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Guidelines for Selecting,


Testing and Applying
Corrosion Inhibitors
in E&P Operations
(June 2007 Edition)
BP ETP GN 06-006

Report No S/EPT/54/07

Will Durnie
Integrity Management, EPTG

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Contents
Page No

1. Introduction......................................................................................................................... 3
2. Scope .................................................................................................................................. 4
3. Normative references........................................................................................................... 4
4. Symbols and abbreviations .................................................................................................. 5
5. Corrosion and Corrosion Inhibition ..................................................................................... 6
5.1. Design ......................................................................................................................... 6
5.2. Corrosion Allowance ................................................................................................... 8
5.3. Inhibition Strategies..................................................................................................... 8
6. Corrosion Inhibitors........................................................................................................... 10
6.1. What are they and how do they work?........................................................................ 10
6.2. Solubility ................................................................................................................... 11
6.3. Partitioning ................................................................................................................ 12
6.4. Efficiency .................................................................................................................. 13
6.5. Availability................................................................................................................ 14
6.6. Application technique ................................................................................................ 19
6.7. Changing conditions (i.e., increasing water cut) ......................................................... 19
6.8. Secondary properties.................................................................................................. 22
6.9. Environmental ........................................................................................................... 23
6.9.1. US Region ............................................................................................................. 23
6.9.2. UK North Sea ........................................................................................................ 23
6.9.3. Other regions ......................................................................................................... 23
7. Inhibitor Selection ............................................................................................................. 23
7.1. Planning .................................................................................................................... 23
7.2. Corrosion Assessments .............................................................................................. 25
7.3. Risks of Inhibition ..................................................................................................... 26
7.4. Selection Process ....................................................................................................... 26
7.5. Inhibition System Design Considerations................................................................... 27
8. Inhibitor Injection.............................................................................................................. 28
8.1. Inhibitor Injection into the Process Stream................................................................. 28
8.2. Inhibitor Dilution....................................................................................................... 29
9. Inhibitor Dosage Rates ...................................................................................................... 30
9.1. Continuous injection .................................................................................................. 30
9.2. Batch Treatment ........................................................................................................ 32
9.2.1. Batch inhibitor volume calculations for pipelines ................................................... 33
10. Inhibitor Injection Pumps................................................................................................ 33
10.1. Inhibitor Pumping Problems .................................................................................. 33
10.2. Compatibility of Inhibitor with Injection System Materials .................................... 34
11. Applicability, Limitations and Performance of Inhibitors ................................................ 35
12. Testing of Inhibitors........................................................................................................ 35
12.1. Performance testing ............................................................................................... 35
12.2. Secondary properties.............................................................................................. 35
13. Combination Products..................................................................................................... 35
14. Field trials/testing ........................................................................................................... 44
15. Performance Management/Measurement......................................................................... 44

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1. Introduction

Corrosion mitigation via inhibition is a key component of corrosion management, which in turn is a
key component of integrity management, mandated by “Getting Health Safety and Environment
Right” and by the Group Integrity Management Standard.

These guidelines cover the deployment of corrosion inhibitors downhole, in flow lines, processing
equipment, as well as export pipelines in oil and gas production facilities. The text covers many
aspects of corrosion inhibition including; why they are used, how they are tested, how they are
selected, and how to achieve maximum performance in the field to alleviate internal corrosion of
facilities. The application of corrosion inhibitors both by batch treatment and continuous injection
is discussed in this document. Corrosion inhibition strategies can vary greatly and as such there is
not a standard, however this is typically outlined within a corrosion management strategy.

Whilst corrosion inhibitors are described in textbooks and industry monographs (e.g. from NACE -
the National Association of Corrosion Engineers; and various oilfield chemical companies) it is
often in very general terms. Much of the detailed, accumulated expertise on corrosion inhibitors for
the oil and gas industries resides within production companies and chemical suppliers. Often this is
disseminated via verbal communication amongst personnel and is not formally recorded or
summarized.

This document is intended to supplement previously published documents, i.e., “Corrosion


Inhibitor Guidelines, A practical guide to the selection and deployment of corrosion inhibitors in oil
and gas production facilities” (BP Sunbury report number ESR.95.ER.050 April 1995) and “The
use of corrosion inhibitors in oil and gas production” (European Federation of Corrosion
Publication Number 39).

The application of chemical corrosion inhibitors should be supported by corrosion monitoring and
inspection programs, which provide a measure of the corrosivity of the process fluid contacting the
equipment (monitoring) and provide information on actual equipment condition (inspection). GP
06-70 “Corrosion Monitoring” provides detailed technical guidance for corrosion monitoring while
GP 32-40 “Guidance on Practice for Inspection and Testing – In-Service Equipment - Common
Requirements” provides detailed technical guidance for equipment-specific inspection and testing.

Meeting our increasing obligations with regards to safety, health and the environment requires
increased consideration to corrosion management systems particularly those that currently do or
will rely on high inhibitor efficiencies and high availability injection systems.

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2. Scope
This document provides guidance for the testing, selection and field application of corrosion
inhibition used for the mitigation of internal CO2 or CO2/H2S corrosion within in-service piping and
equipment. It is applicable to onshore and offshore (sub sea) oil and gas production facilities,
pipelines and distribution facilities.

The document outlines typical inhibitor selection strategies in the context of the design and
operational stages of a project.

The use of appropriate testing procedures and performance management systems are discussed.
Requirements for the successful deployment of corrosion inhibitors and their limitations for a range
of applications are outlined.

Minimum requirements for adopting corrosion inhibitor performance and availability for design
purposes are outlined.

3. Normative references
The following normative documents contain requirements that, through reference in this text,
constitute requirements of this technical practice. For dated references, subsequent amendments to, or
revisions of, any of these publications do not apply. However, parties to agreements based on this
technical practice are encouraged to investigate the possibility of applying the most recent editions of
the normative documents indicated below. For undated references, the latest edition of the normative
document referred to applies.

BP
GP 06-70 Guidance on Practice for Corrosion Monitoring
GP 32-40 Guidance on Practice for Inspection and Testing – In-Service Equipment
- Common Requirements
S/ESR.96.ER.066 Corrosion Prediction Modelling: A guide to the use of corrosion
prediction models for risk assessment in oil and gas production and
transportation facilities
S/ESR.95.ER.050 Corrosion Inhibitor Guidelines, A practical guide to the selection and
deployment of corrosion inhibitors in oil and gas production facilities
S/ESR.95.ER.054 Corrosion Inhibitor Test Methods

NACE

RP 0775 Preparation and Installation of Corrosion Coupons and Interpretation of


Test Data in Oil Field Operations.

RP 0497 Field Corrosion Evaluation Using Metallic Test Specimens.

RP 0195-95 Recommended Practise for Corrosion Control of Sucker Rods by


Chemical Treatment

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4. Symbols and abbreviations


For the purpose of this document, the following symbols and abbreviations apply:

CS Carbon Steel

CI Corrosion inhibitor

CRA Corrosion Resistant Alloy

CO2 Carbon Dioxide

H2S Hydrogen Sulfide

O2 Oxygen

E % Inhibitor Efficiency

A % Inhibitor Availability

LPR Linear Polarisation Resistance

ER Electrical Resistance

PPE Personal protective equipment

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5. Corrosion and Corrosion Inhibition

Carbon steel (CS) in combination with corrosion inhibition remains one of the most economical
options for many oil and gas projects. In many conditions, however, corrosion resistant alloys
(CRA’s), CRA lined or clad steel or the use of non-metallics (lined pipe) may be more cost
effective particularly on a life cycle basis (i.e., for highly corrosive conditions or those conditions
where inhibition is difficult to achieve with high rates of success). In high temperature, high CO2
downhole environments where CS is highly vulnerable, corrosion inhibitors (CI’s) are difficult to
deploy (particularly offshore) and can have poor efficiency. The use of CRA (e.g. 13%Cr) for
tubulars often provides significant cost savings due to the reduction in required work-overs, tubing
replacements etc.

CS/CI becomes a more technically viable option for process pipework and for in-field flowlines.
However, concern about the effects of complex geometries, crevices and dead legs on CS/CI means
that CRA’s are often preferred for process equipment, particularly offshore.

Increasingly, CS is being asked to contend with escalating severity of conditions, i.e., fields
containing higher CO2 contents, higher temperatures, increasing water cuts in addition to tightening
environmental regulations which dictate chemicals that can and cannot be used. These factors
along with others increase the demand placed on the performance of CI chemicals and the
requirements to ensure they are selected and applied rigorously.

5.1. Design

Corrosion prediction models assist the corrosion engineer make decisions for the design of the
production and treatment facilities, e.g. the need for CI injection, the appropriateness of pH
control, the need to define a corrosion allowance (CA) and required CI availability etc. The
objective is primarily to predict the order of magnitude of the CO2 corrosion rate, ideally
including localised corrosion.

The predicted corrosion rates together with other parameters, such as protectiveness of
corrosion product scales, and scaling tendency etc. can be used to help define the severity of
corrosion. In addition, the possibility of using corrosion inhibition is often evaluated taking into
account inhibitor availability and efficiency, which may be affected by operating parameters
such as flow pattern, fluid velocity and presence of solid particles.

The process for a typical corrosivity prediction along with factors commonly considered is
outlined in Figure 1.

A corrosion prediction model such as the well known de Waard and Milliams approach (or
modifications thereof, i.e., Cassandra) is commonly used in this work if CO2 is present in the
process stream. These models are typically conservative with regards prediction of the general
CO2 corrosion rate (i.e. they overestimate the general corrosion rate) and as such, are often
considered typical of the rates possible if localized corrosion occurs. More information
outlining the current BP approach to corrosion prediction can be found in ”Corrosion
Prediction Modelling: A guide to the use of corrosion prediction models for risk assessment in
oil and gas production and transportation facilities” Sunbury Report Number ESR.96.ER.066

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November 1997 as well as “A Prophetic CO2 Corrosion Tool - But When is it to be Believed?”,
Hedges et al. NACE paper number 05552.

Undissociated Acetic acid


pH calculation
concentration
Thermodynamics
Input parameters Flow velocity & flow regime
Wall shear stress

Bare steel
corrosion

Other parameters influencing bare steel corrosion rate

Oil wetting
Glycol
Flow regime
Water condensation rate
Scaling & protectiveness
H2S and S
Pitting tendency /pitting factor

Final corrosion rate

Without chemical treatment


Corrosion likelihood
Corrosion Rate

Inhibitor availability Wall shear stress

Inhibitor efficiency Solids

With chemical treatment


Final corrosion likelihood
Corrosion rate

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Figure 1. Graphical representation of typical corrosion prediction.

5.2. Corrosion Allowance


Oil and gas systems constructed from CS are designed with a corrosion allowance (CA)
typically between 3-8 mm with the purpose of facilitating sufficient lifetime based on a gradual
controlled metal loss over the required lifecycle.

Industry standards are used along with the operational pressure and the mechanical properties of
the fabricated steel to determine the minimum wall thickness required to sustain the working
load. The corrosion allowance is then judged based on the expected total metal wastage that
may occur during production and shut-down periods and is the outcome of a combined
assessment of the technical and economic risks. Some of these risks include:

1. predicted uninhibited corrosion rates


2. efficiency of the CI
3. likelihood of localised corrosion, i.e., pitting, erosion and erosion-corrosion
4. likely CI dosage required and approximate annual cost
5. the inhibitor availability – related to the time the CI is actually dosed into the
system at or above the minimum effective concentration
6. estimated life cycle cost of the inhibition program – including initial investment
cost of equipment (injection skid etc.) as well as training and direct costs
associated with operation of the injection system
7. expected cost per unit thickness of steel in $/mm.

Typically, the design assumes that metal wastage occurs from uniform corrosion.

A corrosion allowance is not a means of corrosion control, but should be considered, together
with inspection and monitoring as a corrosion risk mitigation method since it extends time of
operation.

5.3. Inhibition Strategies


Development of inhibition strategies requires that consideration be given to the design,
procurement and installation of injection equipment in addition to the operation and maintenance
requirements. Ultimately the strategy adopted will be site specific and depends on factors such
as age, history, location, business criticality and experience of personnel.

The basic intention should be to maintain inhibited fluids and clean steel surfaces at all times.
Experience shows that once corrosion becomes established it can be difficult to eliminate or cost
effectively control. Inhibition is a prudent insurance policy to maintain safety and integrity.

When considering an inhibition strategy, several objectives should be considered:

1. ensuring integrity of assets


2. minimize HSSE impact
3. maximize hydrocarbon production and minimize downtime
4. minimize life cycle costs;

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As mentioned, the typical choices for corrosion control strategies are either corrosion resistant
materials or carbon steel with inhibition. Other methods involving the modification of the
corrosive environment, i.e., pH stabilisation could also be considered.

Corrosion inhibitors have been used successfully in the oil and gas industry for several decades
for both sweet (CO2) and sour (H2S) conditions. The effectiveness of a CI in protecting a steel
surface is dependant on a number of factors and these must be considered in the choice of an
inhibitor product. The main issues influencing the effectiveness of CI’s are the availability and
the efficiency of the inhibitors in the field – both of which are discussed in more detail later in
this document.

Although general guidance can be offered with regards to the use of inhibition, it should be
recognised that alternative corrosion control techniques may have to be considered for specific
areas of a system, i.e., use of CRA for downhole tubulars and equipment.

When process facilities are commissioned and placed into full production there is a question
over when to begin adding CI’s. Some philosophies suggest not adding CI until the water cut
rises above a certain level (e.g. >1% water in a crude oil stream), reasoning that if there is no
water then there is no corrosion. While this is unarguably true, the key point is whether it can
unequivocally be demonstrated that there is “no water” or no water accumulation at isolated
locations in the system. Even with very low average water cuts there is still a chance of droplets
gradually wetting the steel surface and accumulating, perhaps augmented by sporadic slugs of
water not picked up by routine monitoring - and corrosion will occur. As flow velocities
decrease within a pipeline, the critical angle (elevation change) required to hold up free water in
a line decreases. Recent calculations indicate that for very low velocities, i.e., < 0.15 ms-1 this
may be as low as 0.1o which could be attributed to little more than a small flow disturbance or
weld bead in a pipeline. Inhibition from day 1 is especially advisable for sub-sea lines which are
expensive, inaccessible and inherently difficult to monitor or inspect.

