Corrosion

Inhibitor
Guidelines
A practical guide to the
selection and deployment
of corrosion inhibitors in
oil and gas production
facilities
A J McMahon, S Groves

Sunbury Report No. ESR.95.ER.050

dated April 1995

Main CD
Contents
Contents

Summary 1

Acknowledgements 7

Introduction 9

System Design and Commissioning 11

Why Use Carbon Steel + Corrosion Inhibitor? 11

Corrosion Engineering Design 15
The Value of Pre-Start-Up Internal Epoxy Coatings for Carbon Steel
Pipelines 16
Hydrostatic Testing and Commissioning of Carbon Steel Lines 17
Keypoints 20

Corrosion Inhibitor Selection 23

Choosing a Batch Treatment Corrosion Inhibitor 23

Choosing a Corrosion Inhibitor for Continuous Treatment 26
Oil/Water Partitioning of Corrosion Inhibitor 36
Deciding Field Dose Rate 41
Compatibility Issues 41
Environmental Issues 44
Keypoints 46

Deployment 49

Oil Company/Chemical Company Alliances 49

Quality Control of Corrosion Inhibitor Supplies 51
Corrosion Inhibitor Pumping Problems 52
Injecting Inhibitor into the Process Stream 54
Corrosion Monitoring 56
Dealing with Process Changes 56
Dealing with Process Interruptions 60
Responsibilities 61
Keypoints 62

References 65

Index 69
Summary

These guidelines cover all aspects of inhibitor deployment including

why they are used, how they are selected, and how to achieve
maximum performance in the field to alleviate internal corrosion of
facilities. This type of information is often passed on verbally
amongst personnel in oil companies and inhibitor suppliers and is not
formally recorded or summarised in any reference book.
Consequently, the authors of this document carried out an extensive
series of interviews with staff from BP, inhibitor suppliers, and other
oil companies (Shell, Elf, Conoco, Statoil, Phillips, Norsk Hydro and
Arco) to try and gather as much accumulated experience as possible.
We have now collated all the information and present here a
summary of industry views on corrosion inhibitors together with our
recommendations on best practises. The main conclusions are
summarised by the bullet points below. More examples and industry
opinions are given within the document.

System Design and Commissioning

❍ Many corrosion problems arise from poor facilities design (e.g.

probe locations, injection points) or poor interpretation of the
design during installation. Corrosion engineers should be
involved in the front end engineering design, at least to review
proposals.

❍ Corrosion resistant alloys (CRAs) are used increasingly at

production sites, e.g. 13%Cr steel has become a virtual standard
for downhole use where CO2 corrosion is a concern.

❍ Carbon steel is still economically favoured for long pipelines

particularly because of its lower initial capex.

❍ Non-metallic materials such as glass reinforced plastics and

plastic lined carbon steel pipe offer potentially major cost
savings but are yet not well proven for production duties.

❍ Drying the process stream (gas or oil) will prevent carbon steel
corrosion. By itself this approach can be risky for oil lines and
it is more reliable to use chemical corrosion inhibitors.

❍ Low-build internal epoxy primer coatings for carbon steel

pipelines are often considered a cost-effective way to minimise
internal corrosion until production starts and corrosion inhibitor
injection begins, but they do not give long term corrosion
protection.

1
SUMMARY

❍ Hydrotest water should always contain at least two treatment

chemicals; oxygen scavenger and a compatible biocide. An O2
corrosion inhibitor is only necessary if the oxygen scavenger
might be consumed by the atmosphere during dosing.

❍ Corrosion inhibitor should be dosed from day 1 of operation

because one can never be sure that the process stream is
completely dry.

Corrosion Inhibitor Selection

❍ Corrosion inhibitor squeezes into the reservoir are uncommon.

As much as two-thirds of the inhibitor may be “lost” and, due to
its surfactant nature, there can be reductions in well
productivity.

❍ Batch treatment inhibition is not fully understood and can not

be used confidently until various uncertainties are removed, in
particular, doubts about the persistency of the inhibitor film after
lay down. Continuous treatment is universally preferred
amongst the oil and chemical companies we contacted.

❍ Batch treatment is only suitable when the application is non-

severe, when continuous treatment is technically difficult (e.g.
downhole in gas wells, remote locations) or when batch and
continuous treatment are used together for severe or upset
conditions.

❍ A batch or continuous inhibitor which performs well in one field

may be inefficient in another under different conditions.
Therefore, it is wise to check the performance beforehand in lab
tests.

❍ A full corrosion inhibitor selection programme in the laboratory

is an efficient way to choose a product. However, laboratory
testing is only ever an approximation of real conditions and so it
gives approximately the best products. These must then be
further assessed in the field.

❍ The BP selection strategy for continuous corrosion inhibitors has

evolved over more than ten years. A shortlist of products is
narrowed down through a series of solubility tests, static and
dynamic corrosion tests, and water/oil partitioning runs.

2
 SUMMARY

❍ The main purpose of a partitioning test is to estimate the

inhibitor dose rate required on total fluids. For example, a
product may show good efficiency at 25 ppm in water-only
tests, but 60 ppm may be needed in a water/oil mixture in order
to reach the same efficiency.

❍ Due to the many components in proprietary corrosion inhibitor

packages and also measurement artefacts, partitioning should
be regarded as 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 dose rate determined in the lab should be introduced in the

field and then gradually reduced or increased to an optimum
value using field monitoring. However, cutting the operational
dose rate is sometimes regarded as a soft target for cost savings.
It should be done carefully in order to avoid undesirable
repercussions.

❍ Field corrosion monitoring must be effective and reliable before

an operator can confidently justify a reduction in dose rate,
especially by a large amount.

❍ It is essential to check the compatibility of a corrosion inhibitor

with every material, lining, seal, and oilfield chemical with
which it is likely to come in contact. Incompatibilities of any
sort can cause serious operational problems.

❍ Environmental concerns are increasingly likely to influence the

selection of all types of oilfield chemicals. To date there has
been some evolution towards environmentally friendly corrosion
inhibitors but not yet any definite legislation to enforce it or
recommendations to guide it.

Deployment
❍ Alliances or contracting relationships already exist in many
important oilfield areas so it is no surprise that such
arrangements are now being introduced more widely for the

3
SUMMARY

selection and deployment of oilfield chemicals. There are

potential advantages and disadvantages in this trend.

❍ Only those suppliers meeting a recognised quality standard such

as ISO9000 should be used. A simple performance test on every
batch of corrosion inhibitor is a useful precaution easily
accommodated by suppliers.

❍ Pump problems can be due to both poor design and poor

operation. Many of the operational problems (e.g. bad
calibration, inhibitor supply exhausted) can be avoided through
good procedures and training.

❍ The corrosion inhibitor should be injected as far upstream as

possible. This often means at the wellhead in order to protect
process equipment already known or predicted to give a
corrosion problem (possibly certain bends or tees).

❍ Injection immediately downstream of the final stage oil/water

separator is appropriate if the separation process might be upset
by corrosion inhibitor, if large amounts of corrosion inhibitor are
likely to be lost with the separated water, and if the corrosion
inhibitor is primarily intended to protect an export pipeline
rather than the processing equipment.

❍ The inhibitor must be added just upstream of a turbulent region

(e.g. bend, valve, pump) or directly into a turbulent process
stream to ensure good mixing.

❍ Typically the injection quill should be positioned midstream,

facing against the flow (unless pigging requirements prevent it).
Direct injection into any water phase is needed for laminar or
stratified flow conditions.

❍ Corrosion inhibitor is often diluted in solvent for use in gas

lines, downhole injection, and batch treatment. There must be
adequate control over both the diluent and the dilution process.

❍ Field corrosion monitoring is covered in detail in a companion

document.

❍ An immediate response to certain key process changes will

reduce the corrosion risk. The inhibitor type and dose rate
should be continuously matched to the process throughput,

4
 SUMMARY

water cut, CO 2 level, O 2 level, H2S level, pH and sand

production.

❍ Process interruptions like shutdowns and acid returns require

their own special set of precautions to prevent corrosion
damage.

❍ It is essential to actively manage corrosion using a Corrosion

Management Strategy with all parties having clearly understood
accountabilities.

❍ Sharing information about corrosion experiences and near

misses, both within BP and externally, often repays the effort
required.

5
Acknowledgements

We thank the following BP staff for their help,

Paul Badelek
Steve Cooper
Laurence Cowie
Mike Fielder
Hans Grunnar
Don Harrop
John Martin
Joanne McKenzie
Ingar Ovstetun
John Pattinson
Tom Pendlington
David Ray
Phil Smith
Simon Webster
Chris White
Richard Woollam

We also thank representatives from the following companies for their

co-operation,

ARCO
Baker Chemicals, Hartlepool
Baker Chemicals, Aberdeen
Champion Technologies Inc.
Conoco UK
Dyno Chemicals, Aberdeen
Elf Enterprise Caledonia
Exxon Chemicals, Fawley
Exxon Chemicals, Aberdeen
Norsk Hydro
Petrolite, Liverpool
Petrolite, St Louis
Phillips Petroleum
Shell Expro UK
Statoil
TR Oil Services, Aberdeen

7
Introduction

These guidelines cover the deployment of corrosion inhibitors

downhole, in flow lines, processing equipment, and export pipelines
in large oilfields. The text covers all aspects of inhibitor use including
why they are used, how they are selected, and how to achieve
maximum performance in the field to alleviate internal corrosion of
facilities. This type of information is not easily available elsewhere.
Whilst corrosion inhibitors are described in textbooks and industry
monographs (e.g. from NACE - the National Association of Corrosion
Engineers; and various oilfield chemical companies) it is usually in
fairly general terms. Much of the detailed, accumulated expertise on
corrosion inhibitors for the oil and gas industries resides within the
production companies and chemical suppliers. Often this is passed
on verbally amongst personnel and is not formally recorded or
summarised. In short, there is no existing written reference source for
detailed information about corrosion inhibitor deployment.

This document is intended to fill the gap. We carried out an extensive

series of interviews with staff from BP, inhibitor suppliers, and other
oil companies (Shell, Elf, Conoco, Statoil, Phillips, Norsk Hydro and
Arco) to try and gather as much experience and anecdotal information
as possible. We have now collated all the information and present
here a summary of industry views on corrosion inhibitors together
with our recommendations on best practise.

The related issue of field corrosion monitoring is of particular interest

at the moment. This is covered in the companion “Corrosion
Monitoring Manual” document [1].

We found much common opinion on many corrosion inhibitor issues.

However, there was also abundant evidence of the same expensive
lessons being relearned over and over again. This report should help
BP to avoid “reinventing the wheel” in the same way by making sure
that important experience is quickly available to those making
decisions about inhibitors. The information is intended to
complement the detailed procedures listed in the Corrosion
Management Systems already adopted or being developed by many
BP assets.

9
System Design and Commissioning

Why use Carbon Steel + Corrosion Inhibitor?

Overview of options There is an ongoing debate about the relative merits of corrosion
resistant alloys (CRAs) and carbon steel + corrosion inhibitor (CS/CI)
in the oilfield. Circumstances will differ from case to case and
obviously must be considered individually. Nevertheless, it is
interesting that opinions on both sides of the argument often relate to
the technical backgrounds of those concerned. Metallurgists and
Materials Scientists will usually promote the advantages of CRAs and
the limitations of CS/CIs (e.g. “I don’t really believe in inhibitors”)
whilst chemists will enthuse about the efficiency and flexibility of
inhibitors (e.g. CI type and concentration). It is no surprise either that
the inhibitor supply companies tend to take the latter view!

An objective view recognises advantages and disadvantages for both

options. In the high temperature, high CO2 downhole environment CS
is highly vulnerable, CIs are difficult to deploy and have poor
efficiency. 13%Cr has therefore become a virtual standard for
downhole use for sweet corrosion, despite its higher cost. BP’s
experience is certainly favourable [2]. 13%Cr usually works out cheaper
than the many workovers normally required on carbon steel tubulars.
CS/CI becomes a more technically viable option for process pipework
and for in-field flowlines. However, concern about the effects of
complex geometries, crevices and dead legs on CS/CI means that CRAs
are often preferred for process equipment, especially offshore. For
long (>5km), large diameter export lines CS/CI has significant capex
advantages (see Box 1).

Box 1: Relative Costs of Different Metals

The details below are semi-quantitative only. Precise costs will depend on many factors such as
location, timescale, quantity, dimensions etc.
10

6
Figure 1: Approximate Relative
5

4
Costs of Various Steels and Alloys
3
(material costs only)
2

0
CARBON 13%Cr 22% or 25% INCONEL
STEEL STEEL DUPLEX 625

The new 36 inch 180 km Forties main-oil-line installed cost was £160 million in 1987, the majority
of which was for the carbon steel pipe. One can see how expensive a higher metallurgy would
have been for this long pipeline. The costs of CRAs become more bearable for smaller quantities
of material.

11
SYSTEM DESIGN AND COMMISSIONING

An intermediate option between CRA and CS/CI is to internally clad

CS selectively with a thin layer of CRA [3]. This is often adopted for
regions of high fluid velocity such as bends and tees.

The new generation of non-metallic materials (see Box 2) has so far

been limited mainly to water duties and requires further development
for production duties. Hence, overall, materials selection depends
critically on location and the prevailing fluid conditions. Further
information on selection is available in detailed documents describing
BP’s current practises [e.g. 4].

Box 2: Non-Metallic Materials Options

Polymer based non-metallic materials offer a number of corrosion-free piping options all with
particular capabilities and envelopes of operation [5]. Water service is already well proven and
although oil production experience is more limited, this is likely to change as the industry becomes
more accustomed to the new possibilities.

GRP - Glass Reinforced Plastic composites offer a number of benefits such as weight savings, no
corrosion and reduced maintenance. The realisation of this potential has been slow but application
of GRP is now beginning, for example on Phillips J Block and Ekofisk, Shell Brent and Draugen,
British Gas Armada, and Amoco AMOSS. The applications are generally fire water mains and sea
water cooling and - on AMOSS - tankage, gratings, ladders. However, the material is more brittle
than steel and requires a completely different set of installation procedures. There are also
concerns over temperature limitations, long term ageing effects and inspection difficulties.

