Académique Documents
Professionnel Documents
Culture Documents
for Selecting
Downhole Tubular
Materials for
Oil & Gas
Production Wells
(2000 Edition)
J W Martin
Major contributors: D Harrop, W Hedges
Sunbury Report No. S/UTG/023/00
dated February 2000
Main CD
Contents
S/UTG/023/00
Contents
CONTENTS
1. INTRODUCTION
7
11
13
40
50
52
58
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Introduction
1. INTRODUCTION
Material selection of downhole tubulars is an important aspect of completion design. If the wrong
material is selected then premature failure can result, with considerable cost implications in both
replacing the tubulars and lost production.
The purpose of this document is to provide clear guidance that can be used by engineers to
carry out a first stage evaluation of the material requirements for the downhole tubulars. The
guidelines cover all aspects of corrosion and stress corrosion resistance, including sulphide
stress cracking in sour environments. Where the guidelines are unable to give unequivocal
recommendations on the material to be selected, test protocols are referenced which will allow
the choice of the optimum material for the intended duty.
Guidance is given on:
(a)
(b)
Materials selection for downhole tubulars, by the application of flow charts (road
maps) with references back to the text where necessary.
(c)
(d)
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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
corrosion-resistant alloys. Therefore, BP developed a methodology based upon laboratory test
results and some limited field experience, to allow the user to select the correct material for
the intended service. This methodology is discussed in the appendix.
Appendix E. What other factors need to be considered?
This appendix covers the issues of:
Mechanical Properties - limits on the maximum strength of materials to be used in sour
conditions are discussed, as are the effects of elevated temperature on the material strength
and isotropy in the cold worked duplex stainless steels.
Flow-Induced Damage - Erosion and Erosion-Corrosion - mechanisms of erosion and
erosion-corrosion are discussed, together with how to avoid and/or account for such attack in
downhole tubulars.
Galvanic Corrosion - the mechanism of galvanic corrosion is discussed, together with how to
avoid it in completion design.
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Information Required
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Information Required
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INPUT
NO
CONSULT
in situ
pH?(2)
pH Isoplots
YES
H2S
present?
YES
CONSULT
Materials Selection for
Sour Conditions Road
Maps
NO
Solids
present?(2)
Yes/Dont
Know!
CONSULT
NO Specialist
Advice
Erosion Rate
0.1 mm/y
Erosion Section of
Appendix E
YES
YES
V > 13 m/s
NO
Detailed
analysis
CONSULT
NO
CR 0.1 mm/y
YES
Specialist
Advice
0.1mm/y<CR<10 mm/y
T 100oC
YES
q Carbon steel + corrosion
Inhibitor can be considered(3, 4)
q Check economics and logistics
against 13%Cr
q If H2S present consult Materials
Selection for Sour Conditions
Road Map
NO
0.1mm/y<CR<10 mm/y
T 150 oC
NO
YES
q Seek specialist advice on feasibility
of carbon steel + corrosion
inhibitor (3, 4)
q 13%Cr likely to be best option(5, 6) but
care needed above 120 oC
q If H2S present consult Sour Service
Road Map
CR>10mm/y
T 175 oC
T>175 oC
Specialist
Advice
YES
q 13%Cr should be considered(5, 6) but
care needed above 120 oC
q Super or Hyper grades 13%Cr for T
< 175 oC
q If H2S present consult Materials
Selection for Sour Conditions Road
Map
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Apply Requirements
of NACE MR-0175
Yes
Is the
use of NACE MR-0175
a statutory requirement
for this
area?
No
=>65oC
What is
the MINIMUM
exposure
temperature?
=<95ksi
What is
the required
material strength?
Solution pH
6.5
=>80oC
Acceptable
5.5
4.5
Unacceptable
3.5
0.003
0.001
=>107oC
0.1
1.0
10
>95ksi
6.5
Acceptable
Solution pH
Notes.
1. If temperatures below this minimum are expected, even for short
periods of time, then the higher temperature limit criteria for non-sour
grades should not be used.
2. Regardless of the requirements for the current edition of API Spec. 5CT,
the Q125 grades 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).
3. For H40 material in sour conditions at temperatures less than 80oC
the maximum permissible yield strength is 80ksi
Solution pH
6.5
February 2000
0.01
pH2S (bara)
5.5
4.5
Acceptable
5.5
4.5
Unacceptable
Unacceptable
3.5
3.5
0.003
0.003
0.001
0.01
0.1
pH2S (bara)
1.0
10
0.001
0.01
0.1
1.0
10
pH2S (bara)
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Notes:
1. Where more than one possible candidate material is identified,
the materials should be considered in terms of increasing
cost/corrosion resistance, i.e.
