQ!}_
~~!bQ~~

The standard calculation method applied is the Stiff, Davis


modification of the original work carried out by Langalier. l ,2
The method extends the "Langalier Saturation Index" to apply to
high dissolved salt waters (oilfield 5rines).
The stability Index (SI) is determined, where
SI pH - pHs
pH actual pH of water
pHs the predicted pH value the water would attain when
saturated with calcium carbonate at a given temperature.
pHs K + pCa + p Alk
and hence SI = pH - (K+ pCa + pAlk)
where K is an empirical constant used to compensate for the
dissolved salts content and temperature. Dissolved salts
content is expressed as ionic strength.
r t u P
Water Scaling Problems in the Oil Production Industry 139

pCa = log
Mols Ca++/litre

pAl k log
Equivalents total alkalinity/litre

The details of the calculation procedure a~e not given here but are
presented fully in the literature.3,4
A positive SI value indicates that scaling is likely i.e. pH>pHs:
water is supersaturated with respect to calcium carbonate.
At SI = 0 the water is on its saturation point with respect to
calcium carbonate.
A negative SI value indicates that scaling is unlikely t.e. pH(pHs:
water is not saturated with respect to calcium carbonate.
It must be appreciated that the method is not absolute. A calculated
low order positive index water (say up to + 0.5) may not under some
conditions deposit carbonate scale; however the posibi.lity should not
be overlooked. For waters of higher positive SI value it would be
unwise to assume no scaling will occur and to take some form of
scale control measure.

The possibility of calcium sulphate scaling from waters is calculated


using the Stillman, McDonald, and Stiff Method. 5
The solubility of calcium sUlphate is effectively independent
of pH value. The method compares the theoreti'cal solubiltty of
calcium sulphate in the solution concerned at a given
temperature with the actual amounts of calcium and sulphate tons
present.
The calculated solubility of CaS04 in meq/litre liS"

S = 1000[(X 2+4K)O.5_ X]

where K is the solubility product constant (from ionic strength


and temperature)
X is excess corrmon ion diffet'ence (i .e. difference in Ca 2+ and S042-
ion concentration) in moles/litre.
If S is found to be less than the actual amount of CaS04 present
the. scaling is likely. Conversely for a ca'lculated value of S
greater than the actual for Ca504, scaling would not be predicted.
The method is fully detailed with calculation graphs etc in the
recommended reference books.
r t u P
140 Chemicals in the Oil Industry

The solubility of barium sulphate in water is v~ry low. Waters


that contain barium and sulphate ions should be treated with
concern. Dissolved salts content and temperature will affect
the solubility.
GRAPH 5 gives a basis for determination whether a calculated
barium sulphate content will remain in solution at the temperature
considered or will precipitate.

A graph of strontium sulphate solubility is given in GRI\PH 6.


Calculated strontium sulphate contents in waters under constderation
that are above the solubility curve would indicate that stronttum
sulphate d~position is likely. It should however be remembered
that strontium has a tendency to co-precipitate with barium sulphate
even at contents well within its normal solubility.