When CS/CI is selected as the preferred corrosion control strategy, corrosion inhibition shall be
applied from day 1 irrespective of the anticipated water cut in accordance with the outcome of a
Risk Assessment study. In case of deviation from the above, the risks of not applying inhibition
must be demonstrated to be acceptable and shall be approved by the Engineering Authority.

Due to the difficulties associated with demonstrating there is no water or water accumulation at
very low water cuts, when water cuts of less than or equal to 0.5% are present in a pipeline
system it shall be assumed 0.5% water is present. Calculations of inhibitor dosage rates (if
based on water) shall be based on the assumption that 0.5% water is present. Above 0.5%, the
measured water content should be used for such purposes.

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6. Corrosion Inhibitors

6.1. What are they and how do they work?


A corrosion inhibitor is a substance, which, when added to a corrosive environment in small
concentrations effectively decreases the corrosion rate of metals within it. Corrosion inhibitors
function using one or combinations of three fundamental mechanisms:

1. Adsorption at the surface as a thin protective molecular film


2. Formation of precipitates or viscous layers which coat the metal
3. Changing the characteristics of the environment i.e., use of pH stabilisation in gas
condensate systems

Typically, the continuous injection CI’s utilized in oilfield environments are organic compounds
which when applied in relatively low concentrations (10’s-100’s parts per million, either µL/L,
or mg/L) adsorb to the steel surface and inhibit the anodic reaction, cathodic reaction or both.
Batch treatment CI’s are typically deployed at concentrations in the 1000-10,000’s of ppm
range.

Organic corrosion inhibitors are generally hydrocarbon-based chemicals with nitrogen, oxygen,
sulfur or phosphorous containing polar groups. Examples of such chemicals include, amines,
amides, fatty acids, quaternary amines, mercaptans, phosphate esters, imidazolines, heterocyclic
amines, betaines and ethoxylated/propoxylated amines - to name a few. These inhibitors are
thought to reduce corrosion by attachment of the active polar group to the surface (which
ultimately displaces water). The hydrocarbon chain which is attached (generally between 10-20
carbon atoms long) imparts a certain level of oil solubility to the molecules and also acts to
attract oil from the process stream. This change in wettability of the surface to effectively oil-
wet provides a barrier between the corrosive water phase and the metal surface.

In a hydrocarbon-water system, the inhibitor exists in equilibrium between the two phases with
a certain number of inhibitor molecules being dissolved in each phase. Additional inhibitor will
exist as colloidal micelles which are not necessarily surface active and function mainly as
reservoirs to maintain the concentration of free film forming molecules in each phase. As free
inhibitor films onto the metal surface, more is released from the micelles to maintain the free
inhibitor concentration. The attraction of the polar group to the metal surface is much stronger
than to the hydrocarbon/water interface and the attraction is not easily reversible. This translates
to the inhibitor persisting at the surface for some time, even where there are no reserves in the
environment, such as when addition of inhibitor is interrupted. This persistency characteristic
depends greatly upon the particular inhibitor molecule and the environment in the system.

Commercial corrosion inhibitors are invariably a blend of 15 to 50% active components (there
may be three or four different base molecules) blended with 50 to 85% carrier solvent
comprising a basic solvent together with additional surfactants with specialized characteristics
(co-solvent, surfactants, demulsifiers, antifoam, etc.). For use in extreme climate areas, i.e.,
sub-zero temperatures, products require winterisation or addition of a solvent with a depressed
freezing point such as ethylene glycol or methanol.

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6.2. Solubility
Corrosion inhibitors are often classified according to their solubility and dispersibility in water
and hydrocarbon. This physical characteristic is of prime importance as it can significantly
influence the filming properties. In its simplest form, this classification provides a comparative
tendency of solubility or dispersibility in water or oil via the formation of micelles or micro-
emulsions.

An inhibitor is generally considered soluble in a solvent if the inhibitor-solvent mixture remains


clear and miscible upon standing. An inhibitor is considered dispersible in a solvent if it can be
evenly dispersed in the solvent (formation of stable or meta-stable emulsion) by moderate
agitation. To conduct such comparative tests, the quantity of solvent is often equal to or greater
than the quantity of inhibitor. If a dispersion breaks rapidly (<1 minute), it is not considered
dispersible. An inhibitor that remains uniformly dispersed in the solvent is classified as a
“dispersible inhibitor.”

The usual classification given to inhibitors based on their solubility is:


1. Oil or water soluble (clear solutions)
2. Oil or water dispersible (cloudy solutions)
3. Limited solubility (‘gunkers’)
4. Gas phase or volatile corrosion inhibitors

Examples of water soluble products would include those containing quaternary amines, amine
salts, salted imidazolines, salted phosphate esters, betaines etc. and are most often applied
continuously into water containing systems. Solubility of these products in water can be
affected by the typical factors affecting any solubility, i.e., temperature, salinity, etc. Water
soluble products do not necessarily contain water as a solvent.

Oil soluble inhibitors are generally considered more persistent than water soluble inhibitors
where persistency refers to strength of the film adhesion to the surface. Oil soluble inhibitors
typically contain materials such as imidazolines, long chain amines, fatty acids, acid reaction
products with polyamines, amides and other higher molecular weight organic compounds.

Limited solubility inhibitors are generally considered the most persistent as they are neither
particularly soluble in water or hydrocarbon, however, their limited solubility decreases the
feasibility of transporting them to the area of corrosion. They are most often applied as meta-
stable dispersions in hydrocarbon solvents which deposit or ‘gunk’ onto the surface as the
dispersion breaks.

Volatile corrosion inhibitors are typically low molecular weight amines or amine reaction
products with aldehydes which have high vapour pressures.

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6.3. Partitioning
The great majority of chemical corrosion inhibitors are surface-active materials that possess
separate hydrophilic and hydrophobic groups in the same molecule. It is this combined
hydrophilic/hydrophobic nature that causes an inhibitor to adsorb onto a metal surface, forming
a barrier that retards the electrochemical corrosion process. However, this property also means
that most chemicals will distribute between the hydrocarbon and aqueous phases present in a
production system according to their partitioning coefficient.

Knowledge of oil/water partitioning is required in order to ensure that the required


concentration of corrosion inhibitor is achieved in the water phase and delivered to the metal
surface, where it is needed. The amount of a corrosion inhibitor in the aqueous phase is
significantly dependent on the relative amounts of oil and brine present, hence, as the water cut
increases the inhibitor will distribute at different concentrations between the oil and water
phases.

Partitioning is a concept that is often examined via testing, where the main purpose is to
estimate the inhibitor dosage required based on total fluids. A product may show good
efficiency at 50 ppm in water only tests, but if it is added at 50 ppm to a l:l v/v water/oil mixture
then most of the material may migrate into the oil (if Pw/o = 0.1) giving concentrations of 90
ppm in the oil phase and only 9 ppm in the water (see Table K-1, Annex K). 9 ppm may not be
sufficient to fully inhibit the water.

In this example a dose rate of 275 ppm on total fluids would be required to give 50 ppm in the
water phase. This illustrates the importance of conducting partitioning tests at realistic water/oil
ratios, and also of adjusting injection rates with changing water cut. Table K-1 illustrates how
resultant aqueous and hydrocarbon concentrations can vary with partitioning coefficient
depending on dosage basis over a range of water cuts between 0 and 100%. The theoretical
basis of partitioning is discussed in more detail in Annex K.

Ideal partitioning behaviour for a CI would imply that a completely water soluble product will
fully inhibit the aqueous phase if present in sufficient concentration – however, a product such
as this may not disperse in high oil cut/low water cut systems. In this case, it could be
envisaged that this type of product may deposit on the pipe wall near to the injection point and
not reach the water wet or water containing regions of the pipeline further downstream.
Equally, the product could remain as discrete droplets in the continuous oil phase which may or
may not ‘find’ water.

In contrast, although a completely oil soluble product would be well dispersed in the
hydrocarbon phase, it may be so oil soluble that it may not efficiently inhibit the water wet
surface. The compromise is to apply a product with a certain affinity for both oil and water
such that it may distribute well in the hydrocarbon phase and partition into the water phase
if/when it is encountered.

It is recommended that for low water cut multiphase environments, i.e., < 5-10% water, an oil
dispersible/water soluble or water dispersible/oil soluble corrosion inhibitor should be

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considered. This typically contains active components that partition to water well (have a high
affinity for water), i.e., quaternary amines, salted imidazolines etc. but may be contained within
a hydrocarbon or hydrocarbon miscible solvent. This allows the product to effectively disperse
into the oil phase but also to ‘find’ the water in the system.

A difficult concept to account for is the fact that most corrosion inhibitors are a mixture of
components, perhaps as many as six or more - each of which has its own individual partition
coefficient. The “overall” partition co-efficient for the product will be a composite of the
individual values and so will be even more dependant on conditions. Therefore, it is unwise to
regard a partition co-efficient, obtained under one set of conditions, as a constant which can be
extrapolated quantitatively to other conditions. Partitioning should be regarded as a more
qualitative concept as in “preferentially water soluble” or “preferentially oil soluble”. This
advice is reinforced by the potential error in any measurement of partition co-efficient in the lab.
Not only are there bulk oil and water phases but also oil/gas, oil/glass, water/glass and oil/water
interfaces. Each of these may influence the perceived distribution across the oil and water and it
is difficult to tell how much inhibitor may be retained in these interfaces because although the
amount of inhibitor in the bulk water may be measurable, the amount in the bulk oil may be
impossible to determine.

6.4. Efficiency
The performance of a corrosion inhibitor chemical is a combination of the efficiency of the
chemical (% reduction in the uninhibited corrosion rate) and the injection reliability or
availability (% of time the chemical is applied at or above the concentration required to attain
the desired efficiency level).

Very simply, the efficiency can generally be related to the % coverage of the steel surface by
adsorbed inhibitor molecules. This is most commonly related directly to the uninhibited and
inhibited corrosion rates by the following expression:

Uninhibited Corrosion Rate - Inhibited Corrosion Rate


% Inhibitor Efficiency = x 100
Uninhibited Corrosion Rate

Traditionally, pipeline designs were based on mediocre inhibitor efficiencies of between 60-
80%. Originally, the determination of a corrosion allowance was based on inhibitor efficiencies
alone, i.e., the corrosion allowance was equated to the inhibited corrosion rate (based on
assumed efficiencies) multiplied by the design life. The fundamental flaw when this approach
is used in isolation is the assumption that the inhibitor efficiency remains constant. In addition
to this, if the efficiency is considered in isolation from the actual corrosion rate resulting from
that level of efficiency, it is possible that the inhibited rate may still be unacceptable (i.e., where
the uninhibited corrosion rates are very high, i.e., CR>20 mm/year).

BP currently does not consider corrosion inhibitor efficiency per-se; however, the assumption is
made that the corrosion rate can be reduced to 0.1 mm/year. With a predicted uninhibited
corrosion rate of 1 mm/year this equates to an efficiency of 90% while for an uninhibited
corrosion rate of 10 mm/year this is an efficiency of 99%. Laboratory tests often indicate that
high inhibitor efficiencies can be achieved, i.e., >95% depending on the concentration of
chemical applied. The use of efficiency assumes that corrosion inhibitors reduce the corrosion
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rate by a fixed percentage. In reality, the concentration required to achieve this reduction will
vary depending on the prevailing conditions. In laboratory tests with well controlled conditions,
extremely low corrosion rates can be achieved and measured, i.e., significantly less than 0.05
mm/year. In the field however, inhibited corrosion rates between 0.05-0.1 mm/year are
typically recorded.

The approach of using a constant inhibited corrosion rate for design purposes is still valid and is
the recommended approach. As mentioned, lower inhibited corrosion rates may be achievable
however, there is little to be gained in design from making such an assumption. Table 1
provides indicative values of inhibited corrosion rates as a function of temperature. If
uninhibited corrosion rates are predicted to be excessive (i.e., >20 mm/year) testing is
recommended in order to ensure that inhibited rates of 0.1 mm/year or less are achievable with
realistic chemical concentrations.

6.5. Availability
Inhibitor availability refers distinctly to the time that the inhibitor is present in the system at or
above the concentration required to achieve the required efficiency. This is expressed as a % of
time, i.e., an inhibitor availability of 95% suggests there were 18 days in one 365 day period in
which inhibitor was dosed below the required concentration.

Once the inhibitor selection is complete it is important to quantify the performance. For new
developments this is used to determine the corrosion allowance (CA) that should be applied.
Historically the concept of efficiency was used, however the availability approach is now
commonly used. The availability concept in combination with the target inhibited corrosion rate
is the preferred method of determination of the corrosion allowance. Corrosion allowance =
inhibited corrosion allowance + uninhibited corrosion allowance, i.e.,

A% A%
CA = CR inh x x Design Life + CR uninh 1 − x Design Life
100 100

Where CRinh = Inhibited corrosion rate (mm/year) and CRuninh = uninhibited corrosion rate
(mm/year). This simplified approach takes no account of persistency and assumes production
continues during uninhibited events. Inhibitor distribution after an uninhibited event is not
considered and the details of individual uninhibited events are not considered.

Due to the difficulties in testing and quantifying inhibitor persistency both in the laboratory and
in field applications, no account of inhibitor persistency shall be taken for inhibitor availability
determinations. For all practical purposes, the inhibitor availability will relate to time of
continuous injection when the inhibitor is present at or above the minimum effective bulk
concentration to achieve the required inhibited corrosion rate.