PCT - Plastic Coated Tubing employs a thin epoxy coating on carbon steel (ca 100-200 micro-
metres). The performance of PCT is very variable in both water injection and production service as
a result of coating quality and damage. Joint sealing can be a problem, and gaps in the coating
(“holidays”) are difficult to detect and repair.

GRP lined pipes - These comprise a GRP annulus bonded to the inside of a steel pipe using a ca
1 mm layer of cement grout. The pipes have screwed connection systems which are already used
for downhole water injection tubing and are currently being developed and qualified for some
pipeline applications, mainly in the USA. Effective sealing at the joints can be a problem.

PE and PVDF liners - Polyethylene polymer liners have long been used for land based water and
wet gas service. They have now been used subsea for water injection and hydrocarbon service is
likely to follow. The liner is installed onshore and fits tightly inside, though remains unbonded. It
is ca 10-15 mm thick so that holidays are not a concern. Continuous lengths up to ca 1 km can be
lined at one time so there is a joining problem to be overcome between sections during pipe-
laying. Nevertheless, lined carbon steel offers cost savings over duplex and other high metallurgy
options. Polyvinylidene Fluoride (PVDF) is a new material now being introduced for liners.

Comparing CS/CI The capex advantage of CS/CI for long pipelines is important. Less
and CRAs for money is required up-front during development of a field. Once it
Pipelines
starts production the revenue generated can be used to cover opex
costs. This situation is frequently preferred to specifying CRA which,
although it may have a lower “whole life cost” (capex + opex), will still

12
 SYSTEM DESIGN AND COMMISSIONING

require much higher up-front capex. There are a number of computer

models in use which forecast lower “whole life costs” (or “net present
values”) for CRA compared to CS/CI for both short and long pipelines.
The comparison is complicated and requires assumptions about several
unknowns such as the discount rate (depends on tax regime, interest
rate, company strategy). Some of these models are generally available
(e.g. NiDI [6], NACE) and some are in-house in the oil companies.

CS has some other advantages over CRAs. It is much more readily

available in large amounts, from more sources, and in different
dimensions (diameter, thickness etc). For example at least 5 years
notice might well be required for a manufacturer to supply enough
CRA for a major pipeline. Fabricators and contractors tend to have
more experience of CS. It is also a versatile material. Its physical and
mechanical properties can be varied over a wide range by small
changes in composition. A particular advantage is the relative ease of
welding during installation; welding time is a major factor in
determining overall installation time, especially offshore. Generally, CS
is easier to weld than CRAs, though there are exceptions: for example
high strength carbon steels require great care when welding, especially
in thick sections. Screwed connections may be attractive for CRAs with
poor weldability. They have a good but not perfect record for 13%Cr
downhole tubulars where occasional small leaks do occur but can often
be tolerated until the next workover. In contrast, pipeline leaks often
demand a shutdown in order to effect a satisfactory repair.

Although CRAs are much more resistant to general corrosion than CS

they do have their own particular set of corrosion problems. When
CRAs do corrode it tends to be in a localised rather than a general
manner. Dissolved oxygen and high chloride concentrations are well
known for causing CRA pitting. This can be a problem, for example,
when a 13%Cr producing well is turned round to become a sea water
injector. If sea water deaeration is inefficient then there is a real risk
of oxygen induced pitting of 13%Cr downhole, as well as crevice
corrosion at the connections. As another example, one North Sea
operator lost many km of 13%Cr line due to severe pitting after
hydrochloric acid flow back. CRA’s are also susceptible to stress
corrosion cracking. Alloys with ferritic, martensitic or duplex
microstructures are likely to have only limited resistance to sulphide
stress corrosion cracking in sour environments. Alloys with austenitic
or duplex microstructures may be susceptible to chloride ion stress
corrosion cracking, particularly if they have been welded or cold
worked and are exposed to high chloride low pH environments.

CS has many advantages but unfortunately it does corrode readily in

many environments. Coatings are effective for external protection of

13
SYSTEM DESIGN AND COMMISSIONING

pipelines, often backed up by cathodic protection (CP). This protection

is more difficult internally due to problems of application, quality control
and the risk of coating delamination and erosion (see Box 3).
Furthermore, conventional CP will not protect internal surfaces. One
viable alternative for major pipelines is to dry the process stream since
water is needed to support corrosion reactions. Dry gas export
pipelines are still fairly common. The prevailing temperature along the
whole length is kept above the water dew point so that no aqueous
liquids will condense. However, the increasing trend offshore is to
operate with unmanned or limited facilities at the wellhead and this
requires transport of wet gas.

Some operators use drying for crude oil streams (to <0.5%v/v water)
backed up by regular pigging to remove any accumulations of residual
water. This can be a high risk policy if corrosion monitoring is poor. It
is only really appropriate if the pipeline corrosion allowance can
accommodate high corrosion rates for the lifetime of the oilfield.

In a wet gas line a buffer such as sodium bicarbonate (NaHCO3) or

diethanolamine (DEA) can be added to raise the pH to a less corrosive
value, > ca 6 (i.e. “gas buffering”). However, the most common approach
to controlling CS corrosion in wet gas and wet crude oil streams is to use
chemical corrosion inhibitors. There can be problems here too but the
rest of this document is aimed at discussing these problems and
recommending best practises. Some operators have used CS/CI
successfully for 15-20 years in crude oil export pipelines in the North Sea.

Box 3: Coatings
One can not rely entirely on internal coatings for long term corrosion protection in oilfield
production pipework. Major problems can include coating "holidays" (ie gaps), delaminations and
bad joints (creating preferential corrosion damage), and general poor wear performance (making
the coating susceptible to damage by pigging, wireline, sand impingement etc). Gas export lines
have been coated to reduce pressure drop but corrosion inhibitors have still been employed to
protect bare metal at welds and areas of damaged coating.

However, internal pipeline coatings are used to protect pipewalls during laying and hydrotesting.
BP have used a thin epoxy primer layer, typically 50 microns thick, which just covers the peaks on
a grit blasted surface. This British Gas idea adds around 5% to the cost and has been used on
Forties, Miller, Emden, Brae, and Prudhoe pipelines. The coating is not "high build", and is not
present at field welds. It is resistant to blistering, flaking and pigging but over a period of time it
will wear away at the metal peaks thereby exposing more of the surface.

Process vessels on produced water duty are often made of carbon steel and are protected by a
combination of cathodic protection (CP) and a bottom-half or a complete coating of, for example,
glass flake epoxy. In such applications, inspection and repair is more straightforward than for pipe
internals. However, QA during application is still a major problem which may mean that CRAs are
cheaper in the long term.

14
 SYSTEM DESIGN AND COMMISSIONING

Corrosion Engineering Design

The design of most oilfield facilities in BP follows the traditional

sequence of,

❍ feasibility
❍ statement of requirements - SOR
❍ front end engineering design - FEED
❍ engineering procurement, installation, construction - EPIC

At one time all of this would have been done in-house but now more
and more is being handled by contractors with BP defining the initial
scope and then maintaining a supervisory or, increasingly, a
partnership role. Corrosion engineers are currently involved mainly in
the feasibility and SOR phases. They help to choose the optimum
material and, if it is CS, will also specify an appropriate corrosion
allowance to be used in the FEED phase. A corrosion prediction
model such as the well known de Waard and Milliams approach is
likely to be used in this work if CO2 is present in the process stream.
This model has now reached its fifth or sixth revision [7]. It is
conservative in predicting the general CO2 corrosion rate (i.e. it
overestimates the general corrosion rate) but it has underestimated the
localised corrosion measured in certain BP locations. This is possibly
because the local conditions have not been fully accounted for, are not
known, or are outside the scope of the model. However, de Waard
and Milliams has not yet been supplanted by anything more accurate
and it remains a reasonable and well proven starting point for design.

Insufficient attention to corrosion engineering design during FEED can

lead to problems. The classic example is the location of corrosion
monitoring probes. Many people we interviewed spoke with dismay
about the number of access fittings they’d encountered which were
useless, perhaps as many as 70%. Some were sited on the bottom of
pipe (six o’clock position) but with insufficient clearance below to
allow probe insertion or removal. Some were placed at the 12 o’clock
position in low velocity, low water cut lines. It was as if these fittings
had simply been inserted neatly on the process drawing without any
thought as to their purpose. Retrofitting new access fittings is rarely a
convenient remedial measure. BP Recommended Practice RP 6-1 on
“Corrosion Monitoring” describes the locating and fitting of probes [8],
however, the advice to use a 12 o’clock orientation is not always
appropriate. In most situations the probe should be oriented so that
it will experience the water phase.

15
SYSTEM DESIGN AND COMMISSIONING

The installed location of corrosion inhibitor injection points has also

led to problems, e.g.,

❍ An injection point was sited just upstream of a “tee” and in

operation the inhibitor was preferentially swept into one branch
but not the other. Injection points were actually required on
both lines downstream of the “tee”.

❍ A single corrosion inhibitor injection pump delivered chemical

into a manifold which was linked to several flow lines at a
production site. The flow rate of chemical into each wellhead
depended on the respective well pressures so that some wells
received a lot of inhibitor and some virtually none.

❍ Several onshore wellheads had their own injection points but no

electrical power available to operate a local injection pump.

❍ On one North Sea platform the corrosion inhibitor delivery line

led into a platform drain rather than a process pipe.

These kinds of design/installation errors can cause major problems

during operation. They could be avoided by proper attention to, and
awareness of corrosion issues during the FEED and installation
phases.

The Value of Pre-Start-Up Internal Epoxy Coatings for Carbon Steel Pipelines
BP has used “low build” internal epoxy primer coatings for wet gas
and wet oil lines in order to protect carbon steel linepipe during
transport, installation and storage until production starts (Figure 2).
The coating is not expected to give much protection in service, indeed,
it is expected to be progressively worn away. Therefore, a full
corrosion inhibitor deployment programme is still necessary. The
epoxy coating simply complements this. In any case, the coating stops
short of the pipe ends and so the welds are unprotected (welding
would burn any coating off anyway). Inhibitor is certainly needed for
those bare areas even if the rest of the epoxy does remain intact.

Some coating suppliers argue that this situation with a lower area of
bare surface allows a lower corrosion inhibitor dose to be used. This
is not true for a batch treatment corrosion inhibitor because some
inhibitor will inevitably coat the epoxy. Neither is it true for a
continuously injected inhibitor because the same inhibitor
concentration is needed to protect one bare patch as to protect a

16
 SYSTEM DESIGN AND COMMISSIONING

Figure 2: Epoxy Coating

on Inside of Miller Gas
Line.

20 mm

whole uncoated pipeline. The inhibitor efficiency is proportional to

the bulk inhibitor concentration, whatever the surface area.

Applying the epoxy coat typically adds about 5% to the cost of the pipe
for a major pipeline. However, the potential benefits are clear. There
is much reduced risk of scrapping batches of stored pipe which have
corroded badly due to puddles of water forming along the bottom.
Operators gave us several examples of this for batches of uncoated
pipe sitting at a supply base ready to go offshore. Even if there is no
major penetration, enough pre-corrosion can occur to make some areas
susceptible to general corrosion or pitting when in service. An epoxy
coating overcomes this hazard and also aids protection when the line is
full of hydrotest fluid awaiting start-up. Furthermore, the lack of
substantial amounts of corrosion deposits reduces the risk of internal
plugging and seat damage of pipeline valves. BP’s Forties replacement
main-oil-line, Bruce export line, Miller gas line and Miller crude oil line
have all successfully used epoxy coatings for pre-service protection.
Ultimately it is designers and planners who must decide if the extra cost
for epoxy is justified and, despite the above, some do feel that it is not
cost-effective.

Hydrostatic Testing and Commissioning of Carbon Steel Lines

After installation all oilfield lines are pressure tested with a liquid,
invariably water, to ca 1.25 times the service rating (i.e. hydrostatic
testing). The water can be fresh or saline depending on what is
available. Whichever is used it may remain in the pipe for up to 2
years before production starts and before corrosion inhibitor is added,
although a period of a few weeks to a few months is more typical.

17
SYSTEM DESIGN AND COMMISSIONING

However, we encountered one example from Africa where a line still

remains dormant five years after hydrotesting.

In all these cases a number of treatment chemicals must be added to

the hydrotest water in order to prevent corrosion (see Box 4). This is
true even for a gas line which is drained and then dried (by a gas
stream, e.g. nitrogen; or by alcohol pig) after the hydrotest. There is
always a chance of some hydrotest water being left behind so it must
be adequately treated beforehand. Vapour phase corrosion inhibitors
do exist (e.g. volatile substances like trimethylamine) although some
people doubt their efficiency. They may be added to the drying gas
as an extra precaution.

Box 4: Chemicals for Hydrotest Water

A simple approach has been used by one North Sea operator. A short sub-sea line was filled with
fresh water adjusted to a pH >9 where carbon steel does not corrode. Other operators and
suppliers recommend combinations of oxygen scavenger, biocide, corrosion inhibitor and dye. The
recommendations range from oxygen scavenger alone through to all four components. Typical
concentrations are shown in the table.

TABLE 1: Chemicals for Hydrotest Water

ppm
(in fresh or saline water)

Oxygen Scavenger 125

Biocide ...short dwell time (up to 4 weeks) 100-200
...long dwell time 200-500
Corrosion Inhibitor ...short dwell time (up to 4 weeks) 100
...long dwell time 500
Dye -

oxygen scavenger: ammonium bisulphite (NH4HSO3) or sodium bisulphite (NaHSO3) is normally

used. Both operate as reducing agents,

O2 + 2HSO3- → H2O + 2SO42-

About 3 ppm NH4 HSO3 or NaHSO3 (i.e. ca 5 ppm of 65% solution) are required to consume 1
ppm dissolved oxygen. Air saturated fresh water contains ca 10 ppm dissolved oxygen at 10°C,
therefore, a 125 ppm scavenger dose rate is a ca 4 times overdose. This is required because there
is likely to be some loss of scavenger to atmospheric oxygen, depending on how it is dosed. Some
operators and suppliers feel that all the scavenger will be lost in this way and so it is not worth
adding. They argue that the dissolved oxygen will be rapidly consumed anyway by corrosion
inside the pipe. On the other hand some say that only oxygen scavenger is needed since, if the
oxygen is removed, there will be no bug growth or corrosion.

biocide: This is not needed for very short dwell times, as long as these are assured. One operator
had to abandon a line because of bacterial problems after omitting biocide from hydrotest water
and then leaving it in place for a considerable time.

