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;

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

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 production 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 associated 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

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 souring, 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
iron

H2CO 3

carbonic acid

FeCO3
+
H2
iron carbonate
hydrogen

At temperatures below 60C 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
70C and the reaction then becomes cathodically controlled, resulting in a reduction 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 temperature and pH (controlled primarily by the bicarbonate ion concentration) and flow
conditions. A maximum rate of corrosion is typically found at around 70C.
'Sweet' corrosion is typically observed as metal wall thinning and shallow
pitting. Under high velocity conditions and particularly downstream of flow disturbances (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 concentrations 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
iron

+
H2S
=
hydrogen sulphide

FeS
+
H2
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

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, <40C, 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 operational 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:

Corrosion Allowance
Thickness for strength

Fig. 1 Corrosion allowance concept.

Extra thickness that is lost

during service life

Introduction

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.

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, particularly where organic acids are present, and sour systems are also prone to
localised pitting. In these cases inhibitor packages and dose rates must be carefully 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 velocities 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 environmentally assisted cracking (stress corrosion cracking and sulphide stress cracking). 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 operated with inhibition. These include older constructions and fields that have
become sour. The risks associated with the use of inhibition on hydrogen diffusion 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

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.