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Casing Materials

Selection &
Corrosion
Guidelines
J W Martin

BP Amoco report no. BPA-D-003


dated September 1999

Main CD
Contents
BP Amoco
Casing Design Manual BPA-D-003

Page

15.1 Scope 15-1

15.2 Material Selection Process 15-2


15.2.1 Casing Exposed to Muds and Brines 15-2
15.2.2 Sour-service Exposed to Produced Fluids 15-3

15.3 Corrosion Control 15-9


15.3.1 Exploration/Appraisal Wellls 15-10
15.3.2 Development Wells 15-11

15.4 External Corrosion 15-14

15.5 Flowchart for Corrosion Control Measures 15-14

Figure

15.1 Material Selection for Casing 15-3


15.2 Sour Gas Systems 15-4
15.3 Sour Multiphase Systems 15-4
15.4 Sulphide Stress Cracking Performance Domain
of Grade P110 Carbon Steel 15-9
15.5 Sulphide Stress Cracking Performance Domain
of Grade N80 Carbon Steel 15-9
15.6 Major Corrosion Control Measures for Casing 15-15

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Section C15 Material Selection and Corrosion Guidelines 15-17
BP Amoco
Casing Design Manual BPA-D-003

15.1 Two types of service need to be considered when selecting materials for
casing strings:
Scope
• Casing strings that will normally only be exposed to completion brines/
drilling muds

Materials selection for such strings is covered in Sections 15.1.1 and


15.1.2.

• Casing strings that will/may be exposed to production/injection fluids


for a significant part of their life (eg liners, some dual completion wells)

Materials selection for such items is a complex issue, with many


parameters that need to be taken into account. In addition, materials
for such components change frequently as new corrosion-resistant
options come onto the market. For these reasons the selection of
materials for such casing strings and for tubular strings are covered in
a stand-alone document entitled ‘Guidelines for Selecting Downhole
Tubular Materials for Oil and Gas Wells’.

This section contains two flow diagrams designed to assist the user in the
selection of casing materials and corrosion control requirements
respectively. These flow diagrams are not intended as exhaustive
‘stand-alone’ documents. Rather, the intention is to ‘flag’ the major
considerations that need to be taken into account when selecting
materials and/or corrosion control methods. With the very complex
issues that are involved, it is not possible to be certain that nothing has
been omitted from these flow diagrams. Therefore it is incumbent upon
the users of the flow diagrams to ensure that all necessary aspects have
been addressed before making the final selection.

In the flow diagrams, decision points at which it will be necessary to


consult the relevant specialist(s) have been highlighted. If you are unsure
who the relevant specialist is, advice on contacts should be available
from one of the Materials/Corrosion Engineers within UTG, BP Amoco.

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Section C15 Material Selection and Corrosion Guidelines 15-1
BP Amoco
BPA-D-003 Casing Design Manual

15.2
Materials Selection
Process

15.2.1 For such duties, casing materials are normally carbon or low-alloy steels.
Casing Exposed to There is a wide range of strength grades available for these steels, as
Muds and Brines indicated in API 5CT/ISO11960. In addition, there are a number of
proprietary grades not contained within the API/ISO Standards, eg 110ksi
‘sour-resistant’ grades. Usually, final selection of the strength required will
be based upon the mechanical requirements of the casing design.

Corrosion resistance is not usually a critical issue in the selection of


materials for casing strings which are normally only exposed to completion
brines or drilling muds. However, there is one significant exception to this
rule and that is the temporary exposure of the casing string to hydrogen
sulphide, ie sour conditions. The reason for this is that sulphide stress
corrosion (SSC) cracking, which can result from exposure to sour
conditions, can occur very rapidly. In addition, SSC can result in a
catastrophic failure, with the material acting in an apparently brittle
manner. If sour conditions are anticipated, the use of an SSC-resistant
casing is often required. Guidelines for materials selection in the case of
sour conditions are discussed in Section 15.1.2.

It is becoming more common within BP Amoco to specify L80 in preference


to N80 when available. The L80 grade meets the requirements of NACE
MR-0175 and is normally no more expensive nor more difficult to source
than N80.

The use of API controlled hardness grades for sour-service can lead to
extremely thick wall designs for high-pressure wells which require
sour-service casing. As an alternative, the proprietary high strength
(eg 110ksi) grades of sour-service casing can be considered. Testing within
BP Amoco has indicated that these proprietary high-strength sour-service
steel grades cannot be considered fully sour-resistant. However, they are
acceptable for slightly sour conditions (refer to Section 15.1.2 for further
details). A BP Amoco specification for the supply of 110ksi grade
sour-resistant casing is also available.

The flowchart in Figure 15.1 can be used when selecting casing materials
that will be exposed to drilling muds and/or completion brines.