18
 SYSTEM DESIGN AND COMMISSIONING

Not all biocides are compatible with oxygen scavengers, e.g. glutaraldehyde reacts with ammonium
bisulphite. Care must be taken to select a compatible combination.

corrosion inhibitor: A common error is to use a CO2 corrosion inhibitor. These are not effective
for oxygen corrosion. An efficient oxygen corrosion inhibitor is required. Inorganic substances
such as chromates and nitrates perform well but have environmental drawbacks. Ortho and meta
silicates are possible alternatives. There are also effective organic inhibitors such as
organophosphates. Combined biocide/corrosion inhibitors (typically quaternary ammonium salts)
are also available for hydrotests.

dye: This is only required to aid divers searching for possible leaks in a sub-sea line. Fluorocein
is preferred to rhodamine because rhodamine reacts with oxygen scavenger.

In conclusion, hydrotest water should always contain at least two treatment chemicals, biocide and
oxygen scavenger. These will be effective if they are added correctly. An O2 corrosion inhibitor is
only necessary if the oxygen scavenger might be consumed by the atmosphere during dosing.

Eventually the hydrotest water must be discharged. This is normally

done at the seaward end of the pipe in the case of an offshore line.
In any location the treatment chemicals (biocide, oxygen scavenger,
corrosion inhibitor, dye) must meet all the local environmental
regulations. These regulations are becoming increasingly more
stringent in many parts of the world. As a result manufacturers are
actively developing more environmentally friendly oilfield production
chemicals. However, the concept of an environmentally friendly
biocide for hydrotests does sound peculiar. The description relates to
the biodegradability of the product over a certain period, rather than
its initial toxicity. The issue of environmentally friendly corrosion
inhibitors is fully discussed later (see p.44)

When the process facilities are started up for commissioning and then
for full production there is a question over when to begin adding
corrosion inhibitor. In the past some operators have not added CI
until the water cut rose above a certain level (e.g. >1% water in a
crude oil stream) reasoning that if there is no water then there’s no
corrosion. While this is undoubtedly true the key point is whether
one can ever really say that there is “no water”. Even if the average
water cut is very low there is still a chance of droplets gradually
wetting the steel surface and accumulating, perhaps augmented by
sporadic slugs of water not picked up by routine monitoring.
Corrosion will then occur, as some operators have discovered. We

19
SYSTEM DESIGN AND COMMISSIONING

were given a number of examples of this. Unfortunately the addition

of CI at this stage has not always controlled the problem.

Most operators now seem to recognise that corrosion inhibitor should

be added from day 1. In other words as soon as the hydrotest water
has been discharged. The intention is to try and maintain inhibited
fluids and a pristine steel surface at all times. Experience shows that
once corrosion becomes established it can be difficult to eliminate or
cost effectively control. Day 1 inhibition is especially advisable for
sub-sea lines which are expensive, inaccessible and difficult to
monitor. Inhibition is a prudent insurance policy to maintain safety
and integrity. Monitoring and repair are less difficult on topsides or
onshore facilities and so some operators do not add any inhibitor
here until the measured water cut reaches a defined level. They rely
on efficient inspection to give them early warning of any corrosion
problem and then hope to respond quickly.

KEYPOINTS: System Design and Commissioning

❍ Many corrosion problems arise from poor facilities design (e.g.

probe locations, injection points) or poor interpretation of the
design during installation. Corrosion engineers should be
involved in the front end engineering design, at least to review
proposals.

❍ Corrosion resistant alloys (CRAs) are used increasingly at

production sites, e.g. 13%Cr steel has become a virtual standard
for downhole use where CO2 corrosion is a concern.

❍ Carbon steel is still economically favoured for long pipelines

particularly because of its lower initial capex.

❍ Non-metallic materials such as glass reinforced plastics and

plastic lined carbon steel pipe offer potentially major cost
savings but are yet not well proven for production duties.

❍ Drying the process stream (gas or oil) will prevent carbon steel
corrosion. By itself this approach can be risky for oil lines and
it is more reliable to use chemical corrosion inhibitors.

❍ Low-build internal epoxy primer coatings for carbon steel

pipelines are often considered a cost-effective way to minimise
internal corrosion until production starts and corrosion inhibitor
injection begins, but they do not give long term corrosion
protection.

20
 SYSTEM DESIGN AND COMMISSIONING

❍ Hydrotest water should always contain at least two treatment

chemicals; oxygen scavenger and a compatible biocide. An O2
corrosion inhibitor is only necessary if the oxygen scavenger
might be consumed by the atmosphere during dosing.

❍ Corrosion inhibitor should be dosed from day 1 of operation

because one can never be sure that the process stream is
completely dry.

21
Corrosion Inhibitor Selection

Choosing a Batch Treatment Corrosion Inhibitor

Batch treatment and continuous treatment are the two main choices
for corrosion inhibitor deployment. Each of these requires different
selection tests so it is necessary to decide which will be used before
starting the selection. The third deployment method is corrosion
inhibitor squeezing.

Corrosion Inhibitor A corrosion inhibitor squeeze is analogous to the more common scale
Squeeze inhibitor squeeze where the chemical is injected into the reservoir at
the bottom of the well so it can leach slowly back into the wellbore
fluids when production restarts. This requires that the chemical is
sufficiently held back by adsorption onto the reservoir rock and
therefore the approach is only viable for certain formations. The
amount and degree of dispersion of the scale inhibitor in the reservoir
is calculated so that the leach-back provides protection over an
extended period [9].

Squeezes are rarely used for corrosion inhibitors. They are expensive
and as much as two thirds of the inhibitor may remain in the
reservoir. This is less of a concern in scale inhibitor squeezes since
many reservoirs actually require scale inhibition due to mixing of
formation water and injected sea water. In contrast, no corrosion
inhibition is ever required in the reservoir. The missing two thirds is
simply wasted. Even when corrosion inhibitor squeezes have been
carried out they can give poor results. Production rates have
sometimes gone down due to reduced sand permeability, permanent
skin damage and damaged gravel packs [10]. These downhole effects
are no surprise since corrosion inhibitors are normally surface active
materials with the potential to alter the wetting properties of the
reservoir. There is also a decreasing concentration profile for the
inhibitor over time which requires careful monitoring and which will
eventually demand that another squeeze is carried out. There are
many drawbacks to squeeze treatment and, therefore, batch or
continuous addition are better deployment options for corrosion
inhibitors.

Batch Treatment The small oil producers of West Texas are familiar with batch
treatment. Tankers visit periodically and travel round each field
pumping a few gallons of corrosion inhibitor down every well. The
idea is to coat vulnerable surfaces with a film of inhibitor which will
persist until the next scheduled treatment (see Box 5). For larger

23
CORROSION INHIBITOR SELECTION

scale operations, however, we found that continuous treatment was

preferred universally amongst oil and chemical companies. Batch
treatment was only recommended for remote sites with no power
where there is little alternative; when the application was non-severe
(e.g. low predicted corrosion rate in almost dry fluids); or when
continuous treatment was technically difficult (e.g. downhole in gas
wells, gas flow lines, large diameter gas export lines). As conditions
become more severe the recommended deployment method changes
from batch, to continuous, to batch plus continuous. One chemical
company estimated that only 10% of their corrosion inhibitor business
came from batch treatment products.

Box 5: Corrosion Inhibitor Mechanisms

The chemistries of batch and continuous treatment corrosion inhibitors are different, though the
suppliers are vague about the precise details. Whereas continuous treatment inhibitors tend to form
monomolecular films on the steel surface [11], batch inhibitors are designed to form thicker
“macrofilms”. This is achieved by using mainly high molecular components which have only
marginal solubility in the carrier solvent. When the mixture is washed by production liquids the
carrier solvent is removed and the solute precipitates as an insoluble layer on the surface.

Liquid Figure 3: Schematic Corrosion

Inhibitor Mechanisms

Metal
Continuous Inhibitor Batch Inhibitor

Estimates of initial film thickness (i.e. before washing with the production fluids) are required in
order to calculate the volume of inhibitor needed to coat a certain surface area. Various rules of
thumb exist specifying thicknesses of 0.001 - 0.004 inch. These figures apparently arise from
unspecified studies in the paint industry and elsewhere. Simple coupon immersion tests at Sunbury
using a commercial batch corrosion inhibitor gave a figure of 0.0006 inch.

When a batch inhibitor is applied in a pipeline as a slug between two pigs the pigs should be tight
fitting so that the inhibitor is smeared onto the surface. Otherwise the inhibitor will simply flow
out round the edges of the pig over a short length of pipe. Some operators preflush the system
with methanol in order to clean up the surface and make it ready for the inhibitor.

24
 CORROSION INHIBITOR SELECTION

The Problems of The most common use of batch treatment is downhole in gas wells.
Continuous Treatment Continuous treatment downhole can be difficult. Operators have had
Downhole
problems with corrosion of the injection strings, valve and connection
leaks, and blocking of the string. In the new high angle wells it is
physically difficult even to install a chemical injection string. An
alternative approach is to fill the annulus with a large volume of
inhibitor and allow it to run slowly into the produced fluids through a
partially open valve above the packer. One operator tried this and
eventually found out that the valve was only opening every 3 days.
Also, filling the annulus means there is a large volume of inhibitor to
handle and dispose of if it is found not to be performing.

Continuous dosing via the annulus has also been used during gas lift.
Careful formulation is necessary for gas lift corrosion inhibitors in
order to avoid the solvent flashing off at high downhole temperatures.
This causes the viscous solute to “gunk” out on the annulus wall and
fouling of the injection valves. High boiling solvents such as glycerol
are required to avoid this. Such gunking can be a particular problem
with combined corrosion inhibitor/scale inhibitors since water is often
used in the formulation to dissolve the scale inhibitor component.
This water will flash off at high temperature.

Drawbacks of Batch Although batch treatment may be the only viable option in certain
Treatment circumstances many people have reservations about its efficiency.
The key question is how persistent is the inhibitor film after it is laid
down. Patches may be stripped off very quickly, perhaps by high
velocity, and there is no way of knowing this unless one is fortunate
enough to have monitoring probes at those precise locations. In
continuous injection there is always a reservoir of dissolved inhibitor
available to patch up stripped areas. In batch treatment these areas
remain unprotected until the next batch is applied. And how frequent
should the treatments be? Ideally, on-line monitoring should reveal
when film breakdown starts and more inhibitor is needed. In practise
it is logistics (e.g. the need to shut-in a well for a downhole
treatment), economics (“how many treatments can we afford”) or
limited lab data that often decide. Batch treatment is not fully
understood and can not be used confidently as the only treatment
method until the various uncertainties are removed.

Lab Test for Batch The lab test for batch inhibitors is a rough but straightforward
Inhibitors approximation of the full scale process. Steel specimens are dipped
in the inhibitor, washed with distilled water to remove excess
material, and then placed in the corrosion test cell or autoclave. The

25
CORROSION INHIBITOR SELECTION

corrosion rate is monitored against time for perhaps up to several

months to see when breakdown occurs. A series of such tests
enables the protection efficiencies and breakdown times of several
different inhibitors to be compared (Figure 4). The washing step may
be carried out with a hydrocarbon solvent instead of water. The
intention is to remove any inhibitor which is simply adhering to the
specimen via surface tension and is not actually associated with the
surface film (this adhering material would be quickly washed off in
the real system as well). The corrosion test is more realistic if
dynamic fluid conditions are used (e.g. rotating annular cell, rotating
cylinder electrode, recirculating flow loop...these are all described
later).
Figure 4: Hypothetical Data 140

from Static Persistency Tests on A

120 B
Batch Treatment Corrosion
C
Inhibitors 100 D

80

60

40

20

0
0 5 10 15 20 25 30
Time (days)

Choosing a Corrosion Inhibitor for Continuous Treatment

General Outline Some Middle East operators take a fairly direct approach to selecting a
corrosion inhibitor. They will simply ask a supplier for large
quantities of a specific product based on its performance elsewhere
even though the operating conditions may be completely different
from their own installation. No further testing is carried out. This
could well lead to problems. A product that works well in one
environment may not do so in a different one so it is wise to check
the inhibitor performance in a programme of lab tests.

The procedure used by BP in the UK North Sea is also followed by

several other operators who do not have a service company alliance
arrangement. A number of suppliers are invited to submit one or two

26
 CORROSION INHIBITOR SELECTION

products for evaluation which is carried out either in-house or by a

contractor laboratory. In the European Community there are fair trade
regulations requiring that any contract worth >£280,000 over 4 years is
openly advertised for tender. Therefore, any supplier who meets
certain qualification criteria (e.g. British Standard or ISO accreditation)
has a right to submit samples for consideration. The test programme
will use a number of techniques - which are outlined below - to
progressively narrow the shortlist down from ca 20 to ca 3 products.
There can be subtle differences between labs in how the tests are
carried out and interpreted. One lab may study dynamic conditions
using a flow loop while another will use a rotating cylinder electrode.
There are no standards in this area from a body such as the National
Association of Corrosion Engineers. This situation is not ideal but
ultimately it is the performance of the best lab products in field trials
which will decide which product is finally selected.

Effective field performance is the over-riding objective. Laboratory

testing is only ever an approximation of real conditions and while it
will eliminate unsuitable products it can not guarantee to identify the
best ones. Indeed, one North Sea platform apparently no longer
bothers to carry out corrosion inhibitor pre-testing in the lab. The
operator puts selected products straight into the field for testing. This
is a high risk, trial and error strategy which relies entirely on effective
field monitoring. Some preliminary testing is wise, if not in the lab
then by a sidestream device in the field. Some inhibitor suppliers and
corrosion consultancies have suitable sidestream equipment. Even
here one must appreciate that the sidestream only approximates the
true conditions. Flow regime, total pressure, and oil/water ratio are
some of the variables that are likely to differ from those in the
process line.