The inhibited corrosion rate, CRi, is the corrosion rate that occurs in the system when the
inhibitor is providing protection. Based on laboratory and field data default values for
achievable inhibited corrosion rate in new designs can be used – see Table 1.

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Table 1: Typical achievable inhibited corrosion rates

Temperature Range, °C Inhibited Corrosion Rate, CRinh, mm/y


Up to 120°C 0.1

> 120 °C and ≤150°C 0.2

Above 150°C Inhibition not recommended without specific testing

For a system in operation, the inhibitor availability can be determined from historical data and
from a detailed review of uninhibited events. In addition to this, the actual inhibited corrosion
rate should be measured and this data should then be used to determine the actual overall
corrosion rate that is used in any Risk Based Inspection assessments.

In design, a minimum value of 95% (0.95) shall be used for inhibitor availability (A). This
value of A equates to 18 days inhibitor system downtime per year and is considered achievable
with a typical inhibition system (as outlined in Table 2). Many inhibition systems are designed
to satisfy availabilities of 0.95 and such availabilities are achievable with this type of system,
however, availabilities as low as 0.50 have been assessed in actual field situation, where the
operations element has not been adequately addressed. Back up systems and automation should
be considered during the design to avoid such problems and facilitate higher inhibitor
availabilities.

Inhibitor availability targets of 100% shall be in place for all facilities. In order to demonstrate
mandatory minimum compliance, availabilities of not less than the design availabilities shall be
achieved and demonstrated continuously according to guidance in Table 2.

Using the same basic inhibition system, high values of A may not be practically achievable if
there are known specific operating difficulties in the location the pipeline will be installed (e.g.
limited access, maintenance problems, taking account of comparable performance on existing
systems etc.). This should be critically assessed in the pre-conceptual design and conceptual
design phase.

The value of A used in the design can potentially be increased with the use of more automated
systems, faster response monitoring, back up systems etc. Requirements for adoption of higher
availability values for corrosion inhibitor injection systems are outlined in Table 2, however
specialist advice should be sought before consideration is given to availabilities higher than
0.95. Providing guidance is sought and the necessary system requirements outlined in Table 2
are implemented, a maximum inhibitor availability of 98% can be considered in design,
however for all practical purposes the availability should be limited to 95%. Availabilities of
100% shall not be used for design or operating conditions but should be considered as a target.

Attached to this document is a tool which facilitates comparison of availabilities. Inputs for the
tool are as follows:
• Predicted or measured uninhibited corrosion rate (mm/yr)

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• Design corrosion allowance (mm)


• Original design life (yrs)
• Time remaining of original design life (yrs)
• Life extension required – beyond original design (yrs)
• Remaining corrosion allowance – average or minimum (mm)

The output provides an indication of the required inhibited corrosion rate and efficiency to
satisfy the total remaining design life (between 90-100% availability). Note: even if 100%
inhibitor efficiency were possible (it is not), the design life may not be achievable because of
availability. This is a function of the fact that the uninhibited corrosion rate is assumed for
periods when the chemical injection system is unavailable.

!
! "
#

Note: Use of remaining corrosion allowance in this tool enables its use for in-service situations
where some of the design (or originally available) corrosion allowance has been consumed (as
determined by inspection data and/or inferred from corrosion monitoring and/or from
application of the predicted corrosion rate and the period in service). If new build, set
remaining corrosion allowance to same as original corrosion allowance.

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Table 2. Requirements to assume inhibitor availability levels.

Requirement A = 0.95 A 0.95-0.97 A = 0.98


Detailed chemical Detailed chemical
Inhibitor demonstrated as suitable Detailed chemical selection
selection in conjunction selection in conjunction
for the application in conjunction with vendor
with vendor with vendor
Pump reliability at least Pump reliability at least Pump reliability at least
Inhibitor injection pumps equivalent to required equivalent to required equivalent to required
inhibitor availability inhibitor availability inhibitor availability
Availability of back-up inhibitor
pumps
Manual check that pump is Daily manual check
Daily manual check Daily manual check
operating Automated alarm

Injection pump capacity flexibility


(Turn-up and turn-down)

Pump planned maintenance In line with manufacturers recommendations

Complete inventory of Complete inventory of Complete inventory of


Inventory of pump spare parts spare parts for primary spare parts for primary spare parts for primary and
and secondary pump and secondary pump secondary pump
Inhibitor supply logistics Sufficient stock access to Sufficient stock access to
Sufficient stock access to
(Stock access does not necessarily mean guarantee 1 month guarantee 3 month
guarantee 6 month supply
stock on hand at site) supply supply
Daily manual check,
Automated with alarm to
Inhibitor tank levels Weekly Manual Check preferably automated with
control DCS
alarm
Automated metered chemical
Desirable Desirable Required
injection

Frequency of manual check on


Weekly Daily Daily
pump calibration
No flow alarm (zero differential
pressure across a critical
component, or in line flow meters)

Spare inhibitor injection location Desirable Required Required

Spare umbilical cores Desirable Required Required

Maximum cumulative time with no


inhibition per annum 18 days 4 days 0 – 4 days
(not necessarily in succession)

Shut in if inhibition system goes


Recommend shut-in if Recommend shut-in if Shut-in if event is 12-24
down for greater than a defined
event > 48 hours event 24-48 hours hours
period of time
Report on inhibitor used (or report
on compliance with key
Weekly Daily Daily
performance indicators) to
responsible corrosion engineer

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Liquid samples for analysis of


Monthly Biweekly May be required more often
inhibition

Requirement A = 0.95 A 0.95-0.98 A = 0.98

Persistency of chemical taken into


account

On line, continuous data


On line, continuous data
logging, fast response
logging, fast response
monitoring systems;
Typical choices for corrosion Minimum on line ER monitoring systems;
response time 1-24 hrs
monitoring equipment and system probes; response time 7 response time 1-24 hrs in-
recommend use of in-line
response times days line monitoring spools
monitoring spools
(particularly for sub-sea
(particularly for sub-sea
applications)
applications)

Comprehensive review of
Required Required Required
uninhibited events

Identify Operations Technician with


responsibility for the inhibition
injection system

Corrosion Engineering Involvement Weekly review Weekly review Daily review

Key Performance Indicators set for


Operations Technicians and
Corrosion Engineers

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6.6. Application technique


Inhibitors can be applied continuously or in batches.

Continuous inhibition is typically the preferred method of application and is more common for
the treatment of oil and gas systems. Continuous inhibition can be used to treat downhole and
topside equipment including; wellheads, separation facilities, flowlines, pipelines, etc.

Batch inhibition is commonly used for downhole treatments of low-medium producing oil and
gas wells in on-shore locations, i.e., on-shore North America. Batch treatment is also adopted
where technical or economic considerations preclude continuous injection. Other situations also
lend themselves to the application of batch treatment, i.e., high corrosivity and /or very sour
service where batch treatment can be used in addition to continuous injection or where there is a
risk of top of the line corrosion in stratified flow.

Batch inhibition is generally only used to handle specific problems such as:
1. protection of downhole tubing when continuous injection is difficult
2. protection against top of line corrosion in pipelines operating in stratified flow, when
inhibitor distribution to the top of the line cannot be ensured by other means
3. in combination with continuous inhibition for very severe or upset conditions
4. low flow, slow transient lines with low uninhibited corrosion rates

The persistency of batch inhibitors needs to be tested and verified to ensure the viability of
batch treatments.

6.7. Changing conditions (i.e., increasing water cut)


It is essential to actively manage corrosion inhibition. Once an inhibitor is selected and
deployed it shouldn’t be forgotten about. When there is no corrosion management strategy or a
badly defined strategy then the response to a corrosion problem is likely to be slow at best and
non-existent at worst.

Weight loss coupons provide a means of visual inspection of specimens exposed to the
corrosive/inhibited environment and can provide a means of determining pitting rates or swabs
for sessile bacteria. Copper ion displacement tests are commonly used for monitoring efficacy
of batch treatment programs. Monitoring by weight loss coupons however, only reveals an
adverse change in the process after it has happened. These warnings are retrospective and metal
loss has already occurred. It is obviously more efficient to pick up the process change as quickly
as possible and respond immediately.

Methods such as LPR (Linear Polarisation Resistance), which give an instantaneous measure of
the corrosion rate, can be used for this but only if the conditions are suitable (probe is exposed
to continuous aqueous phase). LPR probes however, are typically unsuitable for production
systems due to difficulties in ensuring consistent/complete immersion in an aqueous phase.

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Another type of corrosion sensor, based on electrical resistance, can be used with probes
intermittently exposed to non-aqueous phases. These probes integrate the metal loss that occurs
during a certain period of time, and can be designed to give an early warning of changing
corrosive conditions.

An alternative, or complementary approach is to continuously monitor a number of process


parameters (e.g. flow rate, water cut, temperature etc.) and be ready to alter the corrosion
inhibitor application appropriately. In general, it is recommended to design a corrosion
monitoring system based on the combination of different complementary techniques.

The process data can later be correlated with corrosion monitoring information in order to check
whether corrosion was adequately controlled. Corrosion inhibitor dose rate is clearly a crucial
parameter and should be checked daily. This apparently simple task is nevertheless prone to
error.

Table 3 lists the main process parameters affecting corrosion which should be measured and
acted upon whenever they change. Corrosion inhibitor type and concentration (i.e., dosage) are
the two controlling variables accessible to an operator. The inhibitor delivery rate is usually
matched to the maximum throughput in the process so as to give the desired concentration on
total fluids. Slight changes in the operating parameters can be compensated by changing the
corrosion inhibitor dosage. On the other hand, a significant change in operating conditions may
require reselection of the corrosion inhibitor type.

Table 3. Process parameters affecting corrosion rate and influencing CI injection.

Parameter Direction of Change Action

Flow Rates Adjust CI concentration to maintain concentration in water


↑ or ↓
(oil/water/gas) - may require higher shear resistant CI

May have to adjust CI injection or reselect product


Water Cut ↑ or ↓
depending on partitioning characteristics

↑ May need to increase CI injection or reselect CI


Temperature
↓ Possibility to reduce CI injection

↑ May need to increase CI injection or reselect CI


pCO2 and pH2S in
gas
↓ Possibility to reduce CI injection or reselect CI

↑ Possibility to reduce CI injection


pH
↓ May need to increase CI injection or reselect CI

Increase CI dosage or reselect corrosion inhibitor, reduce


Sand ↑
velocity, install sand screen
Increase/reselect CI
pO2 ↑ Remove O2 contamination source
Scavenge O2

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If the production throughput drops for a limited period such as a day, then the inhibitor delivery
will likely not be adjusted and the prevailing concentration will therefore rise. However, if the
throughput goes up then the inhibitor delivery rate must also go up to compensate. If the
throughput substantially increases, it may be necessary to reselect the inhibitor if it can not cope
with a substantially higher wall shear stress which may result from such increased flow.

Water cut is a key parameter. It affects how the inhibitor partitions between oil and water
phases. This is illustrated in section 6.3 and Annex K. The response to water cut changes will
depend on whether the inhibitor is preferentially oil or water soluble. When the water cut
increases then the concentration on total fluids of a preferentially water soluble inhibitor must
also increase in order to maintain the same concentration in the water phase (Table K-1). In
other words, the concentration with respect to the water phase must remain constant. A policy
could be in place such that the inhibitor concentration on total fluids is changed depending on
the water cut (e.g. 15 ppm for <5% water, 20 ppm for 5-10% water, 30 ppm for >10% water).
Ideally this link could be automated but would only be feasible if the water cut was
continuously monitored.

Regular pigging of pipelines to remove the water that can accumulate in low spots will help to
minimize corrosion and improve effectiveness of the corrosion inhibition program. This is
because even if the water starts off as fully inhibited it is possible for the inhibitor to gradually
degrade in a stagnant pool and to become ineffective. For pipelines with very low water cuts
(e.g., < ~ 0.1%) an elastomer cup type pig applied once a month may be sufficient. Higher water
cuts may require more frequent pigging, perhaps as often as once every few days. Removal of
the stagnant water by pigging will also help to reduce/minimise microbiological activity in the
pipeline such that it will minimise the chances of corrosive colonies becoming established on
the pipe wall and causing microbiologically influenced corrosion (MIC). Some operators take
the extra precaution of batch dosing with a biocide every month.

Regular pigging also helps to remove any settled solids/debris or scale flakes. Settled solids
could increase the local corrosion rates at the surface under the solids by a number of
mechanisms;
1. Provide locations for bacteria proliferation
2. Prevent access of CI to the covered surface
3. Galvanic effects (area under deposit at more negative potential than area immediately
adjacent to deposit)
4. Formation of concentration cells/gradients

Free oxygen is not normally encountered in oil and gas production streams. Any oxygen
originally present in the reservoir will have been consumed in oxidation reactions with the
hydrocarbons during the millions of years of storage at high temperature and pressure.
However, free oxygen can enter the production process inadvertently and then cause corrosion
problems because the corrosion inhibitors selected for CO2 and H2S environments are generally
not effective against O2 corrosion. In addition, the presence of oxygen can disrupt the ability of
many inhibitors to protect against CO2 and H2S corrosion.

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6.8. Secondary properties


In addition to efficiency testing of corrosion inhibitors, various other physical tests may be
important depending on the application (these are illustrated in Section 12.2).

In brief, the corrosion inhibitor should:


1. be compatible with the injection system materials of construction, chemical storage
tanks, pumps, valves, seals and umbilical materials (see Section 10.2). Many corrosion
inhibitors are corrosive in their neat form often resulting in a requirement for injection
equipment which will be in contact with the neat chemical to be constructed from
corrosion resistant materials.
2. be compatible with other production chemicals: scale inhibitors, oxygen scavengers,
biocides, hydrate control chemicals, wax or asphaltene inhibitors.
Some production chemicals which are known to have potential compatibility problems
with corrosion inhibitors include:
a. scale inhibitors – particularly products containing quaternary amines
b. aldehyde based biocides
c. demulsifiers
d. hydrate control chemicals (solvents and kinetic hydrate inhibitors)
e. concentrated brines

If changes are made to the application of production chemicals, such as significant dosage
changes or replacement with new/alternate products - an assessment of the effects of these
changes on the performance of the incumbent corrosion inhibitor should be conducted.