Er~~!i~~!_h~~2r~~2!:~_~~~b2~_2f_~~~!i~9_!~~~~~~t_E!:~~i~!!Q~_~~9
~~~!~_!~~i~i~2r_~~~!~~~12~

There are two basic methods in general use by oil and chemical service
companies.
Static Scale Precipitation method and the dynamic "Tube Blocking ll

technique.
The static precipitation method was developed by BP Research~ Sunbury;
the dynamic test method was originated by Shell Petroleum but has been
modified and improved by others.

The method is essentially a beaker technique whereby a formation water


(either real or synthesized) is mixed with seawater in a number of
volume ratios, generally from 90:10 to 10:90 formation water to
seawater. The pH values of waters to be mixed are adjusted to
6.0 prior to mixing. The mixed waters are held at a temperature of 70 0 e
for a fixed time neriod (usually 16 hours) after which each is separately
filtered through a 0.45 micron Millipore filter. The concentrations of
calcium, barium and strontium remaining in solution are then determined.
Tests are carried out on "blanks" (not containing scale inhibitor)
and then, if the intention is to identify the best inhibitor chemical, on
a number of potential candidate chemicals at a range of concentrations.
A plot of inhibitors efficiencies at a given dose level for the range
of water ratios considered will indicate the ranking of the chemicals
studied. By considering a range of dose levels the best performing
chemical and its optimum application level may be determined.
r t u P
Water Scaling Problems in the Oil Production Industry 141

The method is applicable to scale inhibitor performance evaluation


for calcium carbonate, calcium sulphate, barium sulphate and strontium
sulphate scaling either singly or in combination by preparation of suitable
synthetic water mixtures.

Variously modified testing units have been made to the initial concept
by workers in the field of oilfield water scaling problems.
The basic principle, however, is essentially the same. The method
depends on the rate at which the pressure drop increases through a
standard length of capillary tubing. The tubing bore diameter is
normally of the order 1.Omm; length is dependent on individual
preference but should be no less than 1 metre. Generally stainless
steel tubing wound into a coil is used; care must be taken to ensure
the tubing configuration is the same for each comparative test since
change in bend radius will significantly alter the results.
The apparatus is shown diagrammatically in FIG 1 set up for calcium
carbonate scaling work.
It consists of a water storage reservoir for the water under test and
a second reservoir containing either a solution of the scale inhibitor
to be evaluated or the second water with or without added scale inhibitor.
Flow from the two reservoirs ;s accurately ratioed to give the required
values by two variable speed peristaltic pumps.
The two flows are mixed in the magnetically stirred mixing unit from
where the mixed waters (or water minus scaling ion + water with scaling
ion and scale inhibitor) are transferred to the test coil. The coil
is inrnersed in a constant temperature bath at the test temperature.
Flow from the coil is to waste or may be collected in an automatic
sampler for ions analysis. The pressure change across the system
(really the change across the capillary tube since the volume of the
rest of the system is a constant) is measured by a pressure transducer,
the signal from which is amplified and displayed on a moving chart
recorder.

The tinit described is a low pressure system generally operating


up to 15 psi. Other more sophisticated units have been designed
to work at typical reservoir pressures.
Typical results obtained from the low pressure unit are shown in
GRAPH 7.
GRAPH 7 shows (lhs) the rate of pressure increase for the scaling
solutions alone; (rhs) the effect of partially scaling the capillary
tube and then applying scale inhibitor. It can be seen that at
4ppm the inhibitor was effective (i.e. no increase in 6P occurred);
at 3ppm there was insufficient inhibitor present to stop scaling.
It can be seen that the unit can differentiate to the extent of lppm
change in inhibitor dose level. The test procedure is rapid (cf the
Static Test) and is found in practice to be highly reproducible.
Work is in hand to modify the apparatus for barium and strontium
sulphate scaling \>/oy'k. As yet however no firm data are available.
.,J::..
N
STI'l.E.R.

L, I ,~,. C.01\_
i

r
\,1'\
WATER. FEEl)
PUMP w(-\~T

~F:NSwc...e:tt

t
\JRTER. ~
~c.ALE .. -rE,.t\'. c.oN~RoL.
INHH~rrOI<
PUNP

u
WfllER
~T~A(4E

Lw A-rE.f'.. lA.~i)ER.
__ IAHP.
All. X
-r"'E.S T) Qu:,..r=tu. Q

.
~

P
~
~.
DATA ~
c;;--
S
S.
A/b UNI' ..2..n:b fttt-02.1l ER..
~

~
~
;:::
FIG. 1 Diagramnatic Representation of Dynamic Tube Blocktng ~
~
Apparatus - set up for Calcium Carbonate work. ~

~
r t u P
Water Scaling Problems in the Oil Production Industry 143

i
i lkR; I 3HR
! '~ I ;. i ;
i I
.. _._.~
I I i I
L_ .....L_ .. .J.. _.1... __.

Control of scale formation in oilfield water is generally achieved


by the addition of scale inhibition chemicals.
There are two main mechanisms by which scale inhibitors act.
1. Crystal distortion.
2. Threshold effect.
Crystal distorters act by becoming incorporated into the crystals as
they are formed. This has the effect of distorting the normally
regular crystals, thus reducing significantly adhesion between
individual particles or any solid surface with which they come into
contact.
Threshold effect chemicals act in sub-stoichiometric concentrations
to adsorb into the forming crystal nuclei preventing further crystal
growth and hence deposition as scale.
Threshold effect chemicals, used at well below the stoichiometric
concentrations of the potential scaling species they are intended to
control) are most suitable for oilfield water applications.
Dose level of an effect scale inhibitor is normally in the range of
1 - lOppm. Chemical must be added before the point of initial
scale formation. Chemicals of this type only work effectively from
solution.
Three basic chemical types have been shown to have the required
scale inhibition properties. These are:-
Organic polymers: - generally of the polyacrylamide or polyacrylate
type.
r t u P
144 Chemicals in the Oil Industry

Chemicals of this type may be used in high temperature conditions


(up to 200 0 C) for the control of calcium carbonate, calcium
sulphate, barium sulphate and strontium sulphate scale.
They would probably be the leading type of product for well
downhole "squeeze" applications if it \'Iere not for the problems
of monitoring the returning inhibitor {see later). They have
been shown to be very effective in scale control in production
systems separators and oily water clean up units when added at
the well-head manifold; scale deposition is often induced by
pressure drop through the separator train.
A new range of phosphino-substituted polycarboxylic acid inhibitors
has recently been developed where the active ingredient is a
phosphorus-containing polycarboxylic acid. The addition of the
phosphorus enables the product to be monitored at low concentrations.
The type of chemical may well find application in downhole squeeze
treatments ~ince it combines the high temperature stability of a
polycarboxylate with a means of analytical measurement in separated
produced water.
It is primarily designed to inhibit barium and strontium sulphate
scale formation but also displays some effect against calcium carbonate.

Organic phosphonates are generally effective on carbonate and sulphate


scales. They have reasonable thermal stability and may be used
at temperatures up to about l75 0 C without efficiency losses due to
decomposition. They have therefore been the most widely used chemical
type for production well squeeze treatments since they have a readily
analysed functional group. The phosphonate is generally reduced to
phosphate which may be readily determined by colorimetric means.

Phosphate esters are generally effective against carbonate and sulphate


scale formation. They are more commonly used in low temperature conditions
since they have lower thermal stability.
They may be used for protection against scaling in water injection systems
where the temperature of the injection water is unlikely to be very high/
even where water is pre-utilised for heat exchanger duties, and in
production separator and oily water systems.
Their use in squeeze applications would be limited to low bottom hole
temperature wells. They have the advantage, where they can be used,
of ease of analysis at low levels via the phosphate grouping.

~~g~lr~~~~!_~~9_~ee!!~~!!2Q_2!_~~~1~_!~~!~!!Qr~

As discussed above, water scaling problems occur in the following


oilfield systems.
1. Water injection.
2. Downhole/in production tubing.
3. In production process train (separators, oily water clean up systems).
r t u P
Water Scaling Problems in the Oil Production Industry 145

For water injection systems it is convenient to add the chemical


into the water flow line by means of a metering pump. Chemical
is generally added as early as possible into the injection water
system and certainly ahead' of heat exchanger/oil cooling units.
A general flow diagram of a water injection system is shown in
FIG 2, indicating preferred addition point for scale-inhibitive
chemical. Little maintenance is required in carrying out scale
inhibitor addition. The chemical is supplied in liqUid form
and the dose level is determined with respect to the as supplied
chemical. It is only required therefore to ensure that the
dosing pump output is at all times correctly ratioed with the
seawater injection throughput to maintain an effective scale
inhibition treatment.

Scaling problems from produced waters - formation or mixed


formation + returning injected seawater - may occur at the well
bottom (i.e. at the perforation levels) or as the produced fluids
progress up the production tubing.
Scaling species may be seeded out by pressure~ temperature or
velocity changes in the production well system.
Generally wells are not completed such that a chemical dosing
line (macaroni string) extends from the surface facility to the
bottom of the well and hence chemical cannot be added continuously
to the produced fluids to inhibit scaling.
The only practical method therefore of getting scale inhibitor into
the fluids is by the technique known as "squeezing". This consists
of reverse flowing a production well by applying excess pressure from
the surface facility and adding to the reverse flow scale inhibitor
solution.
In practice~ the procedure is generally carried out as follows:-
Surfactant "Spearhead" injection - a dilute solution of a stJrfactant
in water is injected into the production well to overcome any emulsion
block that may occur. Sufficient is added such that it is pushed
outward from the perforated zones of the well bore into the formation
itself, the main purpose being to water-wet the formation and allow
adsorption of scale inhibitor solution added subsequently.
Scale Inhibitor injection - the scale inhibitor to be used is injected
into the rroduction well at low concentration in water (generally 1 -
3% of as supplied chemical). The quantity required is a matter of
conjecture~ most service companies having their own ideas of the
amount needed to give an effective duration squeeze.
Overflush Injection - to ensure the ~cale inhibitor is pushed
away from the well-bore and into the formation such that it may
be adsorbed an overflush of water (or possibly disel or even
produced gas) is used. The extent that the scale i'nhibitor
r t u P
146 Chemicals in the Oil Industry

~ .,
..-------1..~1.1 0

\">.n
1 :f
'4.l
\.9. ,

LI
WI
1-1
V>I
>-1
V>I
I
ZI
01
~I
1-1
UI
WI
'"":)1
ZI
~I
I
0:=1
lI\ WI

..."2 ~
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I
3:1

....- - . ~~
:J I
-11
c::(1
..... UI
~I
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>-1
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l.L-1
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:i:
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Lt.. I
I
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NI
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.1
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~I
lJ...1
r t u P
Water Scaling Problems in the Oil Production Industry 147

is pushed in terms of radius from the well-bore is again


subjective; in general though it should be in the range of
8 - 15 ft radial displacement into the formation.
Generally the well is shut for some 24 hours after completion
of the squeeze chemicals application; it is then slowly brought
back to full production. Adsorbed scale inhibitor is desorbed
from the formation into passing fluids. Initially aesorption
is high leading to an excess of scale inhibitor present over
actual requirement. Gradually the amount of chemical present
in the produced fluids falls to a level at which it is no longer
giving full inhibition protection. At this point, it is necessary
to re-squeeze the well. An effective squeeze treatment should last
some 3 - 4 months.
The explanation of adsorptionjdesorption given above is an over-
simplification; there are many papers written on this subject
which look closely at the possible squeeze mechanism. 7 , 8
It is important to be able to determine quantitatively down to the
performance threshold level of the scale inhibitor in order to
determine when it is necessary to carry out a further squeeze
treatment. Hence the chemical used must have a parameter or
functional group capable of being accurately determined. It is
here when the phosphonate and phosphino polyacrylate inhi'bitors
score over the straight polyacrylate. Being essentially a hydro-
carbon species it is difficult to differentiate between the
polyacrylate and residual oil in the separated water.

In many caseS serious scaling does not occur down-hole but i~


seeded out in the separation and oily water clean up systems.
A typical system is shown diagrarrmatically in FIG j . If it
can be shown that downhole scaling is not a current problem and
providing regular checks are made to ensure that no change towards
down-hole scaling is occurring (by study of water anaylsis results),
it is convenient to add the scale inhibitor at the topside facility.
The chemical should be added as neat downstream of the Christmas
tree valve system as possible for each individual well to be treated.
The production volume/water cut of the well or wells to be treated
should be determined on a regular basis and the dose level of chemical
adjusted accordingly to ensure effective treatment.
Dependent on the scaling tendency and the potential amount of scale
it may be necessary in some instances to add chemical at two points,
at the wellheads and again upstream of the oily water separation units.

With treatment for scale inhibition under any conditions, it


must be stressed that it is important that the application of
the chemical is not taken for granted. Routine checks on a
shift basis should be made to ensure the chemical is in fact
being added at the correct level. Then assuming an effective
chemical was selected, few scale related problems should be
experienced.
r t u P
148 Chemlcals in the Oil Industry

-~.J.'4'~d'lS od'"
.J-~,...,~~

~I
WI
cA t-I
(/')1
~+--
.., .t to I >-1
(/')1

~
., ~ ~, I 2:1
01
I

....-s ~i -- - - -
~ ...... 1
-.J L t-I
e:t:1
0
..J ,.. -.
Cl( 0::1
e:t:1
0-1
Wl
(/')1
.........1
2:1
01
...... 1
t-I
UI
::::>1
01
01
0::1
0-1
I
WI
01
::::>1
0::1
UI
I
-ll
e:t:1
UI
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0-1
>-1
t-I
I
u...1
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~:
0::1
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c:(1
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- - - -~y>q--e::================
01
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-ll
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D
I
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MI
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-I
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u...1
r t u P
Water Scaling Problems in the Oil Production Industry 149

References
----------

1. Langa1i er WF. JAl,WA Vo 1. 28 (1936) .


2. Stiff H.A. and Davis L.E. "A Method for Producting the
Tendency of Oilfield Waters to Deposit Calcium Carbonate".
Trans AIME 1952 195.
3. "Oilfield Water Systems" (Second Edition) Dr. C. C. Patton
Campbell Petroleum Series 1977.
4. "Water Technology in the Modern Oil Industry" - McKenzie D.
Hydrotech Ltd. 1981.
5. Skil1man H.L., McDonald J.P. Jr., and Stiff H.A.
American Petroleum Institute Meeting, Division of Production
Paper 906-14-1 March 1969.
6. Hughes C.1. and Whittingham K.P. B.P. Research Centre
European Petroleum Conference, London. Oct. 1982.
7. Vetter O.J. "Adsorption-Desorption - Is it the basis of
Chemical Squeeze Technique?" Trans AIME - 1971 SPE Paper 3544.
8. Tinsley J.M., Lesater R.M., Knox J.A. AIME 1967. SPE Paper
1771.
r t u P
The Chemistry of Corrosion Inhibitors Used in Oil
Production

By J. A. Kelley
TRETOLITE DIVISION, PETROLITE CORPORATION, ST. LOUIS, MISSOURI 63119, U.S.A.

INTRODUCTION

Corrosion inhibitors are r-outinely used in oil production at rates varying from a few
parts per million (mg/I) to thousands of parts per million. Many of the commercial
corrosion inhibitors are unique mixtures that may contain surfactants, film enhancers,
demulsifiers, or an oxygen scavenger in addition to the inhibitor moiety. The purpose of
this paper is to provide a brief discussion of the chemistry of t!le inhibitor moieties and
provide a few illustrative examples of formulation considerations. This paper does not
attempt to describe all of the commerically available formulations, but rather the broad
chemistries within which they fall.

The majority of corrosion inhibitors used in petroleum production are nitrogenous in


nature and can be classified in a method similar to Bregmanf s 1 as follows:

1) Amides/lmidazolines
2) Salts of nitrogenous molecules with carboxylic acids
3) Nitrogen Quaternaries
4) Polyoxyalkylated amines, amides, and imidazolines
5) Nitrogen heterocyclics

There are other, non-nitrogenous inhibitors that contain phosphorus, sulfur, or oxygen
atoms but they are used less frequently.

AMIDES/lMIDAZOLINES

Many of the common oil and water soluble corrosion inhibitors contain amides
and/or imidazolines which are produced by condensing a carboxylic acid with a primary
amine. The carboxylic group is often derived from low cost natural sources such as crude
or refined tall oil. 2 The typical fatty acid derived from tall oil is composed primarly of
C18 linear saturated and unsaturated chains with minor amounts of C16 linear chains and
some rosin acids. 3,4 Naphthenic acid mixtures derived from petroleum are also used. 5
r t u P
The Chemistry ofCorrosion Inhibitors Used in Oil Production 151

The amine frequently used in the reaction is a polyamine having the structure H2N(-
R-NH)x H where R is an alkylene group containing 2 to 6 carbon atoms and x is a
small whole number greater than 1. A frequently used polyamine is diethylene
triamine (R=CH2CH2 and x=2). Mixtures of higher homologs (x=4 etc.) can also be used. 2

An example of a common imidazoline is :

where R is derived from the previously mentioned tall oil fatty acids. A water soluble or
water dispersible inhibitor blend is often made from such an imidazoline by adding a low
molecular weight organic acid and a mixture of solvents and perhaps a surfactant. 6,7

SALTS OF NITROGENOUS MOLECULES WITH CARBOXYLIC ACIDS

There are numerous references that discuss salts formed by the neutralization of the
basic nitrogen by tall oil fatty acids, polymerized fatty acids, naphthenic acids, or simple
organic acids. 8,9,10,11,12,13,14 A recent example utilizes a high molecular weight
polymerized carboxylic acid neutralized with a tallow amine.l S The use of polymerized
fatty acids in inhibitor formulations is estimated to be in the millioM of pounds per
year. 16 In general, any unreacted basic amine or the imidazoline itself can be fully or
partially neutralized with wide variety of acids.

QUATERNARY NITROGEN

The term quaternary nitrogen applies to compounds in which all of the hydrogens of
the ammonium ion have been replaced by linkages to carbon. These are often referred to
as cationics as shown:
+
R'
I
R~N -R X-

R
1",
r t u P
152 Chemicals in the Oil Industry

The quaternary nitrogen compounds are excellent cationic surfactants and may
possess biocidal, demulsifying, or corrosion inhibiting properties.l 7,18 In the fatty
amine quaternaries, at least one of the R groups consists of a long alkyl chain and
may have more than one cationic nitrogen atom.l 9 Other nitrogen containing
compounds that are quaternized include imidazolines,20 polymerized amines,21,22
and pyridines. 8

POLYOXYALKYLATED AMINES, AMIDES, AND IMIDAZOLINES

Any reactive site can be oxyalkylated to modify solubility or dispersibility of


the inhibitor intermediates. Examples include an ethoxylated rosin amine,
polyamines 'with epichlorohydrin,21 beta amine ethoxylates,23 and ethoxylated
imidazolines and amines. 24

NITROGEN HETEROCYCLICS

There are numerous examples of heterocyclic nitrogen compounds in the


patent literature. Typical are alkyl piperazine and alkyl pyridine hydrochlorides,25
and alkylated polymerized pyridine. 26

INlDBITOR CONTAINING PHOSPHORUS, SULFUR, AND/OR OXYGEN

There are a variety of inhibitors that contain phosphorus, sulfur, or oxygen


atoms in the molecule. Their use is often limited to narrow areas. Examples
include dialkyl disulfide oils,27 phosphate esters of cyclic amidines,28 quinoline
phosphonates,29 pyrophosphates,30 and amino phosphonic acids. 31

INHIBITOR FORMULATION

Many of the successful corrosion inhibitors are carefully formulated mixtures


that may contain one or more inhibitor moieties from the classifications mentioned
earlier. In addition to the inhibitor, a surfactant, demulsifier, scale inhibitor,
biocide, or oxygen scavenger may also be incorporated.

A low cost water soluble inhibitor can be made using the imidazoline depicted
earlier by simply adding acetic acid and a suitable solvent. In an oilfield water system
where solid deposition such as iron sulfide is a problem, a suitable amount of a nonionic or
cationic surfactant has to be added to reduce the tendency for solids to deposit on metal
surfaces. A buildUp of iron sulfide often leads to a pitting type of corrosion under the
deposits. If the oilfield water contains low levels of oxygen, a small amount of a suitable
r t u P
The Chemistry ofCorrosion Inhibitors Used in Oil Production 153

sulfite or hydrazine oxygen scavenger might be included in the fc,rmulation. It is also


important to reduce solids deposition in waters that contain low levels of oxygen to
prevent a severe pitting type of corrosion. Likewise, if a mineral scale problem exists in
the system, a suitable scale inhibitor that is compatible with the corrosion inhibitor has to
be added.

A laboratory test called the C02 sparge test is often used to screen water
soluble/water dispersible inhibitors. The results correlate well with field experience. The
test is based on the linear polarization principle. There are numerous multichannel
instruments that allows ten or more inhibitors to be evaluated in a twenty-four hour
period. The test can be run as a sweet or sour system, in straight brine or a
brine/hydrocarbon ,mixture, and up to a temperature of 150 0 F. See Appendix 1 for more
details.

An effective oil soluble inhibitor can also be made from the same imidazoline by
simply replacing the acetic acid with a high molecular weight acid and using an aromatic
based solvent. To aid in uniform distribution of the inhibitor and ease of application, a
suitable nonionic or cationic surfactant is often added to make the oil soluble inhibitor