Before submitting a product, suppliers will normally carry out their

own tests using conditions, and possibly fluids, supplied by the oil
company. Existing products on the shelf will be examined first since
it is a major task to start from scratch and formulate for a particular
application (see Box 6), especially when there is no guarantee of any
eventual revenue. This hardly limits the options available since many
suppliers have hundreds of existing corrosion inhibitors in their range.

27
CORROSION INHIBITOR SELECTION

Box 6: Corrosion Inhibitor Composition

Oilfield CO2 corrosion inhibitors typically contain from one to six organic components dissolved in
a carrier solvent. The total solute fraction adds up to ca 30% w/w. The active components
comprise mainly surface active (i.e. surfactant) type molecules such as alkyl amines, alkyl
quaternary amines, alkylethoxyphosphates, imidazolines etc. Demulsifier species (e.g. ethoxylated
phenol-formaldehyde resins) may also be included in order to reduce any impact on water/oil
separation in the field. The carrier solvent can be water, alcohol or hydrocarbon. A low freezing
point solvent (e.g. ethylene glycol) is required for products used in very cold conditions.

CH3
CH3[CH2]13N - CH3 Cl
CH3[CH2]13NH2
tetradecylamine
CH3
tetradecyl-trimethyl-ammonium chloride
Figure 5: Some Examples of
Simple Corrosion Inhibitor
CH3[CH2]17
0 Na
Components
N
CH3[CH2]13P = 0 N
0 Na H2N
disodium-tetradecylphosphate oleic imidazoline

The efficient commercial products used today have evolved through much trial and error testing.
Staff moves within the suppliers ensure that effective new ideas are eventually spread around since
patents are not always issued or, if they are, can be difficult to enforce. However, there has been
little real change in the basic chemistry used over the last 15 years. This may change with the
current drive towards environmentally friendly products.

Detailed Selection Protocol Many types of corrosion inhibitor test are used routinely for selection
work in oil industry laboratories. The most sophisticated methods try
to simulate field conditions as closely as possible by reproducing all
aspects of composition, temperature, pressure and hydrodynamics.
Other methods sacrifice some realism for speed and convenience.
Ultimately, however, all tests are approximations of the full scale
system. Slugging flow in multiphase flow lines and pipelines (i.e. gas
+ liquid) is an example of one particular case where realistic lab tests
have not yet been fully developed or proven.

Figures 6 and 7 shows the steps currently followed by BP Sunbury to

select the best corrosion inhibitor from a collection of products
submitted by suppliers. This is a basic protocol and it would be
altered accordingly to deal with specific demands or circumstances of
any particular case. For example, in a high temperature situation
(>100ºC) an autoclave would be used instead of a bubble test and an
annular flow reactor instead of a flow loop. At each step along the
arrow some products would be eliminated. Flow loop and

28
 CORROSION INHIBITOR SELECTION

Figure 6 - BP Corrosion
Inhibitor Selection
Methods

(a) Solubility Test (b) Bubble Test

corrosion inhibitors in water;
left: insoluble, not dispersible
right: dispersible

(c) Flow Loop (d) Oil/Water Partitioning

(e) Rotating Cylinder Electrode (f) High Pressure Flow Loop

29
CORROSION INHIBITOR SELECTION

partitioning tests are time consuming, and therefore a maximum of ca

6 products would be considered by that stage. Full details of all the
techniques are already available [12]. Some outline notes are given
opposite.

(a) decide test conditions - This is arguably the most important step:
deciding how to simulate the field conditions and what
compromises are possible, e.g.,

❍ use simulated brine instead of field brine. Field brine may

not be available at all, may only be available with
corrosion inhibitor already added, or may be unstable due
to scaling.

❍ use carbon steel specimens throughout. This will not give

specific information about weld corrosion. Making up
representative weld specimens for corrosion testing is a
difficult and expensive task though it can be addressed if
necessary.

❍ use CO 2/N2 mixtures to simulate the gas phase and so

omit the natural gas components. The CO2 partial
pressure (i.e. pCO 2) is used to mimic field conditions.
Normally pCO 2 < 1 bar and so a CO2/N2 mixture with 1
bar total pressure can be used. For a liquid stream in the
field pressurised above its bubble point, the CO2 partial
pressure of the last gas phase in contact with the liquid is
used, i.e. on the upstream side; the “virtual” partial
pressure of CO 2 [13]. Alternatively, this value can be
calculated using software such as the BP “SPARTAN”
package.

❍ for a wet gas system use a simulated liquid phase by itself

rather than the complete gas/liquid mixture.

❍ use wall shear stress to simulate hydrodynamics. There

are many hydrodynamic variables which could be used
(e.g. velocity, turbulent kinetic energy, Reynolds number,
mass transfer co-efficient). Wall shear stress is appropriate
to the region next to a metal surface and is especially
relevant to the tendency to remove a corrosion inhibitor
film. Box 7 shows equations for calculating wall shear
stress in pipes.

30
 CORROSION INHIBITOR SELECTION

Figure 7: BP Corrosion
Inhibitor Selection
Strategy

Decide Test Conditions

Solubility Test
..check dispersal in both oil and water

Bubble Test
..rapid screening of all products under
static conditions

Flow Loop Test

..best products examined under dynamic
conditions

O/W Partitioning Test

..partitioning followed by flow loop to
assess optimum field dosage on
total fluids

rotating cylinder electrode compatibility tests

..does neat inhibitor attack metal?
..high shear (up to 80 Pa)
..does corrosion inhibitor interfere with
..persistency tests
demulsification or scale inhibition?

Other Tests?

jet impingement loop high pressure loop

..high shear (up to 300 Pa) ..for accurate simulation of real field
..persistency tests conditions (3 days/test)

Recommend Products

31
CORROSION INHIBITOR SELECTION

Box 7: Equation for Wall Shear Stress in a Pipe

The standard equation is derived from the work of Blasius [14, 15].

2
τp = 0.039 ρ up Re-0.25

τ is wall shear stress (Pa)

p is pipe
ρud
Re is the Reynolds number, Re = η

ρ is density (kg/m3 ...1000 for water)

u is velocity (m/s)
d is diameter (m)
η is viscosity (Pa s ...0.001 for water)
4Q
up =
πdp2

Q is pipe flow rate (m3/s)

..therefore, τp = 0.060 ρ0.75 Q1.75 d -3.75 η0.25

NACE Standard MR-01-75 defines a system as sour if the partial

pressure of H2S in the gas is >0.05 psi in a total pressure >65
psi. Materials selection to control sulphide stress cracking is
then required. When selecting a corrosion inhibitor for a system
containing both H2S and CO2 the BP Sunbury guideline is more
qualitative. A useful rule of thumb is that CO2 will produce
three times as much aqueous corrosion as the same partial
pressure of H2S [16]. Therefore, when p CO2 >> p H2S most of
the corrosion will be caused by CO2. In these circumstances it
is reasonable to omit the H2S component in the corrosion tests.
This is because at low concentrations H2S can form FeS films on
steel surfaces which can be protective. Reducing the baseline
corrosion rate makes it more difficult or even impossible to
discriminate between corrosion inhibitor candidates. Once an
inhibitor has been selected in a CO2-only system then H2S can
be included in final confirmation tests. However, it is worth
remembering that some corrosion inhibitors are formulated to
perform best on a complete or partial FeS film. These products

32
 CORROSION INHIBITOR SELECTION

are not likely to do well when H2S is omitted from tests. A

related point is that some corrosion inhibitors formulated for
CO2-only systems actually contain a sulphide component
intended to enhance protection by deliberately forming FeS
films.

When pCO2 ~ pH 2S then H 2S must be included in the tests

since it could be making a significant contribution to the overall
corrosion. High H2S situations are amongst the most difficult to
inhibit, for example, in Canada where some wells produce >30%
H2S in the gas and require several hundred ppm of corrosion
inhibitor [17]. High density polyethylene liners (HDPE) are often
used instead.

After considering all these issues the main parameters required

for the test programme are brine composition (including other
oilfield chemicals, see “Compatibility Issues”, p.41), gas
composition, temperature and wall shear stress. The tests
should cover the expected variation in each parameter during
the life of the field. Brine composition, for example, can
change due to sea water breakthrough in the reservoir.

(b) solubility test - The wheel test is still often used as the first stage
in selection. Weight loss coupons 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 type of test is the only one which
can be used at low water cuts (<5%) to evaluate oil soluble
corrosion inhibitors. Nevertheless, random wetting effects can
sometimes influence the trends observed. In contrast, the BP
approach - bubble tests, flow loop tests and the others
described below - concentrates on using a water phase and so
water soluble inhibitors may arguably be favoured. This could
cause problems because an entirely water soluble product is not
suitable for deployment in a low water cut crude oil system: it
would be difficult to deliver to all the water wet areas of the
pipewalls.

To address this concern all products in the BP selection are first

qualitatively checked for their solubility in brine and in crude oil
(Figure 6(a)). A transparent oil such as “maltenes” (l:l:l v/v
xylene/kerosene/gas oil) is used to simulate crude oil [11].
Corrosion inhibitors must be soluble or dispersible in both brine
and maltenes in order to proceed to the next stage of testing.

33
CORROSION INHIBITOR SELECTION

(c) main tests - The bubble test, flow loop test and the others in
Figure 6 are fully described elsewhere [12]. Table 2 briefly
summarises the main pros and cons of each method.

TABLE 2: Corrosion Inhibitor Test Methods

Method Pros Cons Maximum Maximum

T P (bar
(°C) absolute)

Bubble test Convenient; Static 80 1

many tests in
short period; low
liquid volume

Autoclave High T and P Static; time 200 100

consuming

Glass flow Dynamic; Time consuming 80 1

loop <7 Pa in 5 ltr (1 day/test)
loop; <50 Pa
in 16 ltr loop

High pressure Dynamic; Time consuming 90 100

loop high T and P (3 day/test)

Rotating Convenient; Can underestimate 80 1

cylinder up to 80 Pa corrosion compared
electrode shear to a flow loop and
so is not as severe a
test

Rotating High T and P Can underestimate 120 30

annular corrosion compared
cell to a flow loop and
so is not as severe a
test

Jet High shear Can underestimate 80 1

impingement (up to 300 Pa) corrosion compared
loop to a flow loop and
so is not as severe a
test

Figure 8 presents typical data from each stage of the testing

showing how the best products are selected. In this
hypothetical example six products are examined in the static
bubble test (Figure 8(a)). Most give a satisfactory efficiency of
>90% with respect to the baseline corrosion rate (ca 110 mpy)
but two perform poorly (inhibitors A and B) and are eliminated.
Two further products are eliminated under dynamic conditions
in the flow loop (Figure 8(b)). The remaining inhibitors (E and
F) are examined in more detail using water/oil partitioning tests.
In each test a certain concentration of inhibitor is added to a

34
 CORROSION INHIBITOR SELECTION

water/oil mixture, allowed to partition, then the water is

separated and then transferred to the flow loop. Data for a
range of concentrations reveals the optimum concentration (on
total fluids) for a particular water cut, i.e. the onset of the plateau
in Figure 8(c). Partitioning effects mean that this optimum
concentration changes with changing water cut depending on the
preferential solubility of the inhibitor. For example, going from
50 to 20% water cut reduces the inhibitor E efficiency but
improves the inhibitor F efficiency (Figures 8(c) and (d)). This is
because E is preferentially oil soluble and F is preferentially
water soluble (Box 8). Overall, Figure 8 shows that F is the best
product and it will give ca 95% inhibition efficiency when dosed
at 15 ppm on total fluids into 20 - 50% water cuts.

Figure 8: Hypothetical (a) Bubble Test inhibitor A

Data from Corrosion inhibitor B
140
Selection Tests inhibitor C
inhibitor D
120
Inhibitor E

100 inhibitor F

80

60

40

20

0
0 5 10 15 20 25
Time (hrs)

(b) Flow Loop : 25 ppm corrosion inhibitor in Brine

40 inhibitor C
inhibitor D
35
inhibitor E
30 inhibitor F

25

20

15

10

0
0 5 10 15 20 25
Time (hours)

35
CORROSION INHIBITOR SELECTION

(c) Flow Loop : Brine Separated from 50:50 v/v Water/Oil

Partitioning Runs

50

45

40 inhibitor E
35 inhibitor F
30

25
20

15

10

0
0 10 20 30 40 50 60 70 80 90 100
Inhibitor Concentration (ppm) on Total Fluids in Partitioning
Run

(d) Flow Loop : Brine Separated from 20:80 v/v Water/Oil

Partitioning Runs

50

45 inhibitor E
40 inhibitor F

35

30
25
20
15

10
5
0
0 10 20 30 40 50 60 70 80 90 100
Inhibitor Concentration (ppm) on Total Fluids in Partitioning
Run

Note that BP Sunbury prefers to carry out partitioning in a

dedicated vessel, separate the water, and then transfer the water
to the test facility. This avoids the possibility of oil wetting
effects obscuring the performance of aqueous corrosion inhibitor
which is likely to happen if a l:l v/v brine/crude oil mixture is
circulated round a flow loop. Since the use of a large dedicated
vessel can be time-consuming, brine/crude oil mixtures ar e
sometimes used directly in the bubble test if qualitative
partitioning data is required quickly. Oil wetting of the probes
can be avoided in the bubble test. Further details of the
oil/water partitioning test are discussed in the next section.

Oil/Water Partitioning of Corrosion Inhibitor

All the suppliers and users whom we approached realised the

importance of oil/water partitioning and accepted that it should be
examined in any selection programme. Some commented that certain

36
 CORROSION INHIBITOR SELECTION

corrosion inhibitors actually require oil in order to perform well. This

particular feature can actually be tested simply by adding 500 ppm oil
to the bubble or flow loop tests in Figure 7. It doesn’t require a full
partitioning test. Nevertheless, a partitioning test will have the same
effect due to the dissolved and dispersed oil carried over in the
separated water.