If
no material with suitable pH/pH2S
resistance can be identified
refer to relevant specialist
6.5
Acceptable
Further Assessment
Required
Solution pH
Acceptable
Acceptable
5.5
5.5
5.5
4.5
4.5
4.5
Further Assessment
Required
Unacceptable
3.5
Unacceptable
3.5
3.5
Unacceptable
0.02
0.001
0.01
0.1
1.0
10
0.001
pH2S (bara)
Domain diagram for the Sulphide Stress Cracking Limits
of 22Cr Duplex Stainless Steel
0.01
0.1
1.0
10
0.001
0.01
0.1
1.0
10
pH2S (bara)
Domain diagram for the Sulphide Stress Cracking Limits
of 110ski Super 13Cr Alloys in high Chloride (120,000 ppm Cl) Waters
pH2S (bara)
Domain diagram for the Sulphide Stress Cracking Limits
of 95ski Super 13Cr Alloys in high Chloride (120,000 ppm Cl-) Waters
6.5
6.5
6.5
Solution pH
Solution pH
Acceptable
Acceptable
5.5
4.5
5.5
5.5
0.5
4.5
4.5
0.25
3.5
4.5
Further Assessment
Required
Unacceptable
Unacceptable
3.5
Further Assessment
Required
Acceptable
5.5
Acceptable
3.5
Unacceptable
3.5
Unacceptable
0.003
0.001
0.01
0.1
1.0
10
pH2S (bara)
Domain diagram for the Sulphide Stress Cracking Limits
of API5CT L80 13Cr Steel
February 2000
0.001
0.01
0.1
1.0
10
pH2S (bara)
Domain diagram for the Sulphide Stress Cracking Limits
of 25Cr Duplex Stainless Steels
0.001
0.01
0.1
1.0
10
pH2S (bara)
Domain diagram for the Sulphide Stress Cracking Limits
of 95ski Super 13Cr Alloys in low Chloride (1000 ppm Cl-) Waters
0.001
0.01
0.1
1.0
10
pH2S (bara)
Domain diagram for the Sulphide Stress Cracking Limits
of 110ski Super 13Cr Alloys in low Chloride (1000 ppm Cl-) Waters
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"Materials Assessment for Downhole Sour Service Applications; An overview", Sunbury Branch
Report PFB/135/124159, 14th May 1991.
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Appendix A
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Appendix A
little as 10 ppm acetic acid can present a problem and Specialist Advice should be sought
where acetic acid is present.
Finally the presence of erosion, leading to erosion-corrosion, needs to be determined as under
certain conditions the CO2 corrosion rate is moderated by the presence of an iron carbonate
corrosion scale. If erosion is an issue this may lead to under prediction of the associated CO2
corrosion rate when simply applying the BP Amoco Guidelines(2). Erosion and erosioncorrosion are addressed in Appendix E of these Guidelines.
2. Materials selection for sweet conditions Road Map
The Materials Selection for Sweet Conditions Road Map is given in Section 4 of these
Guidelines. This is based primarily on consideration of the CO2 corrosion rate, but also takes
account of other key factors which will affect materials selection.
2.1. Use of the Road Map
The following text gives guidance on the use of the Road Map. The section headings in bold
letters refer to the various Information (indicated by a ) or Decision (indicated by a ) boxes
on the Road Map.
Input
The primary inputs are temperature (T in oC) and partial pressure of CO2 (PCO2 in bara)
defined as:
PCO2 = (mole % CO2 x Ptotal)/100.
The worst downhole conditions (upper limit) will be at the Bubble Point which defines
the maximum amount of dissolved CO2 and hence the maximum PCO2 in terms of CO2
corrosion rate. If the Bubble Point is not known the default should be the bottomhole
flowing or reservoir conditions - a conservative position. The lower limit will be
determined by the wellhead flowing conditions.
In situ pH?
For corrosion to occur free water must be present at the pipe wall. For a gas well
operating above the dew point corrosion should not be a concern. For oil wells the
water cut and flow regime will be critical to determining if the pipewall is waterwetted. A complicating factor for oil / water systems is the emulsion tendency of the
crude oil. For fully mixed flowing conditions the resulting emulsion will be water-inoil at low water cuts inverting to oil-in-water at high water cuts. The inversion point
will depend on the water cut, temperature and pressure and typically sits at about 30%
to 40% water. Exact determination will normally require measurement so the worst
case of water wetting should be assumed and refined later subject to specialist advice.
It should also be recognised that under certain specific conditions (e.g.
conditions/regions close to the gas break-out point) corrosion of carbon steel has been
experienced downhole even at very low water cuts (around 1% or even less).
Under multiphase conditions a range of flow regimes are possible - eg. for vertical
flow: bubble, churn and annular - which will depend on the superficial velocities of the
liquid and gas phases, the gas/liquid ratio (GLR) and the angle of inclination. Any
concerns should prompt specialist advice being sought. Again the worst case of water
wetting should be assumed for the first pass assessment.
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Appendix A
0.0001
Not affected
0.001
0.01
0.01
0.01
0.1
0.1
Where H2S is present below the above PCO2 limits increased acidification will result ie.
PCO2/PH2S 10. This can range between 0.5 and 3 pH units depending on the actual
PCO2/PH2S ratio and here pH modelling for the specific conditions is required.
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Appendix A
Once the pH has been fixed the CO2 Corrosion Isoplots can be consulted subsequent
to satisfying the remaining questions in the Road Map. For many cases where H2S is
present a protective iron sulphide film is readily formed often leading in practice to
very low corrosion rates below those given in CO2 Corrosion Isoplots. However,
should this protective film breakdown highly localised corrosion can result at rates at
least equal to those given in the Corrosion Isoplots: the risk will be greater where
erosion is a concern. Consequently, designing on the basis of achieving protection
from formation of an iron sulphide film is not recommended. Furthermore, subsequent
inspection and corrosion monitoring should pay particular attention to the possibility of
pitting corrosion being present.
Solids Present?
Here the principal concern is erosion-corrosion. Pure erosion provides a source of
metal wastage that will be at least additive to that due to the CO2 corrosion. Appendix
E provides guidelines for limiting the erosion rate to 0.1 mm/yr. It is considered that
as long as the rate of erosion can be limited to 0.1mm/yr or less then the risks of
unacceptable levels of erosion or of synergistic erosion-corrosion are acceptably low.
