European Federation of Corrosion

Publications
NUMBER 39

A Working Party Report on

The Use of Corrosion Inhibitors

in Oil and Gas Production
Edited by J. W. Palmer, W. Hedges and J. L. Dawson

MANEY
Published for the European Federation of Corrosion
on behalf of the Institute of Materials, Minerals and Mining
 B0804
First published in 2004 by
Maney Publishing
1 Carlton House Terrace
London SW1Y 5DB
UK

on behalf of
the Institute of Materials, Minerals and Mining
© 2004 Institute of Materials, Minerals and Mining
All rights reserved

ISBN 1-904350-33-X

Typeset, printed and bound in the UK

by The Charlesworth Group, Wakefield
 Acknowledgements

This document has been put together by members of the EFC Working Party
13 - - 'Corrosion in the Oil and Gas Industry', chaired by Stein Olsen (Statoil).
Guideline documents produced by BP and Shell provided the basis for several
sections of the document and permission to use this information is greatly
appreciated. Significant contributions were also received from the following:
Chris Bowman Baker Petrolite
John Dawson CAPCIS Ltd.
Drew McMahon Helix RDS
Rolf Nyborg IFE
Liane Smith Intetech
Jim Stott CAPCIS Ltd
Mark Gough Ondeo Nalco
Stein Olsen Statoil
In addition, the sections on inhibition of preferential corrosion of weldments
have included new information from a recent Joint Industry Project. The project
was entitled 'Risk of Preferential Weldment Corrosion of Ferritic Steels in CO2 -
Containing Environments' and was conducted jointly by CAPCIS, TWI and IFE.
The permission of the sponsoring companies to include this information is greatly
appreciated. The sponsors were: BP, Clariant, ENI SpA, HSE, Petrobras, Saudi
Aramco, Shell and Tfe.

The Co-Chairmen of the Work Group would like to thank all who have
contributed their time and effort to ensure the successful completion of the
document.

Jim Palmer Bill Hedges

CAPCIS Ltd. BP
Co-Chairmen
 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
corrosion prevention.
Membership of the EFC is based upon participation by corrosion societies and
committees 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, refin-
eries, surface science, physico-chemical methods of measurement, the nuclear
industry, the automotive industry, computer based information systems, coatings,
tribo-corrosion and the oil and gas industry. Working Parties and Task Forces 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 Secre-
tary. 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, Minerals and Mining 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 publi-
cation are still available, it is expected that the Working Parties of the EFC will
use The Institute of Materials, Minerals and Mining for publication of reports,
proceedings, etc.. wherever possible.
The name of The Institute of Metals was changed to The Institute of Materials
on 1 January 1992 and to The Institute of Materials, Minerals and Mining with
effect from 26 June 2002. The series is now published by Maney Publishing on
behalf of The Institute of Materials, Minerals and Mining.

P. McIntyre
EFC Series Editor, The Institute of Materials, Minerals and Mining, London, UK
xii Series Introduction

EFC Secretariats are located at:

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

Dr J P Berge
F6ddration Europ6ene de la Corrosion, Soci6t6 de Chimie Industrielle, 28 rue
Saint-Dominique, F-75007 Paris, FRANCE