somewhat dispersible in the water. Secondly, a small amount of surfactant usua.lly
increases the effectiveness of the inhibitor. The table below illustrates the effect of the
addition of a surfactant and polymerized fatty acid to an amine based inhibitor. The
corrosion data was obtained from a dynamic corrosion test commonly known as a wheel
test, the details of which are given in Appendix 2.

Table 1 31

Inhibitor 96 Protection at 60 ppm inhibitor


Amide 18
Amide + Polymerized acid 62
Amide + Polymerized acid + surfactant 96

To minimize or avoid creating stable emulsions, a small amount of demulsifier may also
be added.

There are additional problems to consider when formulating an inhibitor for gas
wells. Care must be taken to devise a formulation that provides a uniform dispersion of
the inhibitor on the tubular goods for the selected application method. The inhibitor must
also possess good thermal and chemical stability in well fluids under production
conditions. Two of the inhibitor removal processes that exist in gas wells are washing by
r t u P
154 Chemicals in the Oil Industry

produced fluids and evaporation. Thus, the inhibitor moiety and any additives should have
a very low vapor pressure under production conditions and be as insoluble as possible in
well fluids, depending on the treatment method. 33

Inhibitors for use in gas wells are usually evaluated under higher pressures and
temperatures than are obtainable in the wheel test. Special test cells are often used to
simulate the acid gas partial pressure in these wells (u~ to 200 psi Pco2 or PH2 S).
Alternately, high pressure autoclaves capable of accomodating field fluids under the
conditions encountered in deep gas wells are often used. A typical autoclave test may run
for several weeks.

Most oil companies use a variety of laboratory tests to qualify inhibitors for field
use. These tests determine the need to add or delete components to achieve the desired
properties for a given application. Emulsion tendencies, solubility, partitioning
coefficient, and effectiveness in a variety of corrosion tests are among the qUalification
tests.,34,35,36

Considering all of the blend components and their possible combination, including
hundreds of surfactants and other additives, it is easy to understand the great number of
commercially available corrosion inhibitors.

APPENDIX 1: C02 Sparge Test

The test relies on the linear polarization technique and utilizes the three electrode
system. One of the electrodes is called the reference electrode; the second the test
electrode; and the third the auxiliary electrode. The corrosion rate value (mpy) obtained
with the meter is the corrosion rate of the test electrode.

About 800 mls of a laboratory brine or a brine/hydrocarbon mixture in a 1000 ml


beaker is sparged with C02 (or H2S) for one hour with stirring to saturate the brine with
C02 (or H2S) and remove oxygen. The electrodes are degreased in acetone and immersed
in 15% hydrochloric acid for ten seconds and removed. They are then allowed to
precorrode for two hours while C02 is continuously sparged into the solution. Neat
inhibitor is injected under the surface of the brine and the corrosion rate is continuously
monitored. An uninhibited blank is always included. The test is allowed to run for 24
hours after which the final inhibited and uninhibited corrosion rates are measured and the
corrosion protection calculated from:
r t u P
The Chemistry ofCorrosion Inhibitors Used in Oil Production 155

% Protection = (Final blank MPY - Inhibited MPY) 100


Final Blanks MPY

CURRENT SOURCE

t
CORROSION
METER [
~CO 2

-OIL

-BRINE

STANDARD BRINE
ION Mg/L
Na + 20,000
Mg ++ 2,000
Ca ++ 400
Cl - 32,500
SO - 590
4
r t u P
156 Chemicals in the Oil Industry

Appendix 2: Wheel Test

The wheel test is a dynamic corrosion test for evaluation of corL"osion inhibitors.
There are basically two versions of the test, both of which rely on determining the weight
loss of a steel coupon to calculate the corrosion rate. The first version (constant contact)
simulates treatment by continuous chemical application. The second (film peristency)
test corresponds to the conditions experienced during slug or batch type application of
chemicals. The procedure involves placing preweighed coupons into test cells with either
hydrocarbon (e.g. kerosene) and synthetic brine or actual produced fluids that have been
saturated with carbon dioxide, hydrogen sulfide or a combination of both. The chemical is
introduced into the cells at actual use concentration which may be in the fifty to one
hundred parts per million level for the constant contact version or thousands of parts per
million for the film persistency version. The coupons are added to the cells (care being
taken to exclude oxygen) and the cells loaded on a wheel that rotates inside a heated
cabinet. In the film persistency version the coupons are removed after a short period of
time (e.g. one hour), placed in fresh uninhibited fluids, and the test continued.

The total test period varies but is usually from twenty-four to seventy-two hours.
At the end of the specified time the coupons are removed, cleaned, and reweighed and a
percent protection for each inhibitor calculated as below:

96 Protection (uninhibited coupon loss - inhibited coupon loss) 100


uninhibited coupon loss

REFERENCES

1. J.I. Bregman, "Corrosion Inhibitor", Macmillan Company, New York, 1963, p.


197.

2. G.D. Chappell and J.R. Stanford, Corrosion Inhibitor Used in Brines Containing
Oxygen, U.S. 4,010,111, Mar. 1, 1977.

3. J. Drew and M. Propst, ''Tall Oil", Pulp Chemical Association, New York, 1981,
p.98.

4. L. Zachary, H. Bajak, and S. Eveline, "Tall Oil and Its Uses" Pulp Chemical
Asociation, New York, 1965, pp. 25-26.

5. C.L. Howle, Corrosion Inhibition with Oil Soluble Diamides, U.S. 3,997,469,
Dec. 14, 1976.
r t u P
The Chemistry ofCorrosion Inhibitors Used in Oil Production 157

6. K.H. Nimerick, Inhibitor to Corrosive Attack and Method of Use, U.S.


3,692,675, Sept. 19, 1972.

7. M. Safar et al., A Mixed Corrosion Inhibitor, GB 2,064,985 A, June 24, 1981.

8. M.D. Coffey, Corrosion Inhibitor for Aqueous Brines, G.B. 2,027,686 A, Feb.
27, 1980.

9. S.E. Jolly, Corrosion Inhibitors, U.S. 3,661,981, May 9, 1972.

10. L. W. Jones, Water Dispersible Corrosion Inhibitor, U.S. 2,839,465, June 17,
1958.

11. J. Maddox Jr., Carboxylic Acid Salts of 1-Aminoalkyl-2-Polymerized


Carboxylic Fatty Acid Imidazolines, U.S. 3,758,493, Sept. 11, 1973.

12. G.D. Chappell and J.R. Stanford, Corrosion Inhibitor Used in Brines Containing
Oxygen, Canadian 1,019,554, Sept. 25, 1977.

13. J. Maddox, Jr. and W. Schoen, Composition and Process for Inhibiting
Corrosion in Oil Wells, Canadian 856,824, Nov. 24, 1970.

14. Improvements in or Relating to the Prevention of Corrosion, U.K. 809,001,


Feb. 18, 1959.

15. J.R. Stanford and G.D. Chappell, High Temperature Corrosion Inhibitor for
Gas and Oil Wells, U.S. 3,959,158, May 25, 1976.

16. E.C. Leonard, Polymerization-Dimer Acid, J. Am. Oil Chemists' Soc., 1979,
~ 782A.

17. P.M. Quinlan, Sulfur-containing Bis-Quaternaries, U.S. 4,057,390, Nov. 8, 1977

18. T.J. Bellos, Method of Protecting Metal Surfaces Against Abrasive Wear in
Submersible Pumps, U.S. 3,661,784, May 9, 1972.
19. E.H. Pryde, "Fatty Acids", American Oil Chemists' Society, Champaign,
Illinois, 1979.

20. T. Kataoka, Chigasaki-Shi, and A. Takada, Method of Inhibiting the Acid


Corrosion of Metals, U.S. 3,736,098, May 29. 1973.

21. D. Redmore and T. Welge, Method of Inhibiting the Corrosion of Metals in an


Acidic Environment Using Quaternary Ammonium Salts of Polyepihalohydrin,
U.S. 3,885,913, May 27, 1975.

22. T.J. Bellos, Method of Protecting Metal Surfaces Against Abrasive Wear in
Pumps with Polyquaternaries, U.S. 3,751,364, Aug. 7, 1973.

23. J.L. Walker and T.E. Cornelius, Filming Amine Emulsions, U.S. 3,931,043, Jan.
6, 1976.

24. W.B. Hughes, Composition for and Method of Inhibiting Corrosion of Metals,
U.S. 2,940,927, June 14, 1960.

25. P. Merchant, Jr., C.O. Ohaji and F.L. Powell, Water Soluble Waterflood
Corrosion Inhibitor, U.S. 3,989,460, Nov. 2, 1976.
r t u P
158 Chemicals in the Oil Industry

26. P.M. Quinlan, Quaternized Derivatives of Polymerized Pyridines and


Quinolines, U.S. 4,297,484, Oct. 27, 198!.

27. S.P. Sharp, Inhibiting Corrosion in High Temperature, High Pressure Gas Wells,
WO 80/02700, Dec. 11, 1980.

28. D. Redmore, Corrosion Inhibitors Employing Phosphate Esters of Cyclic


Amidines, U.S. 3,711,403, Jan. 16, 1973.

29. D. Redmore, Use as Corrosion Inhibitors: Quiaoline and Isoquoline


Phosphonates, U.S. 3,888,627, June 10, 1975.

30. D. Redmore, B.T. Outlaw, and R.L. Martin, Pyrophosphates, U.S. 4,075,291,
Feb. 21, 1978.

31. L Jones, Oil-Soluble Phosphonic Acid Composition, U.S. 3,770,815, Nov. 6,


1973.

32. J. Stanford, Inhibition of Corrosion of Metals, U.S. 3,412,024, Nov. 19, 1958.

33. R.R. Annand, 28th Annual Southwestern Petroleum Short Course, April 1981,
Texas Tech. Unv., Lubbock, Texas, pp. 8,9,

34. A.C. Nestle, Materials Performance, Jan. 1968, Vol. 7, No. 1, p. 3l.

35. L. Gatlin, Materials Performance, May 1978, Vol. 17, No. 5, p. 9.

36. NACE Publication ID 182, Material Performance, Dec. 1982, Vol. 21 No. 12,
p.9.
r t u P
Quaternary Ammonium Compounds: Evaluation and
Application in the Control of Sulphate- reducing Bacteria
By E. Bessems
AKZO CHEMIE, DUREN, WEST GERMANY

A. F. Clemmit
AKZO CHEMIE U.K. LTD., HOLLINGWORTH ROAD, LITTLEBOROUGH,
GREATER MANCHESTER OL15 OBA, U.K.

1. Introduction

The objective of biocide addition to oilfield systems is


to eliminate/control the growth of sulphate reducing
bacteria (SRB). The SRB, in anaerobic coditions, generate
hydrogen sulphide by reduction of sulphate ions thus:

The hydrogen sulphide produced is toxic and corrosive


reacting with iron:

Fe +

The prevention of H S formation is therefore necessary for


2
the safe and efficient operation of an oil producing
installation.

2. Chemical Types

If firstly we look at chemicals which are considered to have


general biocidal activity they fall into a number of
categories:

i) Chlorine and Chlorine Release Chemicals


e.g. chlorine
sodium hypochlorite
chloramines
chlorinated guanidines
chlorinated tripotassium phosphate
(Iodophors)
r t u P
160 Chemicals in the Oil Industry
Advantages
Cheap, wide spectrum, short kill time.

Disadvantages
oxidation of system
potentially corrosive
reaction with organic material

( ii) Phenolics
e. g. dichloroxylenol, benzyl cresol

Advftntages
long time of activity.

Disadvantages
Too toxic and environmentally unacceptable.

( iii) Organometallics
Mainly compounds of copper, tin and mercury.

Advantages
Excellent biocidal activity.

Disadvantages
Toxic, environmentally unacceptable.

( iv) Oxidants
e. g. Hydrogen peroxide

Advantages
Ease of handling, cheap.

Disadvantages
Their strong oxidising potential precludes their
use in many systems.

v) Aldehydes
e.g. Formaldehyde
Glutaraldehyde
r t u P
Quaternary Ammonium Compounds in the Control ofSulphate- reducing Bacteria 161
Advantages
Cheap, long time of activity.

Disadvantages
Toxic
Can have handling problems.

( vi) Quaternary Ammonium Compounds


e.g. trimethylalkylammonium chloride

Advantages
Cheap, long time of activity.

Disadvantages
Require careful selection for sea water compatibility.
Readily absorb on surfaces (can also be an advantage).
Foaming.

Typical MIC values against gram + and gram - bacteria of the


various biocide types are given Table 1.

3. Mechanism of Operation

For oilfield operations, the biocide types normally encountered


are:
i) Chlorine
ii) Aldehydes
(iii) Quaternary Ammonium Compounds
Relatively little work has been done on how biocides work
but outlined below are possible mechanisms of operation:

i) Chlorine

Whilst there are a number of theories to explain the


antimicrobial action the most acceptable ones are those
based on the investigations of Green et al (1946)1
and Knox ~ (1948)2. The chlorine is believed to
penetrate the cell wall where it contacts the enzyme
system oxidising SH groups on the enzymes and blocking
the life cycle of the cell.
r t u P
162 Chemicals in the Oil Industry

TABLE 1

MIC ppm

Biocide g + g - fungi

-Quaternaries
alkyltrimethylammonium
chloride 5 200 25 -100
alkyldimethylbenzylammonium
chloride 2 50 1-50
heteraoaromaticammonium
chloride 80 150 1500-3000

-Formaline
formaldehyde 30 30 30-1000
formaldehyde release compounds 50 50 1000

-Phenolic compounds
phenolics 1000 1000 300-1000
alkylphenolics 200 3000 5000
chlorinephenolics 4 200 25-150
diphenyl derivatives 100 500 500

-N containing compounds
biguanidines 20 100-250 1000
chlorhexine 3-25 10-25 10-100
triazine
thiocynates 5-60 10-15 4-35

-Halogen compounds
chlorine 1-5 100
chlorine release compounds 100 300 20 -300
iodophors
r t u P
Quaternary Ammonium Compounds in the Control ofSulphate-reducing Bacteria 163

( ii) Aldehydes

These are believed to operate again by penetration


of the cell walls and reaction with the free amino
3
groups of proteins.

( iii) Quaternary Ammonium Compounds

Very little is known about the mode of operation of


quaternaries. A possible mechanism can be attributed
to the cationic nature of the chemicals causing
disruptign of the cell wall by reaction with the
phospholipids of the cells. At high concentrations
the QAC penetrates the cell and reacts with both
protein and nucleic acids.

4. Chemical Aspects of Biocides

In this section we shall cover the chemistry of amines and


quaternary ammonium compounds examined as biocides. Various
types of "amines" are illustrated below:

Amines
Primary Secondary Tertiary
R1 R3
'-N/
I
R2

Ethoxylated Amines

Quaternary Ammonium Compounds

Cl
r t u P
164 Chemicals in the Oil Industry

Cl

Ethoxylated Quaternaries

Cl

Amine Salts

R'COO

The alkyl groups (R) attached to the nitrogen can of course


vary but we shall be mainly concerned with those of carbon
chain lengths CS-C1S.

The biocidal activity of a range of the above products against


SRB has been determined and the effects of the various
molecular modifications, e.g. quaternisation, ethoxylation
and carbon chain length of constituent groups can be seen.

Before discussing these structural effects, the techniques


used to assess the biocidal activity of the chemicals will be
explained.

5. Test Methods

The concentration of biocide needed to prevent growth of


SRB is called the bacteriostatic activity and is expressed
as the Minimum Inhibiting Concentration (MIC). This
concentration will prevent further growth of SRB but will not
kill them.

The MIC value is measured by the dilution technique, where


the SRB isolates are incubated anaerobically for two days and
r t u P
Quaternary Ammonium Compounds in the Control ofSulphate-reducing Bacteria 165
the growth of the SRB suspension is determined by photometric
analysis. This SRB suspension is then injected into a series
of serum bottles containing seawater, medium and different
quantities of biocide. The lowest level of biocide preventing
SRB growth gives the MIC.

Bact~ricidal Activity

This is the concentration needed to kill the SRB and is a


higher concentration than the bacteriostatic activity. The
bactericidal activity is expressed in terms of concentration
and killing time. It is measured by the Suspension Test.

Care must be taken in the interpretation of bactericidal


activity taking account of influencing factors such as
number of colonies, temperature and storage conditions.

6. Structural Effects on Bacteriostatic Activity.

Recent results on the range of amines and quaternary


ammonium compounds are given in Table 2.

From the table i t is apparent that only the quaternary


ammonium compounds as a group show any real bacteriostatic
activity to SRB though some amine salts also show promise.
It can be seen that amines and ethoxylated amines show little
activity and the effect of ethoxylation of a quaternary
ammonium compound reduces the activity.

Within the group of quaternaries some effects of chain


length and distribution can be seen. (Table 3 gives chain
length distributions considered). Quaternaries based on
tallow (mainly C , C chains) were unsuitable due to water
16 18
insolubility. A chain length of 10 carbon atoms i.e.
decyltrimethylammonium chloride is largely ineffective
against SRB but increasing chain length to C or using
12
two C chains on the molecule reduces the MIC from 800 to
10
100. The use of coco derived quaternary, which is mainly
C /C chain length though i t contains C -C chains, gives
12 14 8 18
r t u P
166 Chemicals in the Oil Industry

TABLE 2

MIC in ppm

Product SRB 1 SRB 2

Quaternaries
Trimethyltallowammonium chloride I N S 0 L U B L E
Trimethyldecylammonium chloride 800 800
Dimethyld~decylammonium chloride 100-200 100-200
Trimethyldodecylammonium chloride 100-200 100-200
Trimethylcocoammonium chloride 50 50-100
Dimethyldicocoammonium chloride 3200 3200
Dimethylcocobenzylammonium chloride* 400 100-200
200 50-100
(Middle cut)
Dimethyltetradecylbenzylammonium chloride* 400 400

Amines
N,N-dimethyldodecylamine 3200 800-1600
N,N-dimethyltetradecylamine 3200 3200
N,N-dimethylcocoamine 3200 3200

Ethoxylated Amines
bis (2-hydroxyethyl) cocoa~ine 3200 3200
polyoxyethylene (5) cocoamine 3200 3200

Ethoxylated Quaternaries
Methylbis (2hydroxyethyl) cocoammonium 800 200-800
chloride
Methylpolyoxylene(15)cocoammonium chloride 3200 3200

Amine Salts
Cocoamine acetate 3200 400-800
N,N-dimethylcocoamine acetate 400-800 200-800
N-coco-1,3-diaminopropane diacetate 50 50-100
(Q
:;::
~
~
~
;:::::
~
~
~
~
~
a

r
;:::::
Eo
TABLE 3 Chain Length Distributions ~
g
~a
:;::
;:::::
~

t
C C C C C C C 18=
8 1D 12 14 16 18
5
So
~
6 19
Trimethylcocoammonium chloride 5 53 9 2 6
g
;:::::

u
Trimethyldodecylammonium chloride - 1 98 1 - - -
~
Dimethyltetradecylbenzylammonium chloride - - 3 94 3 - - ~
~
~
~

Trimethylcocoammonium chloride (Middle Cut) - 1 67 28 4 - - ~

P
~
~
~

5
Oq

~
~

~
~
~o

0"1
-......J
r t u P
168 Chemicals in the Oil Industry

some further improvement over the C based quaternary


12
indicating a beneficial effect of a mixed C /C chain
12 14
length. The benzyl quaternary ammonium compounds have
similar activity to their methyl equivalents. Chain length
effects can again be seen comparing the performance of the
three * chemicals in Table 2. Here the derivative based on
a pure C chain length has relatively poor performance
14
compared with a coco derivative (mainly C /C ). By
12 14
removing the lower and higher components to give almost
entirely C /C chain lengths a further performance
12 14
improvement results.

It was also apparent from the work that a specific chemical


had different performance against SRB from different sources
(Table 4).

TABLE 4

SRB
- -

Product Source 1 Source 2 Source 3 Source 4

DMCB 50 100 200 100


DMMCB 50 50 200 50
DM14B 400 400 200 25
TMC 100 200 200 100

This illustrates the importance of biocide selection for


specific SRB.

Synergistic Effects

Some work on the effect of combining an aldehyde with a


quaternary was also studied. Results are given in Table 5.
r t u P
Quaternary Ammonium Compounds in the Control ofSulphate-reducing Bacteria 169

TABLE 5

MIC

SRB 1 SRB 2

Quaternary -Aldehyde +Aldehyde -Aldehyde +Aldehyde

TMC 50 50 50-100 100


TM12 100-200 50 100-200 50
DMCB 400 100 100-200 50
DMMCB 200-400 50 50-100 50

Footnote: DMCB Dimethylcocobenzylammonium chloride


DMMCB Dimethylcocobenzylammonium chloride
(middle cut)
TMC Trimethylcocoammonium chloride
TM12 Trimethyldodecylammonium chloride
DM14B Dimethyltetradecylbenzylammonium
chloride

Factors other than MIC must of course be taken into account


when assessing a chemical or chemical mixture:

Sea water compatibility.


Compatibility with other chemical used.
Effects of pH and temperatures.
Partition coefficient between oil and water.
Corrosivity.
Toxicity and environmental hazards.

Monitoring

The regular monitoring of field conditions and biocide


performance is necessary for their proper applications.
r t u P
170 Chemicals in the Oil Industry
A simple method consists of using serum bottles filled with
medium and sealed with a rubber septum. A sample of water
suspected of containing SRB is injected into the bottle.
If the medium turns black then SRB are present and can be
further investigated by the techniques previously discussed.

REFERENCES

1. D. E. Green and P. K. Stumpf J. Am. Water Works Assoc.,


38, ~Ol (1946)

2. W. E. Knox, P. K. Stumpf, D. E. Green and V. H. Auerbach,


J. Bacteriology, 55, 451, (1948).

3. H. S. Rosenkranz, Bull. Environ. Contam. Toxicol., ~,

242 (1972).
r t u P
The Role of the Service Company in Offshore Operations

By G. E. Payne
CONOCO (U.K.) LIMITED, RUBISLAW HOUSE, ANDERSON DRIVE, ABERDEEN AB2 4AZ, U.K.

Introduction

Chemical service companies have been involved with the U.K. Offshore
oil industry since the first well was drilled. Drilling muds are
sophisticated blends of chemicals supplied by service companies.
When oil is found and production starts another whole range of
chemicals may be required as outlined in other papers. Some of
the service companies specialise in mud chemicals and some in
production and treating chemicals. A few companies can supply products
for both the drilling and production phases. Yet another group
tend to deal more with maintenance products.

Some cynics might say that all a service company does is to buy
bulk chemicals from the manufacturer and blend them with other materials
which may be only water or cheap solvent and then sell them at a
handsome profit. Whilst this has undoubtedly happened at different
times in different places the offshore oil industry generally requires
such a diverse range of chemicals that this approach is not generally
possible.

The service company must supply chemicals which effectively solve the
problems being encountered. If the existing products are not wholly
suitable new ones need to be developed. Having chosen the chemical
it must then be supplied in a form suitable for shipping to the offshore
installation and for its safe use there. If required chemical service
company personnel must also visit the rig or platform to help ensure
that the chemical does the job that it is supposed to do.

Selection of Chemicals

In selecting a chemical an operator is making two choices, that~of


the chemical itself and also the company supplying it. When one
considers that over thirty companies are active in the area the choice
of chemical can be a difficult task. The selection may be carried
out in various ways and each operator may take a different approach.
r t u P
172 Chemicals in the Oil Industry
The nature of the chemical will often aid its selection. As already
mentioned certain chemical types are only supplied by a proportion
of the service companies and very few companies are in a position to
offer a chemical for every need. Of the companies that can offer
a particular type of chemical an operator may only consider those
with local representation and stocks. If a chemical is needed
urgently even those companies with local stock points may not be
able to supply the particular chemical required due to temporary
shortage or other reasons. Of the chemicals which are available
previous usage or knowledge gleaned from other operators may give
an idea of relative effectiveness. So the selection process may
proceed by ~ series of eliminations.

For a problem which is likely to be long standing many operators


will initially use a readily available chemical which may only be
partially effective whilst carrying out tests and trials to find
a more suitable product. OPerators with extensive laboratory and
test facilities may require samples to be submitted from as many
sources as possible to find the most cost effective chemical. Where
