20312e00 Guidelines For Chemical Treatments of Pipelines

Eni S.p.A.
Exploration & Production Division
COMPANY STANDARD
GUIDELINES FOR CHEMICAL TREATMENTS OF

PIPELINES
20312.VAR.COR.PRG
Rev. 0 - January 2009
ENGINEERING COMPANY STANDARD
Documento riservato di proprietà di Eni S.p.A. Divisione Agip. Esso non sarà mostrato a Terzi né utilizzato per scopi diversi da quelli per i quali è stato inviato.
This document is property of Eni S.p.A. Divisione Agip. It shall neither be shown to Third Parties not used for purposes other than those for which it has been sent.
Eni S.p.A. 20312.VAR.COR.PRG
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PREMISE
Rev. 0 January 2009
The present Guideline replaces and voids ENI Company Standard 06575.VAR.PRC.SPC
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TABLE OF CONTENTS
GUIDELINES FOR CHEMICAL TREATMENTS OF PIPELINES

1. INTRODUCTION
1.1 Foreword
1.2 Scope
1.3 Document organization
1.4 Summary
1.5 References
1.5.1 Codes and Standards
1.5.2 ENI Company Standards
1.6 Symbols and abbreviations
1.7 Glossary
2. CHEMICAL TREATMENTS FOR INTERNAL CORROSION CONTOL OF PIPELINES
2.1 Forewords
2.2 Corrosion inhibitors
2.3 Glycol control
2.4 pH stabilization
2.5 Biocides
2.6 Oxygen scavengers
3. SELECTION OF CHEMICAL TREATMENTS FOR CORROSION MITIGATION
3.1 Data collection
3.2 Corrosivity assessment
3.3 Flow analysis
3.4 Chemical treatment performance
3.4.1 Efficiency model
3.4.2 Availability model
3.5 Selection of chemical treatment method
3.5.1 Gas-condensate pipelines
3.5.2 Wet-gas pipelines
3.5.3 Oil-multiphase systems
3.5.4 Liquid-hydrocarbon systems
3.5.5 Chemical injection methods
3.5.5.1 Continuous injection
3.5.5.2 Batch treatments
3.5.6 Applicability of chemical treatments
3.6 Economics evaluation
4. SELECTION AND QUALIFICATION OF CHEMICAL PRODUCTS
4.1 Selection of chemical products and performance evaluation
4.1.1 Solubility
4.1.2 Compatibility
4.1.2.1 Compatibility with materials
4.1.2.2 Compatibility with other chemicals and downstream process
4.2 Previous operational experience
4.3 Local area experience
4.4 Vendor recommendations
4.5 Laboratory testing
4.5.1 Test fluid
4.5.2 Performance evaluation
4.5.2.1 Initial screening
4.5.2.2 Dynamic tests
4.5.2.3 Autoclave test
4.5.3 Partitioning evaluation
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4.6 Field testing

5. DESIGN OF CHEMICAL TREATMENT SYSTEMS
5.1 Introduction
5.2 Specifications
5.3 Preliminary examination of compatibility
5.4 General requirements
5.6 Design dosages
5.6.1 Continuous injection of corrosion inhibitors
5.6.2 Batch treatments of corrosion inhibitors
5.6.3 Adjustment of glycol dosage for corrosion control
5.6.4 pH stabilization
5.7 Dilution
5.7.1 Solvent
5.8 Chemicals injection system
5.8.1 Components
5.8.2 Storage
5.8.3 Chemical injection pumps
5.8.4 Pumping issues
5.8.4.1 Pumping issues related with the inhibitor
5.8.4.2 Pumping issues related with the pump
5.8.4.3 Maintenance
5.9 Injection points location
5.10 Injection quill
5.11 Preliminary operations to prepare for chemical treatment
5.11.1 Cleaning with pigs
5.12 Materials for chemical injection equipment
6. DATA ACQUISITION, OPERATION AND MAINTENANCE
6.1 Data acquisition and storage
6.2 Maintenance and inspection of injection facilities
6.3 Process changes and shut-in conditions
6.3.1 Monitoring process changes
6.3.2 Production rates
6.3.3 Water cut
6.3.4 pH
6.3.5 Oxygen
6.3.6 Shut-in conditions
7. REFERENCES
APP A INTERNAL CORROSION OF PIPELINES
A.1 Pipelines for hydrocarbons transportation
A.1.1 CO2 Corrosion
A.1.2 Sour service
A.1.3 Top of line corrosion “TLC”
A.1.4 Formation water
A.1.5 Biological Corrosion “MIC”
A.2 Pipelines for water transportation
APP B CHEMICAL TREATMENTS FOR CORROSION CONTROL
B.1 General
B.2 Corrosion Inhibitors
B.3 Glycol Control
B.4 pH Stabilisation
B.5 Biocides
B.5.1 Types of Biocides
B.5.2 Biocide selection and evaluation
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B.5.3 Chlorination
B.5.4 Glutaraldehyde
B.5.5 Quaternary phosphonium
B.5.6 Quaternary Amine
B.5.7 Copper ion
B.6 Oxygen scavengers
B.6.1 Types of oxygen scavengers
B.6.2 Reaction between oxygen scavenger and other chemicals
B.6.3 Oxygen scavenger in sour systems
APP C ADDITIONAL TREATMENTS
C.1 Additional treatments during normal service
C.1.1 Additional batch treatment combined to continuous injection
C.1.2 Batch treatment with inhibitors in low corrosive systems
C.1.3 Batch treatment with biocides
C.1.4 Treatments for TLC corrosion control
C.1.4.1 Conventional Batch treatment
C.1.4.2 Spreading or spray method
C.2 Chemical treatments for corrosion avoidance during temporary operations
C.2.1 Hydrostatic testing
APP D ENVIRONMENTAL ISSUES
D.1 General
D.2 Paris commission (PARCOM)
D.2.1 Environmental Testing
D.2.2 Chemical Hazard Assessment and Risk Management (CHARM) Model
D.3 Harmonized Mandatory Control System
D.4 Development of environmentally friendly corrosion inhibitors
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1. INTRODUCTION
1.1 Foreword
This document deals with chemical treatments for the control of internal corrosion of pipelines used
in upstream hydrocarbon production for the transportation of:
− untreated well fluid from the reservoir, consisting of hydrocarbons in gas, liquid or multiphase
phase and associated water,
− stabilised or separated crude oil or condensate from the upstream process units,
− dehydrated or separated gas from the upstream process units,
− seawater, production water or their mixture for water injection purpose.
The term “pipelines” is herein intended to include:

− “flowlines” for the intra-field connection of individual wells with the upstream process or with a
manifold to convey untreated hydrocarbon produced from the reservoir or gas or water for
injection into the reservoir,
− “pipelines” or “trunklines” for the intra-field connection of manifold (collecting the well flowlines) to
upstream process,
− “pipelines” or “trunklines” for the export of treated or partially treated hydrocarbons from first
upstream process.
Pipelines may be situated onshore, offshore subsea or offshore topside in the case of short flowlines
connecting topside wells to separation unit onto offshore platforms.
1.2 Scope
This document is intended to provide a practical guide to aid the materials and corrosion engineers in
identification and selection of viable chemical treatments for internal corrosion control of pipelines.
The primary objective is focused on chemical treatments for the control of corrosion of carbon and
low-alloy steel pipelines for the transportation of hydrocarbons during normal operational service, in
order to recover their use as a cost-effective alternative to expensive CRA’s.
Chemicals injected for this purpose includes primarily the category of “corrosion inhibitors”.
Alternative or complementary methods are recently taking place in gas and gas-condensate pipelines
to counter balance the limits of conventional corrosion inhibitors in controlling the gas-phase
corrosivity. These techniques take advantage from the natural inhibitive effect on corrosion displayed
by glycol, “glycol control”, which is often required for hydrate prevention: if that is the case glycol
dosage is adjusted to optimise also its effect on wet-gas-phase corrosion control. Glycol action in
corrosion mitigation may also need to be complemented by additions of a pH stabiliser agent, in the
“pH stabilization” technique, or with small quantities of corrosion inhibitor, to enhance the effect of
glycol particularly in controlling the corrosivity of the stratified liquid phase where stratification is
anticipated.
1.3 Document organization
The organization of this document was outlined as follows:

− a main body of the document, which is intended to provide practical information regarding the
viable chemical treatment for corrosion mitigation, the selection of the most appropriate
treatment, the qualification criteria and the design of the chemical injection system,
− a list of appendixes attached to the document’s main body, with the intention to provide more
detailed information for a better understanding of specific corrosion and corrosion control issues
that are of concern when chemical treatment are performed, which can be consulted when a
close examination of specific topics is required.
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The technical content of the main body of the document is arranged in Sections 2 to 6.
Section 2 provides a list of quick guidelines to permit a rapid identification of the chemical treatment
that best tailors the case under study and whether chemical treatments are applicable.
Section 3 covers Guidelines for selection and applicability assessment of chemical treatment
methods. The viability of the chemical treatment method is subordinated to an assessment
demonstrating its suitability with no compromise to integrity, operational safety and environmental
aspects. The main limitations and constraints associated to chemical treatment techniques are
identified.
Section 4 discusses criteria for chemical products qualification. Particularly in presence of fluid
characterized by severe corrosivity and/or approaching conditions where the efficiency of chemical /
inhibitor may result compromised, it has become a normal practice to qualify chemicals by laboratory
or field testing to verify the design efficiency and to identify the limits of their application. This
document is not intended to provide a procedure for the conduction of laboratory testing: its scope is
limited in providing guidance in addressing the need, importance and typology of testing required for
the qualification of the pre-selected chemicals.
Section 5 deals with design aspects of chemical treatment system. The deployment of the chemical
treatment shall guarantee a mitigation of the predicted corrosion rate such that the reduction of the
cumulative corrosion occurring within the design life be manageable with an appropriate corrosion
allowance.
Section 6 deals with data acquisition, operations and maintenance issues
App A covers some aspects of the fluid corrosivity in pipeline which is important to bear in mind
when corrosion control based on chemical treatments is applied, whereas App B provides details
concerning chemical treatment methods and techniques.
App C provides details for additional chemical treatments that may be required for avoidance of
specific corrosion issues, including:
additional treatments during service:
− biocide addition to prevent microbial induced corrosion in hydrocarbon or water systems if the
conditions for MIC are expected,
− oxygen scavenger addition to complement process removal of oxygen in deaerated water
systems,
− top of line corrosion avoidance by periodic batch treatment of corrosion inhibitor using pigs,
− periodic batch treatment with corrosion inhibitor for corrosion avoidance at low spot areas of
pipelines,
− additional treatments during upsets or similar conditions,
treatments during non-operational phases:
− additional treatments during prolonged shut-in conditions,
− treatment of temporary service fluids with specific chemicals package for corrosion avoidance of
either carbon steel or CRA pipelines during:
o hydrotesting or pre-commissioning,
o installation (sealines),
o inactivity preceding hook-up,
The above chemical treatments do not drive material selection but represent a good practice to avoid
collateral corrosion problems.
App D covers environmental issues.

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1.4 Summary
The topics and items coverage of this document is emphasised in the below table.
Pipelines Flowlines
Intra-field pipelines or trunklines
Export pipelines or trunklines
Location Onshore
Offshore (subsea)
Fluid transported Liquid hydrocarbon
Oil multiphase
Gas and condensate
Wet gas
Water (seawater, production water or commingled)
Service Hydrocarbon production
Water injection/disposal
Gas injection
Environment Characterisation Sweet fluid, containing CO2
Sour fluid, containing H2S
Stratified flow, top of line corrosion
Formation water, organic acids
Aerated / deaerated water
Water cut trends
High flow rates, sand, shear stress
High operating temperature
Chemicals Corrosion inhibitors
pH stabilisers
Glycol
Biocides
Oxygen scavengers
Injection methods Continuous injection
Batch treatments
Chemical treatment planning Pre-selection
and design Applicability assessment
Chemicals qualification
Injection system design
Operations and maintenance issues
Field feedback and performance evaluation
Issues Compatibility
Formation water
Reliability
Shut-downs
Persistency (batch treatments)
Dealing with changes
Need of pigging
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1.5 References
1.5.1 Codes and Standards

API 5L Specification for Line Pipe.
API 5LC Specification for Corrosion Resistant Alloys (CRA) Line Pipe.
API Publication 581 Base Resource Document. Risk Based Inspection.
ASME B31G Manual for Determining the Remaining Strength of Corroded
Pipelines.
ASME B31.4 Liquid Transportation Systems for Hydrocarbons, Liquid Petroleum
Gas, Anhydrous Ammonia, and Alcohol’s.
ASME B31.8 Gas Transmission and Distribution Piping Systems.
ASTM E122 Choice of Sample Size to Estimate a Measure of Quality.
ASTM G 1 Preparing, Cleaning, and Evaluating Corrosion Test Specimens.
ASTM G 3 Conventions Applicable to Electrochemical Measurements in
Corrosion Testing.
ASTM G 4 Conducting Corrosion Coupon Tests in Plant Equipment.
ASTM G 5 Standard Reference Method for Making Potentiostatic and
Potentiodynamic Anodic Polarisation Measurements.
ASTM G 16 Practice for Applying Statistics to Analysis of Corrosion Data.
ASTM G 31 Practice for Laboratory Immersion Corrosion Testing of Metals.
ASTM G 46 Examination and Evaluation of Pitting Corrosion.
ASTM G 59 Conducting Potentiodynamic Polarisation Resistance Measure-
ments.
ASTM G 96 Guide for On-Line Monitoring of Corrosion In Plant Equipment
(Electric and Electrochemical Methods).
ASTM G 102 Corrosion Rates and Related Information from Electrochemical
Measurements, Calculation of Corrosion Rates.
ASTM G 170 Evaluating and Qualifying Oilfield and Refinery Corrosion Inhibitors
in the Laboratory
NACE Doc. 001/87 Corrosion Control Engineering Joint Venture. “Review of Current
Practices for Monitoring Bacterial Growth in Oilfield Systems”.
EFC N° 16 Guidelines on Material Requirements for Carbon and Low Alloy
Steels for H2S Containing Oil and Gas field Service”. The Institute of
Materials.
EFC N°23 Design Consideration for CO2 corrosion in Oil and Gas Production
GPA Standard 2166 Obtaining natural gas samples for analysis by gas chromatography.
GPA Standard 2174 Method for obtaining liquid hydrocarbon samples using a floating
piston cylinder.
HS (G) 65 (HSEx) Successful Health and Safety Management.
ISO 15156 / NACE MR0175 Standard Material requirements for Sulphide Stress Cracking
Resistant Metallic Materials for Oil Field Equipment
NACE RP0175 Control of Internal Corrosion in Steel Pipelines and Piping Systems.
NACE RP0192 Monitoring of Corrosion in Oil and Gas Production with Iron Counts.
NACE TM0194 Field Monitoring of Bacterial Growth in Oilfield Systems.
NORSOK M-001 Material Selection
1.5.2 ENI Company Standards

02555.VAR.COR.PRG Design criteria. Internal corrosion. Corrosion parameters and
classification of the fluid.
20555.VAR.COR.PRG ENI Company Specification. Internal Corrosion Monitoring.
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20556.VAR.COR.FUN ENI Company Specification. Internal Corrosion Monitoring.

Specification. Functional Requirements.
14059.PLI.COR.PRG Inspections with Intelligent Pigs.
6805.SLI.OFF.SPC Offshore Pipelines. Pigging Procedure.
6806.PLI.MEC.SPC Pigging of On-Shore Pipelines.
20384.PLI.MEC.SPC Pipeline Hydraulic Testing
1.6 Symbols and abbreviations
CRA Corrosion Resistant Alloy

CI Corrosion Inhibitor
CLAS Carbon and Low Alloy Steels
PREN Pitting Resistance Equivalent Number
TLC Top of Line Corrosion
BLC Bottom of Line Corrosion
m.w. Molecular weight
1.7 Glossary
Corrosion Inhibitor Partitioning: oil/water partitioning of inhibitor expresses a qualitative concept - as

in “preferentially water soluble” or “preferentially oil soluble” - rather than a numerical constant to be
used for extrapolating to different conditions. The main purpose of a partitioning test is to estimate
the inhibitor dose rate required on total fluids.
Corrosion Inhibitor Solubility: inhibitors are classified by their solubility in oil and water, i.e. are
classified as oil-soluble or water-soluble. This classification reflects their predominant behaviour on
this regard, as most inhibitors exhibit at least partial solubility or dispersibility in both liquid phases.
Availability: the availability of a chemical treatment is a quantitative expression of the fraction of time,
as an average over long term periods, during which the chemical treatment is performed
appropriately and with an efficiency in dropping down the fluid corrosivity such that the residual
corrosion rate is not higher than the design value.
Efficiency: the efficiency of a chemical treatment is a quantitative expression of the capability of the
chemical in reducing corrosion rate.
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2. CHEMICAL TREATMENTS FOR INTERNAL CORROSION CONTOL OF PIPELINES
2.1 Forewords
The main methods based on chemical treatments for internal corrosion control of pipelines herein
considered are:
− corrosion inhibitors,
− glycol control,
− pH stabilisation
Additionally, other chemical treatments based on biocide or oxygen scavenger may be also required.
The criteria for the selection of the chemical treatment method are based on:
− predicted un-inhibited corrosion rate and its variation with time
− expected corrosion morphologies
− type of fluid/service
− flow velocities, shear stress
− required design life
− corrosion allowance
− presence of H2S
− high temperature stability of chemicals,
− economical and practical aspects.
The viability of chemical treatments is mainly related to the following aspects:

− the expected capability of the selected method to reduce corrosion rates within limits that may be
managed by corrosion allowance,
− the capacity of the chemicals injection facilities (reliable injection facilities, chemicals storage
capacity) to provide the chemical at the design dosage, continuously or with the design
frequency without or with acceptably low long-term shutdowns (chemical availability),
− the expected compatibility between chemicals,
− the environmental issues.
The following paragraphs provide guidance highlighting the main issues associated with chemical
treatment methods herein covered. For further details, App B provides information regarding the
chemical treatments methods covered by this document. Section 3 provides the criteria herein
recommended for the selection of the most appropriate chemical treatment.
2.2 Corrosion inhibitors
CORROSION INHIBITORS GUIDELINES

• It is the most common chemical treatment method for corrosion control of hydrocarbon pipelines
manufactured from carbon and low alloy steels.
• Effectively inhibits liquid phase corrosivity even in severe corrosive systems, either in presence of H2S.
• Not effective in controlling wet-gas phase corrosivity in stratified flow. TLC may be an issue in gas or
multiphase pipeline in stratified regime where inhibitors are not able to control the corrosivity of the
gas-phase region.
• Do not control oxygen corrosion in case of oxygen contamination.
• Careful selection and qualification of specific products is required, especially if chemical treatment is
critical for pipeline integrity.
• High shear stress induced by high flow velocity is critical for corrosion inhibitor effectiveness. Critical
shear stress threshold is about 50 Pa (REF). Slug flow may require a higher concentration due to more
severe flowing conditions and shear stress.
• Preparation of corrosion inhibition is required for an effective treatment. Cleaning by pigging or
descaling treatments (to be carefully evaluated) are required to remove scaling or debris that may
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CORROSION INHIBITORS GUIDELINES

compromise the effectiveness of the inhibitor, especially for existing pipelines.
• Temperature stability shall be careful evaluated above some 100°C. Not recommended above 130°C.
• Environmental aspects
2.3 Glycol control
GLYCOL CONTROL GUIDELINES