The main purpose of a partitioning test, however, is to estimate the

inhibitor dose rate required on total fluids. A product may show
good efficiency at 28 ppm in water only tests, but if it is added at 28
ppm to a l:l v/v water/oil mixture then most of the material may
migrate into the oil perhaps giving concentrations of 37 ppm in the
oil phase and only 18 ppm in the water (see Figure 9, Box 8). 18
ppm might not be sufficient to fully inhibit the water. In this example
a dose rate of 56 ppm on total fluids would be required to give 28
ppm in the water phase. This illustrates the importance of conducting
partitioning tests at realistic water/oil ratios, and also of adjusting
injection rates with changing water cut.

Note that some operators specify a recommended inhibitor

concentration in the water phase. They then use experimental data
to work out the necessary concentration on total fluids for a given
water cut.

Box 8: Theory of Corrosion Inhibitor Partitioning Between Oil and

Water Phases.

The following information is only theory and must be used with care for any real situation.

Partitioning Equations

if Co Vo + Cw Vw = Ct and Cw/Co = P

where C is concentration
V is volume fraction
w is water phase
o is oil phase
t is total fluids
P is partitioning co-efficient (water/oil))

then Cw = Ct P/(Vo + PVw) and Co = Ct/(Vo+ PVw)

Illustrations

The Figures below show the partitioning behaviour for, (a) a preferentially water soluble
component (P=2.0), and (b) a preferentially oil soluble component (P=0.5), added at 28 ppm on
total fluids to a mixture containing 1:1 v/v oil/water.

37
CORROSION INHIBITOR SELECTION

Box 8: Continued

60 60

Conc in water
50 Conc in water 50 Conc in oil

Inhibitor Conc (ppm)

Conc in oil
Inhibitor Conc (ppm)

40 40

30 30

20 20

10 10

0 0
0 10 20 30 40 50 60 70 80 90 100 0 10 20 30 40 50 60 70 80 90 100

Water Cut (%) Water Cut (%)

Figure 9: Theoretical Effect of Water Cut on Figure 10: Theoretical Effect of Water Cut on
Inhibitor Partitioning for a Preferentially Water Inhibitor Partitioning for a Preferentially Oil
Soluble Inhibitor (partitioning co-efficient W/O = Soluble Inhibitor (partitioning co-efficient W/O =
2) Added at 28 ppm on Total Fluids. 0.5) Added at 28 ppm on Total Fluids.

These figures demonstrate some rules of thumb for a constant dose rate on total fluids;

❍ for a preferentially water soluble component the aqueous concentration will vary inversely
with the water cut

❍ for a preferentially oil soluble component the aqueous concentration will vary directly with
the water cut

Ideal Partitioning The ideal partitioning behaviour for a corrosion inhibitor is relatively
Behaviour
clear. A completely water soluble product will fully inhibit the
aqueous phase if present at the optimum concentration. However, it
will be difficult to disperse in a mainly oil and low water system.
Depending on the formulation it could well plate out on the pipewall
downstream of the injection point and not be delivered efficiently to
water wet regions by the flowing liquid. Completely water soluble
components are also said to form poor protective films anyway
because they have little or no hydrophobic character. In contrast a
completely oil soluble product will be well dispersed but will not
inhibit the water. The best approach is to have a product with some
affinity for both water and oil. In this way it can be dispersed in oil
and also inhibit water once it encounters any. The ideal distribution
between oil and water is still a matter of debate and will also depend
on the application. Whatever characteristic is desired by a supplier it
can be achieved by tailoring specific components (e.g. by lengthening
a hydrocarbon chain to increase affinity for oil) or by mixing several
components or solvents which have different properties.

38
 CORROSION INHIBITOR SELECTION

Partitioning is a Qualitative The issue of components raises a problem over the use of “partition
Concept co-efficients” in the way they are defined in Box 8. Many corrosion
inhibitors are a mixture of components, perhaps as many as six or
more and each of these will have its own individual partition co-
efficient dependent on the prevailing conditions. The “overall”
partition co-efficient for the product will be a compound of the
individual values and so will be even more dependant on conditions.
Therefore, it is unwise to regard a partition co-efficient, obtained
under one set of conditions, as a constant which can be extrapolated
quantitatively to other conditions. Partitioning should be regarded as
a more qualitative concept as in “preferentially water soluble” or
“preferentially oil soluble” [18]. This advice is reinforced by the
potential error in any measurement of partition co-efficient in the lab.
Not only are there bulk oil and water phases but also oil/gas,
oil/glass, water/glass and oil/water interfaces. Each of these may
influence the perceived distribution across the oil and water. It is
difficult to tell how much inhibitor may be retained in these interfaces
because although the amount of inhibitor in the bulk water may be
measurable, the amount in the bulk oil may be impossible to
determine.

Measuring Corrosion The measurement of small concentrations of corrosion inhibitor in

Inhibitor Residuals in Water brine samples is not easy. Rigorous analysis would require a specific
analytical technique for every single component in the formulation,
obviously an onerous task. Accurate techniques for even one main
component may be difficult given the low concentrations and possible
interference from dissolved and dispersed contaminants. Sample pre-
conditioning is normally required. A variety of colorimetric and
spectral methods have been developed which are specific for
particular component chemistries. This area has taken on new
importance with the increasing focus on environmental management
and regulation because the type and amounts of substances in waste
water often have to be declared and controlled.

BP Sunbury avoid the technical problems of residual inhibitor analysis

simply by measuring the corrosivity of the brine sample. The
corrosion rate will be dependant on the mixture of components and
the total amount of product which is present in the water phase. A
calibration curve of corrosion rate versus corrosion inhibitor
concentration in water can be used to relate the corrosion rate for any
sample (e.g. water separated from a partitioning run) to the
appropriate inhibitor concentration.

39
CORROSION INHIBITOR SELECTION

Water Cut Any water cut can be examined in a partitioning test though for low
water cuts the amount of brine available for separation and testing
can become rather small. A 2% v/v water cut in a 20 ltr vessel means
there is only 400 ml of brine. This is enough for a bubble test but
not a flow loop test. Four repeats would be necessary to produce the
1.7 ltr needed for a flow loop test. BP’s largest lab partitioning vessel
is currently 20 ltr which means that ca 15% is the lowest water cut
which can be simulated in order to produce 1.7 ltr of brine for a flow
loop test.

Deciding Field Dose Rate

The standard approach described by the suppliers and operators we

interviewed was to determine an approximate dose rate from
partitioning tests in the lab, start with this in the field, and then gradually
reduce or increase the concentration to an optimum value using field
monitoring. Typical concentrations are given in Box 9. Field
monitoring must be effective and reliable before an operator can
confidently justify a reduction in dose rate, especially by a large amount.
The short term cost saving may not be worth the risk especially with a
critical, high valve asset such as a sub-sea pipeline. The recent
“Corrosion Monitoring Manual” [1] describes the techniques which can
be used to manage gradual reductions in the dose rate.

Box 9: Typical Field Dose Rates for Corrosion Inhibitor

The following data were gathered from suppliers and operators. The values are merely illustrations
of typical dose rates for various cases and should not be used as definitive recommendations. Some
examples of extreme situations are included.

TABLE 3 : Typical Field Concentrations of Corrosion Inhibitor

Location Corrosion inhibitor dose on total

fluids (ppm)

Oil well 50
Infield oil line 50
Short oil transport line 15
Long oil transport line 30
Long gas transport line 2 pint/MMSCF

Extreme cases:
Hot, deep gas well 2000
50% H2S gas line 1000
High velocity, high water oil line 250

40
 CORROSION INHIBITOR SELECTION

Cutting the Dose Rate Many interviewees felt that cutting the inhibitor dose rate was a “soft
target” for cost savings and was often done carelessly because the
repercussions were not always apparent until several years afterwards.
Corrosion inhibitor can be described as a maintenance chemical rather
than a process chemical. Operations can continue in the absence of
inhibitor. However, degradation may eventually stop operations at
some time in the future.

BPX Alaska are currently using a model which compares the whole
life cost of corrosion inhibition plus associated monitoring against the
risk and cost of line replacement [1]. This shows that high inhibitor
dose rates maintain a low corrosion rate but are expensive in terms of
chemical costs. Low inhibitor dose rates allow a high corrosion rate
and are also expensive due to premature line replacement. There is
an optimum dose rate between these extremes which gives the
minimum whole life cost. At this concentration there is a small, non-
zero corrosion rate and the chemical costs are balanced against the
line replacement costs. The analysis shows that increasing the dose
rate may sometimes be more cost effective overall than reducing the
dose rate.

Even after a specific dose rate is decided it may still not be achieved
in practise due to operational problems, errors or oversights. This
issue is discussed in more detail under “Deployment” (p.49).

Compatibility Issues

Metals Strange as it may seem, some neat corrosion inhibitors can actually
corrode metals [19]. They only perform as corrosion inhibitors when
they are diluted to a small concentration in a process liquid. Because
of this effect it is necessary to check the compatibility of neat
corrosion inhibitor with the material used to fabricate the storage and
delivery system. Simple coupon weight loss tests in aerated neat
inhibitor are sufficient. 316 stainless steel understandably has a
broader range of resistance than carbon steel and is the preferred
material amongst several operators. 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 (see also Box 14). If a
carbon steel pipe and quill is already in place then it may rule out the
use of certain “corrosive” corrosion inhibitors. This must also be
considered when batch treating a carbon steel line with neat or
partially diluted (ca 20% v/v) corrosion inhibitor.

Lining Materials Lined carbon steel storage vessels and delivery piping can be used as
a compromise between stainless steel and carbon steel. Nevertheless,

41
CORROSION INHIBITOR SELECTION

lining materials themselves have their own limitations and can also be
attacked by certain corrosion inhibitors. Compatibility tests are again
necessary. The elastomer materials used as seals in pumpheads must
also be considered. Viton A, for example, is vulnerable to the amines
used in many corrosion inhibitors. There is a range of alternative
materials (e.g. AFLAS, perfluoropolymers etc) which may be more
effective (see Box 10). Unfortunately, with elastomer seals there is
always a trade off between chemical resistance and useful mechanical
properties.

Box 10: Seal Materials for Pumps

Although a rubber O-ring may only cost a few pounds, the cost and safety consequences of seal
failure can be extremely large. It is, therefore, well worth giving detailed thought up-front to all
the seals in inhibitor pump and control equipment, as well as in production and injection service.
Just because most seals are “black and stretchy” does not necessarily mean that all O-rings will
perform the same in any given oilfield service.

Many plastic and rubber materials are available for use as either primary or secondary pump seals.
The ASTM abbreviations for some of the more common materials are:-

NBR - Nitrile elastomers

FKM - “Viton”/”Fluorel” fluoroelastomers
TFEP - Tetrafluoroethylenepropylene; “Aflas” fluoroelastomers
FFKM - Perfluoroelastomers “Chemraz” and “Kalrez”
PTFE - Polytetrafluoroethylene; “Teflon” is not an elastomer, but is chemically very resistant and
can be made to seal by pressure or springs

Each of these materials has an envelope of conditions under which they show satisfactory long
term sealing performance, and the user should refer to the “BPX Elastomer Selection Guidelines” for
further details [20].

The process for the selection of seal material and geometry takes place through a logical
consideration of the temperature, pressure and chemical environment of the sealing duty. These
factors determine the requirements for not only the chemical resistance but also the mechanical
properties of the seal. It is important to define the service conditions as completely as possible in
order to select the most appropriate seal geometry and material.

The major chemical factors determining the effect of corrosion inhibitors on elastomers will be:

❍ Amine content, e.g. amines affect both nitriles and “Vitons”.

❍ Acidity/alkalinity, e.g. acids affect nitriles, alkalis affect “Vitons”.
❍ Solvent package, e.g. methanol swells “Viton A”, aromatics swell nitriles.

In general, pump seals see neat chemicals at relatively low temperature, while production seals see
mostly dilute chemicals at somewhat higher temperature. If there is any doubt regarding the
performance of a seal, testing should be carried out with particular inhibitors to demonstrate that
the seal can function under the appropriate conditions.

42
 CORROSION INHIBITOR SELECTION

Other Oilfield Once a corrosion inhibitor is injected it must be compatible with the
Chemicals other oilfield chemicals present in the system such as demulsifiers,
scale inhibitors, anti-foams, wax inhibitors etc, and vice-versa. To
simplify the selection procedure the best approach is to decide which
function has the highest priority (corrosion inhibition, scale inhibition,
demulsification), choose the best chemical for that function, and then
find compatible chemicals for the other functions. For example, if
scale inhibition is the priority and a scale inhibitor has been selected
then this should be included at an appropriate concentration in all the
corrosion inhibitor selection tests (Figure 7). A number of suppliers
said they were not always given correct details about other chemicals
and this made it more difficult to submit effective products for
consideration. They were “at the mercy of customers” in this respect.
Generally, however, they felt that corrosion inhibitor performance
tends to be robust towards other oilfield chemicals. On the other
hand demulsifiers and scale inhibitors are often adversely affected by
corrosion inhibitors. Because of this the corrosion inhibitor is added
downstream of the water separation train in many installations.

Co-mingled Fluids Compatibility issues can become extremely complicated when fluids
from different installations are co-mingled in shared pipeline facilities.
The Forties main oil line is a good example. This already has ca 20
separate contributors although some of these are very small. A policy
of uniform chemical usage in such systems will reduce the chances of
compatibility problems. However, if the “standard” corrosion inhibitor
is inefficient for any particular contributing stream then another will
have to be used there after making sure that it won’t interfere with
the “standard” inhibitor in the shared line. All contributors should
have to notify the system operator well in advance of any potential
changes in chemical type or dose rate (see also “Responsibilities”,
p.61).