the test facilities are limited or if the nature of the laboratory
work involved in evaluating chemicals is time consuming or expensive
a degree of selection may be made and only a few products evaluated.
A few service companies may be asked to submit only one product each.
A service company in this case has to try to assess the problem and
make the best choice of the chemicals it has available.

In some cases an operator may only carry out plant trials. In this
instance generally only a few products will be tested. These may
be from different companies or perhaps only fro@ one company.

Supply Arrangement

Having chosen a chemical it must then be delivered to the place where


it will be used. The operators arrange shipment from the supply
base warehouse or quayside to the offshore installation. The service
company must deliver the material to the supply base in a form most
suited for the particular installation.
r t u P
The Role ofthe Service Company in Offshore Operations 173
For small usage volume products the usual form of supply is the
45 imperial gallon drum for li.quid materials. Other smaller sized
containers may also be appropriate. Solid products used in the
preparation of drilling muds and fluids are usually supplied in
50 kg bags.

Because the volumes o~ fluid being treated are often very large
even modest chemical treatment rates at the part per million level
may mean substantial quantities of chemical are being consumed.
The unit quantities quuted above for liquids at least are too small
in this instance. Many liquid chemicals are now supplied offshore
in intermediate bulk containers which range from about 100 to 500
gallons in size .,-

If a chemical is CLassified as being a Dangerous Good its packaging


for carriage on a ship is governed by the Merchant Shipping (Dangerous
Goods) Regulations 1981. For some chemicals this means an IMCO
Type 1 tank for the size of load mentioned above. Such tanks must
withstand without damage a rigorous test programme after which
they will be certified as conforming to the type 0 The requirements
of these tanks is such that they will cost approx. 3,000 - 5,000
depending on the actual size and design.

An average round trip for any tank travelling regularly to an offshore


installation is about three weeks. If one tank full of chemical
is used every week a minimum of three tanks will be required to supply
one installation with one chemical. A service company will therefore
have a considerable capital investment tied up in the form of tanks.

Bulk tanks of any type must also be regularly maintained, inspected


and tested. This operating cost associated with the tank together
with the initial capital cost will generally be recouped by loading
the price of the chemical. Thus a service company that has been
active for a number of years and which has written off much of its
tank costs will have an advantage over a company setting up and having
to purchase or lease tanks afresh.
r t u P
174 Chemicals in the Oil Industry

Some operators"have decided to supply tanks to the chemical service


companies for shipment of chemicals to their installations. The
operator then has a better means of comparing one service company's
prices with another. An operator may supply tanks which it has
purchased especially for this purpose. Another alternative now
available is for the operator to contract out the supply and handling
of tanks to a specialist service company providing this facility.

Platform or rig storage is generally limited. Prompt delivery to


keep the offshore stores topped up is often essential to maintain
drilling or production operations. Service companies with stocks
close to the offshore supply bases have an advantage over those
delivering 'from more distant stock points. This is expecially true
when supplies are required unexpectedly due to a spillage or other
temporary shortage offshore. It goes without saying that companies
who literally miss the boat will tend not to be looked at favourably.

Giving Service Offshore

Some operators restrict the access of service company representatives


to their offshore installations. Other operators expect the service
company to provide personnel to assist with the administering of the
chemicals to the system. In the latter case representatives may
spend a considerable time offshore especially when trials are being
carried out. This service is generally given to the operator free
of charge. However nothing is free and these costs are taken into
account in the pricing of the chemical.

Even when the service company personnel do not visit the offshore
installation they will generally be expected to give advice pertinent
to the use of their company's products. The type of injection equipment
required including material of construction requirements and the point
of injection into the system illustrate the type of information
required. The level of treatment to be applied to the system will also
need to be given if this has not already been determined.
r t u P
The Role ofthe Service Company in Offshore Operations 175

A particular point to be e10phasised by the chemical supplier is the


safety aspects associated with individual chemicals. All chemicals
should be supplied with adequate information to allow safe usage.
Product notes and/or material safety data sheets must be available
giving relevant precautions to be taken in handling and using different
chemicals. Point of usp. hazard warning cards should also be supplied
for those chemicals of a hazardous natuLS.

Monitoring of Effectiven~~

In selecting a chemical laboratory tests may have been carried out.


Alternatively a chemical known to work at other locations may have
been chosen. However until a chemical h,.... .3 been used in a plant
trial and the system ~~-itored the effectiveness cannot be fully
predicted. Service company representatives are often present at
plant trials and in some cases will supervise the trial. Personnel
involved must therefore be practical and capable of troubleshooting
and improvising.

Effectiveness may be monitored in various ways depending on the nature


of the chemical. Corrosion inhibitors can be monitored relatively
easily using well known techniques. Demulsifiers may also be shown
to be effective quite easily. An important part of effectiveness
monitoring is to ensure that using a chemical to solve one problem
does not create other problems in the system being treated or other
ancillary systems. It is no good getting good corrosion inhibition
with a product that may cause problems like foaming or emulsion
formation. If more than one chemical is used in a system it is
important that the chemicals are compatible with each other and will
not cause gunk at the treating levels of concentration. If the
chemicals are injected at the same point or close to each other
the products must be compatible at full strength as well. These
are points that the service company should check prior to any chemical
being used.

In drilling operations the properties of the mud need to be adjusted


according to the depth at which drilling is proceeding. This adjustment
requiIesconstant monitoring throughout the drilling operation and this
r t u P
176 Chemicals in the Oil Industry

is carried out by a mud engineer supplied by the service company.


Similarly in cementing operations the cement engineer supplied by the
service company will monitor the mixing of chemicals into the cement
so that the right properties are achieved.

Monitoring effectiveness may be possible in a relatively short period.


However if the period becomes extended it is essential that proper
records of the levels of chemical treatment used are kept over the
period. The service company representative may visit the installation
and check injection rates from time to time and also take other
interim measurements. He should also check that the amounts "used"
on the platform correlate with that supplied by his company.

As part of effectiveness operators are looking for ease of handling


of chemicals. Materials which flow easily in a warm laboratory may
be more difficult to coax out of a drum or tank having been exposed
to wintry conditions on the deck of a supply boat to get offshore
and then kept exposed on the cellar deck of the platform once there.
Also chemicals which require diluting before being injected are not
generally liked unless proper mixing tanks are installed on the
platform.

Once the effectiveness and ease of handling of a chemical have been


demonstrated and the rate of usage established an operator can then
determine the cost effectiveness of a particular product. At the
end of the day it is the cost effectiveness rather than the parts
per million used which is important.

Safety

The safety aspects of using chemicals anywhere cannot be over-


emphasised. Earlier it was stated that a service company must
be able to supply chemicals safely and help ensure their safe use
offshore.

The legislation governing Dangerous Goods has already been mentioned.


This was enacted to protect warehousemen, dockers and supply boat
r t u P
The Role ofthe Service Company in Offshore Operations 177
deck crews from injury due to substandard packaging. Legislation
is usually only taken to mean the minimum standard required and
anything over and above this is to be welcomed.

Many goods may not be classified as dangerous but may still require
special handling in the case of spillage. Some chemicals which are
not dangerous by themselv~s may be potentially hazardous when mixed
with other materials. Such information must be supplied preferably
on the container itself.

Personnel on the offshore ~nstallation must be made aware of any


hazard associated with a particular chemical or combination of
chemicals. Protective clothing must be provided if appropriate.
All pertinent information is covered in the form of a Material Safety
Data Sheet which shoula De supplied by the service company.

Environmental ASPects

Any chemical used offshore will sooner or later find its way into
the sea. This may be deliberate or accidental. Whilst those chemicals
which are deliberately added to overboard discharges must be scrutinised
closest the consequences of accidental discharges of all chemicals
should be known.
In 1979 the Department of Energy introduced a notification scheme
for chemicals used offshore. Service companies were invited on a
voluntary basis'to submit information to the Department of Energy
to enable a category of useage to be allocated to each chemical.
The categories range from 1 to 5 for the different levels of usage
for which notification is requested. category 0 requires no
notification.

The list published by the Department of Energy indicates that


information on only a fraction of the chemicals presently being
offered to the operators has been submitted thus allowing a category
to be allocated. Clearly if the voluntary scheme becomes mandatory
some service companies may be disadvantaged.
r t u P
178 Chemicals in the Oil Industry
Environmental aspects should be taken into account by operators
when selecting chemicals for certain uses. If the chemical is
ultimately going to be discharged as in the case of a pipeline
preservation chemical a license to discharge may be required.
~oxicity data may have to be submitted to the Ministry of Agriculture,
Fisheries and Food (MAFF) or the Department of Agriculture and Fisheries
for Scotland (OAFS) and the Department of Energy to allow the license
to be issued and the discharge to take place. A service company
would be required to supply such information.

Conclusion

This paper has given an outline of the type of service expected by


the operators from the supply companies. Some operators place more
emphasis than others on the different aspects of the service required.
In some cases the chemicals supplied and the prices charged by different
companies are much of a muchness. To aid the selection in these
cases the operator may look for the best service. If a supplier does
decide to become a service company it must be prepared to offer the
service required as well as the chemicals.
r t u P
The Market for Chemicals in the Oil Industry

By R. C. Parker

SHELL INTERNATIONALE PETROLEUM MAATSCHAPPIJ, DEN HAAG, THE NETHERLANDS

SYNOPSIS

Speciality chemicals are used extensively by the petroleum industry and in


particular for oil and gas field exploration, drilling and production.
Drilling activity fluctuates, but recently around 100,000 wells have been
drilled each year. World crude production (outside the Eastern Block
countries) now runs at around 40 million barrels per day (bId) and the
associated water production is estimated at 16 million bId. The world gas
production averages 3000 billion cubic ft per day.

Hundreds of chemicals are used in significant quantities to enable wells to


be drilled and to treat and recover the large streams of oil, water and gas.
Current sales of chemicals related to drilling and associated activities are
estimated at around 3300 million per year, for production related use 300
million per year and for enhanced recovery techniques around 150 million per
year. Significantly of the total estimated expenditure of 3750 million per
year, approximately 80% is accounted for in the United States. Based on
present oil production, the chemical cost associated with producing one
barrel of oil is approximately 25 pence. Market growth rate will depend to a
major extent on world demand for hydrocarbons; however a value of at least
10% per annum may be foreseen.

Whilst these statistics indicate an impressive chemical market, evaluation


should be tempered with a degree of caution. The chemical spectrum associated
with oil and gas exploration and production is highly diversified and
specialised and application invariably necessitates dedicated service back-up
and operational expertise. As such it is a highly competitive and well
established business and great care should be exercised if considering market
participation, especially since the success, or otherwise, of participation
may often depend on the now very unpredictable value of a barrel of oil at
any particular moment in time.

A review of the market for chemicals in oil and gas development will be
presented with particular emphasis on types and quantities of chemicals,
reasons for application and future trends.

N.B. Cost trends on a world wide basis are difficult to establish.


Reference to pertinent literature and trade journals has been augmented
by personal communication and trend extrapolation. As such, the economic
figures quoted in this paper are meant to portray order-of-magnitude
expenditures and should not be interpreted as absolute values.
r t u P
180 Chemicals in the Oil Industry
I. INTRODUCTION

1. GENERAL

Oil and gas development follows a logical and sequential course of events. In
its broadest terms, an exploration well will be drilled in an unknown area to
prove (or otherwise) the presence of hydrocarbons. Should the well
successfully encounter hydrocarbons, so-called appraisal wells will be
drilled in the immediate vicinity to gain more knowledge of the extent of the
accumulation and the approximate quantity of hydrocarbon present. Thereafter,
should the size of the discovered field prove attractive for development in
the prevailing economic climate, development wells will be drilled according
to an optimised subsurface pattern to efficiently produce and drain the
reservoir. Production facilities will be installed close to the development
wells to process the oil and/or gas and water streams which will be produced
from the reservoir. The oil and/or gas will then be evacuated from the field
by the most appropriate method e.g. pipeline or tanker.

In all these activities, from the drilling of the exploration well to


evacuation of the product, significant quantities of chemicals are used. In
some extreme cases, development of a particular oil or gas field could not be
economically undertaken without the use of specialised treatment chemicals.
This section (I) will introduce the principal areas of chemical application
and the following sections will describe in more detail types and quantities
of chemicals, used in the principal areas.

2. SPECIFIC AREAS OF CHEMICAL APPLICATION

The use of chemicals in oil and gas development can be more specifically
indicated by itemising the numerous activities.

2.1 Drilling, Cementing, Completing and Stimulating Wells

Drilling a well requires the use of a drilling fluid, also known as a "mud".
Significant quantities of commodity and speciality chemicals are used in
formulating drilling fluid systems.

Once a borehole has been drilled, steel pipe known as casing must be cemented
in the hole to prevent borehole collapse and allow drilling to continue to
deeper geological horizons. Correct cementing formulations are critical to
the integrity of the well and necessitate the use of chemical additives.

If a well has encountered hydrocarbons, the hydrocarbon bearing interval will


usually be cased off with steel pipe. Clear completion fluids (e.g. brines)
will then be used in the well to minimise production impairment to the
reservoir rock. The casing will be perforated in selected intervals
corresponding to the productive zones. In many cases, the wells will not
produce to their maximum efficiency either because the rock in the immediate
well bore was damaged by the drilling fluid, or the actual properties of the
rock matrix itself are inferior (e.g. low porosity or permeability). In these
circumstances the well will be stimulated by a selective treatment designed
to improve the productivity. A wide range of chemicals from inorganic acids
to highly developed polymers are used in stimulation activities.
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The Market for Chemicals in the Oil Industry 181

2.2. Producing Hydrocarbons

In a typical oilfield development, a combined stream of oil, associated gas


and water must be separated and processed to give acceptable products either
for sale (i.e. oil and gas) or disposal/reinjection (water). Separation of
oil and gas usually takes place initially, which now and again may require
the use of chemical defoamers. Thereafter the crude oil stream often
containing emulsified water must be treated with suitable demulsifiers to
reduce the water content of the crude to sales specification. The separated
water may then require treatment with de-oiling chemicals to render it
acceptable for either disposal or subsurface reinjection. Depending on the
characteristics of the crude oil it may then require further chemical
treatment with wax depressants, fluidity improvers, friction reducers etc. to
allow economic transportation. Depending upon the characteristics of the
produced water, and its eventual mode of disposal, it may require further
chemical treatment with biocides, corrosion inhibitors, scale inhibitors,
polyelectrolytes etc.

In a typical gas field development, chemical requirements for corrosion


inhibition and hydrate reduction are often called for.

2.3. Additional Oil Recovery

Primary production of oil, which usually relies upon the natural driving
forces in the reservoir to produce the oil to surface, seldom recovers an
appreciable quantity of the total oil present in the subsurface strata. In a
typical sandstone reservoir, primary recoveries of 30-50% may be obtained,
whilst in limestone reservoirs, recoveries can often vary from 5% to 25%. In
order to maximise recovery of oil, alternative production methods are
required to augment the primary process.

Typical secondary recovery processes are water injection and gas injection.
So called enhanced recovery processes aim to recover oil left behind or not
producible by the natural drive mechanisms or secondary recovery methods. The
enhanced recovery processes may be arbitrarily split into thermal methods and
miscible/chemical methods. Thermal methods encompass hot water injection,
steam injection and in situ combustion. Miscible methods involve the
injection of enriched hydrocarbon gases, or carbon dioxide or nitrogen.
Chemical processes involve the injection of polymers and/or surfactants or
caustic. In all these additional recovery processes, significant quantities
of speciality chemicals are used, especially in chemical/surfactant flooding.

1. ACTIVITY SCENE

Approximately 100,000 wells are drilled annually worldwide (excluding China


and Eastern Block Countries) of which about 80% are drilled in the United
States. In Western Europe, some 400 wells are expected to be drilled in 1982
and of these, around 200 will be drilled in the United Kingdom. Just over
half the UK wells are expected to be development wells, whilst the remainder
fall in the exploration/appraisal category. Drilling for oil and gas in
Western Europe nowadays predominantly takes place in remote offshore areas,
r t u P
182 Chemicals in the Oil Industry

for example the North Sea. The operating cost of an offshore drilling rig can
amount to 60,000 per day (40 per minute). The cost of a well itself in such
an area can range from 2 million to 20 million, depending upon the severity
and complexity of the operating and drilling conditions. The cost of
chemicals utilised in drilling and completion operations can typically vary
between 5% and 15% of the total well cost.

2. DRILLING CHEMICALS

2.1 Functions of a Drilling Fluid

The majority of chemicals used in the drilling and completion of a well are
utilised in preparation and maintenance of a suitable drilling fluid or
"mud". In the conventional rotary drilling process, mud is pumped down
through the drillpipe string, out through the bottom of the drilling bit and
circulated back to the surface. The mud circulation system is the heart of
the drilling process and it would be impossible to drill a well without a
suitable drilling fluid. The principal functions of the drilling fluid are as
follows:
i) Transportation of drilled rock cuttings out of the borehole
ii) Maintenance of the stability of the borehole
iii) Prevention of the ingress of oil, gas or water into the borehole during
the drilling process
iv) Provision of lubrication and cooling to the drilling bit.

2.2 Design and Choice of a Drilling Fluid

Drilling fluids are prepared from a variety of commodity and speciality


chemicals. The choice of drilling fluid is principally dependent upon the
characteristics of the foreseen geological strata which will be penetrated.
Since, in any well, differing geological conditions are encountered, the
resultant choice of drilling fluid will be a flexible compromise to cope with
the anticipated problems. Hence, each drilling fluid is prepared specifically
for the well being drilled and calls upon the talents of research chemists,
practical chemists and engineers to devise the most appropriate formulation.
An improperly designed drilling fluid can, in extreme circumstances, result
in the complete loss of a well, with all the financial and operational
ramifications which result. The components of drilling fluids are usually
purchased in 50 pound sacks or drums and mixed at the drilling site. Some are
bulk delivered.

2.3 Classification of a Drilling Fluid

The classification of a drilling fluid is primarily dictated by the


characteristics of its base liquid. The major classification is as follows:
i) Water based (e.g. fresh water, seawater, brine, mixed salts)
ii) Oil based (e.g. diesel oil, "non-toxic" oil, invert oil emulsion)
iii) Others (e.g. air, gas, mist or foam systems)

In terms of usage worldwide, approximately 99.5% of wells are drilled with


water based mud systems, 0.4% with oil base mud systems and 0.1% with other
systems. Water based muds are generally cheaper and more environmentally
r t u P
The Market for Chemicals in the Oil Industry 183