Professor Dr G Kreysa
Europaische F6deration Korrosion, DECHEMA e.V., Theodor-Heuss-Allee 25,
D-60486 Frankfurt, GERMANY
 OTHER VOLUMES IN THE EFC SERIES
1 Corrosion in the Nuclear Industry
Prepared by the Working Party on Nuclear
Corrosion
2 Practical Corrosion Principles
Prepared by the Working Party on Corrosion
Education (Out of print)
3 G e n e r a l G u i d e l i n e s for Corrosion
Testing of Materials for Marine
Applications
Prepared by the Working Party on Marine
Corrosion
4 Guidelines on Electrochemical
Corrosion Measurements
Prepared by the Working Party on
Physico-Chemical Methods of Corrosion
Testing
5 Illustrated Case Histories of Marine
Corrosion
Prepared by the Working Party on Marine
Corrosion
6 Corrosion Education Manual
Prepared by the Working Party on Corrosion
Education
7 Corrosion Problems Related to Nuclear
Waste Disposal
Prepared by the Working Party on Nuclear
Corrosion
8 Microbial Corrosion
Prepared by the Working Party on Microbial
Corrosion
0 Microbiological Degradation of
Materials - - and Methods of Protection
Prepared by the Working Party on Microbial
Corrosion
10 Marine Corrosion of Stainless Steels:
Chlorination and Microbial Effects
Prepared by the Working Party on Marine
Corrosion
11 Corrosion Inhibitors
Prepared by the Working Party on Inhibitors
(Out of print)
12 Modifications of Passive Films
Prepared by the Working Party on Surface
Science and Mechanisms of Corrosion and
Protection
XHl
13 Predicting CO2 Corrosion in the Oil and
Gas Industry
Prepared by the Working Party on Corrosion
in Oil and Gas Production (Out of print)
14 G u i d e l i n e s for Methods of Testing and
Research in H i g h Temperature
Corrosion
Prepared by the Working Party on Corrosion
by Hot Gases and Combustion Products
15 Microbial Corrosion (Proc. 3rd Int. EFC
Workshop)
Prepared by the Working Party on Microbial
Corrosion
16 G u i d e l i n e s on Materials Requirements
for Carbon and Low Alloy Steels for
H2S-Containing Environments in Oil
and Gas Production
Prepared by the Working Party on Corrosion
in Oil and Gas Production
17 Corrosion Resistant A l l o y s for Oil and
Gas Production: Guidance on General
Requirements and Test Methods for H,S
Service
Prepared by the Working Party on Corrosion
in Oil and Gas Production
18 Stainless Steel in Concrete: State of the
Art Report
Prepared by the Working Party on Corrosion
of Reinforcement in Concrete
19 Sea Water Corrosion of Stainless Steels
- - Mechanisms and Experiences
Prepared by the Working Parties on Marine
Corrosion and Microbial Corrosion
20 Organic and Inorganic Coatings for
Corrosion Prevention - - Research and
Experiences
Papersfrom EUROCORR '96
21 Corrosion-Deformation Interactions
CDI '96 in conjunction with EUROCORR
'96
22 Aspects of Microbially Induced
Corrosion
Papersfrom EUROCORR'96 and the EFC
Working Party on Microbial Corrosion
23 CO2 Corrosion Control in Oil and Gas
P r o d u c t i o n - - D e s i g n Considerations
Prepared by the Working Party on Corrosion
in Oil and Gas Production
xiv The Use of Corrosion Inhibitors in Oil and Gas Production
24 Electrochemical Rehabilitation
Methods for Reinforced Concrete
Structures - - A State of the Art Report
Prepared by the Working Party on Corrosion
of Reinforcement in Concrete
25 Corrosion of Reinforcement in Concrete
- - Monitoring, Prevention and
Rehabilitation
Papersfrom EUROCORR "97
26 Advances in Corrosion Control and
Materials in Oil and Gas Production
Papersfrom EUROCORR '97 and
E UROCORR '98
27 Cyclic Oxidation of High Temperature
Materials
Proceedings of an EFC Workshop,
Frankfurt~Main, 1999
28 Electrochemical Approach to Selected
Corrosion and Corrosion Control
Studies
Papersfrom 50th ISE Meeting, Pavia, 1999
29 Microbial Corrosion (Proceedings of the
4th International EFC Workshop)
Prepared by the Working Party on Microbial
Corrosion
30 Survey of Literature on Crevice
Corrosion (1979-1998): Mechanisms,
Test Methods and Results, Practical
Experience, Protective Measures and
Monitoring
Prepared by F. P. IJsseling and the Working
Party on Marine Corrosion
31 Corrosion of Reinforcement in
Concrete: Corrosion Mechanisms
and Corrosion Protection
Papersfrom EUROCORR "99and the
Working Party on Corrosion of
Reinforcement in Concrete
32 Guidelines for the Compilation of
Corrosion Cost Data and for the
Calculation of the Life Cycle Cost of
Corrosion-- A Working Party Report
Prepared by the Working Party on Corrosion
in Oil and Gas Production
33 Marine Corrosion of Stainless Steels:
Testing, Selection, Experience,
Protection and Monitoring
Edited by D. F&on
34 Lifetime Modelling of High
Temperature Corrosion Processes
Proceedings of an EFC Workshop 2001.
Edited by M. Schidtze, W. J. Quadakkers and
J. R. Nicholls
35 Corrosion Inhibitors for Steel in
Concrete
Prepared by B. Elsener with support from a
Task Group of Working Party 11 on
Corrosion of Reinforcement in Concrete
36 Prediction of Long Term Corrosion
Behaviour in Nuclear Waste Systems
Edited by D. F~ronof Working Party 4 on
Nuclear Corrosion
37 Test Methods for Assessing the
Susceptibility of Prestressing Steels to
Hydrogen Induced Stress Corrosion
Cracking
by B. Isecke ofEFC WP11 on Corrosion of
Reinforcement in Concrete
30 The Use of Corrosion Inhibitors in Oil
and Gas Production
Edited by J. W. Palmer, W. Hedges and
J. L. Dawson
40 Control of Corrosion in Cooling Waters
Edited by J. D. Harston and F. Ropital