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15-2 Material Selection and Corrosion Guidelines Section C15
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Casing Design Manual BPA-D-003

FIGURE 15.1
MATERIAL SELECTION
FOR CASING

Known data:
• Pipe size
As defined by NACE MR-0175-91 • Material strength required
(See Section 15.1.2) • Connection type

YS - Specified Minimum Yield


Strength Refer to Guidelines
Completion Brines/ Service Produced for Selecting
Drilling Muds Environment Downhole Tubular
Fluids Materials for
ONLY
Oil and Gas Wells
Use carbon or low-
alloy steel casing

Has
Refer to the appropriate specialists and Guidelines
corrosion resistant
for Selecting Downhole Tubular Materials for
alloy production tbg
Oil and Gas Wells
been specified

Is
Specify materials according to API 5CT and/or
exposure to sour
BP Engineering Standard (BP ES) 145
conditions likely

Consideration can be given


(150°F) (175°F)
to using N80 (Q+T) or C95 What is
65°C 80°C Consideration can be given to using H40, N80, or
in addition to the standard the minimum service
sour-resistant casing P110 grades in addition to the standard sour-resistant
temperature casing materials in API 5CT and NACE MR-0175-91
materials in API 5CT and
NACE MR-0175-91
(150°F)
<65°C

Use only the standard What is Consideration can be given to using proprietary sour-
<95 ksi >95 ksi
sour-resistant casing the required strength resistant casing grades with up to 110 ksi YS
materials in API 5CT and grade - consult with a relevant specialist
NACE MR-0175-91
(Refer to Table 3 of NACE
MR-0175-91 "For all
Temperatures" Column)

Has a suitable Specify materials according to (API 5CT and/or


combination of strength ISO 11960) together with (NACE MR-0175
and SSC resistance and/or BP ES 153)
been achieved
u If in doubt, ask the
appropriate specialists

Refer to Section 15.1.2 and/or


consult the relevant specialists

15.2.2 NACE Standard MR0175 (Standard Material Requirements –


Sour-service Sulphide Stress Cracking Resistant Metallic Materials for Oilfield
Equipment) is recommended as the document to be used to define a sour
environment for BP Amoco worldwide.

A ‘sour environment’ is defined in NACE Standard MR0175 as a fluid


containing water as a liquid, together with hydrogen sulphide at a level
exceeding certain criteria, as detailed in Figures 15.2 and 15.3.

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Section C15 Material Selection and Corrosion Guidelines 15-3
BP Amoco
BPA-D-003 Casing Design Manual

FIGURE 15.2
SOUR GAS SYSTEMS
Grains H2S Per 100 SCF
1 10 100 1000
10000

1000
A

B Sulfide Stress Cracking Region

100
65 PSIA Total Pressure

10
.0001 .001 .01 .1 1 10
MOL % H2 S in Gas
PPM H2S in Gas
1 10 100 1000 10000 100000

FIGURE 15.3
SOUR MULTIPHASE SYSTEMS
Grains H2S Per 100 SCF
1 10 100 1000
10000

1000
A Sulfide Stress Cracking Region

265 PSIA Total Pressure


B

100

10
.0001 .001 .01 .1 1 10
MOL % H 2S in Gas
PPM H2S in Gas
1 10 100 1000 10000 100000

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From Figures 15.2 and 15.3 it is clear that the definition of sour conditions
is different for gas and oil wells. For the purposes of this definition, any
well with a gas/oil ratio of greater than 5000 standard cubic feet per barrel
of oil is taken as a gas well. It is also apparent from these figures that the
definition of sour conditions is normally based upon the partial pressure
of hydrogen sulphide in the gas phase. To determine the partial pressure
of hydrogen sulphide in the gas phase, certain field information is
required.

Considering a gas well, the information required is the bottomhole


pressure and the mole (or volume) fraction of hydrogen sulphide in the
gas. The partial pressure is then calculated simply by multiplying the
mole fraction of hydrogen sulphide in the gas by the bottomhole pressure.
For example, for a 5500m deep gas well with a bottom hole pressure of
14,000psi and a hydrogen sulphide content of 5ppm mole, the partial
pressure of hydrogen sulphide would be 0.07psia (5/1,000,000*14,000),
ie the well would be classified as sour.

For oil wells under circumstances where there is gas present (multiphase
wells), the partial pressure of hydrogen sulphide can be estimated by
multiplying the total pressure by the mole fraction of hydrogen sulphide.
The situation for oil wells in which there is no gas phase present under
downhole conditions is somewhat different. The partial pressure of
hydrogen sulphide that needs to be calculated is that in a gas phase in
equilibrium with that dissolved in the well liquids (oil/water). An alternative
description of this is the partial pressure of hydrogen sulphide in the gas
phase formed at its bubble point. Therefore, a ‘convenient’ method often
used to calculate the partial pressure is to multiply the bubble point
pressure by the mole fraction of hydrogen sulphide in the gas phase.
For example, for a 2000m deep oil well with a bottom hole pressure of
2500psi, a bubble point pressure of 1000psia and a hydrogen sulphide
content of 40ppm mole, the pressure of hydrogen sulphide would be
0.04psia, ie the well would be classified as ‘sweet’.

The major concern with sour conditions for casing string is the possibility
of SSC. The mechanism of SSC is described in Appendix 15A. Two
approaches have been developed to account for SSC in the materials
selection process. These two approaches are described below.

