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European Federation of Corrosion

Publications
NUMBER 23

A Working Party Report on

C O 2 Corrosion Control in Oil


and Gas Production
Design Considerations
Edited by
M. B. KERMANI& L. M. SMITH

Published for the European Federation of Corrosion


by The Institute of Materials

THE INSTITUTE OF MATERIALS


1997
Book Number 688
Published in 1997 by The Institute of Materials
1 Carlton House Terrace, London SW1Y 5DB

© 1997 The Institute of Materials

All rights reserved

British Library Cataloguing in Publication Data


Available on application

Library of Congress Cataloging in Publication Data


Available on application

ISBN 1-86125-052-5

Neither the EFC nor The Institute of Materials


is responsible for any views expressed
in this publication

Design and production by


SPIRES Design Partnership

Made and printed in Great Britain


European Federation of Corrosion Publications
Series Introduction

The EFC, incorporated in Belgium, was founded in 1955 with the purpose of
promoting European co-operation in the fields of research into corrosion and corro-
sion prevention.
Membership is based upon participation by corrosion societies and commit-
tees in technical Working Parties. Member societies appoint delegates to Working
Parties, whose membership is expanded by personal corresponding membership.
The activities of the Working Parties cover corrosion topics associated with
inhibition, education, reinforcement in concrete, microbial effects, hot gases and
combustion products, environment sensitive fracture, marine environments, surface
science, physico-chemical methods of measurement, the nuclear industry, computer
based information systems, the oil and gas industry, the petrochemical industry and
coatings. Working Parties on other topics are established as required.
The Working Parties function in various ways, e.g. by preparing reports,
organising symposia, conducting intensive courses and producing instructional
material, including films. The activities of the Working Parties are co-ordinated,
through a Science and Technology Advisory Committee, by the Scientific Secretary.
The administration of the EFC is handled by three Secretariats: DECHEMA
e. V. in Germany, the Soci6t6 de Chimie Industrielle in France, and The Institute of
Materials in the United Kingdom. These three Secretariats meet at the Board of
Administrators of the EFC. There is an annual General Assembly at which delegates
from all member societies meet to determine and approve EFC policy. News of EFC
activities, forthcoming conferences, courses etc. is published in a range of accredited
corrosion and certain other journals throughout Europe. More detailed descriptions
of activities are given in a Newsletter prepared by the Scientific Secretary.
The output of the EFC takes various forms. Papers on particular topics, for
example, reviews or results of experimental work, may be published in scientific and
technical journals in one or more countries in Europe. Conference proceedings are
often published by the organisation responsible for the conference.
In 1987 the, then, Institute of Metals was appointed as the official EFC
publisher. Although the arrangement is non-exclusive and other routes for publica-
tion are still available, it is expected that the Working Parties of the EFC will use The
Institute of Materials for publication of reports, proceedings etc. wherever possible.
The name of The Institute of Metals was changed to The Institute of Materials
with effect from I January 1992.

A. D. Mercer
EFC Series Editor,
The Institute of Materials, London, UK
viii Series Introduction

EFC Secretariats are located at:

Dr B A Rickinson
European Federation of Corrosion, The Institute of Materials, 1 Carlton House
Terrace, London, SWIY 5DB, UK

Mr P Berge
F6d6ration Europ6ene de la Corrosion, Soci6t6 de Chimie Industrielle, 28 rue Saint-
Dominique, F-75007 Paris, FRANCE

Professor Dr G Kreysa
Europ/iische F6deration Korrosion, DECHEMA e. V., Theodor-Heuss-Allee 25, D-
60486, Frankfurt, GERMANY
Preface

Corrosion is a natural potential hazard associated with oil and gas production and
transportation facilities. This results from the fact that an aqueous phase is normally
associated with the oil a n d / o r gas. The inherent corrosivity of this aqueous phase is
then dependent on the concentration of dissolved acidic gases and the water chemistry.
The presence of H2S, CO 2, brine a n d / o r condensed water with the hydrocarbon not
only give rise to corrosion, but also can lead to environmental fracture assisted by
enhanced uptake of hydrogen atoms into the steel. CO 2is usually present inproduced
fluids and, although it does not cause the catastrophic failure mode of cracking
associated with H2S*, its presence can nevertheless result in very high corrosion rates
particularly where the mode of attack on carbon and low alloy steels is localised. In
fact CO 2 corrosion, or 'sweet corrosion', is by far the most prevalent form of attack
encountered in oil and gas production and is a major source of concern in the
application of carbon and low alloy steels. Hence, the need to have a document which
systematically addresses the steps, considerations and parameters necessary to
design oil and gas facilities with respect to CO 2 corrosion.
This document sets the scene on design considerations specifically related to CO 2
corrosion. It has been developed from feedback of operating experience, research
results and operators' in-house studies. Particular attention has been given to the
chemistry of the produced fluid, the fluid dynamics and physical variables which
affect the performance of steels exposed to CO2-containing environments. The focus
is on the use of carbon and low alloy steels as these are the principal construction
materials used for the majority of facilities in oil and gas production offering
economy, availability and strength.
This document is a practical, industry oriented guide on the subject for use by
design engineers, operators and manufacturers. It incorporates much of the recent
developments in the understanding of the ways in which detailed environmental and
physical conditions affect the risk of CO 2 corrosion. It also describes means of
corrosion control. It is comprehensive in addressing CO 2 corrosion of all major items
of oilfield equipment and facilities incorporating, production, processing and
transportation. As such, it provides a key reference for materials and corrosion
engineers, product suppliers and manufacturers working in the oil and gas industry.

*'Sour corrosion', resulting from the presence of H2S, is the subject of EFC Publications Numbers 16
and 17.
Acknowledgements

The C O 2 Corrosion Work Group of the EFC Working Party on Corrosion in Oil and
Gas Production held its first meeting in September 1993. Since then, several meetings
have been held to address industry-wide issues related to engineering design for CO 2
corrosion. The organisation of the Work Group was undertaken by representatives
from worldwide oil and gas producers, manufacturers, service companies and
research institutions.
In achieving the primary objective, parameters affecting CO 2 corrosion, its
mechanism and methods of control have been discussed during the Work Group
meetings. These aspects form the core of the present document, Sections of which
have been prepared by the Work Group members.
The chairmen of the Working Party and Work Group would like to thank all who
have contributed their time and effort to ensure the successful completion of this
document. In particular we wish to acknowledge a significant input from these
individuals and their respective companies:

J Pattinson, A McMahon and D Harrop, BP, UK


J-L Crolet, Elf, France
A Dugstadt, IFE, Norway
G Schmitt, MFI, Germany
Y Gunaltun, Total, France
E Wade, previously with Marathon, UK
O Strandmyr, Statoil, Norway
W Lang, Bechtel, UK
J Palmer, CAPCIS, UK
M Swidzinski, Phillips, UK
M Celant, MaC, Italy
P O Gartland, CorrOcean, Norway
R S Treseder, CorrUPdate, USA
J Kolt, Conoco, USA
N Farmilo, AEA Technology, UK

In addition, valuable comments from R Connell and B Pots (Shell, The Netherlands)
and T Gooch (TWI, UK) are appreciated.
Finally, one of the editors (MBK) wishes to thank BP for their support and
permission to publish some of the information in this document.

Bijan Kermani Liane Smith


Chairman of CO 2 Corrosion Chairman of EFC Working Party on
Group Workshop Corrosion in Oil and Gas Production
Contents

Series Introduction ................................................................................................................ vii

P r e f a c e ................................................................................................................... , ................ i x

Acknowledgements .................................................................................................................. x

1 Introduction ............................................................................................................... 1

2 S c o p e ........................................................................................................................... 3

3 T h e M e c h a n i s m of CO2 Corrosion ........................................................................ 4

4 T y p e s of CO2 Corrosion D a m a g e .......................................................................... 6

4.1. L o c a l i s e d C o r r o s i o n of C a r b o n Steel ............................................................... 6

4.2. L o c a l i s e d C o r r o s i o n of C a r b o n Steel W e l d s ................................................... 7

5 K e y Parameters A f f e c t i n g Corrosion .................................................................... 9


5.1. W a t e r W e t t i n g ..................................................................................................... 9

5.1.1. W a t e r C h a r a c t e r i s t i c s ................................................................................ 10

5.1.2. H y d r o c a r b o n C h a r a c t e r i s t i c s ................................................................... 10

5.1.3. T o p - o f - t h e - L i n e W e t t i n g ........................................................................... 11

5.2. P a r t i a l P r e s s u r e a n d F u g a c i t y of C O 2 ...................................................................................... 12

5.3. T e m p e r a t u r e ...................................................................................................... 12

5.4. p H ....................................................................................................................... 14

5.5. C a r b o n a t e Scale ................................................................................................. 15

5.6. T h e Effect Of H2S ............................................................................................... 15

5.7. W a x Effect .......................................................................................................... 16

Prediction of the Severity of CO2 Corrosion .................................................... 18


6.1. C O 2 C o r r o s i o n P r e d i c t i o n M o d e l s F o r C a r b o n Steel ................................... 19

CO2 Corrosion Control .......................................................................................... 24

7.1. M i c r o - a l l o y i n g of C a r b o n a n d L o w A l l o y Steels ......................................... 24

7.1.1. Effect of C h r o m i u m ................................................................................... 24

7.1.2. Effect of C a r b o n ......................................................................................... 25

7.1.3. Effect of O t h e r A l l o y i n g E l e m e n t s .......................................................... 25

7.2. Effect of G l y c o l a n d M e t h a n o l ........................................................................ 26


vi Contents

7.3. p H C o n t r o l ......................................................................................................... 27

7.3.1. T h e R o l e of p H ........................................................................................... 27

7.3.2. W e t G a s T r a n s p o r t a t i o n L i n e s ................................................................. 27

7.3.3. D i f f e r e n t C h e m i c a l s a n d T h e i r M e c h a n i s m s ......................................... 27

7.3.4. p H M o n i t o r i n g ........................................................................................... 28

7.4. C o r r o s i o n I n h i b i t i o n ......................................................................................... 28

7.4.1. I n h i b i t o r M e c h a n i s m ................................................................................. 29

7.4.2. I n h i b i t o r Efficiency a n d I n h i b i t o r P e r f o r m a n c e .................................... 30

7.4.3. I n h i b i t o r P a r t i t i o n i n g a n d P e r s i s t e n c y ................................................... 31

7.4.4. C o m m e r c i a l I n h i b i t o r P a c k a g e s ............................................................... 34

7.4.5. I n h i b i t o r C o m p a t i b i l i t y ............................................................................. 34

7.4.6. I n h i b i t o r D e p l o y m e n t ............................................................................... 35

7.4.7. I n h i b i t o r D i s t r i b u t i o n in M u l t i p h a s e P i p e l i n e s ..................................... 36

7.4.8. Effect of F l o w o n I n h i b i t i o n ..................................................................... 36

8 Corrosion Allowance Determination ................................................................. 37

8.1. D e s i g n C o r r o s i o n A l l o w a n c e .......................................................................... 38

8.1.1. D e s i g n C o r r o s i o n R a t e .............................................................................. 38

8.1.2. D e s i g n C o r r o s i o n A l l o w a n c e A s s e s s m e n t ............................................ 38

9 Design Considerations .......................................................................................... 41

9.1 W e l l C o m p l e t i o n s .............................................................................................. 41

9.1.1. C o r r o s i o n D e s i g n ....................................................................................... 42

9.1.2. C o r r o s i o n M o n i t o r i n g ............................................................................... 43

9.2. P r o d u c t i o n Facilities ......................................................................................... 44

9.2.1. C o r r o s i o n D e s i g n ....................................................................................... 44

9.2.2. M u l t i p h a s e F l u i d B e h a v i o u r .................................................................... 46

9.2.3. C o r r o s i o n M o n i t o r i n g ............................................................................... 47

9.3 G a s R e i n j e c t i o n ................................................................................................... 49

9.3.1. G e n e r a l R e q u i r e m e n t s for G a s R e i n j e c t i o n ............................................ 49

9.3.2. O n s h o r e D e l i v e r y L i n e s ............................................................................ 49

9.3.3. O f f s h o r e D e l i v e r y L i n e s ............................................................................ 50

9.3.4. I n j e c t i o n W e l l s A n d G a s Lift A n n u l i ...................................................... 50

R e f e r e n c e s ............................................................................................................................ 51
European Federation of Corrosion Publications
Series Introduction

The EFC, incorporated in Belgium, was founded in 1955 with the purpose of
promoting European co-operation in the fields of research into corrosion and corro-
sion prevention.
Membership is based upon participation by corrosion societies and commit-
tees in technical Working Parties. Member societies appoint delegates to Working
Parties, whose membership is expanded by personal corresponding membership.
The activities of the Working Parties cover corrosion topics associated with
inhibition, education, reinforcement in concrete, microbial effects, hot gases and
combustion products, environment sensitive fracture, marine environments, surface
science, physico-chemical methods of measurement, the nuclear industry, computer
based information systems, the oil and gas industry, the petrochemical industry and
coatings. Working Parties on other topics are established as required.
The Working Parties function in various ways, e.g. by preparing reports,
organising symposia, conducting intensive courses and producing instructional
material, including films. The activities of the Working Parties are co-ordinated,
through a Science and Technology Advisory Committee, by the Scientific Secretary.
The administration of the EFC is handled by three Secretariats: DECHEMA
e. V. in Germany, the Soci6t6 de Chimie Industrielle in France, and The Institute of
Materials in the United Kingdom. These three Secretariats meet at the Board of
Administrators of the EFC. There is an annual General Assembly at which delegates
from all member societies meet to determine and approve EFC policy. News of EFC
activities, forthcoming conferences, courses etc. is published in a range of accredited
corrosion and certain other journals throughout Europe. More detailed descriptions
of activities are given in a Newsletter prepared by the Scientific Secretary.
The output of the EFC takes various forms. Papers on particular topics, for
example, reviews or results of experimental work, may be published in scientific and
technical journals in one or more countries in Europe. Conference proceedings are
often published by the organisation responsible for the conference.
In 1987 the, then, Institute of Metals was appointed as the official EFC
publisher. Although the arrangement is non-exclusive and other routes for publica-
tion are still available, it is expected that the Working Parties of the EFC will use The
Institute of Materials for publication of reports, proceedings etc. wherever possible.
The name of The Institute of Metals was changed to The Institute of Materials
with effect from I January 1992.