Available f r o m

MANEY
M A N E Y PUBLISHING, H U D S O N ROAD, LEEDS LS9 7DL, UK
Tel: 0113 2497481 Fax: 0113 2486983
Email: m a n e y @ m a n e y . c o . u k
 Preface

This practical industry-oriented guide has been compiled to meet the needs of
personnel employed by operators, design engineers, contractors and chemical
suppliers working in the oil and gas industry. The document draws on the expe-
rience of specialists employed in various organisations and incorporates appropri-
ate industry and in-company guidelines. Both technical and management issues
are addressed and key points are provided at the end of each chapter to aid in the
assimilation of the many and varied aspects that contribute to successful corrosion
inhibition.
The background to the document compilation has been the increased drive in
the oil and gas industry towards reducing costs but at the same time decreasing
risks to the operation, the environment and safety by the adoption of appropriate
and auditable systems. Expenditure can be controlled by drilling fewer wells and
producing them at higher rates but this imposes increasing demands on inhibitor
technology. Similarly, the development of high pressure/high temperature reser-
voirs and transportation of multi-phase fluids, often with high CO2 and H2S
contents means that the performance of inhibitor packages must continuously
improve while meeting increasingly restrictive environmental legislation.
The use of carbon steel plus inhibition in ever more stringent conditions also
demands increasingly rigorous approaches to product selection, deployment and
performance monitoring. There are requirements to have management systems
that not only address risks posed by corrosion to facilities but also to have in place
performance indicators that have both proactive and reactive control measures.
The document addresses fundamental concepts to selection criteria, field
deployment, monitoring, data acquisition and management of inhibition pro-
grammes. The early chapters provide basic information for industry personnel not
familiar with corrosion and inhibition but the bulk of the text is concerned with
selection strategies, performance testing, injection issues and typical treatment
scenarios such as downhole, pipelines, and hydrotest fluids. An important feature
is the listing and use of typical key performance indicators as the means by which
inhibition management systems can be benchmarked and audited.
 Contents

Acknowledgements ix

Series Introduction xi
Preface xv

1. Introduction 1
1.1. Aims of the Document 1
1.2. Corrosion in Oil and Gas Equipment 2
1.2.1. Background 2
1.2.2. Causes of Oil Field Corrosion 2
1.2.3. Corrosion and Inhibition Issues 4
1.3. Key Points 7

2. Inhibition Concepts and Issues 9

2.1. General Background and Basics of Inhibition 9
2.2. Inhibitor Efficiency 11
2.3. Inhibitor Availability 12
2.4. Inhibition Terminology 13
2.5. Continuous/Batch Dosage 15
2.6. Condensation, Water Cuts and Oil/Water Emulsions 15
2.7. Downstream Processing Issues 16
2.8. Environmental Issues 17
2.9. Key Points 19

3. Inhibitor Selection Strategies 21

3.1. Planning for the Use of Inhibitors 23
3.2. Corrosivity Assessments 23
3.2.1. Fluid Chemistries 23
3.2.2. Hydrodynamic Considerations 24
3.2.3. Predictive Models 25
3.3. Inhibition Risks 26
3.4. Inhibitor Selection Process 27
3.4.1. Performance Evaluation 28
3.4.2. Inhibitor Compatibility 31
vi Contents

3.5. Design Implications with Inhibition Systems 33

3.5.1. General Design Considerations 33
3.5.2. Inhibition System Components 34
3.5.3. Inhibitor Availability Requirements 34
3.6. Key Points on Selection 35

4. Inhibitor Performance Testing 37

4.1. Test Protocols 37
4.2. Preliminary Screening 39
4.3. Dynamic Tests 40
4.4. Specialised Corrosion Tests 41
4.5. Physical Property Tests 44
4.6. Compatibility Tests 47
4.7. Field Trials 48
4.8. Key Points in Testing 48