It should be noted that these approaches are only concerned with the
resistance of materials to SSC in sour conditions. However, there are
other failure mechanisms that may occur in the presence of hydrogen
sulphide. These need to be borne in mind when selecting materials for
sour-service. For example, some steels used in pipelines and vessels
may suffer from blistering or step-wise cracking as a result of hydrogen
damage in sour environments. This aspect is covered for such materials
in BP Guidance for Specification (GS) 136-1. Also, some austenitic
stainless steels and highly alloyed materials may suffer from chloride
stress corrosion cracking at elevated temperatures (above about 50°C,
120°F), this can be aggravated in some circumstances by the presence
of hydrogen sulphide. Again, this aspect is covered to some extent in BP
GS 136-1.

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Section C15 Material Selection and Corrosion Guidelines 15-5
BP Amoco
BPA-D-003 Casing Design Manual

NACE Standard MR0175 (Standard Material Requirements – Sulphide


Stress Cracking Resistant Metallic Materials for Oilfield Equipment)

The NACE Standard MR0175 is concerned with the resistance of materials


to SSC in sour conditions. In some countries, such as the United States,
the Standard is a legislative requirement, ie it must be applied there. This
document should be referred to for initial information on materials with
adequate resistance to SSC for sour conditions.

Having defined the field conditions to be ‘sour’, the latest version of NACE
MR0175 should be consulted for materials requirements. In general, the
NACE MR0175 Standard classifies the acceptability of various materials
grades for sour-service in terms of their hardness (which is related to
tensile strength). Section 10.2 of NACE Standard MR0175 deals specifically
with materials for well casing and tubing.

When applying Section 10.2 of the NACE MR0175 Standard, it should be


noted that increasing the temperature reduces the likelihood of SSC,
particularly for low-alloy steels. Hence, NACE MR0175 allows the use of
materials with a specified minimum yield strength above that of the fully
sour-resistant grades under circumstances where the minimum operating
temperature is above certain limits. The information in Table 15.1, based
upon Table 5 from NACE MR0175-98, details the acceptable tubular
material grades for different temperature ranges (refer to NACE MR0175
for the full table).

For all For Operating For Operating For Operating


TABLE 15.1
ACCEPTABLE API Temperatures Temperatures Temperatures Temperatures
SPECIFICATIONS FOR (1,2) 65°C or 80°C or 107°C or
TUBULAR GOODS Greater (3) Greater (3) Greater (3)

API Spec 5CT API Spec 5CT API Spec 5CT API Spec 5CT
grades H40 grades N80 grades H40; grade Q125.
(Note 4); J55; (Q + T); C95 N80; P110 See Note 5
K55; L80 (Type 1);
C90 (Type1); T95
(Type1)

Proprietary grades Proprietary Q + T Proprietary Q + T


Per NACE MR-0175 grades with grades with
Section 10.2 110ksi or less 140ksi or less
maximum yield maximum yield
strength strength

Notes to Table 15.1:

(1) Impact resistance may be required by other standards and codes for
low operating temperatures.

(2) Grade 155 casing is not covered in this table and is unsuitable for
sour-service conditions at any of the temperature ranges specified.

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(3) Continuous minimum temperature; for lower temperatures, select


from Column 1.

(4) For H40 material the maximum permissible yield strength is 80ksi.

(5) Regardless of the requirements for the current edition of API Spec
5CT, the Q125 grade shall always (1) have a maximum yield
strength of 150ksi; (2) be quenched and tempered; (3) be an alloy
based on Cr-Mo chemistry. The C-Mn alloy chemistry is not
acceptable.

When using these criteria, it is important to bear in mind that SSC can
occur within a relatively short timespan, so that periods of exposure to
sour conditions at temperatures below those stated in the table could
potentially lead to SSC problems. For this reason it is important to note
that the temperature levels quoted in Table 15.1 are the minimum
operating temperature the casing will experience. If temperatures below
this minimum are expected even for short periods of time then the
non-sour higher strength materials should not be used.

BP Amoco Methodology for Selecting Materials with Adequate SSC


Resistance

It was recognised some time ago that the use of the NACE Standard
MR0175 alone is not sufficient to allow the selection of the optimum
material with adequate SSC resistance. For example, the NACE Standard
makes no reference to the ‘in-situ’ pH, which is known to affect the
likelihood of SSC of materials. In addition, the testing solution used in
assessing the acceptability of materials for sour-service in NACE is very
severe (1 bar H2S, pH 2.8), meaning that the standard is very conservative
regarding which materials are acceptable for hydrogen sulphide service.
Finally, there is insufficient information in the NACE Standard regarding
the operating limits of many alloys. Therefore, BPA have developed a
methodology based upon laboratory test results and field experience, to
allow the user to select the correct material for the intended service.

The decision was made to carry out all testing for the ‘BPA methodology’
under ambient (24°C +/- 3°C) temperature conditions, ie the ‘worst case’
scenario. Therefore, the methodology described here is applicable to all
likely operating temperatures

Note: This methodology need not be applied to the traditional


‘sour-resistant grades’ in API 5CT (ie L80, C90, T95) which it is
assumed are suitable for all sour conditions on the basis of past
experience and test data.