acceptable than the other alternatives. However, such statistics can be


misleading when applied to a specific area. For instance in the UK sector of
the North Sea it is estimated that the distribution is around 60% for water
based systems and 40% for oil based systems. The particularly difficult
development drilling conditions in this part of the North Sea have dictated
the requirement for a more refined and expensive solution (i.e. oil base
muds).

2.4 Chemicals used in Water Based Drilling Fluids

As indicated previously, drilling fluids are prepared from a variety of


commodity and speciality chemicals. Examples of a few of the typical types of
chemicals are as follows:

i) ~~!~~!!~~_~~~~!~
Materials with high specific gravity utilised to provide the required density
of the drilling flGid. Barytes (BaS0 ), iron oxides (haematite, ilmenite),
4
calcium carbonate. Barytes is the most commonly used weighting agent.

ii) ~!~~~~!i!~E~
Materials used mainly to build fluid viscosity. Bentonite clay is the most
commonly used product, together with lesser amounts of other clays e.g.
attapulgite. Polymers are also now being increasingly used e.g. partially
hydrolysed polyacrylamides, cellulose ethers, copolymers of vinyl acetate and
maleic anhydride.

iii) ~!~~E~~~~
Materials which disperse solid particles in the drilling fluid. Examples are
ferrochrome lignosulphonates, chrome-free lignosulphonates, sodium
polyacrylates, phosphates.

iv) ~!~!~_!~~~_~~~!!~~~
Materials which prevent the loss of fluid from the mud to permeable and
porous rock formations. Examples are carboxymethyl cellulose, xanthan gum,
guar gum, polyacrylates, pre-gelatinised starch and lignite.

v) ~~~~~~!~Z_~~~~!~~!~
Appreciable quantities of lime and sodium hydroxide are used for pH
adjustment. Also other chemicals are used to provide correct ionic balance in
the fluid e.g. sodium chloride, potassium chloride, lime and calcium
chloride.

vi) 2~~E_~~~!~!!~Z_~~~~!~~!~
To a limited extent, biocides, corrosion inhibitors, surfactants and
defoamers. Since these chemicals are used more extensively in
production-related problems they will be described in more detail in a later
section.

2.5 Quantities and Costs of Chemicals used in Water Based Drilling Fluids

The mud cost for an average well in the United States is of the order of
15,000 whilst for a deep well (> 15,000 ft) it can accumulate to 300,000.
Approximately 1.5% of the 80,000 wells drilled in the U.S. can be classified
as deep. The total world market value of chemicals used for water based,
drilling chemicals is estimated at around 2500 million per year and an
approximate breakdown would be as follows:
r t u P
184 Chemicals in the Oil Industry

3 6
Category of chemical MT x 10 ( x 10 ) (%)

Weighting agents 10,000 775 31


Viscosifiers 4,500 425 17
Dispersants 350 375 15
Fluid loss additives 70 375 15
Commodity chemicals 450 175 7
Speciality/others 150 375 15

MT = Metric tons
The mud cost of an average well drilled with water based drilling fluids in
Western Euro~e is estimated at around 100,000. The total market value of the
drilling chemicals used in Western Europe is therefore estimated at
approximately at 24 million, broken down as follows:

6
Category of chemical ( x 10 ) (%)

Weighting agents 5.2 22


Viscosifiers 2.3 10
Dispersants 3.6 15
Fluid loss additives 6.2 25
Commodity chemicals 1.5 6
Speciality/other 5.2 22

2.6 Chemicals used in Oil-Based Drilling Fluids

Oil based drilling fluids are used for special drilling applications. They
consist of either 100% base oil (e.g. diesel or a "non-toxic" oil) or invert
emulsions with water contents up to 30% to 40%. In common with water based
drilling fluids, weighting agents (e.g. barytes) and commodity chemicals
(e.g. sodium chloride, calcium chloride, lime) are used in the preparation of
these systems. Examples of other types of chemicals utilised in the make-up
are as follows:

i) ~E!~~E~_~~~!~!~!~E~
Materials required to emulsify water into the base oil to provide a stable
invert oil emulsion mud. Typical chemicals are polymerised/oxidised tall oil
soaps; animal fatty acids plus alkanol amides; oleyl amide + oleic acid +
dimerised oleic acid; magnesium soaps of fatty acids + tall oil resin + fatty
amides; fatty imidazoline derivatives.
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The Market/or Chemicals in the Oil Industry 185

ii) ~~!!!~~_~~~~!~L~~~~~~~E~_~~~!~!~!~E~
Materials designed to preferentially oil-wet solids introduced in the mud and
provide additional stability to the system. Examples are amide derivitives of
tall oil; long chain fatty amides; oleyl amide lignosulphonate; fatty
diamine; imidazolines and ethoxylated alkyl phenols.

iii) Y!~~~~!~!~E~
Materials required to impart viscosity to the system. The main product used
is an organophilic bentonite.

iv) ~!~!~_!~~~_~~~!!!~~~
Materials which prevent the loss of the continuous phase of the mud (i.e.
oil) to permeable and porous rock formations. Examples are oxidised asphalt;
organophillic lignite or mixtures of polyphenols.

v) Q!~~E_~~~~!~!!!~_~~~~!~~!~
To a limited extent, thinners are used e.g. petroleum sulphonates or
naphthenic acids.

2.7 Cost of Chemicals used in Oil Based Drilling Fluids

As indicated in section 2.3 the use of oil base drilling muds in the United
States is very limited. In relation to world activity, a significant
proportion of oil base mud application takes place in Western Europe. The mud
cost for an average well using an invert oil emulsion (20% water) is of the
order of 150,000, of which some 30% of the cost may be attributed to the
diesel oil. Hence chemical additive cost per well would be about 110,000,
and the total market value of these drilling chemicals in Western Europe may
be estimated at around 18 million, broken down as follows:

6
Category of Chemical ( x 10 ) (%)

Weighting agents 5.4 30


Primary emulsifier 4.5 25
Secondary emulsifier 0.9 5
Viscosifier 1.8 10
Fluid loss additive 2.7 15
Speciality/other 1.8 10
Commodity chemicals 0.9 5
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186 Chemicals in the Oil Industry

3. CEMENTING CHEMICALS

3.1 Functions of Oil Well Cement

During the drilling of a well, it is necessary to place steel pipe known as


casing into the drilled hole. The casing is cemented in position, i.e. a
strong cement sheath is placed in the annulus between the outside of the
casing and the borehole itself. The principal functions of the cemented
casing are:
i) Prevention of borehole collapse
ii) Allow drilling to continue to deeper geological horizons
iii) Isolate productive hydrocarbon ZOi ~s from non-productive ones.

The cement commonly used is Portland cement with various additives. The
additives modify the properties of the cement to allow acceptable rheology,
setting timea and to match the formation characteristics of the individual
well.

3.2 Chemical Additives for Cementing

The principal additives used in cementing are as follows:

i) ~~!~~!!~~_~~~~!~
These products are usually required when high pressure conditions are
encountered. They are similar additives as those used for drilling fluids
i.e. barytes, iron oxides.

ii) ~~~!_!E~!~!!~~_~~!~E!~~~
Products which prevent the loss of cement slurry to the formation when low
pressure conditions are encountered. Examples are gilsonite and mica.

iii) ~~!~E~!~E~
Products which will accelerate the setting time of the cement in order to
speed up operations. Examples are sodium chloride (up to 5% by weight),
calcium chloride and sodium silicate.

iv) ~~!~E~~E~
Products which will extend the normal cement setting time to render the
slurry pumpable over an extended period. This feature is often required when
placing cement slurries in deep hot wells. Examples are lignin
retarders-calcium lignosulphonate and calcium sodium lignosulphonate;
carboxymethyl hydroxyethyl cellulose (CMHEC) and saturated salt water.

v) ~!~!~_!~~~_~~~!!!~~~
Products to control the loss of water from the slurry to the formation.
Examples are carboxymethyl cellulose (CMC), polyacrylamides and silica flour.

vi) ~!~E~E~~~!~L~E!!!~~_E~~~~E~
Products designed to improve the rheology of the slurry. Examples are
lignosulphonates, lignins, sodium chloride, aryl alkyl sulphonates.
r t u P
The Market for Chemicals in the Oil Industry 187

vii) Q!~~E_~~~!!!~~~
Other chemicals such as bentonite, pozzolan (volcanic ash) and latex are used
in varying amounts for specific applications.

3.3 Cost of Chemical Additives for Cementing

The chemical additive market for cementing is appreciably less than that for
drilling fluids. The total world market value of chemicals associated with
cementing operations is estimated at around 300 million. An approximate
breakdown would be as follows:

6
Category of chemical ( x 10 ) (%)

,- Weighting agents/
other additives 90 30
Lost circulation
materials 23 8
Accelerators 44 15
Retarders 46 15
Fluid loss additives 76 25
Dispersants 21 7

In the UK sector of the North Sea an average cost for cementing additives
would be around 12,000 per well. Hence the approximate total market value of
these chemicals in this area is 2~ million, i.e. about 1% of the world
market.

4. COMPLETION/STIMULATION CHEMICALS

Completion of a well often involves the use of clean non-damaging (to the
reservoir rock) fluids. The principal fluids used are brines e.g. sodium or
calcium chloride, calcium bromide and in extreme case zinc bromide. In some
cases, the rock may have been damaged by the drilling process and/or is of
poor quality such that a less than optimum productivity is obtained. In such
circumstances, the well may be stimulated to improve the productivity. The
two principal methods of stimulation are acidising and hydraulic fracturing.
In certain specific instances, stimulation can also be achieved by injection
of solvents, surfactants, enzymes, gas-generating compounds or polymers.

4. 1 Acidising

In carbonate rock formations (e.g. limestone, dolomite), hydrochloric acid


(15% or 30% strength) is usually injected to clean the rock around the
immediate well-bore and establish communication to natural fissures and
fractures. Occasionally, other acids are used e.g. formic or acetic. A
combination of hydrofluoric and hydrochloric acids is usually used to
stimulate sandstone formations.
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188 Chemicals in the Oil Industry
4.2 Hydraulic Fracturing

In order to improve productivity from low permeability rocks, a highly


viscous fluid often containing a proppant (e.g. sand or glass beads) is
forced into the well. The viscous fluid fractures the rock, the proppant
enters the induced fracture and then keeps it open to improve the flow from
the rock matrix.

4.3 Chemical Additives

In acidising techniques, additives such as corrosion inhibitors, surfactants,


che1ating agents and polymers are used. In hydraulic fracturing, significant
quantities of polymers are used to engineer an optimum rheo10gica1 and stable
fracturing fluid. The principal additives can be categorised as follows:

i) Viscosifiers. The most widely used viscosifiers are based on


hydroxypropy1 guar gum and some cellulose derivitives. Their main task
is to reduce pressure losses due to friction whilst pumping, provide
carrying capacity for the large volumes of proppant, and to create and
promote wider fractures.

ii) Surfactants, e.g. sulphonates, non-ionics and quaternary ammonium


compounds. The chemicals are required to prevent the formation of
emulsions or precipitates between the treatment fluid and the formation
fluid.

iii) Fluid loss additives e.g. guar gums, hydroxyethy1 cellulose po1yamines.
These chemicals prevent loss of fluid to the formation and assist in
fracture propagation.

iv) Clay stabilisers, e.g. potassium chloride (ca. 2% by weight) hydroxy


alumina, zirconium oxychloride. These chemicals are used to either
prevent or minimise clay hydration in water-sensitive rock formations.

4.4. Cost of Completion/Stimulation Chemicals

Typically, the majority of expenditure for completion and stimulation


chemicals takes place in the United States. An estimated breakdown of cost
for 1982 for chemicals is as follows:

Acidising Chemicals

Acids 190
Corrosion Inhibitors 6
Clay Stabilisers 5
Friction Reducers 5
Others 5

Sub Total 211


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The Market/or Chemicals in the Oil Industry 189

Fracturing chemicals

Viscosifiers 165
Fluid Loss Additives 20
Surfactants 20
Others 20

Sub Total 225

Grand Total 436

In the UK sector of the North Sea, the total market value of these chemicals
is estimated to be about 14 million, i.e. about 3% of the US market.
Acidising is useg extensively in the carbonate reservoirs of the Middle East
and that may be expected to contribute a further approximate 50 million
resulting in a world market of around 500 million. Market growth, dependent
on future activity can be expected to be of the order 10-14%.

5. FUTURE TRENDS

5.1 Drilling Fluids

Drilling activity is moving towards more hostile environments. The search for
oil and gas is becoming more difficult and new and deeper geological horizons
must be explored. Consequently, new chemicals must be developed to perform
under extremes of temperature, pressure and environment e.g. 400-500F;
25,000 psi and appreciable quantities of H S and CO (10-50%). Increased
2 2
emphasis will be directed towards polymers. The industry trend towards
low-solids fluids requires polymers that do not undergo shear degradation,
have good salt tolerance and filtration control and are stable at
temperatures up to 300F. No single polymer displays all these properties and
blends are currently used. Further work is required on polyacrylamides and
polyacrylates to improve their temperature stability and effective use at
lower dosage rates. A final and most important trend is towards the use of
environmentally acceptable chemicals. Increased environmental awareness and
legislation is having a significant impact on drilling operations and
disposal of chemicals.

5.2 Cementing

In line with the future trends for drilling fluids, cementing chemical
additives will also need to be developed to withstand extremes of temperature
and pressure. A continual problem facing the industry is the prevention of
gas migration through cement columns. As a result many wells are
inefficiently cemented and require costly repair work. Extensive research
work is presently being directed towards this problem.
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190 Chemicals in the Oil Industry

5.3 Completion/Stimulation Chemicals

Development in completion fluids will be towards a better understanding of


the physical and chemical properties of mixed brine systems under varying
temperatures and pressure. Corrosion inhibition techniques for such systems
will also require further development.

In hydraulic fracturing the trend will be towards new, improved and more
versatile polymers. Both emulsions and foams are increasing in popularity as
fracturing fluids, and extensive work can be anticipated in this direction.

Ill. PRODUCTION CHEMICALS


--------------------
1. ACTIVITY SCENE
The world demand for speciality chemicals for the treatment of oil, gas and
associated water is obviously highly dependent upon volumes to be treated.
World crude oil production (outside the Communist Block) now runs at about
40 million barrels per day (b/d) and the associated water production is
estimated at 16 million bId. The world gas production averages 3,000 billion
cubic feet per day. Some of the chemical problems which occur during
hydrocarbon production and processing are associated with crude oil
dehydration, foaming, paraffin wax deposition, fluidity and restartability of
waxy crudes, friction reduction of crude flow in pipelines, corrosion,
scales, de-oiling of water, bacterial activity, deposition of gas hydrates
and sulphur. The list is by no means exhausted and serves only to illustrate
the multitude of chemical problems which can be encountered and which are
often specific and unique to a particular situation and usually require an
equally specific and unique solution to the problem.

2. PRODUCTION OPERATIONS

In order better to understand the specific need for chemicals, it is


necessary to overview the actual hydrocarbon production process. After the
drilling of wells in an oil or gas field has been completed, production
operations commence. Production operations are responsible for the handling
of all produced and injected fluids, from the wellhead to the point of
disposal. In a typical offshore production platform development, the
following major processing activities would take place:

i) Wellheads and flowlines


Produced fluids are collected from individual producing wells and gathered
into a common manifold system. Typical chemicals used in this activity are
corrosion inhibitors, scale inhibitors, wax inhibitors, hydrate inhibitors.

ii) Q~!L~~~L~~~~E_~~e~E~~~~
The produced fluids are separated into their three major constituents under
controlled conditions of temperature and pressure. Not all wells produce
water during the early phase of production, but invariably do during the
latter stages. Principal process chemicals used are defoamers and
demulsifiers, fresh water washing (to remove salt).
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The Marketfor Chemicals in the Oil Industry 191

iii) 2!!_~~~~~~~!~~
Crude oil is normally pumped from the separation facility either to a tanker
or pipeline for evacuation. Typical chemicals used in this process, depending
upon the characteristics of the oil, are wax inhibitors, corrosion
inhibitors, and friction reducers.

iv) ~~~_E!~~~~~!~~_~~~_E!~~~~~!~~
Gas which is either produced (natural) or separated from oil (associated) is
normally processed to recover the heavier components, e.g. propanes, butanes
etc., which are often recombined with the oil stream. The gas is then usually
dried prior to being compressed for transmission to shore. Typical chemicals
used are glycols (for drying), hydrate reducers and corrosion inhibitors.

v) ~!~~~~~~_~~~~!
The water whieh is separated from the oil or gas is subject to a degree of
chemical treatment depending upon its final mode of disposal - usually
subsurface re-injection or surface disposal. Typical chemicals used are
corrosion and scale inhibitors, biocides, de-oiling chemicals and
po1ye1ectro1ytes.

3. PRODUCTION CHEMICAL PROCESSES

3.1 Dehydration of Crude Oils

i) !~!~~~!~~_~f_~!!f!~!~_~~~!~!~~~
When oil is initially produced from a well, it usually contains associated
gas but only minor amounts of water (less than 0.5%). With time, and
depending on the production characteristics of the reservoir, the "water-cut"
will increase and it is not uncommon for greater than 50% of the produced
fluids to be water within a period of five years. Under such conditions, the
water is generally emulsified in the oil and it is most important that the
oil and water are efficiently separated from one another.

Three conditions are necessary for the formation of a stable emulsion (a


stable emulsion is defined as an emulsion that will not break down in an
acceptable retention time without some form of treating) :

The liquids must be immiscible


There must be sufficient agitation to disperse one liquid as droplets in
the other
There must be an emulsifying agent present. Without this emulsifying
agent emulsions would be highly unstable.

In forming a normal emulsion (water-in-oi1) there are two forces that are
continually in direct opposition. The surface tension of the water permits
the droplets to form larger droplets which when sufficiently large will yield
to the force of gravity and settle out (Stokes Law).
In opposition, the film of emulsifying agents provides a barrier between
drops and tends to prevent the joining of the water droplets.
r t u P
192 Chemicals in the Oil Industry

ii) ~~~E~~!~E!~!!~~_~~~_~!~~!!!!I_~~_~!!_~!~!~_~~~!~!~~~
~b.e st..a'o-\..\:\..t..~ Cl~ a1:\. ~~~\.S\.()1:\. ,-a~ \)cc. aii'C.c::..'t.'C.~ ~1 ~a\.\1 \.a~\.~.Yt~, 0.\\ \)\ ~\\\.t.\\
can be classified into a chemical or physical category or both. The natural
materials (emulsifying agents) which stabilise crude oil emulsions are either
surface active agents or finely divided solids, which have a tendency to
absorb at the oil water interface, lower the surface tension and increase
emulsion stability. Typical surfactants present within crude oil are
asphaltenes, aromatic and naphthenic compounds of varying degrees of
complexity. Finely divided solids also present within the crude oil stream
such as clays, silica, carbon black, insoluble asphaltenes and various
insoluble inorganics such as iron oxide, iron sulphide and barium sulphate
all aid emulsion stability. A further point on emulsion stability is that for
normal oilfield emulsions, interfacial tension decreases with increasing
emulsifying agent concentration. Crude oil contains dissolved compounds whose
degree of ionisation depends on the pH of the water phase. When crude oil is
in contact with acid solutions, the nitrogen compounds are ionised, absorbed
at the oil-wa~er interface and lower the interfacial tension. At intermediate
pH values, the asphaltenes, resins, and organic acids and bases only
moderately affect the interfacial tension. To minimise emulsion formation,
the crude oil should not contact either high or low pH water because the
interfacial tension between the oil and water droplets is low at either end
of the pH scale.

Other factors influencing the stability of oilfield emulsions are the


temperature/viscosity, particle size distribution of water droplets, density
difference between crude oil and water, water content and age of the
emulsion.

iii) ~E~~~_~!!_~~~l~E~!!~~_i~~~!~!~~_~~~!~~!!!~~!!~~2
For effective dehydration, the following sequential steps are required:
destabilisation of the emulsion
coalescence of the destabilised water droplets
separation of the water from the oil phase

Presently, the most popular method of breaking an emulsion is by the


application of chemicals (demulsifiers).

Chemicals appear to be the most significant factor in treating oil emulsions


and are used to neutralise the emulsifying agents.
Demulsifiers are surface active agents which should easily migrate though the
oil phase to the interface and change its character from oleophilic to
hydrophilic. The basic theory is that an emulsifying agent should be added
which would normally produce an oil in water (reverse) emulsion. By
attempting to reverse phases, the intermediate condition of a destabilised
water drop is obtained. The activity of demulsifiers is related to two
general functions - speed of migration to the interface and performance at
that site.

Depending upon the chemical character of the compound stabilising the


emulsion, the pH of the solution, temperature etc. a demulsifier can be an
anionic, cationic or non-ionic agent.

Anionic demulsifiers are typically oils and alcohols, organic amine-fatty


acid soaps and sulphonated aliphatic and aromatic compounds.
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The Market/or Chemicals in the Oil Industry 193

Cationic demulsifiers are typically quaternary ammonium salts, whilst the


majority of non-ionic agents are esters.

All these compounds have in common that they consist of a non-polar


hydrocarbon chain which is attached to the oil phase and a polar-hydrophilic
part which seeks the water phase. Demulsifiers are usually supplied as a
25-50% solution of active material in alcoholic or aromatic solvents.

With so many variables in the system, a demulsifier is often a chemical or


formulation of chemicals unique to the particular emulsion requiring
treatment. Laboratory tests are required to select from a large number of
chemicals available the most effective one(s) for a certain emulsion. For