A. D. Mercer
EFC Series Editor,
The Institute of Materials, London, UK
viii Series Introduction

EFC Secretariats are located at:

Dr B A Rickinson
European Federation of Corrosion, The Institute of Materials, 1 Carlton House
Terrace, London, SWIY 5DB, UK

Mr P Berge
F6d6ration Europ6ene de la Corrosion, Soci6t6 de Chimie Industrielle, 28 rue Saint-
Dominique, F-75007 Paris, FRANCE

Professor Dr G Kreysa
Europ/iische F6deration Korrosion, DECHEMA e. V., Theodor-Heuss-Allee 25, D-
60486, Frankfurt, GERMANY
1
Introduction

CO 2 corrosion has been a recognised problem in oil and gas production and
transportation facilities for many years. Despite systematic attempts to analyse it
and develop predictive models, it is still not a fully understood phenomenon and
there remains ambiguity and argument on the engineering implications of parameters
which affect it. Furthermore, most of the present predictive models are not based on
adequate information to take into account the increasingly harsh environments seen
in deep wells and they also take little account of hydrodynamic parameters, and so
often lead to conservative designs.
The problem cannot be said to be a diminishing one, since reliable prediction of
the life of carbon steel components in production systems remains unclear [1],
particularly, in the current situation where oil and gas exploration activities have
moved to more marginal areas and harsher operational conditions. Many of these
fields necessitate the transportation of raw wellhead gas and fluids either from wells
(sometimes subsea) or from remote areas to a central processing facility, with the
export of treated fluids to a distant terminal/additional processing facility. Although
such systems have often been designed to operate successfully with corrosion
inhibition, there have been instances where this approach has failed in practice.
Nevertheless, with detailed evaluation of the corrosion risk, combined with a proper
corrosion management programme (control, monitoring, inspection and assessment),
production and transportation of wet hydrocarbon gas and oil in carbon steel facilities
is considered technically viable.
In brief, where there is a risk of internal corrosion in wet production facilities
there is a need for:

A design methodology for reviewing the potential corrosion risks and


developing a suitable design and corrosion allowance where appropriate. This
is the principal subject of this document.

An inhibitor deployment programme including why inhibitors are used, how


they are selected and how to achieve maximum performance in the field to
alleviate internal corrosion of facilities.

A corrosion control management programme which, based on the design


review, details the procedures for corrosion control, how such corrosion is to
be monitored and how the facilities are to be inspected

A defect assessment methodology which determines whether the integrity of


the facility is compromised or likely to be compromised, in the event that a
corrosion defect is detected.
CO2 Corrosion Control in Oil and Gas Production--Design Considerations
In this document, the emphasis has been placed primarily on the first point and
the other three points have been addressed briefly.
The first step in establishing the design methodology is an understanding of CO 2
corrosion. This requires a multi-disciplinary approach, involving knowledge of fluid
chemistry, hydrodynamics, metallurgy and inhibitor performance and partitioning.
Mechanistic understanding of the phenomenon is essential to enable development
of engineering criteria for accurate prediction of the form and rate of corrosion which
may occur. This document aims to address these issues.
2
Scope

This document sets out a proposed design philosophy for the production and pipeline
transportation of wet oil, wet gas and multiphase fluids, for use in the technical/
commercial assessment of new field developments and in prospect evaluations. For
the purpose of this document, wet oil, wet gas and multiphase fluids are defined as
oil a n d / o r gas containing water and CO2.
The mechanism of CO 2 corrosion is explained and the forms that the corrosion
damage can take are described in Section 3. This is followed by a description of the
forms of CO 2 corrosion damage and the steps necessary to minimise localised
corrosion of carbon steel welds (Section 4).
The key parameters influencing the rate of CO 2 corrosion are discussed in Section
5. An understanding of the role of the carbonate scale in influencing the form of the
corrosion is shown to be important in understanding how some inhibitors operate
and how the nature of the scale changes with temperature. This leads to Section 6
which describes a summary of the models available for predicting the corrosion rate
and the parameters they incorporate.
Section 7 deals with various methods of corrosion control, including the addition
of minor alloying elements and changing the corrosive environment through the
addition of pH controller, glycols or corrosion inhibitors.
In considering the application of this knowledge on forms of corrosion damage
and approaches to corrosion rate prediction and mitigation to the question of facilities
design, the first issue is to establish an appropriate corrosion allowance. This is dealt
with in Section 8.
The document then highlights parameters which are significant to different items
within the production facilities. For the purposes of discussing corrosion design,
Section 9 has been divided into:

• Well Completions;

• Production Facilities (including flowlines and pipelines); and

• Gas Reinjection Systems.

Finally, some comments are given on corrosion monitoring appropriate to the


different facilities.
3
The M e c h a n i s m of C O 2 Corrosion

The problem of C O 2 corrosion has long been recognised and has p r o m p t e d extensive
studies. Dry CO 2 gas is not itself corrosive at the temperatures encountered within
oil and gas production systems, but is so w h e n dissolved in an aqueous phase through
which it can promote an electrochemical reaction between steel and the contacting
aqueous phase. CO 2 is extremely soluble in water and brines but it should also be
r e m e m b e r e d that it has even greater solubility in hydrocarbons m potentially 3:1 in
favour of the hydrocarbon. Hydrocarbon fluids are generally produced in association
with an aqueous phase. In m a n y cases the hydrocarbon reservoir will also contain a
significant proportion of CO 2. As a result of this, CO 2 will dissolve in the aqueous
phase associated with hydrocarbon production. This aqueous phase will corrode
carbon steel.
Various mechanisms have been postulated for the corrosion process but all involve
either carbonic acid or the bicarbonate ion formed on dissolution of CO 2 in water
this leads to rates of corrosion greater than those expected from corrosion in strong
acids at the same pH. CO 2 dissolves in water to give carbonic acid, a w e a k acid
compared to mineral acids as it does not fully dissociate.
The steps of carbonic acid reaction m a y be outlined as follows:

CO2(g ) 4- H20 ---> CO2(dissolved) (1)

CO2(dissolved) 4- H 2 0 ¢=) H2CO 3 ~ H ÷ + H C O 3- (2)

The mechanism postulated by de Waard [2-4] is, perhaps, the best known:

H2CO 3 + e- --9 H + H C O 3- (3)

2 H --~ H 2 (4)

with the steel reacting:

Fe --9 Fe 2+ + 2e- (5)

and overall:

C O 2 + H 2 0 + Fe --~ FeCO 3 (iron carbonate) + H 2 (6)

Whilst there is some debate about the m e c h a n i s m of C O 2 corrosion in terms of


which dissolved species are involved in the corrosion reaction, it is evident that the
The Mechanism of CO 2 Corrosion
resulting corrosion rate is dependent on the partial pressure of C O 2 gas. This will
determine the solution pH and the concentration of dissolved species.
In reality, the complete chain of electrochemical reactions is much more complex
than this brief outline. Depending upon which is the rate determining step the
dependance of the electrochemical reactions on pH and dissolved CO 2 varies.
4
Types of CO 2 Corrosion Damage

CO 2 corrosion may manifest itself as general thinning or localised attack. Localised


corrosion is characterised by loss of metal at discrete areas of the surface with
surrounding areas remaining essentially unaffected or subject to general corrosion.
These discrete areas may take various geometrical shapes. Thus, circular depressions
usually with tapered and smooth sides are described as pits. Stepped depressions
with a flat bottom and vertical sides are referred to as mesa attack. Other geometrical
forms of localised corrosion include slits (sometimes referred to as knife line), grooves
etc. In flowing conditions localised attack may take the form of parallel grooves
extending in the flow direction; this phenomenon is known as flow induced localised
corrosion.

4.1. Localised Corrosion of Carbon Steel

CO 2 corrosion can appear in three principal forms, pitting, mesa attack or flow
induced localised corrosion.
Pitting can occur over the full range of operating temperatures under stagnant to
moderate flow conditions. The susceptibility to pitting increases and time for pitting
to occur decreases with increasing temperature and increasing CO 2 partial pressure.
D e p e n d i n g on the alloy composition there exists a t e m p e r a t u r e range with a
m a x i m u m susceptibility for pitting [5].
Inspections of sweet gas wells have indicated that localised corrosion, including
pitting, often occurs preferentially at certain depths (i.e. in certain temperature ranges).
Generally 80-90°C is a temperature range where pitting is likely to occur in sweet
gas wells. Pitting may arise close to the dew point temperature and can relate to
condensing conditions. There are no simple rules for predicting the susceptibility of
steels to pitting corrosion.
Mesa type attack is a form of localised CO 2 corrosion u n d e r m e d i u m flow
conditions [6]. In such attack, corrosion results in large flat bottomed localised damage
with sharp steps at the edges. Corrosion damage at these locations is well in excess
of the surrounding areas.
The conditions most likely to lead to mesa attack are those under which carbonate
films can form but are not strongly stable. Film formation begins around 60°C and
thus mesa attack is much less of a concern at temperatures below this. If the general
filming conditions are borderline then local variations in flow or metallurgy or both
may be enough to de-stabilise films. This type of localised attack results from local
spalling of carbonate scales after reaching a critical scale thickness [7-9]. This local
spalling occurs due to intrinsic growth stresses in the scale [10]. Spalling of the scale
exposes underlying metal which then corrodes and may reform surface scale. On
regaining a critical thickness the newly formed scale can crack and spall again
producing another step.
Types of CO2 Corrosion Damage
Spalling of scale particles or flakes relieves the stress in the scale adjacent to and
around the spalled area. Therefore, this scale remains attached to the surface and
can protect it from localised attack. As a result, the flat bottomed pits obtain sharp
edges. Mesa attack may also simply result from self sustaining galvanic coupling
between protective and non-protective corrosion films.
Flow induced localised corrosion (FILC) in CO 2 corrosion starts from pits a n d /
or sites of mesa attack above critical flow intensities. The localised attack propagates
by local turbulence created by the pits and steps at the mesa attack which act as flow
disturbances. The local turbulence combined with the stresses inherent in the scale
may destroy existing scales. The flow conditions may then prevent re-formation of
protective scale on the exposed metal.

4.2. Localised Corrosion of Carbon Steel Welds

Localised corrosion of carbon steel welds in CO 2 corrosion systems has been


experienced by many operators. It is a complex problem because it is dependent
partly on the environment (and the nature of any carbonate scale formed), partly on
the metallurgy and composition of the carbon steel and the weld and partly on the
geometry of the weld profile (local turbulence).
Initially, preferential attack may arise from galvanic differences across a weld due
to compositional or microstructural differences between the deposited weld metal,
the parent steel and file heat affected zone (HAZ).
The location and morphology of the preferential corrosion is influenced by a
complex interaction of many parameters including the environment, the operating
conditions, the parent ,;teel composition, the deposited weld composition, the welding
procedure and the initial surface state. Changes in any one of these parameters can
cause a significant difference in the weldment corrosion behaviour.
Changing the composition of the weld metal relative to the parent steel can make
the weld metal more, or less, susceptible to preferential attack. Similarly, changing
the grade of parent steel can affect the behaviour of the weld metal but, in conjunction
with the welding procedure, the parent steel composition will also determine the
microstructure of the HAZ and therefore influence the susceptibility to preferential
attack in that region.
The welding procedure will directly influence the HAZ microstructure, but will
also affect the degree of dilution of the weld metal by the parent steel and the
composition at the fusion line of the weld. The presence of welding slags, oxide
films and inclusions increase the complexity of the weld corrosion phenomenon.
It is extremely important to note that a weld consumable selected to avoid
preferential corrosion in one environment could exacerbate the problem in another.
For example, c o n s u m a b l e s c o n t a i n i n g 1% Ni or 0.6% Ni plus 0.4% Cu as
recommended for seawater injection systems may cause problems if used under
certain conditions in sweet hydrocarbon environments [11]. Rapid corrosion of the
weld metal has occurred in some instances while HAZ attack has also been observed.
The window of conditions under which this problem occurs has yet to be accurately
defined. However, in the majority of cases, failures have occurred at temperatures
approaching conditions under which protective scales are expected to form (70-80°C).
CO2 Corrosion Control in Oil and Gas Production reDesign Considerations

The risk of preferential weld corrosion can be minimised by conducting laboratory


tests on the relevant weldment under simulated service conditions using appropriate
electrochemical monitoring techniques, including galvanic coupling through zero
resistance ammeters. It should be noted that although laboratory studies have
generally been successful in simulating weld corrosion problems in other situations
than CO 2 corrosion service, in some instances (such as with higher nickel contents)
cathodic weld metal behaviour has been observed in the laboratory, but anodic
behaviour in service, which may be due to the difference in the initial surface state.
Weldment corrosion behaviour must, therefore, be confirmed by monitoring in
service. The same monitoring techniques can be used, ideally in combination with
other techniques such as ultrasonic wall thickness measurements.
The effects of inhibition (and biocide treatments) on weldment corrosion must
also be considered. Although inhibition can be an effective means of controlling
preferential weld corrosion, inhibitor adsorption can be influenced by weld metal
composition and, in some cases, protection is not achieved. Again, inhibitor tests on
weldments under simulated service conditions can be used to select an appropriate
inhibitor formulation.
The theory of why the scale breaks down at the weld is a combination of:

Local turbulence because the weld root protrusion disturbs the flow and eddys
then break up the scale.

The chemistry of the weld is slightly different from the adjacent metal and for
some reason (e.g. carbide structure) the scale is not as protective.

Solving the problem is not easy. Steps which can be taken include:

• Specifying a maximum root penetration of 0.5 mm.

Using filler metals for the root run with alloying additions of copper and
nickel (e.g. ISO:E51 4 B 120 20 (H) AWS:E7018-G) typically used for welding
so-called weathering steels. Low weld silicon contents are also suggested,
probably < 0.35%, since a few practical problems have been experienced in
the past with weld Si contents of around 0.5% or more. A problem with Si is
that recovery across the arc depends upon the arc length and the local shielding
(i.e. on the joint design, welding position etc.). Thus, the same electrode can
give an appreciable range of Si in the weld deposit with different welders or
joint geometry. However, < 0.35%Si should generally be achievable.

Detailed laboratory testing simulating flowing conditions to select the correct


combination of filler and inhibitor for the given conditions. (Testing is
particularly recommended for operations above 70°C).
5
Key Parameters Affecting Corrosion

CO 2 corrosion is affected by a n u m b e r of factors i n c l u d i n g e n v i r o n m e n t a l ,


metallurgical and hydrodynamic parameters. These are described in this Section.