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Section C15 Material Selection and Corrosion Guidelines 15-7
BP Amoco
BPA-D-003 Casing Design Manual

To apply the BPA methodology, it is necessary to know certain information


about the proposed well, ie the partial pressure of hydrogen sulphide in the
gas phase and the ‘in-situ’ pH of the water associated with the produced
fluids.

Note: If no in-situ pH is available then one of the methodologies outlined


in Appendix A of the ‘Guidelines for Selecting Downhole Tubular
Materials for Oil and Gas Wells’ can be used to assess the in-situ
pH on the basis of certain well information.

Once the necessary information has been collected, the conditions can be
plotted onto the appropriate ‘sulphide stress cracking performance domain’
charts for individual alloys at the end of these guidelines. There are two
domains identified on the individual alloy ‘go/no go’ charts.

(1) If the operating conditions fall within the ‘acceptable’ domain


then the material is likely to have an acceptable resistance to
SSC under the prevailing conditions. However, it is important to
note that the go/no go charts were developed on limited information,
ie it was only possible to tests a selection of the wide range of
materials available on the market and only at one time (manufacturing
techniques can change with time which may also affect their SSC
resistance). Therefore, it is important to check the resistance of the
material to the anticipated conditions before finalising the selection
of a non-sour material grade for potentially sour-service. The
suitability can be confirmed in two ways:

• From prior satisfactory testing or service experience with material


from the same supplier and made by the same manufacturing
route under conditions equivalent to or worse than the intended
service

• From the successful outcome of small scale SSC laboratory tests


under test conditions representative of the intended service on
material from the same supplier and made by the same
manufacturing route. Note that material testing lead times of
perhaps 8 weeks need to be considered in planning

For further information contact the relevant specialist.

(2) If the operating conditions fall within the ‘unacceptable’ domain


then it will be necessary to consider a material with greater SSC
resistance.

It should be noted that the domain charts are not ‘all encompassing’, but
only deal with resistance to SSC.

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15-8 Material Selection and Corrosion Guidelines Section C15
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Casing Design Manual BPA-D-003

FIGURE 15.4
SULPHIDE STRESS
CRACKING PERFORMANCE 6.5
DOMAIN OF GRADE P110 Suitable
CARBON STEEL
5.5

4.5
Unsuitable
3.5

0.001 0.01 0.1 1.0 10 (Bar)


0.015 0.15 1.5 15 150 (Psi)
Hydrogen Sulphide Partial Pressure

FIGURE 15.5
SULPHIDE STRESS
CRACKING PERFORMANCE 6.5
DOMAIN OF GRADE N80
CARBON STEEL Suitable
5.5

4.5
Unsuitable
3.5

0.001 0.01 0.1 1.0 10 (Bar)


0.015 0.15 1.5 15 150 (Psi)
Hydrogen Sulphide Partial Pressure

15.3 It is necessary to consider the two different types of wells separately:


Corrosion Control • Exploration/Appraisal Wells

• Development Wells

The design of downhole completion equipment against corrosion is


beyond the scope of this manual, for further information on this
area reference should be made to the ‘Downhole Equipment
Materials Guidelines’.

In these types of wells, the major corrosive agent is the drilling mud.
Two types of mud are in common use, ie oil-based or water-based.

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Section C15 Material Selection and Corrosion Guidelines 15-9
BP Amoco
BPA-D-003 Casing Design Manual

15.3.1 In the case of oil-based muds, there is little danger of corrosion problems
Exploration/ under normal operating conditions, as oil is the continuous phase in the
Appraisal Wells mud and the metal surface will be ‘oil-wet’. The major exception to this is
the contamination of the mud with water and acid gases (ie CO2 and/or
H2S) due to formation fluid in-flow. Therefore, it is important to ensure that
the drilling fluid hydrostatic head and fluid density are maintained to
minimise this inflow. In addition, it may be necessary to make chemical
additions to oil-based muds, eg sulphide scavengers.

The dissolved gas that most commonly determines the general corrosivity
of water-based drilling muds is oxygen, although the insurgence of acid
gases due to formation fluid in-flow may also be important. In casing
design, general corrosion of the type associated with oxygen or acid gases
is not normally an issue as the periods of exposure are relatively short. In
addition, the pH of the mud is controlled to minimise the likely corrosion
rate.

An important corrosion problem that can occur during drilling is sulphide


stress cracking (SSC). This occurs as a result of hydrogen sulphide in the
mud. This hydrogen sulphide can have a number of sources, the more
important being:

• Inflow of formation fluids containing hydrogen sulphide

• Bacterial activity

• Degradation of the mud

The second and third of these sources can be adequately controlled by the
addition of biocides to the mud and correct mud selection. Although the
likelihood of the first source can be reduced by maintenance of the drilling
fluid hydrostatic head and fluid density to minimise formation fluid inflow,
the possibility of such inflow must still be considered; even a short
exposure time to a ‘sour’ environment can lead to a potentially catastrophic
failure. Therefore, if the presence of hydrogen sulphide is expected,
additional preventative measures need to be taken to ensure that SSC will
not occur, for example:

• Maintain the pH at a value of 10 or higher to neutralise the


hydrogen sulphide

• Use chemical sulphide scavengers

In addition, consideration can be given to the use of sour resistant casing


materials (refer to Section 15.1.2). For wells which are expected to be
‘sour,’ it is normal practice within BPA to use sour-resistant casing grades
for the casing strings likely to be exposed to the sour fluids.