Carbon/Low Alloy steels
The presence / stability of a protective surface corrosion scale - iron carbonate
- on carbon and low alloy steels will be affected by erosion. A stable iron
carbonate scale forms when a critical temperature, Tscale, is exceeded for a
given PCO2. The CO2 corrosion model used to generate the Corrosion Isoplots
treats the influence of protective corrosion scale as being a limiting effect on
corrosion rate ie. for all temperatures > Tscale the corrosion rate is equal to that
at Tscale. The following graph shows how Tscale varies with PCO2.
230
210
190
170
150
130
110
90
70
50
0.0001
0.001
0.01
0.1
10
P C O 2 , bar
The nature of and long term dependence on such scale for protection is a
subject still being researched and one where there are conflicting results and
experience i.e. in practice corrosion rate often decreases for temperatures >
Tscale but there are some examples of the reverse effect. The BP Amoco
approach is therefore a pragmatic one for design purposes.
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Appendix A
As mentioned previously the presence of acetic acid can suppress the formation
of iron carbonate scales and /or maybe raise Tscale to a value higher than that
given above.
Erosion studies at Tulsa University have shown that where a protective iron
carbonate scale is formed but becomes damaged due to erosion rapid, highly
localised corrosion can result. Therefore if the erosion rate is > 0.1 mm/y
and the temperature is > Tscale Specialist Advice should be sought.
13%Cr Stainless Steel
Erosion, where the predicted rate is > 0.1 mm/y, will remove the naturally
forming surface oxide film which normally affords passivity to 13%Cr. (NB.
Film stability is temperature, pH and chloride ion concentration dependent.)
The resulting extent of corrosion will depend primarily on the speed at which
the 13%Cr is able to repassivate. For further information reference should be
made to Appendix E of these Guidelines and the BP Amoco Erosion Guidelines
Duplex Stainless Steels
These materials generally do not suffer from CO2 corrosion and so under
erosive conditions the wastage rate will equal the erosion rate.
u Flow Velocity > 13 m/s?
The 13 m/s limit applies only to carbon and low alloy steels and arises from the fact the
CO2 corrosion model used to generate the Corrosion Isoplots was developed from
corrosion data obtained at velocities up to 13 m/s. As the relationship is principally
empirical, extrapolation beyond this limit is questionable and Specialist Advice should
be sought.
The CO2 Corrosion Isoplots were in fact developed for a nominal fluid velocity of 3
m/s and pipe internal diameter of 4.5. While the CO2 corrosion rate is sensitive to
velocity - it has a mass transfer component to the reaction - for the purpose of this first
pass assessment the Corrosion Isoplots are acceptable up to 13 m/s.
n Consult CO2 Corrosion Isoplots
The CO2 Corrosion Isoplots provide a simple means of quickly estimating what the
corrosion rate for carbon and low alloy steels will be for the conditions of interest. For
13%Cr stainless steel refer to Appendix B. .
If you feel uncomfortable using this simplified approach, a more detailed analysis
maybe appropriate and can be acgieved using the CO2 corrosion model: this is best
done in consultation with Specialist Advice.
2.2. Corrosion Inhibition
This is covered in more detail later in this Appendix. BP Amoco experience and application
predominantly lies with flowlines and main export lines. The logistics, ease of deployment and
ability to effectively monitor performance downhole are important considerations which
generally have limited use of this approach for corrosion control downhole.
There are differences within the industry about how to account for inhibited corrosion rate at
the design stage. The BP Amoco Corrosion Prediction Guidelines2, for design purposes,
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Appendix A
assume for a correctly selected and applied corrosion inhibitor the inhibited corrosion rate will
be 0.1 mm/y. What then determines the acceptability over a given design / field / operational
life will be the time during which inhibitor is effectively deployed - due to upsets, under
injection, failed injections pumps etc. Applying this approach leads to a predicted effective
inhibited corrosion rate (CRinh) of:
CRinh = (0.1 x T + CRuninhib x (DL - T))/DL
where T is the time in years with effective inhibitor deployment (inhibitor availability), DL is
the design / field / operational life in years, (DL - T) is the time in years where effective
inhibitor depolyment is not achieved, and CRuninhib is the uninhibited CO2 corrosion rate taken
from the Corrosion Isoplots or from running a more detailed analysis using the BP Amoco
CO2 Corrosion model2. Inhibitor availability is normally taken as a maximum of 95% of DL
for design purposes.
2.3. Plastic Coated or Lined Tubing
This option is most commonly used for injection tubing. Uncertainties remain about the long
term performance when continuously exposed to hydrocarbons (plastic coated tubing) and
water (GRE lined tubing) and there is the risk of collapse under rapid decompression due to
gas permeating behind the coating / liner. In addition, the coatings/linings have upper
temperature limitations, the limiting temperature being dependant upon which coating/lining is
used. However, mechanical robustness is probably the most important consideration - during
handling / installation and subsequent running of downhole tools and wirelining operations.
Plastic coated tubing is particularly prone to mechanical damage, especially at joints, and as
such must be seriously questioned as a standalone corrosion control measure: the primary
benefit is more likely to lie with friction reduction. GRE lined tubing is therefore the only
standalone corrosion control option. Specialist advise should be sought for temperatures >
80oC for use of GRE lined tubing and 120oC for plastic coated tubing.
2.4. Corrosion Resistant Alloys
Where CO2 corrosion rates are unacceptably high, the use of 13%Cr stainless steel is often the
most cost effective and logistically attractive option. There are limitations with regard to H2S
- e.g. NACE limits the use of L80 13Cr steel to conditions where the partial pressure of H2S is
0.1bara or less and the pH is 3.5 or more - such that the presence or absence of H2S over life
needs to be rigorously questioned if considering this option (refer to Appendix D and the Sour
Condition Road Maps for further information) . The material also has limitations in terms of
pitting resistance which is temperature and chloride concentration dependent (refer to
Appendix B for further information: as a rule of thumb, its use is acceptable for chlorides <
50,000 ppm and temperatures 120oC. For temperatures > 120oC or chlorides above
50,000ppm refer to Appendix B and/or specialist advise should be sought.