5. D e p l o y m e n t of Corrosion Inhibitors in the Field 51

5.1. Deployment Considerations 51
5.1.1. Injection System Requirements 51
5.1.2. Storage and Injection System 51
5.1.3. Monitoring and Data Acquisition 55
5.1.4. Data Storage, Analysis and Information System 61
5.1.5. Management of Inhibition Programmes 62
5.2. Deployment Issues 64
5.2.1. Quality Control of Corrosion Inhibitor Supplies 64
5.2.2. Storage and Dilution Issues 65
5.2.3. Corrosion Inhibitor Pumping Problems 66
5.2.4. Data Analyses and Management 67
5.3. Keypoints - - Deployment 68

6. Inhibitor Treatment of Various Systems 71

6.1. Hydrostatic Testing and Commissioning 71
6.1.1. General 71
6.1.2. Water Treatment for Hydrotest and Wet Lay Up 72
6.1.3. Implementation of Dewatering and Lay Up after 74
Dewatering
6.2. Downhole Applications 75
6.2.1. General 75
6.2.2. Continuous Injection 76
6.2.3. Batch Treatment 77
6.2.4. Squeeze Treatment 78
6.2.5. Inhibitor Selection 79
6.2.6. Performance Monitoring 79
6.3. Pipelines and Flowlines 81
6.3.1. General 81
6.3.2. Continuous Injection 83
6.3.3. Batch Treatment 84
 Contents vii

6.3.4. Inhibitor Selection/Dosage 85

6.3.5. Performance Monitoring 85
6.4. Gas/Oil Separation Plant 85
6.4.1 General 85
6.4.2 Inhibitor Injection 86
6.5 Key Points 87

7. Management of Inhibition Programmes 89

7.1 General 89
7.2 Key Performance Indicators 92
7.2.1 Development of Performance Criteria 92
7.2.20rganisational Performance Measurements 94
7.3 Assessment/Audit of Inhibitor Management Systems 98
7.4 Key Points 99

8. References 101

Appendix: Examples of Inhibitor Risk Categories 105

 1
Introduction

This document has been prepared by members of Working Party 13 of the

European Federation of Corrosion (EFC). It covers many aspects of corrosion
inhibition, from fundamental concepts to selection criteria, deployment issues,
monitoring/data acquisition and management of inhibition programmes.
The guidelines have drawn on documentation normally provided by BP and
Shell for their contractors and suppliers [1-5] plus significant contributions from
experienced corrosion personnel in specialist organisations, inhibitor suppliers,
and operating companies.
The use of corrosion inhibition to mitigate the effects of corrosion in oilfield
equipment is well established in many production fields. However, the use of
C-Mn steel plus inhibition results in greater risks to projects concerned with more
corrosive environments a n d / o r extreme operational conditions, such as high CO2
and H2S concentrations or slug flow regimes. The development of improved
inhibitor packages to meet these challenges requires a rational and formal quality
assurance and quality control (QA/QC) approach to inhibitor selection and
deployment.
Further obligations are placed on the industry by legislation that emphasises
increasing concerns with regard to risks to safety, health and the environment.
There are requirements not only to have management systems that address risks
posed by corrosion to facilities but also to have in place performance indicators
that have both proactive and reactive control measures. This is an important
management consideration for production systems that rely on high inhibitor
efficiencies and high dosage availability/injection reliability to ensure safe
long-term operation.

1.1. A i m s of the D o c u m e n t

The main objectives of the document are:

1 to provide a practical introduction to oil and gas field corrosion inhibition;

2 to outline typical inhibitor selection strategies in the context of the design and
operational stages of a project;

3 to consider the requirements for the successful deployment of corrosion

inhibitor packages for a range of applications.