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Casing Design Manual BPA-D-003

In the case of high-temperature/high-pressure wells, the situation was


somewhat more complex for UK sector North Sea applications in the
past. Document CSON 59, produced by the Department of Environment,
required the operator to provide supporting data that non-sour casings
can be relied upon not to fail catastrophically during:

• A temporary period of exposure to sour reservoir fluid (eg whilst


circulating out a kick or if there is a leak in the test string during
production testing) and not subsequently thereafter in the remainder
of its service life, or

• The time between first exposure to sour reservoir fluids and completion
of evacuation of the drilling installation in the event of total displacement
of the well bore contents to such fluids

These requirements have led operators to consider thick-wall


sour-resistant casing or proprietary high-strength sour-resistant grades
(normally up to 110ksi minimum specified yield strength). These are
discussed in the section on materials selection (Section 15.1) and
reference should be made to that section before specifying these types
of material.

Note: CSON 59 has now been superseded by PON13 which imposes


no requirement other than notification of expected H2S and
incident reporting to PON 11.

15.3.2 Well design should endeavour to contain the corrosive produced fluids
Development Wells within the production tubing, eg by the correct selection of tubing material
and the use of tubing strings with premium connections, where necessary.
Therefore, the prime consideration in accounting for corrosion in well
casing design is to ensure the correct selection of the annulus fluid.
However, it is recognised that tubing leaks and subsequent pressurised
annuli are possibilities. Therefore, measures need to be taken to ensure
the adequate protection of the casing under such circumstances.
These aspects are discussed in this section.

Any part of the casing that is likely to be exposed to the produced fluids
for a significant length of time should be designed to withstand such an
environment. This means that when designing such casing, considerations
very similar to those given for production tubing need to be addressed
when selecting materials. This area is addressed in the ‘Guidelines for
Selecting Downhole Tubular Materials for Oil and Gas Wells’.

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Section C15 Material Selection and Corrosion Guidelines 15-11
BP Amoco
BPA-D-003 Casing Design Manual
Corrosion Control in Completion Fluids

Completion fluids can be defined as any borehole fluid placed across the
producing zone prior to bringing on a well. These fluids are field/well
specific and fulfil many roles. Brine completion fluids are used in well
testing operations, workovers, completions and as packer fluids. The
function in a completion is to fill the annulus space between the production
tubing and casing.

Completion fluids are commonly brines and are selected based upon the
required specific gravity. Examples of some of the brines used and the
specific gravity ranges they cover are given in Table 15.2.

TABLE 15.2
TYPICAL BRINES USED AS Brine Specific Gravity Range PPG
COMPLETION FLUIDS
Sea Water 1.02 8.5
KCl 1.16 9.7
NaCl 1.19 10.0
NaBr 1.50 12.5
CaCl2 1.39 11.6
CaBr2 1.39 to 1.71 11.6 to 14.3
ZnBr2/CaBr2/CaCl2 1.82 to 2.31 15.2 to 19.3

A number of chemical additives can be made to these muds to assist in


corrosion control, ie:

Biocide

Biocide is added to prevent the growth of aerobic and/or anaerobic


bacteria. Such bacteria can lead to corrosion problems, eg by the
production of hydrogen sulphide. Therefore, it is necessary to prevent
their activity. There are a number of biocides commercially available. Final
selection will be based upon many factors. However, one of the most
important factors is the salinity of the completion brine. Where the brine
salinity is very high (greater than 12% wt/wt), the addition of a biocide is
unnecessary, as the high salinity is sufficient within itself to prevent
bacterial activity. Another factor that will affect the selection of a suitable
biocide is the presence of an oxygen scavenger (compatibility). Therefore,
it is important to get the input of a suitable specialist when selecting
biocides for completion brines.

Oxygen Scavenger

Oxygen scavenger is required to remove dissolved oxygen from the


completion brine to reduce its corrosivity. The chemicals most commonly
used for this function are ammonium or sodium bisulphite. The dosage
rate will depend on the oxygen content of the brine. It is important to avoid
overdosing of the oxygen scavengers as these can be corrosive in their
own right and/or can lead to the deposition of iron sulphide scales. It is
recommended that the oxygen level of the treated fluid is monitored to
ensure effective treatment.
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Casing Design Manual BPA-D-003

If the completion brines are not deaerated, the available oxygen may in
any case be quickly consumed by the superficial corrosion of the carbon/
low alloy casing where the two are in contact. Therefore, a decision must
be made on whether or not an oxygen scavenger is required. This decision
needs to be based upon a number of factors. For example, even the short
period of enhanced corrosion in non-deaerated solutions may produce
significant quantities of corrosion product. There may be concerns that
this corrosion product dropping to the bottom of the annulus will block
injection valves. Therefore, future use of the annulus needs to be
considered. Additionally, if corrosion-resistant alloy (CRA) tubulars are
specified then the presence of oxygen may initiate corrosion, eg pitting
corrosion, crevice corrosion, galvanic corrosion, or even SSC, especially
if the oxygen is not rapidly consumed by superficial corrosion of carbon/
low alloy steel (eg if the fluids are inside the tubing for any reason, areas
where carbon steel is not present in the region of CRA tubulars). If in any
doubt, the relevant specialists should be consulted.