5.1. Water Wetting

For CO 2 corrosion to occur there must be water present and it must wet the steel
surface. The severity of CO 2corrosion attack is proportional to the time during which
the steel surface is wetted by the water phase. Consequently the water cut is an
important parameter. However, the influence of the water cut on the corrosion rate
cannot be separated from the flow velocity and the flow regime effects. In o i l / w a t e r
systems emulsions can form. If a water-in-oil emulsion is formed then the water
may be held in the emulsion and water wetting of the pipewall prevented or greatly
reduced leading to a consequential reduction in the rate of corrosion. If, on the other
hand, an oil-in-water emulsion is formed, then water wetting of the pipewall will
occur. The transition from a water-in-oil emulsion to an oil-in-water emulsion occurs
around 30 to 40 wt% water in oil and, in straight pipe with emulsified liquids, a clear
jump in the corrosion rate can be demonstrated [12]. This had lead to a rule-of-thumb
that corrosion is greatly reduced for water cuts below around 30 wt% water cut in a
crude oil line.
However, the 30 wt% rule-of-thumb is only valid if an emulsion is formed and no
water drops out along the line. This is a stringent criterion and is not usually met in
flowlines and export lines. Operators' experience in systems such as Forties is that
water drop out can occur at very low water cuts (ie less that 5 wt%) and that emulsions
cannot be relied on for corrosion control. Thus, the 30 wt% rule-of-thumb is not
normally recommended and analysis of corrosion risk should assume that water
drop-out will occur at some point in the line.
Principal factors influencing water wetting include:

• O i l / w a t e r ratio;
• Flow rate and regime;
• Surface condition (roughness, cleanliness);
• Water drop-out (low spots);
• Water shedding due to changing flow profile (bends, welds); and
• 3rd party entries (mixing effect).
10 CO2 Corrosion Control in Oil and Gas Production--Design Considerations

5.1.1. Water Characteristics


The water associated with oil and gas production arises from two principle sources:

As 'Condensed Water'; this water is formed by the condensation of water


vapour from the gas phase.

As 'Reservoir Water'; this is reservoir (or formation) brine entrained with the
main hydrocarbon well stream fluids.

Reservoir water contains a wide range of dissolved salts which can influence the
pH of the wet CO2-containing hydrocarbon system. Bicarbonates can be particularly
beneficial as they can usefully increase system pH rendering the CO2-bearing liquids
potentially less harmful.
Further information on water characteristics is given in EFC Publication Number 17.

5.1.2. Hydrocarbon Characteristics


Crude oils can successfully entrap water to form stable water-in-oil emulsions.
Significant levels of water can be effectively held up in this manner thereby preventing
the water from wetting and corroding the steel. Depending on the water content
and other variables an oil-in-water emulsion can form, resulting in water wetting
of the steel.
The ability of crude oils to form stable emulsions will depend on oil chemistry,
specific gravity, viscosity, velocity and system pressure, temperature and flow
conditions. In general it has been found that most crude oils can incorporate water
up to at about 20 vol.% as long as the liquid flow velocity is above a critical level [13].
For any particular pipe diameter the critical velocity for water uptake by flowing
crude oil can be predicted after the method proposed by Wicks and Fraser [14].
Typically this critical velocity is around 1 ms -1 for most crude oils or as low as 0.5
ms -1 in deviated wells where temperature has a major influence.
In practice the emulsion forming capability of the crude oils of interest should be
determined experimentally to establish the actual amount of water that can be held
in an oil-based emulsion.
Lighter hydrocarbon condensates (e.g. NGLs) do not hold up water as effectively
as crude oils. The emulsions that are formed are weak and can break down rapidly
resulting in water wetting.
The corrosion problems in the oil lines and deviated oil wells with stratified flow
regime are well established (water line corrosion). At velocities below the critical
velocity for water/oil separation, the flow regime is generally of the segregated type.
The steel surface is almost permanently wetted by the water phase even for the water
cuts as low as 1%. Corrosion products and other solid particles coming from the
reservoir accumulate in the water phase at the lower side of the line or tubing and
may erode the corrosion product scale on the steel.
Some field results show that the water/condensate or oil/water separation is
possible even in slug flow where the flowing gas pushes the separated condensate/
oil phase above the water phase [15]. The water phase may remain at low spots until
Key ParametersAffecting Corrosion 11
its volume becomes large enough to disturb the gas flow. Consequently full water
wetting may occur even in slug flow and with very low water cuts.
For the design of new installations, the evaluation of the flow regime, based on
the estimated development of the production rates during the field life, is of a
paramount importance. Whatever the water cut is, the line or tubing diameter should
ideally be selected in order to prevent segregated flow.
It is also important to consider the impact of production/process chemical
treatments on crude oil emulsion stability. Emulsion breakers are often introduced
into production facilities to enhance water/oil separation. It is not unusual for these
to carry through with the separated liquid hydrocarbon stream if they are used in
excess. The carry through of such treatment chemicals to later parts of the plant will
influence the ability of the crude oil to entrain and retain water as a stable emulsion
through the production facilities.
The separation of water from crude oils (with or without added de-emulsifiers)
may occur even at very low water cuts (e.g. less than 5%) at low points in a
pipeline. Consequently, for pipeline corrosion control a regular pipeline pigging
campaign may be required to ensure that any separated water accumulations
are effectively removed, particularly as flow rates decrease towards the end of
the field life.

5.1.3. Top-of-the-Line Wetting


In gas/condensate pipelines the corrosion rate may vary between the top and the
bottom of the pipe. Under stratified flow regimes, the top-of-line (TOL) location in a
pipeline is not continually water wetted. However, there is always some condensation
of water on the inner pipe wall. If this water is rapidly saturated with corrosion
products, the pH in the water increases and causes the formation of fairly protective
corrosion product films on the steel surface which can reduce the corrosion rate. A
constant corrosion rate is obtained when the corrosion rate has been reduced so
much that it is balanced by the rate at which corrosion products are transported
away from the surface by the condensed water. (At high condensation rates the water
may be undersaturated and remain acidic and corrosive).
Experiments at IFE showed that the corrosion rate could be calculated when the
condensation rate and the solubility of iron carbonate in the condensed water are
known, and a simple model was developed [16]. At moderate condensing rates
(< 0.25 gm-2s -1) the corrosion rate will be less than 0.1 r a m / y e a r over a wide range of
CO 2 partial pressures (0-12 bars) and temperatures (20-100°C).
It is also possible to calculate the TOL corrosion rate using the Shell corrosion rate
prediction model as a condensation factor is included [3]. The factor Fcondis equal to
1 for high condensation rates (= 2.5 g m-2s -1) and is reduced to Fcond= 0.1 when the
condensation rate is less than 0.25 gm-2s -1. The factor is regarded as conservative.
Excessive corrosion rates can be mitigated by reducing the cooling rate of the
pipe wall and by avoiding cold spots. Under practical conditions, at low cooling and
condensing rates, it seems to be generally accepted that no serious corrosion problems
have been experienced in gas pipelines with CO 2 only, but that traces of H2S have
led to some attack in a few cases (in these cases the buffering by corrosion products
is lowered by the lower solubility of iron sulfides). Nevertheless, TOL corrosion can
12 CO2 Corrosion Control in Oil and Gas Production--Design Considerations

be difficult to control with a reasonable degree of certainty, since injected chemicals


can not in general be expected to be present in the condensing water.

5.2. Partial Pressure and Fugacity of CO 2

CO 2 corrosion results from the reaction of a steel surface with carbonic acid arising
from the solution of CO 2 in an aqueous phase m i.e. it is not a direct reaction with
gaseous CO 2. The concentration of CO 2 in the aqueous phase is directly related to
the partial pressure of CO 2 in the gas in equilibrium with the aqueous phase. Thus in
CO 2 corrosion, estimates of corrosion rate are based on the partial pressure of CO 2 in
the gas phase.
It should be noted that if there is no free gas present then the CO 2 content of the
water will be determined by the PCO2of the last gas phase in contact with the fluids
(e.g. the PCO2at the bubble point for well bore fluids; the PCO2in the low pressure
separator gas for fluids in an export pipeline).
Strictly, it is the thermodynamic activity of the CO 2 in the aqueous phase that will
be important in the corrosion reaction rather than its concentration per se. This activity
will vary with concentration depending on the chemical composition of the aqueous
phase. However, the activity of the CO 2 in the aqueous phase is directly linked to the
activity in the gas phase, known as the fugacity. The fugacity of a gas is effectively
the activity of the gas and for ideal gases, this is equal to the partial pressure.
However, with increasing pressure the non-ideality of the natural gas will play an
increasing role, and instead of the CO 2 partial pressure, the CO 2 fugacity fc02 should
be used with some models:

fco 2 = f'Pco2 (7)

where f is the fugacity coefficient. Figure 1 provides a conservative estimate for f.


The presence of other gases will generally further reduce the fugacity coefficient.
When necessary, the fugacity should certainly be taken into account in any predictive
model for system pressures exceeding 100 bar.
However, it is important to keep a consistent approach for both gas and water
phases. If there is insufficient information to establish the non-ideality in the aqueous
phase, then Pco2should be used in considering the gas phase. This is particularly
true for pH calculation.

5.3. Temperature

The corrosion of carbon and low alloy steels in a w e t C O 2 environment can lead to
iron carbonate as a reaction product. Although recent work suggests that an iron
carbide matrix may be first exposed on the surface of corroding steel, a carbonate
scale which may protect the underlying metal can often be formed [17]. The formation
and protectiveness of such a scale depends on a number of factors that are described
in Section 5.5.
Key Parameters Affecting Corrosion 13

0.9

------..44o oC

0.8 120~
,

O
0.7
40 " ~ ~

U_
0.6

0.5

0.4
0 50 1O0 150 200

Total system pressure, bar

Fig. 1 Fugacity coefficient for CO 2 in methane for gas mixtures with less than 5 mole% CO 2 [4].

H o w e v e r , at h i g h e r t e m p e r a t u r e s (e.g. a r o u n d 80°C) the iron c a r b o n a t e


solubility is decreased to such an extent that scale formation is more likely. Under
laboratory conditions, rates of u n i f o r m corrosion are consistently reduced at
higher temperatures.
Some laboratory studies show that the initial rate of uniform corrosion increases
up to 70-90°C, probably due to the increase of mass transfer and charge transfer
rates [2,3]. Above these temperatures, the corrosion rate starts to decrease. This is
attributed to the formation of a more protective scale due to a decrease in the iron
carbonate solubility and also to the competition between the mass transfer and
corrosion rates. As a result, a diffusion process becomes the rate determining step
for the corrosion rate.
Field evidence for a m a x i m u m t e m p e r a t u r e for CO 2 corrosion has been found
in some wells. These case histories s h o w that in oil and gas wells m a x i m u m
corrosion takes place where the t e m p e r a t u r e is b e t w e e n about 60 and 100°C
[2,18,19] which m a y coincide with d e w point t e m p e r a t u r e in gas wells. In these
cases, below 60-70-°C, the corrosion rate increased with increasing t e m p e r a t u r e
and above 80-100°C the corrosion rate decreased with increasing temperature.
Conversely, very high corrosion rates have been observed up to 130°C at the top
of some gas wells exascerbated by high rates of water condensation.
14 CO2 Corrosion Control in Oil and Gas Production reDesign Considerations

5.4. p H

The pH value is an important parameter in corrosion of carbon and low alloy steels.
The pH affects both the electrochemical reactions and the precipitation of corrosion
products and other scales. Under certain production conditions the associated
aqueous phase can contain salts which will buffer the pH. This tends to decrease the
corrosion rate and lead to conditions under which the precipitation of a protective
film or scale is more likely.
For bare metal surfaces which are representative for worst case corrosion,
laboratory experiments indicate that a flow sensitive H + reduction dominates the
cathodic reaction at low pH (pH < 4.5) while the amount of dissolved CO 2 controls
the cathodic reaction rate at higher pH (pH > 5).
In addition to the effects on the cathodic and the anodic reaction rates, pH has a
dominant effect on the formation of corrosion films due to its effect on the solubility
of ferrous carbonate, as illustrated in Fig. 2. It is seen that the solubility of corrosion
products released during the corrosion process is reduced by just five times when
the pH is increased from 4 to 5 but by a hundred times with an increase from 5 to 6.
The lower solubility gives a much higher FeCO 3 supersaturation on the steel surface
and a subsequent acceleration in precipitation and deposition of iron carbonate scale
[17]. The likelihood of protective film formation is therefore increased significantly
when the pH is increased beyond 5 and this can explain w h y low corrosion rates
have been reported for many fields where the pH is in the range 5.5--6. However, the
solubility of FeCO 3 must not be confused with that of ferrous ions (Fe2+).

100

10-
(p
LI_

E
C)..
C~.
1 -
o~
o~
..O

cO 0.1 m
o
oQ)
Li.

0.01 -

0.001 I I
5 6

pH

Fig.2 Solubility of iron carbonate released during the corrosion process at 2 bar CO 2 partial
pressure and 40 °C [17].
Key ParametersAffecting Corrosion 15

5.5. Carbonate Scale

Reliance on carbonate scales/film as described in section 5.3 to give continuous


protection is not totally warranted. In particular, in regions of high flow or at welds,
scale breakdown can lead to rapid rates of localised corrosion ('mesa attack').
Recent extensive work on the subject has shown that the corrosion process involves
the initial production of an iron carbide matrix on the surface of corroding steel.
Corrosion product film of FeCO 3 or Fe30 4 will then form as a scale on the surface
resulting in a reduction in the corrosion rate [20]. The formation and protectiveness
of such a scale depends on a number of factors such as the solubility of iron carbonate
(which will vary with pH and the presence of other salts), the rate of reaction of the
underlying steel and the surface condition (roughness/cleanliness/prior corrosion).
The scale [9] may be weakened by high chloride concentrations, by the presence
of organic acids or it can be eroded by high speed liquids. Practical velocities for
smooth flow in systems with single phase liquid flow are often too low to achieve
this; only the impact of high speed liquid droplets can damage the scale. The
occurrence of such a disturbed flow pattern in practical systems can be predicted
from the suggestion made by Smart [21] that the onset of erosion-corrosion is
coincident with the transition to the annular mist flow regime in multiphase flow.
With the superficial liquid velocities associated with wet gas transport, this transition
arises at superficial gas velocities between 15 and 20 ms -1. Above these velocities the
scale protectiveness may be impaired.
The effects of short term scaling will often make interpretation of short-term
laboratory experiments difficult and for this reason such data must be treated with
care m especially results that give unexpectedly low rates of corrosion.