• Can be considered if glycol needs to be used for hydrate prevention (otherwise it may not be practical).
If that is the case glycol dosage is adjusted to optimise also its inhibitive effects on corrosion control.
• Glycol is normally regenerated and re-circulated and the common method is by heating to distil off the
water phase. All ions remain in the “lean glycol” which typically consists of 10% water and 90% glycol.
• Glycol efficiency in reducing corrosion is predicted with a correction factor included in CO2 corrosion
models (FGLY).
• Well proved technique to control wet-gas corrosion or TLC in stratified flow. TLC residual corrosion
rates lower than 0.1 mm/y are easily achieved.
• In corrosive systems, BLC by stratified liquid may be more difficult to control and require impractical
high dosages of glycol, depending on the amount of produced water. Additions of pH stabiliser or of
small amounts of corrosion inhibitor (~1 ppm) may be required to reach full corrosion control, including
BLC (Ref./9/).
• At high flow rates and/or highly corrosive systems the corrosion inhibition ability of glycol is reduced
and may require combined use of corrosion inhibitor at high dosages (up to 1,500 ppm) (Ref./10/).
• Appropriate corrosion inhibitor shall be selected to stay with glycol and survive the high-temperature
regenerator step with minimum degradation to ensure that only small amounts are needed to maintain
the required concentration (Ref./10/).
• Accumulation of salts or iron ions or acetates not removed by the regeneration process may be
experienced when re-circulated several times. Additional treatment may be required (e.g. desalting or
actions).
• Monitoring concentrations of several ions is necessary to control that all salts are below their saturation
points in the glycol injection line
• Glycols are environmental friendly products (low toxicity, not surface active, not bioaccumulable,
degradable, recycled in the process
2.4 pH stabilization
pH STABILIZATION GUIDELINES
• NaHCO3 and Na2CO3 can be used, but larger volumes compared to NaOH are required and this may
not be practical. Reason for using NaHCO3 and Na2CO3 is handling as these chemicals are harmless.
MDEA poses an environmental issue.
• Requires glycol. It is a well proven technique if use of glycol is foreseen. On the contrary, only a few
experiments were carried out without hydrate preventer and corrosion rates were much higher; it
seems to be more difficult to form protective films without glycol. As the experience with pH
stabilization without a hydrate preventer is very limited, such application is not recommended unless
qualified by testing.
• Not suitable with formation water. Monitoring equipment for a prompt detection of formation water and
a backup with corrosion inhibitors or scale inhibitors should be considered.
• Not recommended with H2S containing fluids.
• pH stabilizers may be recovered together with glycol in the regeneration process.
• Both from an environmental and an economical point of view, it might be desirable to regenerate the
pH stabiliser. Regeneration in glycol is simple as it remains in the glycol during boiling; this is not the
case with methanol.
• pH stabiliser should have a good temperature stability to survive the glycol regeneration process
(MDEA have best temperature stability)
• Glycol regeneration is limited by the content of iron ion and salts in the solution (indicatively within 10
ppm). Even at acceptable corrosion rates, the iron ion content may be too high for the regeneration
unit. It is thus important to keep the iron content low. Experience shows that it is possible to control and
achieve a content of total iron lower than 10 ppm (Ref./5/).
• Effectiveness of pH stabilization is sensitive to high flow rates / shear stress which may remove
protective scales. Laboratory testing shown that protective films promoted by pH stabilisers are
compromised exceeding a shear stress of approximately of 32 Pa (Ref./11/).
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pH STABILIZATION GUIDELINES
• The required concentration of pH stabilizer can be estimated by calculation. For conditions not
supported by test or field data, specific qualification testing is recommended.
• In establishing the required quantities of pH stabiliser, solubility limitations shall be considered. Only a
limited amount of pH stabiliser can be transported with glycol, because of the low solubility. The
highest pH achievable in the pipeline is therefore restricted and depends on the glycol type (MEG or
DEG). As the dosage of bicarbonate increases with corrosivity and target pH, it might be necessary to
use MEG, whose solubility is higher compared to that of DEG, in order to achieve the target pH. On the
other hand, DEG requires less quantities of pH stabiliser to reach the same pH.
• As a conservative approach it is assumed that it is safe to operate with glycol concentrations of 50% or
higher (more typically 70-80%). The amount of pH stabiliser that is required to add to the glycol
solution varies with the CO2 partial pressure; indicatively adequate stabilisation, e.g. pH 6.5, is reached
-
with 100-200 mM HCO3 per kilogram.
2.5 Biocides
BIOCIDES GUIDELINES
• Sulphate reducing bacteria, “SRB”, can cause serious problems in oilfield injection systems. H2S as a
by-product can be produced and plugging issues can be a concern.
• Chlorine is the most widely used inorganic biocide for water injection systems.
• Beside chlorine, most market available biocides are organic.
• Bacteria have a habit of developing strains which build up a resistance to a particular chemical. Use of
two or more different chemicals is often advised.
• Compatibility with water in highly salty brines and other chemicals should be assessed to avoid biocide
“salt-out”.
• A preliminary cleaning of the pipeline is key for biocide treatment effectiveness. Solvents, acid and pigs
are used for this purpose.
• Chlorination is widely used due to its low cost and high effectiveness. At higher pH (8-9) biocide
activity is drastically reduced. However, in waters containing bromide ions, Chlorine is still an effective
biocide.
• The amount of chlorine depends also on the temperature.
• Chlorine is a very strong oxidising agent, hence it is necessary to establish the required quantity of
chlorine based on water composition and chlorine lost by metal oxidation.
• In case of high H2S content or the ferrous iron content, it should be considered to use Corrosion
Resistant Alloys.
• If sodium sulphite is used as oxygen scavenger, chlorine must be injected at a sufficient distance
downstream to complete the oxygen-sulphite reaction prior to reaching the chlorine injection point,
whereby avoiding chlorine consumption.
2.6 Oxygen scavengers
OXYGEN SCAVENGERS GUIDELINES

• At normal operating temperatures sodium sulphite typically reacts very slowly with oxygen, which
means that a catalyst is required (typically cobaltous based chemicals).
• Ammonium bisulphite normally does not require a catalyst.
• Sulfur dioxide is often considered when large quantities of scavenger are needed.
• Sodium bisulphite, which is often used as oxygen scavenger during hydrotesting, stimulates the growth
of SRB. Biocides should be therefore added: typically glutaraldehyde at a concentration of ≥250ppm.
• Consumption of oxygen scavenger by reaction with biocides or organic inhibitors shall be avoided by
locating the relevant injection point at an appropriate distance.
• Certain biocides such as the quaternary ammonium compounds can complex with the cobaltous (Co2+)
ions, which nullify their effect as a catalyst.
• Care should be taken in using oxygen scavenger in sour systems.
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3. SELECTION OF CHEMICAL TREATMENTS FOR CORROSION MITIGATION
At the early stage of the pipeline design, a preliminary material selection shall identify, based on the
results of corrosion assessment, the margins for the applicability of carbon and low alloy steels
“CLAS” with corrosion allowance.
The prediction of internal fluid corrosivity for “CLAS” - and its expected variation during the service
life - allows the estimation of the minimum required corrosion allowance. For pipeline applications,
practical values of corrosion allowance normally range from 3 to 6 mm. Only exceptionally values as
high as 10-12 mm are considered.
In many cases the estimated cumulative thickness reduction for carbon and low alloy steel pipelines
for the transportation of corrosive fluids is impractically high and alternative solution shall be sought,
which include:
− the mitigation of fluid corrosivity achieved by modifying the service environment by chemical
treatment,
− the isolation of the carbon steel pipe from the environment by means of an inherently resistant
internal lining made of a non-metallic material (plastic lined pipes) or a metallic CRA (clad or
lined pipe),
− the upgrade of carbon and low alloy steel to inherently resistant CRAs,
− reconsider processing sequence in order to mitigate fluid corrosivity by upstream process
treatment if practical.
For relatively short pipelines (e.g. intra-field flowlines) the use of CRAs, solid or clad, or plastic lined
pipe may represent a reasonable solution, whereas for long pipeline the cost for upgrading to CRAs
becomes very high and the CLAS with chemical treatment option should be pursued at best.
To use chemical treatments effectively to control corrosion, the corrosion engineer shall be able to
identify the corrosion threads that pose a risk for the system integrity, functionality or performance,
and which one of these threads may be effectively controlled by chemical treatments. Then, the
economics involved shall be considered.
This section deals with the viability assessment of the chemical treatment to mitigate internal
corrosion of CLAS and the pre-selection of the most appropriate method to consider.
The procedure to evaluate the viability of chemical treatments encompasses the following steps:
− data collection
− corrosivity assessment
− selection of type of chemical treatment method
− evaluation of chemical treatment applicability
− economics aspects
Chemical treatment may result:

− impractical or not suitable, or not cost effective, and material upgrading to CRAs be preferred,
− feasible, in which case the chemical treatment performance shall be verified by selecting and
qualifying the specific chemical product(s) to inject (covered by paragraph 5).
3.1 Data collection
The following list summarises the main information to be collected for corrosion assessment and
chemical treatment feasibility assessment. The variations of these parameters over the design life
and along with the full pipeline length have also to be considered.
− Operating conditions
• Pressure
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• Temperature
− Flow rates
• Oil flow rate
• Gas flow rate
• Water flow rate
− Gas composition
• CO2 content
• H2S content
− Water origin (formation or condensed)
• Water composition (for formation water)
total salinity
bicarbonates
organic acids / acetates
− Flow analysis results
• Expected flow regimes
• Water condensation rate
− Corrosivity assessment results (see paragraph 4.3)
• Predicted corrosion rate
• Water wetting evaluation
• Top of line corrosion predictions
− Presence of sand, wall shear stresses and erosive conditions assessment,
− Pigging capabilities
3.2 Corrosivity assessment
A corrosion assessment encompassing all corrosion mechanisms typically met in hydrocarbon

production and gas or water injection pipeline is required. The corrosion forms encountered in oil and
gas production can be divided into two main categories:
a) Weight-loss corrosion: the damage occurs in the form of uniform or diffused metal wastage,
quantified by a “corrosion rate”, producing a gradual thickness reduction until integrity is
compromised. Weight-loss corrosion is a time-dependent cumulative process and the
assessment is based on the comparison of the corrosion rate over the required lifespan with the
tolerability to thickness reduction before integrity is compromised. Transitory conditions are
usually not significant and material suitability is related to the steady-state operating conditions.
Corrosion assessment is based on the use of model, algorithms or rules which allow a prediction
of corrosion rate “CR”.
b) Environmentally assisted cracking and localised corrosion: the attack is characterized by an
initiation phase followed by rapid propagation, not accompanied by appreciable metal loss. This
category includes sulphide and chlorides stress corrosion cracking, hydrogen induced cracking,
pitting and crevice. The corrosion assessment shall ascertain the inherent resistance to the
initiation phase (or conversely its sensitivity and failure likelihood) of the applying
material/environment. Temporary or exceptional conditions, even if limited in time, may be
sufficient to develop failures; accordingly, worst-case conditions shall be considered (typically,
water wetting in dry system, worst-case pH, H2S and chloride carryover and temporary
contamination with sour fluid shall be anticipated even if not expected in normal service).
Carbon and low alloy steels are typically subject to weight-loss corrosion, but may also be sensitive
to sulphide stress corrosion cracking, whereas corrosion resistant alloys “CRA” are resistant to
uniform or diffused weight-loss corrosion in ordinary conditions but they may typically fail by cracking
or localised corrosion attacks.
Page 16 of 68
During service, chemical treatments for corrosion control are techniques applied for CLAS pipelines
for the transportation of corrosive hydrocarbon, primarily due to the presence of CO2 and water.
Chemical treatments for this purpose include primarily the injection of corrosion inhibitors and in
some cases of pH stabiliser and glycol.
Use of chemical treatments to control cracking or localised corrosion of CRA pipelines during normal
operational service is not a practice recommended by this Guideline. These corrosion mechanisms
involve rapid initiation and propagation, which would lead to rapid failure in case of chemical
treatment upsets.
Conversely chemical treatments are practices applied to prevent localised corrosion of CRAs when
service fluids are temporarily displaced into the pipeline during special operations. Normally the
pipeline CRA material is not designed to resist this temporary environment, which may cause rapid
damage if not treated with package of chemicals appropriately formulated to prevent corrosion during
these operations. This issue is covered at Section C.2 of this document.
3.3 Flow analysis
A flow analysis is required to determine the flow regimes which are likely to establish in all portion of
pipelines and in all conditions envisaged during pipeline service.
This analysis is of particular importance with oil-multiphase or gas-condensate pipelines to verify if

stratified flow regime is expected to prevail during service and for significant time.
The set up of stratified regime establishes different corrosion conditions in the upper region of the
line, in contact with the gas phase, and at the bottom of the line, in contact with the stratified liquid
phase. Corrosivity of the liquid is usually more critical, but the corrosivity of the gas phase is more
difficult to be controlled by chemical treatments and in some cases requires alternative and relatively
new techniques.
Flow analysis is therefore a key aspect for a correct understanding of corrosion in all portions of the
line and the selection of the appropriate technique for chemical control of corrosion.
The flow analysis and flow assurance model shall consider the following:
− Key items:
• temperature profile along the line
• flow regimes during steady state low and upsets
• composition and phase behaviour changes along the length of a large diameter line
• inhibitor distribution during batch pigging application
− Associated water quantity and parameters for gas and gas-condensate pipelines: potential of
formation water, amount of condensed water and water cut with condensed hydrocarbons.
− Analysis of condensation of water at the top of the line, water condensation rate determination
and conditions for top of line corrosion occurrence.
− Multiphase flow analysis to predict entrainment and deposition of liquid droplets, batch or
continuous treatment.
− Multiphase flow modelling to determine the optimum velocity of dual or single pig batch treatment
to allow sufficient contact time and minimize production losses.
The performance of chemical treatments in controlling corrosion is expressed by its ability in reducing
the residual corrosivity, or “efficiency”, and by the ability of the system to provide this control
continuously over long term periods. The first aspect is related to the specific chemical product
selected and qualified and the second is related to engineering and operational aspects that affect
the reliability of the chemical treatment system in maintaining low treatment system downtime or
upsets.
Page 17 of 68
At the preliminary phases of design assumptions shall be made regarding the above aspects to
evaluate the applicability of chemical treatments. For this purpose the “efficiency” model and, more
recently, the “availability” model are used.
3.4.1 Efficiency model

The “efficiency” model of the chemical treatment in mitigating corrosion uses “efficiency” as a
quantitative expression of the capability in reducing corrosion rate which is given by the following
formula:
E = 100 x ( CR – CRR ) / CR
where:
− E is the chemical treatment efficiency
− CR is the fluid corrosion rate without treatment (“blank” corrosion rate)
− CRR is the residual corrosion rate after treatment
The efficiency model assumes that inhibitors shall reduce the uninhibited corrosion rate by a design
value of the efficiency “E” which shall be then demonstrated by laboratory testing.
In recent years inhibitor technology has improved significantly and all the major producers can offer
chemicals which are highly effective even in demanding applications. Observations from
experimental work and field experience revealed that effective chemical treatments performed
appropriately are able to reduce residual corrosion to very low or negligible values independently
from the blank fluid corrosivity CR. This is in conflict with the efficiency model.
Another limit of the efficiency model is that it assumes that chemical will be supplied at the correct
dosage, without interruption during the whole design life, i.e. it is available for 100% of the time.
The two above flaws of the model in predicting real conditions led to abandon the efficiency model in
favour of the “availability” model, which is more appropriate to characterize modern and highly
efficient chemical treatment methods for corrosion control. The efficiency model may be considered
for batch treatments where average efficiency over long-term periods is a more appropriate concept
than availability.
3.4.2 Availability model

The “availability” of a chemical treatment is a quantitative expression of the fraction of time, over long
term periods, during which the chemical treatment is performed appropriately. Metering pumps can
fail or be set incorrectly, injection valves and pipe-work block or leak, supplies of inhibitor may be
interrupted, production rate or water cuts change and dosages are not promptly adjusted, deposits
can build-up in the line preventing the inhibitor reaching the surface. These aspects are more
realistically at the origin of wall thickness consumption due to corrosion and in recognition of this the
design of the chemical treatment system shall be focused in increasing inhibitor availability.
In the “availability” model the residual corrosion rate CRR is set equal to a realistic “maximum” value,
which experience indicates being within 0.1 mm/y. Higher values meaning “upset” of the chemical
treatment, requiring intervention.
The Corrosion Inhibition Availability “CIA” is the percentage fraction of time over the service life the
chemical treatment system shall be able to supply the fluid with the appropriate dosage of chemical
in order to neutralise its corrosivity. The recommended maximum CIA value to assume at the design
phase is within 90 to 95% depending on the operational context.
The two assumptions of the availability model undertaken at the preliminary phase of design, i.e. the
residual corrosion rate is lower than 0.1 mm/y and the assumed CIA value, shall be supported by
laboratory testing and robust engineering/operational criteria to keep down the cumulative timing of
system upsets.
Page 18 of 68
Design CIA values exceeding 95% are not recommended unless in exceptional cases, characterised
by a favourable operational context and the enforcement of those engineering and operation criteria
that can guarantee a high reliability, a prompt detection and the full redundancy of the chemical
treatment systems, and such a high design availability resulting justified.
3.5 Selection of chemical treatment method
The selection of the type(s) of chemical to consider in chemical treatments for corrosion control of
pipelines depends on the intended application and should be analysed on a case by case basis. The
validation by laboratory testing of the chemical treatment performance which is assumed in the
applicability evaluation is usually required, unless adequately supported by successful operational
experiences (field feedback) or previous laboratory testing results and consolidated techniques.
Qualification by laboratory testing is strongly recommended in case of high fluid corrosivity, where
the pipeline integrity highly relies on chemical treatment, and in any case to verify compatibility with
other chemicals injected and non-metallic materials.
The primary technique to consider for corrosion mitigation of pipelines for hydrocarbon transportation
is the continuous injection in the fluid stream of corrosion inhibitors.
In some conditions the injection of corrosion inhibitor is not suitable to mitigate corrosion adequately
in all portions of the pipeline or under all service regimes: in such cases the following options can be
evaluated:
− continuous injection of other chemicals such as glycol and pH stabiliser, which are more
appropriate than corrosion inhibitors in the specific conditions,
− combined injection of other chemicals as glycol or pH stabiliser continuously injected with
corrosion inhibitors to complement their reciprocal action
− supplement the continuous injection of inhibitor with periodical batch treatments specifically
designed to supply with inhibitor the metal surface which are not wet by the fluid phase carrying
the inhibitor.
This is particularly the case of gas pipelines where corrosion inhibitors are not effective in mitigating
corrosion of steel exposed to the wet condensing gas.
Based on the fluid transported, the criteria provided in the next paragraphs and summarised in Figure
3.1 are used for a pre-selection of the most appropriate chemical treatment.
3.5.1 Gas-condensate pipelines

Corrosion inhibitors disperse and provide effective corrosion control to the liquid phase. In dispersed,
mist or annular flow, the liquid phase carrying the inhibitor is able to reach the full section of the pipe
and effective inhibition is obtained.
In slug flow, cyclical wetting of the top of the line by slugs of liquid carrying inhibitor guarantees the
formation and the replenishment of the corrosion inhibitor film resulting in effective corrosion
prevention either at the top of line.
In stratified flow, on the contrary, the liquid phase remains stratified at the bottom of the line and is
not able to reach the top of the line which remains deprived of protection. In this condition corrosion
inhibitors are not suitable to control corrosion at the upper part of the line exposed to condensing
water from the gas phase and top of line corrosion “TLC” may occur if the water condensation rate
exceeds a critical threshold. For TLC avoidance different techniques may be considered.
If injection of glycol is required for process reasons, to prevent the formation of gas-hydrates, it is
possible to take advantage from the beneficial side effect of glycol (MEG or DEG) in controlling
corrosion. The quantity of glycol injection may need to be increased and injection should be extended
to the whole annual period to give glycol injection this twofold function. Glycol is efficient in controlling
gas phase corrosivity (TLC) and, to a lower extent, also the corrosivity of the stratified liquid at the
bottom of the line (BLC); however residual corrosion of the liquid phase may remain too high and
Page 19 of 68
additional injection of corrosion inhibitor, or more conveniently pH stabiliser, is required to achieve

adequate corrosion control. Methanol is sometimes injected instead of glycol for the same purposes:
its effect on corrosion is also similar, but its efficiency in corrosion control is less reliable than glycol
and special investigation and testing are required in this case.
If injection of hydrate preventer is not necessary, the injection of glycol for the sole purpose of TLC
corrosion control is usually not practical and other methods shall be sought. The most common
technique is based on batch treatments of corrosion inhibitor between to pigs (see paragraph C.1.4).
3.5.2 Wet-gas pipelines

For wet gas pipelines, corrosion is more efficiently controlled by injection of glycol (see paragraph
3.5.1) with small additions of pH stabiliser or corrosion inhibitors. The set-up of stratified flow is
usually less likely than in gas-condensate systems, given the small quantity of associated liquid,
however if stratified regime is expected the same criteria given at paragraph 3.5.1 apply.
3.5.3 Oil-multiphase systems

For pipelines transporting liquid hydrocarbons with associated gas and formation water, the main
chemicals to consider are conventional corrosion inhibitors.
If conditions for TLC occurrence are expected additional methods shall be implemented to control
this issue. Glycol injection in oil system is usually not required, therefore the most common technique
is based on batch treatments with pigs (see paragraph C.1.4).
3.5.4 Liquid-hydrocarbon systems