The use of appropriate testing procedures and corrosion monitoring and data
gathering/interpretation systems are also addressed, but not in a detailed or
prescriptive manner. Sources of additional information are referenced where
appropriate.
 The Use of Corrosion Inhibitors in Oil and Gas Production
1.2. C o r r o s i o n in Oil and Gas E q u i p m e n t

1.2.1. Background
Carbon steel (C-Mn) plus corrosion inhibition (CI) is the most economic option
for many oil/gas projects, including in-field flow lines and long, large diameter
export lines. Key factors, discussed in detail below, are inhibitor effectiveness or
inhibited corrosion rate and the inhibitor system availability.
In some operating conditions corrosion resistant alloys (CRAs), CRA lined or
clad steel or non-metallics (GRE pipe or lined pipe) may be used. These may be
cost effective, particularly on a life cycle basis, for highly corrosive conditions or
where inhibition is difficult to achieve with a high rate of success. Other issues
affect materials selection including the operating philosophy (preference for
unmanned operations in some cases) or expectation of likely changes in produc-
tion conditions with time. For example, the use of 13% Cr compared to C-Mn steel
for tubulars in reservoirs containing high CO2 may be effective if the cost savings
due to a reduction in workovers (i.e. overhauls) is also taken into account.
Concern regarding complex geometries, crevices and dead legs means that CRAs
are also often preferred for some processing facilities.
In recent years the use of C-Mn steel has had to contend with the trend
towards transportation of multiphase fluids, the development of fields containing
very high levels of CO2, increasing water cuts (the proportion of water in the
produced fluid) and an increasing drive towards use of more environmentally
friendly treatment chemicals. All of these trends have increased demands for
corrosion inhibitor formulations with improved performance and there has been
even greater emphasis on ensuring that the right product is selected for each
application. There is also the criterion that performance in the field must meet the
required and necessary standard.
Consideration should always be given to the life cycle costs and risks associ-
ated with various options. With existing facilities the requirement is often to
increase the throughput or to handle increasing water cuts and sometimes to tie in
new fields that produce fluids with different chemistries; these necessitate the
adoption of management of change procedures.

1.2.2. Causes of Oil Field Corrosion

The causes of oil and gas field corrosion are summarised briefly in the sections
that follow. Further details are given in the following EFC documents.

EFC 23 'CO2 Corrosion in Oil and Gas Production'.

EFC 16: 'Guidelines on Material Requirements for Carbon and Low Alloy
Steels for H2S Containing Environments in Oil and Gas Production'.

In oil and gas production, the produced fluids comprise:

Hydrocarbon phases - - oils of various compositions and gases such as

methane and ethane. Some fields contain organic acids, such as acetic acid,
that increase corrosion rates in CO2-containing systems.
 Introduction 3

Produced water - - formation waters that may cause scaling due to dissolved
salts such as calcium carbonate, barium sulphate, sodium sulphate and
sodium chloride. Water injection may lead to water breakthrough and sour-
ing, which can also cause scaling due to mixing of water chemistries and
production of H2S.

• Acidic gases - - carbon dioxide a n d / o r hydrogen sulphide that dissolve in

water to form corrosive electrolytes.

'Sweet' or C02 corrosion.

Carbon dioxide corrosion mechanisms are complex [6-8]; the C O 2 gas first
dissolves in water to form carbonic acid, bicarbonate ions and hydrogen ions. All
these species are able to diffuse to the metal surface and partake in the overall
reduction reaction. Reactions that involve bicarbonate ions result in corrosion
rates that are greater than expected from the acidity measured by pH. The overall
process is:

Fe + H2CO 3 = FeCO3 + H2
iron carbonic acid iron carbonate hydrogen

At temperatures below 60°C and pH values less than 4, corrosion is controlled by

the rate of production of ferrous ions, with the surface being covered primarily
with iron carbide (the residue of the cementite from the steel) and a thin layer of
iron carbonate. In many cases, semi-protective iron carbonate scales form above
70°C and the reaction then becomes cathodically controlled, resulting in a reduc-
tion in the corrosion rate. Corrosion rates are determined by the partial pressure
of the CO2 (the product of the total pressure and the mole fraction), the tempera-
ture and pH (controlled primarily by the bicarbonate ion concentration) and flow
conditions. A maximum rate of corrosion is typically found at around 70°C.
'Sweet' corrosion is typically observed as metal wall thinning and shallow
pitting. Under high velocity conditions and particularly downstream of flow dis-
turbances (e.g. sudden expansions, bends or weld protrusions), deep elongated,
sharp-edged 'pits' can be formed, sometimes referred to as 'mesa' corrosion.

'Sour" or H2S corrosion.