3. not cause downstream processing issues: i.e., separation problems, fouling/degradation


in condensate stabilization process, fouling/degradation/foaming in glycol regeneration
process, water disposal (environmental), adverse effects during crude refining.
a) Emulsion and foaming tendency should be evaluated using actual field fluids to
ensure that application of the CI has minimal effect on both. A key part of
inhibitor selection testing should involve assessment of the corrosion inhibitor
effect on downstream water quality. Although a general consideration with
regards water quality and demulsification, this is a particular concern for
offshore environments where produced water is discharged into the ocean and
oil-in-water specifications must be attained consistently. The effect of
increasing/decreasing inhibitor concentration on the emulsion tendency and
resultant water quality should be understood.

b) The main problems associated with condensate stabilization include: increased


water into the condensate (unacceptable for stabilizer specifications and
additional dewatering may be required); the inhibitor components may
thermally decompose in the stabilizer re-boiler, and lead to fouling and/or
contamination.

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c) In addition to this, if inhibitors are exposed to glycol re-boilers, the efficiency


and stability should be thoroughly examined.

4. be environmentally “benign”, as defined by relevant regulations (See section 6.9).


6.9. Environmental
The environmental classification of production chemicals, including corrosion inhibitors, is
often specific to each country or geographical area. The environmental impact of any chemical
supplied to oilfield installations is of critical importance and must be approved for use within
the regulation framework appropriate for the country.
6.9.1. US Region
See Annex L.
6.9.2. UK North Sea
See Annex M.
6.9.3. Other regions
Specific environmental regulations may apply in other geographical regions and the relevant
regulatory and government agencies should be contacted for further information. In some
regions, such as West Africa, South East Asia and Azerbaijan, local regulations have not yet
been implemented, and the operator is expected to follow a prudent operating practice to
minimize environmental damage. In the absence of a universally accepted approach, the use of
North Sea regulations in areas that lack local regulations is recommended.

7. Inhibitor Selection
The basic aim of corrosion inhibition is to provide an adequate level of corrosion control to satisfy the
required lifetime of an asset. CI selection and ultimate introduction to the field is often divided into a
series of activities which may form part of the front end engineering design (FEED) process or the
procurement stage of a project. For an existing facility the (re-)selection may form part of an audit of
the facility or in response to changing conditions.

7.1. Planning
The major issue associated with the use of carbon steel and inhibition is generally the technical
and financial risks associated with their use in comparison to the use of a corrosion resistant
alloy. Initial front end studies generally involve assessment of corrosivity along with associated
hydrodynamic issues in order to reach a corrosion control decision. Typically, initial front end
design and engineering studies do not involve inhibition evaluations or material testing. Often
this is undertaken much later in the process unless unique conditions exist indicating that a
standard approach may not be appropriate.

Variations of parameters likely to impact the system corrosivity over the life should be
considered and this information used to define the corrosivity of the environment, the expected
corrosion rates and hence the requirements of the inhibition system.

Typical information required to plan, select and design the inhibition program is summarised in
Table 4. Consideration should be given to the fact that these parameters will vary over the life
of the project. Supplementary useful information may include inspection reports,
microbiological analyses and pig debris analyses which can be used to determine the type
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(general, localized), rate, and nature of corrosion. Much of this information is used in operation
to define the corrosivity of the environment, the current condition of the equipment, the
expected corrosion rates and consequently the requirements on the inhibition system.

Typically, low CO2 pressures, low flow rates, and low temperatures result in low corrosion
rates. Exceptions can include under deposit corrosion and/or bacterial corrosion which are often
encountered in low velocity pipelines. The opposite is generally true for high temperatures, high
CO2 pressures and high flow velocities: inhibitor effectiveness can be lower, and lack of proper
inhibition has more serious consequences for the integrity of the equipment. This ultimately
means higher inhibitor concentrations, higher on-line availability of the injection system, and/or
high shear resistant inhibitors are needed.

Corrosion inhibitors can be less effective in old, corroded pipelines, and in pipelines containing
large amounts of debris (corrosion products, sand, scale). The inhibitor may be adsorbed on the
debris reducing the active concentration, or may have difficulty penetrating some
scales/deposits. The inhibitor dosage may need to be increased, or the pipeline may have to be
cleaned using a suitable technique to remove the scale and debris to prevent these problems.

Inhibition of severely corroded, pre-damaged pipelines where significant pitting may already
exist may require more specialised inhibitor testing and stringent application. In this case,
expert advice should be sought in development of an inhibitor treatment regime. Requirements
of the inhibition system should be clearly defined. This involves obtaining all information
necessary in order to design and operate the inhibition system.

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Table 4. Operating information required for inhibition program design.

Parameter Comments
Total Pressure Bar
o
Temperature Maximum or Temp range in C
Production Volumes
Gas mmscf/d
Oil mbd
Water mbd
Water Cut %
Gas Composition
CO2
H2S mol %
O2
Water Composition
Cations
Anions Concentration mg/L (ppm)
Bicarbonate
Organic Acids Distribution (C1-C5) and concentration
Hydrocarbon Phase
Oil/Condensate
Viscosity API or cP
Sand Production lbs/day
Equipment to be protected Downhole, topside, onshore, offshore
Age and Condition years, known anomalies and repairs
Remaining Corrosion Allowance mm
Estimated uninhibited corrosion rate mm/year
Environmental concerns Environmental regulations/restrictions
Pigging capabilities Can the line be cleaned/inspected
Remaining life of equipment years

7.2. Corrosion Assessments


A corrosion assessment at the concept stage of a new development is often aimed at
identification and clarification of the main corrosion issues likely to be faced. This involves
obtaining accurate and representative chemical analyses of fluid compositions. Key parameters
in order to estimate system pH, corrosivity and risk of pitting and cracking (for CRA’s) include
temperature, partial pressure of acid gas (CO2/H2S), bicarbonate, flow rates, and chloride
concentration, [Cl-].

Hydrodynamic studies are also conducted at this stage to assess flow patterns, pressure drops,
water hold-ups and water condensations rates, many of which are required as inputs for

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corrosivity prediction models. Specific concerns include the development of slug flow or sand
particle impact both of which can have a significant effect on inhibitor performance.

Many corrosion prediction models are available for the estimation of corrosion due to CO2.
Information regarding corrosion prediction methodologies can be found in “Corrosion
Prediction Modelling: A guide to the use of corrosion prediction models for risk assessment in
oil and gas production and transportation facilities” Sunbury Report Number ESR.96.ER.066
November 1997.

Use of field chemical analyses, hydrodynamic modelling, corrosion prediction, guidelines and
field experience to identify the main corrosion issues that are likely to be faced.

7.3. Risks of Inhibition


Use of corrosion inhibition to control corrosion presents risk. In general, inhibition risks may
be associated with the following:
1. Criteria adopted in prediction of maximum expected corrosion rate
2. Estimation of inhibitor efficiency required – and selection process employed to evaluate
this
3. Inhibitor availability requirements and ability of operationally being able to achieve the
required availability
4. Increase of temperature that may significantly affect the performance of the inhibitor
5. Risk of microbially influenced corrosion (inhibitors may not be effective mitigating
MIC) and should not be relied upon as a replacement to biocide treatments
6. Risk of erosion corrosion due to high velocities and presence of sand/solid material
7. Presence of low/no-flow regions, dead-legs, deposits which may prevent inhibitor
access
8. Presence of and ability to inhibit preferential weld corrosion
9. Age of the system (cleanliness, condition, presence of corrosion product)
10. Available corrosion allowance and required life
11. Access to repair, maintain or replace

Issues that require consideration include high temperatures, high CO2/H2S contents, high
salinity or unusual brines. Consideration must be given to inhibitor efficiency, inhibition
availability in addition to monitoring and inspection requirements.

7.4. Selection Process


Inhibitor selection is an important step in the development of an inhibition program. Selection
is more than testing, in-fact, testing makes up a small part of the selection process. Examples of
factors that should be addressed during an inhibitor selection process include the following:
1. Performance related parameters i.e.,
a. Inhibitor solubility
b. Inhibitor partitioning characteristics
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c. Inhibitor efficiency
d. Optimal concentration (concentration versus corrosion rate)
e. Inhibitor persistency or film stability
2. Compatibility related factors, i.e.,
a. Compatibility with production fluids
b. Compatibility with other production chemicals
c. Impact of chemical on downstream processing (i.e., demulsification/water
quality)
d. Material compatibility between the chemical and the injection equipment
components, i.e., metals, elastomers, pumps and pump materials, storage
containers etc.
e. Environmental impact of discharge/spill of chemical
3. Life-cycle economics (cost of inhibition)
4. Local availability of service and products from vendors
5. Commercial issues
6. Past experience

The ultimate objective is to select the best inhibitor product based on performance, cost,
technical merit, business requirements etc. Consideration should also be given to downstream
impact of chemical presence as well as compatibility issues (chemical-chemical and chemical-
material), as described in sections 6.8 and 8.6.

7.5. Inhibition System Design Considerations


Inhibition systems may be designed either by a project, the project’s main design contractor or
by the inhibitor supplier. In each case, clear functional specifications that reflect the
requirements and best industry practice should be written. Typically, the important factors
requiring consideration include;
1. Inhibition system reliability
To ensure high availability is achieved, spare injection pumps should be plumbed in parallel
with one being on standby. Appropriate redundancy and safeguards should be provided
particularly in high risk inhibition systems.
2. Operability and control of the injection system
Covers human factors i.e., clear design, easy access as well as automation of operations. Also
ensure that system is sized such that future requirements can be met, i.e., >50% excess capacity
as well as turn-down requirements for early field life when water production may be low.
3. Safety and environmental aspects
Covering toxicity, flammability and flash point of products and solvents. The disposal of waste
streams and unwanted product should be clear. In off-shore installations, the fate of the
inhibitor products in the environment (if discharged or spilled) should be considered. Suitable
personal protective equipment (PPE) and adequate ventilation should be provided for those
dealing with chemicals.
4. Monitoring inhibition effectiveness
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Data collection and storage requirements should be defined and consideration given to
automated data collection and analysis techniques if appropriate.

Injection systems typically comprise the following components:


1. Storage tank
2. Mixing tank (if inhibitor is to be diluted)
3. Injection pumps and connections
4. Injection points (Tubes/Quills/Valves)
5. Control equipment and instrumentation
6. Secondary containment to confine leaks and spills

In addition to design of the injection system and secondary containment system, consideration
should also be given to identification of monitoring requirements as well as selection of the
monitoring methodologies, as described in GP 06-70 Guidance on Practise for Corrosion
Monitoring.

8. Inhibitor Injection
Inhibitor injection methods often differ according to the requirements of each application. Some
factors influencing the choice of a system include:
1. injection location, i.e., downhole, surface, onshore/offshore
2. nature of the produced fluids, i.e., oil, gas, multiphase
3. expected corrosivity
4. downstream processing requirements, i.e., separation, hydrocarbon processing
5. accessibility

8.1. Inhibitor Injection into the Process Stream


Many operators do not use corrosion inhibitor to protect process equipment. This is either
because corrosion resistant alloys are in place, coatings are used or carry over of inhibitor
injected upstream is relied upon.

The industry rule of thumb is to inject the corrosion inhibitor as far upstream as possible. This
should enable the inhibitor to reach all vulnerable areas, however it can be difficult to deliver
inhibitor effectively into stagnant bypass or drain line piping. Regardless of the injection point
location, it is very important to ensure that the inhibitor is well mixed into the process stream.
This is often achieved by injection of the chemical immediately upstream of an area of high
turbulence (i.e., a bend, valve or pump) or into a turbulent process stream. The greater the
turbulence, the shorter the required distance; in general, a mixing distance of 50 to 100 pipe
diameters will be required to achieve good mixing (90 to 99 %) in a pipeline, while 10-20
diameters is more likely for injection into truly turbulent flow. In high risk applications, this
mixing length may actually be of CRA construction.

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An injection “quill” or a “nozzle” should be used to inject the chemical at the centre of the
pipeline; this arrangement is schematically shown in Figure 2. Caution: some neat corrosion
inhibitors are corrosive and could corrode the pipe wall if left in contact with the pipe wall
undiluted by the production stream.

Figure 2. Location of injection quills in pipeline.

If pigging is to be performed in a line, a tube which is retractable or which is flush to the


pipewall is required. A mark or scale on the side of the tube helps to ensure correct positioning;
quills have sometimes been pushed so far into a pipe that they contact the opposite wall. Local
turbulence will always improve the dispersion efficiency and it is particularly necessary for
flush injection. In a laminar or stratified flow system the quill tip should be placed directly in
the water phase.

Atomising quills can be used to achieve good dispersion in gas systems or laminar liquid
systems. The higher the differential pressure across the tip then the smaller the dispersed
droplets. Typical quills for liquid and gas streams have a quarter inch internal diameter. In some
gas systems where the inhibitor is diluted into a large volume of methanol or glycol (i.e. hydrate
inhibitor) before injection then a larger delivery tube may be necessary and the injection point
becomes more like a “tee”. As a rule of thumb, chemical inhibitor applied via an atomiser into
a gas stream will revert back to liquid flow after approximately 30-60 metres.