reliable conclusions it is required that representative emulsion samples be
used and that the test temperature be adjusted to that expected to prevail in
the field. Consequently the most reliable results are those obtained from
testing on site.

Final conclusions on the best demulsifier for a certain emulsion can only be
drawn from a comparison of several promising chemicals in a field test. Such
field trials are usually conducted under supervision of the chemical supplier
on a no-cure, no-pay basis. The ultimate objective is to find a chemical
which, at acceptable cost, effectively separates oil and water at the lowest
possible temperature, yielding dry oil, clean water and a minimum of
interfacial sludge.

In view of the constantly expanding development of new and improved chemicals


it is essential to review from time to time the particular approach to a
demulsification problem and attempt to achieve a more cost-effective
solution. As an example, a specific crude oil stream in South East Asia had
persistently caused dehydration problems ever since production commenced.
Considerable effort was spent on attempting to solve the problem during the
early 1970's, and it was ultimately found that with the state of the art at
that time, the crude could only be effectively dehydrated using acid
demulsifiers albeit at high chemical dosage rates (500-600 ppm). This method
of dehydration continued until the late 1970's, when a concerted campaign was
again started to try to improve the situation. After appreciable work,
utilising Service Company assistance, it was found that the crude could be
effectively dehydrated with a non-acid demulsifier, at chemical dosage rates
an order of magnitude less. As a result of this optimisation, an annual
saving on dehydration chemicals of around 2~ million was realised.
Typically, in a production area and depending upon the severity of the
treatment, chemical costs for demulsification can vary between 5 and 30 per
1000 bbl water processed.

In field operations, demulsifier is injected as close to the wells as


possible - sometimes even into the wells. In offshore operations, where
possible, chemical destabilisation takes place on the production platforms,
coalescence in the trunk lines and settling/water separation in onshore
facilities.

Traditionally, the Oil Companies have not become involved in the development
of demulsifiers; this was usually left to the Service Companies.
However, to a certain extent this approach is changing and now some of the
major international Oil Companies are diversifying their interests into this
business. Furthermore, in the face of increased operating costs, Oil
Companies are concentrating their attention on optimising the application
aspects of chemical demulsification in creating favourable conditions for
chemical destabilisation, coalescence, settling and liquid phase separation.
r t u P
194 Chemicals in the Oil Industry
During 1981, the cost of demulsifiers in North Sea applications was estimated
at around 3 million (in the United States some 60 million).

3.2 Defoaming of crude oils

Foaming of crude oil is a persistent industry problem causing poor well


productivity performance, inefficient oil/gas separation and measurement
difficulties. The mechanism of defoaming is to deactivate the surface active
compounds in the crude oil and alter the surface tension of the oil films
surrounding the gas bubbles. This weakens the surface film and releases the
entrapped gas.

Many defoamers are commercially available (e.g. phosphate esters, metallic


soaps of fatty acids). However, the category most ideally suited for crude
oil application are the organic silicone compounds. The dimethyl silicone
fluids appear the best performers under a wide range of conditions. They
exhibit exceptiional stability and resistance to oxidation and heat. Compounds
with viscosities (at 75F) between 500 and 15,000 cp seem most effective.
Laboratory screening followed by field testing is usually required to
optimise exact type and concentration. Dosage requirements are usually very
low. In a recent field example, a silicon dosage rate of less than 1 ppm
eliminated foam carry over and improved throughput capacity of a production
unit from 93,000 bid oil to 114,000 bid. The successful treatment not only
resulted in future reduced equipment savings but also an accelerated oil
income of around 350,000 per day for a chemical treatment cost of no more
than 1 per day!

Silicones have appeared compatible with most other chemicals added to the
crude and their effect on downstream processes is minimal.

3.3 Wax Deposition Inhibitors for Crude Oil

Paraffin wax deposition is prevalent in the oil industry. Depending on the


characteristics of the particular crude oil and producing temperature
conditions, wax can deposit at any part in the producing system from well to
pipeline.

As crude oil containing parraffin wax cools, the wax molecules begin to
precipitate and build up a crystalline matrix. The wax crystal is both
hydrophobic and oleophobic and in practical terms this means that the crystal
does not go with either the water or the oil phase. Thus it preferentially
precipitates from solution, adhering to exposed surfaces, for instance pipe
walls.

Prevention of wax deposition is achieved by deposition inhibitors, which are


either dispersants or crystal modifiers. Dispersants are developed to
coat small paraffin wax particles chemically and change their ability to
adhere to each other or to pipe surfaces. In the small particle state, wax
will stay suspended in the crude oil for trouble-free movement. The
dispersant is chemically structured so that it has a large, dense head on one
end and a low density tail on the other. The head has an attraction for the
wax particle and the low density tail may be either water or oil soluble,
depending on the phase into which the paraffin wax is to be dispersed. In
most cases it is easier and more desirable to disperse wax in the oil phase.
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The Market jar Chemicals in the Oil Industry 195

Crystal modifiers co-crystallise with paraffin crystals and prevent the


crystals from attaching to each other and forming a network of large
crystals. The compound will also help to reduce the adhesiveness of the wax,
preventing it from sticking to a pipe surface. Wax crystal modifiers are
generally linear polymeric molecules with branched side chains.

Dispersants and crystal modifiers are usually injected continuously; when


using the latter compounds, the application temperature is critical and
should be higher than the cloud-points, i.e. the temperature below which
crystallisation begins.

There is limited experience with dispersant type wax inhibitors, which


appeared ineffective in the few cases applied. The crystal modifiers are very
successful and these compounds have been used where economically justifiable.
The most effective compound used so far has been a copolymer of
alkylacrylate.

In a West African oil field, where wax deposition in down-hole tubing and
flowlines necessitated frequent scraping and pigging, application of this
copolymer dramatically reduced clean-out frequencies. This was achieved at
additive concentrations of 100-200 ppm, injected down-hole with the lift gas.

In another case, in an European oilfield, it appeared possible completely to


eliminate wax deposition in a 10 mile 4 inch trunk line at an injection rate
of 200 ppm.

Similar experience has been reported from some Canadian oil fields.

Nett savings reported have been modest, of the order of one penny per barrel
of crude treated. The reason is that - compared with other additives -
comparatively high concentrations of chemical have to be applied;
furthermore, conventional mechanical treatments are in general not very
costly. Most benefit .~ derived from the fact that the chemical treatment -
contrary to mechanical treatment - renders continuous production possible;
therefore, in many cases the major pay-out for chemical treatment is in fact
derived from the elimination of deferred production of crude oil.

Screening of wax deposition inhibitors can be carried out in the laboratory


with special test equipment, including a miniature pipeline. Usually field
trials are carried out to confirm the results of laboratory investigations.

3.4 Fluidity and Restartability Improvers for Crude Oils

The use of these compounds is to improve the pumpability of waxy crude oils
which are subjected to low temperatures. Their principal application is to
reduce the viscosities and gels under such conditions.

When waxy crude oil is cooled off paraffin wax crystallises; this causes a
change in the structure of the crude resulting in viscosity increases and
subsequent increased pumping and flowline pressures. Fluidity improvement is
needed.

These oils also exhibit a yield value. When the crude sits still at a
critical temperature, it sets up. When pressure is applied, a greater amount
of energy is needed to start the fluid flowing than is necessary to maintain
a constant pumping rate. Restartability improvement is needed in this case.
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196 Chemicals in the Oil Industry
Crystal modifiers are used as fluidity and restartability improving
additives. These additives are chemically similar to the compounds used to
prevent wax deposition.

The use of fluidity additives permits waxy crudes to be produced and pumped
over long distances without applying diluents or heat, while the use of
restartability additives permits line shutdown and static cooling of waxy
crude. Depending on the type of crude, additive concentrations of 100 to 200
ppm are usually sufficient to achieve the required results.

The effectiveness of candidate compounds is normally evaluated both in the


laboratory and the field. Laboratory tests are carried out in a pipe line
loop test rig.

Fluidity and restartability improving additives find growing application,


specially now more crude oil is being produced offshore in both temperate and
arctic zones.

In one case waxy crude pumped through a 170 mile pipeline can be kept fluid
at temperatures ranging between 50 and 60F by doping with 150 ppm of a
copolymer of alkylacrylate.

Restartability presented no problems at temperatures as low as 40F.


Laboratory tests had shown that the pour-point of this crude could be reduced
from 70 to 20F by doping w!ih 150 ppm of this additive. The viscosity during
pumping (shear rate 200 sec ) could be reduced from 110 to 25 cP at 60F.

3.5 Pumpability Improvement (Drag Reduction) for Crude Oils

Drag reduction is the increase in pumpability of a fluid caused by the


addition of small amounts of chemical to the fluid. Drag reduction occurs
only in turbulent flow.

The only extensive practical use of drag reducers has been with aqueous
systems. In the oil industry these compounds have been used in hydraulic
fracturing treatments. Water soluble polymers such as guar gum or high
molecular weight carboxymethyl cellulose have been effective in reducing
horsepower requirements and/or increasing injection rates during treatments.

The state of the art of drag reduction in oil pipelines is just beyond the
experimental stage because it was difficult to find suitable materials able
to reduce drag in aliphatic hydrocarbons.

Long chain polymers of high (one to ten million) molecular weight, such as
synthetic rubber compounds, have been found effective drag reducers for crude
oil. An almost unsurmountable problem appeared to be the shear degradability
of these compounds; the effect of high-shear conditions encountered in
centrifugal pumps causes a degradation of the long-chain polymers whereby
less effective, short-chain compounds are formed. A solution was found by
adding these chemicals in solid form. This allows the chemical to dissolve
slowly, producing drag reduction as it moves through the line. At the same
time, useful polymer in the form of undissolved solids passes undegraded
through the pump stations and continues to dissolve down-stream of the pump.

Chemical additions of the order of 50 ppm are required to achieve a friction


reduction of some 10%. There is some decrease in drag reduction with
increasing pipe diameter.
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The Market/or Chemicals in the Oil Industry 197

3.6 Deoiling of Produced Water

Deoiling of produced water is usually carried out with the help of equipment
operating on the principles of gravity (skim tank, API separator, Corrugated
Plate Interceptor or Tilted Corrugated Plate Interceptor) or gas flotation.
In some cases, where very low oil contents are required (e.g. for
re-injection, the generation of steam), the gas flotation stage is followed
by either filtration or a combined treatment of flocculation and filtration.

For gravity separation, conventional de-oiling chemicals are used, which


functionally and physico-chemically resemble the demulsifying compounds used
in crude oil dehydration. Their purpose is to destabilise oil-in-water
emulsions; this is achieved by eliminating the predominantly hydrophilic
compounds present in the oil-water interface.

De-oiling chemicals are therefore surface-active agents which alter the


characteristics of the interface. They should easily migrate through the
water phase to the interface and concentrate there, changing the character of
the interface from hydrophilic to oleophilic. To achieve this the non-polar
hydrocarbon part of the compound, which orients itself in the oil phase,
should dominate the polar-hydrophilic part, which seeks the water phase. The
majority of the chemicals that can be used for de-oiling are represented by
three categories:

i) Alkyl quaternary ammonium compounds.


ii) Alkyl benzyl quaternary ammonium compounds.
iii) Pyridinium compounds.

Finding the most suitable de-oiling compounds for a given oil-contaminated


water is a matter of trial and error and resembles the finding of a
demulsifier for crude oil emulsions. Again Service Companies play an
important part in the selection process.

Chemical is injected as far upstream of the gravity separation equipment as


operationally possible, in order to give sufficient opportunity for
coalescence of the destabilised oil droplets in the line system.

For oil removal by gas flotation often other chemicals, so called flocculants,
are used. Their task is to increase the size of the oil droplets by
flocculation. Mostly organic flocculants are used for gas flotation; they are
polyelectrolytes, which have cationic, anionic or non-ionic functional
groups. Inorganic flocculants have been found unsuitable, because they make
the floc heavy and are detrimental when returned with the oily froth to the
oil treating system.

If oil has to be removed from water by flocculation followed by filtration,


then inorganic flocculants such as alum, ferrous sulphate, ferric chloride
and copper sulphate can be used, often in combination with a small amount of
organic flocculant. The separated oily floc is usually disposed of by burning
in special inclnerators.

Deoiling compounds of various types are used in international operations.


Upstream of gravity separation equipment surfactants in concentrations of
10-20 ppm have been used. Depending on the degree of coalescence the oil-in-
water emulsions are subjected to, oil removal efficiencies of 80 to 95
percent have been achieved. For mechanically induced gas flotation units
flocculant concentrations of up to 10 ppm are usually adequate to achieve
r t u P
198 Chemicals in the Oil Industry
over 90% removal of suspended oil. In one production area a mini emulsion
(droplet size one micron average) containing up to 1000 ppm suspended oil is
treated with inorganic flocculant and almost 100% oil removal is achieved in
the floc separation and filtration equipment.

3.7 Gas Hydrate Reduction

Gas hydrates are solid compounds formed by the reaction of gas with water.
They resemble snow in appearance and form as crystals. When formed in well
tubulars, pipelines and gathering systems gas hydrates cause partial or
complete blocking, reducing or stopping gas flow ("Line freezing").

Chemical compositions are:

Methane Hydrate CH 7 H 0
4 2
Ethane Hydrat~ C H S H 0
2 6 2
Propane Hydrate C H IS H 0
3 S 2
Also CO and H S form hydrates.
2 2
The temperature at which hydrates form increases with pressure and gas
density. For instance, methane hydrate can be formed at 40F and 500 psi.
When the pressure is increased to 2000 psi, the temperature critical for the
formation of hydrate increases to 60F.

Hydrates are most conveniently controlled by preventing their formation.


The three accepted methods are:

Dehydration
Chemical additives
Heating

Free water is necessary for the formation of hydrates. If the water dew point
of the gas is lower than its temperature, no hydrates are formed.

The chemical additives used depress the hydrate temperature of gas. Although
ammonia, sodium chloride or calcium chloride have been used, one of the more
widely used chemicals for this purpose is methyl alcohol. It is more
effective than ethyl or isopropyl alcohol, and is also the least expensive.
Alcohol is not readily reclaimed from an aqueous solution, so its use is
restricted to applications where it is expendable. The amount of alcohol
required for any specific condition is usually calculated. A general practice
is to inject alcohol into a flowline near the well head. This eliminates the
need for a header and permits the total production to be transported to a
central facility where the free liquids can be removed and the gas processed.
Gas produced offshore is treated with alcohol before transportation by
pipeline to an onshore facility.

Glycol has also been used and has the advantage that it can be recovered from
an aqueous solution by boiling off the water. The regenerated glycol is then
returned to the injection point. Ethylene glycol is the preferred glycol.
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The Market/or Chemicals in the Oil Industry 199

4. OTHER PRODUCTION SPECIALITY CHEMICALS

Typical production speciality chemicals, over and above those outlined in the
foregoing sections are corrosion inhibitors, scale inhibitors and biocides.

4.1 Corrosion Inhibitors

These are chemicals which protect metals, exposed to an agressive


environment, against corrosion in wells and surface facilities.

Oil Environment
The type of corrosion which can take place in oil wells, pipelines and
facilities is usually sweet (C0 ) or sour (H S); oxygen corrosion seldom
2 2
occurs. No corrosion takes place when dry oil is produced or handled; as
ionic reactions between CO or H S are the cause of metal corrosion, the
2
presence of water in the system 2~s essential for these reactions.

The corrosion inhibitors used for this application are usually the surface
active - adsorptive type, the so called film formers. Almost 90 percent of
the inhibitors in successful use today are either based on the long chain
aliphatic diamines or on long carbon chain imidazolines. Various
modifications have been made of these structures to change the physical
properties of the material. For example, ethylene oxide is commonly reacted
with these compounds in various molecular percentages to give polyoxyethylene
derivatives that have varying degrees of brine dispersibility. Many
carboxylic acids are used to make salts of these amines or imidazolines.

Corrosion inhibitors can be applied continuously or by batching. If a


continuous down-hole treatment is required, the chemical can be injected
directly into the annulus of the well with the help of a marcaroni pipe or
in gas lift wells - with the lift gas. Before continuous treatment a single
batch of inhibitor is circulated to lay down an initial protecting film. The
frequency of batch treatments depends on the severity of the corrosion
problem and the fluid velocity in the production conducts. Batch treatments
by squeezing into the formation are often successfully applied.

Selection of a corrosion inhibitor takes place in the laboratory; a


representative mixture of the crude oil concerned with the relevant formation
water and gas phase is brought into dynamic contact with steel coupons, with
and without inhibitor under simulated well condition ("wheel" test or
"rotating bottle test"). Successful candidates are selected for field
evaluation.

The performance of corrosion inhibitors in the field is closely monitored.


Coupon tests and iron counts are still being used for this purpose. Corrosion
rate measurements using polarisation resistance techniques can be used as
well, but periodic changes of electrodes are needed due to fouling.

Water Environment
In produced water systems corrosion can be caused by dissolved oxygen, carbon
dioxide, hydrogen sulphide or bacteria. Dissolved salts, the pH, the
temperature and the water velocity in the system strongly affect the rate of
corrosion. Depending on the final destination of the produced water, a
decision should be made whether measures have to be taken to prevent
corrosion or not. If so, several methods can be applied, including removal of
the corrosive gases, using corrosion resistant material or applying corrosion
inhibitors. A combination of one or more methods is also practised.
r t u P
200 Chemicals in the Oil Industry

When oxygen is the cause of corrosion in a given system then, in most cases,
oxygen will be removed or corrosion resistant materials will be used. This is
because there are hardly any suitable compounds available. The classic
passivating inhibitors such as chromates or nitrites, or inorganic barrier
formers such as zinc salt phosphate combinations or the silicates, are ruled
out for once-through systems because very high concentrations are required
particularly in the presence of a significant chloride content. Combinations
of amino methylene phosphate and zinc salts have been successfully used in
circulating water systems and proved more effective than the inorganic
phosphate-zinc salt combination. Recently an organic sulphophosphate was
introduced which shows promising results as an oxygen corrosion inhibitor.

When HZS and/or COZ cause corrosioq in a given system, barrier forming or
"filming" inhibitors will be used. Because oil is usually absent or only
present in low concentrations, these inhibitors should be water soluble, i.e.
the balance between the hydrophobic hydrocarbon chain and the polar portion
of the inhibitor molecule should be changed in favour of the latter. However,
as the inhibitor film stability is determined by the interplay of a number of
factors involving both the hydrophobic and hydrophylic portions of the
molecule, a delicate balance has to be attained because changes in the
molecule that promote water solubility tend to decrease film stability. This
conflict between solubility and film stability has been one of the basic
obstacles to be overcome in formulating an effective water soluble inhibitor.

However, a wide variety of inhibitor formulations is available for corrosion


control in water systems. Most of these are produced from only a few types of
starting materials. Fatty acids or rosin acids, some form of basic nitrogen
precursor and ethylene oxide are the active ingredients sources.

After transformation into the final product, the resulting ingredients are
usually dissolved in an alcohol-water solution. Actual inhibitor content
ranges from ZO to as much as 65-70%, depending on the solubility of the
compound. Often, more than one type of inhibitor molecule will be used.

The available commercial inhibitors may be grouped as follows:


Primary monoamines (as salts, ethoxylates or unmodified form)
Polysubstituted monoamines (both secondary and tertiary forms)