The corrosion reactions of hydrogen sulphide, water and steel are also complex
[9,10]. H2S dissolves in water to form a weak acid that partially dissociates to form
hydrogen ions (the corrodent) and bisulphide ions. The low solubility of iron
sulphide results in the formation of a corrosion product film that tends to protect
the steel from general corrosion/metal wastage, particularly at high concentra-
tions of H2S. In this context the H2S also acts in a similar manner to a corrosion
inhibitor. The corrosion process can be summarised as:

Fe + H2S = FeS + H2
iron hydrogen sulphide iron sulphide hydrogen

In general, a high concentration of hydrogen sulphide, >200 ppm in the aqueous

phase, and high temperature produces a highly passive film (probably an iron
4 The Use of Corrosion Inhibitors in Oil and Gas Production
rich form of iron sulphide (FeSl_x), either Mackinawite or Pyrrhotite dependent
on the conditions). However, these conductive iron sulphide films are efficient
cathodes and in many systems any local break in the film can result in severe
pitting attack due to the lack of film reformation in the small intense anodic pit
area. At low temperatures, <40°C, and low H2S levels, but particularly in the
presence of CO2, the films are often a loose deposit of iron sulphide over a grey
coloured surface, indicating iron carbonate, and general corrosion is observed. At
intermediate levels of H2S there is a localised form of attack.
Hydrogen sulphide can be present naturally in the reservoir or can be
produced chemically due to physical/chemical changes during abstraction. Of
particular concern with water injection systems is the introduction of sulphate
reducing bacteria (SRB), a major cause of reservoir souring, biofouling of
equipment and microbiologically induced corrosion.
Oxygen and hydrogen sulphide react chemically in a wet environment to
remove the lower concentration gas. The reaction also forms active sulphur
compounds that are extremely corrosive. Ingress of oxygen into a sour system
(through poorly maintained seals, etc.) can therefore have a serious impact on
corrosion control and the life of equipment. A major concern in sour systems is
the possibility of cracking of materials of construction due to hydrogen damage.
Further details on corrosion in the presence of H2S and related materials issues
may be found in EFC 16.

1.2.3. C o r r o s i o n and I n h i b i t i o n Issues

Corrosion allowance.
The majority of oil/gas production systems are constructed from C-Mn steels but
with designs based on a corrosion allowance, Figure 1, of typically 3 to 5 mm.
The purpose of the corrosion allowance is to provide the project with sufficient
lifetime but this implies a gradual and controlled metal loss over the required life
cycle.
The minimum wall thickness required to sustain the working load with an
adequate safety factor is determined by industry standards based on the opera-
tional pressure and the mechanical properties of the fabricated steel construction.
The corrosion allowance is determined by engineering judgement based on the
anticipated total metal wastage that may occur during production and shutdown.
The actual corrosion allowance is essentially the outcome of a combined
assessment of the technical and economic risks. These risk factors include:

Extra thickness that is lost

Corrosion Allowance during service life

Thickness for strength

Fig. 1 Corrosion allowance concept.

 Introduction 5
• the predicted range of corrosion rates without inhibition;

• the anticipated effectiveness of the inhibitor;

• the likelihood of localised attack - - pitting, erosion and erosion-corrosion;

• the probable dosage of inhibitor and annual cost range;

• the inhibitor availability - - a corrosion management concern as to when

inhibitor is actually dosed into the system at the correct rate;

• the estimated life cycle cost of the inhibition programme - - initial investment
cost of equipment and training plus annual operational costs;

the expected cost to the project of unit thickness of metal in $/mm. In some
pipeline projects this can be significant (~ $0.5 m to $1 m). This cost arises
from the increased metal purchased, the increased welding time/costs and
in some cases such as with topside facilities the increased support structure
required for the added weight.

Concepts such as inhibitor efficiency and inhibitor availability are discussed

further in Section 2. In general, the design basis will assume that metal wastage
will occur from uniform corrosion or uniform erosion.
In practice, a pit penetration rate higher than the general corrosion rate may
be tolerated. This is based on a risk concept that corrosion metal loss would result
in a general thinning that could lead to a localised rupture whereas localised
pitting may not lead to a through wall penetration that would give rise to
leakage. For example, moderate corrosion/pitting ratings are: average corrosion
rate 0.025-0.125 mm y-1 (1-5 mpy), pitting 0.3-0.6 mm y-~ (12-24 mpy). [Note the
corrosion unit mpy - - mils (thousandths of inch) per year.] Corrosion inspection
and monitoring during operation combined with trending the changes in wall
thickness and pit penetration rate to identify the time to repair/replacement is a
typical method of mitigating the corrosion risk from pitting.
The use of a corrosion allowance is not a means of corrosion control but should
be considered, together with corrosion inspection and monitoring, as a corrosion
risk mitigation method since it provides an extended time window of operation.