8.2. Inhibitor Dilution


Many commercial inhibitor products are sold in a highly concentrated form and may require
dilution on-site before application.
1. Oil pipelines are normally dosed with as-received corrosion inhibitors.
2. Gas condensate lines often employ inhibitor diluted in methanol, or another alcohol or
glycol (e.g., monoethylene glycol - MEG) based hydrate inhibitor/suppressant.
Concentrations typically range from 0.5% up to 5 or 10% in methanol when hydrate
treatment is required.
3. Dry gas lines, where the product is dew point adjusted and glycol or molecular sieve
dried, will not normally be inhibited.
4. Downhole injection typically employs 1% - 20% corrosion inhibitor diluted in crude oil,
diesel or water. The dilution reduces the total amount of corrosion inhibitor which is
stored in the annulus.

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5. Application of corrosion inhibitors in early field life when water cuts are low potentially
resulting in low volumes of chemical being required may dictate dilution of the
chemical in order to accommodate the minimum pumping capacity of the injection
pumps.
6. Batch chemicals are diluted in a locally available solvent, as large volumes are needed.
The diluent will typically be crude oil, stabilized condensate, diesel or treated water,
with 1:4 v/v inhibitor/diluent between pigs for pipelines.
7. Inhibitors may be concentrated for transportation in order to save on costs or to
introduce local labour and materials into a product. This may then require on-site or
local dilution of the product with appropriate solvents.

Whenever inhibitors are required to be diluted, there must be adequate control over the quality
of the diluent used and proper supervision of the dilution process.

9. Inhibitor Dosage Rates


9.1. Continuous injection
The initial inhibitor dosage rates can be approximated from laboratory tests, field tests, supplier
recommendations, or past experience. Such a dosage rate should be sufficient to ensure the
integrity of the asset until sufficient monitoring data becomes available to assess the actual
performance of the inhibition system.

It is recommended that during the early stages of commissioning new pipelines/equipment or


after process up-sets/shut-downs the corrosion inhibitor dosage be applied above that
determined to be necessary from testing (potentially 2-3 times the typical concentration
requirement). This increased chemical concentration is intended to aid with the early
establishment and formation of protective inhibitor films and should only be required for
relatively short periods of time, i.e., 24-48 hours. Optimization of the dosage can only be
accomplished during operation, based on monitoring and inspection results. For a rough
estimate of inhibitor costs and pumping/tank requirements, and in the absence of relevant
laboratory or field data, the following guidelines are suggested:

a. For gas production: 10 to 20 litres per million m3 (0.5-1.0 pt/mmscf) of gas, or 100 ppm
based on total water, whichever is greater. Both oil and water-soluble products may be
adequate, depending on flow conditions.

b. For oil production: 20 to 100 ppm based on total water - this figure assumes high (better
than 4:1) water/oil partition. The partition coefficient needs to be considered and
possibly measured under realistic conditions.

In addition, more detailed generic recommendations are provided in table 5. Please note that
these values are to be considered a preliminary guide and not used to decide or recommend a
field application dosage but merely to serve as an example of the likely concentrations required.
Application concentrations need to be validated for specific cases.

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A typical approach is to determine an approximate dosage rate from partitioning tests and other
laboratory tests and start with this in the field. The concentration can then be gradually reduced
or increased to an optimum value using field monitoring.

Table 5. Typical water phase concentrations required.


o
Temperature ( C)
Mixture Velocity (m/s) < 60 60 - 120 > 120
<5 20-50 50-100 > 200
5 - 20 100-150 100-200 > 299
> 20 > 200 > 200 > 300
* Inhibition is not recommended for applications where mixture velocity is > 20 m/s.
Extensive product development, qualification, testing and performance monitoring
required.

The values provided in Table 5 are merely illustrations of typical dose rates for various cases
and shall not be used as definitive recommendations.

The previous section on partitioning, solubility and Annex K discuss the principles of solubility
and partitioning. Table 6 illustrates an approximate relationship between these concepts and the
typical dosage values in Table 5. If corrosion inhibitors are considered as falling into one of
four categories as outlined in Section 6.2 and having partition coefficients falling approximately
into the following ranges;
1. Water Soluble (P ~ 10 - 100)
2. Water Soluble/Oil Dispersible (P ~ 1 - 2)
3. Oil Soluble/Water Dispersible (P ~ 0.5 - 1)
4. Oil Soluble (P ~ 0.01 - 0.1)

For example - in order to achieve a concentration of 25 ppm in the water phase, Table 6
illustrates the approximate concentrations required (based on total volume) over a range of
water cuts as a function of the type of chemical applied.

Table 6. Total volume concentrations required to achieve 25 ppm in water phase.


Oil Soluble Water Soluble
Water Cut Oil Soluble Water Soluble
Water Dispersible Oil Dispersible
< 0.5 250-2500 25-50 13-25 0.4-3*
0.5-20 250-2500 25-50 15-25 5-7*
20-40 225-2000 25-45 18-25 10-12
40-60 175-1500 25-40 20-25 15-17

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60-80 125-1000 25-35 23-25 20-21


80-95 75-500 25-30 25 25
95+ 40-150 25-27 25 25
* Minimum of 10 ppm based on total volume to be injected

If 10 ppm is required in the water phase, the values in Table 6 could be multiplied by 10/25
similarly if 50 ppm were required in the water phase, the values in Table 6 could be multiplied
by 50/25 to give an indication of the effect of solubility/partitioning on the dosage required
based on total volume.

If water soluble of highly water partitioning chemicals were to be applied in a low water cut
system, i.e., 0.5% or less it could be envisaged that a fraction of a part per million may
theoretically be required (based on total volume) to result in sufficient chemical concentration in
the water phase. In cases where the water cut is demonstrated to be 0.5% or lower, a minimum
concentration of 10 ppm based on total volume shall be applied. For most cases, this should
ensure that the bulk water concentration is sufficient to afford adequate inhibition, as well as
introducing sufficient numbers of inhibitor ‘molecules’ to the system to provide minimum
surface coverage. In case of deviation from this above, the risks of not applying this level of
inhibition must be demonstrated to be acceptable and shall be approved by the Engineering
Authority.

Although this could potentially result in high concentrations of inhibitor in the water phase
(which in other circumstances may adversely affect water separation), it is unlikely that attempts
would be made to separate oil and water at such water levels.

In translating a laboratory/recommended dosage to field application, an additional 20% should


be considered to account for shortfalls and problems often associated with physically pumping
the chemical. In addition to this, a maximum (such as dosage + 20% + 10 ppm) may be
appropriate to provide operations with a practical range of dosage concentrations within which
to work.

9.2. Batch Treatment


Batch volumes for downhole treatment are often calculated as the volume required to
completely displace all fluids in the tubing. An inhibitor concentration of between 5 to 20 %, in
an appropriate solvent (water, crude, stabilized condensate, or diesel) is commonly used. Care
should be taken to prevent inhibitor entering the reservoir, which may cause formation damage.
For sucker rod pumped wells, a batch consisting of 1 to 2 barrels of corrosion inhibitor, mixed
with produced brine or crude, is injected down the annulus of the well (to by-pass the pump
check valve) and circulated for a period of 1 to 2 hours between tubing and annulus. More
details can be found in the NACE recommended practice RP 0195-95, “Recommended Practice
for Corrosion Control of Sucker Rods by Chemical Treatment”.

Batch inhibition of flowlines is sometimes used in conjunction with continuous injection when
the potential corrosivity is extremely high, for example in highly sour or high temperature
conditions, or when stratified flow conditions prevail that prevents the inhibitor from reaching

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the top of the line. Batch inhibitor persistency increases with contact time, although a
quantitative relationship between these two parameters has not been developed.

9.2.1. Batch inhibitor volume calculations for pipelines


The volume of a batch treatment can be estimated based on the methodology outlined in Annex
N.
10. Inhibitor Injection Pumps
Inhibitor injection can be achieved via numerous means. These can include pressure fed or
gravity fed injection directly from a storage vessel, positive displacement pumps (metering
pumps) and flow proportional injection where the produced fluid flow rate controls the injection
rate.

The most common injection systems involve the use of metering or positive displacement
pumps. The inhibitor injection rate is manually controlled and is independent of production
rates. Pump capacities range from 0.1 gallons per hour (gph) to 2500 gph depending on the
pump head installed. Some pumps are supplied with multiple pump heads to expand the
pumping capacity range. Discharge pressure capabilities range from 20 - 4000 psi, but always
in inverse ratio to the gph capacity (i.e., the higher the pressure capability, the lower the volume
capacity).

The criticality of the inhibitor availability will determine pump selection in terms of quality,
feed range, mode of control, failure alarms and installation of standby units.

Corrosion inhibitor pumps (where installed) should be considered critical for continuous
operation, and designed with full stand-by redundancy. Pump capacities required for changing
conditions and life of field need to be considered during design.

10.1. Inhibitor Pumping Problems


The following separates various pumping problems into those relating to the corrosion inhibitor
product and those relating to the injection pump. First, those relating to the corrosion inhibitor:
1. Inhibitor viscosity - The viscosity of any chemical will rise when it is cooled in sub-sea
umbilicals, or when it is used in cold climates. Viscosity measurements should be
carried out at temperatures appropriate to how and where the inhibitor is to be usedand
it should be demonstrated that the chemical is fit for purpose.
2. Compatibility of inhibitor with pump materials – The neat inhibitor must be compatible
with metals and pump seals with which it will contact.
3. Injection line blockages – Often occurs as a result of poor cleaning when chemicals are
changed over, or contamination in chemicals. This can also occur if products are
inadequately winterised (or cold-weather proof) and they precipitate or solidify in the
injection tubing.
4. Inhibitor storage tank empty - The storage tank must be regularly checked to ensure
timely reordering of inhibitor supplies. Situations where the dose rate are reduced in
order to conserve stocks until the next supply arrives should not occur.

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5. Abrasive particles in inhibitor - If fine solids such as blasting sand find their way into
the inhibitor storage tank pump seals can be damaged/abraded and cause leaks.

Secondly, there are some problems relating to the pump and other hardware,
1. Incorrect dose rate – Often happens when the pump is not calibrated frequently, or is
improperly controlled. Significant errors are also likely when tank level readings or
calibration cylinders at the pump suction are used in order to calculate the dose rate.
2. Incorrectly sized pump - This can make it difficult to dose at the recommended rate. It
may be necessary to reformulate the corrosion inhibitor - either diluting or
concentrating the active components - in order to accommodate the available pumping
capacity. Incorrect sizing may be a particular problem when the dose rate has to be
changed frequently to match variations in process conditions (e.g. changing water cut).
3. Air locks - Certain types of pump are prone to air locks.
4. Poor design/installation of delivery system - One pump may be delivering into several
lines or wellheads all at different pressures. The high pressure lines may not receive any
inhibitor. Such manifolded delivery systems are more difficult to check than dedicated
pumps unless special valves such as “Sko-Flo” are used. These maintain a constant flow
rate despite varying differential pressure.
5. Downhole injection - Injection can be particularly troublesome downhole. Injection via
the lift gas may lead to gunking as the solvents evaporate, and chemical injection valves
operating on annulus pressure may actually dose batch-wise rather than continuously.

It is clear that many pump problems are avoidable if the pumps are designed, maintained and
operated correctly. It is important to have written procedures covering calibration, operation and
maintenance. Operating and supervisory personnel alike need to be made aware of the
importance of dosing on a regular day-to-day basis.

10.2. Compatibility of Inhibitor with Injection System Materials


Corrosion inhibitor products should be compatible with the inhibition system materials of
construction. The injection system includes storage tanks, pumps, valves, delivery lines, seals,
gaskets, and flexible hoses. Concentrated (as received or diluted to injection specifications
with water, condensate, diesel, etc.) inhibitors may be corrosive to carbon steel and the
corrosivity may be due both to the active ingredients or additives in the inhibitor formulation, as
well as oxygen dissolved in the solution.

Stainless steel (AISI 316 or similar) should normally be used, in particular where exposure to air
and moisture is unavoidable. Copper and copper alloys shall not be used.

Non-metallic seals and gaskets, such as Viton, polyethylene, neoprene, and butyl rubber, may be
attacked (swell or lose mechanical properties) in contact with amines and solvents in the
inhibitor formulation. Alternative materials that are more resistant to attack include: PTFE
(Teflon), Buna-N, polypropylene, and ethylene-propylene rubber and perfluoroelastomers such
as Chemraz™ and Kalrez™. Nylon-11, which is sometimes used in umbilical and flexible lines,
can be permeable to and attacked by methanol. The product MSDS should contain information
regarding unsuitable or incompatible materials.

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11. Applicability, Limitations and Performance of Inhibitors


Table 7 provides guidance on application of corrosion inhibitors to various locations within a
production system.

Further information for each treatment method relevant to various system components, i.e.,
applicability, limitations, and efficacy is available in the relevant annexes.

12. Testing of Inhibitors


12.1. Performance testing
Table 8 outlines recommended performance testing for corrosion inhibitor products classified
by treatment method.

Laboratory tests are used in order to identify the best candidate under a specific set of test
conditions and criteria, as well as to estimate an initial inhibitor dosage for an new application.
Laboratory tests are not adequate for optimising chemical dosage rates. Simply, basic exposure
tests are conducted at appropriate conditions of temperature, pressure and fluid composition, to
identify the most suitable products. These are then tested under more severe conditions,
including detailed partitioning tests, high flow tests, persistency tests, etc. Other production
chemicals may also be included in final qualification tests to assess the compatibility of
inhibitors with other chemicals that will be applied in the system.

Wheel/wheel-box weight loss testing is not an appropriate test methodology for the
selection of corrosion inhibitor products for field application.

12.2. Secondary properties


Table 9 outlines recommended secondary property testing to be considered for corrosion
inhibitor products classified by application.

13. Combination Products

A possible method of avoiding compatibility problems between different products is via the use
of combination products. Many combination products are simply mixtures of compatible,
individual products. Perhaps the most common combined products are those that involve
corrosion inhibitors and scale inhibitors. Combined products have the advantage of enabling
one storage tank, one pump, and one injection line to be used for both scale and corrosion
control.