The so called Hyper or Super grades of 13%Cr now available offer improved pitting and SCC
resistance, a higher temperature limit (ca. 175oC and no specific limit on chloride
concentration). However, they are not generic materials and performance is dependent on
composition, which differs from supplier to supplier, and specific application may require
laboratory testing to confirm suitability. Higher strength grades than API 5CT L80 13Cr steel
(i.e. 95ksi and 110ksi) are now readily available but resistance to H2S remains a major
limitation (refer to Appendix D). There also remains some question as to whether these alloys
are prone to chloride stress corrosion cracking (refer to Appendix D).
For use of higher CRAs - this will most commonly be duplex stainless steels - Specialist
Advise should be sought. Here there is a significant Capex cost penalty - duplex stainless steel
grades are typically 6 to 8 times the material cost of carbon steel; 13%Cr steel grades are
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Appendix A
typically 2.5 to 4 times the material cost of carbon steel. These penalties are significantly
lower when comparing installed costs.
3. Use of downhole corrosion inhibition programmes with carbon steel tubulars.
If a consideration of the available information indicates that specifying carbon steel is not
adequate to guarantee a suitable service life, alternatives will need to be sought. One such
alternative is to specify carbon steel, but add a suitable corrosion inhibitor to the fluids.
Generally the use of carbon steel with corrosion inhibition offers a cheap CAPEX option for
corrosion control. However, downhole corrosion inhibition is a complex issue, with the need
to consider many factors, e.g. type of inhibitor, application method, level of protection,
thermal stability, compatibility etc. In addition, there are many pitfalls with the application of
this method, i.e. sand production, flow rate, etc. can all affect the effectiveness of the
corrosion inhibitor programme, logistics of inhibitor supply to remote locations needs to be
considered (whether these are remote onshore locations or subsea well sites), etc. As a result,
great care needs to be taken in the design and operation of a downhole corrosion inhibition
scheme.
For these reasons it had not been common practice within BP to consider downhole corrosion
inhibition as a design strategy, rather this has been viewed as a corrective measure in
circumstances where the specified carbon steel proved inadequate, e.g. due to changing field
conditions. The preference within BP has been to use corrosion resistant alloys in
circumstances where carbon steel proved inadequate. However, given the ever changing face
of new field developments (e.g. the development of onshore gas and oil fields, the need to
minimise capex costs) it is likely that this option will be viewed more favourably in the future.
A very important question before deciding whether to consider a downhole corrosion
inhibition scheme is Does it provide the best whole life economic option ?
For pipelines over a few kilometres in length and all but the highest corrosion rates, inhibition
is usually the most economic option. For very short pipe sections the use of corrosion resistant
alloys is the best option.
For wells the answer is not always clear cut and is dependant on several factors. This usually
simplifies to a consideration of the risks involved in using inhibitors and the cost savings vs.
the cost of failure of the inhibitor approach. For offshore wells the high cost of getting
inhibition wrong usually results in corrosion resistant alloys being selected.
Benefits of Inhibition
Where practical, the use of Inhibitors allows the use of carbon steel and thus reduces
CAPEX.
If inhibitors are to be used in the flowline and pipeline systems then moving the location of
the injection point downhole essentially provides inhibition of the well without additional
inhibitor costs.
If the actual conditions differ from those predicted the type of inhibitor can be changed to
deal with them.
Concerns with Inhibition
If corrosion rates are high then any interruption in the scheduled treatment may result in
significant damage.
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Appendix A
Delivery of the chemicals downhole is more problematic than injection into pipe lines.
Installation of delivery systems can increase CAPEX.
Handling Chemicals
May cause operational problems ( e.g. foaming, emulsions )
Corrosion monitoring and/or inspection is essential (although inspection can be difficult)
Increased OPEX.
Treatment Options
There are two types of inhibitor treatment:
Batch Treatment
Periodic treatments with the chemical are applied to the metal surface. The inhibitor forms a
film on the surface which lasts until the next treatment. This method is not preferred, as its
effectiveness is dependant solely on film persistency (determines the time between treatments)
and it requires the well to be shut-in. It should only be used when the continuous method is
not practical.
Continuous Treatment
Inhibitor is continually injected into the fluids upstream of the location of corrosion. As the
fluids contact the metal surfaces the inhibitor adsorbs onto the surface to form a protective
film. Inhibitor must always be present in the fluid for the film and therefore the protection to
be maintained. This is the preferred method of inhibition.
3.1. Batch Treatment Methods
3.1.1. Tubing Displacement
This is the most common method of treating gas wells.
1. The well is shut in.
2. A concentrated solution (1 to 10%) of inhibitor is slowly pumped down the tubing to fill it
completely.
3. Care is taken to ensure the fluid does not enter the formation.
4. The fluid is allowed to contact the tubing for several hours ( 4 -24 )
5. The well is brought back onto production
6. Treatment is repeated every 2 to 12 weeks depending on conditions
This treatment is used successfully on low productivity wells such as rod pumped oil wells in
Texas, USA. Until 1998 BP Alaska used this method for their oil wells. The repeat interval
was 12 weeks. The treatment was stopped when the film life was determined to be less than
one week.
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Appendix A
In one variation on this theme a slug (sometimes called a pill) of inhibited solution is placed
in the tubing which is then pushed down to contact all of the tubing by a solvent. This
minimises the volume of inhibitor used and potential problems encountered when the well is
returned to service and the inhibitor flows back into the production stream.