Blocked Injection Incompatibilities between different chemicals can become all too
Lines evident when they mix in the same injection line, usually accidentally.
Many suppliers gave examples of blockages caused by neat corrosion
inhibitor going into a line previously used to dose wax inhibitor or
scale inhibitor. Adequate flushing with a solvent or water is obviously
necessary before changing a chemical in this way. Blockages are of
particular concern in inaccessible umbilicals and flexibles leading to
sub-sea wellheads because repairs can be difficult. Sometimes the
blockage is not due to products mixing but to a carrier solvent (e.g.
methanol) forming a viscous gel with the corrosion inhibitor or even
dissolving some polymer tubing. All these examples reiterate the
importance of checking the compatibility of the corrosion inhibitor
with all materials it encounters.

43
CORROSION INHIBITOR SELECTION

Combined Products One way of avoiding compatibility problems between different

products is to use combined products. Combined scale and corrosion
inhibitors are available from a number of suppliers. Many of these
are simply mixtures of compatible, individual products although some
multifunctional, single component products are being assessed [21].
Combined products have the advantage of enabling one storage tank,
one pump, and one injection line to be used for both scale and
corrosion control. This is especially attractive for minimum facilities
installations. On the negative side, there is some loss of flexibility in
this approach. If the combined product is being dosed at a particular
rate and then there is a sudden need to increase the concentration of
scale inhibitor, this can only be done by also putting in more
corrosion inhibitor which may not be needed. The product could be
reformulated to meet the new balance between scale and corrosion
inhibition (e.g. 2:1 v/v → 4:1 v/v scale inhibitor : corrosion inhibitor)
but realistically this is likely to take a few weeks.

Environmental Issues

Environmental concerns are increasingly likely to influence the

selection of oilfield production and drilling chemicals in all parts of
the world. Currently there is no uniform, worldwide legislation and
local regulations vary from place to place. The industry view is that
North Sea activity is setting the trend in developing environmental
legislation, particularly the Norwegian sector where there is already a
CO2 tax. At present each national sector in the North Sea requires its
own specific criteria to be satisfied. However, all the governments are
participating in a working group set up by the Paris Commission
(PARCOM) to develop a common statutory testing and approval
system for North Sea exploration and production chemicals. When
that happens, the current voluntary notification scheme in the UK
sector will become mandatory. The UK already has strict limits for
onshore water disposal regulated by the National Rivers Authority.
One operator felt that some NRA limits were already too strict.

Future Legislation Until the PARCOM Working Group and other bodies around the world
report their findings no-one is quite sure what sort of legislation will
emerge. Suppliers and operators felt strongly that this was hindering
the development of environmentally friendly oilfield chemicals. The
environmental targets were either varied, moving or hidden. For
example, it is not yet clear whether products which act and remain in
a crude oil phase, like demulsifiers and anti-foams, even need to be
especially environmentally friendly. They are present at ppm level in

44
 CORROSION INHIBITOR SELECTION

crude oil which itself is comprised of potentially worse toxins

(benzene, polyaromatics etc). Some suppliers have already made
progress towards “green” corrosion inhibitors and most have a
medium term aim to produce a complete range of green products.

This is certainly consistent with the demand from some North Sea
operators. One said they “have a policy to use category 0 and 1
chemicals at all times” given acceptable performance and that “a
green corrosion inhibitor would be preferred even if slightly less
efficient than a competitor” (NB - 0 and 1 are the lowest
ecotoxicological risk categories in current UK legislation). One
supplier is already advertising a green corrosion inhibitor which is 60-
70% biodegradable in 28 days and which performs as well as existing
products. In all of this the issue of performance is key. It is no use
having a green corrosion inhibitor for its own sake if it doesn’t do its
job. As one operator put it, “a pipeline failure is very unfriendly to
the environment”. Another operator said that the SFT, the Norwegian
environmental authority, is prepared to accept usage of a
conventional, more toxic product on performance grounds as long as
greener products were included in the selection process and were
shown to be inferior. The SFT has less stringent regulations on the
corrosion inhibitor if the produced water is destined for re-injection.

New Chemistry Suppliers now have a challenge to develop green corrosion inhibitors
which match or exceed the performance of conventional products. A
more efficient product will mean a lower dose rate in the field which
is another environmental benefit. There is a need to remove the
occasional view that “if it’s green, it’s no good”. Some promising new
chemistries have already been reported [21], including work on
polyaspartates by BP [22]. But more remains to be done. One barrier,
though, to looking at completely novel chemistry is the European
Inventory of Existing Commercial Chemical Substances (EINECS). Any
chemical substance first marketed by the manufacturer or importer
after 18 September 1981 must be notified to the national competent
authority. Notification requires a dossier of information about the
chemical covering identity, uses, quantities, disposal, physical
properties, toxicology and ecotoxicological tests. It can cost up to ca
$50,000 to register a new chemical for the first time. Oilfield chemical
suppliers understandably prefer to avoid this large cost by only
considering substances already on the list when they select possible
components for corrosion inhibitor formulations and other products.

45
CORROSION INHIBITOR SELECTION

Box 11: EINECS - European Inventory of Existing Commercial

Chemical Substances

EINECS lists and defines those chemical substances which were on the European Community
market between 1 January 1971 and 18 September 1981 and to which the pre-marketing notification
provisions of the European Commission Directive do not apply. EINECS runs to 8 volumes. The
overriding purpose of the Directive is to establish a single testing and notification system for new
chemical substances marketed in the European Community. A chemical substance marketed or
imported for the first time after 18 September 1981 must be notified to the national competent
authority at least 45 days in advance. Notification must contain a dossier of information about the
characteristics of the chemical: identity, uses, quantities, disposal and results of physico-chemical,
toxicological and ecotoxicological tests.

Overall, there is a trend towards environmentally friendly products but

little definite legislation so far to enforce it. The trend is for evolution
rather than revolution. One supplier even went as far to say that the
oil companies “pay lip service to environmentalism” but in many
regions are under little short term pressure to change their ways.
Only when legislation is scheduled or announced are they likely to
take significant action.

KEYPOINTS: Corrosion Inhibitor Selection

❍ Corrosion inhibitor squeezes into the reservoir are uncommon.

As much as two-thirds of the inhibitor may be “lost” and, due to
its surfactant nature, there can be reductions in well productivity.

❍ Batch treatment inhibition is not fully understood and can not

be used confidently until various uncertainties are removed, in
particular, doubts about the persistency of the inhibitor film after
lay down. Continuous treatment is universally preferred
amongst the oil and chemical companies we contacted.

❍ Batch treatment is only suitable when the application is non-

severe, when continuous treatment is technically difficult (e.g.
downhole in gas wells, remote locations) or when batch and
continuous treatment are used together for severe or upset
conditions.

❍ A batch or continuous inhibitor which performs well in one field

may be inefficient in another under different conditions.
Therefore, it is wise to check the performance beforehand in lab
tests.

46
 CORROSION INHIBITOR SELECTION

❍ A full corrosion inhibitor selection programme in the laboratory

is an efficient way to choose a product. However, laboratory
testing is only ever an approximation of real conditions and so it
gives approximately the best products. These must then be
further assessed in the field.

❍ The BP selection strategy for continuous corrosion inhibitors has

evolved over more than ten years. A shortlist of products is
narrowed down through a series of solubility tests, static and
dynamic corrosion tests, and water/oil partitioning runs.

❍ The main purpose of a partitioning test is to estimate the

inhibitor dose rate required on total fluids. For example, a
product may show good efficiency at 25 ppm in water-only
tests, but 60 ppm may be needed in a water/oil mixture in order
to reach the same efficiency.

❍ Due to the many components in proprietary corrosion inhibitor

packages and also measurement artefacts, partitioning should
be regarded as 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 dose rate determined in the lab should be introduced in the

field and then gradually reduced or increased to an optimum
value using field monitoring. However, cutting the operational
dose rate is sometimes regarded as a soft target for cost savings.
It should be done carefully in order to avoid undesirable
repercussions.

❍ Field corrosion monitoring must be effective and reliable before

an operator can confidently justify a reduction in dose rate,
especially by a large amount.

❍ It is essential to check the compatibility of a corrosion inhibitor

with every material, lining, seal, and oilfield chemical with
which it is likely to come in contact. Incompatibilities of any
sort can cause serious operational problems.

❍ Environmental concerns are increasingly likely to influence the

selection of all types of oilfield chemicals. To date there has
been some evolution towards environmentally friendly corrosion
inhibitors but not yet any definite legislation to enforce it or
recommendations to guide it.

47
Deployment

Oil Company/Chemical Company Alliances

Oil company/chemical company alliances are starting up around the

world as a new way of organising the selection and deployment of
oilfield chemicals. The details of each arrangement vary enormously
from a virtual sub-contracting of all aspects of chemical usage to
simply a closer working relationship. All the alliance partners to
whom we spoke stressed the careful planning necessary to define
specific targets and roles. It is not yet clear if this alignment of
operators with one particular supplier is just a fashion or is a long
term trend. The arrangements themselves are really still on trial.

The points below summarise industry arguments we noted for and

against the general concept of alliances, with particular regard to
corrosion inhibitor deployment. Firstly, the main arguments in favour,

❍ more streamlined logistics - some suppliers regard the

traditional relationship with operators as like a “one way
mirror”, handing over samples and information and receiving
little or no feedback. In an alliance the two can work together
towards a common performance target, “rowing the boat
together”, and bringing more resources to bear on a problem.

❍ cost savings - Instead of the operator buying just a corrosion

inhibitor from a supplier they buy an “agreed corrosion rate”
and both sides can share the cost benefit arising from a possible
reduction in dosage levels. There might also be scope to share
R&D spending.

One operator emphasised that alliances were a new way of thinking

and working, and that “fear” was preventing some companies
pursuing the idea. They further stressed that in order to be effective
the concept had to be grasped company-wide and should not simply
be adopted piecemeal by individual operating units.

Here are the main arguments against,

❍ operator bears all risk - Although the supplier may be closely

involved in day-to-day deployment of corrosion inhibitor it is
the operator who bears all the risk for liability and replacement
costs in the event of a failure. Because of this, some say that
the operator should take direct responsibility for inhibitor

49
DEPLOYMENT

deployment and not work through a contractor. The opposing

view is that the operator will always be supervising the
performance targets and the supplier is motivated by the risk of
losing a contract.

❍ supplier no longer competing - Once in an alliance a

supplier is no longer actively competing with other companies
for business with the particular operator. There is a chance that
complacency may creep in. After a few years it may become
very difficult to change suppliers, if the need arises, because by
then they will have become well integrated into operations and
also hold a lot of important expertise and experience.

❍ other suppliers stop co-operating - The alliance supplier

would prefer to use all its own products wherever possible but
it can not always match the performance of the incumbent
chemicals, so it may need to retain some of these. One
problem so far has been that the alliance supplier sometimes
has problems purchasing a product from another supplier either
because of technical or commercial confidentiality or just plain
envy. One solution is for the oil company to purchase from the
other supplier. Oilfield chemical alliances are in their infancy
and the industry is still developing appropriate working
practises.

❍ lose small suppliers - If alliances become the norm there is a

danger that only the large suppliers will survive. The smaller
companies, perhaps specialising in niche products, may not be
able to compete. If they disappear there may be less innovation
and certainly less choice.

❍ operator dictates supplier profits - Some suppliers speculate

whether alliances are really a way for operators to cynically
squeeze prices by demanding a detailed knowledge of supplier
costs using “open book” policies.

This section is only a summary of the main industry views. It does

not seek to make an overall judgement about alliances. However, it is
worth remembering that alliance or contracting relationships already
exist in many important oilfield areas such as fabrication, drilling,
supply etc It is no surprise that such arrangements are being
introduced more widely given the reorganisations and the focus on
performance which have taken place in most oil companies over the
last few years.

50
 DEPLOYMENT

Quality Control of Corrosion Inhibitor Supplies

The majority of manufacturers of production chemicals apply strict

QA/QC at all stages of processing, from receipt of raw materials to
supply offshore. There is, therefore, an auditable quality trail
throughout manufacture and supply. The use of the various quality
standards such as BS 5750 and ISO 9000, although burdening in terms
of paper work, ensure best practise and assure product quality (Box
12). Chemical manufacturers will provide a certificate of analysis
(COE) if requested. Many methods are used for QC during
manufacture and for final product analysis. Techniques employed
may range from colour and amine number determination through to
more sophisticated chemical analysis techniques such as HPLC, GPC,
FTIR, ICP, MS, and NMR (see Box 13). Essentially the customers can
have whatever QC and documentation they require.

Box 12: ISO Quality Standards

Customer expectations drive the basic requirements for the quality of any product or service.
Moreover, continual improvements in quality are usually needed to improve or even sustain good
economic performance. In this respect, the organisational system which produces a product or
service is as important as the technical specification to which it is produced. In order to manage
this aspect of quality, an extensive set of international quality system standards is now available and
widely used.

The series of ISO standards - 9000 through 9004 - bring together and rationalise many of the
individual national approaches to quality. ISO 9000 is a general overview and ISO 9001 - 9004 refer
to specific aspects of providing a product or service to a customer. For example, ISO 9001 covers
design/development and manufacturing while ISO 9002 covers production and installation. Quality
systems essentially complement the requirements laid out in technical specifications, and provide the
supplier and customer with an auditable trail of documented quality measures and checks. Most
oilfield chemical suppliers are now accredited to ISO 9000 or equivalent.

Box 13: Some Acronyms

QA .... quality assurance
QC ... quality control
HPLC ... high pressure liquid chromatography
GPC ... gel permeation chromatography
FTIR ... Fourier transform infra-red spectroscopy
ICP ... inductively coupled plasma emission spectroscopy
MS ... mass spectroscopy
NMR ... nuclear magnetic resonance spectroscopy
ISO ... International Standards Organisation

51
DEPLOYMENT

The approach of operators to quality is rather more variable. In terms

of frequency and complexity of independent analysis, it often
depends on previous experience, with major past problems often
leading to major current effort in QA. Several operators rely solely on
quality standard accreditation of pre-qualified and audited service
companies. The degree to which regular auditing occurs after this
qualification is very variable. By contrast, other operators insist on
analysing samples taken from every tanker, pod or drum which they
receive, and several companies have developed complex analytical
routines for the QA of chemical supplies. The tendency to use this
extreme approach is lessening, however, due to the increased
influence and success of quality standards and the reasonable view
that supplier partners merit some trust. Several operators adopt a
compromise between these extremes by making brief checks on
occasional random samples.