5.6. The Effect of H2S

Leaving aside the cracking and corrosion problems associated with sour service,
H2S can have a beneficial effect on wet hydrocarbon CO 2 corrosion as sulfide scales
can give protection to the underlying steel. The effect is not quantified but it does
mean that facilities exposed to gas containing low levels of H2S may often corrode at
a lower rate than completely sweet systems in which the temperatures and CO 2
partial pressures are similar.
The acid formed by the dissolution of hydrogen sulfide is about 3 times weaker
than carbonic acid but H2S gas is about 3 times more soluble than CO 2 gas. As a
result, the contributions of CO 2 and H2S partial pressures to pH lowering are basically
similar. H2S may cause corrosion also in neutral solutions, with a uniform corrosion
rate which is generally very low [22]. Furthermore, H2S may play an important role
in the type and mechanical resistance of corrosion product films, increasing or
decreasing their strength.
Many papers have been published on the interaction of H2S with low carbon steels
under ambient conditions and the work relating to H2S corrosion problems in the oil
and gas industry is well documented. However, literature data on the interaction of
H2S and CO 2 is still limited. The nature of the interaction of H2S and CO 2 with carbon
16 CO2 Corrosion Control in Oil and Gas Production ~Design Considerations

steel is complex. From past experience corrosion product layers formed on mild steel
can be protective or can lead to rapid failure depending on the production conditions.
This is primarily because an iron sulfide (FeS) film will form if H2S is predominant
and iron carbonate (FeCO 3) will form if CO 2 is predominant in the gas.
The majority of the open literature does indicate that the CO 2 corrosion rate is
reduced in the presence of H2S at ambient temperatures. However, it must be
emphasised that H2S may also form non-protective layers [23], and that it catalyses
the anodic dissolution of bare steel [24]. There is a concern that steels may experience
some form of localised corrosion, but very little information is available.
Published laboratory work has not been conclusive, indicating that there is a need
to carry out further study in order to clarify the mechanism [25,26]. A recent failure
showed how the corrosion rate in the presence of a high concentration of H2S may
be higher than predicted using CO 2 corrosion prediction models [27]. However, in
spite of the work on H2S corrosion of steels, no equations or models are available to
predict corrosion as is the case for CO 2 corrosion of steels.
Cracking of metals in production environments containing H2S is a major risk.
Hydrogen sufide can cause cracking of carbon and low alloy steels within certain
conditions of H2S partial pressure, pH, temperature, stress level and steel metallurgy
and mechanical properties (e.g. hardness). The type of damage manifests itself in
the form of cracking such as sufide stress cracking (SSC), stepwise cracking and
other forms of damage which are discussed at greater length in EFC Publication No.
16.

5.7. Wax Effect

The presence of wax in main oil lines can influence C O 2 corrosion damage in two
ways; exacerbating the damage or retarding it, the effects depending on other
operational parameters such as temperature, flow, etc. and uniformity and the nature
of the wax layer.
Field experience in sweet oil lines in the USA, have shown that a layer of wax
(paraffin) deposited on a carbon steel surface can result in severe pitting of the steel
in anaerobic aqueous solutions of carbon dioxide [28]. Severe pitting occurred along
the bottom of the pipe. Pitting (small random pits) tended to concentrate at the start
of an uphill run where water could collect. Scale analysis showed the presence of
iron sulfide. This was attributed to the presence of bacteria. (The detection of sulfide
in a sweet oil line is not usual. In fact in the case of microbially assisted corrosion,
scale analyses often show 15-30% Fe x S.y ). Velocity was an apparent factor affecting
the location of pits; there being a decrease in the number of pits at flow velocities
above about 0.6 ms -1. (The principal practical observation was that conventional
commercial corrosion inhibitors were ineffective in controlling corrosion; the corrosion
control measure finally adopted for the gathering lines was to install pull-through
polyvinyl chloride liners). In this case the proposed corrosion mechanism is of
diffusion of carbon dioxide through the wax layer which is thought to provide a
large cathodic area that supports anodic dissolution of the steel at discontinuities of
the wax layer. The effect was reproduced in laboratory tests with paraffin coated
specimens exposed to CO 2 saturated water at atmospheric pressure and ambient
Key ParametersAffecting Corrosion 17

temperature. Localised corrosion only took place where there was no wax deposit.
The areas covered with wax were protected from the CO 2 containing solution. The
difficulty in controlling this type of localised corrosion with commercial oilfield
inhibitors was demonstrated in these laboratory tests [28].
In contrast, field experience of a 20 in. (50.8 cm) oil line in Indonesia (about 20 km
length) showed almost nil corrosion rate during about 10 years service which was
attributed to a wax deposit on the pipe wall. The water cut was up to 50%. Internal
corrosion started when light hydrocarbon condensate produced from a gas field was
injected into the line. This dissolved the wax deposit exposing the steel surface, as
confirmed by internal inspection of a corroded pipe section.
6
Prediction of the Severity of CO 2 Corrosion

It is apparent that C O 2 corrosion of carbon and low alloy steels has been, and remains,
a major cause of corrosion damage in oil and gas field operations [1]. The industry
relies heavily on the extensive use of these materials, and thus there is a desire to
predict the corrosivity of CO2-containing brines w h e n designing production
equipment and transportation facilities.
A true industry standard approach to predicting CO 2 corrosion does not exist
although there are aspects of commonality between the approaches/models offered
by a number of operators, research organisations and academic establishments. Apart
from limited reference in National Gasoline Association of America [29] and American
Petroleum Institute [30] publications, there is no professional body or agency to
provide a standard guideline on CO 2 corrosion prediction. However, in particular,
the work of Shell in this area has provided a reference point. The Shell (de Waard et
al.) equation or nomogram has been developed as an engineering tool. It presents, in
a simple form, the relationship between potential corrosivity (worst case) of aqueous
media for a given level of dissolved CO 2, defined by its partial pressure, at any given
temperature. The relative simplicity of the Shell approach and its ease of use have
undoubtedly been positive factors in its broad acceptance. This is in contrast to the
arguably more 'all-encompassing' models of, for example, Southwestern Louisiana,
VERITEC, CAPCIS and others which require more detailed input data to run them.
Also input of inspection/monitoring data may be called for to refine the models'
accuracy or field/well specificity.
There would appear to be a trade-off between a model's relative ease of use versus
availability, detail and reliability/accuracy of necessary input data/conditions
combined with the degree of accuracy/absoluteness required in the assessment of
the corrosion risk. The last will also be influenced by the ease and sensitivity of
subsequent corrosion monitoring and inspection.
There still remains an absence of any strong systematic correlation between
predicted and actual field corrosion rates and experience, although CORMED goes
someway in this respect [31]. Future development of predictive models should contain
a much stronger element of field correlation.
The engineer ideally wants a predictive tool that can be readily applied and is
suitable for application at all stages of project development and subsequent operation.
This may seem a tall order but it may nevertheless be argued that the fundamentals
of the CO 2 corrosion process will be common to all situations; It is the overlying
effects of such factors as flow regime, film formation/deposition, hydrocarbon phase
and corrosion inhibitor which cloud or complicate the picture. Both the Shell and
CORMED models have been developed from a basic consideration of the CO 2
corrosion reactions, the former more empirical in origin and the latter more theoretical.
Both have then attempted to account for the overlying effects either by applying
correction factors (Shell) or through field correlation (CORMED).
Prediction of the Severity of CO2 Corrosion 19
Notwithstanding the above discussion, the intent of the present document was
not to provide or recommend a particular corrosion prediction tool, but leave the
decision to the individuals. Nevertheless, this section provides an overview of CO 2
corrosion models and parameters considered in each model. Furthermore, the
parameters which are considered essential in designing for CO 2 corrosion and are
therefore needed, no matter which predictive tool is used, are presented in Fig. 3.
Based on the foregoing discussion, the procedure for predicting CO 2 corrosion
damage is described in Fig. 4. A key feature is the positive and ongoing interaction
between the corrosion engineer and petroleum engineer to ensure that relevant service
conditions are defined and detailed. There has to be a common understanding of
what is required against the limitations of the selected predictive model and
subsequent monitoring/inspection. A case is made for rationalising monitoring and
inspection data with predicted rates, to strengthen the relevance and validity of the
latter, whilst working to introduce a stronger predictive element to the former.
Figure 5 summarises the necessary overall critical steps identified in working to
define a risk of CO 2 corrosion. It should also be recognised that characterising the
flow regime/shear stress to establish water wetting (Section 5.1) may also be critical
to achieving effective corrosion inhibitor selection and deployment (Section 7.4).

6.1. C O 2 Corrosion Prediction M o d e l s For Carbon Steel

Different oil companies and research institutions have developed a large number of
prediction models. Table 1 (p.22) gives an overview of the parameters treated in

To Hydrodynamics: ~ [ Acid(H2s)Co2gases:
]
Local/bulk flow regimes |
p of line/Bottom of lineJ

Steel: Fluid chemistry:


Composition CO 2 corrosion design Local/bulk analyses
Microstructure pH, organic acids
eld; composition, profile

Operating condition:
Controlling Parameters: Temperature, pressure
Micro-alloying elements Number of phases, water cut
Corrosion inhibition (over the life of the field)
Glycol and methanol
pH-control r-

Others:
Initial production condition
Trend of water cut
Carbonate scale
Scale inhibitor
Other additives

Fig. 3 Parameters affecting CO2 corrosion design.


20 CO2 Corrosion Control in Oil and Gas Production--Design Considerations
COMMENTS
Specific case

PETROLEUM I • r CORROSION Positive interaction at all times.


I
ENGINEER I • • ENGINEER

• Water analysis IT I SERVICE Consider total life of the field.


• Total P or Bubble Point CONDITIONS
• Temperature
• mole% CO 2
• H2S present?
Check on solution pH.
CONSIDER Validate measured pH.
CHEMISTRY
Flow Regime ~ EFFECT
Analysis •

Worst case corrosion rate.


PREDICTIVE Erosion not considered.
r-- m MODEL
(Oil/water ratio/flow regime
I I
, , need to be considered, cf.
water or oil wetting.)
I I
~ I I .k Check sensitivity to velocity.
RATIONALISE I I
I I (vs monitoring I
L m "1 and/or inspection ~- --" Does not predict corrosion rate
I data) I in presence of H2S.
J
+
CORROSION Determine total accumulative
DAMAGE/RATE corrosion damage over field life.

Fig. 4 Procedure for predicting C02corrosion damage for a given water composition, CO 2 partial
pressure and temperature.

those models which have been fully or partly described in the literature. It is seen
that different parameters are used as inputs and it is also seen that some of the key
parameters listed in Fig. 3 are not included at all.
Very different results are obtained when the models are run for the same test
cases. This is due to the various philosophies used in the development of the models.
Some of the models give a worst case corrosion rate based on fully water wetting
and little protection from scale and inhibitors. These models have a built-in
conservatism and they probably over-predict the corrosion attack significantly for
many cases. Other models are partly based on field data and predict generally much
Prediction of the Severity of CO 2 Corrosion 21

Define risk of water we


of pipe wall and criticalareas ~'

~ _ L
1.
Number of
Phases

Stratified Bends
Bulk flow Local flow Welds
Annular conditions conditions
Slug Damaged Areas

Local flow
condition
(at pipewall)

otentia,
tacting aqueous p ~

Laboratory
testing
,.t
1 J
~__~L rl
Predictive
modelling
i r'--m I 1
L ~ Field I--J
I monitoring/inspectionj
L

5
CORROSION DAMAGE/RATE

Fig. 5 Critical steps in defining CO 2 corrosion damage.

lower corrosion rates. In these models it is assumed that reduced water wetting a n d /
or formation of protective scale can reduce the corrosion rate from many r a m / y e a r
to less than 0.1.
The most frequently referenced model has been developed by Shell (de Waard et
al.). The first version, based on temperature and Pco2 only, was published in 1975
[2]. The model has since been revised several times. Correction factors for the effect
of pH and scale were included in 1991 [32]. To account for the effect of flow a new
model was proposed in 1993 where the effect of mass transport and fluid velocity is
taken into account [3]. A revised version including steel composition was published
in 1995 [33]. This model represents a best fit to a large number of flow loop data
generated at IFE [34].
Table 1. An overview of the parameters treated in the various prediction models

Models

Parameters Shell 75 Shell 91 Shell 93 Shell 95 CORMED LIPUCOR SSH KSC fiFE) USL PREDICT

Pco2 • • • O • 0 O • • •

Temperature 0 • O O • • • • • •

pH • • O • • O • • •

Flow rate • • • • • • • •

Flow regime • [] • • • • •

Scale factor • • • [] • • • •

Ptot • • [] • • • • •

Steel • [] • •

Water wetting [] [] [] [] • • •

Ca/HCO3 • •

H2S • • • •

HAc • • •

Field data • • • •

Ref, 2 32 3 33 3I 35 36 37 38 39

Parameters considered directly


Parameter considered indirectly or not considered highly influential.
Prediction of the Severity of CO2 Corrosion 23

The CORMED model developed by Elf predicts the probability of corrosion in


wells [31]. It is based on a detailed analysis of field experience on CO 2 corrosion
mainly from Elf's operations, but also from data supplied or published by others
(e.g. Total, Phillips). The model identified the CO 2 partial pressure, in situ pH, Ca2+/
HCO 3- ratio and the amount of free acetic acid as the only influencing factors for
downhole corrosion and predicts either a low risk, medium risk or a high risk for
tubing perforation within 10 years.
The LIPUCOR corrosion prediction program calculates corrosion rates based on
temperature, CO 2 concentration, water chemistry, flow regime, flow velocity,
characteristics of the produced fluid, and material composition [35]. The program
which is developed by Total is based on both laboratory results and field data. More
than 90 case histories have been used in the development.
The SSH model is a worst case based model mainly derived from laboratory data
at low temperature and a combination of laboratory and field data at temperatures
above 100°C [36]. The model has been developed by Hydro, Saga and Statoil in
collaboration with IFE.
IFE is developing a new predictive model for CO 2 corrosion based on mechanistic
modelling of electrochemical reactions, transport processes and film formation
processes. The first part of the model which applies for the case when no surface
films are present has been published recently [37].
The USL model predicts corrosion rates, temperatures, flow rates, etc. for gas
condensate wells [38]. It is a package of programs developed by University of
Southwestern Louisiana.
Predict TM is a software tool developed by CLI international [39]. The basis of the
model the de Waard-Milliams relationship for CO 2 corrosion, but other correction
factors are used and a so-called 'effective CO 2 partial pressure' calculated from the
system pH.
7
C O 2 Corrosion Control

CO 2 corrosion damage and its severity can be mitigated by a number of measures.


These primarily fall into two broad categories of (i) modifications to carbon and low
alloy steels, to enhance their resistance to corrosion, and (ii) alteration of the
environment to render it less corrosive.

7.1. Micro-alloying of Carbon and Low Alloy Steels

Much work has been done to try to improve the corrosion resistance of carbon and
low alloy steels with small additions of alloying elements. The corrosion rate is
controlled by the transport of the reacting agents through the corrosion product layer
and the different alloy additions may affect the protectiveness of the surface film.
The microstructure of the steel is also important. It is apparent that the alloying
elements and the microstructure do not necessarily have the same effect when the
steel is exposed at a low pH, in formation water, in injection water or in inhibited
solutions or when different corrosion products accumulate at the steel surface. This
may be the reason why there is conflicting information on.this subject in the literature.
Note that the control of corrosion in carbon steel welds was discussed in Section
4.2.