Diamines/polyamines/imidazolines (either unmodified or as derivatives)
Quaternary ammonium compounds (after as trimethylalkyl)

Concentrations ranging between 5-Z5 ppm are required, depending on water


temperature, pH, salinity and flow velocity. The chemical is usually injected
continuously at strategic locations into pipe-line, pump suction, etc. The
effectiveness of the inhibitor is evaluated by monitoring the corrosion rate;
rates of 10-Z0 mpy are considered acceptable from the metal-loss point of
view.

Gas Environment
---------------
Corrosion in gas production wells and surface system is usually caused by
COZ' HZS or a combination of these two acid gases. Protection of off-the-
shelf carbon steel is needed when the partial pressure of CO 2 in the system
exceeds 7 psi and that of H S exceeds 0.05 psi*). In the latEer case stress
corrosion cracking occurs. tn all cases the presence of condensated water is
required to have any corrosion at all.

*) Partial pressure of H S in a system containing 0.01 mol % HZS (100 ppm or


2
6.7 grains per 100 SCF) at a total pressure of 1000 psi equals 0.1 psi.
r t u P
The Marketfor Chemicals in the Oil Industry 201

The corrosion inhibitors used resemble those applied in oil wells; they are
film-forming and adsorb onto metal surfaces. They create a hydrophobic layer
that prevents the corrosive gases from contacting the metal surface
intimately enough to allow chemical reactions to proceed.

Corrosion inhibitors can be introduced into the well by c~ntinuous down-hole


injection via the annulus, by conventional batch treatment or by
batch-squeezing. The inhibitor is usually dissolved in diesel oil, kerosene
or - if available - gas condensate; 5-10% solutions are applied.

Subsurface CO corrosion occurs in a major European gas field.


This results trom 0.9% CO (20 psi partial pressure) in the gas, together
2
with water vapour, which condenses in the tubulars causing formation of
corrosive carbonic aid. Originally corrosion was controlled by batch
treatments. However, when well production rates were increased (increasing
gas velocities in the tubing from 40 to 65 ft/sec.), protection by batch
treatment appeared inadequate.

Continuous treatment was started by injecting 60-70 GPD of 8% inhibitor


solution into the wells via the annulus and an injection valve at 8500 ft.
Some 285 wells now on production are continuously treated. Corrosion rates
average 1.4 mpy, which means an average tubing life of 11 years.

A high-pressure (20,000 psi), high-temperature (380F) sour gas field in the


USA produces a mixture of 27-45% H S, 3-9% CO and 45-65% methane from 19,700
2 2
22,200 feet deep horizons. Production averages 15 million cu ft per well.

The gas is water-saturated at bottom hole conditions and produces no


hydrocarbon condensate. This composition, coupled with the high pressure and
high temperature, constitutes a very corrosive environment. A successful
corrosion prevention system was developed which was continuous chemical
inhibition. A key feature of the well completion design is the absence of a
down-hole packer between the production casing and tubing to provide for
circulating fluids (API grade C-75 and P-I05 steel are used for the well
tubulars for the upper and lower parts respectively).

The inhibition fluid has to meet the following requirements:

Must prevent corrosion


Have proper phase behaviour
Be of predictable and uniform quality
Be manageable
Be able to be dehydrated
Have a low vapour pressure
Be non-scaling

The greatest problem was to find an inhibition system which maintained a


liquid phase in the entire tubing string. This problem was empirically solved
by duplicating bottom hole conditions in surface test facilities with various
carrier oils until one was found which yielded sufficient liquid phase at
acceptable ratios of circulated carrier oil to gas.

To keep the inhibition system manageable, the viscosity had to be low enough
to be pumped in cold weather.
r t u P
202 Chemicals in the Oil Industry

The ability to separate water from the inhibitor system is important. This
water is picked up from the water-saturated sour gas system at a rate of
6-8 barrels per million cu ft gas produced. A low vapour pressure of the
system is an economic necessity, because carrier oil and inhibitors are both
expensive. It is an obvious prerequisite that the inhibitor system is
non-scaling or non-fouling; it reduces well production and inhibitor
circulation and necessitates expensive work-overs.

The most suitable inhibitor system appeared to be 50-50 mixture of two


specially refined oils containing 1% of inhibitor (an imidazole with an
olefin chain). The results of the application of this technology have been
very successful since its introduction in 1974. Tubing inspection revealed no
internal corrosion. Some minor pitting (20-40 mils) was observed after 3-4
years of service.

4.2 Scale Inhibitors

These chemicals prevent or m1n1m1se the deposition of scale from water as a


result of an instability condition induced by a change of temperature or
pressure. Also mixing with an incompatible water causes instability and scale
deposition. Scales of calcium carbonate, calcium sulphate and barium sulphate
have been encountered both down-hole (in formation, perforations, casing,
tubing) and at the surface (flowlines, oil/gas separators, transfer pumps).

The action of most scale inhibitors is basically one of adsorption on the


microcystalline nuclei to inhibit growth to full-fledged scale crystals; a
small amount of chemical can tie up a large amount of scale-forming material.
These inhibitors are usually phosphorus compounds in several forms. Some
inorganic polyphospates, such as sodium hexametaphosphate, characterised by
a P - 0 - P link, are very effective in the low to medium temperature ranges
(up to about 150F) against deposition of calcium carbonate and calcium
sulphate. At higher temperatures these compounds are ineffective. The
protection against calcium carbonate scale is excellent (2-5 ppm inhibitor
needed), against calcium sulphateJfair (10-20 ppm), and against barium
sulphate, poor (> 50 ppm).

Organic phospate esters, characterised by a R- 0 - P link, are generally


more stable than the inorganic phosphates, especially at elevated
temperatures (up to 250F). However, they are not compatible with high-
calcium waters and in some formation squeezes they can produce emulsion
blocks. The protection against carbonate and sulphate scale is fairly good
with required additions ranging from 10-20 ppm.

Organic phosphonates J characterised by a R - C - P link, have a high heat


stability (350C), excellent solubility in high-calcium waters and do not
seem to cause emulsion blocks on squeezing. Protection against carbonate and
sulphate scale is very good with required additions ranging from 5 ppm (for
CaC0 ) to 20 ppm (for BaS0 ).
3 4
Organic amino-phosphates are intended not only to provide scale control but
also corrosion control. The phosphate-ester portion of the molecule is the
same as in the organic phosphate ester. In addition, there is a nitrogen-
hydrogen link in the molecule which enables it to serve the dual function.

Some organic polymers are also active as scale inhibitors; it is believed


their activity is also based on an adsorption mechanism which prevents
crystal growth. This type of inhibitor is comparatively new on the market and
little practical experience is available.
r t u P
The Market for Chemicals in the Oil Industry 203
Some scale inhibitors function by a chelating mechanism wherein one molecule
of sequestrant reacts with one atom of calcium or barium to form a soluble
complex. In this way calcium or barium ions are unable to combine with
carbonate or sulphate ions and precipitate. An example of a chelating agent
is EDTA (ethylenediaminetetraacetic acid). This compound is rarely used
because comparatively large quantities are required and it is expensive.

Most scale inhibitors are already effective at the threshold concentration of


2 ppm. However, in practice concentrations of 5-20 ppm are maintained. For
operational reasons, the liquid form is preferred for field use; this implies
that the originally solid polyphosphates have to be dissolved before use.

The selection of scale inhibitors is carried out on basis of laboratory


evaluation tests followed by field trials. On basis of the temperature
prevailing in the system to be protected, a first selection is made before
the laboratory tests. A simple apparatus is available to screen scale
inhibitors. Scaling solutions, containing inhibitor, are pumped at constant
rate through a long capillary tube and the pressure measured. If scale
deposition occurs; this pressure shows an increase. The compound that can
prevent a pressure increase at the lowest concentration is selected for
field trials.

Down-hole, scale inhibitors can be applied by batch-squeezing, continuous


injection via the annulus or using slowly dissolving compounds.

Batch-squeezing has been successfully applied by the industry in several oil


fields. In one field severe production losses occurred due to deposition of
carbonate scale in valves, well tubing, production sleeves and even in the
producing formation. Liquid scale inhibitors provided a method of preventing
scale deposition using the squeeze technique. This technique has been applied
in more than hundred wells, squeezing being combined with acid clean-out
treatments to remove scale that had previously been deposited.
Amino-methylene phosphonate is used in 40 barrel batches, consisting of fresh
water containing 3% active material. After squeezing into the formation, the
inhibitor is displaced with diesel oil to five feet distance from the
borehole. Although scale deposition is effectively prevented, in some of the
treatments a decrease in production rate was observed. It is believed this is
caused by the formation of emulsion blocks during squeezing.

Retreatment is done when phosphonate residuals drop below 10 ppm. Squeeze


treatment cycles of three to fourteen months have been obtained.

4.3 Biocides

The problems caused by micro-organisms can be numerous and varied in effect


and impact. Micro-organisms that can cause significant problems in produced
water are slime producing bacteria (blockage of filters), iron bacteria
(blockage of filters, corrosion), yeasts and filamentous fungi and sulphate
reducing bacteria (SRB). These latter anaerobic micro-organisms cause the
most serious material problems which plague production operations. Their main
feature is that they can reduce inorganic sulphur compounds to sulphide. The
typical overall equation for the metabolism of SRB is:

The problems caused by SRB are therefore associated with the generation of
H S and CO and the removal of hydrogen from an aqueous system.
2 2
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204 Chemicals in the Oil Industry

A biocide can either be bactericidal or bateriostatic, largely depending on


concentration. Which of these two properties are required in a particular
location will depend on circumstances. Thus if a large bacterial population
needs to be reduced or eliminated, a bactercidal action will be required.

Although there are many service companies who provide a multiplicity of


biocide formulations, there are relatively few biocides in common use. These
are quaternary ammonium compounds, amines, chlorinated phenols, chlorine,
aldehydes and thiocyanates. Formulations may contain more than one of these
compounds. In most situations this list is reduced for various reasons. Thus,
incompatibility with other chemicals, partition into oil, insolubility in
water, environmental considerations and insufficient biological activity can
all permit the sensible use of only an extremely limited selection.

Most micro-biological activity can be suppressed by the cheapest bactericide


available, chlorine. The disinfecting effect is mainly due to the formation
of oxygen in "statu nascendi" which kill bacteria by oxidation. There is also
evidence that the chlorine kills bacteria by precipitating their proteins as
chlorinated p'rotein compounds. Chlorine can be inj ected as gas from pressure
bottles or as hypochlorite. Hypochlorite can originate from common bleaching
powder or from on-site electrolytical generators. Injection is usually
continuous; the required concentrations depend on the BOD of the water -
residual chlorine concentrations of up to one ppm are normally maintained.

SRB are often insensitive to chlorine and more potent biocides such as
quaternary ammonium compounds, aldehydes or a mixture of these compounds are
required. Shock treatments are given; weekly or twice weekly 3-6 hour, 50-100
ppm slugs of biocide are added. Every 2-3 months the biocide is changed to
eliminate the possibility of the SRB becoming immune to treatment.

Screening of biocides takes place in the laboratory using cultures of SRB


isolated from the water concerned in accordance with API recommended practice
No. 38. Often a modified method is used, whereby a medium prepared from the
subject water is applied.

Monitoring of SRB in a system is crucial; SRB counts are established using


method API RP 38 or, where possible, measurement of adenosine triphosphate
(A.T.P. photometry). The latter method has the advantage of rapidity, but
suffers from the disadvantage on non-selectivity.

5. COSTS OF PRODUCTION SPECIALITY CHEMICALS

On a world market scale, the following breakdown of production speciality


chemical expenditure is estimated:

Demulsifiers 135
Corrosion Inhibitors 85
Surfactants 15
Biocides 10
Scale Inhibitors 35
Wax Inhibitors 10
Others 10

300

Approximately 7 million is expected to be spent in the United Kingdom.


r t u P
The Market for Chemicals in the Oil Industry 205
6. FUTURE TRENDS

Some typical examples of new product needs for production speciality


chemicals are as follows:
i) Development of non-toxic non-polluting chemicals for corrosion and
biocidal inhibition, especially for offshore.
ii) Development of biocides which will be effective throughout the reservoir
and will not adhere to the rock, or degrade under extremes of
temperature and pressure.
iii) Improved de-oiling compounds to process water from thermally affected
crude.
iv) Non-emulsifying corrosion inhibitors which are stable at high pressure
and temperature.
v) Improved corrosion and scale inhibitors for high temperature and
pressure application in both oil and gas wells.

Ill. OIL RECOVERY CHEMICALS


----------------------
1. ACTIVITY SCENE

Primary recovery of oil and gas generally relies on the natural drive energy
(usually pressure) within the reservoir. Typical recoveries (as a percentage
of original oil in place) vary, among other parameters, on the nature of the
crude oil. For example, heavy and viscous crudes may yield only 1-5% whilst
light crudes can yield from 10-40%. Secondary recovery processes such as
water injection and gas injection are often utilised to recover additional
oil. Enhanced oil recovery is the description applied by the oil industry to
non-conventional techniques for getting more oil out of subsurface reservoirs
than is possible by primary or secondary recovery processes. The oil not
producible, or left behind, by these conventional recovery methods may be too
viscous or too difficult to displace. It may also be trapped by capillary
forces in the flooded parts of the reservoir, or by-passed by the injected
water or gas. In general, the aim of enhanced oil recovery techniques is to
recover more oil by improving the displacement efficiency. Enhanced oil
recovery techniques are conveniently subdivided into various categories, i.e.
miscible, chemical and thermal processes.

Small amounts of speciality production chemicals are utilised in primary and


secondary recovery processes. However, the significant potential for

world cr?2e oil reserves of some 5.5 x 10


r
chemical utilisation is within the enhanc 2 oil recovery techniques. Of the
barrels, only around
1.5 x 10 barrels (27%) is eSf~mated to be recoverable by conventional
methods. The remaining 4 x 10 barrels may be seen as a target for enhanced
recovery.

2. SECONDARY RECOVERY METHODS

2.1 Water/Gas Injection

Over the years it has been established that maintaining reservoir pressure
can yield more oil than can be obtained by primary recovery alone. By such
techniques, the reservoirs natural energy and displacing mechani~m, which are
responsible for primary recover~ are supplemented by the injection of water
or gas.
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206 Chemicals in the Oil Industry
In the case of water injection, over 90% of the North Sea fields have on
their platforms a seawater injection facility, capable of producing
sufficient treated water to replace the extracted oil and gas volumetrically.
Typical chemicals used in water treatment are biocides (sodium hypochlorite,
glutaraldehydes etc.), scale inhibitors, corrosion inhibitors and oxygen
scavengers (sodium bisulphite, ammonium bisulphite) most of these chemicals
have already been mentioned in the foregoing sections.

Little or no chemical treatment is required for gas injection, since the gas
is usually dried and compressed prior to re-injection.

3. ENHANCED OIL RECOVERY METHODS

3.1 General

Although each_EaR method (chemical, miscible or thermal) has its own range of
application, 'these methods are to a large extent complementary and thus
together cover a wide range of reservoir conditions.

In spite of the considerable effort spent on research and field testing


during the last 30 years, enhanced oil recovery techniques are, on the whole,
still very much in a stage of development.

Most successful so far have been thermal recovery methods, particularly those
employing steam. For many years steam drive and steam soak have been applied
on a large scale in e.g. Venezuela, the USA and the Netherlands. Obvious
targets for the application of thermal recovery are the large heavy oil
accumulations in Venezuela.

The prospects for "miscible" recovery (including e.g. non-miscible nitrogen


injection) techniques are promising. Large-scale miscible gas injection
projects are underway in various parts of the world.

Although the mechanism of chemical flooding is now much better understood


than ten years ago, these processes are still in the testing stage.
Nevertheless, for a large fraction of the light oil in place world-wide,
chemical flooding is considered to be the only method for increasing the
ultimate recovery above what can be produced by conventional methods.
Consequently, its long term potential should not be overlooked.

It is important to realise that EaR methods always have to be tailored very


carefully to the specific conditions of the reservoir where they are to be
applied. This also means that extensive field testing is a prerequisite for
large-scale application.

The long-term future for enhanced oil recovery is promising, but it is not
expected to contribute significantly on a world scale before the end of the
century. Even that will require a considerable further technical and
financial effort.

3.2 Thermal Processes

The purpose of these methods is primarily to reduce the oil viscosity and
thereby improve the sweep efficiency for heavy oil (specific gravity 0.95 to
1.01 at 60F).
r t u P
The Market/or Chemicals in the Oil Industry 207
Steam Drive
Because-of tts relatively low density and viscosity, steam tends to by-pass
the oil along the top of the reservoir. This negative effect is, however,
more than compensated by several positive aspects:

i) its large heat content

ii) the relatively high pressure gradient in the steam zone due to the
high velocity of the condensing steam

iii) effective heating of the underlying oil by water of condensation

iv) low residual oil saturation in the steam zone due to (partial)
vaporisation

As a result, steam drive has been a very effective recovery method for
heavy-oil reservoirs, and has found wide application during the last few
decades.

Steam Soak
This process,-also referred to as "cyclic steam injection", "steam
stimulation" or "huff and puff", was developed in the late 1950s for the
heavy-oil fields on the Bolivar Coast in Venezuela. Steam soak is
essentially a stimulation method which will activate natural drive mechanisms
(rock compaction, solution gas drive, gravity segregation) which are dormant
under "cold" conditions. It is also applied in combination with steam drive.

The success of the steam soak method is due to a combination of factors:

i) the strong reduction in oil viscosity between, say 50 and 100C

ii) the effective redistribution of heat around the well bore due to
the fact that steam overruns the oil and thus forms a thin steam
zone on top of the oil

iii) storage of a large fraction of the heat injected in the rock, which
acts as an effective heat exchanger slowing down shrinkage of the
hot zone around the well bore during the production phase.

As a result, high oil/steam ratios can be obtained.

!!o!. ~a!.e.!:.i.nie~ti.0E.
Although less effective, both as a heat carrier and as a displacement fluid,
hot water may find application in reservoirs where pressures are too high for
steam injection. At very high temperatures (around 350C) hot water may act
as a solvent for oil and thus bring about a reduction of the residual oil
saturation.

In-situ combustion
Two pri~cipal-techniq~es have been tested, both in the laboratory and in the
field - forward and reversed combustion. In forward combustion, the
combustion front moves in the same direction as the injected air, whereas in
the reversed combustion process, it moves in the opposite direction. Forward
combustion is now generally preferred to reversed combustion.

The attraction of the ISC process is that heat is generated in situ,


utilising the heavy ends of the crude that would otherwise b~behind.
r t u P
208 Chemicals in the Oil Industry

On the other hand, of course, energy is needed for compression of the air to
be injected. There are no heat losses in injection wells. Furthermore, by
injecting water together with the air, the process can, in principle, be
turned into an in situ steam generation process.

Unfortunately, it is difficult to control this process under reservoir


conditions. In the case of "dry" combustion (air injection only) the problem
is how to control movement and temperature of the combustion front. In the
case of "wet" combustion water and air tend to follow different paths as a
result of gravity. High temperatures and the presence of corrosive fluids
lead to frequent well failures.

In spite of all this, there are still a number of - reportedly successful -


in situ combustion projects in operation. It seems unlikely, however, that
this number will grow substantially until the operational problems described
above have been solved.

f.h~m..!:c~~ ~t..!:l..!:s~d_i~.!..h~r~al.E.r~c~s~e~
In steam projects, water treatment chemicals (inhibitors, softeners, oxygen
scavengers) are used extensively to render the source water suitable for
boiler feed water for steam generation. On the processing side, steam-
affected crude is notoriously difficult to dehydrate and requires specialist
expertise and chemicals for both demulsification and de-oiling of the produced
water. Furthermore, thermally affected crude often generates significant
quantities of H2 S and CO 2 which require appropriate inhibition chemicals.

3.3 Miscible Drive Methods

The principle of a miscible or near-miscible drive process is to eliminate or


strongly reduce the interfacial tension between the displacing and the
displaced fluid, with the purpose of mobilising the oil trapped by capillary
forces after water or gas drive.

Two types of miscibility can be distinguished; direct miscibility in which