In another variation the inhibitor is dissolved in a weighted carrier fluid such as a high
density brine. This allows the inhibitor to fall to the bottom of the well under the influence
of gravity and thus minimises the volume of solvents and intervention required. There is
insufficient evidence that this method works and hence it can not be recommended.
The following batch methods are designed to provide a continuos stream of inhibitor and may
be thought of as pseudo continuous methods. They can provide longer times between
treatments.
3.1.2. Formation Squeeze
1. The well is shut in.
2. A concentrated slug of inhibitor is pushed down the tubing and into the formation.
3. The inhibitor is allowed to contact the formation rock for several hours (4 to 24).
4. The well is brought back onto production.
5. Treatment is repeated every 3 to 12 months depending on conditions.
This method is used widely for scale control. For corrosion inhibitors the concern is with
plugging the formation and it is not recommended for low porosity (tight) formations.
3.1.3. Slow Release Inhibitors
The inhibitor is encapsulated in a slow release agent such as a wax, gel or capsule. This is
usually fabricated into spheres or sticks which are dropped or placed down the tubing where
they locate at the bottom of the well (in the rat hole).
In a variation on this method a container of inhibitor (a dump bailer ) is run on a wire line to
the bottom of the well. The bailer is tripped to release the product into the bottom of the well
There is little experience with such systems.
3.2. Continuous Treatment Methods
As already stated, continuous treatment is the preferred method. However, it is essential that
regular checks be made to ensure that:
1. The product is transported throughout the entire system to be protected.
2. The inhibitor is providing the required corrosion protection
3.2.1. Capillary String (Macaroni string)
A capillary string, typically 6mm ( ) diameter, is run from the wellhead and down the
annulus space to the bottom of the well, where it is connected to an injection valve into the
tubing. This location is usually just above the packer and so tubing below this must be
resistant to corrosion or be in non corrosive service.
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Appendix A
The capillary tubing is used to inject inhibitor into the bottom of the well.
This is probably the preferred method and is used in many locations.
Problems can occur with either the capillary tubing or the injection valve becoming blocked.
The capillary strings have a reputation for being difficult to install and retrieve ( e.g. Bruce,
June 1998 ).
3.2.2. Annulus Injection
In this method an injection valve is fitted at the bottom of the well just above the packer to
allow fluid in the annulus to be pumped into the tubing. The annulus is filled with a solution of
the inhibitor which is also pumped into it on a continuous basis. As the pressure in the annulus
rises it will exceed the differential setting on the valve and product will be injected into the
tubing.
Shell use this method on many of their gas wells around the world.
There have been problems with sludge formation in the annulus and blocking of the valves
(both open and closed ).
The valves usually sit in side pockets and can be removed using a wire line.
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Appendix A
pH ISOPLOTS
10
P CO2 , bara
0.1
0.01
0.001
0.0001
-4
-3
-2
-1
Log(Pco2)
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Appendix A
pH ISOPLOTS
Condensed Water
6.00-6.50
5.50-6.00
5.00-5.50
4.50-5.00
4.00-4.50
3.50-4.00
3.00-3.50
6.50
6.00
5.50
5.00
4.50
4.00
-4
3.50
-3
3.00
120
-2
110
100
-1
90
80
Temperature, degC
70
Log(Pco2)
0
60
50
40
1
30
This case assumes no significant concentration of dissolved salts present and represents
water condensing from a wet gas.
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Appendix A
pH ISOPLOTS
8.00-8.50
7.50-8.00
8.50
7.00-7.50
8.00
6.50-7.00
7.50
6.00-6.50
5.50-6.00
7.00
5.00-5.50
6.50
4.50-5.00
6.00
4.00-4.50
5.50
3.50-4.00
5.00
3.00-3.50
4.50
-4
4.00
-3
3.50
3.00
120
-2
110
100
-1
90
80
70
Temperature, degC