Corrosion Inhibitor

Some of the high-density brines can be corrosive in their own right


(eg zinc bromide). In such circumstances it will often be necessary to use
a film-forming corrosion inhibitor to reduce the corrosion rates to
permissible levels. There are many corrosion inhibitors available on the
market therefore selection should be made with care. It is recommended
that due reference is made to the relevant specialists. One corrosion
inhibitor commonly used is a quarternary amine, which is dosed at a rate
of 5% v/v (50,000ppm). As a rule of thumb, the cut-off point when
deciding whether to consider a corrosion inhibitor or not is a specific
gravity of 1.2 (10ppg), with a corrosion inhibitor being given consideration
above this specific gravity. Compatibility with the formation itself should
also be considered to avoid formation swelling or blocking.

Scale Inhibitor

This is the final chemical additive in completion brines. It is not added to


control the corrosivity, but rather to prevent scales forming when the
completion brine comes into contact with the formation brine. If a
compatible completion brine has been selected, or where the completion
brine will not come into contact with the formation fluids, a scale inhibitor
is unnecessary. For example, where a sodium or potassium based brine
is used, the high solubility of the products formed by mixing with formation
water means that the addition of a scale inhibitor is unnecessary. Under
normal conditions, scale inhibitors are only necessary in calcium chloride/
bromide completion brines. Under such circumstances, it is recommended
that the relevant specialist be contacted.

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Section C15 Material Selection and Corrosion Guidelines 15-13
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BPA-D-003 Casing Design Manual

To avoid corrosion problems resulting from completion fluids, the use of


alternative ‘non-aqueous’ fluids is sometimes considered, eg diesel oil. It
has been found that one alternative fluid (bromoil/densoil) can be corrosive
at elevated temperatures (>400°F, 200°C). Therefore, care needs to be
exercised when using these types of fluid.

15.4 External corrosion of casing can be a problem, especially where the


External Corrosion casing passes through aquifers. If such problems are expected or
encountered, consideration may need to be given to external cathodic
protection or cementing across the zone of concern. The design of such
systems is outside the scope of this manual and reference should be made
to the appropriate specialists.

15.5 The purpose of the flow diagram in Figure 15.6 is to assist in deciding the
corrosion control measures required for the fluids normally in contact with
Flowchart for
the casing, ie completion brines or drilling muds. When selecting the
Corrosion Control chemical treatment package for completion brine, it is important to contact
Measures the relevant specialist(s), to ensure the suitability/compatibility of the
various additives.

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15-14 Material Selection and Corrosion Guidelines Section C15
BP Amoco
Casing Design Manual BPA-D-003
FIGURE 15.6
MAJOR CORROSION
CONTROL MEASURES
FOR CASING

What type of
well is it?

Is Have
the casing Refer to Guidelines for carbon/low alloy
steel tubulars been
exposed to Selecting Downhole
selected
produced Tubular Materials for throughout?
fluids Oil and Gas Wells

Have What
carbon/low alloy Where corrosion-resistant fluids are in
steel tubulars been alloys are being specified,
selected for casing contact with the
contact the specialists
or tubing casing?

Select completion brine


Use normal corrosion Are the
control measures for fluids going to
drilling be sour at any
stage?

Select the required brine based on the


specific gravity Maintain a pH of 10 or greater
in the drilling mud

Is the brine Add biocide


salinity >12% Add a sulphide scavenger to the
l drilling mud prior to drilling
wt/wt
sour interval

Is
superficial
initial corrosion apt to Add oxygen
cause problems scavanger l
s

Is the
specific Add corrosion
gravity >1.2 inhibitor l

Has a
CaCi2/CaBR brine Add scale
been selected inhibitor l

Check fluid is non-damaging to


the formation. Consult the l Consult the specialists and ensure
Completion Design Manual compatibility

Consult the specialists on superficial


s
corrosion plugging valves
Draw up the specification for the
completion brine

01112174

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Section C15 Material Selection and Corrosion Guidelines 15-15
BP Amoco
Casing Design Manual BPA-D-003

Appendix 15A
CORROSION BACKGROUND

15A.1 One of the prerequisites for corrosion to occur is the presence of an


aqueous phase, although even a trace of water can lead to corrosion.
General
Corrosion is an electrochemical process, so that an electrical current
flows during corrosion. For an electrical current to flow, there must be a
driving force, ie a voltage source, and a complete electrical circuit.