The QA/QC of chemical supplies essentially guarantees chemical

composition but says little about chemical performance. A sensible
approach is, therefore, to closely monitor the field performance of
chemicals and to trace back along the quality audit trail if there are
any performance problems or doubts which require further
investigation. In the case of corrosion inhibitors, a performance test
on every batch using a laboratory bubble test (Figure 6(b)) is a simple
and useful precautionary measure which can easily be carried out by
suppliers. Not many do this at the moment.

Corrosion Inhibitor Pumping Problems

Operators and suppliers have encountered many problems simply

trying to pump corrosion inhibitor into a system. A number of these
are obvious in hindsight. Suppliers commented that when they are
called onto a site to examine a corrosion problem the first question
they ask is, “...is the corrosion inhibitor going in?”. Frequently it is
not. Good procedures and training are required to ensure that the
inhibitor is effectively delivered to where it is needed.

The following list divides the various pumping problems between

those relating to the inhibitor and those relating to the pump. Firstly,
those relating to the corrosion inhibitor,

❍ inhibitor viscosity - The viscosity of any chemical will rise

when it is cooled in sub-sea umbilicals, or when it is used in

52
 DEPLOYMENT

cold climates. Viscosity measurements should be carried out at

temperatures appropriate to how and where the inhibitor is to
be used.

❍ compatibility of inhibitor with pump materials - The

compatibility of neat inhibitor with metals has already been
covered in detail (p.41). The inhibitor must also be compatible
with the pump seals (Box 10, p.42).

❍ line blockages - Due to poor cleaning when chemicals are

changed over.

❍ inhibitor storage tank empty - The storage tank must be

regularly checked to ensure timely reordering of inhibitor
supplies. One should avoid getting into a situation where the
dose rate must be halved in order to conserve stocks until the
next supply arrives.

❍ 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.

Secondly, here are problems relating to the pump and other

hardware,

❍ wrong dose rate - This can happen if the pump is not

calibrated, or is improperly controlled. If certain valves are
closed then the dose rate may be zero. Errors are also possible
when using tank level readings or calibration cylinders at the
pump suction in order to calculate the dose rate.

❍ pump wrongly sized - This can make it difficult to dose at the

recommended rate. It may be necessary to reformulate the
corrosion inhibitor - either diluting or concentrating the active
components - in order to accommodate the available pumping
capacity. Incorrect sizing may be a particular problem when the
dose rate has to be changed frequently to match variations in
process conditions (e.g. changing water cut).

❍ air locks - Certain types of pump appear to be prone to air

locks.

❍ poor delivery system design/installation - One pump may be

delivering into several lines or wellheads all at different pressures.

53
DEPLOYMENT

The high pressure lines may not receive any inhibitor. Such
manifolded delivery systems are more difficult to check than
dedicated pumps unless special “Sko-Flo” valves are used. These
maintain a constant flow rate despite varying differential pressure.
In another example an operator described how the inhibitor
delivery line was inadvertently routed into the platform drain
rather than the process, an extr eme example of poor installation.

❍ dosing downhole - Injection can be particularly troublesome

downhole (see p.23). Injection via the lift gas may lead to
gunking as the solvents evaporate, and chemical injection valves
operating on annulus pressure may actually dose batch-wise
rather than continuously.

In summary, it is clear that many pump problems are avoidable if the

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

Injecting Inhibitor Into The Process Stream

Injection Location The industry rule of thumb is to inject the corrosion inhibitor as far
upstream as possible. This will enable the inhibitor to reach all
vulnerable areas. In practise, downhole injection is difficult and prone
to problems (see p.23). Therefore, the inhibitor can be added at the
wellhead. However, it is more appropriate to inject immediately
downstream of the final stage oil/water separator if the separation
process might be upset by corrosion inhibitor, if large amounts of
corrosion inhibitor are likely to be lost with the separator water, and if
the corrosion inhibitor is primarily intended to protect an export pipeline
rather than the processing equipment.

Many operators do not use corrosion inhibitor to protect process

equipment. This is either because corrosion resistant alloys are
prevalent or because uninhibited carbon steel sections are regularly
checked and replaced when necessary. Furthermore, it can be difficult
to deliver inhibitor effectively into stagnant bypass or drain line piping.
Inhibitor might only be added upstream of an area which prediction or
experience has shown to be at high risk, e.g. high velocity bends, tees.

All of this discussion describes the optimum situation, which is reliant

on good corrosion engineering design. Many production sites have to

54
 DEPLOYMENT

make do with the injection points that are in place and which may not
be ideal. Retrofitting a new injection point might be necessary if a
particular corrosion problem gets out of control.

Mixing Inhibitor into Whatever injection points are used it is important that the inhibitor is
the Process Stream well mixed into the liquid or gas stream. This is achieved by injecting
just upstream of a turbulent region (e.g. bend, valve, pump) or directly
into a turbulent process stream. The mixing length will be a function
of the process conditions (e.g. Reynolds number, pipe diameter etc) but
for true turbulent flow is likely to be less than ten pipe diameters (this
mixing length is actually CRA construction in a few installations). In
contrast, the inhibitor may never thoroughly mix in laminar flow. An
atomising injection quill or creation of turbulence using a valve may be
required in this case. Details of the types of injection tube available,
and the optimum position of the tube in the pipe are given in Box 14.
Details on whether the inhibitor should be used as-received or diluted
in a solvent are given in Box 15.

Box 14: Injection Tubes for Pipelines

It is important to use correctly positioned injection Flow Flow

tubes in order to disperse the corrosion inhibitor
and also to prevent the neat product contacting
the pipewall (see Figure 11) because some neat
corrosion inhibitors can corrode the pipewall (see
p.41). The injection tube itself must also be
resistant to the neat inhibitor. Tubes with
diagonally slanted tips, i.e. quills, are widely used
[23]. Typically, the quill tip should have a 45°
Corrosion
spray and be located midstream, facing back into CORRECT SHORT Site
the direction of flow. However, one operator said
they “had looked at all sorts of configurations and
it made no difference”. Figure 11: Injection Quills

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

Atomising quills can be used to achieve good dispersion in gas systems or laminar liquid systems.
The higher the differential pressure across the tip then the smaller the dispersed droplets. Typical
quills for liquid and gas streams have a quarter inch internal diameter. However, in some gas
systems where the inhibitor is diluted into a large volume of methanol or glycol (i.e. hydrate
inhibitor) before injection then a larger delivery tube is necessary and the injection point becomes
more like a “tee”.

55
DEPLOYMENT

Box 15: Dilution of Corrosion Inhibitor in the Field

• Oil pipelines are normally dosed with as-received corrosion inhibitors.

• Gas lines employ inhibitor diluted in methanol, or some other alcohol based hydrate
inhibitor/suppressant. Concentrations typically range from 0.5% up to 5 or 10% in methanol
when hydrate treatment is required. It should be remembered that many corrosion inhibitors
are only marginally soluble in methanol at low temperature. Dry gas lines, where the
product is dewpoint adjusted and TEG dried, will not normally be inhibited.

• Downhole injection typically employs 1% - 20% corrosion inhibitor diluted in crude oil or
diesel. The dilution reduces the total amount of corrosion inhibitor which is stored in the
annulus.

• Batch chemicals are diluted in a locally available solvent, as large volumes are needed. The
diluent will typically be crude oil, condensate, diesel or deaerated seawater, with 1:4 v/v
inhibitor/diluent between pigs for pipelines.

• Whenever inhibitors are employed in diluted form there must be adequate control over the
quality of the diluent used and proper supervision of the dilution process.

• More generally, inhibitors may also be concentrated for international business to save on
transportation costs or to introduce local labour and materials into a product.

Corrosion Monitoring

After choosing carbon steel and corrosion inhibitor for a process

system, selecting the inhibitor, and finally deploying it, the crucial
question is, “does it work?”. Corrosion monitoring should be able to
provide the answer. Monitoring is such an important area that it is
covered in detail by a companion set of guidelines [1]. As with other
aspects of corrosion control, care and attention to detail are required
in order to obtain meaningful results.

Dealing with Process Changes

Managing Corrosion It is essential to actively manage corrosion inhibition. Once an

inhibitor is selected and deployed an operator shouldn’t just forget
about it and think that “no news is good news”. This policy, or really
lack of policy, has led to significant problems in the past.
Furthermore, the responsibilities of everyone involved in corrosion

56
 DEPLOYMENT

control must be well defined in order to manage effectively.

Organisations where “everyone has a dabble” are likely to have
problems such as the case of a Middle Eastern operator who had to
put a lock on the corrosion inhibitor delivery pump to prevent
unauthorised changes in the dose rate. When there is no strategy or
a badly defined strategy then the response to a corrosion problem is
likely to be slow at best and non-existent at worst. Several operators
quoted a slow initial response as the primary cause of some of their
most serious corrosion problems. Therefore, a well thought out
corrosion management strategy (CMS) which includes clearly defined
roles and responsibilities is recommended for all BPX sites in order to
assign the day-to-day responsibilities for confirming effective
performance, and to specifying responses to the common process
changes.

Monitoring Process Certain types of corrosion monitoring (e.g. weight loss coupons) only
Changes 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 quickly 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 (e.g. flow rate, water cut, temperature
etc) and be ready to alter the corrosion inhibition conditions
appropriately. In BPX Alaska the production rates, pCO2 and quantity
of sand in multiphase flow lines are put into a flow model to
calculate the optimum corrosion inhibitor dose rate and the necessary
inspection frequency. These process data can later be correlated with
corrosion monitoring information in order to check whether corrosion
was adequately controlled.

Inhibitor Dose Rate Corrosion inhibitor dose rate is clearly a crucial parameter (see p.41)
and should be checked daily. This apparently simple task is
nevertheless prone to error. One operator described a case where its
staff were reading the pump sight glasses incorrectly and so were
putting in a much lower dose rate than planned. Sometimes it is the
supply company who first notices this type of mistake because they
eventually see that the quantity of inhibitor ordered over a certain
period is not consistent with the stated dose rate. Figure 12 shows an
actual field record from a site where the target inhibitor concentration
of 50 ppm was rarely achieved over a 18 month period.

57
DEPLOYMENT

Figure 12 : Corrosion Inhibitor

Dose Record 100

80

60
Target = 50ppm

40

20

0
January March May July September November January March May
1993 1993 1993 1993 1993 1993 1994 1994 1994

Table 4 (p.60) lists the main process parameters which affect

corrosion and which should be measured and acted on whenever
they change. Corrosion inhibitor type and concentration are the two
controlling variables accessible to an operator. The inhibitor delivery
rate is usually matched to the maximum throughput in the process
(No.1, Table 4) so as to give the desired concentration on total fluids.
If the throughput goes down for a day or so then the inhibitor
delivery may not be adjusted and the prevailing concentration will
therefore rise. However, if the throughput goes up then the inhibitor
delivery rate must also go up to compensate. It may even be
necessary to reselect the inhibitor if it can not cope with a
substantially higher wall shear stress.

Water Cut Water cut is a key parameter (No.2, Table 4). It affects how the
inhibitor partitions between oil and water phases. This is described in
detail on p.36. The response to a water cut change depends on
whether the inhibitor is preferentially oil or water soluble. When the
water cut increases then the concentration on total fluids of a
preferentially water soluble inhibitor must also increase in order to
maintain the same concentration in the water phase (Figure 9).
Another way of saying this is that the concentration with respect to
the water phase must remain constant.

These implications of partitioning are widely understood amongst

suppliers and operators. Most operators have a policy for changing
the inhibitor concentration on total fluids depending on the water cut
(e.g. 10 ppm for <5% water, 20 ppm for 5-10% water, 30 ppm for
>10% water). Ideally this link could be automated but this would only
be feasible if the water cut was continuously monitored. Most
operators only measure it a couple of times per day. This of course

58
 DEPLOYMENT

means that changing water cuts may pass through the system without
corrosion inhibitor adjustment until the next water cut measurement is
made. More frequent water measurements are advisable if water
slugging is prevalent. Sometimes periods of high water cut are entirely
predictable such as when an export line is used as a drain because of
problems with produced water treatment plant. The corrosion
inhibitor concentration on total fluids should be adjusted accordingly.

Regular pigging of pipelines to remove the water accumulated in low

spots will help to minimise corrosion. This is because even if the
water starts off as fully inhibited it is possible for the inhibitor to
gradually degrade in a stagnant pool and to become ineffective. For
pipelines with very low water cuts (eg < ca 0.05%) an elastomer cup
type pig applied once a month is likely to be sufficient. Higher water
cuts will require more frequent pigging, perhaps as often as once
every few days.

Removal of the stagnant water by pigging will also help to reduce

microbiological activity in the pipeline. It will minimise the chances
of corrosive colonies becoming established on the pipewall and
causing microbiologically induced corrosion (MIC). Some operators
take the extra precaution of batch dosing with a biocide every month.
In BP, however, most operators have tended to rely on regular
pigging and also the biostatic action of certain continuous corrosion
inhibitors in order to minimise any MIC.

Aqueous pH The liquid pH (No.6, Table 4) is difficult to measure on-line and is

sometimes calculated from the brine composition and pCO2 instead.
When sea water breakthrough occurs in a reservoir the overall salinity
and buffering capacity (i.e. [NaHCO3]) of the produced water will
change possibly for the worse. One operator described how sea
water breakthrough caused the pH to decrease and the corrosion rate
to rise from 0.5 to 6.0 mm/year.

Free Oxygen Free oxygen is not normally encountered in oil and gas production
streams (No.5, Table 4). Any oxygen originally present in the
reservoir will have been consumed in oxidation reactions with the
hydrocarbons during the millions of years of storage at high
temperature and pressure. However, free oxygen can enter the
production process inadvertently and then cause corrosion problems
because the corrosion inhibitors selected for CO2 and H2S
environments may not be effective against O2 corrosion. It may be
necessary to reselect or augment the original inhibitor. A case where
aerated sump oil was injected back into the process train is one
example of oxygen ingress.