Corrosion damage and inhibition.

In the context of corrosion risk assessments corrosion is not a cause of plant
and equipment failure but is a contribution to the mode of failure [11]. Typical
engineering failure modes are local leakage, rupture, collapse or buckling and
are important in the assessment of risk and in ensuring the integrity of a facility.
Failure modes are the result of interaction of the operational or accidental loads
with the corrosion damage. Corrosion damage includes uniform corrosion, flow
induced corrosion, erosion-corrosion, localised pitting, cracking and grooving
(weldment corrosion). Typical loads include internal/external pressure, localised
stresses and impacts.
6 The Use of Corrosion Inhibitors in Oil and Gas Production
Inhibition is typically employed to control uniform corrosion, including flow
assisted general corrosion. Sweet systems often suffer from pitting attack, par-
ticularly where organic acids are present, and sour systems are also prone to
localised pitting. In these cases inhibitor packages and dose rates must be care-
fully selected. Some produced fluids cause significant scaling or sludge deposits
that result in crevice type corrosion and pitting. In these cases corrosion control
often requires a higher dosage of inhibitor together with other treatments such as
scale control and biocides plus the use of cleaning pigs in lines.
The industry standard API RP 14E [12] defines maximum fluid erosional veloci-
ties for gas and liquids based on fluid density. However, a number of sweet
systems, such as the BP Prudhoe Bay fields [3], that experienced 'mesa corrosion'
due to multi-phase high velocity or slugging type flow have been successfully
treated using a combination of specially designed and selected inhibitors plus
field monitoring to manage the system. The onset of mesa corrosion appears to
depend on the corrosion product film structure formed on the steel, as well as on
the flow conditions, which leads to fracture and loss of iron carbonate scales by a
fatigue type of mechanism [13,14]. Schmitt and co-workers also suggest that some
inhibitor molecules not only provide protection but are able to decrease the fluid
drag slug related peak wall shear stress gradients and hence lower the energy
transfer process that causes film fatigue [15,16].
It is not normally recommended that inhibition be employed to control envi-
ronmentally assisted cracking (stress corrosion cracking and sulphide stress crack-
ing). However, there are a significant number of pipelines worldwide that were
originally constructed from steels that are susceptible to hydrogen damage in sour
service (hydrogen induced cracking and blistering) but are now successfully oper-
ated with inhibition. These include older constructions and fields that have
become sour. The risks associated with the use of inhibition on hydrogen diffu-
sion and susceptibility to hydrogen damage can be assessed using the Full Ring
Test [17] under simulated process conditions. The use of inhibition to mitigate
hydrogen damage is a high risk strategy that requires good management of the
corrosion monitoring and dosage system. It must also be noted that this approach
is contrary to NACE advice [18] but relies on the principle that the cracking
damage is a function of the diffusion rate of atomic hydrogen in the particular
steel microstructure. The diffusion and concentration of hydrogen in the metal
can in turn be controlled by the rate of corrosion/hydrogen generation. It must be
emphasised that the normal approach is to select and use materials that have been
qualified as being suitable for sour service.
From a corrosion management point of view the mechanisms that result in
corrosion damage are understood and predictable, whilst corrosion control and
mitigation procedures are well established. A prime reason for many corrosion
related failures is now considered to be human error/poor management control
[19]. This together with more stringent safety, health and environmental (SHE)
requirements worldwide are reasons for increased emphasis on implementation
of improved management procedures for inhibition programmes from selection
through to deployment. The management structures, allocation of responsibilities
and reporting routes adopted play a vital role in many high risk corrosion
systems.
 Introduction 7

1.3. Key Points

Corrosion and the use of inhibition is typically determined by the following

factors.

Partial pressures of C O 2 and H 2 S - - the concentrations and total pressures of

these gases control fluid corrosivity, rates of general corrosion, sour service
criteria and materials selection.

• Fluid chemistry - - important factors are scaling tendency, pH and presence of

organic acids in sweet systems that may induce pitting corrosion.

• Temperature - - higher temperatures influence the degree of scaling and

corrosion rates and decrease the adsorption ability of inhibitors.

Fluid composition - - water cut, hydrocarbon gas and condensate contents and
oil density and viscosity influence conductivity, holdup, and wetting of steel
surfaces.