The voltage source is the metal itself. All metals contain stored energy,
eg as a result of refining, mechanical working. This means that metal will
adopt an electrical potential when it is put into an aqueous solution,
known as the ‘equilibrium potential’.

FIGURE 15A.1
DIAGRAMMATICAL
REPRESENTATION OF THE
CORROSION PROCESS FOR IRON
Anode
Fe -> Fe++ + 2 Electrons

Current Electrolyte
Flow

Cathode 2H+ + 2 Electrons -> H2 (Gas)


Metal

The electrical circuit consists of three parts. These are shown


diagrammatically in Figure 15A.1 and consist of:

The Anode which is the portion of the metal surface which is dissolving
or ‘corroding’. For iron this can be represented by the chemical reaction:

Fe ⇒ Fe2+ + 2 electrons

The Cathode which is the portion of the metal surface at which the
electrons formed by the anodic reaction are ‘consumed’. There are many
cathodic reactions that can occur, depending on the composition of the
solution. For an acid the cathodic reaction would typically be:

2H+ + 2 electrons ⇒ H2 (gas)

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BP Amoco
BPA-D-003 Casing Design Manual

The Electrolyte which is the electrically conductive solution on the metal


surface through which the electrical current (or electrons) necessary to
support the corrosion process flows.

In the case where there is no externally applied electrical current, the


anodic and cathodic reactions are balanced, ie there will be no ‘total’
current flow measured.

The reasons why some areas of the metal surface act as anodes,
whereas others act as cathodes, are complex. A major factor is
inhomogeneity in the metal surface and/or electrolyte. In general corrosion,
the anodes and cathodes will be randomly distributed over the surface
and will ‘move’ during the corrosion process. In localised corrosion,
eg pitting, the anodes will be restricted to certain, small areas.

Many different types of corrosion damage can occur. The more likely to
be experienced by downhole casing can be classified as follows:

(1) General Corrosion

This results in a fairly uniform loss of material across the surface


of a component, leading to a loss in load carrying capacity, eg the
ability to contain a pressure, tension, collapse.

(2) Localised Corrosion

This results in uneven wastage of the component eg pitting


corrosion. Pitting corrosion is a particularly damaging form of
corrosion in which components can fail by perforation with only a
small percentage weight-loss. In addition, pits will act as stress-
concentrators, reducing the load-carrying capacity of the
component. Alternatively, localised corrosion may occur at particular
locations, eg crevices, mixed metal sites (galvanic attack), areas
of high turbulence (erosion-corrosion).

(3) Environment-sensitive Cracking (ESC)

These mechanisms can lead to catastrophic, brittle failures.


Cracking can occur rapidly and without the accompaniment of
significant material wastage. In addition, the cracks can be very
fine, making them difficult to detect using conventional inspection
techniques. Examples of ESC are sulphide stress cracking (SSC),
chloride stress corrosion cracking (CSC) and corrosion-fatigue.

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Casing Design Manual BPA-D-003

15A.2 As has already been indicated, there are many mechanisms by which
corrosion damage can occur. This section covers the corrosion damage
Corrosion that can be accrued as a result of chemical contaminants and some of
Mechanisms the other corrosion mechanisms that must be considered in casing
design.

15A.2.1 Carbon dioxide is commonly found associated with well fluids. Carbon
Carbon Dioxide dioxide dissolved in water forms a weak acid, known as carbonic acid,
which can cause corrosion. This is of particular importance for carbon
steel, in which case an iron carbonate film is sometimes formed on the
metal surface. CO2 corrosion of carbon steels often occurs at locations
where the iron carbonate film is deficient, resulting in a particular form of
localised pitting corrosion, known as ‘mesa’ attack. In circumstances
where there is no iron carbonate film, the corrosion will be general.

The rate of CO2 corrosion will be dependent on a number of factors,


including CO2 partial pressure, pH, temperature, flow velocity, and
the presence and nature of other chemical species (eg oxygen, chlorides,
H2S).

There are numerous guidelines that can be used to predict the severity
of CO2 corrosion. Contact relevant specialist.

15A.2.2 There are a number of possible sources of hydrogen sulphide in


Hydrogen Sulphide downhole fluids. These include:

• Associated with the well fluids

• Generated as a result of bacterial activity. In this case sulphate-reducing


bacteria (SRBs) can reduce sulphates in the fluids to hydrogen
sulphide

• Breakdown products of chemical species in the fluids. One such


source could be bisulphites added to remove oxygen from
injection water

Hydrogen sulphide dissolved in water can react with a steel surface,


producing an iron sulphide scale. H2S corrosion often results in deep pits
in regions where the iron sulphide scale is not present. In practice, this
type of H 2S corrosion has little practical significance unless the H2S
content is high, ie several mole %.