Chemical treatments of pipelines for the transportation of liquid hydrocarbons (oil or condensate) and
production water are based on the injection of corrosion inhibitors.
Page 20 of 68
HYDROCARBON
PIPELINES
Wet Gas /
Oil/Multiphase Stabilised Oil /
Gas-Condens. Dry Gas
(GOR<890) Condensate
(GOR > 890)
Corrosion No continuous
Glycol for No Treatment
No Inhibitor treatment
hydrates?1 Required
(continuous inj.) required
Yes
No
Glycol control of
corrosion (dosage
adjustment) Flow regime is
No stratified?
Low Yes
Batch treatment
with inhibitor for
Yes
low spot areas
CO2 corrosivity
TLC is
expected?
High
Flow regime is Yes

No Yes
stratified?
TLCC by batch
treatment of
Addition of H2S is
corrosion inhibitor
Corrosion present?
using Pigs
Inhibitor to glycol
no
Yes
Shear stress is
Yes
high (>32Pa)? NOTES:
1) Glycol is foreseen for hydrate prevention purposes?
No
LEGEND:
Amount of Formation TLC = Top of Line Corrosion
Formation Yes water is TLCC = Top of Line Corrosion Control
High
Water present? BLC = Bottom of Line Corrosion
BLCC = Bottom of Line Corrosion Control
consider further
Low addition of CI if No 50% DEG/MEG
is required
required
Corrosion
pH Adjustment pH Stabilization
inhibitor for
for BLCC for BLCC
BLCC
Glycol dosage
TLC is
Yes adjustment for
expected?
TLCC
Figure 3.1 – Selection of chemical treatment for corrosion control of hydrocarbon pipelines
Page 21 of 68
3.5.5 Chemical injection methods

Chemicals injection may be performed via continuous injection, periodical batch treatment or a
combination of both.
Continuous treatment is the primary method to consider, and should be prioritised in any conditions
where it is feasible and economical.
Combinations of continuous and batch treatment are sometimes required when the continuous
injection of chemicals for the control of the main corrosion process is not effective in controlling other
corrosion issues which require another type of chemical (e.g. biocide) or a different method to supply
the chemical onto the surface to protect from corrosion. Typical is the case of top of line corrosion
occurring in stratified flow regime, where the corrosion inhibitor injected in continuous, dissolves in
the liquid phase and is not able to reach the upper part of the line, exposed to the wet gas. To
overcome this problem, batch treatments should be performed to lay corrosion inhibitor onto the
upper section of the line by using two pigs carrying a solution of inhibitor in between. The pipeline
shall be piggable and equipped with pig launcher and pig receiver.
Batch treatments alone are rarely considered for corrosive system: they can be selected when the
system is lightly corrosive or normally non-corrosive, to prevent corrosion during upset conditions or
at unfavourable locations. Typical are the cases of separated oil carrying traces of water which may
stratify at low flow conditions and remain trapped at low spot areas of pipeline, or dry gas pipelines
which may undergo occasional “wet” periods. Batch treatments with biocide may be also required
when conditions promoting MIC are met.
The selection of the chemical injection method is based on:

− expected corrosion forms,
− predicted corrosion rate,
− operating conditions,
− risk of top of line corrosion,
− pipeline piggability.
The chemistry of corrosion inhibitors to be used for batch or continuous treatment are different and
the two methods require different selection tests. It is therefore necessary to establish which will be
used before starting selection and qualification.
3.5.5.1 Continuous injection

Continuous injection is practiced by providing the required devices to pump continuously a specific
quantity of the liquid chemical solution at predefined locations. The equipment include storage tanks,
mixing facilities, pumps and tubing to transfer the chemical solution from the tank to the injection port
which is usually equipped with a quill to disperse appropriately the chemical into the pipeline.
Continuous injection is mandatory for highly corrosive systems which shall be constantly neutralised
by a well controlled and highly effective treatment capable to supply the fluid with the design dosage
of chemical.
With continuous injection, the effectiveness of the treatment in mitigating corrosion is usually very
high, with very low or negligible residual corrosion rates. The total corrosion counted as cumulative
wall thickness consumption after long-time service is mostly related to the reliability of the system in
supplying inhibitor continuously and at the desired dosages rather than on residual corrosion.
By implementing a careful design of the injection system, addressing equipment redundancy and
online monitoring, and by enforcing control during operation to assure the injection system is
appropriately and efficiently working, high corrosion inhibitor availability “CIA” may be achieved,
which allows a reduction of corrosion allowance.
Page 22 of 68
3.5.5.2 Batch treatments

Batch treatment for corrosion inhibition may be considered as an alternative to continuous injection in
low or mildly corrosive systems, where pipeline integrity is not endangered by corrosion, or as an
additional method performed in conjunction with continuous treatment to overcome its limits in
controlling corrosion of pipeline:
a) due to secondary corrosion mechanisms (the primary being controlled by continuous treatment),
b) at specific locations (low spot areas, upper part of the pipeline “top of line”),
c) during special service conditions (upsets of process treatments, wet events of dry systems etc.).
A batch treatment consists in periodical injections of “slugs” of a corrosion inhibitor solution to form a
persistent film onto the steel wall of the pipeline which prevent corrosion for a reasonable period of
time.
The treatment effectiveness in mitigating corrosion decays after a certain period of time which is
related to the persistency of the film of inhibitor deposited onto the pipe wall and may be reduced by
the shear stress action of the fluids flowing during service. Treatment needs therefore to be repeated
with an adequate frequency. The effectiveness of the batch treatment is generally poorly controlled
and possibly not uniform along the whole pipeline length; the overall efficiency is lower than in
continuous injection.
Batch treatments for corrosion inhibition of pipelines may be considered as an alternative to

continuous injection in the following conditions:
− technical or economic considerations preclude continuous injection and the fluid corrosivity is
mild,
− the fluid is normally not corrosive, but traces of residual water may stratify and accumulate at low
spot areas of the pipeline,
− operating conditions (flow regime, shear stress, temperature etc.) are such that the persistency
of the inhibitor deposited onto the steel pipe surface is not compromised for a reasonable elapse
of time (e.g. one month)
Batch treatments may also be required as an additional method to continuous injection for the control
of side-effect corrosion forms in the following cases:
− gas-condensate or multiphase systems operated in stratified flow regime, which prevent the
inhibitor (injected continuously) from reaching the top of the line and the inhibitor distribution to
the top of the line cannot be ensured by other means (e.g. by injection of glycol),
− severe corrosivity or temporary upset conditions,
− conditions are such that bacterial activity is promoted and MIC shall be controlled by biocides.
Compared with inhibitors for continuous injection, inhibitors for batch treatments use high molecular
compounds, limitedly soluble in the carrier solvent, which give place to thick macrofilms of the order
of 25 to 100 μm. The action of production fluid after treatment removes primarily the solvent from this
film and the solute tend to precipitates on the pipe surface.
The batch inhibitor concentration are usually around 10 to 15% in weight and a convenient and
inexpensive solvent, such as lease crude, stabilised condensate, or diesel, can be used to dilute the
inhibitor.
Batch treatments of pipelines often use a slug of inhibitor sealed between two tight pigs to avoid
leaks through the trailing pig, resulting in shrinking of the slug as it progresses through the pipeline.
The operation may need preparation with a pre-flush with methanol to clean the surface from
deposits and make it ready for filming with inhibitor.
The persistency of the inhibitor film deposited by batch treatments increases with the contact time
during the deployment operation. Persistency is improved by allowing adequate contact time,
considering constraints dictated by practical aspects as pumping capacities and limitations in
handling large slug volumes by gas treatment facilities. A minimum contact time of 15 to 30s is often
chosen as a reference design; during operation effectiveness is checked and contact time is adjusted
for optimisation.
Page 23 of 68
The persistency of batch inhibitors needs to be tested in the laboratory, particularly with respect to
shear stress induced by the flowing fluid, and verified in the field to ensure batch treatment
effectiveness for a reasonable time.
3.5.6 Applicability of chemical treatments

At the design stage a pre-assessment of chemical treatment suitability shall be performed to verify
that the selected chemical treatment and injection methods are potentially applicable to control
corrosion effectively for the service life required.
As a general rule, the treatment with chemicals for corrosion mitigation should be capable to reduce
general corrosion below penetration rates of 0.1 mm/y and to avoid any localised corrosion. Any of
the conditions that may compromise the inhibitor performance shall be carefully investigated.
The assessment is based on:

− expected un-inhibited corrosion rate “CR”
− corrosion rate variation during service life
− assume residual corrosion rate with chemical treatment “CRR” equal to 0.1 1 mm/y
− type of service/fluid
− required design life, “DL”
− corrosion allowance, CA”
− sweet or sour service
− temperature that may cause loss of inhibitor performance
− flow velocities
− age of pipeline.
The viability of chemical treatments is mainly related to the following aspects:

− the expected capability of the method to reduce corrosion rates within limits that may be
managed by addressing an appropriate corrosion allowance for the desired service life,
− the ability of the chemical injection facilities (reliable injection facilities, chemicals storage
capacity etc.) to provide the chemical at the design dosage, continuously or with the design
frequency without or with acceptably low long-term breakdowns (chemical availability),
− the expected compatibility between chemicals.
If pre-assessment of chemical treatment suitability is verified, the operational context shall be

analysed to plan an optimised deployment strategy, which should be practical and reliable in
providing a continuous and well controlled supply of chemicals with minimized downtimes or
inefficiencies of the injection system. Context analysis and deployment strategy should permit the
prediction of the chemical availability “CIA” that may be assumed for design.
The procedure for suitability pre-assessment verification is performed by applying the following
procedure:
1. Chemical treatments shall be considered as not applicable if discouraged or prohibited by HSE

requirements.
2. The applicability of corrosion inhibition treatment shall be subject to further investigation, possibly
supported by experimental work planned for a latter stage of the project, if one or more of the
following conditions are verified:
a. the “blank” weight-loss corrosion rate “CR” exceeds 10 mm/y (unless the design life is
lower than 20 years)
b. the max CO2 partial pressure in CO2 dominated systems (CO2/H2S > 20) is above 10 bar
1
For severe corrosive conditions, e.g. with corrosion rate above 5 mm/y, higher residual corrosion rate should be anticipated
to account for efficiency of corrosion inhibitor which may not be able to drop down the residual corrosion rate below 0.1 mm/y.
In such conditions it is recommended to use a maximum corrosion inhibitor efficiency equal to 95% for design purposes.
Page 24 of 68
c. the maximum operating temperature exceeds 120°C

3. The opportunity of chemical treatments in critical applications such as subsea deep-water or
other harsh context, where pipeline integrity highly relies on chemical treatments shall be careful
considered.
4. Based on the “blank” weight-loss corrosion rate predicted, the required design life, and the
corrosion allowance, the minimum required corrosion inhibitor availability “CIA” is calculated with
the following formula:
CA
CR −
CIA = DL
CR − CR R
Where:
CIA = corrosion inhibitor availability, defined as
CR = blank “weight-loss” corrosion rate (mm/y)
CA = corrosion allowance (mm)
DL = required tubing design life (years)
CRR = residual (inhibited) corrosion rate (mm/y): at the design phase it may be assumed equal to 0.1 mm/y
(or CRR = 0.5 × CR for CR > 5mm/y).
At the design phase, if no testing or field-experience data are available to support other figures, it
is normally assumed that the “inhibitor performance” is such that the residual corrosion rate with
inhibitor “CRR” is 0.1 mm/y. For highly corrosive systems (CR > 5 mm/y) it should be considered
that the efficiency of inhibitor may not be able to drop down the residual corrosion rate below 0.1
mm/y. For this reason a maximum inhibitor efficiency E equal to 95% should be imposed for
design purposes, and therefore the residual corrosion rate is calculated as follows: CRR = (1 – E)
× CR ( see efficiency model at paragraph 3.4.1).
In summary the following equation is used:
CA = (CRR x DL x CIA) + CR x DL x (1 – CIA)
Where:
CRR = residual (inhibited) corrosion rate = 0.1 mm/y (or CRR = (1-E) × CR for CR > 5mm/y)
CIA = corrosion inhibitor availability
If the required “CIA” is not higher than 90% no further investigation is required.
If “CIA” is between 90% and 95% the overall CIA shall be demonstrated by documented
corrosion management strategy design.
If the required “CIA” is higher than 95% then the corrosion inhibition treatment option should be
abandoned and upgrading to a suitable CRA is recommended. Alternatively, higher corrosion
inhibitor performance and overall “CIA” shall be demonstrated by laboratory testing and
documented corrosion management strategy design.
5. If based on the required availability “CIA”, the continuous injection of corrosion inhibitor is
required, the following conditions shall be verified:
a. the shear stress induced by flowing production fluid is not higher than 50 Pa (high shear
stress removes corrosion inhibitor adhering to the pipeline wall).
6. If based on the required level of CIA batch injection treatment may be sufficient (e.g. CIA ≤ 50%),
the feasibility of this method shall be assessed by checking the following conditions are verified:
a. batch method deployment is feasible? facilities are available (e.g. if pigging is required,
pigging facilities are available or may be included?)
b. the shear stress induced by the flowing fluid is not higher than 20 Pa (high shear stress
removes corrosion inhibitor adhering to the tubing wall and too frequent replenish is
required)
Page 25 of 68
PRE-ASSESSMENT OF
CHEMICAL TREATMENT
SUITABILITY
Chemical 1. HSE require-

treatment is ments prohibit 2.a CR>10
Yes No Yes
not Chemical treat- mm/y ?
applicable ments?
No
Applicability
2.b CO2>10
Yes to be futher
bar ?
investigated
No
2.c Tmax >

Yes
120°C
No
3. Critical
Applicability
applications as
4. Calculation of No Yes to be further
minimum required subsea deep
investigated
CIA water?
CIA > 95%
90% < CIA < 95 % CIA < 90%
Overall CIA shall be CIA may be assumed

demonstrated by to recalculate
corrosion manage- minimum corrosion
ment strategy design allowance (see 4.4.6)
Upgrade to CRA Based on the

required CIA which
injection treatment is
sufficient?
5. continuous 6. Batch treatment is

injection is required sufficient
Shear stress Shear stress

< 50 Pa? < 20 Pa?
Yes Yes Yes No
Method Method not Method Method not

suitable suitable suitable suitable
Figure 3.2 – Applicability assessment of chemical treatments

Page 26 of 68
Key aspects for pre-selection of the chemical which are important for technical integrity are:
− Performance: it is expected to provide the required performance used for design as a minimum,
given a figure of concentration, film stability, partitioning behaviour.
− Chemicals compatibility: compatibility with other chemicals injected, either for corrosion control or
other purposes.
− Materials compatibility: shall not damage other metallic or non-metallic materials, organic or
metallic coatings, linings, plastics, elastomeric seals etc. that may come in contact with the
treated fluid also in the downstream process.
− Past operational experience
− Pre-qualification by laboratory testing
• the intended application needs to be fully analysed prior to initiating any testing, to
identify the critical factors relevant to corrosion and inhibition and determine the proper
testing sequence,
• the cheaper and faster screening tests are performed first to limit the most expensive
testing to the best candidates,
• compatibility issues, such as the effect of inhibitors on water disposal, downstream
processing and environment should be considered early in the selection process to avoid
finding an incompatible product at the end of the process.
− Certifications by recognised institutions
Other important aspects are related to economics, legislative regulations or practical issues:
− Environmental compatibility: the chemical shall be environmental friendly (only “green” products
shall be considered)
− Process compatibility: compatibility with process functionality at downstream fluid treatments
fluids (e.g., oil/water separation, water quality, potential for foaming or emulsions in separators,
strippers, stabilisers etc.)
− Cost: considering a preliminary figure of the dosages required
− Local availability
− Commercial issues
− Local HSE policies and regulations
Risk category Maximum

(chemical treatment Comment
criticality)
required “CIA”
Chemical treatments are not strictly required. Batch or continuous
- 0% treatments may be considered for safety reasons.
Chemical treatments are required, but there will be time to review
low 50 % the need for inhibition based on inspection data. Batch treatments
may also be considered.
medium 90 % Continuous injection of chemicals is required from day one.
Continuous injection required from day one. Design of chemical

high 95 % injection system shall demonstrate adequate reliability and control.
CRA should be considered or reduced design life accepted (plan
critical > 95 % repairs). Best endeavour is required in maximise chemical
performance and availability.
Page 27 of 68
3.6 Economics evaluation
Economics evaluation of the chemical treatment, if practical and suitable, shall be based on the
balancing of benefits and costs associated with this option. Compared with the alternative use of
CRA, this assessment consists in the comparison of the reduced CAPEX with the increased OPEX,
which shall also consider a quantification of the risk associated. If compare with CLAS without any
treatment, the assessment consists in the quantifications of benefits (e.g. extended life, shutdown
prevention, accidents prevention) with the increased OPEX and CAPEX costs.
Potential savings must therefore be based on a risk quantification approach, further than on
apparatus and consumables costs, and on these basis the opportunities of chemical treatments be
apprised.
The most typical costs associated with chemical treatments include:

− chemical products based on consumption,
− chemical products storage and refilling,
− injection system equipment, spares and backups,
− injection system maintenance and inspection,
− system and operational changes to accommodate inhibitor,
− corrosion monitoring system upgrading for inhibitor efficiency detection,
− corrosion monitoring system alarms for inhibition system upsets detection,
− cleaning operation to prepare treatments,
− operational impact and direct cost for batch treatment operations,
− increased/reduced risk of major shutdowns involved,
− increased/reduced risk for operations/environment/safety related to failure and leaks,
− personnel safety issues for increased need of operational activities,
− waste disposal.
Page 28 of 68
4. SELECTION AND QUALIFICATION OF CHEMICAL PRODUCTS
4.1 Selection of chemical products and performance evaluation
Selection of chemical products for corrosion control is based on several factors as:
− corrosion rate reduction efficiency (performance),
− past practice,
− compatibility,
− cost, local availability and commercial issues,
− environmental aspects
From the standpoint of asset integrity, the most important are: performance and compatibility.
To develop methodology for chemical product screening and selection the key factors which need to
be considered are:
− solubility,
− optimum concentration,
− film stability / persistency,
− partitioning behaviour,
− compatibility issues.
The performance of chemicals, i.e. its ability to reduce fluid corrosivity, is the main aspect that needs
to be evaluated for products’ qualification. One or more of the following methods could be used for
this purpose:
− Previous experience,
− Vendor recommendations,
− Laboratory testing,
− Field testing.
Laboratory testing is only one step of the selection process, probably the most trustworthy; however
the performance of inhibitors may also be based on vendor’s recommendations, past experience and
industry practice which may be used as initial screening criteria.
A frequent cause of ineffectiveness is due to loss of chemical before coming in contact with the metal
surface to protect or to the impossibility to reach the surface. Loss of chemical may result due to
precipitation, adsorption or reaction with the fluid, or because of inappropriate solubility or
dispersibility. Testing in actual fluid at actual conditions, ideally by field testing, is the key to identify
these issues.
Performance testing is usually required, even if it can be waived in low critical or mildly corrosive
systems. Chemical and process compatibility testing is always recommended. The environmental
compatibility of inhibitors is usually performed by the supplier.
The recommended testing procedures intend to optimise resources by screening a large number of
candidates using simple tests and using more sophisticated (expensive) testing on a few of the best
promising products which survived the preliminary tests.
4.1.1 Solubility
Corrosion inhibitors are classified by their solubility. Inhibitors for continuous injection can be oil-
soluble, water-soluble and water or oil dispersible (this classification only reflects a tendency, as
most inhibitors exhibit at least partial solubility or dispersibility, forming micro-emulsions, in both oil
and water).
The most convenient solubility properties for the specific application shall be identified based on the
fluid characteristics, particularly GOR, water cut and liquid phase density and viscosity.
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Oil soluble inhibitors (long chain primary amines, imidazolines, fatty acids, phosphate esters) are
generally more effective, particularly at high temperatures and high velocities. However, reaching the
surface to protect can be a problem in pipelines operating in stratified flow. Water-soluble inhibitors
(quaternary amines, amine salts, salted imidazolines) can result more appropriate in certain
situations. These inhibitors may desorbs and lose effectiveness at high temperatures, and they may
lose solubility (salt-out) in high salinity brines.
The solubility features influence the selection of the diluents.
4.1.2 Compatibility
Compatibility aspects include other chemical products, any materials that may come in contact with,
including downstream process, and process functionality.
Compatibility testing includes aspects related to:

− the storage and service conditions and the fluid characteristics
− the materials of injection and production systems (tanks, lines, seals, gaskets)
− other chemicals in use (scale inhibitors, wax inhibitors, demulsifiers)
To evaluate the compatibility of the corrosion inhibitors formulation (including solvents, dispersants,
demulsifier and other additives) with the injection and production systems it may be necessary to re-
run flow loop tests and involve specific tests which include viscosity measure (pumping problems),
foaming and emulsification tendency, thermal stability, effect of shear stress on viscosity.
4.1.2.1 Compatibility with materials

Metallic materials: Some concentrated formulation of corrosion inhibitors can corrode metals. They
perform as CI only when diluted to small concentrations in the fluid to inhibit. As a consequence it is
necessary to check the compatibility of neat CI with the material used to fabricate the storage and the
delivery system. The stainless steel injection quill must also be designed so as to avoid any neat
inhibitor coming in contact with carbon steel pipe prior to mixing.
Lining Materials: Lining materials (lined carbon steel for vessels and delivery piping, elastomer
materials used as seals in pumpheads) can also be attacked by certain CI (Amines). The major
chemical factors determing the effect of corrosion inhibitors on elastomers will be: Amine content,
Acidity/alkalinity, Solvent package (e.g. methanol).
4.1.2.2 Compatibility with other chemicals and downstream process

Chemicals injected for corrosion control must be compatible with the other chemicals which may be
used for other reasons. Some production chemicals that have known compatibility problems with
corrosion inhibitors are:
− scale inhibitors;
− biocides;
− demulsifiers;
− hydrate control chemicals;
− concentrated brines;
− wax or asphaltene inhibitors.
To simplify the selection procedure the best approach is to decide which function has the highest
priority, choose the best chemical for that function and then find compatible chemicals for the other
functions.
Incompatibility effects include:

− foaming;
− formation of solids due to loss of solubility or due to a chemical reaction;
− loss of performance or activity, due to interference among the chemicals;
− emulsions formation / reduced separation efficiency.
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The above undesired effects are the same at the origin of incompatibility with downstream process.
Chemical compatibility can be effectively determined by laboratory testing. Wherever practical, field
verification of chemical compatibility results from laboratory testing is recommended.
4.2 Previous operational experience
Previous successful experience with a specific product is an important reference in favour of its
further use. However, a product that performed successfully in a given condition may result
ineffective in a different operating envelope, as characterised by different fluid, temperature, flow
velocities, sand presence, water cut, water chemistry etc. The conditions of use and selection criteria
adopted by other operators needs to be thoroughly reviewed before the same product is selected for
a new application. These issues takes more importance as more the chemical treatment is key for
pipeline integrity, higher the predicted corrosion rate and poorly experienced or affirmed is the
technique pre-selected for chemical control of corrosion.
4.3 Local area experience
Some useful information can be obtained by investigating field feedback of operators in the same
area. This represent a convenient route to take advantage from lessons learned and experienced
issues dealing with common fluid characteristics, operating conditions, atmospheric conditions or
chemicals procurement.
4.4 Vendor recommendations
Suppliers will normally recommend one or two products from the large number of corrosion inhibitor
packages from their range. Before submitting a product for approval a supplier may carry out tests
run at conditions as instructed by the oil company (possibly including actual field fluid).
Vendors should be provided with sufficient information about the proposed application. Factors such
as changing production conditions, sand production, other treatment with chemicals and
environmental concerns should also be indicated.
Vendor recommendations should be supported by results from laboratory test data or documented
case history. Documents should be provided to report the following information:
− chemical composition and physical properties
− material safety data sheets “MSDS”
− environmental aspects: toxicity, biodegradability, oil/water partitioning data
− compatibility with non-metallic materials
− compatibility with other chemicals
− expected performance in corrosion reduction
− recommended dosage and application method
− storage criteria and expiring time
− laboratory test results
− documented case history records
Vendor recommendations reliability should be verified by independent product qualification. They

usually represent a valuable starting point for chemical pre-selection and to set up qualification
testing by the independent laboratories.
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4.5 Laboratory testing
Laboratory testing is an efficient way to select the most adequate product to reach the required level
of corrosion control. However, laboratory tests cannot fully reflect the real conditions and therefore,
verification of laboratory results by field testing and monitoring is also required.
Laboratory tests are run to identify the best out of candidate products under the specific set of test
conditions and criteria, and to estimate the initial inhibitor dosage. There is general agreement in the
industry that products selected on the basis of well designed and executed laboratory tests usually
perform adequately in practice. Laboratory tests, however, are not adequate for fully optimizing and
final tuning of dosage rates.
There is no universally accepted testing protocol to run experimental evaluation of chemicals: the
recommended approach is to perform exposure of a first set of tests to quickly screen a large number
of products (initial screening). The best candidates selected in these tests are then tested under
more severe conditions, including high flow, persistency, water partitioning, etc.
In this phase the wheel test is still often used as the first stage in selection. Corrosion probes are
added to many bottles containing a corrosion inhibitor in a test solution. The bottles are then sealed,
mounted on the spokes of a wheel, and rotated to agitate the contents. This test can be run at low
water cuts (< 5 %) to evaluate oil soluble corrosion inhibitors. Other tests use water as main test
solution and therefore water soluble inhibitors may arguably be favoured. Problems may arise
because water soluble products are not suitable for deployment in low-water crude, being difficult to
deliver the inhibitor to all the water wet areas of the pipe walls.
To address this concern all products should first qualitatively be checked for their solubility in brine
and in crude oil.
Laboratory tests are also used to determine the compatibility of inhibitors with other chemicals.
The laboratory tests shall confirm that the performance of the chemical products is not lower than the
figure assumed in design for pre-selection of chemical treatment, otherwise the design shall be
reviewed or the chemical treatment option abandoned.
Method Type Remarks T (°C) P (bar)

Bubble test Static. Short duration Initial screening lower than
atm.
100
Autoclave Static. Long-duration High pressure and temperature up to about up to about
200 100
Flow loop Dynamic. Flow-loop Long Limited shear stress lower than
atm.
duration 100
High pressure Dynamic. Flow-loop Long High pressure and temperature lower than up to about
flow loop duration 100 100
Rotating cylinder Dynamic. Rotating Limited shear stress. lower than
atm.
Result may be not conservative 100
Rotating cell Dynamic. Rotating High pressure and temperature up to about
about 30
Result may be not conservative 120
Jet impingement Dynamic. Impingement High shear stress lower than
atm.
Loop 100
4.5.1 Test fluid

Fluids are often not available for testing, and tests are usually conducted with ‘synthetic’ fluids.
Ideally, some tests should be run also with field produced fluids, even if this can only be done after
production is initiated. These tests should include the performance, the physical-chemical properties
(such as solubility and oil/water partitioning) and the compatibility (emulsion, foaming solid formation)
of inhibitors. Autoclave tests are the most efficient for corrosion testing with field fluids since the
appropriate temperature and pressures can also be recreated.
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4.5.2 Performance evaluation

Corrosion inhibitors are compared on the basis of the efficiency, as defined at paragraph 3.4.1, in
mitigating the corrosion rate. The required concentration to achieve an optimised balance of
efficiency and quantity is also identified.
The chemical product shall satisfy certain requirements associated with the specific application,
which typically include: thermal stability at high temperature, sensitivity of efficiency with
concentration and flow velocity, flow velocity limitations.
A first set of simple tests are carried out initially with the purpose to rule out the unsuitable products
(initial screening).
Products which survive the initial screening are submitted to more demanding dynamic tests (flow
loops autoclave) focused on identify the product displaying the best performance.
4.5.2.1 Initial screening

Solubility. The solubility test is to check the dispersal of the corrosion inhibitor in the carrier media:
oil, water and glycol. Corrosion inhibitors must be soluble or dispersible in both brine and the oil in
order to proceed to the next stage of testing. Synthetic oil is used to simulate the hydrocarbon fluid.
Bubble Test. Bubble test is a simple test which allows a rapid screening of all products under static
conditions. They are run at ambient pressure and limited temperature which provide an effective
method for screening chemicals on simple basis. Bubble tests use a vessel to contain the test fluid
(simulated brine/oil), accurately deaerated and gas-purged to control CO2 and/or H2S partial
pressure. The tube in the centre is used for introducing a standard linear polarisation resistance
(LPR) corrosion probe. Weight loss coupons may also be employed to check the general corrosion
obtained electrochemically.
4.5.2.2 Dynamic tests

The main limitation of the bubble test is that the actual flow conditions experienced in the pipeline are
not reproduced. Shear stress is a limiting factor for many chemicals which may loose their ability to
control corrosion if a critical threshold of shear stress, i.e. flow velocity, is exceeded. Consequently it
is essential to reproduce the actual flow conditions in laboratory.
Medium and high shear stress methods like 'flow loop', 'rotating cylinder electrode' and 'Jet
impingement loop' can simulate wall shear stress in the laboratory under realistic conditions. Wall
shear stress is a surface parameter which defines the influence of a flowing fluid on the formation
and stability/persistency of an adsorbed inhibitor film.
Flow Loop Tests. In the flow loop tests the best products are examined under dynamic conditions.
Flow Loop tests are generally intended to reproduce the flow effects occurring in service, i.e. flow
velocities, mass transfer coefficients and wall shear stresses. Flow loop tests can be carried out
either as standard glass flow loop at ambient pressure and limited temperature (standard flow loop)
or in autoclave at high pressure and temperature (high pressure flow loop).
Rotating cylinder electrode. With the rotating cylinder electrode (RCE) high shear stress can be
obtained in an electrochemical cell similar to the bubble test device as described in 4.5.2.1. RCE
gives turbulent flow but at the lowest speed. The tests are carried out at ambient pressure and limited
temperature. With a typical commercial system providing rotation speeds up to 10’000 rpm it is
possible to achieve shear stresses up to 90 Pa. The RCE is especially useful for examining inhibitor
film persistency, which is a key aspect for batch treatment.
Jet Impingement (High velocity). The highest shear stresses in a pipeline occur at locations such as
bends, T’s and sharp edges. A jet impingement loop can simulate the shear (up to 300 Pa) in these
situations using a high speed jet of liquid impacting onto a test specimen.
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4.5.2.3 Autoclave test

Autoclave Tests are final static tests to imitate field conditions. They are expensive and restricted to
inhibitors which are most promising based on the previous tests. The autoclave tests can be
conducted at high temperature (max 200 °C) and pressure (max 100 bar) and may take an indicative
duration of 48 hours. The corrosion coupon is frequently a rotating cylinder or cage, to study the
effect of velocity on inhibitor performance.
4.5.3 Partitioning evaluation

The main purpose of a partitioning test is to investigate the partitioning of the chemical between
hydrocarbon and water. It is run to estimate the inhibitor dosage required on total fluid, e.g. based on
partitioning the dosage in water may be inferred by the dosage in total liquid.
This illustrates the importance of conducting partitioning tests at realistic water/oil ratios, and also of
adjusting injection rates with changing water cut. Experimental data are used to identify the chemical
concentration on total fluids at given water cuts.
Wherever possible, these tests should be carried out with the actual fluid rather than syntactic test
fluid.
The dose rate determined in the laboratory should be introduced in the field and then gradually
reduced or increased to an optimum value using field monitoring.
4.6 Field testing
Laboratory testing is always an approximation of the real system, as not all field parameters can be
reproduced in a laboratory set-up. Field testing is ideally the best way to determine inhibitor
performance. In reality, field testing is often not feasible due to technical or economic constraints.
The field test program should reflect the following general requirements:
− establish limited and clear objectives: the main is to determine the performance and compatibility
of a single product in the specific real application;
− develop a robust plan for monitoring corrosion rates and other operating parameters (injection
rates, production rates, inhibitor residuals, water chemistry, potential compatibility problems such
as foaming or emulsions) over an extended period. The duration of the test will depend on specific
conditions, but it should be on the order of 3 to 6 months, or even longer to allow proper
measurement of low corrosion rates;
− clearly assign roles and responsibilities to all participants in the field test, including: chemical
suppliers, operators, corrosion engineer, production chemist, and possibly production technologist
and facilities engineer.
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Figure 4.1 – Procedure for selection and qualification of chemical products

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5. DESIGN OF CHEMICAL TREATMENT SYSTEMS
5.1 Introduction
This section provides guidelines for aspects related to design of the chemical treatment system in
order to fulfil requirements regarding:
− reliability and availability in ensuring that the chemical is appropriately delivered by the system to
the pipeline,
− safety and environmental aspects like toxicity, flammability and flash point of the products and
solvents. Disposal of waste streams,
− operability of the system like clear design, easy access,
− monitoring effectiveness including data collection, storage and data analysis.
The design of the chemical treatment system covers requirements for:

− the injection or delivery system,
− the monitoring and data acquisition system.
The chemical injection system shall be considered a critical item for pipeline integrity.
5.2 Specifications
The design of the system for chemical treatments requires adequate specification to enable the
Contractor to purchase appropriate equipment and instrumentation.
This includes design of the injection system, secondary containment, corrosion monitoring
requirements and data acquisition criteria.
The injection system consists of storage tank, mixing tank (if product needs to be diluted), injection
pumps, connecting lines, injection ports (valves, quills), control equipment (valves, gauges,
instrumentation).
5.3 Preliminary examination of compatibility
If a chemical treatment is planned, the pipeline system and the downstream process shall be
preliminary examined to identify possible undesirable effects associated to the chemicals.
As discussed at paragraph 4.1.2, compatibility issues shall be verified during chemical treatment
system design. Compatibility aspects include materials of construction, flow assurance, and
downstream process functionality. The evaluation shall include possible plugging issues induced by
chemical presence as scales, precipitates and suspending in the fluid and might require prevention
by cleaning actions.
Careful assessment of possible issue with metallic and non-metallic materials that may come in
contact with the selected chemical, in the diluted or concentrated form, shall be performed.
A full list of the materials in use, including small items, gaskets, instrument and control devices,
should be prepared to check for suitability and possible need of materials changes.
Chemical compatibility can be effectively determined by laboratory testing as discussed at paragraph

4.1.2; however, field verification of laboratory results may be required.
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5.4 General requirements
The design of the chemical treatment system should consider the following general requirements:
− installation of flow meters with automated no-flow alarm installed on the injection line. For
redundancy reasons, two flow meters are generally installed, plus one at stock further than spare
parts for maintenances;
− two pressure instrument, in order to cover possible out of service to be installed on inhibitors
injection line;
− pumps motors and instrumentation to be included in the list of items to be connected to the
emergency diesel power generation in case of emergency and connected to UPS;
− all instrumentation, pumps status and alarms should be connected to DCS and to a local control
panel; pump control should be possible either from the control room and the local control panel;
− materials in contact with corrosion inhibitors shall be checked for compatibility with the
requirements of corrosion inhibitors supplier;
− portable pumps should be provided for refilling of storage tank from delivered corrosion inhibitor
drums;
− the continuous injection into the line should be performed through spray nozzle. The point of
injection should be out of the pig path or the spray nozzle should be retractable. A spare spray
nozzle connected to the inhibitors injection system shall be provided;
− the injection system operating manual should list all the required spare parts, frequencies of
maintenance, frequency of replacement, activities and prescriptions to be performed in order to
maintain the required availability (for skid and relevant components, in particular pumps);
− inhibitors injection rates should be adjusted based on results/information from chemical analysis,
production data and corrosion monitoring system, in order to allow the continuous control of the
efficiency of corrosion inhibition;
− measurements of the residual quantity of corrosion inhibitor in the water phase at the pipeline
outlet shall be carried out in the initial phase of the production to check for adequate dosage.
Once this concentration has been reached, routine measurements are required;
The performance of the chemical treatments in controlling fluid corrosivity is related to the concepts
of residual corrosion rate, or efficiency and availability as discussed at paragraph 3.4.
During the following phases of design, the value of the residual corrosion rate, or efficiency, shall be
demonstrated by laboratory testing for the qualification of the chemical products as discussed at
Section 4. The required availability assumed for design shall be supported by criteria for the design
of the chemical treatment system, as well as operation aspects, to demonstrate its adequacy in
achieving the desired level of reliability.
As high is the fluid corrosivity, as high is the required availability and critical the chemical treatment
system, in that pipeline integrity is highly dependent on it. The design of the system for chemical
treatment deployment shall reflect its criticality, i.e. advanced and reliable design shall be enforced,
including backup of injection pumps for full redundancy, shut-off alarms and real-time corrosion
monitoring for a prompt detection and fix of upset conditions.
5.6 Design dosages
For the design of the chemical treatment equipment, it is necessary to know the quantities of the
chemical product that needs to be injected into the pipeline.
This datum is given by the combination of production flow rates and water flow rates data with the
design dosages of the chemicals.
Optimised dosages of chemicals used for corrosion control are determined by laboratory testing
performed during the qualification process of the selected products. These data are usually not yet
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available at the design stage of the chemical treatment system, which typically precedes the
qualification phase, and in any case sizing of chemical injection equipment shall be based on larger
quantities for conservative reasons.
“Design dosages” figures given by the next paragraphs should be used to determine the system
capacity required and the sizing of relevant equipment (e.g. pumps and storage tanks).
5.6.1 Continuous injection of corrosion inhibitors

The initial inhibitor dosage rate can be determined by laboratory tests, field tests, supplier
recommendations, or past experience. The initial dosage should be sufficient to ensure the integrity
of the asset until monitoring data becomes available to asses the actual performance of the inhibition
system. When monitoring data and inspection results become available, dosage optimisation is
accomplished during service.
In absence of laboratory or field data, for a rough estimation of the inhibitor costs and injection
system sizing (pumping and tankage capacity), conservative dosages can be assumed based on
target concentrations on either water phase or total fluid and depending on fluid type, operating
temperature and flow velocity.
− Liquid or multiphase systems
In most common situation the operating temperature is within 60-80°C and flow velocity is
within some 5 m/s. In this conditions corrosion inhibitor dosage should guarantee a
minimum concentration in the water phase in the range from 20 to 50 ppm. Based on the
water cut, the typical concentration in the total liquid ranges from 10 ppm (low water cut <
5%) to 30 ppm (high water cut > 10%).
At high temperature (80°C – 120°C) or high flow velocities (5 – 15 m/s) the possible need
for higher dosages, as high as 200-300 ppm in the water phase shall be anticipated until
results from laboratory testing can demonstrate adequate water/oil partitioning and
effectiveness at lower concentrations.
− Gas systems
For gas systems, default dosage ranges between 10 and 30 litres per million of standard
cubic meter of gas produced, or 100 ppm based on total produced water (condensed plus
formation) whatever is greater.
The inhibitor delivery rate is usually set to the maximum production throughput to give the desired
concentration on total fluids. If production is temporarily reduced (e.g. one day) the inhibitor delivery
may not need to be adjusted, however if the throughput goes up then the inhibitor delivery rate must
also be increased for compensation. In some cases the higher wall shear stress may need the
inhibitor to be re-selected to cope with erosion-corrosion.
Water cut is the key parameter and the response to a water cut change depends on whether the
inhibitor is preferentially oil or water soluble, the concentration with respect to the water phase must
remain constant.
The injection rates are linked to production rates. Ideally, this relationship could be automated but
this would only be feasible if the water cut was continuously monitored.
In the case of long pipelines, it may be necessary to increase the dosage of inhibitor injected to
account for the lost of a fraction of inhibitor adsorbed onto the pipeline surface and which is therefore
no longer available. For this reason an extra dosage may be required which is calculated with the
following formula:
extra dosage [litres/day] = 0.2 × pipeline diameter [inches] × length [km]

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Furthermore, a minimal dosage equal to about 2 litres per day per each pump should be considered
to account for the fact that the dosage supplied by commercial pumps becomes unreliable at lower
rates.
5.6.2 Batch treatments of corrosion inhibitors

The concentration of corrosion inhibitor solution used for batch treatment usually varies between 10
to 15% in weight. The inhibitor is diluted in a convenient solvent.
For batch treatment of pipelines the volume of inhibitor solution required is calculated starting from
the assumption that a certain inhibitor thickness film “t” will be deposited onto the steel surface of the
pipeline (D × L), and a formula like the following is used:
inhibitor volume ∝ D × L × t
Alternatively, the slug volume is calculated based on the minimum desired contact time, and a
formula of the following shape is used:
slug volume ∝ V × ct × D2
5.6.3 Adjustment of glycol dosage for corrosion control