7.1.1. Effect of Chromium


Chromium is the most commonly used alloying element added to steel to improve
the corrosion resistance in wet CO 2 environments. Independent work at Sumitomo
[40], Kawasaki [41] and IFE [42] shows a beneficial effect of small amounts of
chromium in CO 2 saturated water at temperatures below 90°C. It is suggested that
Cr is enriched in the iron carbonate film and makes it more stable. Alloys with 0.5%
Cr seems to be a good choice giving good corrosion properties and hardly any loss
of toughness.
At higher temperatures the effect of chromium seems to be more unclear and
several authors have reported a reduction in corrosion resistance above 100°C for
low alloyed chromium steels [5,43,44]. In contrast it has also been reported that the
temperature giving a maximum corrosion rate increases with increasing Cr content
in the steel [40].
Field experience does indicate an improvement of the corrosion resistance with
small amounts of chromium and several companies have recently specified 0.5-1%
Cr for their pipelines.
CO 2 Corrosion Control 25
7.1.2. Effect of Carbon
The effect of carbon is linked to the carbide phase, cementite (Fe3C) which forms
part of the microstructure of carbon steels. There are two effects of cementite that
can be emphasised:

Iron carbide is exposed at the steel surface when the iron is dissolved and it
then causes an increase in the corrosion rate. This is explained by a galvanic
effect where the cementite acts as a cathode.

The cementite can act as a framework for build-up of a protective corrosion


film.

Both these points are connected to the microstructure. The literature is mainly
focused on ferrite-pearlite structures and quenched and tempered (QT) steels. A
ferrite-pearlite structure can form a continuous grid of cementite after the ferrite
phase is removed by corrosion. Under conditions where film formation is impeded
(low temperature and low pH) this carbide phase increases the corrosion rate due to
a galvanic coupling between the cementite and the ferrite leading to local acidification
and further difficulty in establishing protection. Such a grid of carbide could also be
a good anchor for a protective iron carbonate film under film forming conditions. A
fine ferrite-pearlite structure will improve this tendency. These effects will be stronger
at a high carbon content (> 0.15% C).
Quenched and tempered steels contain mainly martensite or bainite where more
carbon is in solid solution and the carbide phase does not make a continuous grid as
for the ferritic-pearlitic steels. In these steels the galvanic effect will be reduced and
the chance of anchoring a protective film less. Most reports on the effect of
microstructure maintain that ferrite-pearlite is favourable with respect to film
formation [43,45-47] while other workers suggest that QT steels with needle-like
carbides can anchor a film better than a ferrite-pearlite steel [44]. This might depend
on the very first period of exposure.
Since new pipeline steels have low carbon content (< 0.1% C); the effect of cementite
will be of less importance in these types of steels.

7.1.3. Effect of Other Alloying Elements


Nickel is often added to the steels and in welding electrodes for pipeline steels to
improve weldability and the toughness of the weld deposit. There has been some
disagreement about the effect of small amounts of nickel on CO 2 corrosion [41,42,48].
Most reports indicate a negative effect, but it seems to be slight. Varying effects have
also been reported in different sources with small additions of copper [41,44,48].
A positive effect of molybdenum [49], silicon [44,49] and cobalt [39,49] has been
reported, but a more systematic study is required to confirm this.
26 CO2 Corrosion Control in Oil and Gas Production ~Design Considerations

7.2. Effect of G l y c o l a n d M e t h a n o l

Large quantities of glycol or methanol are often introduced into wet gas-producing
systems to prevent and control hydrate formation which can cause plugging
problems. Both of these chemicals, if present in sufficient concentrations can inhibit
CO 2 corrosion. Of the two, glycol is much more effective and a correction can be
made to the predicted corrosion rate to take this into account. Combined with a pH
controlling agent, the water/alcohol phase may be rendered less corrosive (Section
7.3).
The glycol additives which are mainly used for hydrate prevention are MEG
(mono-ethylene glycol) and DEG (di-ethylene glycol), but TEG (tri-ethylene glycol)
can also be used for dehydration. These are effective in reducing the rate of CO 2
corrosion by diluting free water and reducing the corrosivity of the resulting water
phase
Methanol, too, can effectively suppress the rate of wet CO 2 corrosion in wet gas
transmission systems although it is more difficult to use in the design of corrosion
protection of gas pipelines. Operators of wet gas pipelines in the UK Sector of the
North Sea have found that with controlled additions of methanol carbon steel
corrosion rates can be maintained below I mpy (0.025 m m / y ) provided a methanol
excess is used. For effective control the concentration of methanol in water at the
pipeline reception facilities needs to be kept in excess of 80%.
Although some operators do use glycol as a means of controlling CO 2 corrosion,
this is not a recommended practice by others, as corrosion inhibition is preferred
and the two effects are not normally considered additive (in some cases less
concentrated glycol is used with inhibition). However, it is important to consider the
effect that glycol carry-over from drying systems can have in an otherwise 'dry'
pipeline. The glycol may absorb any residual water (further lowering the pipeline
gas dewpoint) and in doing so create a water-glycol phase which could sustain
corrosion, albeit at a low rate.
When evaluating corrosion protection by glycol addition, the actual composition
of the condensed glycol/water mixture is of prime importance. Models are used for
these predictions, but there are no global models available which can predict all
possible situations with respect to carbonate and sulfide films and the corrosion
protection levels along wet hydrocarbon pipelines. The commonly used model for
design with glycol effects in CO 2 corrosive wet gas pipelines and other systems, is
the Shell model [3]. In normal flowing conditions the glycol/water mixture will
always be in an equilibrium with the wet gas. Condensation may take place along a
pipeline on the relatively colder pipewall in the top section. Nevertheless, the
condensing phase will then have the same water content as the stratified glycol,
thus reducing its corrosivity.
The pH should be controlled to obtain non-corrosive conditions. In the higher pH
ranges above 7-8, the corrosion of carbon steel cannot propagate. Different pH
controlling products can be used for this purpose. However, in waters containing
calcium or magnesium, there is a risk for scale precipitation at higher pH values and
pH control will then be impractical. Similarly, organic acids, e.g. acetic acid etc., can
reduce the buffer capacity and hence the pH.
To be cost-effective and environmentally acceptable, it is standard practice to
CO 2 Corrosion Control 27
regenerate (i.e. reboil) the glycol/methanol after use in a system. Over time, the
glycol may be partially decomposed and the pH value may decrease. In such a case,
pH stabilising to obtain a system pH > 6 is necessary. Possible agents are MDEA or
TEA.
A combination of glycol and corrosion inhibitors is sometimes used. As many of
the data available on corrosion predictions are laboratory data, a total risk evaluation
can result in the need to plan for corrosion inhibitor injection and even implement
this from start-up. A question which then arises is how much additional corrosion
protection the corrosion inhibitor can give. Laboratory data indicate up to 50%
additional corrosion reduction, but this level of corrosion control will be dependent
on the actual glycol concentration and type of inhibitor in the system.
The method of using glycol treatments to control CO 2 corrosion in the field
should be combined with corrosion monitoring and intelligent pig inspection
programme.

7.3. p H Control

7.3.1. The Role of pH


As a dissociation product of the water molecule, H ÷ (or its counterpart OH-) is
universally involved in the kinetics of aqueous corrosion, and in the equilibria of
water chemistry. The pH control or buffering by the natural alkalinity of produced
waters (if any) is thus a key issue for the prediction of the CO 2 corrosion rate (both
the initial corrosion rate of bare metal, as well as the long term corrosion rate) [50-
52].

7.3.2. Wet Gas Transportation Lines


In long sweet natural gas transmission lines, pH control of hydrate preventors has
been implemented successfully [53]. This is a cost effective option to control corrosion,
although subject to the absence of Ca 2+ or Mg 2+ ions in the formation water (since
they would cause precipitation of scale if pH controllers are added).

7.3.3. Different Chemicals and Their Mechanisms


Various chemicals that have been used in operation to control the pH in natural gas
lines are reviewed in this Section. Alkaline additives have changed over the years.
Historically, the technique was developed by Elf in Italy (1970s) and Holland (1980s).
Further developments have been as follows:

NaMBT (Sodium mercaptobenzothiazole) was used in glyco. However, in the


long term it does lead to gunking problems through precipitation of a resin-
like compound.

MDEA (methyldiethanolamine) was also used in glycol in the later 1980s. It


has a lower freezing point than NaMBT and has no secondary effects.
28 CO2 Corrosion Control in Oil and Gas Production --Design Considerations

Na2CO3.10H20,(sodium carbonate or 'soda ash'), which may be used either


with glycol or methanol, is the proposed new additive as it interacts directly
with the CO2/HCO3- equilibrium [50].

All pH controllers remain with the liquid phase during the regeneration of the
hydrate preventer by reboiling.

The present understanding of the beneficial effect of pH control is that high pH


conditions decrease the solubility limit of siderite (FeCO3), thus favouring the
establishment of highly protective corrosion layers. Consequently, the effect of pH is
nearly the same for all chemicals (NaMBT, MDEA, NaHCO 3) and all solvents (MeOH,
MEG, DEG ..... or fresh water).
The in situ pH should be buffered to about 6.5, whatever the system and
temperature being considered. It is worth noting that pH is here an index of the
buffering level, which is the same at any temperature. Therefore, pH is measured
and reported only at room temperature, whereas corrosion rates, of course, are
measured at all the temperatures met along the pipeline.

7.3.4. pH Monitoring
Acetate is not a buffer for carbonic acid [54], and there is a progressive shift of the in
situ pH in the presence of free acetic acid, which must be compensated by adding
some fresh pH controller. Therefore, there is a need for a periodic monitoring of pH
in order to detect and correct any pH shift. This is a simple pH measurement, in a
sample where pure CO 2 is bubbled under ambient condition (1 bar) in the presence
of the intended chemical. This laboratory measured pH 1 can be used to determine
the in situ pH under pressure by:

pH(Pc02 ) = pH 1 - log Pc02 (8)

It is suggested to monitor this on a weekly basis for the first month after start up,
and then on a monthly basis.

7.4. Corrosion Inhibition

Corrosion inhibitors continue to play a key role in controlling corrosion associated


with oil and gas production and transportation. This primarily results from the
industry's extensive use of carbon and low alloy steels which, for many applications,
are ideal materials of construction, but generally exhibit poor CO 2 corrosion resistance.
Clearly economics also has a major part to play in materials selection. As a
consequence, there is a strong reliance on inhibitor deployment for achieving cost
effective corrosion control, especially treating long flowlines and main oil lines.

7.4.1. Inhibitor Mechanism


Corrosion inhibitors used in hydrocarbon transmission lines are long chain
c o m p o u n d s . Generally these are nitrogenous (eg. amines, amides, imides,
CO 2 Corrosion Control 29
imidazolines), but they can also be organophosphates. These compounds are either
polar or ionised salts with the charge centred on the nitrogen, oxygen or phosphorus
groups and as such they will be surface active. A metal surface in an aqueous
environment will have a surface charge and the inhibitor will rapidly be adsorbed
onto the metal surface. This process is rapid and reversible (the concentration of
adsorbed inhibitor will rapidly decrease if the local environment is depleted).
However, once adsorbed in this manner (physisorption) charge transfer between
the inhibitor and the metal occurs resulting in a form of chemical bonding which is
much more stable m i.e. the inhibitor is chemisorbed. The process of chemisorption
leads to the formation of a stable inhibitor film on the surface.
Corrosion is an electrochemical reaction which takes place at various anodic and
cathodic sites on a metal surface - - the presence of an inhibitor film of long chain
organic c o m p o u n d s depresses both the anodic and cathodic reactions. The
mechanisms are not fully clear but as well as providing a physical barrier the inhibitor
modifies the surface potential and consequently limits the adsorption-desorption
processes and reaction steps that occur in both anodic and cathodic reactions m thus
controlling corrosion.
The whole process is critically dependent on both the initial physisorption and
s u b s e q u e n t c h e m i s o r p t i o n processes. These are strongly d e p e n d e n t on the
environment (e.g. pH, temperature and liquid shear stresses), the state of the metal
surface (e.g. roughness, scales, oxide films, surface damage and carbonate films)
and competition from other surface active species (e.g. scale inhibitors and
demulsifiers). The last is particularly important in oil and multiphase systems where
a wide range of oil-field chemicals may be employed. When selecting inhibitors it is
important to carry out full compatibility trials to confirm that the different chemicals
in a given package do not detrimentally effect each others performance beyond certain
limits. Similarly, in linked systems (e.g. branch lines into a main trunk line) it is
recommended that only one inhibitor be used for all of the fluids in the system.
Inhibitor molecules adsorb, however, not only on the bare metal surface but also
on the carbonate scale [55]. Thus, the morphology and degree of crystallinity of the
scale and, hence, its porosity (homogeneity) will be influenced by adsorbed molecules.
The presence of effective inhibitors thus decreases the intrinsic stresses and increases
the critical strains for cracking and spalling of the scale [56].
Incorporation of inhibitors in the surface scale and adsorption of inhibitors on it can
also lead to drag reducing effects, i.e. to a reduction of wall shear stresses and local flow
intensities created at flow imperfections (e.g. pits, grooves, weld beads etc.).

7.4.2. Inhibitor Efficiency and Inhibitor Performance


For an inhibitor to work effectively it must be dispersed to all wetted surfaces and
under the system conditions it must be sufficiently effective to provide adequate
protection. Calculations of corrosion allowances for given design lives assume
effective dispersion and a certain level of success. Areas which cannot be inhibited
effectively (e.g. tees) will either have to be clad or allowance made for reduced
inhibitor effectiveness.
The inhibitor effectiveness can be defined in two ways, inhibitor efficiency or
inhibitor performance.
30 CO2 Corrosion Control in Oil and Gas Production--Design Considerations
7.4.2.1. Inhibitor Efficiency
Inhibitor efficiency is defined from laboratory measurements, as the relative corrosion
rate with and without inhibitor:
CRo-CRin h
Inhibitor efficiency = x 100% (9)
CR o
where GRinh = corrosion rate in the presence of inhibitor and CR o = corrosion rate in
the absence of inhibitor.
The inhibitor efficiency is a function of inhibitor concentration and, is typically
above 90% for successful inhibitors. This figure is often used in the determination of
corrosion severity and the subsequent corrosion allowance. The system inhibitor
efficiency will, of course, be influenced by the dispersion m e c h a n i s m and, in
particular, how the inhibitor partitions between the different phases present (Section
7.4.3). In this respect, it differs when measured in water alone or water/oil mixtures.
The calculation of corrosion allowances or design lives generally starts by
calculating the expected corrosion rate in the absence of inhibitor m determined by
the prediction models (Section 6.1) and adjusting factors outlined above in Section 6.
The expected corrosion rate is then calculated by multiplying by (1 - f~ 100), where f
is the system inhibitor efficiency; the required corrosion allowance is then the design
life times the inhibited corrosion rate.
Proposed values for the system inhibitor efficiency vary between 80 and 99%. The
corrosion allowance (or design life for a given allowance) is very sensitive to the
value of system inhibitor efficiency chosen; thus an efficiency of 85% will require 3
times the corrosion allowance of an efficiency of 95% and 15 times the corrosion
allowance of an efficiency of 99%; an efficiency of 90% would require an allowance
of 2 and 10 times, respectively.
At 99% the design lives are so large that the effects of temperature and CO 2 partial
pressure are negligible, i.e. when based on this quality of inhibition.
Until recently, most operators using this approach recommended a figure of 85%
for design purposes. However, in light of past experience and recent advances in
inhibitor performance, design figure have increased to 90%. Tests in the laboratory
have given efficiencies well above 95% and it is felt that, given careful inhibitor selection,
values of 90% can be achieved in the field in straight pipe under typical pipe wall
shear stresses and in the absence of highly energetic flow (e.g. at tees and in slug
flow conditions). This value is more in line with industry practice.