Log(Pco2)
0
60
50
40
1
30
8.00-8.50
7.50-8.00
8.50
7.00-7.50
8.00
6.50-7.00
7.50
6.00-6.50
5.50-6.00
7.00
5.00-5.50
6.50
4.50-5.00
6.00
4.00-4.50
5.50
3.50-4.00
5.00
3.00-3.50
4.50
-4
4.00
-3
3.50
3.00
120
-2
110
100
-1
90
80
Temperature, degC
February 2000
70
Log(Pco2)
0
60
50
40
1
30
Page 25
S/UTG/023/00
Appendix A
pH ISOPLOTS
8.50-9.00
8.00-8.50
7.50-8.00
9.00
7.00-7.50
8.50
6.50-7.00
8.00
6.00-6.50
7.50
5.50-6.00
7.00
6.50
5.00-5.50
4.50-5.00
6.00
5.50
5.00
4.50
4.00
3.50
3.00
120
4.00-4.50
3.50-4.00
3.00-3.50
-4
-3
-2
110
100
-1
90
80
70
Temperature, degC
Log(Pco2)
0
60
50
40
1
30
8.50-9.00
8.00-8.50
7.50-8.00
9.00
7.00-7.50
8.50
6.50-7.00
8.00
6.00-6.50
7.50
5.50-6.00
7.00
6.50
5.00-5.50
4.50-5.00
6.00
5.50
5.00
4.50
4.00
3.50
3.00
120
4.00-4.50
3.50-4.00
3.00-3.50
-4
-3
-2
110
100
-1
90
80
Temperature, degC
February 2000
70
Log(Pco2)
0
60
50
40
1
30
Page 26
S/UTG/023/00
Appendix A
pH ISOPLOTS
8.50-9.00
8.00-8.50
7.50-8.00
9.00
7.00-7.50
8.50
6.50-7.00
8.00
6.00-6.50
7.50
5.50-6.00
7.00
6.50
5.00-5.50
4.50-5.00
6.00
5.50
5.00
4.50
4.00
3.50
3.00
120
4.00-4.50
3.50-4.00
3.00-3.50
-4
-3
-2
110
100
-1
90
80
70
Temperature, degC
Log(Pco2)
0
60
50
40
1
30
8.50-9.00
8.00-8.50
7.50-8.00
9.00
7.00-7.50
8.50
6.50-7.00
8.00
6.00-6.50
7.50
5.50-6.00
7.00
6.50
5.00-5.50
4.50-5.00
6.00
5.50
5.00
4.50
4.00
3.50
3.00
120
4.00-4.50
3.50-4.00
3.00-3.50
-4
-3
-2
110
100
-1
90
80
Temperature, degC
February 2000
70
Log(Pco2)
0
60
50
40
1
30
Page 27
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Appendix A
pH ISOPLOTS
9.00-9.50
8.50-9.00
8.00-8.50
7.50-8.00
9.50
9.00
8.50
8.00
7.50
7.00
6.50
6.00
5.50
5.00
4.50
4.00
3.50
3.00
120
7.00-7.50
6.50-7.00
6.00-6.50
5.50-6.00
5.00-5.50
4.50-5.00
4.00-4.50
3.50-4.00
-4 3.00-3.50
-3
-2
110
100
-1
90
80
70
Temperature, degC
Log(Pco2)
0
60
50
40
1
30
8.50-9.00
8.00-8.50
7.50-8.00
9.00
7.00-7.50
8.50
6.50-7.00
8.00
6.00-6.50
7.50
5.50-6.00
7.00
6.50
5.00-5.50
4.50-5.00
6.00
5.50
5.00
4.50
4.00
3.50
3.00
120
4.00-4.50
3.50-4.00
3.00-3.50
-4
-3
-2
110
100
-1
90
80
Temperature, degC
February 2000
70
Log(Pco2)
0
60
50
40
1
30
Page 28
S/UTG/023/00
Appendix A
pH ISOPLOTS
9.00-9.50
8.50-9.00
8.00-8.50
7.50-8.00
9.50
9.00
8.50
8.00
7.50
7.00
6.50
6.00
5.50
5.00
4.50
4.00
3.50
3.00
120
7.00-7.50
6.50-7.00
6.00-6.50
5.50-6.00
5.00-5.50
4.50-5.00
4.00-4.50
3.50-4.00
-4 3.00-3.50
-3
-2
110
100
-1
90
80
70
Temperature, degC
Log(Pco2)
0
60
50
40
1
30
9.00-9.50
8.50-9.00
8.00-8.50
7.50-8.00
9.50
9.00
8.50
8.00
7.50
7.00
6.50
6.00
5.50
5.00
4.50
4.00
3.50
3.00
120
7.00-7.50
6.50-7.00
6.00-6.50
5.50-6.00
5.00-5.50
4.50-5.00
4.00-4.50
3.50-4.00
-4 3.00-3.50
-3
-2
110
100
-1
90
80
Temperature, degC
February 2000
70
Log(Pco2)
0
60
50
40
1
30
Page 29
S/UTG/023/00
Appendix A
pH ISOPLOTS
9.00-9.50
8.50-9.00
8.00-8.50
7.50-8.00
9.50
9.00
8.50
8.00
7.50
7.00
6.50
6.00
5.50
5.00
4.50
4.00
3.50
3.00
120
7.00-7.50
6.50-7.00
6.00-6.50
5.50-6.00
5.00-5.50
4.50-5.00
4.00-4.50
3.50-4.00
-4 3.00-3.50
-3
-2
110
100
-1
90
80
70
Temperature, degC
Log(Pco2)
0
60
50
40
1
30
9.00-9.50
8.50-9.00
8.00-8.50
7.50-8.00
9.50
9.00
8.50
8.00
7.50
7.00
6.50
6.00
5.50
5.00
4.50
4.00
3.50
3.00
120
7.00-7.50
6.50-7.00
6.00-6.50
5.50-6.00
5.00-5.50
4.50-5.00
4.00-4.50
3.50-4.00
-4 3.00-3.50
-3
-2
110
100
-1
90
80
Temperature, degC
February 2000
70
Log(Pco2)
0
60
50
40
1
30
Page 30
S/UTG/023/00
Appendix A
0.1
0.01
0.001
0.0001
-4
-3
-2
-1
L o g (P c o 2)
February 2000
Page 31
S/UTG/023/00
Appendix A
55
50
45
n > 10 mm/y
n 5 - 10 mm/y
n 0 - 5 mm/y
40
35
30
25
20
15
10
-1
0
30
Log(Pco2)
-2
40
50
60
70
-3
80
90
100
110
120
Temperature, degC
130
140
-4
150
pH 3
n
n
n
n
n
n
n
n
n
n
1.0
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
-1
0.1
-2
Log(Pco2)
-3
0.0
30
40
50
60
70
80
90
100
Temperature, degC
February 2000
110
120
130
-4
140
150
Page 32
S/UTG/023/00
Appendix A
45
40
35
n > 10 mm/y
n 5 - 10 mm/y
n 0 - 5 mm/y
30
25
20
15
10
0
-1
0
30
Log(Pco2)
-2
40
50
60
70
-3
80
90
100
110
120
Temperature, degC
130
140
-4
150
pH 3.5
n
n
n
n
n
n
n
n
n
n
1.0
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
-1
0.1
-2
Log(Pco2)
-3
0.0
30
40
50
60
70
80
90
100
Temperature, degC
February 2000
110
120
130
-4
140
150
Page 33