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BP Amoco
BPA-D-003 Casing Design Manual

Of greater importance, at the relatively low H2S levels often found in


downhole fluids, is the mechanism known as ‘sulph ide stress cracking’
(SSC). Sulphide stress cracking occurs as a result of the entry of atomic
hydrogen into the metal. Aqueous corrosion will produce atomic hydrogen
which would normally tend to recombine via the reaction:

2H+ 2 electrons ⇒ H + H ⇒ H2 (gas)

These hydrogen gas molecules are too large to enter the metal and are
thus not harmful to it. However, hydrogen sulphide is thought to discourage
the recombination of hydrogen atoms to form H2 gas and hence
encourages the entry of atomic hydrogen into the metal. Once in the
metal the atomic hydrogen will diffuse to ‘trap’ sites, where it will lead to
a local increase in the stress and/or a reduction in the strength of the
metal lattice. For a material under load, there is evidence to suggest that
the atomic hydrogen will concentrate near stress concentrators and may
give rise to crack initiation at such points, hence leading to a brittle-like
fracture. This type of cracking can occur quite rapidly. Thus, even if
materials are only to be exposed to sour conditions for short periods of
time, they must be resistant to SSC. This aspect is covered in some detail
in Paragraph 15.1 (Materials Selection) of this manual.

15A.2.3 The presence of dissolved oxygen can have a marked influence on the
Oxygen corrosion of oil-field goods. High corrosion rates can result even at
relatively low concentrations of dissolved oxygen (much less than
1ppm). In this process iron is converted by a corrosion reaction to oxides
and/or hydroxides. The cathodic reaction in this case is:

O2 + 2H2O + 4 electrons ⇒ 4OH-

The corrosion rate in oxygenated near-neutral solutions is often controlled


by the rate at which oxygen can diffuse to the cathodic areas to support
the corrosion reaction. As such, the corrosion rate will be increased by
flow etc.

Oxygen corrosion is not normally a problem with produced fluids, as they


contain no dissolved oxygen. However, it can be a significant issue in
water-based drilling muds, in which case it may be necessary to control
the dissolved oxygen content using oxygen scavengers. Another area
where oxygen corrosion can be a significant issue is in injection water
systems, in which case care must be taken to reduce the dissolved
oxygen to acceptable levels, eg using gas stripping or vacuum degassing.

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Casing Design Manual BPA-D-003

15A.2.4 Halide ions, eg chloride and bromide ions, are present in many of the
Halide Ions fluids likely to be encountered downhole, ie formation waters,
injection waters, completion brines, workover fluids, etc.

Halide ions can cause localised corrosion damage to materials used for
downhole equipment in the form of corrosion pitting and/or crevice
corrosion. In addition, they can increase the corrosion damage resulting
from the effect of other corrodants.

Halide ions can also give rise to stress corrosion cracking (SCC) of
susceptible materials, principally austenitic stainless steels. This type of
cracking will normally only occur at elevated temperatures, typically above
50°C (120°F) for austenitic stainless steels, and under the action of
tensile stresses. This can also include residual stresses from mechanical
working.

Stress corrosion cracking can be defined as crack initiation and growth


in an alloy caused by the conjoint action of corrosion and tensile stress.
This cracking can occur at stresses well below the yield strength.
The mechanism by which this occurs is not fully understood, but it
requires the presence of certain specific alloy/environment combinations,
eg austenitic stainless steel in chloride-containing solutions. The result of
SCC is that normally ductile materials can suffer from catastrophic,
apparently brittle, failures.

15A.2.5 This is the preferential corrosion that can occur to one of the metals, when
Galvanic Corrosion two different metals are electrically coupled in a corrosive environment.
In such a couple, one of the metals will act as an anode (ie it will corrode
at an enhanced rate) and the other will act as a cathode (ie there will be
a certain degree of protection). The susceptibility of a material couple
towards galvanic corrosion of the ‘anodic’ metal (ie the metal with the
lower equilibrium potential) is influenced by a number of factors, such as
the conductivity of the corrosive medium, the relative surface area of the
two metal components and the difference in the equilibrium potentials of
the two metals in the corrosive environment.

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BPA-D-003 Casing Design Manual

15A.2.6 There are two types of localised corrosion that are likely to be encountered
Localised Corrosion downhole, ie corrosion pitting and crevice corrosion. As has already
been indicated, corrosion pitting occurs when certain regions in the
metal act as strong anodes. An example of this is the corrosion pitting of
certain stainless steels in chloride-containing environments. In this case,
pitting is enhanced by the presence of dissolved oxygen. The pitting
process is strongly affected by temperature. There are often temperatures
below which corrosion pitting will not occur in a particular environment,
this is known as the ‘critical pitting temperature’. Pitting is more damaging
than general corrosion as it can result in penetration in much shorter
times and is more difficult to detect. This is an aspect that should be
borne in mind when selecting materials for downhole service, particularly
corrosion-resistant alloys.

Crevice corrosion is the localised damage that can result at a narrow gap
or ‘crevice’ between two adjacent components. The crevice may be
between two similar materials, two different materials (in which galvanic
corrosion may also play a role), or even between a metal and a non-metal
(eg elastomers). An important factor in determining whether crevice
corrosion will occur is the size of the gap. Crevice corrosion is often
exacerbated at higher temperatures. The local environment produced
within a crevice can be quite different to the bulk fluid environment,
leading to corrosion damage which could not be predicted from the
general fluid composition.

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15A-6 Material Selection and Corrosion Guidelines Section C15