7.4.2.2. Inhibitor Performance


It has been frequently shown that the residual corrosion rate under inhibition does
not display the same sensitivity to operational parameters as the corrosion rate
without inhibitor. It results that the above mentioned approach cannot be but an
approximation, especially if the prediction of CR o itself is questionable. Therefore,
some operators are directly selecting inhibitors according the resulting residual
dissolution r a t e Cain h. As an example, the choice of chemical and dose rate must
achieve a certain corrosion damage or rate.
In such an approach, the corrosion allowance is chosen first, on a technical and
economical basis. This defines the mandatory inhibitor performance on the basis of
CO2 Corrosion Control 31

which, treatment conditions are then selected.

7.4.3. Inhibitor Partitioning and Persistency


7.4.3.1. General
In a multiphase flow, any chemical which is soluble in more than one phase
partitions between them according to the solubility equilibrium. This is true for gases,
and especially CH 4 and CO2; this is also true for organic corrosion inhibitors which
are soluble to some extent in water and oil. Consequently, an inhibitor can adsorb on
a surface if, and only if, it is present in the wetting (oil or water) phase in sufficient
concentration.
On the other hand, the beneficial effect of a corrosion inhibitor is achieved in the
corrosive phase only, which is the water phase. Two basic treatment philosophies
can be established, respectively based on oil or water soluble products:
1 Oil soluble inhibitors (OS): display the best persistency in water, but they can be
washed out if not replenished by a periodic wetting of the wall by oil.
2 Water soluble inhibitors (WS): have a weaker persistency. In case of high flow
rates, they are also more sensitive to mechanical stripping, particularly if a high
shear stress is applied.

The reduction in corrosion rate due to inhibition depends on a number of factors


n the basic efficiency of the inhibitor under standard conditions, the effect of flow
and turbulence on the inhibitor efficiency and the dispersion of the inhibitor into the
corrosive medium. For the oil phase, after the first stage separator, the inhibitor injected
will need to be oil soluble to be dispersed throughout the oil phase. However, the
greatest risk of corrosion will be at bends in the pipework where water is likely to
drop out and the flow regimes at these locations may greatly reduce the inhibitor
efficiency. In the produced water phase the inhibitor will have to be water soluble or
water dispersible to ensure dispersion through the medium. If injected at a sufficient
dosage, then this should be effective even at bends for moderate velocities. In the gas
phase, inhibition is not likely to be effective, the high turbulence and flow rates will
disrupt inhibitor films, hence no inhibited corrosion rates are presented for the
amended corrosion rates for gas streams. In separators, there will again be the problem
of inhibitor partitioning into the produced water phase from the oil phase. In addition,
eddies and turbulent vortices set up by weir and vessel attachments will greatly
reduce inhibitor efficiency.

7.4.3.2. Partitioning
The injection rate of a commercial inhibitor is usually calculated according to the
total liquid flow. It is then reported as an average c o n t e n t (Cmean), whereas the
significant concentrations are the respective concentrations in water (Cw) and in oil
(Co). At the solubility equilibrium, the activities of any chemical in water and oil are
equal. Provided the activity coefficients do not change with concentrations, then the
ratio of their concentrations is constant. This is the partitioning coefficient K between
water and oil:
32 CO e Corrosion Control in Oil and Gas Production--Design Considerations

K - Cw/C o (10)

For oil soluble inhibitors (OS), K is very low (e.g. < 0.1): these products 'do not
pass' into water. For commonly available WS products, however, K is often balanced.
It is thus necessary to make a distinction between 'water soluble' products (K _=_1)
and products with a "preferential solubility in water" (K >> 1).
For WS, the purpose is to actually get them into the water phase, whereas they are
added with respect to the total liquid flow. Whence a first notion of 'partitioning
efficiency' (PE), which is the ratio of what is obtained in the water to what is injected
[57]:
c K
P E - -_____ww = (11)
Cmean 1+
BSW (K - 1)
100
This efficiency may be >1.
However, if the efficiency of a treatment depends on concentrations, its cost
depends on the corresponding quantities. Whence a second notion of 'economic
efficiency' (EE), which is the ratio of what is useful to what is paid:

EE= CwVw _-~BSW x P E (12)


CmeanWtot 100

where OS = oil soluble inhibitors, WS = water soluble inhibitors, PE = partitioning


efficiency, EE = economic efficiency, Cmean average inhibitor concentration based
--

on total fluids, C o = concentration in oil, C w = concentration in water, BSW = water


cut (%), K - partition coefficient, V w = volume of water, Vto t - total volume, G R i n h =
corrosion rate in the presence of inhibitor, CR o = corrosion rate in the absence of
inhibitor, and f = inhibitor efficiency.
PE and EE are not only dependent on the partition coefficient K, but also on the
BSW (Fig. 6). In particular, for traditional products with K < 1, severe underdosage
may be encountered at low BSW. Despite a water solubility, if its K is < 1, all the
added product may then pass into oil, resulting in an unexpected depletion of C w
much below the 'expected' Cmean.With the recent practice of transporting unprocessed
crude oil, m a n y of the recent inhibition failures are believed to be due to this
unexpected underdosage at low water cuts.
Unfortunately, this convenient approach cannot be quantitatively applied. In fact,
all the components of a commercial blend have their own partitioning coefficient. It
follows that partitioning varies for one component to another. Consequently, what is
usually called a partitioning effect is indeed a 'fractioning effect'. The usual presence
of surfactants in a commercial blend also make the partition coefficient of all its
components to vary with the added doses of the blend. This makes any modelling
totally non-manageable.
The only way to take partitioning into account then is to replicate it experimentally.
The fabrication of the test solution for electrochemical testing thus requires to stir
strongly the real virgin oil and reconstituted water at the expected BSW, and then
carefully to separate that water. During this extraction procedure, the in situ pH
CO 2 Corrosion Control 33
must be truly reproduced. The corresponding acid gases must also be present, at
least qualitatively. Temperature m u s t be as close as possible to the expected
temperature. This is not a problem as long as the latter remains below 60-80°C. Above
this some approximations cannot be avoided.

7.4.3.3. Persistency
As already stated, this word covers two notions, namely physical and mechanical
persistency.

Physical persistency expresses the ability of an adsorbed molecule to resist


washing out in virgin water. It is measured by a 'time of defilming'. It is much
higher for OS than WS, and it is i m p r o v e d by chemisorption and film
polymerisation. It is a major feature for OS and batch treatments.

Mechanical persistency expresses the ability to resist a peeling effect by the


fluid flow. It is traditionally measured in flow channels or on rotating devices,
at increasing shear stresses or mass transfer coefficients, and on bare surfaces.

The relevance of this experimental method to field conditions is explained below.

High shear stresses are invariably present in the field, at least locally. With the
success of inhibition, it can be postulated that high local flows in general do
not necessarily prevent inhibitor effectiveness.
Cwatet/Cmean
3.0
K= Cwatet/Coil
-- 0.1
.... 0.3
--- 0.5
2.q --- 1
2
3

.-'" s
.--'" s

. . . . ~ ~ ~ ~ ~

0.0

20 40 60 80 100

% water

Fig. 6 Influence of water content on the partitioning efficiency (Cwater/Cmean),for different


partitioning coefficients (Cwater/Coi1) [57].
34 CO2 Corrosion Control in Oil and Gas Production reDesign Considerations

Inhibition is an electrochemical process. It thus occurs at the metal-electrolyte


interface, i.e. beneath any solid, but porous, surface layers (corrosion layers
or original mill scale or rust layers). On the other hand, hydrodynamic effects
only occur at the interface between a macroscopic solid and the bulk fluid, i.e.
on the top of the solid surface layers. It follows that on scaled surfaces there is
no shear stress applied where inhibition actually occurs, and that the mass
transfer coefficient there is not flow dependent.

The loss of inhibition in the presence of high flow rates may resemble features
similar to morphologies of erosion-corrosion. This has been interpreted as a
flow-dependent loss of inhibition. However, this can also be due to erosion-
corrosion after a totally flow-independent loss of inhibition. In view of this,
field experience needs to be reconsidered.

As an example, oxygen entries can arise in the field, in the form of air entries into
low pressure circuits, or in the recycling of aerated liquids (e.g. slops, sump caisson).
This does change the performance of oil field corrosion inhibitors. For example, some
may become slightly anodic, and overpass their critical pitting potential [57], thus
explaining a loss of inhibition.
Similarly the existence of multiple steady states in CO 2 corrosion [53] is related to
the irreversibility of surface states. This may also occur for inhibitor films, a subject
not addressed to date and requiring further extensive research.

7.4.4. Commercial Inhibitor Packages


Commercial corrosion inhibitor packages contain active molecules, a solvent which
is the carrier fluid, and additives, which are aimed at optimising the properties at all
stages from delivery and storage to injection and production (e.g. co-solvents,
surfactants, stabilisers, antifoaming agents, etc.). A 'commercial' inhibitor is thus a
blend, whose activity is currently much higher than that of the non-formulated active
molecule.
Prior to being applied, an inhibitor must be proven to be an innocuous additive.
Therefore, its technological properties (non-foaming, non-gunking, etc), often
improperly called 'secondary', must be tested before the field application. Based on
these requirements, an inhibitor package needs to incorporate a combination of
characteristics to be effective.

7.4.5. Inhibitor Compatibility


It should be noted that corrosion inhibitors can act as emulsifying agents and can
lead to foaming which may decrease the effectiveness of the separation process.
Similarly, emulsifying agents added to the process stream can interfere with effective
inhibition. There may, in addition, be compatibility problems between the corrosion
inhibitor best suited to the oil phase and the corrosion inhibitor best suited to the
produced water. Finally, the presence of thick scales may reduce the effective inhibitor
efficiency, but increase inhibitor performance!
CO 2 Corrosion Control 35
7.4.6. Inhibitor Deployment
Since corrosion inhibitors are relied u p o n to protect an entire h y d r o c a r b o n
transmission line, transport of inhibitors to all areas needing protection is necessary.
Three methods of transport include:

dissolution (or suspension) in the p r o d u c e d fluids and relying on the


movement of the produced fluid to transport the inhibitor;
transport in a carrier fluid added to the flow stream; and
transport between p i g s - batch treatment.

Combinations of the above such as inhibited gel transport between pigs are also
possible.
The application required governs the method of transport as explained in this
Section.

Downhole: For downhole applications, inhibitors have been injected neat, added
with hydrate inhibitors such as methanol, or added to gas condensate or other fluids
such as diesel. The presence of co-solvents such as methanol or glycol may affect
inhibitor solubility and partitioning. Different types of downhole equipment are used
to inject the inhibitor into a well. The dissolution of the carrier fluid into the production
stream (vaporisation or preferential solvent dissolution) leaving undissolved inhibitor
behind, is a potential problem with this method of transport. Elevated temperatures
exacerbate such problems.
Another method of downhole inhibitor transport is the addition of inhibitors into
gas lift. The inhibitor can be transported as a mist for short distances. Again,
vaporisation of the solvent can limit applicability as well as contributing to the basic
difficulty of homogeneous distribution between several wells.
This type of application is dealt with in Section 9.1.

Dry gas pipeline: Pipelines dried to a sufficiently low dew point should not need
inhibition. However, some projects plan inhibition programs as a contingency. Such
pipelines do not contain a fluid that can transport and distribute corrosion inhibitors
adequately. Inhibitor application by a batch treatment, or between pigs or as gel pigs
at appropriate time intervals provides such a contingency.

Crude oil/condensate export pipelines: Because of the low fraction of water in export
pipelines, water soluble inhibitors are often preferred, although they should also
have a tendency to oil solubility. The crude oil/condensate is relied upon to transport
the inhibitors, especially when these possess some solubility in the oil.

Pipeline commissioning: Inhibitors for use during commissioning of pipelines can


be applied, possibly dissolved in a drying agent (methanol), between pigs. Gel pigs
containing inhibited gels are also used. Treatment of hydrotest fluids by inhibitors
and biocide is also recommended.
36 CO 2 Corrosion Control in Oil and Gas Production --Design Considerations
7.4.7. Inhibitor Distribution in Multiphase Pipelines
Because of transient behaviour in multiphase flow, both inhibitor transport and
inhibitor dilution effects are important parameters.
The transportation time of inhibitors needs to be known for proper inhibition. For
example, different phases move at different velocities along a pipeline. The liquid
residence times and consequently the time to transport inhibitor to the desired
location, can be very long. At low demand conditions, or towards the end of field
life, a gas or liquid pipeline may be greatly oversized and times to transport corrosion
inhibitor from the inlet to the outlet may be very long, even exceeding a few months.
Inhibitor distribution along the top of the line is limited in stratified flow.
Furthermore, inhibition of fluids flowing in the slug flow conditions poses a major
problem and is less effective.
Fluid flow will affect the deposition and movement of sand and other debris in
the flowline. The design must consider inhibition under the various flow conditions
and determine whether movement or settling of sand will have an impact on inhibitor
performance.
Inhibitor dilution can occur in multiphase (especially wet gas) pipeline sections
due to both hydrocarbon or water condensation. The inhibitor concentration may be
reduced significantly from the concentration determined at average inlet flow
conditions.