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Appendix A
40
35
30
n > 10 mm/y
n 5 - 10 mm/y
n 0 - 5 mm/y
25
20
15
10
1
0
5
-1
0
30
Log(Pco2)
-2
40
50
60
70
-3
80
90
100
110
120
Temperature, degC
130
140
-4
150
pH 4
n
n
n
n
n
n
n
n
n
n
1.0
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
-1
0.1
-2
Log(Pco2)
-3
0.0
30
40
50
60
70
80
90
100
Temperature, degC
February 2000
110
120
130
-4
140
150
Page 34
S/UTG/023/00
Appendix A
30
25
n > 10 mm/y
n 5 - 10 mm/y
n 0 - 5 mm/y
20
15
10
1
5
0
-1
0
30
Log(Pco2)
-2
40
50
60
70
-3
80
90
100
110
120
Temperature, degC
130
140
-4
150
pH 4.5
n
n
n
n
n
n
n
n
n
n
1.0
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
-1
0.1
-2
Log(Pco2)
-3
0.0
30
40
50
60
70
80
90
100
Temperature, degC
February 2000
110
120
130
-4
140
150
Page 35
S/UTG/023/00
Appendix A
25
20
n > 10 mm/y
n 5 - 10 mm/y
n 0 - 5 mm/y
15
10
5
0
-1
0
30
Log(Pco2)
-2
40
50
60
70
-3
80
90
100
110
120
Temperature, degC
130
140
-4
150
pH 5
n
n
n
n
n
n
n
n
n
n
1.0
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
-1
0.1
-2
Log(Pco2)
-3
0.0
30
40
50
60
70
80
90
100
Temperature, degC
February 2000
110
120
130
-4
140
150
Page 36
S/UTG/023/00
Appendix A
20
15
n > 10 mm/y
n 5 - 10 mm/y
n 0 - 5 mm/y
10
1
0
-1
0
30
Log(Pco2)
-2
40
50
60
70
-3
80
90
100
110
120
Temperature, degC
130
140
-4
150
pH 5.5
n
n
n
n
n
n
n
n
n
n
1.0
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
-1
0.1
-2
Log(Pco2)
-3
0.0
30
40
50
60
70
80
90
100
Temperature, degC
February 2000
110
120
130
-4
140
150
Page 37
S/UTG/023/00
Appendix A
15
n > 10 mm/y
n 5 - 10 mm/y
n 0 - 5 mm/y
10
5
1
0
-1
0
30
Log(Pco2)
-2
40
50
60
70
-3
80
90
100
110
120
Temperature, degC
130
140
-4
150
pH 6
n
n
n
n
n
n
n
n
n
n
1.0
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
-1
0.1
-2
Log(Pco2)
-3
0.0
30
40
50
60
70
80
90
100
Temperature, degC
February 2000
110
120
130
-4
140
150
Page 38
S/UTG/023/00
Appendix A
10
n > 10 mm/y
n 5 - 10 mm/y
n 0 - 5 mm/y
5
1
0
-1
0
30
Log(Pco2)
-2
40
50
60
70
-3
80
90
100
110
120
Temperature, degC
130
140
-4
150
pH 6.5
n
n
n
n
n
n
n
n
n
n
1.0
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
-1
0.1
-2
Log(Pco2)
-3
0.0
30
40
50
60
70
80
90
100
Temperature, degC
February 2000
110
120
130
-4
140
150
Page 39
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Appendix B
February 2000
Page 40
S/UTG/023/00
Appendix B
downhole tubulars known as the alloyed martensitic 13%Cr steels. These alloys are a
development of the conventional 13%Cr steels (e.g. API 5CT L80 13%Cr steel) to which
alloying elements of nickel (typically 4 to 6%), molybdenum (typically 0.5 to 2.5%) and
possibly copper (up to 1.5%) have been added. These have a number of advantages over the
conventional 13%Cr steels, including:
Higher strength/toughness (available in strengths up to 110ksi)
Much better corrosion resistance at high temperatures (>120C)
Slightly better resistance to sulphide stress cracking under sour conditions (i.e. for
the same strength level)
These have been found to have good general (and pitting) corrosion resistance over a wide
range of conditions up to a temperature of 200C. Indeed, tests undertaken at BP Sunbury3
indicated good general (and pitting) corrosion resistance in a high chloride (120,000ppm)
solution at a pH of 3.5 and a temperature of 200C. Some manufacturers on the other hand
indicate that these alloys have good general/pitting corrosion resistance for all levels of
chlorides only up to a temperature of 175C. Therefore, given that this is a relatively new
family of materials with a potentially wide range of chemical compositions and that field
experience is relatively limited further laboratory testing will be required for specific field
applications.
2. Localised corrosion of corrosion-resistant alloys.
2.1. Pitting Corrosion.
Pitting corrosion occurs when certain regions on the metal surface become fixed anodic sites.
An example of this is the pitting of stainless steels in chloride-containing solutions. The
likelihood/rate of pitting corrosion is dependant on a number of factors, notably produced
water chemistry (particularly chloride content, pH), level of dissolved gases (CO2, H2S and
O2) and operating temperature.