If the injection of glycol is a requisite dictated by process reasons to prevent gas-hydrate formation, it
may result opportune to adjust timing and dosages of the quantity of glycol injected for this main
purpose to accomplish the twofold target of corrosion control.
The quantity of glycol required for corrosion control depends on the fluid corrosivity and if control by
glycol is focused on the mitigation of the bulk liquid phase or of wet gas phase corrosivity (e.g. top of
line corrosion).
In the first case the quantity of glycol that is necessary to inject depends on the quantity of produced
water, on the water phase corrosivity and on the level of efficiency in corrosion mitigation that is
required. By using the glycol factor equation at paragraph B.3 as a sort of corrosion inhibition
efficiency, it result that the glycol quantity to inject to achieve full protection of the liquid phase, which
may be assumed given by a residual corrosion rate equal or below 0.1 mm/y, may be very high,
typically such that the water/glycol percent is lower than 5%.
In the second case the target is to drop down with glycol the water dew point of the wet gas so that
condensation of water is prevented or limited to a point that corrosion from wet gas is lower than 0.1
mm/y. This target is achieved with lower quantities of glycol injected.
In summary, the required dosages of glycol depend on the amount of liquid water present and if
glycol control of corrosion is mainly focused on wet gas, with control of the liquid phase controlled by
additions of corrosion inhibitor or pH stabilizer.
If the quantities of glycol to inject are important, the injection system usually includes a glycol
regeneration treatment with piggyback line for back transportation of regenerated glycol to the
injection point. pH stabilizer, often added to glycol to complement its action in liquid phase corrosion
control, are regenerated together with glycol.
5.6.4 pH stabilization
The dosage of pH stabiliser to be added depends on the CO2 partial pressure and therefore on fluid
corrosivity. The target is to increase and keep pH in the range 6.5 to 7.5. Presently there are no
generally accepted rules for determining the required concentration to achieve this goal.
The super-saturation of iron carbonate in all pH stabilized systems is the driving force to obtain
protective films. Intuitively, one way of scaling the required concentration from one partial pressure of
CO2 to another could be by maintaining the same degree of super-saturation of iron carbonate. As
the concentration of iron cannot be controlled directly, the parameter to control should be the activity
--
of carbonate (CO3 ), i.e. the concentration of pH stabilizer. This requires that the activity of carbonate
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and the solubility product for iron carbonate be calculated for a water/MEG system. Kaasa (Ref./1/)
et. al. have published data on solubility and activity of various species in a MEG system. All the data
are included in a commercially available program. Seiersten (Ref./1/) has shown a method how to
determine acid constants in glycol by potentiometric titration.
As observed by laboratory testing carried out by Dugstad (Ref./1/) et.al, with increasing level of CO2
partial pressure, it was necessary to increase from 100 to 200 mM/kg the amount of HCO3- (in a
solution of 50% glycol) to achieve the same supersaturation of iron carbonate. These tests have
shown that the required target pH to reach corrosion control varies with the partial pressures of CO2.
At temperature higher than 20°C the formation of stable protective films is easily achieved. Conversely
below 20°C, the formation of stable products is difficult and this may result in a residual corrosion rate
that may exceed the target value of 0.1 mm/y in highly corrosive systems. Laboratory testing are
required to determine this value.
5.7 Dilution
Inhibitor formulations are purchased in a ready-to-use “pre-mixed” form or in a concentrated “neat”

form. Active compound may be 1 to 20% in weight in the first case and 20 to 80% in concentrated
form, the remaining are solvents, surfactants and demulsifiers.
Concentrated products need on-site dilution with an appropriate solvent. Mixing tanks can be used
for dilution
On-site mixing of concentrated products requires handling of large volumes of toxic or flammable
substances and a proper dosage.
5.7.1 Solvent
The choice of solvent depends on the oil/water solubility of the products, local availability, cost etc.
Typical solvents are fresh water, alcohols, glycol (MEG or DEG), condensate, crude oil or diesel.
Water is cheap and usually available and is often chosen for water-soluble inhibitors.
Water shall be of controlled quality and shall be carefully deaerated to less then 20 ppb residual
oxygen to prevent oxygen ingress. Additions of oxygen scavenger (ammonium or sodium bisulphite)
is the usual method to deaerated water.
Seawater, abundant in offshore applications, is sometimes used: compatibility with salinity, which
may limit solubility, and bacterial corrosion problems shall be investigated and prevented by proper
treatments.
Liquid hydrocarbons are used for diluting oil soluble inhibitors.
Pipeline / Treatment Diluent /Concentration Remarks

Oil/Multiphase Pipeline With as-received corrosion inhibitors
Methanol, alcohol. At low temperature many CI are
Gas Pipeline not fully soluble in methanol
0.5 % up to 5 %.
Gas Pipeline, hydrate Treatment Methanol, alcohol. At low temperature many CI are
required up to 10 %. not fully soluble in methanol
Crude oil, condensate, diesel or
Diluted in a locally available
deaerated seawater.
Batch Chemicals solvent, as large volumes are
1:4 v/v inhibitor / diluents between needed.
pigs for pipelines.
Whenever inhibitors are employed in diluted form by on-site mixing of concentrated product there
must be adequate control over the quality of the solvent used and proper supervision of the dilution
process.
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5.8 Chemicals injection system
5.8.1 Components
The system for chemical injection comprises the following main components:
− storage tank,
− mixing tank, if the product is purchased concentrated and need to be diluted,
− injection pumps and connecting lines,
− injection points (ports, quills, valves),
− control equipment (metering system, valves, gauges, instrumentation and alarms),
− secondary containment to capture leaks and spills.
5.8.2 Storage
Chemicals should be stored in sealed containers in a well-ventilated and sheltered area, with fire
protection and electrical classification of other facilities and safety devices corresponding to the class
of stored products.
Tanks shall be equipped with a level gauge and with an inspection hole if capacity exceeds 2 m3.
The storage tanks shall be made of materials resistant to corrosion from the stored product, which
are often corrosive when concentrated. Blanketing may be required for products easy to oxidise or
volatile. The typical material to handle chemicals is stainless steel type AISI 316L.
A single tank shall be dedicated to each chemical product. Each tank shall be equipped with an
individual filling system allowing filling either from products delivered in bulk or semi-bulk containers
or in drums.
The storage tank capacity required is project specific and depends on factors such as:
− the accessibility to the site,
− possible difficulties in deliveries,
− required on-line availability of the inhibitor,
− shelf-life of the chemical product.
In the case of gas pipelines, the basic assumption is that the inhibitor is injected as a 10% solution.
The storage tank should be sized to accommodate dilution, i.e., on the basis of a consumption rate of
200 litres of solution per million of treated standard cubic meters.
In case combination of batch and continuous treatments are envisaged, tanks shall be sized
taking also into account the inhibitor quantity for batch treatments.
5.8.3 Chemical injection pumps

The injection of chemicals in pipelines is usually achieved by using a metering pump consisting of a
positive displacement pump with capacity range setting that may be adjusted by varying the stroke
length. The chemical injection rate is controlled by setting the stroke frequency and the volume
displaced per stroke.
The adjustment of injection rate to keep dosage constant with flow rate variations may be manual, by
acting on a micrometer screw adjustment or on an electronic actuator for remote control, or
automatic.
Chemical injection pumps should be sized in order to allow an extra 50% in excess of the maximum
injection rate.
Chemical injection pumps should be classified as critical equipment for continuous operation.
Based on service criticality, consideration should be given to the following aspects:

− back-up with standby pumps in parallel for full redundancy,
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− shut-off alarms to increase reliability,

− automatic adjustment with flow rate.
Use of standard skid mounted equipment should be preferred to reduce costs and increases
reliability. The supplier of the inhibitor injection system should provide evidence, in the form of field
experience or a component reliability analysis, that the required availability can be achieved.
Each injection point shall be driven by a dedicated pump head. Parallel injection over several points
are not allowed unless instruments are provided to control the injection rate at each point.
For each injected product, one complete spare pump shall be provided. The total number of heads in
reserve shall not be less than 25% of the number of heads in service.
For each injected product, an auxiliary tank with a graduated level gauge enabling control and
monitoring of the flow shall be installed next to the pumps. Auxiliary tank size and design shall be
such that level fluctuation is approximately one inch per minute for average flow rate assuring supply
of the pump to be adjusted for at least 20 minutes.
Each head shall be equipped with a safety valve to limit discharge pressure to the required
pressure value.
The discharge line shall be looped back to the storage tank.
All piping and valves required for proper operation shall be provided.
A pressure gauge shall be installed on each outlet for enabling regulation of pressure in the piping.
5.8.4 Pumping issues
5.8.4.1 Pumping issues related with the inhibitor

• The viscosity of chemical products will rise when cooled in sub-sea umbilicals or when used in
cold climates. Viscosity measurements should be carried out at the appropriate service
temperatures.
• The neat inhibitor must be compatible with the pump seals.
• Line blockages: due to poor cleaning when chemicals are changed over.
• The inhibitor storage tank must be regularly checked to ensure timely recording of inhibitor
supplies.
• Abrasive particles in inhibitor: if fine solids such as blasting sand find their way into the inhibitor
storage tank they can abrade pump seals and cause leaks.
5.8.4.2 Pumping issues related with the pump

• If the pump is not calibrated or improperly controlled (closed valves) it can come to a wrong
dose rate.
• If the pump is wrongly sized it can be 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.
• Certain types of pump appear to be prone to air locks.
• One pump may be delivering into several lines or wellheads all at different pressures. The
high pressure lines may not receive any inhibitor. It is suggested to use special “Sko-Flo”
valves. These maintain a constant flow rate despite varying differential pressure.
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5.8.4.3 Maintenance
Many pump problems can be avoided if the pumps are designed, maintained and operated correctly.
It is important to have written procedures for calibration, operation and maintenance. The personnel
for operating and supervisory has to be made aware of the importance of routine dosage adjustment.
5.9 Injection points location
Common injection points include: (a) at each wellhead, at the inlet of individual flowlines, (b) at the
flowlines manifold, at the inlet of intra-field trunklines, (c) at the inlet of export pipelines or trunklines.
The most appropriate location of the injection point is selected considering the following factors:
− avoid unprotected or poorly protected section by injecting inhibitor upstream of the pipeline inlet,
− flow regime, to minimize distance required to mix the chemical in the fluid (turbulent conditions
are preferred),
− accessibility of the injection points,
− operational limitations (such as temperature stability of the inhibitors),
− processing limitations.
Injection methods will vary depending on the application (processing facilities, pipelines), location
(onshore/offshore), accessibility, etc. The criticality/availability of the inhibition system needs to be
linked to the criticality of the production system.
It is important that the chemical injected is well and promptly mixed into the liquid or gas stream. This
is more easily achieved by injecting just upstream of a region inducing turbulence (e.g. bend, valve,
pump) or directly into a turbulent area of the stream.
The mixing length, i.e. the length required to have the chemical uniformly mixed into the fluid at the
proper dosage and fully effective, varies with the flow regime and pipe size.
Turbulent flow: for turbulent flow ten (10) pipe diameters are assumed as mixing length.
Laminar flow, atomising quills: in laminar flow the inhibitor will never mix completely and turbulence
shall be induced, e.g. by using an atomising quill or a valve to create turbulence.
To facilitate line piggability, injection points using protruding quills should be preferably located
upstream of the pig launcher.
5.10 Injection quill
Tubes with diagonally slanted tips, i.e. quills, are widely used to disperse the chemical into the
stream. Typically, the quill tip should have a 45° spray and be located midstream, facing back into
the direction of flow.
The injection quill shall be appropriately designed to disperse the chemical injected in a way that:
− the mixing length required results minimized, especially in laminar flows,
− a direct contact of concentrated product with the steel pipe be prevented when dispersing the
chemical into the flowing fluid
Concentrated (neat) chemicals contacting the pipe wall can be corrosive to steel. The injection tube
itself must also be resistant to neat chemicals.
Local turbulence will always improve the dispersion efficiency and is necessary for flush injection.
Atomising quills can be used to achieve good dispersion in gas 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. However, in some gas systems where the inhibitor is
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diluted into a large volume of methanol or glycol before injection, then a larger delivery tube is
necessary and the injection point becomes more like a “tee”.
In a laminar or stratified flow system the quill tip should be placed directly in the water phase.
Injection quills located within a piggable section shall be flush mounted or retractable, with a mark to
help positioning the quill tip.
5.11 Preliminary operations to prepare for chemical treatment
Chemicals perform better in clean lines and routine pigging is usually required to ensure
effectiveness of the chemical treatment. This is particularly important with existing pipeline, possibly
corroded or covered by scales or deposits. Cleaning may involve the use of descaling acids which
shall be used with care to avoid damaging the line.
Cleaning is typically performed by running specially designed scraper pigs with solids removed at the
receiving pig trap. The pigs can be run with oil or gas, or with treated water. The type of pig (foam,
sphere, cups) and frequency of runs should be specified in the operating manual and a supply of pigs
kept available to deal with planned and any unplanned needs.
Mill scale should be removed from the internal surface during preparation for external coating in
order to limit the amount of debris produced when the line goes into service. A temporary primer can
be used to provide protection prior to operation in order to limit corrosion debris formation.
5.11.1 Cleaning with pigs

Scraper pigs can be used to remove scales, sand or debris accumulated at the bottom of the pipeline
which may compromise the effect of corrosion inhibition performance, e.g. under-deposit corrosion,
adsorption of the inhibitor on the debris and enhanced conditions for bacterial growth.
Even if periodic pigging can be problematic due to high costs, exposure of operators to health
hazards and need large slug volumes that cannot be handled by separation facilities, periodic pigging
is recommended for all inhibited pipelines.
Pigging is particularly important in the following cases:

− oil or multiphase pipelines: if the possibility of microbial corrosion is anticipated, where inhibitor or
biocides action is shielded under deposit,
− sour gas pipelines: due to possible H2S corrosion under deposit,
− slow flowing conditions.
5.12 Materials for chemical injection equipment
The material for the fabrication of equipment for the storage or transportation of chemicals shall be
resistant with the specific formulation and concentration in use. These include the active compound,
solvents, surfactants, and diluents.
Stainless steel should normally be used. Cooper and cooper alloys should not be permitted.
Non-metallic seals and gaskets shall be resistant to amines and solvents in the inhibitor formulation.
Resistant materials include: PTFE (Teflon), Buna-N, polypropylene, and ethylene-propylene rubber.
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6. DATA ACQUISITION, OPERATION AND MAINTENANCE
To support the evaluation of the chemical treatment performance the following data should be
collected:
− corrosion monitoring data,
− chemical injection data,
− residuals dosage of chemicals,
− production flow rates,
− systems upsets (shutdowns, power failures),
− maintenance data (repair status and condition of chemical treatment equipment),
− water chemistry,
− chemical analysis (e.g. iron count, bacteria etc;).
A large variety of corrosion monitoring methods is available, the most common are weight loss
coupons, electrical resistance probes, electrochemical probes. The best-suited method is specific for
each application. More than one method is normally adopted for a reciprocal complementation and
verification of the measurements obtained. The success of the monitoring programme is depending
on the location and maintenance of the probes, sensors and sampling equipment. For further details
regarding design and specification of the corrosion monitoring system see ENI specifications:
“20555.VAR.COR.PRG - ENI Company Specification. Internal Corrosion Monitoring” and
“20556.VAR.COR.FUN - ENI Company Specification. Internal Corrosion Monitoring. Specification.
Functional Requirements.”
6.1 Data acquisition and storage
Data from corrosion monitoring system should be gathered and correlated with relevant process data
and other information.
Corrosion monitoring data may require the extraction of the coupon to carry out weighing and visual
examination: the main disadvantage of these probes is that only average corrosion rates can be
determined. Other probes allow collection of information in a variety of methods. Real-time corrosion
measurements by highly sensitive measurements, with a signal response taking place essentially
instantaneously while the corrosion rate changes allow continuous monitoring. These probes may be
'hard-wired' back to the control room to keep corrosion rates and therefore chemicals treatment
effectiveness under continuous control, also with the possible aid alarms to be adequately set. The
use of real-time devices for corrosion measurements is particularly useful for a prompt detection of
changes in operational parameters which may affect corrosion and chemical treatment effectiveness
and during the initial phase of chemical injection when optimised dosages need to be validated by
field observations.
Electronic storage of data allow rapid analysis of historical readings and longer term trends of
information. The use of electronic data storage, trend analysis with preset/agreed criteria for alert and
alarm levels is recommended.
6.2 Maintenance and inspection of injection facilities
All components of the chemical injection system shall be routinely maintained and inspected. The
frequency of inspections to verify full working conditions of the chemical injection system should be
based on the system criticality in assuring pipeline integrity in order to avoid significant damage in
case of prolonged upsets, and adjusted any time this is suggested by inspection findings.
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6.3 Process changes and shut-in conditions
In order to minimise integrity risks, the chemical injection system shall be promptly adjusted in case
of changes of key parameters and adapted to new scenarios that may establish during operational or
non-operational conditions.
Especially in case the pipeline integrity highly relies on corrosion control by chemical treatments, the
system should be promptly detect these changes and control an adjustment of the chemical injection
system in order cope with this new conditions.
For this purpose, key operational parameters such as production rates, water cuts, changes in fluid
chemistry, bio-chemical conditions or residual oxygen in case of deaerated systems, should be
constantly monitored to provide real-time data and trends. The data should be analysed and used to
identify the need for intervention on the chemical treatment system to avoid or prevent uncontrolled
conditions.
6.3.1 Monitoring process changes
Certain types of corrosion monitoring only reveal 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 quick as possible and respond to it 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 (water cut > ca 40 % v/v
required for accurate LPR).
An alternative or complementary approach is to continuously monitor a number of process