7.4.8. Effect of Flow on Inhibition


Flow conditions can influence inhibitor effectiveness in a variety of ways. Inhibitor
transport to the pipe surface will depend upon the flow regime while adsorption/
desorption processes will be affected by the local fluid conditions or fluid-to-wall
shear stress.
Pipelines operating under annular, mist or dispersed flow regimes can be inhibited
relatively easily because the mixing of the turbulent gas and liquid phases provides
good contact of inhibitor with the pipe wall. Effective inhibition is more difficult
under stratified flow where there are two main areas of concern. Firstly, at low spots
in the line where stagnant liquid may collect and the local turbulence may not be
sufficient to allow adequate mixing of inhibitor. The second problem area is on the
top of the line where fresh and renewed condensing water is corrosive. In this case,
vapour transport of inhibitor to the top of the line is required. Alternatively, frequent
batch treatment by an inhibitor slug is needed.
The removal of inhibitor films is generally worse when flow conditions fluctuate,
as, for example, under slug flow, when periods of local flow intensities are produced
in an otherwise low shear system. These effects have been demonstrated in field
trials at Prudhoe Bay [58]. The severity of these effects appear to depend upon the
ability of the inhibitor to re-film and the frequency of slugging.
8
Corrosion Allowance Determination

In the design of piping and piping components, pressure vessels, subsea, etc., a
minimum required wall thickness is calculated based on the appropriate standards
of ANSI, API, BS, ASME etc. This minimum calculated wall thickness includes two
parts; the 'pressure containment' part of the wall thickness plus a part called the
corrosion allowance. This declared design corrosion allowance is normally regarded as
that part of the pipe wall thickness required by design because of corrosion, in addition
to that required for pressure containment. It is either determined from the predicted
corrosion rate and the design life of the pipeline, or, conversely, it is chosen from
experience.
In practice, some wall thickness loss (defect allowance) in excess of the corrosion
allowance can often be tolerated during pipeline operation without necessitating a
reduction in the design pressure. Therefore, by also assessing the effect of the defect
allowance in determining the corrosion allowance, the resulting actual design corrosion
allowance predicts the true extent to which corrosion could be tolerated during
pipeline operation.
The result of such an assessment could have benefits, for example, during the
design stage, in providing guidance on the robustness of the pipeline design and
assumptions made with regard to corrosion rate; the selection of the nearest API
thickness or the potential for an extended design life.
When evaluating a system's corrosivity, carbon steel is normally the first choice
material. Based on the estimated corrosion rate (ram/year) for the system, the required
corrosion allowance (mm) can be defined by summing the corrosion rate for the
specified design lifetime. The corrosion allowance for topside equipment is often 0,
1.5, 3.0, 4.5 or 6 mm. For design of subsea pipelines it may be economically attractive
to use higher corrosion allowances. It is an economical and technical exercise to
evaluate the optimum corrosion allowance for a system and to compare this with
the use of corrosion resistant alloys.
The m a x i m u m permissible corrosion allowance will be partly determined by
a combination of the total wall thickness and the capability of the proposed
inspection system, taking into account the commercial issues and design
practicalities. In practice a typical figure is 6 or 8 mm, and this will be determined
principally b y the m a x i m u m depth of local corrosion which can be protected by
corrosion inhibitors.
The 6-8 mm figure is a somewhat arbitrary value for main oil lines or trunklines.
The reason for a maximum corrosion allowance is that if corrosion does occur as
predicted, then it is most likely to be localised. Such localised corrosion is likely to
take the form of steps or pits in the surface of the pipe material. Such steps or pits
will exacerbate the corrosion and the 8 mm figure might be taken as a corrosion limit
beyond which the prediction model breaks down. The value is somewhat a rule-of-
thumb and deviations from the model are probably likely from the time a pit initiates.
Another and possibly more significant reason is that such figures allow sufficient
38 CO2Corrosion Control in Oil and Gas Production reDesign Considerations
time for inspection, feedback and improvement of corrosion prevention until a
satisfying regime is achieved.
In addition, the thicker a pipe wall the greater the problems likely with fabrication
of the pipe and subsequent welding. This means that there is an additional limit on
the total thickness (corrosion allowance plus pressure containment plus tolerance)
which will be a function of the pipe diameter and the sizes of pipe that can be
manufactured and welded. Once in service, a thick pipe wall will also mean that the
smallest dimensions resolvable by the inspection system will increase and corrosion
will be more difficult to detect in the early years.
Based on the type of system to be designed, an evaluation should be made to
determine if the corrosion allowance should include a factor for erosion allowance.

8.1. D e s i g n Corrosion Allowance

To establish the design corrosion allowance, a procedure is presented which


determines both the declared design corrosion allowance and the actual design
corrosion allowance for pipelines and flowlines.
The following sections describe the procedure in detail.

8.1.1. Design Corrosion Rate


The approach by which the design corrosion rate is determined has been described
in Section 6.1. This takes account of the pipeline conditions (eg. pressure, temperature),
the use or otherwise of corrosion inhibitors, inhibitor efficiency, flow regime, local
flow effects, scaling, main stream constituents (eg. CO 2, H2S, water) and chemical
additives (e.g. hydrate/scale inhibitors).
Both the inhibited corrosion rate and the uninhibited corrosion rate (base line
corrosion rate) should be considered in assessing the design corrosion allowance.
Consideration of the uninhibited case will enable the consequences of upset conditions
or local internal conditions (where there is no effective inhibition) to be assessed.
This has particular importance where the potential uninhibited corrosion rate is
predicted to be high and the design corrosion allowance is small.

8.1.2. Design Corrosion Allowance Assessment

8.1.2.1. Declared Design Corrosion Allowance


An evaluation should be made of the consequences of considering both the inhibited
and uninhibited corrosion rates in the calculations.

Step 1;
Determine the expected corrosion thickness (t c) from the predicted corrosion rate
and the design life.
Corrosion Allowance Determination 39
Where:
t c - corrosion rate x design life (13)

Step 2:
Determine the design pipe wall thickness (tmin) required for pressure containment,
based on the design pressure and hoop stress formula (using e.g. BS 8010 Parts 2.8
and 3), excluding any pipe manufacturing tolerance.

Step 3:
Determine the pipe wall thickness (tre q) required for corrosion and pressure
containment, such that:
treq = t c + tmi n (14)

Step 4:
Establish the pipe manufacturing tolerance (a factor < 1) on wall thickness using the
material code (usually API 5L).
Determine the nominal wall thickness (tnom) of the pipe, where:

t nom -- t req/tolerance (15)

Step 5:
Select the API pipe wall thickness (tap i) nearest (normally larger, but could be smaller)
to tnom. (If the API pipe wall thickness is chosen to be less than tnom, then the declared

I tcd tca I
I ' I I
,
tapi I tapi x
~. tolerance
I I
I I I
I tmin tco r I
I
I I (0.8 x tmin) I

v v V V
Declareddesign Actual design
corrosionallowance corrosionallowance
( tcd) ( tca)

Fig. 7 Corrosion allowance.


40 C O 2 Corrosion Control in Oil and Gas Production reDesign Considerations
corrosion allowance will be slightly less than the value of t c. The acceptability of this
would then need to be reviewed.)

Step 6:
Determine the declared design corrosion allowance (tca) such that:

tca - (tapi X tolerance) - tmi n (16)

8.1.2.2. Actual Design Corrosion Allowance

Step 7-
Determine the corroded pipe wall thickness (tcor), required for pressure containment,
which would not require detailed defect analysis.
Hence:
t cor = 0.8 x t min (17)

Step 8:
Determine the actual design corrosion allowance (tca).
Hence:
tca- (tapi X tolerance) - tcor (18)

8.1.2.3. Further Considerations


For thick walled pipes, the calculated tca may be much greater than tc~. In this instance
it may be beneficial to reconsider the basis of the corrosion rate a n d / o r the assumed
inhibitor efficiency, the selection of the API thickness, and the design life as initially
used in the design corrosion allowance calculations.
If the pipeline operating pressure is anticipated to decline over the design life,
then consideration may be given to progressive derating of the pipeline with a
corresponding progressive increase in the design corrosion allowance. This may have
the benefit in avoiding unduly high design corrosion allowances at the outset of
pipeline operation.
For thick walled pipes (D/t < 20), use of the thick walled formula for the design
pipe wall thickness (train) may provide a useful reduction in the required nominal
(API) wall thickness.
9
Design Considerations

In consideration of the requirements for the design of oil and gas production systems,
this Section has been divided into three areas; well completions, production facilities
and gas reinjection systems.
Well completions are taken to include all equipment up to the Xmas tree outlet
that is intentionally wetted by produced fluids. This includes the well bore liner (if
used), the production tubing including jewellery (subsurface safety valves (SSSVs),
expansion joints, nipples, hangers etc.), and the Xmas tree itself.
In designing well completions, normally, the principal criteria for the tubing wall
thickness are adequate mechanical strength and collapse resistance. For this
application, corrosion allowance is not normally considered.
Once oil reaches the surface, it must be transported to the refinery for processing,
but the fluid which flows out of the ground is almost never pure crude oil. It is a
mixture of oil, gases, water and, sometimes, solids like sand. The mixture must be
separated into its constituent parts before the saleable elements go to the customer.
Traditionally, oil companies have tended to separate the mixture near the well (surface
facilities) or on the production platform itself in the case of offshore wells (topside
facilities). The fluids that are of no value, like water, are disposed of or reinjected
into the reservoir. The hydrocarbon parts (crude oil and gas) are sent off to central
terminals or gathering stations through dedicated pipelines.
Production facilities include flowlines, piping, valves, vessels (separators) and
export pipelines. Transportation systems include mail oil lines or trunklines. These
facilities are designed to meet the mechanical requirements of pressure containment
and hydrostatic collapse. In addition the wall thickness may be increased to allow
for wall loss due to corrosion (the corrosion allowance).

9.1. Well Completions

Conventionally, the equipment required for well completions is specified in carbon


and low alloy steels (CLAS) with the aim of achieving the required function at
minimum cost. The principal industry standards available for this equipment are
API 5CT and API 6A.
Completions designs are dominated by:

• The tubing size required to provide necessary flow performance;


• Mechanical integrity requirements (principally: tension, burst and collapse);
and
• Life expectancy.

Life expectancy for well completions is subject to the reservoir production


characteristics. Normally, the design life of well completions is for a maximum of
42 CO2 Corrosion Control in Oil and Gas Production--Design Considerations

about 10 years as this would typically coincide with the maximum period before a
well workover would be required for operational reasons. The most appropriate
choice of material should be selected to eliminate the possibility of an unexpected
workover due to corrosion failure which results in a heavy cost penalty.

9.1.1. Corrosion Design


CO 2 corrosion may cause localised or general weight loss corrosion and consequent
failure (i.e. loss of pressure integrity) of the completion. Penetration of the tubing
string by general or localised corrosion is the most common mode of failure, but
functional failure of liners, seals, SSSVs, special purpose jewellery or Xmas tree valves
may also occur.
Depending upon the severity of the environment specific alternative design
approaches may be taken to incorporate some protection against CO 2 corrosion, e.g.:

Provision of a corrosion allowance by increasing the wall thickness of the


tubing a n d / o r liner over the minimum mechanical r e q u i r e m e n t - this option
is not normally used;

Control of local fluid velocities to reduce corrosion/erosion by increasing the


tubing size or restricting the flow rate;

Use of 'flow couplings', (i.e. extra thick tubing), either side of tubing restrictions
to prevent premature corrosion/erosion failure caused by the local flow
disturbance;

Use of internally 'flush' tubular connections to minimise the local flow


disturbance;

Improved jewellery life by selective use of 9CrlMo or 13Cr or other corrosion


resistant alloys;

Improved liner integrity by use of a corrosion resistant material, particularly


where the liner function is critical to well control (since liners cannot be as
readily replaced as tubing or other well completion components); and

Selective protection of critical Xmas tree components by use of corrosion


resistant components a n d / o r overlays.

For more corrosive conditions where the above measures do not provide
sufficiently reliable performance the following further options may be considered.

Internally Coated/Lined Tubing: Plastic coating/lining increases the cost of


CLAS tubulars. The additional cost may be recovered by improved flow
performance through lowering the tubing pressure drop or simply by reducing
workover duration, even if the tubing life time itself is not significantly
increased. The life of coatings is critically dependent on selection, application
Design Considerations 43
practice, subsequent tubular handling, connection suitability, well intervention
practice with wireline/coiled tubing/chemicals. Operating practice may also
influence coating disbondment. Internal plastic coatings are probably
inappropriate for liners as perforation will cause systematic damage to the
lining.

Mixed Completions: More extensive, selective use of corrosion resistant


materials to control known corrosion concerns, with retention of CLAS where
appropriate.

Internal Cladding: Cladding of components with corrosion resistant alloys


(CRA), retaining CLAS as the strength element. Selective (e.g. gates, seats
and seat pockets) and full internal overlaying of CLAS Xmas trees is established
practice. Internal CRA cladding of tubulars has been little used to date.

Treatment with Corrosion Inhibitors:


(i) Periodic tubing displacement treatments.
(ii) Periodic squeeze treatments in which the inhibitor is forced into the
reservoir.
(iii) Continuous inhibitor injection:
In these options, the whole tubing string may be treated through an open
annulus, or a dual or concentric completion or part of the tubing may be
selectively treated through a chemical injection mandrel or gas lift stream.

Corrosion Resistant Material Completion


If the above options are uneconomic or insufficient, completions made entirely
of appropriate corrosion resistant materials is required. Conventionally, these
would be metallic i.e. CRAs, but fibre reinforced plastics may also be
considered for some service conditions.

9.1.2. Corrosion Monitoring


Downhole corrosion monitoring capabilities are constrained by problems of access.
The addition of equipment for corrosion monitoring and interventions to obtain
samples or make measurements is both unwelcome as added costs and in causing
possible operational complications. Therefore, apart from basic checks of annulus
pressurisation to identify loss of tubing integrity, other methods of corrosion
monitoring are not routinely implemented. The techniques that are available may be
divided according to whether they provide direct measures of corrosion or are
indicators of corrosion risk. They may also be divided according to the need for well
intervention for their application. The list below is compiled on this basis.

9.1.2.1. Direct measures of tubing condition

Without well intervention:


Annulus pressure monitoring to detect tubing leaks.
44 CO2 Corrosion Control in Oil and Gas Production--Design Considerations
Downhole corrosion probes (under development).

With well intervention:


Closed circuit television visual inspection.
Mechanical callipers.
Ultrasonic internal diameter callipers.
Ultrasonic wall thickness callipers.
Pressure tests and leak tests.
Inspection (logging) of recovered tubing.

9.1.2.2. Indirect measures of tubing condition (i.e. indicators of corrosion concerns)

Without well intervention:


Fluid samples for analysis which may include:
- iron counts;
- inhibitor returns.
Corrosion and erosion monitoring in surface flowlines using conventional
techniques.

With well intervention:


Downhole corrosion coupons.
Inspection of recovered tubing including that from other wells with similar
conditions.

A cursory review of the above list indicates that the cost of obtaining reliable data
is likely to be prohibitive. A further consideration that discourages corrosion
monitoring is that wells are not normally designed to accept premature tubing failure.
Hence, interventions aimed at determining tubing condition prior to failure are
seldom economic as they are an additional cost to the workover costs that will usually
not be reduced by the inspection.
There are some exceptions to this practical limitation. For example, gas wells that
have seasonal shut-in periods may be inspected without incurring lost production.
Reliable data may then allow prioritisation of a workover programme aimed at
minimising tubing failures during the following season of peak production. Other
exceptions exist on a case by case basis.