the fluids mix in all proportions, and developed miscibility where the fluids
are not directly miscible, but develop miscibility as a result of component
exchange between two fluids.

Processes of this kind, based on the injection into the oil reservoir of a
suitable solvent or gas, have been studied since the early 1920s, and in
theory they can recover all the hydrocarbons left behind by conventional
recovery methods. But, since the miscible drive fluid is often more mobile
and less dense, it tends to by-pass the oil by over-running it or fingering
through it, thus leading to low displacement efficiency.

The main miscible-drive fluids are: hydrocarbon solvents, (enriched or


high-pressure) hydrocarbon gas, carbon-dioxide and nitrogen. The
applicability of these fluids depends largely on reservoir pressure,
availability and cost.

Hydrocarbon solvents
Any s;l;e~t-miscibl~ ;ith oil (for example, LPG, kerosine or gasoline) can be
injected into a reservoir. But, since the cost of such refined products is
high, the miscible fluid is not injected continuously but in the form of a
slug - typically 10 to 20 per cent of the reservoir pore volume - followed by
a gas or water drive. This technique is effective at low pressure and
temperatures. Nevertheless, the cost of these solvents will usually be
prohibitive.
r t u P
The Market/or Chemicals in the Oil Industry 209

!!.Y.Q.r~c~rE..0~.&a~
A lean gas is miscible with the crude at high reservoir pressures. In the
case of developed miscibility, the injected gas contacts the oil, and the
intermediate hydrocarbon components evaporate from the oil into the gas. At
the displacing front a rich gas mixture develops, and this may become
miscible with the oil. By, adding intermediate components (C3-CS) miscibility
is achieved at lower pressures. Because of its high value natural gas
injection is usually justified only as a combined EOR/gas conservation
project.
Carbon dioxide
The minim~m-miscibility pressure for CO 2 varies, depending on temperature and
purity. In addition to miscibility CO 2 injection has several other
favourable effects, such as swelling and viscosity reduction of the oil and
reduction of the gas-oil interfacial tension. It also dissolves to a
significant extent in the water and lowers the pH, which may effect
wettability.

CO 2 can be injected as a slug typically at pressures of 1200-2500 psi and


displaced by hydrocarbon gas or nitrogen. Alternatively, CO 2 can be applied
under conditions where viscous forces are predominant, which involve either
continuous injection, or CO 2 alternated with water.
Apart from technical problems (corrosive effect on lines, tubulars) the main
limitation of this method is the availability of CO 2 Large-scale
application of this process is foreseen in the USA, where natural carbon
dioxide reservoirs have been found within a reasonable distance of target
projects.

CO 2 injection, in particular for well stimulation, has also been considered


for deep heavy oil reservoirs, where the pressure is too high for steam
injection and injectivity too low for hot water injection. It seems
doubtful, however, whether the CO 2 will dissolve fast enough in the oil.

Nitrogen
Increas~d-i~terest in the use of nitrogen developed when it became cheaper to
manufacture and inject this inert gas than a hydrocarbon gas. At first,
waste gases such as stack gas, flue gas and exhaust gas were considered and
field tested. But the problem with these is that they contain waste products
such as nitrogen oxides and sulphur oxides which give rise to corrosion and
pollution problems. Later, attention turned to producing nitrogen
cryogenically.

Although nitrogen is not miscible with the reservoir oil at low pressures, it
can develop miscibility at sufficiently high pressures. Its application is
not, however, limited to miscible recovery pressures; in view of its
unlimited supply it can be used to replace non-miscible hydrocarbon gas
injection in secondary recovery projects, or as a drive fluid for more
expensive miscible slugs.

Chemicals utilised in miscible processes


There-are-f~w-miscibl~proj~cts-pre;e~tly-i~
operation and chemical
requirements are low, predominantly corrosion inhibition chemicals.

3.4 Chemical Processes

Chemicals can be added to change the physico-chemical properties of the


displacing fluid and those of the oil. The primary objective is to reduce
capillary forces, to increase the viscosity of the displacing fluid or to
plug off thief zones and so improve recovery efficiency.
r t u P
210 Chemicals in the Oil Industry

Chemical recovery methods employ polymers, surfactants or caustic soda. A


new technique that has shown promise is the use of foam as a mobility-
reducing agent in steam and miscible drive projects. This is very much in
the experimental stage.
Polymer flooding
A polymer-dlsso1ved-in the injection water will reduce water mobility and
prevent bypassing of the oil. The principal water soluble polymers are
polyacrylamides and polysaccharides. Polyacrylamides can be very effective
where the salinity of the reservoir brine is below, say, 1 per cent (compared
with 3.5 per cent in sea water). They are prone to shear degradation in less
permeable reservoirs. Polysaccharides are less sensitive to shear
degradation and salinity and can therefore be used in most reservoirs with
moderately saline reservoir waters. However, polysaccarides need protection
against biological degradation and a biocide therefore has to be injected
with them. Their long-term stability at reservoir temperatures is under
appraisal.

The increased viscosity of the displacing fluid resulting from the addition
of polymer leads to more efficient displacement of the oil but reduces the
fluid's injectivity. Depending on oil viscosity, a polymer flood project
could double the recovery obtainable with a conventional water drive. With
the high cost of polymers and reduced injectivity, however, there is a limit
to the maximum concentration that can be used. For all practical purposes
the application of this technique is restricted to reservoirs containing oil
with viscosities in the range 10 to 100 cP at temperatures below 80C.

Surfactant flooding
This process,-llke ;iscfble drive, aims at producing the residual oil left
behind by water drive by reducing the oil-water interfacial tension. The
surfactant solution is followed up by a polymer slug (for stability) and,
finally, by water.

Factors that influence the formation of oil-in-water or water-in-oil


emulsions are the composition of the oil, reservoir temperature, reservoir
brine salinity and the type of concentration of surfactant.

At present, systems containing specifically tailored surfactants can be


designed for application in sandstone reservoirs at temperatures up to 80C.
Oil viscosity preferably should be low, as well as salinity 10% TDS).
Excessive clay, because of its cation exchange capacity, can be harmful to
the surfactant slug.

The overall recovery efficiency of a surfactant flood could be of the order


of 30 to 60 per cent of the oil left behind by conventional recovery methods.
The main problem in surfactant flooding is still to maintain the integrity of
the surfactant slug while displacing it through the reservoir. Even then,
there will always be a considerable time lag between injection of the first
chemicals and the arrival of the oil bank at the production wells. This
obviously leads to long pay-out times.

Caustic flooding
Caustfc-floodfng(dflute solutions of sodium hydroxide or sodium
orthosilicate) is based on the principle that the organic acids naturally
present (e.g. naphthenic) in some oils can react with the alkali in a caustic
solution. This reaction leads to the in situ formation of surfactants and
emulsification at the oil/water interface. The result is a decrease in
interfacial tension between the oil and the water, comparable to that brought
about by surfactant flooding.
r t u P
The Market/or Chemicals in the Oil Industry 211

A pre-condition for in situ emulsification is the presence of sufficient


petroleum or organic acids in the oil. This is almost exclusively the case
with medium and heavy oils.

The caustic solution reacts not only with the oil but also with the reservoir
rock and brine. ConsequentlYt it is rapidly depleted t and it is this effect
that complicates the design and control of caustic flooding projects. More
laboratory and field testing will have to be done before this method t which
is promising in principle t can be implemented on a large scale.

R.l~g.B.iE.g_oif_tE.i~f_z~n~s
The target of miscible and surfactant drives is the residual oil in the
water-swept part of (primarily) light oil reservoirs. In addition t a large
volume of oil is left behind in the non-swept part of the reservoir.
Recovery rif this oil would require in-depth plugging of the swept zones or
areas without t however t damaging the remaining, oil-saturated parts.
Obviously, this is one of the most delicate problems to be solved in recovery
process research. ,No satisfactory solution has been offered as yet t but in
view of the large possible rewards a continued research effort in this area
seems fully justified.

Chemicals utilised in chemical processes


As indicated pr;vio~sly-:- typical ~h;U1Tc-;(; ;sed for polymer flooding are
partly hydrolysed polyacrylamides t biopolymers t and hydroxyethyl celluloses.
Effective polymers ~re required which offer high viscosifying power at low
concentrations. In practict the latter are usually in the order of 600 ppm
but can range from 100-2000 ppm depending on field conditionR t polymer type
etc. These concentrations refer to initial flooding s~dges. In prolonged
flooding t the polymer concentration is gradually dropped to cut costs. The
polxmer, should be highly water soluble and of high molecular weight
(lOD- IO ) in order to provide for large swollen and hydrated coils in
solution and high viscosifying power. In addition t the polymer cha~ns m~y he
charged and possibly branched or partly cross-linked for l1a~imum coil
stiffness and extension by electrostatic repulsion and sterfc hindering
effects. Polymer retention shou16 be low. Anionic pGlyrners tend to show
better t lower retention than non-ionic polymers. Both types are superior to
cationic polymers t which are highly retained in most reservoirs. In the
reservoir, during flooding, the polymer may be exposed to conditions of high
temperature (up to 110C) and high salinity (Na+ > 2 M, Mg 2 + 'V 0.11'1, Ca 2 +
ions and others) for periods of up to 10 years. Such severe conditions may
cause viscosity reduction t precipitation and/or chemical breakdown of the
polymer. So far all polymers tested have stability shortcomings. Durin~l
flood injection t the polymer is exposed to high shear rates ( 1000 sec )
which may also cause molecular breakdo~ln. Natural polymers show low
resistance against biodegradation and hence the use of biocides or
stabilizers has to be considered. In the case of micellar polymer flooding
(surfactant followed by polymer)t the polymer used in the drive water must be
compatible with the components in the preceding surfactant slug. Neither
phase separation defects (floccing t gelling t precipitation etc.) nor chemical
reactions (cross-linking etc.) should occur at the interface of the two
flooding compositions. Typical surfactants which are used in micellar
flooding are based on hydrocarbon sulphonates (for example petroleum or
synthetic sulphonates) which are added in concentrations of up to about 5% w
to the drive water.
r t u P
212 Chemicals in the Oil Industry

4. Economic Aspects and Long Term Prospects

The predominant future chemical requirements will be based on EOR techniques.


The time from laboratory test to first oil response in a field pilot depends
on the scope of the pilot, but may be as much as ten years. The reason for
this is not only that EOR processes are complicated, but also that they have
to be tailored carefully to the specific conditions of the target reservoir.
Against this background the number of active EOR Projects world-wide is
rather impressive: nearly 400 in 1981, of which some 250 in the USA.
Together, these projects produce nearly 900,000 bid, about equally divided
between the USA and the rest of the world. Since 1973 there has been a
steady increase in activity. Although the EOR production potential is minor
on a world-wide scale, it has become a significant factor for some countries,
certainly in terms of technical effort and expertise required.

Steam plays a predominant role, with more than two-thirds of the projects and
of the total EOR production. Most of the activity is in the USA, Venezuela
and the Netherlands. Steam injection is likely to continue its relatively
rapid expansion, in view of the very large scope for further application in
the various heavy oil provinces of the world.

The other EOR methods together show a very slow growth in activity, without,
however, a corresponding increase in oil production. These processes still
suffer from technical problems and/or high costs. There are, however, a
number of large-scale gas injection projects in operation and others planned
in the North Sea, Middle East, Africa, the USA and Canada. There are also
encouraging signs for carbon dioxIde and polymer injection, which have both
seen a relatively rapid growth in recent years.

Nitrogen injection is a newcomer, but shows promise for one or more large
North Sea reservoirs.

It is important to keep in mind that polymer injection and thermal methods


find application only in reservoirs containing medium viscosity and heavy
crudes. A large volume of oil is left behind in light oil reservoirs, either
by-passed by water or gas or trapped by capillary forces. It will be
necessary to rely primarily on miscible and chemical drive methods for
recovering this oil. Hence, it must be expected that in the long term,
depending of course on the development of crude prices, these methods will
begin to play a more important role.

The scope for EOR world-wide is large: perhaps an additional 400 billion
barrels recoverable from conventional reservoirs and an additional
300 billion barrels from "tar-sands". However, even under the most
favourable crude price scenario, the build-up of enhanced oil recovery
potential will be severely constrained by long lead times and by the heavy
technical and financial effort required.

As far as chemical flooding is concerned, the economics of surfactant and


polymer flooding are affected to a great extent by the amounts and costs of
applied chemicals and by the timing and volume of additional oil produced.

The size and concentration of the surfactant slug depends on the expected
loss of surfactant in the formation due to absorption on rock and the
interaction with reservoir fluids. Thus the amount of surfactant needed is
primarily determined by relevant formation properties, irrespective of the
amount of residual oil present. The concentration of the polymer slug is
r t u P
The Market/or Chemicals in the Oi/Industry 213

determined by the increase in viscosity dictated by the oil viscosity and by


the degree of retention in the formation.

The amount of additional oil producible is determined by the amount of oil


left behind by conventional production methods and by the expected recovery
efficiency of the surfactant or polymer flood.

In the following table the chemical requirements per barrel oil additionally
produced used for the surfactant and polymer flood are presented. These
figures serve as bases for cost estimates and the estimated future
requirements of polymers and surfactants.

Type Injection Fluid Chemical Requirement


Chemical Concentration
(ppm) (lbs/bbl)

Polymer flooding
Polymers 500 - 1,500 1.5 - 3.0

Surfactant flooding
Surfactant 40,000 - 60,000 12 - 24
Polymers 500 - 1,500

Table 1: Chemical requirements per barrel additional oil produced.

As an example of unit costs for chemical flooding, with a world oil price of
US $35/barrel, the total cost per barrel of oil produced by a surfactant
flood could be US $15-35, while the cost of a barrel produced by a polymer
flood could be US $15-25.

To put these cost figures in perspective, they are compared with those of
alternative energy sources in Table 2.

Type Production cost (US $)


per barrel oil equivalent

Coal 3 - 15
Conventional oil 1 - 15
Liquid Gas 10 - 23
Liquid from heavy oil/tar 15 - 25
Liquids from shales 15 - 35
Liquids from coal 30 -+40
Biomass for fuel 30+
Solar hot water 50

Table 2: Cost per barrel oil equivalent for alternative energy.


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214 Chemicals in the Oil Industry
It is estimated that the total cost of chemical expenditure on EOR techniques
presently runs at about 150 million per year. The majority of this
expenditure is on surfactants and polymers in an approximate ratio
one-third/two-thirds.

On the long term the potential of chemical flooding cannot be neglected. For
some 30% of the medium and light oil found so far, chemical flooding is
considered to be the only possibility to increase the ultimate recovery,
above what can be obtained by conventional proven processes (i.e. water or
gas injection). Hence, it appears reasonable to assume that by the year
2000 chemical flooding will claim its appropriate share of the total EOR
production.

As a result, future world-wide surfactant and polymer requirements for


chemical flooding during the early next century could reach some 5 million
ton per year of surfactants and 1 million ton per year polymers, representing
a total chemical business for those two types of chemicals alone of some
10 billion per year ( 1982).

5. Future Trends

From the performance point of view, there is an evident demand for novel and
improved polymers, which can be tailored to meet specific field conditions.
So far no polymer has been obtained which possesses all the properties
required (see Table 3). Biopolymers appear to be highly effective
viscosifiers, with low salt and shear sensitivity and generally favourable
filterability. The present polymer types, however, are relatively
temperature sensitive, not very storage stable and rather costly. Hydrolysed
polyacrylamides have excellent water solubility and good storage stability
and low temperature sensitivity. They are, however, shear and salt-sensitive
and some exhibit filterability defects. Their viscosifying power under
reservoir conditions is probably restricted.

Service companies are presently looking into the possibility of using on-site
polymerisation techniques with the objective to reduce transportation costs
and allow complete tailoring of the polymer to the reservoir.

In the longer term, certain oil companies are looking at microbes to generate
polymers in situ.

v. CONCLUSIONS

The world market for chemicals in the oil industry is presently estimated at
around 3750 million. Market growth rate will depend to a major extent on the
world demand for hydrocarbons; however a value of at least 10% per annum may
be foreseen. Significant potential lies in the development of new polymeric
chemicals which are multi-functional, cost effective and stable at extremes
of temperature and pressure. There will be an increasing trend towards
expansion of chemical recovery methods for oil but economic techniques are
not expected to be fully developed until the next decade.

A final point of emphasis is that the world market for chemicals in oil and
gas exploration and production is highly diversified, specialised and
application invariably necessitates dedicated service back-up and operational
expertise. As such, it is a highly competitive and well established business
and great care should be exercised if considering market participation,
especially since the success or otherwise of participation may often depend
on the now very unpredictable value of a barrel of oil at any particular
moment in time.
r t u P
The Market for Chemicals in the Oil Industry 215

TABLE 3
COMPARATIVE PROPERTIES OF POLYMERS
AND THE IR AQUEOUS SOLUTIONS EVALUATED FOR EOR

Properties Polyacrylamide Xanthan gums Hydroxyethyl


(anionic) cellulose

Mode of action -Permeability agent Viscosifier Viscosifier


-Viscosifier

Concentration 100 110 >250


required for
say a visco-
sity 20 CP
at 10 5- 1
23 c in fresh
water'-
(rel. units)

Ease of disso- Both hydration and High shear mix- Hydration takes
lution gel dispers ion ing required to a long time. Ge 1
proceed rapidly. disperse (dis- can be dispersed
'ro avoid mechanical integrate) gel. at low shear.
degradation low
shear mixing should
be applied.

Fil terability Sharp viscosity Restricted vis- Distinct visosity


(Le. visco- decrease. Molecules cosity reduction, decrease. Polymer
sity reduction tend to associate provided disso- is retained on
upon filtering and are fi 1 tered lution contains filter. probably
over 0.45-1.2 lJm off. Shear degrada- no gel. because of high
filter) tion does also concentrations
required to reach
practical viscocity
levels

Pseudo plasti- high medium low


city

Salt sensiti- high restricted low


vity (Le.
viscosity
reduction upon
addition of
Na 2 +, Ca 2 +,
Mg 2 +)

Temperature low medium high


sensi tivity
(i.e. viscosity
reduction upon
increasing temp.)

Mechanical low high high


(shear)
stability

Storage Good. No viscosity No viscosity re- Poor storage stabi-


stability of reductions/gel duction, but gel lity owing to severe
polymer formation after formation owing biodegradation. Use
o
solution 6 months at 23 C to biodegradation of biocides (H2C-0)
Filtering of required
solution prior to
storage, aids
stability

Polymer price 2.50-400* 5.00-6.50 2.70-3.30


indication
($/kg)

* Speciality products, developed for EOR.


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216 Chemicals in the Oil Industry

VI. GENERAL BIBLIOGRAPHY

I. "Composition and Properties of Oil Well Drilling Fluids"


G.R. Gray, H.C.H. Darley, W.F. Rogers
Gulf publishing Company, Third Edition, Fifth Printing,
September 1979

2. "Drilling and Drilling Fluids"


G.V. Chilingarian, P. Vorabutr
El sevier, I 981

3. "Cementing" SPE/AIME Monograph


D.K. Smith, 1976

4. "Hydraulic Fracturing" SPE/AINE Monograph


Howards, Fast 1970

5. "Acidizing Fundamentals" SPE/AIME Monograph


B. Williams, J.L. Gidley, R.S. Schechter, 1979

6. "~~ater Problems in Oil Production"


L.C. Case, 2nd Edition, PPC Books, Tulsa Oklahoma, 1977

7. "Oilfield Water Systems"


C.C. Patton, Campbell Petroleum Series, 1977

8. "Water Formed Scale Deposits"


J.C. Cowan, D.J. Weintritt, Gulf Publishing Company, Houston,
Texas 1976

9. "H 2 S Corrosion in Oil and Gas Production - A Compilation of


Classic Papers"
R.N. Tuttle, R.D. Kane, NACE, Houston, Texas 1981

10. "Corrosion Inhibitors"


C.C. Nathan, NACE, Houston, Texas 1974

11. "Corrosion Control Handbook"


Energy Communications Inc. Dallas, Texas, 1975

12. "Introduction to Oil Recovery Techniques"


Shell Technology Series, 1/1981

13. "Enhanced Oil Recovery by Thermal Methods"


Shell Technology Series, 1/1982

14. "Enhanced Oil Recovery by Miscible and Chemical Methods"


Shell Technology Series, 2/1982

IS. "State of the Art of Enhanced oil Recovery"


H.J. de Haan, H.M.L. v. Breen, Second European Symposium on Enhanced
Oil Recovery, Paris, November 1982
r t u P
The Market for Chemicals in the Oil Industry 217
16. "Scraping the Barrel, the Worldwide Potential for Enhanced Oil
Recovery"
R. Dafter, 1980, Financial Times Business Information Ltd, London

17. "\Alinning More Oil, Increasing Importance for Enhanced Oil Recovery"
R. Dafter, 1981, Financial Times Business Information Ltd, London

18. Oil and Gas Journal

19. World Oil

20. The Petroleum Engineer

21. Chemical Week

22. Chemical and Engineering News

23. Abstracts Oilfield Chemicals

24. UK Department of Energy Brown Book

25. Journal of the Society of Petroleum Engineers


r t