This is especially attractive for minimum facilities installations. A significant disadvantage of


this approach is that there is a loss of flexibility. If the combined product is being dosed at a
particular rate and a sudden need to increase the concentration of say scale inhibitor arises, this
can only be achieved by also injecting more corrosion inhibitor - which may not be required.

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This may have an adverse effect on water quality not to mention the added cost of injecting
unnecessary chemical.

The product could be reformulated to meet the new balance between scale and corrosion
inhibition (e.g. 2:1 v/v → 4:1 v/v scale inhibitor : corrosion inhibitor) but realistically this is
likely to take quite some time.

Expert advice should be sought before selecting, testing or applying combination products.

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Table 7. Inhibitor application guide.

Relevant
System Relevant Batch
Continuous
Requiring Treatment Annex Annex Comments/Considerations/Further information
Treatment
Treatment Methods
Methods
Annulus
Annulus Batch A F
Continuous
Tubing Treatment of rod-pumped oil wells similar to Annulus Batch treatment which typically
B Via Gas Lift G
Displacement involves high concentration of inhibitor circulated around well for a given time.
Downhole Tubing Recirculated around annulus to tubing - requires access to annulus.
Inhibitor Squeeze C Capillary H
May be applicable to other artificial lift wells, i.e., ESP
Solid Inhibitor Chemicals must be compatible with elastomers/seals.
Sticks or D
Granular
Downstream carry Continuous application recommended for multiphase systems.
over from Transient flow behaviour makes inhibitor transport, partitioning and dilution effects
Pipeline Batch E F important.
Annulus
Continuous Pipelines operating under annular, mist or dispersed flow regimes may be inhibited more
Downstream carry easily due to increased fluid mixing and contact with pipe wall.
Multiphase Well over from Effective inhibition may be more difficult under stratified flow due to low spots or areas of
or Flow lines G water stagnation or water condensing at the top of the line.
injection via Gas
Lift Oil dispersible/water soluble or oil soluble/water dispersible products at low water cut <5-
10%.
Capillary or For greater than 15-20%, water soluble corrosion inhibitor recommended.
H Often lower temperature & pressure than downhole, but higher velocities can be
Injection Tubing
experienced (film stability)

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Relevant
System Relevant Batch
Continuous
Requiring Treatment Annex Annex Comments/Considerations/Further information
Treatment
Treatment Methods
Methods

Downstream carry
Inhibition applicable to both sweet and sour gas systems.
over from
Pipeline Batch E F pH stabilisation applicable to sweet only (pH2S < 5 mbars).
Annulus
Supplementary batch treat may be required if highly corrosive (presence of sulfur).
Continuous
Increasing chloride, increasing temperature can impair inhibitor performance.
Presence of methanol/glycol can affect inhibitor performance.
Downstream carry H2S/CO2 contents and ratios can affect performance.
over from TOL corrosion specific concern to some wet gas pipelines - commonly mitigated by
G
injection via Gas batch treatment supplementing continuous treatment or by use of special pigs (V-Jet™)
Lift which deliver inhibited liquids from bottom to the top of the line.
Gas Condensate
If water content of gas is greater than >7lbs/mmscf and liquid water present at injection
Pipelines or
Capillary or point a suitable water soluble corrosion inhibitor can be applied. If no liquid water
Wet Gas H
Injection Tubing present at injection point a product containing water partitioning actives carried in a
Pipelines o
hydrocarbon carrier solvent can be applied but if temperature is >150 C, attention should
be paid to prevent solvent stripping when the product is injected.
If water content of the gas is < 7lbs/mmscf and liquid hydrocarbon present at injection
point, a hydrocarbon soluble/dispersible product containing water partitioning actives is
recommended. If no liquid hydrocarbon present at injection point the same type of
product described for no liquid water at injection point could be used (with same
pH Stabilisation K temperature limitation).
Emulsion/separation problems common due to over-injection with low quantities of
water.

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Relevant
System Relevant Batch
Continuous
Requiring Treatment Annex Annex Comments/Considerations/Further information
Treatment
Treatment Methods
Methods

Treated by presence of corrosion inhibitor continuously injected upstream (well head or


manifold).
Specific chemicals are applied purely for protection of the risers, the product and
concentration applied to flow-lines should be sufficient to mitigate corrosion in the risers.
Risers present exceptional case of terrain effects due to inclination and directional
changes.
Risers Umbilical H
Higher flow velocities compared to horizontal pipelines that may remove protective or
inhibitor films.
Flow regime prediction important - high velocities and high shear; slugging.
May be very high uninhibited corrosion rates.
Monitoring/inspection difficulties.
Is inhibition suitable? Material solution?
Some operations rely on carry-over of corrosion inhibitor injected further up-stream, i.e,
well-heads, manifolds or separators.
This is an acceptable practise provided it is demonstrated there is consistently sufficient
chemical present in the export fluids to afford adequate corrosion inhibition.
Downstream carry Other issues can arise in export/transmission lines i.e., low velocities resulting in
over from Capillary, accumulation of water at low spots/elevation changes, settling of solids/debris,
Export Pipelines H
Tubing or Umbilical deposition of wax, bacteria growth etc.
Injection Many can be addressed simply by incorporation of maintenance pigging in the corrosion
control program.
Excursions of BS&W specifications may require immediate sphering/pigging.
Supplemental injection into partially stabilised export pipelines should be considered if a
corrosive environment could potentially exist.

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Relevant
System Relevant Batch
Continuous
Requiring Treatment Annex Annex Comments/Considerations/Further information
Treatment
Treatment Methods
Methods

Corrosion in gas compressor systems is caused by condensation of water saturated with


Capillary or acid gases CO2 and/or H2S in cooler/scrubber.
H
Injection Tubing Common solution is to apply an organic inhibitor and/or neutraliser chemical. Inhibitor
Intercompression can be continuously applied neat, via an atomiser upstream of the cooler. Often,
Stages products with anti-fouling properties are required.
If volatile, neutralizing amines are used they should be chosen and dosed at a level to
pH Stabilisation K buffer the pH to an acceptable level.
Monitor via water sampling at knock-out vessels.

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Table 8. Performance testing requirements for Batch Treatment Corrosion Inhibitors

Recirculating or Once Through


3. Expose in Uninhibited Soln.

Rotating Cylinder Autoclave


2. Expose to Inhibited Soln.

Preferential Weld Corrosion


(Could use any technique)

Rotating Cage Autoclave

Jet Impingement Test


Rotating Cylinder
Persistency Test
Wheel Box Test

Flow Loop Test


Glass Cell Test

Pre-partitioned

Inhibition Test
1. Precorrode

Low Pressure
Bubble Test

Bubble Test
Traditional Batch
Treatment √ N/A N/A
Methods
BATCH

Solid Inhibitor
NOT ACCEPTABLE

√ √ √ √
in Rat Hole*

Continuous
injection of
CONTINUOUS

√ √ √ √ √
corrosion
inhibitor
Application of pH
stabiliser (Gas
N/A √ N/A √ √ N/A
Condensate or
Wet Gas systems)
Plant
(Inter

Compression
Stages)
√ Recommended minimum testing
Additional testing that may provide useful performance information
N/A Testing may not be applicable (e.g., products may not partition to water in glass cell test)
* Considered semi-continuous type application

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Table 9. Secondary Property testing requirements for Batch Treatment Corrosion Inhibitors.

Chemical-chemical Compatibility

Hydrate formation tendency at


Solvent Stripping or Fouling

Low temperature stability

Compatibility with Glycol


Formation Compatibility

Material Compatibilities

(Gross & Performance)

Umbilical Pumpability
Downhole Conditions

Regeneration System
(low temp. viscosity)
Compatible Diluents
Emulsion Tendency

Particulates in fluid
Foaming Tendency

(Thermal Stability)
Partitioning Test

Injection Point
Dispersibility
Solubility

Traditional
Batch Treatment √ √ √ √ N/A √ √ √ N/A √ N/A N/A N/A N/A
BATCH

Methods
CI squeeze √ √ √ √ √ √ N/A √ √ √ N/A N/A N/A N/A

Solid Inhibitor in
√ √ √ √ √ √ N/A N/A N/A √ N/A N/A N/A N/A
rat hole

Annulus
√ √ √ √ √ √ √ N/A √ √ N/A N/A
CONTINUOUS

Continuous
Gas lift √ √ √ √ √ √ √ N/A √ √ N/A N/A
Capillary +
√ √ √ √ √ N/A √ √ √ √ √ √
Umbilical

pH Stabilisation N/A N/A N/A N/A N/A N/A N/A N/A √ √ N/A √
Plant
√ √ √ N/A √ N/A √ √ N/A N/A N/A
(Inter

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Compression)

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14. Field trials/testing


It is difficult to prescribe a universal protocol for field testing of corrosion inhibitors.
Consideration should be given to each field trial as many factors will vary from location to
location, i.e., location and ability to inject chemical, location and ability to monitor chemical
performance, allowable duration of the trial, type of system, speed and response of corrosion
monitoring equipment used to monitor trial etc. All participants in the field trial should
contribute to the development of the trial program.

Some general recommendations can however be provided which can be adapted to site specific
applications.

1. Clear and defined objectives should be established jointly with all stakeholders
(including the inhibitor supplier, the operators, corrosion engineer, production chemists,
asset owner etc.). In its simplest form, the objective of the field trial and tests is to
demonstrate the performance of a single chemical in a specific application.

2. A detailed and robust corrosion rate monitoring plan should be developed. Other
process/operating parameters should also be recorded before, during and after the
chemical trial, i.e., inhibitor injection rates, production rates, inhibitor residuals, water
chemistry, observed compatibility problems such as foaming or emulsions.

3. The duration of the test will often depend on specific conditions, but an extended test
should be in the order of 3 to 6 months to allow proper measurement of low corrosion
rates. Ideally, corrosion rates should be monitored before, during and after the actual
test, to determine the product performance.

4. Roles and responsibilities should be clearly assigned to all participants. Participants in


the field test include: chemical suppliers, operators, corrosion engineer, production
chemist, and possibly production technologist and facilities engineer.

5. Test data should be evaluated critically and promptly. This should be done jointly by
the corrosion engineer, production chemist, and the supplier’s experts and the results
should be discussed extensively with the other stakeholders.

15. Performance Management/Measurement


In simple terms, performance refers to the effectiveness of a specific corrosion inhibitor and is
derived from comparison of the (measured) inhibited corrosion rates with the (measured,
calculated or estimated) uninhibited corrosion rates.

Therefore, it is imperative to understand the corrosivity of the system from corrosion monitoring
data collected from isolated points (corrosion probes) or from an overall analysis of the fluids
(iron counts, inhibitor residuals). Various techniques are available for measuring chemical
residuals dependant on the level of detail required. Spectrophotometric techniques provide a
rapid measure of the total product based upon components that respond to the technique.
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Chemical suppliers should be able to recommend the most appropriate spectrophotometric
technique for a particular product. More sophisticated techniques such as those involving mass
spectrometry (Electrospray mass spectrometry or ES-MS) can provide detail and quantification
at the component level in both the water and oil phase, however these techniques are more time
consuming and not applicable for on-site analysis.

This analysis should be performed by an experienced and proficient corrosion engineer, usually
belonging to the OU, with participation of the supplier. As a minimum, analysis of the
performance of the inhibition system should include the following elements:

1. inhibited corrosion rates - obtained via monitoring – correlation of


monitoring/operations data with predictions (corrosion rates, foaming, emulsification,
water quality)
2. inhibitor usage which can most easily be obtained from injection rates and purchasing
records
3. review of inspection data/results
4. impact (adverse or beneficial) of inhibition on operations, i.e., separation problems
5. mechanical performance and maintenance costs of the system (pumps, valves, probes)
which can be obtained from obtained from operators and maintenance records
6. changes in production conditions that may warrant the inhibition program to be
modified, i.e., increase in dosage, change in product etc.
7. system on-line availability obtained from monitoring

A set of performance measures would be developed to monitor the effectiveness of the


corrosion control program as part of the corrosion management strategy.

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Annex A - Annulus Batch

Applicability - Where it works, requirements and conditions to make it work

Can be used for packerless (open hole) completions as long as there is access to the annulus. Is applicable to artificial
lift wells, i.e., rod-pumped and ESP. Can be applied to gas wells however solvent stability at temperature must be
considered. Application technique not commonly used in BP.
If there is a high liquid level in annulus, typically a high concentration of inhibitor in diluent is circulated around the
well for a given time period. This application relies of deposition of an inhibitor film on the surface and on-going
protection is afforded by the persistency of the chemical.
If there is a low liquid level in the annulus, a batch of concentrated chemical in diluent can be deposited into the
annulus. Inhibition is afforded by continual diffusion of the inhibitor chemical through the liquid column and into the
production fluids. This is akin to a semi-continuous treatment.

Inhibitor Type - General description of the most appropriate inhibitor

Oil soluble chemicals with good persistency (such that film life typically lasts between 1-4 weeks) are utilised. Higher
water dispersibility and/or surfactancy may be required depending on the application technique.
Emulsified products can also be used. These can either be oil or water continuous meta-stable emulsions. Generally the
emulsions are generated in-situ using a treater truck and then pumped into the annulus. This requires a truck fitted with
pumps etc. but has the benefit of being able to adjust the emulsion parameters (if required) on a well by well basis. The
concept is that the emulsion becomes situated primarily at the interface of the oil and water layers since its density is
usually between that of crude oil and water - hence acting as a reservoir of chemical something between batching and
continuous treatment.

Efficacy – Factors critical to success

Factors influencing success of treatment include:


1. Circulation time
2. Batch frequency
3. Impact of well foaming additives
4. Film tenacity (persistency, film life)
5. Higher flows diminish film life
6. Higher water cuts diminish film life
7. Higher temperatures diminish film life
8. Presence of solids diminish film life

Testing

See Tables 8 and 9.