9.2. P r o d u c t i o n F a c i l i t i e s

The principal design considerations for production facilities, flowlines, processing


equipment (piping, valves, vessels etc.) and export pipelines, are similar whilst there
are specific aspects which are of particular significance to each. This is governed by
local flow regimes, logistics and whole life considerations.

9.2.1. Corrosion D e s i g n

The analysis of potential C O 2 c o r r o s i o n rate/damage is discussed in Section 6. Where


hydrocarbons containing CO 2 are transported, there is potential for high corrosion
Design Considerations 45
rates if water is present. Therefore, a distinction may be made between equipment
which is upstream or downstream of water removal facilities (separators and glycol
contactors). The benefit of dehydration in controlling corrosion has to be carefully
considered, particularly in the context of offshore operations where there is a drive
to reduce costs by eliminating heavy dehydration equipment and demanning.
A proposed approach to corrosion design is therefore:

• Establish if there is a likelihood of water wetting of the steel surface.

Estimate the corrosion r a t e / d a m a g e (Section 6), taking into account the


variability due to operating conditions (e.g. pressure, temperature); the use
or otherwise of corrosion inhibitors and their efficiency; flow regime; scaling;
local flow effects; main stream constituents (e.g. CO2, H2S, water) and chemical
additives (e.g. hydrates and scale inhibitors) etc. These are discussed in Section
6 and summarised in Fig. 3.

Determine the design corrosion allowance, based on the estimated corrosion


loss over the life of the pipeline or conversely, the m i n i m u m inhibitor
performance required by the selected corrosion allowance.

• Set out a corrosion control strategy which will:


• Detail the corrosion control methods and procedures (e.g. corrosion inhibitor
injection rates) (see Section 7);
• Detail the corrosion monitoring programme and requirements;
• Detail the inspection programme, identifying appropriate inspection
methods and frequencies; and
• Review the design corrosion allowance assumptions based on the inspection
information gathered.

Dehydrated hydrocarbons may be safely transported in carbon steel purchased


to API 5L requirements. Where hydrated (CO 2 containing) hydrocarbons are
transported the principal materials selection options are:

• Carbon steel (purchased to API 5L) protected by inhibitor injection.


• Corrosion resistant alloys (e.g. duplex stainless steel) purchased to API 5LC.
• Internally clad carbon s t e e l s - purchased to API 5LD.

The final choice will depend on the corrosivity of transported fluid, life expectancy
and whole life cost.
A proposed approach to bringing equipment into operation (particularly carbon
steel with inhibitor injection) is:

• Implement the corrosion control methods and procedures defined in the design
and inhibitors selection stages from the outset of operation.
• Implement the corrosion monitoring programme from the outset of operation.
• Implement the inspection programme from the outset of operation.
• Apply a corrosion (defect) assessment methodology when corrosion defects
arise.
46 CO2 Corrosion Control in Oil and Gas Production reDesign Considerations
Interpret the consequences of the corrosion assessment.
Reappraise the basis of further operation and the corrosion monitoring/
inspection programme.

In considering the potential corrosion rate/damage in flowlines, the relatively high


water cut and flow rates compared to pipelines and trunklines will tend to indicate
rather higher corrosion rates relative to other parts of the production facilities. Similar136
the processing facilities themselves will normally be regarded as experiencing turbulent
flow conditions which will often be shown to result in potentially high corrosion rates.
In the case of offshore, 'topside' facilities on platforms or floating production and
storage offtakes (FPSOs), there is a desire for weight minimising which means that
selection of corrosion resistant alloys may be favoured instead of adding corrosion
allowances to carbon steel. This may also be the case for short flowlines in surface
facilities when supported by a whole life cost analysis or operational constraints.
Equipment downstream of the water separator(s) (including export lines) will
often have minimal water content and slower fluid flow velocities resulting in less
aggressive corrosion conditions which can be handled with carbon steel, with, or in
some cases, without, any corrosion allowance or corrosion inhibitor injection.

9.2.2. Multiphase Fluid Behaviour


For wet multi-phase systems, unlike single phase systems, corrosion inhibitor contact
with all of the pipe's surface is not necessarily assured. The flow behaviour in
multiphase flowlines determines which portions of the pipelines' internal surfaces
are wetted. It is important, therefore, in any design, to establish the variation in flow
regime along the line, also taking into consideration the increasing liquid mass
flowrate attributable to condensation. This in turn requires an understanding of
variation in seasonal flow rates (the winter rate often being higher than the summer),
fluid properties, topography of the pipeline, phase behaviour and heat transfer
characteristics, to enable the modelling of the multiphase fluid behaviour.
Another source of segregated flow in the oil trunklines and main oil lines is the
variation in flow rates over the duration of the field life. The lines are designed for the
optimum expected flow rates during the field life. In cases where the field life is
developed in several phases, the flow rates during the first phase of the development
are much less than the design flow rates. In these situations, water separation in the line
may occur leading to severe corrosion. Similarl~ production rates and pressure may
decline in the later phases whereas gas oil ratio (GOR) and phase velocities increase.
Having established this information then the optimum inhibitor additive package,
pigging practice and pre-treatment of the pipeline (such as internal blasting to remove
internal cathodic scales) can be developed to meet the various expected flow regimes.
Hydrate formation control, utilising additives such as glycols with or without pH
control, should also be considered as these have been found to have beneficial effect in
reducing corrosion rates.

9.2.2.1. Pigging
Usually wet gas flowlines are pigged when the flow rate falls below a minimum
value. The primary requirement for pigging is to control slug size and maintain an
Design Considerations 47
acceptable pressure drop in the line. Pigging, however has several other beneficial
effects with respect to corrosion control:

It can remove stagnant water layers where water may have separated from
the oil phase;

• It can transport inhibitor to the upper portion of the pipe surface;

It can be used for batch inhibitor filming over the full pipe circumference
when the inhibitor is contained between two pigs; and
°

It assists removal of solids (waxes, solids within the production fluid or


corrosion products) which otherwise prevent inhibitor filming of the surface.

Given the essential need for pigging it is important to control the gap between pig
and inner pipe wall. If the pig leakage rate is too low then the corrosion inhibitor
inventory remaining in the pipe, following passage of the pig, can be less than that
required for complete inhibition, and if too high, lowers the overall efficiency of the
operation, necessitating more frequent pigging. Thus, factors such as tolerance on
internal pipe diameters and ovality as well the use of large radius bends and control
of weld root bead should be addressed in the design of pipelines. The profile of the
root bead and bend radius can of course also affect local turbulence and so can also
affect the maintenance of protective inhibitor films and or scales.

9.2.3. Corrosion Monitoring


The inclusion of a corrosion monitoring system is also an extremely important area
for consideration. Monitoring of corrosion rates has typically been based on coupons
(flush mounted) and iron counts in combination with pH and chloride levels, the
reading and interpretation of which are carried out at set intervals. Such systems,
however, reflect average rates of corrosion for the facilities or pipeline as a whole,
and do not reflect the situation at specific localised sites or transient upset conditions.
The monitoring of transient conditions can be particularly useful in relation to
correlating unexpected rates of corrosion with particular production practices.
One of the principal uses of corrosion monitoring is the evaluation of corrosion
inhibitor efficiency and hence optimisation of its injection rate. However, it must be
emphasised that the corrosion rate measured at one location does not necessarily
represent the corrosion rate of the complete equipment.
Corrosion coupons, because of the requirements for access, are normally located
at the entrance and exit of the pipeline; thus for subsea lines, the topside pipework
and shore areas are generally chosen. Similarly, water samples are generally taken
at the wellhead and exit of the pipeline.
Corrosion monitoring of subsea systems is utilised when it is expected that topside
monitoring cannot provide the information required. Sub sea monitoring provides
the measure of the inhibitor efficiency at the positions where the efficiency of the
inhibitor may be reduced due to flow effects or other environmental influence.
Optimum monitoring positions may be identified by using the knowledge about the
48 CO2 Corrosion Control in Oil and Gas Production --Design Considerations

CO 2corrosion mechanism/inhibitor performance, temperature profile and operating


conditions.
Subsea corrosion monitoring is a relatively young technolog~ and technically much
more complex than monitoring topside or surface facilities. Non-intrusive techniques
are normally the preferred option subsea. For the purpose of monitoring inhibitor
performance the non-intrusive technique should have a sensitivity approaching 0.1%
of the wall thickness.

9.2.3.1. Non-intrusive Methods


Ultrasonic methods are usually associated with manual inspection, but automatic
systems are also available. Such systems have recently been tested in the North Sea
for subsea monitoring via cables to the nearby platform. The principle of the ultrasonic
method is based on reflection of sound waves. Sound waves are emitted from one or
several probes attached to the pipe on the outside. The time from the submission of
the sound wave to its echo reflection back to the probe is used to determine the wall
thickness. The sensitivity is of the order 1% of the wall thickness.

The field signature method (FSM) is based on the principle of measuring the changes
in the pipe wall resistance due to corrosion or erosion on the inside. During the
measuring period a large, pulsed current is sent through the monitored pipe section,
and voltage signals are monitored by pairs of electrodes welded to the pipe on the
outside. Uniform corrosion causes a uniform increase in the voltage drop across the
electrode pairs, while pits and cracks distort the electric field less uniformly. Thus,
both uniform and local corrosion can be detected within the monitored area. The
sensitivity is about 0.1% of the wall thickness. Several subsea installations have been
completed and put in regular operation, with signal transmission through cables or
by the use of hydro-acoustics.

Thin layer activation (TLA) or neutron activation (NA) methods are based on the
principle of inducing radioactivity in the pipe wall and calculating the wall thinning
from the measured reduction in the gamma radiation, using a suitable gamma
detector. The sensitivity is about 0.1% of the thickness of the activated layer. The
technique has been tried subsea in the North Sea, based on diver operation.

9.2.3.2. Intrusive Methods


Intrusive monitoring methods can be based on the use of the same intrusive probes
that are used for topside or surface facilities, i.e. linear polarisation resistance (LPR)
probes, electrical resistance (ER) probes, potentiodynamic scans, electrochemical
impedance spectroscopy (EIS) and electrochemical noise (ECN). Such probes can
provide values for the corrosion rates within a very short period of time, and can
therefore be an alternative or a supplement to the non-intrusive methods when a
very short response time is required. For all the probes based on electrochemical
signals (except the ER probe) however, the interpretation of the measurements can
be difficult in a non-continuous electrolyte, e.g. water dispersed in a hydrocarbon
fluid. Most intrusive probes have a limited lifetime, and long term operation subsea
may therefore require a probe retrieval/replacement system that can be operated
subsea.
Design Considerations 49

9.3. Gas Reinjection

9.3.1. General Requirements for Gas Reinjection


In the absence of a gas market, the associated gas produced with oil was traditionally
burnt. Nowadays, however, it is increasingly reinjected, either into the reservoir for
the purpose of pressure maintenance, or simply into producing wells for gas lifting.
For a petroleum engineer, the injected gas is strictly the same as the produced gas,
whereas it is totally different in terms of corrosion. Condensation of water in injected
gas systems is limited, and therefore, its corrosivity is restricted resulting in much
reduced corrosion r a t e / d a m a g e in injection systems w h e n compared to gas
production systems. Where the design considerations described below have been
taken into account, no field failure of gas re-injection systems by CO 2 corrosion has
ever been reported. Conversely, departures from these guidelines may lead to severe
failures [59].
The gas to be injected is normally separated at low pressure in a low pressure
separator. At this stage, it contains a rather high molar fraction of water, since the
partial pressure of water vapour at the temperature of separation is far from negligible
and the total pressure is low. This separated gas is rarely transported over long
distances. In design terms, the gas should be considered like any wet CO2-containing
gas.
Subsequently, the gas intended for reinjection is compressed in one or several
steps. At each compression step, the gas heats up. Before the next step, the gas is
then cooled back to moderate temperatures (usually ca. 40°C). During this cooling
step, most of the water vapour present is condensed, but this condensed water is
immediately separated in a scrubber, in order to prevent liquid carryover to the inlet
of the next compression step. In the presence of acid gases (CO 2 a n d / o r H2S), this
freshly condensed water is inevitably corrosive to carbon steel. Due to the negligible
amount of dissolved iron in the water phase, there is no mechanism for building up
protective corrosion layers [20].
The compressed gas is then delivered to injection wells through 'delivery' lines or
'gas injection' lines. In these lines, the corrosivity depends on the conditions after
completion of the compression process.

9.3.2. Onshore Delivery Lines


For the onshore production, the last compression stage is usually followed by the
same cooling and scrubbing steps as the previous stages. Consequently, the dew
point of the gas stream is precisely its temperature at the inlet of the line, and it is
close to ambient temperature. This results in very favourable conditions regarding
CO 2 corrosion:

• low temperature;
• low condensing rate [16];
• very low water content; and
• very low volume/surface ratio e.g. 0.01 cm3/cm 2 for an average thickness of
the 'stratified' water film less than 0.1 mm.
50 CO2 Corrosion Control in Oil and Gas Production wDesign Considerations

Due to the low temperature, the corrosion rate of bare metal would already be
low, and, in addition, protective corrosion layers readily form. Therefore, in normal
conditions, corrosion cannot occur on carbon steel.
Nevertheless, the statistical risk of 'upset' conditions may require some intermittent
batching of the lines (e.g. on a six months basis) with:

• a batch of biocide in case of microbial contamination (at least once at


commissioning), and
• a batch of oil soluble inhibitor, in case of reduced cooling capacity after the
last compression step.

9.3.3. Offshore Delivery Lines


Weight constraints and space limitations on platforms often lead design engineers
to cancel the last step of cooling and water scrubbing after final compression. This
results in a higher water dew point, and also a much higher gas temperature than in
the case of onshore delivery lines. Initially the gas at the inlet of the delivery line is
hot and dry. As the gas flows along the line it is cooled and water condenses out
progressively. However, there are major differences with a producing well or a flow
line:

• there is no mist/annular flow, just stratified flow, and


• condensation does not occur in the bulk gas, just on the colder pipe wall.

Therefore, there is no accumulation of fresh, acidic, condensed water in the gas


stream. The condensing water is immediately saturated in corrosion products [28].
Thus, it is buffered and much less corrosive than in production wells or flow lines.
Despite this, it is not yet possible to state whether or not this postulated saturation
effect is totally sufficient to prevent carbon steel from corrosion. Therefore, it is
recommended to batch treat the line with water soluble inhibitors, in order to prevent
corrosion in side streams.

9.3.4. Injection Wells And Gas Lift Annuli


Once the reinjected gas has passed the well head into the injection tubing, the pressure
and temperature of the gas progressively rises. At the top of the well, the gas is still
wet, but the residual water phase is still the same 'non-corrosive' water coming from
the delivery line. Consequently, there is no more corrosion at the top of the well than
along the delivery line.
However, deeper in the well, the gas repasses its water dew point. The gas flow
then becomes dry, and there is no corrosive medium and, thus, no corrosion.
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