59
DEPLOYMENT

TABLE 4: Some Process Parameters Which Can Affect Corrosion

Rate

Parameter Change Action

1. Flow rates + or - Alter CI delivery rate to maintain

(oil/water/gas) concentration in water

2. Water cut + or - May increase or decrease CI delivery

depending on its o/w partitioning
properters

3. Temperature + Increase [CI]

- Scope to reduce [CI]

4. pCO2 and pH 2 S + Increase [CI]

in gas - Scope to reduce [CI]

5. pO2 in gas + May need to reselect CI

6. pH + Scope to reduce [CI]

- Increase [CI], may need to reselect

7. Sand + Reselect CI and/or increase [CI],

reduce velocity, install downhole
sand screen

Notes: + ...increase
- ...decrease
pCO2 ...partial pressure of CO2

Dealing with Process Interruptions

This is not intended to be an exhaustive list of interruptions. There

are likely to be other possibilities. Industry views on interruptions
and changes varied from “not that frequent” to “probably happens
more often than you think and normally goes unnoticed”. After any
severe interruption or upset it may be necessary to apply a batch
treatment before resuming continuous inhibitor injection.

Shutdowns When shutting down a process line it is wise to shut-off the corrosion
inhibitor delivery at the same time. Otherwise, neat inhibitor will be
injected into a region of static fluid and quickly build up the

60
 DEPLOYMENT

concentration to possibly corrosive levels. If a shut-in line is

subsequently filled with water for inspection purposes then this water
must be fully deaerated and inhibited. Care is also necessary when
restarting the line because, in some facilities, the pipelines must be
restarted before the water treating equipment. This means that high
water cuts can go down the pipe until the water treatment begins.
Extra corrosion inhibitor may be needed.

Acid and Scale Acid stimulation of producing reservoirs and acid descaling of
Squeeze Returns production tubing have gained notorious reputations for causing
corrosion problems, though in some cases they may simply be
convenient scapegoats for shortcomings elsewhere. The BPX Forties
asset has developed a neutralisation procedure for acid returns using
caustic soda solution (NaOH) which will substantially reduce the brine
corrosivity should any of it enter the production stream. Initial fluid
returns from scale squeezes may also be slightly acidic because many
scale inhibitors are derivatives of weak phosphorus based acids.
However, the real problem with scale squeeze returns is that they
may be incompatible with the corrosion inhibitor. Compatibility
should be checked before deployment.

Responsibilities

With the advent of the various types of alliance there is now a wide
range of organisational structures for selecting and deploying
corrosion inhibitors in oil and gas fields. Whatever approach is
chosen it is important to define responsibilities as closely as possible
through a Corrosion Management Strategy (CMS) or an Alliance
Agreement. Many corrosion problems occur through complacency
which often arises because the consequences of action, or inaction,
may not be apparent for several years. It may be a cliché but it’s
nevertheless true that effective corrosion control requires genuine
commitment to the management strategy by all parties. This includes
operational staff who are in control of many routine but nonetheless
critical aspects of inhibitor deployment. Some awareness training may
be necessary to ensure that these personnel view inhibitor issues with
enough priority and interest. This will be helped by simple measures
such as making staff aware of the results of sampling and
measurements they have taken, and thereby showing how their
actions (care or lack of care) can influence important decisions.
Overall, the CMS should describe how process, dosing, monitoring
and inspection data are brought together and analysed. Complete
and continuous records are necessary to enable this.

61
DEPLOYMENT

Sharing information and learning from mistakes and near misses is

also important. Networks can work well within operating companies,
e.g. between production chemists, corrosion engineers etc. However,
industry cutbacks now mean that fewer people have the time to
organise them. Real effort is needed to ensure that individual assets
can learn from each other’s mistakes and experiences. On an
industry wide level there is no specific, formal mechanism for sharing
corrosion inhibitor experience. Successful applications may be
discussed at relevant conferences and meetings, but the open
discussion of problems and failures is generally more problematic.
Despite the fact that time and money can be saved via dialogue, there
is often only frank exchange of views and experience if there is a
common short term interest.

KEYPOINTS : Deployment

❍ Alliances or contracting relationships already exist in many

important oilfield areas so it is no surprise that such
arrangements are now being introduced more widely for the
selection and deployment of oilfield chemicals. There are
potential advantages and disadvantages in this trend.

❍ Only those suppliers meeting a recognised quality standard such

as ISO9000 should be used. A simple performance test on every
batch of corrosion inhibitor is a useful precaution easily
accommodated by suppliers.

❍ Pump problems can be due to both poor design and poor

operation. Many of the operational problems (e.g. bad
calibration, inhibitor supply exhausted) can be avoided through
good procedures and training.

❍ The corrosion inhibitor should be injected as far upstream as

possible. This often means at the wellhead in order to protect
process equipment already known or predicted to give a
corrosion problem (possibly certain bends or tees).

❍ Injection immediately downstream of the final stage oil/water

separator is appropriate if the separation process might be upset
by corrosion inhibitor, if large amounts of corrosion inhibitor are
likely to be lost with the separated water, and if the corrosion
inhibitor is primarily intended to protect an export pipeline
rather than the processing equipment.

62
 DEPLOYMENT

❍ The inhibitor must be added just upstream of a turbulent region

(e.g. bend, valve, pump) or directly into a turbulent process
stream to ensure good mixing.

❍ Typically the injection quill should be positioned midstream,

facing against the flow (unless pigging requirements prevent it).
Direct injection into any water phase is needed for laminar or
stratified flow conditions.

❍ Corrosion inhibitor is often diluted in solvent for use in gas

lines, downhole injection, and batch treatment. There must be
adequate control over both the diluent and the dilution process.

❍ Field corrosion monitoring is covered in detail in a companion

document.

❍ An immediate response to certain key process changes will

reduce the corrosion risk. The inhibitor type and dose rate
should be continuously matched to the process throughput,
water cut, CO 2 level, O 2 level, H 2S level, pH and sand
production.

❍ Process interruptions like shutdowns and acid returns require

their own special set of precautions to prevent corrosion
damage.

❍ It is essential to actively manage corrosion using a Corrosion

Management Strategy with all parties having clearly understood
accountabilities.

❍ Sharing information about corrosion experiences and near

misses, both within BP and externally, often repays the effort
required.

63
References

1. S Webster, R Woollam, “Corrosion Monitoring Manual”, Sunbury

Report No. ESR.95.ER.053.

2. M B Kermani, T Pendlington, G Elliot, G Weighill, “Operational

Experience of Using 13%Cr Tubular Steels”, NACE CORROSION
95, 1995, paper no. 95096

3. L M Smith, M Celant, “Clad Pipes for the Oil and Gas Industry:
Market Analysis and Technical Trends”, Intech Ltd (Chester) and
Materials and Corrosion Ltd (Milan), report no. MI-33.94, January
1994

4(a) I D Parker, J Pattinson, A S Green, “A Corrosion Philosophy for

the Transport of Well Oil and Multiphase Fluids Containing
CO2”, Sunbury Report No. ESR.93.ER.013, dated March 1993.

4(b) I D Parker, J Pattinson, A S Green, D B L Walker, D Ray, T Hill,

“A Corrosion Philosophy for the Transport of Wet Hydrocarbon
Gas Containing CO 2”, Sunbury Report No ESR.94.ER.016, dated
28/8/94

4(c) J W Martin, “Guidelines for Selecting Downhole Materials With

Particular Reference to Sour Conditions”, Sunbury Report No.
ESR.94.ER.043, dated 25/4/94

4(d) J Pattinson, “Erosion Guidelines: Guidelines on Allowable

Velocities for Avoiding Erosion and on the Assessment of
Erosion Risk in Oil and Gas Production Systems”, Sunbury
Report No. ESR94ER070, dated July 1994

4(e) M B Kermani, D Harrop, M L R Truchon, J L Crolet, “Limits of

Sour Service for tubular Steels”, NACE CORROSION 91, 1991,
paper no. 21

4(f) M B Kermani, “Eastern Trough Area (ETAP): Guidelines on the

Corrosion Inhibitor Efficiency for the Design of Multiphase
Infield Flowlines”, Sunbury Report No. ESR94ER085, Dated
9/9/94

5(a) R J Franco, “Materials Selection for Produced Water Injection

Piping”, Materials Performance, vol.51, January 1995, p.47

65
REFERENCES

5(b) M Wainwright, “The Use of Internal Liners for Corrosion

Protection and Pipeline Rehabilitation”, BP Engineering
Technical Briefing Note, No. PCAG 8, January 1991

6. L M Smith, M Celant, A Taylor, “What is the Real Cost of Carbon

Steel in Comparison with Corrosion Resistant Alloys”, Corrosion
Management (Inst. Corr.), Oct/Nov 1994, p.8

7(a) C de Waard, U Lotz, D E Milliams, “Predictive Model for CO2

Corrosion Engineering in Wet Natural Gas Pipelines”, Corrosion,
47 (1991) 976.

7(b) C de Waard, U Lotz, A Dugstad, “The Influence of Liquid Flow

Velocity on CO 2 Corrosion: A Semi-Empirical Model”, NACE
CORROSION 95, 1995, paper no. 95128

8. Standards Group/ESS/BP Sunbury, “Corrosion Monitoring”, No.

RP 6-1, dated October 1992

9. C J Houghton, R V Westermark, “Downhole Corrosion Mitigation

in Ekofisk (North Sea) Field”, Materials Performance, vol.22,
January 1983, pp16 - 22

10. H J Endean, “Oilfield Corrosion Detection and Control

Handbook”, Champion Technologies Inc., Houston, Texas, 1989,
p.24

11. A J McMahon, “The Mechanism of Action of Oleic Imidazoline

as an Oilfield Corrosion Inhibitor”, Colloids and Surfaces, 59
(1991) 187

12. S Webster, “BP Corrosion Inhibitor Selection Protocols”, BP

Sunbury Manual, issued 3/4/94 by MIE/ESS

13. D Harrop, “Predicting CO 2 Corrosion Associated with Oil and

Gas Production and Transportation”, Sunbury Report No 124
234, dated 22/10/91

14. J G Knudsen, D L Katz, “Fluid Dynamics and Heat Transfer”,

McGraw-Hill, New York 1958

15. S Webster, D M E Paisley, T Moros, D Harrop, “Flow Related

Corrosion: An Experimental Comparison of the Rotating Cylinder

66
 REFERENCES

Electrode and Full Pipe Flow for the Evaluation of Flow Induced
Corrosion”, Sunbury Report No ESS.93.ER.156, dated 4/11/93

16. L W Jones, “Corrosion and Water Technology for Petroleum

Producers”, OGCI Publications, Tulsa, 1988, p.15

17. J A Dougherty, B A Alink, D F Ho Chung Qui, K van Gelder,

“Corrosion Inhibition in Supersour Gas Production”, Materials
Performance, vol.51, January 1995, p.41

18. D M E Paisley, “A Study into the Partitioning Characteristics of

TROS C787C for the Forties Pipeline System”, Sunbury Report
No ESR95ER003, dated 4/1/95

19. J Gutzeit, “Corrosion Inhibitor Can Cause Corrosion”, Materials

Performance, July 1993, p.64

20. S Groves, “Elastomer Selection Guidelines”, Sunbury Report No

ESR 93ER151, dated 16/12/93

21(a) J A Haselgrave, W M Hedges, H T R Montgomerie, T M O’Brien,

“The Development of Corrosion Inhibitors with Low-
Environmental Toxicity”, 67th SPE Annual Conference,
Washington DC, October 4 - 7 1992, paper no. SPE 24846

21(b) B A M Oude-Alink, T G Braga, R L Martin, J A McMahon, R

Weare, “Environmentally Friendly Corrosion Inhibitors”, 6th
Middle East Corrosion Conference, Bahrain, January 24 - 26,
1994

22. A J McMahon, D. Harrop, “Green Corrosion Inhibitors: An Oil

Company Perspective”, NACE CORROSION 95, 1995, paper
number 95032

23. M Wainwright, “Corrosion Inhibitor Injection Methods and

Factors Affecting Efficiency”, BP Engineering Technical Briefing
Note, No PCAG5, dated February 1991

67
Index

A
acid 61
alliances 49 - 50

B
biocide 18 - 19, 59
BS 5750 51

C
carbon steel 13 - 14
cladding 12
coatings
epoxy 16 - 17
general 13 - 14
corrosion
design 15 - 16
effect of process variables 60
management 56, 61 - 62
microbiologically induced. . 59
monitoring 15, 56, 57
prediction 15
corrosion inhibitor
batch treatment 23 - 26
compatibility 33, 41 - 44
composition 28, 44
continuous treatment 24 -27
dilution 56
field dose rate 40, 57 - 58
injection 16, 43, 54 - 56
mechanism 24
metal surface area and.. 16
mixing 55
partitioning in oil and water 36 - 40
residual analysis 39
selection 25 - 46
solubility 33
squeeze treatment 23
vapour phase inhibitors 18
viscosity 52
when to start injecting 19 - 20

69
INDEX

corrosion inhibitor tests

batch treatment 25 - 26
conditions in.. 30 - 33
continuous treatment 25 - 46
H2 S and.. 32
limitations 27
list of.. 29, 34
corrosion resistant alloy (CRA) 11 - 13

E
environmental issues 19, 44 - 46

G
gas buffering 14
gas pipelines 14

H
hydrostatic testing 17 - 20

Iinterruptions 60 - 61
ISO 9000 51

N
non-metallic materials 12

O
oxygen 18, 19, 59, 61
oxygen scavenger 18

P
pigging 14, 59
pitting corrosion 13
pumps
problems 52 - 54
seals 42

Q
quality control 51 - 52
quills 55

70
 INDEX

Sscale squeeze 61
shared pipelines 43
stress corrosion cracking (SCC) 13

T
13% Cr steel 11

W
wall shear stress 30, 32
water cut 58 - 59
welds 13, 16, 30
whole life costing 13

71