Practical application issues

♦ No inhibition below point inhibitor contacts production fluids.

Performance Management – Monitoring options and corrective actions

Monitoring:
♦ Number of treatments versus plan
♦ Inspection/caliper survey or other suitable techniques
Corrective Action:
1. Increase frequency
2. Increase batch size
3. Consider continuous injection

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Annex B - Tubing Displacement

Applicability - Where it works, requirements and conditions to make it work

If the well is a closed completion, i.e., the tubing is set on a packer, the most practical batch inhibitor treatment method
would be tubing displacement. Application relies of deposition of inhibitor film on the surface and on-going protection
is afforded by the persistency of the chemical and is typically applicable to lower production rate wells. Can also be
applied to gas wells.
Tubing displacement is accomplished by pumping a slug of inhibitor, diluted in diesel oil, crude/condensate, or water,
into the well through the crown valve or gauge fitting with a pump. This should be followed by sufficient displacement
fluid to move the inhibitor slug to the bottom of the tubing. The well is then returned to production.
The treatment interval is function of the production characteristics and the inhibitor performance, and must be
optimized for each well. Treatment intervals of one-week or less are likely uneconomical. If this is because of high
producing rate or severe corrosivity, either a different inhibitor or alternative control method such as CRA tubulars
should be considered. Intervals of longer than one month are excessive - the program is likely ineffective or not
necessary.

Inhibitor Type - General description of the most appropriate inhibitor

Oil soluble chemicals with good persistency are typically utilised. Higher water dispersibility and/or surfactancy may
be required depending on the application technique. Emulsified products can also be used.

Efficacy – Factors critical to success

Factors influencing success of treatment include:


1. Contact time
2. Batch frequency
3. Impact of well foaming additives
4. Film tenacity (persistency, film life)
5. Higher flows diminish film life
6. Higher water cuts diminish film life
7. Higher temperatures diminish film life
8. Presence of solids diminish film life

Testing

See Tables 8 and 9.

Field Application – Practical application issues

♦ Generally used for closed completions.


♦ Due to high pressure and fluid column in flowing oil wells, may be difficult to pump required amount of
fluid to displace to bottom - pump selection should provide both volume and pressure capability.
♦ Care should be exercised that wells are not fractured during tubing displacement treatments and that
inhibitor is not displaced into the formation.
♦ No inhibition below point inhibitor contacts tubing.
♦ Lost production during treatment.
♦ Initial flow back of chemical may cause plant upsets.

Performance Management – Monitoring options and corrective actions

As per annulus batch.

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Annex C - Corrosion Inhibitor Squeeze

Applicability - Where it works, requirements and conditions to make it work

Squeeze treating is potentially applicable to any well with sufficiently porous strata. It essentially results in continuous
treatment as the inhibitor is slowly released with the produced fluids. A primary advantage of this method is that several
wells could be successfully treated which are either packed off or have high fluid levels and are difficult to treat by
other methods. This method is analogous to scale inhibitor squeezing.

Corrosion inhibitor application by squeeze treatment not used in BP. If this were to be considered,
specialist advice should be sought before application.

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Annex D - Solid Corrosion Inhibitors (Sticks or Encapsulated)

Applicability - Where it works, requirements and conditions to make it work

Likely more suited to oil or gas wells with lower water production. Solid sticks are placed in well rat hole and dissolve
with time into produced fluids returning measurable chemical residuals over time - analogous to a squeeze.
Encapsulated products are designed to offer an extended release application method to the annulus batch treatment
approach outlined in Annex A. Chemical is delivered to the annulus in a free-flowing solid state and is suspended in
the annular fluids. Chemical release is said to be more controlled than use of emulsified chemistries as dissolution rate
of solid micro spheres is better understood than kinetics of breakdown of metastable emulsions.

Application of corrosion inhibitors by this technique is not common within BP and specialist advice
should be sought before application.

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Annex E - Pipeline Batch Treatment to Supplement Continuous Injection

Applicability - Where it works, requirements and conditions to make it work

Pipeline batch treatment shall only be used to supplement continuous injection in low water cut, low velocity pipelines
and high corrosivity (or badly corroded) systems . Also may be used in wet gas lines to mitigate top-of-line (TOL)
corrosion to supplement continuous injection. It’s an intermittent treatment that achieves persistent filming by batching
of large quantities of inhibitor. The inhibitor may be used undiluted, as a special mix with diluents or mixed with a
portion of well fluid. Contact with the metal may be assisted by pipeline scrappers, pigs or other devices. Gel pigs
containing corrosion inhibitor are also available.

Inhibitor Type - General description of the most appropriate inhibitor

Oil soluble chemicals with good persistency are typically utilised. Higher water dispersibility and/or surfactancy may
be required depending on the application technique. Emulsified products could potentially be used.

In treatment of wet gas lines where batch treatment is used to supplement continuous injection, the same continuous
injection chemical can be considered for application via a batch to mitigate against TOL if suitable.

Efficacy – Factors critical to success

Factors influencing success of treatment include:


♦ Contact time
♦ Chemical concentration
♦ Batch frequency
♦ Film tenacity (persistency, film life)
♦ Higher flows diminish film life
♦ Higher water cuts diminish film life
♦ Higher temperatures diminish film life
♦ Presence of solids diminish film life

Testing

See Tables 8 and 9.

Field Application – Practical application issues

♦ Cleaning (using pigs) usually required


♦ Limited equipment
♦ Chemical can be applied between pigs, or behind/in front of one pig
♦ Chemical loss during treatment by extrusion of chemical around pig cups
♦ Plant upset and separation problems possible with high initial concentration of chemical after treatment

Performance Management – Monitoring options and corrective actions

Specialist advice should be sought on performance monitoring if pipeline batch treatments are to be
applied in supplement to continuous injection.

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Annex F - Annulus Continuous

Applicability - Where it works, requirements and conditions to make it work

Applicable to both oil and gas wells but more commonly applied to gas wells. Continuous treatment downhole can be
afforded through the tubing/casing annulus. Inhibitor enters the production stream through injection valves in a side
pocket mandrel, or through the open annulus. Injection valves can be spring-loaded to open at a determined
annulus/tubing differential pressure. Applicable only to simple down hole completion designs.

Inhibitor Type - General description of the most appropriate inhibitor

Water or oil soluble chemical is suitable; however a product formulated in hydrocarbon solvent but with high affinity to
partition to water preferable. Chemical often applied as dilution in condensate or hydrocarbon.

Efficacy – Factors critical to success

♦ Concentration of the chemical active components and the product being applied
♦ Dispersibility/partitioning of active components in production stream
♦ Chemical availability (injection up-time)
♦ Basis of injection rates, i.e., total fluids, water, oil.
♦ Blockage of injection valve/delivery tube
♦ Residence of chemical at downhole conditions – stability
♦ Efficient mixing of chemical in production stream – turbulence
♦ Slugging/high velocities may affect inhibitor film stability
♦ Solids may impact performance

Testing

See Tables 8 and 9.

Field Application – Practical Application Issues

♦ Blocking or failure of injection valve


♦ Only treats above injection point – corrosion resistant material required below this point
♦ Potential solvent evaporation and product fouling or ‘gunking’ at injection valve
♦ Potential slugging of large inhibitor volumes if valve malfunctions
♦ Product stability at downhole conditions for extended time periods
♦ Large inventory of chemical stored in annulus - difficult to remove if problems occur

Performance Management – Monitoring options and corrective actions

Monitoring:
♦ Injection concentration versus target
♦ Corrosion inhibitor residuals (use with care)
♦ Monitoring and inspection as per GP 06-70 and GP 32-40
Corrective Action:
1. Increase chemical concentration – restricted by chemical injection valve operation
2. Reselect chemical – requires removal/displacement of product from annulus
3. Consider installing capillary string for injection
4. Consider material option

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Annex G - Gas Lift

Applicability - Where it works, requirements and conditions to make it work

In fields where gas lift systems originate from a central gas lift header or manifold, treatment can be provided by
injecting the corrosion inhibitor continuously into the individual gas lift lines at the manifold. The inhibitor should
enter the gas lift zones as a liquid - attempts should not be made to atomize the chemical. Calculations and experience
indicate that atomized inhibitor will not be carried further than 100-200 feet before reverting to a liquid form in a gas
system. Movement of liquid inhibitor into wells has been found to be feasible in gas lift lines as large as 2 ½ inches
O.D. and several thousand feet long. It is likely that the inhibitor accumulates and moves along as slugs or slowly
through the line, but the net delivery of inhibitor appears to plateau by the time passes through the gas lift valve.

Inhibitor Type - General description of the most appropriate inhibitor

Typically an oil soluble chemical is preferred for this type of application; however some success has been reported with
the use of water soluble products (Alaska) in gas lift applications. Generally, this requires an inhibitor that has been
specifically formulated to avoid solvent evaporation, gunking or polymerization in dry gas lift gas streams (i.e.,
inclusion of >10% TEG in solvent of product).

Efficacy – Factors critical to success

♦ As per annulus continuous (see Annex G)

Testing

See Tables 8 and 9.

Field Application – Practical Application Issues

♦ Inhibits from the active gas lift valve (GLV) upward - fluid below valve needs to be inhibited some other
way
♦ Care with single injection point into lateral distribution manifold – ensuring each well receives sufficient
chemical
♦ Potential solvent evaporation and product fouling or ‘gunking’
♦ Potential slugging of large inhibitor volumes through gas lift system
♦ Compatibility of neat chemical with gas lift gas delivery lines

Performance Management – Monitoring options and corrective actions

Monitoring:
♦ Injection concentration versus target
♦ Corrosion inhibitor residuals (use with care)
♦ Monitoring and inspection as per GP 06-70 and GP 32-40
Corrective Action:
1. Increase chemical concentration
2. Reselect chemical
3. Consider alternative application technique
4. Consider material option

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Annex H - Capillary and Umbilical

Applicability - Where it works, requirements and conditions to make it work

Chemical injection via capillary injection strings downhole provide a better way of controlling inhibitor flow and
removes many of the risks or problems associated with injection via valves in the annulus or open annuli.

In an extension of injection via capillary, many sub-sea chemical delivery systems rely on the use of umbilicals for
application of corrosion inhibitors. Often used for offshore and deepwater applications, umbilicals are commonly used
to carry chemical to well-heads and manifolds etc. Downhole delivery of corrosion inhibitors in sub-sea applications
are not common in BP and generally not recommended – however other chemicals, i.e., scale inhibitors may be applied
in this way.

Generally, this is the most effective and preferred method of chemical deployment as it offers greater flexibility and
control of chemical injection.

Inhibitor Type - General description of the most appropriate inhibitor

Both oil and water soluble chemicals designed for continuous injection are commonly applied in this way. Product
stability, temperature stability, viscosity and contaminant levels are particularly important for these applications.

Efficacy – Factors critical to success

♦ As per annulus continuous (see Annex G)

Testing

See Tables 8 and 9.

Field Application - Practical Application Issues

♦ Low temperature stability for umbilical applications


♦ High temperature stability for downhole injection via capillary
♦ Pumpability of product (low temperature viscosity) to be understood
♦ Dilution sometimes required for injection rate control via long umbilicals
♦ Hydrate proofing of chemicals to prevent hydrate formation at injection point
♦ Filtration required before entry to umbilical (typically to 10 um) – remove particulates/contamination
♦ Compatibility of chemical with umbilical/injection materials

Performance Management – Monitoring options and corrective actions

Monitoring:
♦ Injection concentration versus target
♦ Corrosion inhibitor residuals (use to complement other monitoring techniques)
♦ Monitoring and inspection as per GP 06-70 and GP 32-40
♦ In-line inspection
Corrective Action:
1. Increase chemical concentration
2. Reselect chemical

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Annex I - pH Stabilisation

Applicability - Where it works, requirements and conditions to make it work

In long sweet natural gas transmission lines (pH2S < 5 mbars) pH control of hydrate prevention chemicals has
been used successfully. This is a cost effective option to control corrosion, although subject to the absence of
formation water (since these would cause precipitation of scale if pH controllers are added.1

Inhibitor Type - General description of the most appropriate inhibitor

♦ MDEA (Methyldiethanolamine) in glycol


♦ NaHCO3 (sodium bicarbonate) used in either with glycol or methanol

Efficacy – Factors critical to success

♦ Day 1 design treatment


♦ Measure pH or calculate in-situ pH – treatment based on control to specific pH
♦ Economic only if regenerable hydrate control chemical (glycol/methanol) used to recover pH control
chemical
♦ Inhibition capability to be installed for potential periods of upset or to replace pH control if necessary

Testing

See Tables 8 and 9

Long term flow loop tests at operating temperature and pressures

Field Application – Practical application issues

♦ Regeneration issues (usually related to the hydrate prevention chemical)


♦ Formation water
♦ Souring
♦ Back-up system to switch over to inhibition under some conditions
♦ Water chemistry

Performance Management – Monitoring options and corrective actions

Monitoring:
♦ Injection concentration versus target
♦ pH measurements
♦ Monitoring and inspection as per GP 06-70 and GP 32-40
♦ Pump reliability
♦ Corrosion Allowance
♦ In-line inspection
Corrective Action:
1. Increase pH
2. Implement inhibition
3. Consider alternative application technique
4. Consider material option

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Annex J – Gravity Feed

Applicability - Where it works, requirements and conditions to make it work

Chemical injection via gravity feed is a simple yet seldom encountered method of chemical introduction into a pipeline
system. Essentially, an inhibitor tank is connected to a producing pipeline and chemical allowed to ‘trickle’ into the
system under gravity via a needle or control valve. A blanket gas (in addition to storage tank being pressurised to line
pressure) could also be used to provide sufficient head pressure for greater injection rates.

No power or chemical pumps are required for this application method and it may be suitable for remote locations which
experience very stable production rates.