Flow conditions - - stratified flow, slugging and gas phase flow considerations
influence the onset of erosion-corrosion, impingement and erosion that may
limit the effectiveness of inhibitors.

Project life cycle costs and perceived risks - - these determine the choice
between the use of corrosion resistant materials compared with C-Mn steel
plus corrosion inhibition.

Corrosion allowance - - provides an extended time window of operation,

a standard mitigation method that requires trending of corrosion inspection
and monitoring data when used in conjunction with inhibition in high risk
systems.

• Management of corrosion control programmes - - most system failures are the

result of human error and poor management control procedures.

Further information on inhibitors and inhibitor performance is found in Sections 2

to 4.
 2
Inhibition Concepts and Issues

Inhibition is one corrosion control option; alternatives include materials selection

(CRAs, lined pipe and GRE), use of protective coatings, and modification of the
process conditions/environment. Typical environmental control procedures used
in pipelines are dehydration and pH control.
General guidance can be given on chemical treatment but it should be reco-
gnised that various corrosion control options may also have to be considered
for specific areas of any system. Typically, inhibitors are used in sweet systems
to control general corrosion but some packages are designed to operate in
highly turbulent flow conditions and are effective against 'mesa corrosion'/CO2
erosion-corrosion. Inhibition is also employed in sour systems to lower the
general corrosion rate but a key feature is often to decrease the risk from pitting
corrosion. Control of pitting in both sweet and sour systems often requires a
higher dosage rate than that needed to reduce general corrosion.

2.1. General Background and Basics of Inhibition

Typical corrosion inhibitors used in oil field applications are organic compounds
and are employed in small concentrations (less than 0.1%). They are often
categorised as mixed inhibitors in that they adsorb on the steel surface and inhibit
both the anodic and cathodic reactions. However, many commercially available
inhibitor packages tend to polarise the steel anodically. Oilfield corrosion inhi-
bitor compounds also displace adsorbed water molecules from the surface and
are referred to as filming inhibitors. For example, inhibitor products used in jet
fuel (a low water content product) operate purely in this manner.
Almost all organic molecules used in oil field corrosion inhibitor packages are
strongly polar functional compounds, with many being based on nitrogen, such
as the amines, amides, imidazolines or quaternary ammonium salts, and include
salts of nitrogenous molecules with carboxylic acids, polyoxyalkylated nitrogen
containing compounds, nitrogen heterocyclics and compounds containing P, S,
and O. The actual species in the package that provides protection is often subject
to debate since, for example, imidazoline hydrolyses in water to give the amide
[20]. Reviews on oil field inhibitors [21,22] and principles of manufacture [23,24]
can be found in the literature. Some typical molecular structures of inhibitors are
illustrated in Table 1.
Typically, the molecules also have a hydrocarbon chain attached, the length of
which varies (e.g. carbon numbers between 12 and 18). The active group of the
molecule provides the functionality that displaces water and causes adsorption
onto the metal surface. The hydrocarbon chain of the inhibitor molecule causes
the molecule to be partially oil soluble and also attracts crude oil molecules
10 The Use of Corrosion Inhibitors in Oil and Gas Production
Table 1. Basic molecular structures of oil field inhibitors

Chemical name Structure

Primary amine R CH2--NH 2

Amide O
II
R1--CH2--C--NH--R 2
Imidazoline

Quaternary ammonium ion

R--cHN~2~N~cH2_CH2_NH2
CHa
[ ~ --~LCH2--R
CH3

Polyethoxylated amines
/ (O--CH2--CH2-~nOH
R-- N"',(O-- OH2- - OH2~nOH

from the process stream. The inhibitor molecules provide a barrier between the
corrosive water phase and the metal surface (Fig. 2).
Commercially available oilfield corrosion inhibitors can contain u p to six
surface active organic c o m p o u n d s dissolved in a carrier solvent. The total solute
fraction adds up to ca 30% w / w . The carrier solvent can be water, alcohol or
hydrocarbon. A low freezing point solvent (e.g. ethylene glycol) is required for

Hydrocarbon chain H~Bectrons available for

~ H C ~ bondmg to metal
Inhibitor mole~le dispersed
Polar amine in processstrea%
nitre . . . . . . . . . Hydrocarbon

Oil molecule

Hydrocarbon
chain "R" " HCH

HCHHCHHCHHCHHCHHCHHCHHCH Chemisorption&
hysical adsorption by

Fig. 2 Schematic of action of oil field corrosion inhibitor.