parameters like flow rate, water cut, temperature etc. and be ready to alter the corrosion inhibition
conditions.
6.3.2 Production rates
Chemicals for corrosion control are dosed based on the production flow rates. Even if the ultimate
objective is to guarantee a minimum concentration of chemical within the water phase, in many
cases the injected rate is sized on the basis of the hydrocarbon flow rate, particularly when the
amount of water is modest. For this reason the production flow rates shall be kept constantly
monitored and the chemical injection system adjusted in case of significant and persistent changes.
Temporary changes of the production flow rate or shut down conditions may be managed with no
need for adjustment of the chemical rate only if very limited in time, otherwise the chemical delivery
rate must compensate significant and steady variations in order to keep reasonably constant its
concentration in the water phase.
6.3.3 Water cut
As for the production flow rate, and particularly when the amount of produced water is significant, a
direct control of the water cut is of paramount importance in order to adjust accordingly the quantity
of chemicals to inject to maintain the desired level of its concentration in the water phase.
6.3.4 pH
pH monitoring by direct measurements is not practical, however the water phase pH may be
estimated on the basis of a set of operational parameters that for this reason should be kept
controlled. These parameters include primarily CO2 and H2S partial pressure, temperature and water
phase composition, particularly bicarbonates, organic acids and total salinity.
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6.3.5 Oxygen
Corrosion inhibitors for hydrocarbon application are not designed to control oxygen corrosion, ingress
of free oxygen in the hydrocarbon production stream can cause severe corrosion problems.
Unfortunately the detection of oxygen ingress in the production stream is not practical and therefore
this event shall be carefully prevented. Injection of chemicals is a potential source of oxygen
contamination in the production streams, particularly when fluids where oxygen is soluble are used,
e.g. water, glycol or methanol or when blanketing gas with low purity are used. Oxygen
contamination avoidance is enforced by using high-purity fluids and by removing accurately any
residual of oxygen by oxygen scavengers before injection into the stream.
6.3.6 Shut-in conditions
Shutdowns may require special precautions to prevent corrosion which should be evaluated on a
case by case basis. The injection of chemicals should be shut-in together with the pipeline in order to
avoid accumulation in concentrated dosages which may result corrosive. During prolonged
shutdowns, the persistency of inhibitors in stagnant fluid may have a limited efficiency with time
which shall be investigated, with possible need to replenish the line with a freshly inhibited fluid.
Temporary fluids that may need to be displaced into the pipeline shall be adequately treated. After
any prolonged shutdown or upset, it may be necessary to apply a batch treatment before resuming
continuous inhibitor injection.
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7. REFERENCES
/1/ S. Olsen, “Corrosion control by inhibition, environmental aspects and pH control. Part II: Corrosion
control by pH stabilization”, Paper No. 06683 Corrosion NACExpo 2006.
/2/ A. Dugstad, R. Nyborg, M. Seiersten, “Flow Assurance in pH Stabilised WetGas Pipelines”,
CORROSION/2003, Paper no. 03314, Nace International, Houston, TX, 2003.
/3/ A. Dugstad, M. Seiersten “pH stabilisation, a reliable method for corrosion control of wet gas
pipelines”, SPE87560, Society of Petroleum Engineers, 2005.
/4/ R. Nyborg, “Controlling Internal Corrosion in Oil and Gas Pipelines
/5/ O. Hagerup, S. Olsen, “Corrosion Control by pH Stabiliser, Materials and Corrosion Monitoring in a
160 km multiphase offshore pipeline”, Paper No. 03328, NACE Corrosion 2003.
/6/ Gracki, J.A., R.A. Everett, H. Hack, P.F. Landrum, D.T. Long, B.J. Premo, S.C. Raaymakers, G.A.
Stapleton and K.G. Harrison “Critical Review of a Ballast Water Biocide Treatment Demonstration
Project Using Copper and Sodium Hypochlorite” September 2002. Michigan Environmental Science
Board, Lansing. xii + 30p.
/7/ BMT Fleet Technology, Ltd. and ESG International, Inc. [2002]. [Draft] Final Report: Ballast Water
Treatment “Evaluation Using Copper and Sodium Hypochlorite as Ballast Water Biocides” April 12,
2002. Kanata, Ontario. 730p.
/8/ A.Bathia, “Cooling Water Problems and Solutions”.
/9/ E. Gulbrandsen, J-H. Morard, “Why does Glycol inhibit CO2 Corrosion?”, Corrosion 98, Paper No. 221
/10/ S. Ramachandran, S. Mancuso, K. A. Bartrip, P. Hammonds, “Inhibition of Acid Gas Corrosion in
Pipelines Using Glycol for Hydrate Control”, Materials Performance, August 2006.
/11/ Institute for Energy Technology, “Corrosion Control with pH adjustment in multiphase pipelines”,
Kjeller pH-stabilisation program Final report, KPP-46.
/12/ J. Kvarekval, A. Dugstad, “Pitting corrosion mechanisms on carbon steel in sour glycol/water
mixtures”, Paper No. 04737, Corrosion 2004.
/13/ J. Kvarekval, A. Dugstad, “Pitting corrosion in CO2/H2S-containing glycol solutions under flowing
conditions”, paper No. 05631, Corrosion 2005.
/14/ L. Smith, M. Celant, A. Pourbaix, “A guideline to the successful use of duplex stainless steels for
flowlines”, Duplex America 2000 Conference, Stainless Steel World.
/15/ “Oilfield Water Systems”, Campbell Petroleum Series, Oklahoma, 1974.
/16/ C. Patton, “Corrosion Control in Water Injection Systems, Environmental effects, August 1993.
/17/ S. Taj, “Development of green inhibitors for oil and gas applications”, Paper No. 06656, Corrosion
NACExpo 2006.
/18/ C. deWaard, U. Lotz, D.E. Milliams “Predictive model for CO2 corrosion engineering in wet natural
gas pipelines” NACE Corrosion 1991, Paper 91976.
/19/ C. deWaard, U. Lotz, D.E. Milliams “Prediction of CO2 corrosion of carbon steel” NACE Corrosion
1993, Paper 93069.
/20/ C. deWaard, U. Lotz, A. Dugstad “Influence of liquid flow velocity on CO2 corrosion: a semi-empirical
model” NACE Corrosion 1995, Paper 95128.
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APPENDIXES
APP A INTERNAL CORROSION OF PIPELINES
A.1 Pipelines for hydrocarbons transportation
Internal corrosion of carbon and low alloy steel “CLAS” hydrocarbon pipelines depends on the fluid
transported and its properties. A primary characterisation is based on the following classification:
− Liquid hydrocarbons (oil/condensate and possibly formation water): include a) untreated well fluid
from oil wells above the bubble point and b) treated (separated or stabilised) oil or condensate.
Liquid hydrocarbon from the wells is usually accompanied by formation water, which partially
remains also after separation, whereas it is not present in stabilised liquid.
− Oil multiphase hydrocarbon (oil with associated gas and formation water): include untreated well
fluid from oil wells below the oil bubble point and with a GOR below 890 st.m3/m3. Formation
water is usually present.
− Gas and condensate (gas with associated condensates and produced water): include untreated
well fluid from gas and condensate wells at/below its water dew point and with a GOR above 890
st.m3/m3. Gas hydrocarbon from the wells is usually accompanied by produced water which
condenses from the wet gas and/or is produced from the formation.
− Wet gas (gas and produced water): include gas from gas wells at/below its water dew point not
accompanied by appreciable quantities of liquid hydrocarbons. Gas hydrocarbon from the wells
is usually accompanied by condensed and/or formation water.
− Dry Gas (gas phase only): include gas from gas wells naturally above the water dew point or
water-free, and gas dehydrated by process treatment to remove water and drop down its water
dew point far below the service conditions.
The above categories, based on the phases present in the hydrocarbon fluid, are typically used to
classify pipelines.
The presence of corrosive agents, primarily CO2 and H2S, the presence of water and its origin and
composition, and the occurrence of water wetting, affect the corrosivity of the transported
hydrocarbon. The repartition of the various phases present in the fluid in combination with an
appropriate flow analysis, is important for a correct understanding of the corrosion phenomena
involved and to identify the most appropriate chemical treatment for corrosion control.
The typical forms of corrosion encountered in association with the above fluids are reported in the
next table.
Internal corrosion is primarily

Transported Fluid Fluid Type
related to:
Liquid hydrocarbons and − CO2, H2S, temperature
Liquid Hydrocarbons
associated produced water − produced water composition
Oil-multiphase Liquid hydrocarbons with
− CO2, H2S, temperature
Hydrocarbons associated gas and produced
− produced water composition
(GOR < 890 stm3/m3) water
Gas hydrocarbons with
Gas and Condensate − CO2, H2S, temperature
associated condensate and
Hydrocarbons − presence of produced water and
produced water (condensed or
(GOR > 890 stm3/m3) its composition
formation water)
− CO2, H2S, temperature
Wet gas Untreated Gas
− water condensation
− residual water and dehydration
Dry gas Dehydrated Gas control issues
− presence of H2S
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In presence of formation water and conditions favouring bacteria growth, MIC issues should be also
considered and contrasted by cleaning (pigging) and chemical treatment performing with biocides if
necessary.
A.1.1 CO2 Corrosion

Carbon dioxide (CO2) corrosion is the most common corrosion issue in hydrocarbon production. CO2
concentrations typically range from < 0.1% to more than 20% molar fraction in the associated gas
phase. The presence of CO2 in combination with a water phase gives place to weight-loss corrosion
of carbon and low alloy steels whereas CRAs are generally resistant.
Chemical treatments based on the injection of amine-based corrosion inhibitors are normally
considered for internal corrosion mitigation of CLAS pipelines. pH stabilisation technique or glycol
control, alone or in combination, are also considered mainly for wet gas and/or gas and condensates
pipelines.
Corrosion mitigation by chemical treatments shall consider the specificities of gas pipelines
compared with oil and oil-multiphase pipelines, which mostly have to do with the mutual repartition of
the gas phase and the liquid phase within the flowing fluid.
Corrosion inhibitors are suitable to avoid corrosion of the portion of steel pipe contacting the liquid
phase, and are optimized by selecting the appropriate dispersibility and solubility in the oil versus
water phases, but they may not efficiently control the corrosivity of the wet gas under condensation
conditions.
Dehydrated gas or dry gas pipelines are not corrosive as far as the gas is kept above the water dew
point temperature and they normally not require the injection of any chemical for corrosion control.
Stabilised oil pipelines are normally free from significant amounts of water. However, corrosion
inhibition treatment, continuous or batch, are frequently considered to avoid corrosion at low spot
areas of pipelines where traces of residual water may stratify and accumulate. Biocide treatments to
prevent corrosion under deposit may also be required.
A.1.2 Sour service

Hydrogen sulphide (H2S) may also be present, although usually at a lower concentration than CO2,
typically ranging within 0 to 10,000 ppm in the gas phase. However in highly-sour field the produced
fluid is characterised by H2S content in the same order of CO2 or higher. Corrosion issues involved
by H2S presence are mainly related to the risk of sulphide stress corrosion cracking for susceptible
materials and weight-loss corrosion of carbon and low-alloy steels by interaction with CO2 corrosion.
In hydrocarbon systems containing only traces of H2S or when the CO2/H2S ratio is higher than about
200 (CO2 system dominated), the presence of H2S in chemical treatment selection and testing is not
relevant and can be ignored in the preliminary phases. Once a product has been selected in CO2
only, final testing with the actual content of H2S may be run to confirm results are satisfactory.
In sour systems with significant presence of H2S (20 < CO2/H2S < 200) the formation of iron sulphide
prevails on iron carbonate and the effect of corrosion kinetic is affected by H2S. A corrosion inhibitor
formulated to perform on a complete or partial FeS scale shall be selected and the selection process
and testing shall be performed in presence of H2S.
In H2S dominated systems (CO2/H2S < 20) CO2 weight-loss corrosion is generally mitigated by the
formation of a stable and protective scale of FeS, however the risk of localised pitting corrosion may
represent an issue at conditions promoting a local breakdown of the FeS scale. The prediction of
these conditions is a very difficult task which is still debated. Qualitatively, scale breakdown seems
promoted by high temperature and high flow rates / high shear stress with erosive effects on the
scale products.
Chemical treatments are generally suitable for the control of H2S-affected or H2S-dominated weight-
loss or localised corrosion of CLAS pipelines. On the contrary, the use of chemical treatments shall
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not be considered to prevent sulphide stress corrosion cracking which must be avoided by selecting
an inherently resistant material and metallurgy/grade.
Even if industry affirmed models for the prediction of corrosion rate in H2S dominated systems are
not available, it is reasonable to assume that corrosion inhibitors may easily drop down weight-loss
corrosion below the typical design threshold of 0.1 mm/y. However qualification process by
laboratory testing of the corrosion inhibitor is in this case mandatory and shall demonstrate that the
inhibitor is also effective in preventing breakdown of the FeS protective scale at the most demanding
service conditions anticipated.
The presence of H2S involve concerns regarding the applicability of chemical control methods based
on glycol (see paragraph B.3) and pH stabilisation (see paragraph B.4), which may result
compromised, and the enhancement of top of line corrosion in multiphase stratified flow (see
paragraph A.1.3). These issues need special investigation and experimental work is recommended.
A.1.3 Top of line corrosion “TLC”

When a stratified flow regime sets-up in oil-multiphase or gas-condensate pipelines, the upper part of
the line remains in permanent contact with the wet-gas phase and the lower part with the stratified
liquid phase.
This condition establishes two distinct corrosive environments at the upper and at the lower region of
the line. For this reason it is necessary to distinguish between top of line corrosion “TLC” and bottom
of line corrosion “BLC” either in the corrosion assessment process and in the selection of the
methods for their control.
Bottom of line corrosion is given by the liquid phase corrosivity. The corrosion assessment and
corrosion rate prediction is performed with the same methodology followed for the other flow regimes
and is based on the evaluation of the water-phase potential corrosivity and on the likelihood of water
wetting occurrence. The control of bottom of the line corrosion by chemical treatments is also not
different, and consists in supplying a corrosion inhibitor which dissolves and disperses in the liquid
phase and neutralise the corrosivity of water.
Top of line corrosion is given by water condensing from the wet-gas phase when the operating
temperature is lower than the water dew point temperature of the gas. Local temperature gradient
between the steel pipe wall and the gas bulk rules the water condensation rate. If cooling is such that
the water condensation rate exceeds a critical threshold, significant corrosion may occur at the top of
the line. Conversely, no significant corrosion is observed at the top of the line if the water
condensation rate is lower than the critical threshold and only bottom of line corrosion is concerned.
TLC is usually less severe than BLC, typically by an order of magnitude, however conventional
corrosion inhibitors are not effective in mitigating corrosion at the top of the line which may become
the most critical site for corrosion and additional or alternative methods shall be sought to control this
issue. Glycol control of corrosion, if practicable, is an effective method to control TLC corrosion,
otherwise periodic batch treatments specifically designed to bring corrosion inhibitor at the top of the
line shall be considered.
The top of line corrosion is a major risk under the following conditions:
− stratified flow regime.
− the temperature is medium to high, typically above 60°C.
− the line is poorly insulated or unburied or cooling is locally enhanced by external factors
− CO2 partial pressure is high
− formation water containing organic acids is present
The problem of top of line corrosion in stratified flow needs special investigation in the following two
conditions:
− presence of formation water with a high content of organic acids (above some 300 ppm)
− presence of H2S (sour fluids)
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In the first case the presence of organic acids (typically acetic acid) enhances the corrosivity of the
condensing water making TLC likely also at very low water condensation rates. In real applications
the problem is successfully mitigated by additions of MDEA to neutralise organic acids.
In the second case the effect of H2S is unclear and still under investigation. Depending on its
quantity, with respect to CO2, and on the operating temperature, some observations show that H2S
mitigate top of line corrosion, and is even capable to prevent completely the problem in H2S
dominated systems. On the contrary, other observations suggest that H2S enhances TLC and
similarly to organic acids decreases the critical threshold of water condensation rate for TLC to occur.
A.1.4 Formation water

The fluid corrosivity is affected by the presence of formation water from the reservoir and its
composition.
In stainless steel pipelines, a carryover of formation water may promote localised pitting or crevice
corrosion or enhance risk of stress corrosion cracking, whereas formation water is usually beneficial
to carbon and low alloys steels corrosion due to the buffering effect on pH, particularly due to
bicarbonates. In some few cases, a high content of organic acids was observed (above 100 ppm)
which enhances the corrosivity of CO2 corrosion and the criticality of top of line corrosion (see
paragraph A.1.3). The effect of organic acids on fluid corrosivity shall be in this case carefully
investigated and included in testing for chemicals qualification. Another important aspect of acetic
acids is that the amount of acetic acid in the water/glycol phase will increase in presence of pH
stabilizer. Beyond a concentration of about 15 mol/l the acetates should be removed. However, the
acetic acid will neutralize the pH stabilizer that will require replenishment.
The presence of formation water, with high ionic content, creates problems with the pH stabilisation
technique which may lead to unacceptable precipitation of calcium bicarbonate scales, making this
treatment not applicable (see paragraph B.4).
A.1.5 Biological Corrosion “MIC”

Biological corrosion rather than a corrosion mechanism is a deterioration of a metal by corrosion
processes that occur directly or indirectly as a result of the activity of living organisms. These
organisms include micro forms such as bacteria – microbial corrosion “MIC” – and macro types such
as algae and barnacles. Microscopic and macroscopic organisms have been observed to live and
reproduce in mediums with pH values between 0 and 11, temperatures between 0°C and 60-80°C,
and resisting extremely high pressures. Biological activity may influence corrosion in a variety of
environments including natural water and sea water as well as natural petroleum products.
A.2 Pipelines for water transportation
In oil and gas production, pipelines are typically used to transport water to injector wells for enhanced
recovery or disposal.
Water for water injection typically includes seawater, production water or both (commingled water).
Internal corrosion of pipelines for water service depends primarily on the presence of oxygen
dissolved in water, i.e. if water is aerated, deaerated or oxygen-free. Presence of bacteria (see
paragraph A.1.5), chlorine (used as biocide), and temperature are also key parameters.
The corrosivity of oxygen-free produced water is related to the presence of CO2 and H2S, and
possibly bacteria, and corrosion mitigation is dealt with as per liquid hydrocarbons (see previous
paragraph).
Deaeration of water by an efficient and well controlled process treatment reducing oxygen to a
maximum residual of 5 to 20 ppb is usually specified. In these conditions carbon and low-alloy steel
(CLAS) is usually considered a suitable solution and only biocide treatment for MIC avoidance is
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required. Oxygen scavenger may also be added to complement deaeration process efficiency and
control.
Deaeration process systems which cannot guarantee the above conditions of treated water (poorly
deaerated water) pose a series of concerns on the integrity of the linepipe and should be avoided. As
a palliative to corrosion of CLAS, chemical treatments consisting in the injection of a package
typically containing corrosion inhibitor, biocide and oxygen scavenger may be considered.
Conversely oxygen control by chemical treatment with CRA pipelines is not recommended due to the
risk of rapid initiation and propagation of localised attacks in case of treatment upsets or poor control.
Aerated waters involve weight-loss oxygen corrosion to CLASs which is normally not acceptable and
mitigation by chemical treatments may be considered for short design lives (e.g. 10 years or lower).
The use of CRAs is normally required and only materials which display fully inherent resistance to
localised corrosion and stress corrosion cracking at the given service conditions have to be
considered, whereas chemical treatments are not a viable option. Seawater is a particular
demanding environment on this regard.
Chlorine or a hypochlorite solution is usually injected to control both marine fouling (in seawater
systems) and bacterial growth. The residual chlorine not reacted and surviving the deaeration
process or the oxygen scavenger, is carried through the system until and represent a strong oxidant
which poses a serious threat particularly by promoting localised corrosion of passive CRA materials,
especially at temperature above ambient.
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App B Chemical Treatments for Corrosion Control
B.1 General
Chemicals for corrosion control are substances which are added to the fluid to decrease corrosion
penetration rate. In oil and gas production, injection of corrosion inhibitor is the most common
method applied to mitigate corrosion of carbon and low-alloy steel pipelines for transportation of
hydrocarbons.
Chemicals for corrosion inhibition are classified in a variety of different ways, based on their
prevalent inhibition mechanism or their chemical nature. Typical classifications include:
− anodic (passivating) inhibitors: slowing down the anodic reaction by steel passivation,
− cathodic inhibitors: slowing down the cathodic reaction by precipitating onto the cathodic area,
increasing circuit resistance and restricting diffusion of reducible species to the cathode,
− mixed inhibitors: when both the above mechanisms are involved,
− film-forming inhibitors: instead of reacting with or remove active corrosive agents, they create a
barrier between the metal and the environment electrochemically insulating the system,
− neutralising inhibitors: decrease hydrogen ion activity, i.e. increase the pH, whereby corrosion is
reduced,
− organic inhibitors: organic-based compounds which affect the entire surface of a corroding metal;
they are adsorbed according to the ionic charge on the metal: cationic inhibitors are amines, or
anionic as sulfunates,
− scavengers: for chemical remove corrosive species as oxygen or hydrogen sulphide (H2S
scavengers are not reliable methods for control corrosion of pipelines),
− biocides: which kill living organisms that can cause corrosion or fouling issues.
When used for hydrocarbon system, the term “corrosion inhibitors” is used to indicate the category of
film-forming, amine-based organic compounds.
To adhere to the oil and gas industry practice, in this document this terminology is applied to refer
mostly to this family of chemicals, to distinguishing from other chemicals herein referred to as “pH
stabilisers”, “scavengers” or “biocides”, even if strictly speaking they may be included in the above
categories of corrosion inhibitors (e.g. pH stabilisers as neutralise inhibitors).
B.2 Corrosion Inhibitors
Fluid treatment with Corrosion Inhibitors “CI” is the most common method used to control internal
corrosion of carbon and low alloy steel pipelines in oil and gas production. If properly selected,
applied and monitored, inhibitors effectively control corrosion over long-term periods.
CI are chemical substances that added in relatively small concentrations to the fluids can drastically
reduce corrosion down to acceptable residual levels.
A detailed discussion on CI chemistry and working mechanisms is out of the scope of this document
and only some few basic information is herein provided. Most of the CI used in the oil and gas
industry are organic compounds that adsorb on the surface of the metal promoting the formation of a
protective “filming” barrier at the metal/solution interface. Adsorption mechanism may be electrostatic
or chemisorption. More simplistically, corrosion inhibitors produce a controlled precipitation of the
inhibitor from its environment onto the metal surface; the CI organic molecules typically include
strongly polar functional groups, which links to the metal, connected to a hydrophobic group, typically
a long aliphatic chain, which creates a protecting barrier. Polar groups are mainly based on nitrogen,
as in amines, amides, imidazolines or in quaternary ammonium salts; they can also include salts of
nitrogenous molecules with carboxylic acids, polyoxyalkylated nitrogen containing compounds,
nitrogen heterocyclic and compounds containing phosphor, sulphur or oxygen.
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Film forming amines are mostly used with proved effectiveness against CO2 corrosion in oil and gas
environments. The primary improvement in inhibitor technology has been the refinement of
formulations, the development of improved methods of applying the inhibitors and of the methods to
evaluate their performance.
Corrosion inhibitors are commercially available in different types and formulations with various
chemical, physical, and handling characteristics. A corrosion inhibitor package may contain one or
more inhibition active principle plus surfactants and solvents.
The techniques used to deploy corrosion inhibitors consist in providing an inhibitor film onto the steel
pipe wall creating a barrier to the corrosive environment and maintaining this film by periodical
replenish (batch treatment) or by continuous subministration of chemicals (continuous injection
treatment).
The effectiveness of an inhibitor depends on many factors, but, in order to be effective, it must reach
the metal surface to be protected, which should be clean from loose debris, foreign matter and
adherent scales or corrosion product.
Solubility of inhibitor is of primary importance: oil soluble, water dispersible, or water soluble
inhibitors are available. Their effectiveness will depend to a large extent on which type can best
dissolve in the metal wetting phase and be absorbed on the surface to promote the formation of a
protective film.
Organic inhibitor molecules can be modified to increase their solubility or dispersibility in the brine.
These modifications include adding more polar groups to each inhibitor molecule. Sometimes, the
dispersibility of an oil soluble inhibitor is increased by blending it with a surfactant. This blending
technique helps to disperse the oil soluble inhibitor into both the oil and water phases.
The oil soluble inhibitors (long chain primary amines, imidazolines, fatty acids, phosphate esters) are
generally more effective at high temperatures and high flow velocities.
The water soluble inhibitors (quaternary amines, amine salts, imidazoline salts) are more effective in
stratified flow conditions. But they may lose solubility in concentrated brines.
Inhibitor effectiveness may be compromised by high flow velocities: very high wall shear stress
induced by high density / high velocity flow can prevent the formation of protective film or
continuously remove it. Critical conditions establish at shear stress approximately above 50 Pa.
CI must be selected very carefully. Generally not less than 5 products, proposed by suppliers and
supported by detailed documentation to backup its suitability for the specific application, are subject
to screening tests that shall be performed preferably by independent laboratories. The best products
may be candidate for possible field test. The CI selection program should be initiated at least 16-24
months before planned start-up and the selected product should be available on site before
production start-up.
High efficiency (above 95%) is easily achieved in laboratory testing if appropriate products are used,
and even with highly corrosive fluids the residual corrosion rate should be lower than 0.1 mm/y. For
the design of pipelines, current engineering practice assumes that CI are available at the metal
surface about 90% of time. The lack of availability may be due to injection pump failure, injection
valve plugging, lack of product, insufficient dosage, and direct or indirect control.
There are several conditions or operational constraints that make corrosion inhibition treatments not
feasible or practical, because of the service restrictions, or not recommended because of the poor
overall efficiency attainable. If that is the case, injection of alternative chemicals such as pH
stabilization and/or glycol may be considered, either as an alternative or as an addition to corrosion
inhibitors. Otherwise material upgrading to CRAs is required.
Inhibitors are proprietary formulations containing several chemicals and the supplier shall give as
much as comprehensive Technical Data Sheet and Material Safety Data Sheets to allow the most
correct and safe management of the products. The technical data sheet should contain the following
minimum set of information:
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− Principal uses,
− Physical properties (e.g. solubility, partitioning etc.)
− Application method,
− Recommended dosages,
− Compatibility with materials,
− Handling,
− Packing,
− Testing data.
B.3 Glycol Control
Glycol is a chemical compound widely used in gas and gas-condensate pipeline to prevent the
formation of hydrates for flow assurance.
Two different glycols are used for hydrate and corrosion control:
− mono-ethylene glycol, C2H4(OH) 2, or MEG, m.w. 62.07;
− di-ethylene glycol, C4H10O 3, or DEG, m.w. 116.12.
Tri-ethylene glycol (TEG) is seldom used for hydrate and corrosion prevention.
Besides its primary scope as hydrate preventer, a beneficial by-effect of glycol is played in mitigating
corrosion. Carbon dioxide corrosion of carbon and low-alloy steels has been observed to be
significantly reduced when glycol forms part of the aqueous mixture (both glycols are miscible in
water in all proportions).
Chemical treatment with glycol has become a proved technique to control corrosion in gas and gas-
condensate pipelines at the top of line in contact with the gas phase above the stratified liquid, where
corrosion inhibitor is ineffective.
The presence of glycol acts on corrosion in two ways:

− by reducing the corrosivity of the water phase it mixes with,
− by absorbing water from the gas phase thereby preventing or limiting water condensation.
The first is given by the glycol effect in inhibiting the anodic reaction (Ref./9/). The corrosion
mitigation effect of glycol can also be correlated to changes in solution properties with increasing
glycol concentration.
The second results in a drying action that lowers the water dewpoint of the gas and prevents the
condensation of pure water and only small amounts of glycol/water solutions may condense, with an
equilibrium composition which is the same of the mixture accumulated at the bottom (or bulk liquid).
The mitigating effect of glycol on corrosion was investigated by laboratory testing and quantified by
an empirical equation proposed by deWaard et.al. and now largely recognised and used (Ref./18/).
The following “glycol” factor FGLY was proposed to correct the base corrosion rate of the water phase.
log FGLY = 1.6 × [log(W/G%) – 2]
Glycol control is particularly effective in mitigating top of line corrosion “TLC” in stratified flow by
reducing the water dew point temperature, limiting water condensation occurrence. TLC is governed
by the amount of water or glycol that wets the upper wall of the pipeline. Glycols have a low vapour
pressure and are effective drying media. Water condensation rate depends on the efficiency of glycol
as a drying medium and how glycol is distributed and equilibrated with the gas phase. Even if the
water dew point temperature still remains above the service temperature, water condensation rate is
reduced and water condenses in solution with glycol, whereby corrosion is reduced.
At the bottom of the line, where condensed liquid stratifies, the mitigation effect of glycol on corrosion
is quantified by the correction factor above illustrated, which is a function of the water percent in the
water/glycol solution. In fairly high corrosive systems, the corrosivity of the stratified liquid is still too
high and to drop down corrosion to less then 0.1 mm/y an impractically high quantity of glycol would
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be required to drop down water percent to less then 5% in the water/glycol mixture. For this reason
additions of corrosion inhibitor, or more frequently pH stabiliser, are required to control corrosion of
the liquid phase at the bottom of the line. Additions of small amounts of corrosion inhibitor (~1 ppm)
drastically improve glycol effectiveness in controlling corrosivity of the liquid phase (Ref./9/).
In typical application the quantities of lean glycol which is injected at the pipeline inlet is such that the
rich glycol at pipeline outlet is diluted by condensed water to about 50-60% weight of glycol.
Glycol can be recovered from the gas and re-circulated after a regeneration treatment that removes
water and inorganic salts.
B.4 pH Stabilisation
The pH stabilization is a method whereby CO2 corrosion of carbon and low alloy steels is mitigated
by promoting the formation of a stable and protective iron carbonate corrosion film.
The pH stabilization technique was developed as an alternative method to corrosion inhibitors for the
corrosion control of gas-condensate pipelines when the use of glycol is used as hydrate preventer, in
which case it may represent a cost effective and reliable solution. The glycol provides a convenient
means to add alkalinity and the combination of glycol and pH stabilisers provides a balanced action
in corrosion mitigation. Regeneration of glycol recovers also the pH stabiliser, so that minimal need
for replenishment is required when re-circulated.
Corrosion at the top of the line, contacting the wet gas phase, is prevalently mitigated by glycol,
whereas pH stabiliser prevalently controls corrosion at the bottom of the line, exposed to the stratified
liquid. Liquid droplets entrained in the gas phase can also wet the wall and studying the quantity of
pH stabilized liquid entrainment and the droplet formation in the gas phase may allow estimation of
the amount and composition of aqueous liquid phase and therefore the contribution of pH stabiliser in
mitigating corrosion on the upper part of the line.
The technique consists in the addition of alkaline compounds which are dissolved in the glycol to rise
the pH of the glycol/water phase, favouring the stabilisation and the precipitation of protective
corrosion products on the steel pipe wall. This is achieved by strong buffering with chemicals as
sodium bicarbonate NaHCO3, methyldiethanolamine MDEA or sodium hydroxide NaOH that will bring
to a concentration of bicarbonate significantly higher than normally found in natural formation waters
and a pH in the range from 6.5 to 7.5. Also potassium based: KOH, KHCO3 or K2CO3 can be
considered for this purpose.
The pH stabilisation technique is limited by the presence of formation water which cause the
formation of calcium carbonate CaCO3 precipitates at high pH with consequent scaling problems.
In some applications “pH adjustment” is applied: this technique is similar to pH stabilization, but gas
is buffered to a lower extent; it is a compromise when a limited quantity of formation water is
envisaged. The amount of the base added is significantly less than required for full pH stabilization.
As pH adjustment alone cannot give full corrosion control, it is normally applied together with a film
forming inhibitor. The reason for using pH adjustment can be a reduced “scaling potential” in case of
formation water production. If significant amounts of organic acids are present in the formation water,
accumulation of acetates by glycol regeneration and re-circulation may reach a critical concentration
which is not tolerated by the regeneration unit.
As observed by laboratory testing and in practical field experience, in sweet gas systems treated with
additions of pH stabilisers to glycol, corrosion rates lower than 0.1 mm/year are normally achieved,
even for high corrosivity and high content of CO2 (Ref./11/, /1/, /12/).
Experimental work conducted in sour systems shows that although general weight-loss corrosion is
easily drop down to less than 0.1 mm/y, pitting corrosion may occur in correspondence of local
breakdown of the iron sulphide scale. Failure in attaining the target pH may lead to pitting corrosion
and high penetration rates. During experimental work localised corrosion was not observed without
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glycol, using pH stabiliser alone with a target pH of 6.5 or more, suggesting that pH stabiliser may be
considered for future application in sour gas systems (Ref./13/).
Due to the limited experience with sour gas systems and the associated risk of localised corrosion,
this method is not recommended, and for the time being the use of traditional corrosion inhibitors
should be preferred.
pH stabilisation was used in several wet gas condensate pipelines and is now a well proven
technique currently being considered for an increasing number of new fields.
B.5 Biocides
A biocide is a chemical substance capable of killing living organisms in addition to bacteria. They are
used to prevent fouling in water and oil pipelines. Biocides are divided in a group of oxidizing and in a
group of non oxidizing ones.
Amongst bacteria, sulphate reducing bacteria, “SRB”, cause more serious problems in oilfield
injection systems than any other bacteria. They reduce sulphate ions in the water, resulting in H2S as
a by-product. They cause corrosion, and the iron sulphide produced by the corrosion reaction may
also give place to plugging issues.
B.5.1 Types of Biocides

Chlorine is the most widely used inorganic biocide for water injection systems.
Amines, chlorinated phenols and quaternary ammonium compounds are common examples of
organic biocides. Beside chlorine, most market available biocides are organic.
One way to classify biocides is based on their oxidising or non-oxidising properties:
− Oxidizing:
• Chlorine or hypochlorite
• Quaternary ammonium chloride
• Copper ions
− Non Oxidizing:
• Aldehyde (formaldehyde, glutaraldehyde)
• Sulfur compounds (Isothiazolone, carbonates, metronidazole)
• Quaternary phosphonium salts
• Amines and diamines
• Quaternary amine compounds
Oxidising biocides are powerful chemical oxidants, which kill virtually all micro-organisms, including
bacteria, algae, fungi and yeasts.
Non-Oxidising biocides are not consumed as fast as the oxidizing types; they remain in the system for
a significant period of time. They have often the advantage of breaking down into harmless, nontoxic
chemicals after accomplishing their bacteria-killing purpose. Non-oxidising biocides are more
expensive. Therefore they are only employed either in small systems or together with an oxidising
biocide in large systems, where an alternative to chlorine is necessary.
B.5.2 Biocide selection and evaluation

The selection of biocide involves aspects similar to those for the selection of chemicals for corrosion
control as discussed at paragraph 3.5.6. Moreover, the following aspects shall be additionally
considered:
− Resistant strains
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• Bacteria have a capability of developing strains which build up a resistance to a

particular chemical over a period of time. Alternate use of two (or more) different
chemicals is often required to overcome this problem.
− Compatibility with water and other chemicals
• Water compatibility shall be considered as in highly salty brines biocide can precipitate or
“salt-out”. Also, compatibility with other chemicals shall be established.
− Bacteriostatic test
• The bacteriostatic test is a laboratory test, which determines the minimum concentration
of a chemical to inhibit the growth of microbial activity. It is used for comparing large
numbers of chemicals under standard defined conditions.
− Time-Kill Test
• The time kill-test, which determines the time for a chemical to kill the bacteria, is used for
the final selection of the best candidates from the bacteriostatic test. The time-kill test
defines the treatment conditions: dose (biocide concentration), contact time (the suitable
length of time of the treatment) and the frequency.
− Treatment Method
• Continuous injection. At start-up, a higher concentration of biocide is usually required for
the initial control of bacterial population (total kill); after this initial action, the biocide
concentration can be reduced, a smaller dosage being sufficient to keep controlled
bacteria activity (maintenance). The optimised concentrations required for these two
phases are estimated by laboratory tests.
• Batch treatment. A slug of biocide highly concentrated is periodically disposed into the
system for a total bacteria kill. Slug volume, concentration, and contact time can be
initially based on time-kill tests, and then adjusted by operational feedbacks.
− Field Evaluation
• The ultimate question is whether the selected product is working effectively. This can be
verified by:
− making sure the biocide is properly injected, i.e. continuously, or with the design
frequency for batch treatment, and at an appropriate concentration,
− monitoring the bacteria present with time (bacteria count).
A preliminary cleaning of the pipeline is the key for biocide treatment effectiveness. Solvents, acid
and pigs are used for this purpose.
For the biocide selection in seawater injection systems it should be paid attention to suspended
solids/scale which may form deposits. Under-deposit corrosion can occur, and in these locations
corrosion inhibitors and biocides is not effective being shielded by the deposit scale. Pigging
operation capable to remove the complex biofilms in which sessile bacteria grow and rendering the
applied biocides ineffective is very important.
B.5.3 Chlorination
Chlorination is widely used due to its low cost and high effectiveness. When added to water, chlorine
forms hypochlorous acid which ionizes to form hydrogen ions and hypochlorite ions. The degree of
ionization is dependent on pH:
pH < 5 Molecular chlorine is present

5 < pH < 6 HOCl (hypochlorous acid) predominates
6 < pH < 7.5 OCl- (hypochlorite ions) are present
pH > 7.5 OCl- predominates
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The effectiveness of chlorine depends on the predominant species; killing power of HOCl is much
greater than OCl-, hence the higher the pH, the less effective the action at a given quantity of
chlorine. At higher pH (e.g. 8-9) biocide activity is drastically reduced. However, in waters containing
bromide ions (such as seawater), chlorine oxidizes the bromides to bromine, which is still effective as
biocide at pH 8-9.
The amount of chlorine required depends also on temperature, the rate of kill increases with
temperature.
Since chlorine is a very strong oxidising agent, it reacts with many metals. It reacts with ferrous iron,
hydrogen sulfide, organic compounds, and sulphite ion. Chlorine is consumed by oxidation reaction;
hence it is necessary to establish the required quantity of chlorine based on water composition and
chlorine lost by oxidation reactions.
The use of chlorine as biocide may be limited in case the H2S content or the ferrous iron to cope with
in the system is high. Use of corrosion resistant materials should be considered.
Chlorine is usually added in gaseous form from steel cylinders. As it is very poisonous, it must be
handled with care.
Hypochlorite (OCl-) can be produced in chloride-containing waters by electrolysis. Packages are

available for electrolytic hypochlorite generation from raw seawater, thus eliminating the need for
transporting and storing liquid chlorine.
Chlorination can be carried out continuously or intermittently:

− Intermittently is meaning, that chlorine is added regularly but for short periods of time, e.g. 30
minutes per day. Intermittent chlorination may prevent biofouling but does not fully sterilize water.
− Sterilization is reached by continuous chlorination, provided chlorine is in contact with seawater
for enough time.
Full sterilization treatment by continuous chlorination is recommended in case MIC is expected to

represent a serious concern.
Dosage. Continuous injection of chlorine should be sufficient to maintain a chlorine residual

concentration of 0.2 to 0.5 ppm.
B.5.4 Glutaraldehyde
The non-oxidising chemical glutaraldehyde is a fast acting biocide, effective to treat sulphate
reducing bacteria and biofilms. It has a minimal effect on the environment. Glutaraldehyde it is widely
used in a blend with other biocides and surfactants to increase its effectiveness. The advantages are
broad-spectrum activity, relatively insensitive to sulphide, it is compatible with many other chemicals
and it tolerates salt and hardness.
B.5.5 Quaternary phosphonium

Quaternary phosphonium salts are new to the oilfield biocide market. They have been reported to
travel through the formation with injection water. They showed good stability and low toxicity and they
are unaffected by sulphides.
B.5.6 Quaternary Amine

Quaternary Amine compounds show a broad-spectrum activity, a good surfactancy and persistency
and low reactivity with other chemicals. The disadvantages are inactivated in brines, they are
foaming and they are slow acting.
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B.5.7 Copper ion

Copper as an ion (Cu2+) at proper concentrations is toxic and is used to control algae and bacteria.
Because of its toxic effects, copper discharge to surface water is of concern. If a copper biocide
treatment is used for ballast discharge, then this discharge water needs to be regulated.
Test results (Ref./6/, /7/) demonstrated that the copper ion biocide was only 33 percent effective at
167 parts per billion (ppb) in freshwater and 70 percent effective at 68 ppb in reducing bacteria in
freshwater and simulated seawater experiments, respectively. These results suggest that at the
concentrations tested, copper treatment was not adequately effective. In order to be effective, higher
concentrations of copper would be needed, which would result in exceedance of the allowable
discharge concentration levels (2 ppb to 50 ppb). In addition to potential limits on copper
concentrations that could be used, the efficacy of copper as a biocide is influenced by the natural
geochemical behaviour of copper in the environment. Being a particle reactive chemical, it will tend to
be adsorbed to sediments, whether suspended or settled, thereby being subtracted to copper
available as a biocide. The behaviour and toxic effects of copper in water also are altered by natural
processes, such as the formation of ion pairs in solution. In solution solutes, copper (Cu2+) can bond
with other solutes, such as bicarbonate (HCO3-), to form new dissolve chemical species known as an
ion pair or complex. The formation of this ion pair decreases the toxicity of a copper. Since copper in
solution is particularly influenced by the presence of dissolved organic matter, bicarbonate, and
carbonate in water, changes in the relative abundances in these solutes might necessitate different
amounts of copper concentrations needed as a biocide.
Copper ion concentrations in water of 0.02 to 0.05 ppm can cause severe corrosion of aluminum.
In summary, toxicity data, as a whole, suggest that in sufficiently high concentrations, copper ion
could be an effective biocide. However, at the concentrations needed to achieve the desired
effectiveness, the copper level could be too high to allow discharging to the sea which may render
this method not practical as biocide alternative.
B.6 Oxygen scavengers
Chemical removal of oxygen is accomplished by adding a chemical to the water which reacts with
oxygen to form a neutral product. These chemicals are referred to as oxygen scavengers. Typical
chemicals used for this purpose include sodium sulphite, ammonium bisulphite or sulphur dioxide.
Ammonium bisulphite is the most widely used product.
Reaction rate between ammonium bisulphite and oxygen decreases with pH, and a catalyst is
sometimes required.
Chemical scavenger reaction with oxygen is favoured by higher temperature.
B.6.1 Types of oxygen scavengers
Sodium sulphite (Na2SO3). At normal operating temperatures sodium sulphite typically reacts very
slowly with oxygen and a catalyst is usually added (cobaltous hexahydarate or cobaltous chloride).
The reaction involved with sodium sulphite oxygen scavenging is:
2Na2SO3 + O2 → 2Na2SO4
Sodium bisulphate/bisulphite (NaHSO4/NaHSO3). Sodium bisulphite/ate is often used as an

alternative to sodium sulphite powder.
Ammonium bisulphite (NH4HSO3). This chemical scavenges oxygen in the same manner as sodium
sulphite and also similar quantities are required. However, it presents some primary advantages,
which are:
− it does not react with air and hence can be stored in open containers.
− it normally does not require a catalyst.
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The main disadvantage of ammonium bisulphite is its known stimulation of SRB growth, with
consequent risk of MIC, and possible souring effects (H2S development) when added to water
injected into low temperature reservoir.
It is marketed under several trade names and supplied as a concentrated liquid solution with pH
between 4.0 and 4.5, which requires storing the chemical in a corrosion resistant vessel. The
reaction involved with ammonium bisulphite oxygen scavenging is:
2NH4HSO3 + O2 → (NH4)2SO4 + H2SO4
B.6.2 Reaction between oxygen scavenger and other chemicals
Oxygen scavengers such as sodium sulphite react with chlorine, which is a commonly used biocide.
A careful selection of the injection points for both chemicals is important (Ref. /15/). Ammonium
bisulphite also reacts with biocides such as aldehydes, quaternary ammonium chloride and
hypochlorite (Ref. /16/).
Organic corrosion inhibitors can also interfere with the oxygen scavenging reaction, and should be
added downstream (Ref. /15/). But most commonly used corrosion inhibitors will not influence
reaction rates (Ref. /16/).
Some biocides such as the quaternary ammonium compounds can complex the cobaltous (Co2+)
ions, annulling their effect as catalysts (Ref. /15/).
B.6.3 Oxygen scavenger in sour systems