Inhibitor Type - General description of the most appropriate inhibitor

Both oil and water soluble chemicals designed for continuous injection can be applied in this way.

Efficacy – Factors critical to success

♦ As per annulus continuous (see Annex G)

Testing

See Tables 8 and 9.

Field Application - Practical Application Issues

♦ Constant production rates


♦ Useful for remote locations with little/no infrastructure

Performance Management – Monitoring options and corrective actions

Monitoring:
♦ Injection concentration versus target
♦ Corrosion inhibitor residuals (use to complement other monitoring techniques)
♦ Monitoring and inspection as per GP 06-70 and GP 32-40
♦ In-line inspection
Corrective Action:
1. Increase chemical concentration
2. Reselect chemical
3. Install more reliable/robust chemical injection system

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Annex K - Partitioning

The theoretical basis of partitioning between oil and water phases can be summarized as
follows:
[X ]
P=
H 2O

[X ] Oil

Where:
P = Partitioning coefficient
[X]H20 = Equilibrium concentration of material in aqueous phase
[X]Oil = Equilibrium concentration of material in hydrocarbon phase

If the total amount of X added is [X]total this is split between both the oil and water phases of
volume fractions Voil and Vwater.

[X ] total = [ X ]water .Vwater + [ X ]oil .Voil

The concentrations in the water and oil can be determined using the following

[X ] =
[X ] .P
total
and [X ] =
[X ] total
water
(Voil + P.Vw ) oil
(Voil
+ P.Vw )
If water cut is defined as WC = Vwater, then Voil = 1-WC and the previous equations can be
written as;

[X ]water =
[X ]total .P and [X ]oil =
[X ]total
1 + WC (P − 1) 1 + WC (P − 1)

Where WC is the water cut (in %) divided by 100.

Table 1 illustrates how different ways of calculating the inhibitor dosage would change the
actual concentration of inhibitor in the water phase, depending on the inhibitor partition
coefficient and water cut.
The total inhibitor concentration added [X]total
1. is independent on water cut, WC, if it is calculated based on total fluids
2. decreases proportionally with increasing WC if calculated based on oil production
3. increases proportional with WC if calculated based on water production

It can be observed how the same dosage of inhibitor will partition in the water phase producing
concentrations that could be too high or too low for the system. Both extremes will make the
treatment inefficient and/or may be detrimental to downstream processes.

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Report No S/EPT/54/07_____________________________________________________________

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Table K-1. Ideal partitioning behaviour of product with P = 10 and product with P = 0.1 over
range of water cuts.

Water Soluble Product Oil Soluble Product


Dosage Basis

P=
[X ]Water =
10
P=
[X ]Water =
1
[X ]oil 1 [X ]oil 10

Corrosion Inhibitor Concentration w ith Varying Water Cut Corrosion Inhibitor Concentration w ith Varying Water Cut

Concentration of Inhibitor Added Concentration in Water Concentration in Oil Concentration of Inhibitor Added Concentration in Water Concentration in Oil

600 400

350
500 50ppm based on Total
Total Fluids

Partitioning Coefficient = 10

Phase Concentration, ppm


300
400
50ppm based on Total 250
Partitioning Coefficient = 10

300 200

150
200
100
100
50

0 0
0% 10% 20% 30% 40% 50% 60% 70% 80% 90% 100% 0% 10% 20% 30% 40% 50% 60% 70% 80% 90% 100%
Water Cut, % Water Cut, %

Corrosion Inhibitor Concentration w ith Varying Water Cut Corrosion Inhibitor Concentration w ith Varying Water Cut

Concentration of Inhibitor Added Concentration in Water Concentration in Oil Concentration of Inhibitor Added Concentration in Water Concentration in Oil

600 60

500 50
50ppm based on Total Partitioning
Phase Concentration, ppm

Coefficient = 10

400 40
50ppm based on Total
Partitioning Coefficient = 10
Oil

300 30

200 20

100 10

0 0
0% 10% 20% 30% 40% 50% 60% 70% 80% 90% 100% 0% 10% 20% 30% 40% 50% 60% 70% 80% 90% 100%
Water Cut, % Water Cut, %

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Corrosion Inhibitor Concentration w ith Varying Water Cut Corrosion Inhibitor Concentration w ith Varying Water Cut

Concentration of Inhibitor Added Concentration in Water Concentration in Oil Concentration of Inhibitor Added Concentration in Water Concentration in Oil

60 350

300
50
50ppm based on Total

Phase Concentration, ppm


Partitioning Coefficient = 10
250
40
Water

200
30
50ppm based on Total Partitioning
Coefficient = 10
150

20
100

10
50

0 0
0% 10% 20% 30% 40% 50% 60% 70% 80% 90% 100% 0% 10% 20% 30% 40% 50% 60% 70% 80% 90% 100%
Water Cut, % Water Cut, %

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59.
Report No
S/EPT/54/07_____________________________________________________________

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Annex L - US Environmental Regulations

Environmental discharges in the Gulf of Mexico are regulated under a permit to discharge system
overseen by the US Environmental Protection Agency (EPA).

EPA Region 6 issues the National Pollutant Discharge Elimination System (NPDES) general
permit for the Western Portion of the Outer Continental Shelf of the Gulf of Mexico (No.
GMG290000) for discharges from new sources, existing sources, and new dischargers in the
Offshore Subcategory of the Oil and Gas Extraction Point Source Category (40 CFR Part 435,
Subpart A).

The general permit authorizes discharges from exploration, development, and production
facilities located in and discharging to Federal waters of the Gulf of Mexico seaward of the outer
boundary of the territorial seas offshore of Louisiana and Texas.

In compliance with the Federal Water Pollution Control Act, , operators of lease blocks in the Oil
and Gas Extraction Point Source Category which are located in Federal waters of the Western
Portion of the Gulf of Mexico (defined as seaward of the outer boundary of the territorial seas off
Louisiana and Texas) are authorized to discharge to the Western Portion of the Federal Waters of
the Gulf of Mexico in accordance with effluent limitations, monitoring requirements, and other
conditions set forth in the attached permit. Also, operators of lease blocks located in the
territorial seas of Louisiana and Texas are authorized to discharge produced water from wells
located in those lease blocks to the Western Portion of the Federal Waters of the Gulf of Mexico
in accordance with effluent limitations, monitoring requirements, and other conditions set forth in
the attached general discharge permit.

If a Miscellaneous Discharges of Seawater or Freshwater has been treated with a “treatment


chemical,” then it is a “chemically-treated miscellaneous discharge” an estimate of the flow must
be recorded once per month.

The concentration of treatment chemicals in discharged seawater or freshwater shall not exceed
the most stringent of the following three constraints:

♦ the maximum concentrations and any other conditions specified in the EPA product
registration labeling if the chemical is an EPA registered product

♦ the maximum manufacturer’s recommended concentration

♦ 500 mg/L

“Treatment Chemicals” means biocides, corrosion inhibitors, or other chemicals which are used
to treat seawater or freshwater to prevent corrosion or fouling of piping or equipment.

Non-toxic scale inhibitors and dyes are not considered treatment chemicals.

$ %&&'((&)* + ), - $ "
.!

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62.
Annex M – North Sea Environmental Regulations

Currently, the environmental scheme in use in UK North Sea oilfield installations is the
Harmonised Mandatory Control Scheme (HMCS), which involves the following:

1. pre-screening
2. submission of HOCNF (Harmonised Offshore Chemical Notification Format) data
3. use of CHARM (Chemical Hazard Assessment and Risk Management) as a
ranking and risk assessment tool

Pre-screening requires biodegradation of all chemical components to exceed 20%. Any


chemical which does not meet this criterion will not be acceptable for use offshore.
Chemical suppliers are responsible for submitting HOCNF data to CEFAS (Centre for
Environment, Fisheries & Aquaculture Science). In addition to biodegradation
information, bioaccumulation and toxicity data are also required to be submitted. In order
for a product to be considered environmentally acceptable, 2 out of the following criteria
must be met:

1. Biodegradation: > 60% in 28 days


2. Marine Toxicity (EC50/LC50) > 10 mg/L where EC represents effective
concentration and LC represents lethal concentration
3. Bioaccumulation - Log Octanol/Water Partition Coefficient (Pow) <3

The pre-screening process which is applied in the UK is summarized in the following


figure.

Figure 3. Summary of UK pre-screening scheme

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63.
The use of chemicals is required to be approved by the operator. The data from the
HOCNF is then used for the CHARM model. CHARM is a computer model for
implementation of the HMCS for PARCOM Signatory Countries. The regulations require
operators to apply for a permit from the UK Secretary of State for Trade and Industry for
the use and discharge of each chemical per installation. Operators use CHARM to perform
specific risk assessments to support their permit applications using site specific data and
ecotoxicological data provided by suppliers. CEFAS will evaluate the environmental
impact of the products using initial pre-screening and then, depending on the outcome,
utilize CHARM to rank products. Products are typically ranked as follows:
a. Permission - although product is allowed, there may be conditions set
against period of validity, discharge etc.
b. Substitution - authorities will request additional data, or apply a
substitution warning for the chemical/component.
c. Temporary Permission - where no substitute is currently available,
authorities will grant temporary permission for a limited period (up to 3
years) whilst a less hazardous chemical is sought.
d. Refusal of Permission - authorities refuse permission for those offshore
chemicals which they consider to be unsuitable.

The outputs from CHARM are based on the hazard quotient, which is essentially a ratio of
the predicted environmental concentration of the material to the concentration which poses
no threat to marine life, i.e., toxicity.
PEC = Predicted Environmental Concentration (derived from bioaccumulation,
biodegradation, dilution effects etc.)
PNEC = Predicted No Effect Concentration (based on toxicity data only)

PEC / PNEC = Hazard Quotient (HQ)

The CHARM model calculates the HQ for each component in a product based on water and
sediment figures. If the HQ is greater than 1 this is taken to indicate that an environmental impact
will occur beyond the immediate vicinity of the discharge site. Products with this result will need
to be further justified. Other European countries with significant North Sea exposure also follow
the CHARM (Chemical Hazard and Risk Management) model, however may place different
acceptability limits on the criteria, i.e., cut-offs for biodegradation, bioaccumulation and toxicity
. The inhibitor supplier usually obtains the environmental classification for a product although
the operator is ultimately responsible to ensure that chemicals are used within the regulations.

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64.
Annex N –Pipeline Batch Treatment Volume Calculations

Calculation to provide a given film thickness

0.86 * D * f t * L
Inhibitor Volume =
Chemical activity (%)

Where inhibitor volume is in gallons (US), “D” – diameter is in inches, “fi” – required film
thickness is in mils and “L” – Length of the line is in miles, and “ai” is the inhibitor
activity in %. Typical film thickness values of between 1 and 3 mil are used in the
calculations. There is no guarantee that these film thicknesses will be achieved in practice.
The basis of the equation is as follows - given that 1-gallon (0.133681ft3) of a liquid will
cover a surface area of 1604 square feet 1-mil thick the coverage of a corrosion inhibitor in
square feet per gallon may be determined by the relationship
1604 * ai
Ci =
100 * f t

where "Ci" is the corrosion inhibitor coverage square foot per gallon at the designated
thickness.

A second term can be included into the above equation to account for potential inhibitor
loss, and account for the fact that not all applied product remains deposited on the
available surface. The expansion becomes
1604 * a i 1604 * a i * i L
Ci = −
100 * f t 100 * 100 * f t
where "iL" is the loss of inhibitor as a percent.

The inside surface area of a tube in square feet is found by


d iπ
Ai = * L = 0.2618 * d i * L
12
where "di" is the internal diameter in inches and "L" is the linear length of the tube in feet.
Assuming no inhibitor loss and combining constants, the volume of corrosion inhibitor is
found by
0.0163217 * d i * L * f t
Vi =
ai
with Vi in gallons. This abbreviated equation is applicable as long as inhibitor loss is
anticipated to be minimal. If “L” is in miles instead of feet, the equation becomes
86.1786 * d i * L * f t
Vi =
ai
For a corrosion inhibitor that is 100% active
Vi = 0.86 * d i * L * f i
where
Vi = inhibitor volume, gallons
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65.
di = internal pipeline diameter, inches
L = tubing/pipeline length, miles
fi = target inhibitor film thickness, mils

For an inhibitor that is 25% active, the constant, 0.86, becomes 3.45.

Batch size to achieve given contact time

Batch Volume = 0.04 * V * t * D 2

V – the velocity of the slug is in ft/s, t – the desired contact time is in seconds. A contact
time of 10-30 seconds is recommended as operationally practical and adequate for
deposition of an inhibitor film.

The concentration of corrosion inhibitor in the slug can be determined using the following;
however, typically 10-20% is used.
2150 * f t * L
Concentration (%v/v) =
Vi * t * D

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66.
Report No
S/EPT/54/07_____________________________________________________________

DISTRIBUTION LIST

NO. OF COPIES NAME LOCATION

1-2 BDM/EPTG Library Bldg C Ground Flr


3 Will Durnie Bldg C Ground Flr
4 Don Harrop Bldg C Ground Flr
5 Sandra Hernandez EPTG Houston
6 Jose Vera EPTG Houston

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EPTG Indexing Sheet
BRANCH REPORT NO. JOB NO.
S / E P T / 0 5 4 / 0 7

AUTHOR(S) TELEPHONE LOCATION DATE

MAIN TITLE

SUB TITLE

CLIENT PRINCIPAL RECIPIENT COMMISSIONED BY

PLEASE TICK

SECURITY CLASSIFICATION UNCLASSIFIED CONFIDENTIAL

TQA COMPLETED YES NO

KEYWORDS

ACKNOWLEDGEMENT RECORD FOR EXTERNAL CLIENT LISTING DISTRIBUTION


PAGE
OVERLEAF

ABSTRACT

PREPARED BY: APPROVED BY: AUTHORISED FOR ISSUE BY:

.................................................... .................................................... ....................................................

ISSUE DATE:

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