In a sour system, H2S reacts with cobaltous ions, used as catalyst, to form insoluble sulphides.
Furthermore, excessive dosages of bisulphite based scavenger can result in sulphur containing
scales formation or increasing of H2S levels.
For the above reason, care should be paid in appropriately selecting or dosing oxygen scavengers in
sour service. Wherever possible, oxygen scavenger should be avoided in presence of H2S. It may be
considered their use in systems containing small amounts of H2S and a large excess of catalyst is
added, even if this is usually not economically practical (Ref. /15/).
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App C Additional treatments
Chemical treatments discussed in Section 3 are considered and selected in order to achieve an
adequate mitigation of the main form of weight-loss corrosion, which can otherwise jeopardize the
integrity of carbon and low alloy steel components during normal hydrocarbon production (typically
CO2 corrosion). In other words, these chemical treatments are methods associated to carbon and low
alloy steels to be considered during material selection process, and may represent a viable
alternative to CRAs if enabling service life extension as required.
Further than chemical treatments pursued for the above scope, additional chemical treatment to be
performed during normal operation conditions may be required to prevent other corrosion mechanism
possibly involved, or to complement the action of the main chemical treatment for corrosion
mitigation.
Moreover, special chemical treatments may be required to control temporary conditions that the
material may undergo during non-operational or transitory phases, and to which the employed
material may not be inherently resistant. Specific chemical treatments may be required in these
situations.
The next paragraphs cover the additional chemical treatments to consider in the above
circumstances.
C.1 Additional treatments during normal service
C.1.1 Additional batch treatment combined to continuous injection

In highly corrosive systems, where the main control of corrosion is based on the continuous injection
of chemicals, additional batch treatment with corrosion inhibitors - to be performed periodically or
under specific circumstances - may be considered to complement the effectiveness of continuous
injection treatment.
C.1.2 Batch treatment with inhibitors in low corrosive systems

Batch treatments with corrosion inhibitors may be required to avoid corrosion that may develop under
unfavourable areas in system that are otherwise non-corrosive or slightly corrosive. This is the case
of pipelines transporting fluids containing corrosive agents (e.g. CO2) but in which corrosion is
impeded by hindering water wetting. Gas pipelines normally dry, stabilised or partially stabilised oil or
condensate pipelines are within this category. However at unfavourable locations (low spot areas)
liquid water could, under certain circumstances, separate and stagnate (e.g. during dehydration
upsets for dry gas systems or during low flow for liquid systems) and if the normal flow, when
restored, is not capable to displace liquid water from these areas, corrosion may occur. As an
alternative to pipeline cleaning by pigging, batch treatment with corrosion inhibitor should be
considered to neutralise water corrosive effect in those areas.
C.1.3 Batch treatment with biocides

Even if MIC is more typical in water pipelines, also hydrocarbon pipelines may be subject to bacterial
growth and MIC. This is more frequent with low temperature systems where bacteria contamination
is likely. To avoid MIC in these pipelines, the standard practice includes batch treatment with biocide
preceded by pig cleaning or descaling treatments to remove deposits which may shield a micro-
environment where bacteria develop and biocide cannot reach (corrosion under-deposit).
C.1.4 Treatments for TLC corrosion control

To control TLC there are the two main established methods:
− glycol control, by continuous injection of glycol at appropriate dosages and possibly with
additions of pH stabiliser and/or conventional film-forming corrosion inhibitors,
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− special batch treatments using pigs specially designed for TLC control. The deployment of this
batch treatment is performed either via a conventional method using two pigs with a batch
solution of inhibitor in between or via a method that was recently developed which is called
“spray-method” and uses special pigs (TLCC-pigs) appositely developed to bring at the top of the
line the solution with inhibitor which is present at the bottom by spraying it in the upper direction
while travelling along the line.
As discussed at paragraph B.3 glycol control is a viable solution only if its injection is already
foreseen for hydrate prevention.
Batch treatments are generally performed by placing a solution of inhibitor (inhibitor slug) between
two pigs. This operation requires generally shut down of the production during preparation/launching
of the batch.
C.1.4.1 Conventional Batch treatment

Conventional batch treatment is applied on a regular basis using an oil soluble corrosion inhibitor,
diluted in condensate or diesel, and placed between two pigs. This operation requires a careful
selection of the inhibitor product and of the adequate treatment frequency, taking into account
production constraints, considering that system shutdown is required. The key aspects in selecting
the inhibitor are film persistency, which should be tested in dynamic conditions, the assessment of
the anodic effect of the filming inhibitor and the emulsion stabilising tendency of the inhibitor.
TLC control by conventional batch treatment requires special arrangements in order to achieve
adequate efficiency, which should ascertain the following:
− No gas bubble should be present at top of the inhibitor batch.
− The length of the batch should be long enough to have sufficient contact time between the pipe
surface and the inhibitor solution.
− If the length of line is long and the diameter is large, the volume of pig launcher may not be
sufficient to place the whole volume of inhibitor.
For the batch treatment the following pigs are used:

− sphere pigs
− sponge pigs (able to adsorb the corrosion inhibitor)
Limits and Problems with conventional batch treatment: the process is expensive, typically requires
special equipment (inhibitor tank, pig launchers and pig receivers, injection pumps, etc;), and involve
production shut-down. It is difficult to ensure that a solid slug remains fully intact between the two
batching pigs.
C.1.4.2 Spreading or spray method

To overcome the drawbacks associated with traditional batch treatment (safety, production shut-
down etc;) special pigs have been developed. These special methods makes use of the spreading
principle which allows transporting corrosion inhibiting compounds in sufficient concentration from the
bottom to the top of the line, overwhelming gravity.
One type is charged with a batch of concentrated inhibitor solution which is projected toward the top
of the line. This method may require a large volume of inhibitor charge and thus may not be feasible
for long and large pipelines.
Another technique was developed for gas and condensate pipelines that use the process of
continuous injection as the primary means in introducing inhibitor chemicals into the line. This
method employs a special pig, not loaded with an inhibitor charge, but which uses the inhibitor
present into the liquid phase at the bottom of the line. Its working principle is based on the Venturi
effect and taking advantage from the pressure difference between the front and the back sides of the
pig, the gas from the back sides is allowed to pass to front side through a nozzle which is connected
to the liquid phase through a Venturi system. The corrosion inhibitor injected in continuous and
dispersed into the liquid phase is sprayed to the top whereby it provides protection by producing an
artificial “slug flow”. In actual field application corrosion for about three weeks have been achieved
with this method.
Page 64 of 68
The spray method presents attractive advantages compared with conventional batch treatment with
ordinary pigs. Principally, they do not required shut-down, thus minimize production loss, reduce the
inhibition cost, increase the safety of batch treatment operations.
C.2 Chemical treatments for corrosion avoidance during temporary operations
C.2.1 Hydrostatic testing
After installation pipelines need to be hydrotested, i.e. pressure-tested with a liquid, which is almost
invariably water. For various reasons, pressure testing water may remain into the pipelines for
prolonged period, even a few weeks.
Depending on local availability, the water can be fresh or saline and it can remain in the pipe for
prolonged time, even years, before hook-up and production start-up and before corrosion inhibitor is
added.
The decision to use chemical treatment will depend on the water analysis and the duration of the
period during which the water will remain in the pipeline. Chemical treatment will be avoided
wherever practicable, appropriate treatment is usually required in order to prevent corrosion.
Any water system that contains sulphate has the potential to support the growth of sulphate-reducing
bacteria. The problem is not only the bacteria themselves but rather the production of corrosive
hydrogen sulphide and carbon dioxide caused by their metabolic pathway.
It is also difficult to control corrosion in the presence of oxygen. At levels as low as 10 ppb there can
be significant corrosion observed. In a closed system oxygen reaction giving corrosion is concluded
when oxygen is consumed.
Chemical treatments for hydrotest water typically include:

− oxygen scavenger,
− biocide,
− corrosion inhibitor.
Hydrotest water should always contain at least two chemical treatments: oxygen scavenger and a
compatible biocide. An oxygen corrosion inhibitor may also be considered, especially if the oxygen
scavenger should be consumed in atmosphere during dosing.
Ammonium bisulphite is commonly used for hydrotest water. This product is water-soluble and has
good environmental friendly properties.
As biocide, THPS (thetrakishydroxymethyl phosphonium sulphate) based products are preferable

choice due to their less hazardous and environmental friendly aspects.
The environmental impacts on water quality during pre-commissioning may be associated to

discharge of hydrotest water. Pressure testing of the pipeline may use filtered seawater as the test
medium. The base case for the pre-commissioning is to use filtrated seawater treated with an oxygen
scavenger and a biocide for flooding. This treatment is assumed to represent a safe solution for the
integrity of the pipeline, even if case by case investigation is required. It is a common objective to
reduce the use of chemicals to an absolute minimum whilst still maintaining the safety and integrity,
i.e. to exclude any risk of detrimental corrosion damages to the pipeline when filled with water. Final
decision on chemical treatment of the hydrotest water should be based on results from laboratory
testing.
The following alternatives may be considered:

− Base case: water treated with an oxygen scavenger and a compatible biocide.
− Filtrated untreated seawater
− Water treated with an oxygen scavenger
− Water treated with an oxygen scavenger and a pH-controller agent as NaOH
− Water treated with an oxygen scavenger and a oxygen corrosion inhibitor
Page 65 of 68
The water treatment in the base case will be based on a typical oxygen scavenger as sodium
bisulphite, NaHSO3; a concentration of some 100 mg/l of NaHSO3 is usually be required.
A typical biocide used for pressure-testing in many pipeline projects is glutaraldehyde with a dosage
of 50-100 mg/l.
Page 66 of 68
App D Environmental Issues
D.1 General
The selection of chemicals used for the oil and gas industry are more and more limited by
environmental aspects. The application of “green chemicals principles” has drawn lot of attention, for
following reasons:
− Oil and gas production is increasingly interesting remote areas, especially offshore and deep
water.
− Chemicals in general and corrosion inhibitors in particular are often toxic and hazardous to the
environment, causing pollution and damage to aquatic and human life.
− Unused inhibitor disposed into the ocean can cause damage to the marine environment.
At the moment a definite and worldwide legislation to enforce the employment of “green chemicals” is
still missing. Local regulations vary from place to place. Though, the use of toxic inhibitors has been
reduced and low-toxic environmentally-friendly formulations have been developed and produced.
D.2 Paris commission (PARCOM)
The North Sea (U.K., Norway, Denmark, and The Netherlands) is exposed to a high potential risk of
pollution and is therefore setting the trend in developing environmental legislation for the use of
green chemicals. The governments are participating in a working group set up by the Paris
Commission (PARCOM) to develop a common statuary testing and approval system for North Sea
exploration and production chemicals.
D.2.1 Environmental Testing

PARCOM guidelines require three tests, which comprise the measuring of toxicity, biodegradation
and bioaccumulation. An ideal green inhibitor according to these guidelines shall be non-toxic, readily
biodegradable and not showing bioaccumulation.
Toxicity: Toxicity testing has to be evaluated on the complete formulation on native environments for
example on organisms like algae, fish and seabed worms. The toxicity is measured as the EC50,
which is the concentration of chemical required to adversely affect 50% of the population and the
LC50, which is the concentration of chemical required killing 50% of the population (Ref. /17/).
Biodegradation: The biodegradation test evaluates how long the product will persist in the
environment and how far is the product decomposed after 28 days.
Bioaccumulation: The Bioaccumulation test is measuring the partition coefficient, which quantifies the
distribution of the product between an octanol and water mixture expressed as the logarithm of the
octanol/water partition coefficient (logPo/w). A Standard High Performance Liquid Chromatography
(HPLC) method is used and this test is performed on all of the components of the product.
As a result to the above the inhibitors are environmentally acceptable in the North Sea when they
fulfil the following criteria:
− Marine Toxicity: EC50 and LC50 > 10mg/l to North Sea species.
− Biodegradability: > 60% in 28 days.
− Bioaccumulation: log(Po/w) < 3.
D.2.2 Chemical Hazard Assessment and Risk Management (CHARM) Model

Following to the environmental testing PARCOM requires an approval system, which aim is to
compare different products for environmental impact. The approval system consists of four modules,
which are Pre-screening, Hazard Assessment, Risk Analysis and Risk Management.
Page 67 of 68
Pre-screening: The aim of the pre-screening is to rank the chemical together with other chemicals
recommended for the same application. The ranking is based on the information on bioaccumulation
potential, biodegradation and acute toxicity of chemicals. Regulatory authorities evaluate also health,
safety, economic factors and technical performance to decide the potential use of the chemical.
In majority of Europe, Chemicals are classified into four categories based on the results of pre-
screening: “permitted”, “replacement required”, “given temporary permission of limited use”, or
“subjected to continuing evaluation”.
Hazard Assessment: The hazard assessment gives information on the potential of a chemical to
cause harm. It is calculated the ratio of “Predicted Environmental Concentration” (PEC) to “No Effect
Concentration” (NEC). If this ratio (Hazard Quotient (HQ)) is less than or equal to one, the ecosystem
is safe.
Risk Analysis: In risk analysis, the probability of occurrence of harmful effects is estimated.
Risk Management: The aim of the risk management is to reduce the risk of harmful effects. Such
measures include target setting, which may involve principles of Best Available Technology (BAT)
and Best Environmental Practice (BEP). Risk Management also allows the comparison of alternative
chemicals, treatment rate, and cost effectiveness.
D.3 Harmonized Mandatory Control System
The Harmonized Mandatory Control System (HMCS) was implemented in 2002 for the reduction of
the discharge of offshore chemicals in the North East Atlantic region.
HMCS first requires pre-screening evaluation. The biodegradability of a chemical must be greater
than 20% and in addition at least two of the following criteria must be fulfilled:
− Biodegradation greater than 70% in 28 days (OECD 301A, 301E) or greater than 60% in 28 days
(OECD 301B, 301C, 301F or 306);
− Toxicity greater than 10mg/l (LC50 or EC50);
− Bioaccumulation log (Po/w) less than 3.
Finally the chemicals are depending on their calculated Hazard Quotient (HQ) in accordance with the
CHARM model.
In UK, Chemicals are assigned to various bands depending on their HQ values. Each band is given a
colour code; “Gold” is the most environmentally friendly one, “Purple” the less friendly one. The
following table shows the different categories:
Category HQ Min Value HQ Max Value

Gold >0 <1
Silver >1 < 30
White ≥ 30 < 100
Blue ≥ 100 < 300
Orange ≥ 300 < 1000
Purple ≥ 1000 ---
A corrosion inhibitor under HMCS is considered ‘Green’ if all its components pass HMCS pre-
screening stage and the HQ value is less than 1 (i.e. In the UK Gold band).
In Norway products that are on the ‘Pose Little or No Risk to the Environment’ list are referred to as
‘Green’ , that pass pre-screening are referred to as ‘yellow’ and those that fail pre-screening are
referred to as ‘Red’ or ‘Black’ depending upon the degree of failure. The Norwegian Pollution Control
Authority has banned the discharge of any ‘Red’ or ‘Black’ substance from 2004; which means only
‘yellow’ substances can be used in formulating corrosion inhibitors.
Page 68 of 68
D.4 Development of environmentally friendly corrosion inhibitors
The intention in developing environmentally friendly Corrosion Inhibitors is to find and produce
Chemicals with low environmental impact and good inhibitor efficiency.
Green corrosion inhibitors have been designed by estimating the aquatic toxicity and the corrosion
inhibition efficiency using the Quantitative Structure Activity Relationship (QSAR) technique (Ref.
/17/) . QSAR is a mathematical relation between property (activity) of a chemical and a number of
structures of the chemicals. The predicted structures with reduced toxicity and improved corrosion
inhibition efficiency were experimentally evaluated leading to green inhibitors.
Inhibitors with improved environmental performance with the following characteristics have been
developed: Marine Toxicity: EC50 > 1.0mg/l to algae; Biodegradability: > 60%-70% in 28 days.;
Bioaccumulation: log(Po/w) < 3, M. W > 1000 (Ref./17/). The environmental screening of candidate
components and inhibitor blends was carried out with Microtox testing, which is the simplest method
for initial screening.
Biopolymers as low toxicity corrosion inhibitors with moderate corrosion protection, high
biodegradability and low bioaccumulation have been evaluated and selected (Ref./17/). These
products were designed especially to use in North Sea oil fields and other environmentally sensitive
areas for CO2 corrosion.
However one barrier in developing new chemistry can be the European Inventory of Existing
Commercial Chemical Substances (EINECS). The costs for registering a new chemical for the first
time can be very high. Oilfield chemical suppliers understandably can prefer to avoid this large cost
by only considering substances already on the list.

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20312e00 Guidelines For Chemical Treatments of Pipelines

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Eni S.p.A.

Exploration & Production Division

GUIDELINES FOR CHEMICAL TREATMENTS OF

ENGINEERING COMPANY STANDARD

Rev. 0 January 2009

GUIDELINES FOR CHEMICAL TREATMENTS OF PIPELINES

4.6 Field testing

The term “pipelines” is herein intended to include:

1.3 Document organization

The organization of this document was outlined as follows:

Section 6 deals with data acquisition, operations and maintenance issues

App D covers environmental issues.

1.5.1 Codes and Standards

1.5.2 ENI Company Standards

20556.VAR.COR.FUN ENI Company Specification. Internal Corrosion Monitoring.

1.6 Symbols and abbreviations

CRA Corrosion Resistant Alloy

Corrosion Inhibitor Partitioning: oil/water partitioning of inhibitor expresses a qualitative concept - as

2. CHEMICAL TREATMENTS FOR INTERNAL CORROSION CONTOL OF PIPELINES

The viability of chemical treatments is mainly related to the following aspects:

2.2 Corrosion inhibitors

CORROSION INHIBITORS GUIDELINES

CORROSION INHIBITORS GUIDELINES

2.3 Glycol control

GLYCOL CONTROL GUIDELINES

2.6 Oxygen scavengers

OXYGEN SCAVENGERS GUIDELINES

3. SELECTION OF CHEMICAL TREATMENTS FOR CORROSION MITIGATION

Chemical treatment may result:

3.1 Data collection

3.2 Corrosivity assessment

A corrosion assessment encompassing all corrosion mechanisms typically met in hydrocarbon

3.3 Flow analysis

This analysis is of particular importance with oil-multiphase or gas-condensate pipelines to verify if

3.4 Chemical treatment performance

3.4.1 Efficiency model

3.4.2 Availability model

3.5 Selection of chemical treatment method

3.5.1 Gas-condensate pipelines

additional injection of corrosion inhibitor, or more conveniently pH stabiliser, is required to achieve

3.5.2 Wet-gas pipelines

3.5.3 Oil-multiphase systems

3.5.4 Liquid-hydrocarbon systems

Flow regime is Yes

3.5.5 Chemical injection methods

The selection of the chemical injection method is based on:

3.5.5.1 Continuous injection

3.5.5.2 Batch treatments

Batch treatments for corrosion inhibition of pipelines may be considered as an alternative to

3.5.6 Applicability of chemical treatments

The assessment is based on:

The viability of chemical treatments is mainly related to the following aspects:

If pre-assessment of chemical treatment suitability is verified, the operational context shall be

1. Chemical treatments shall be considered as not applicable if discouraged or prohibited by HSE

c. the maximum operating temperature exceeds 120°C

In summary the following equation is used:

CA = (CRR x DL x CIA) + CR x DL x (1 – CIA)

Chemical 1. HSE require-

2.c Tmax >

Overall CIA shall be CIA may be assumed

Upgrade to CRA Based on the

5. continuous 6. Batch treatment is

Shear stress Shear stress