However, the pitting process is strongly affected by temperature, with the propensity towards
pitting increasing with increasing temperature. The result is that for many CRAs a critical
temperature can be defined below which pitting corrosion will not be a significant risk. A
programme of work was undertaken within BP to develop a test protocol for determining the
temperature service limits for CRAs. This protocol was used to determine the temperature
service limits for two of the most commonly used CRAs for downhole tubulars, i.e. 13%Cr
steel (which has been found to be prone to pitting in the presence of hydrogen sulphide) and
25%Cr/7%Ni duplex stainless steel. Two temperatures were determined using different
techniques. In the first, an immersion test was used to determine the temperature at which pits
start to form, this was designated the onset of pitting temperature. However, it was
determined that there is a temperature range above the onset of pitting temperature over which
only non-propagating pits form, i.e. pits will form but they will not grow, such that they are
not normally harmful to the integrity of the tubulars. Therefore, an electrochemical noise
technique was developed to allow the determination of the temperature at which significant pit
growth will commence. This was designated the propagating pit temperature. Both these
temperature limits are quoted in Table B1 for a range of environments. These temperatures
can be used as the service limits for the material/environment combination, with the lower
3
Downhole Tubulars - Evaluation of the application regimes for super 13%Cr Alloys;
ESR.96.ER.008, January 1996.
February 2000
Page 41
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Appendix B
(onset of pitting) temperature limit being used for conditions where even superficial pitting is
unacceptable and the upper temperature limit being used where superficial pitting is
acceptable, as long as it will not lead to perforation. Clearly, this is not the end of the story.
Even above the temperature at which propagating pits form there is likely to be a temperature
range over which the rate of pitting is acceptable, i.e. the required service life will be
achieved. For 13%Cr steel, as an initial rough estimate the possible rate of pitting can be
evaluated using the methodology outlined for general corrosion in Section 1 of this appendix
(Appendix B). However, given the different nature of the attack it is recommended that this is
confirmed via service experience under similar conditions or laboratory tests. In the case of
duplex stainless steels the evaluation of such situations is outside the scope of the present
guidelines. If it is intended to consider these materials for use in the pitting regime region, it
will be necessary to undertake service history evaluations/laboratory tests under the specific
field conditions, to demonstrate the acceptability of the candidate materials for the intended
service duty/life.
When using Table B1 for determining the acceptability of candidate materials for the intended
service it will be necessary to know the operating temperature, downhole pH (this can be
evaluated using the Methodology outlined in Appendix A) and equivalent chloride level.
Clearly, if the intended service conditions are less onerous than those quoted in Table B1, then
the material is acceptable up to the temperature given. It is possible that it will be acceptable
to even higher temperatures than those given, if the intended service conditions are
significantly less onerous. This can only be determined by service experience on similar
conditions or a series of laboratory evaluations using the test protocols outlined in Section 4 of
this appendix (Appendix B). In addition, the use of materials other than those stated in Table
B1 will require justification via documented good previous service experience or further
testing if there is a concern about pitting corrosion.
For the alloyed martensitic 13%Cr steels (such as Sumitomos Super 13Cr alloy) tests
undertaken at BP Sunbury indicated good general pitting corrosion resistance in a high
chloride (120,000ppm) solution at a pH of 3.5 and a temperature of 200C. However, given
that this is a relatively new family of materials with a potentially wide range of chemical
compositions and given that field experience is relatively limited it may well be that further
laboratory testing will be required for specific field applications
2.2. Crevice Corrosion.
Crevice corrosion is the localised damage that can result in a narrow gap or "crevice" between
two adjacent components. Examples of crevices that can occur in downhole tubulars are at
interfaces between two joints, under deposits, in contact with downhole jewellery, etc. The
local environment produced within the crevice can be quite different to the bulk fluid
environment, leading to corrosion damage which could not be predicted from the general fluid
composition. The likelihood and rate of crevice corrosion is dependant on a large number of
factors. These include solution chemistry and service temperature, as with pitting corrosion.
However, the factors also include crevice geometry and the changes in this geometry as the
crevice develops. This makes it extremely difficult to establish the "maximum service
temperatures" to avoid crevice corrosion. Therefore, in downhole tubular designs steps need
to be taken to ensure that crevices are, as far as possible, eliminated. In this way the risk of
crevice corrosion can be minimised so that the material can be used up to the service
temperature limit indicated from a consideration of pitting corrosion.
It is recommended that the following steps are taken to minimise the risk of crevice corrosion:
(i) Use only "premium" connections with CRAs. These connections have an energised
metal/metal seal on the inner diameter that minimises the size of any crevice so formed. Good
experience has been achieved with these types of joint and problems of crevice have only been
February 2000
Page 42
S/UTG/023/00
Appendix B
observed under conditions where an unsuitable material was chosen in the first place (e.g. the
use of 13%Cr steel for sea water containing oxygen, even at low levels).
(ii) Prevent significant scale build up. Significant scale build-up, as well as possibly affecting
the well productivity by affecting the throughput of the tubulars, can lead to crevices at the
scale/metal surface interface leading in turn to crevice corrosion. Therefore, if necessary, steps
should be taken to prevent significant scale build-up, e.g. by de-scaling treatments, use of scale
inhibitors, etc.
(iii) Ensure that due consideration is given to the potentially adverse effects of crevices in the
design of any downhole jewellery and that steps are taken to minimise the number of crevices.
3. Stress corrosion cracking of corrosion-resistant alloys.
(a) 13%Cr steel and alloys
The martensitic 13%Cr steels (e.g. API 5CT L80 13%Cr Steel) are not prone to stress
corrosion cracking in downhole environments. Hence there is no need to consider the stress
corrosion cracking behaviour of these materials for downhole applications.
There have been some indications in the literature that the alloyed martensitic 13%Cr steels
(such as Sumitomos Super 13Cr alloys) may be prone to chloride stress corrosion cracking
(CSC). However, tests undertaken at Sunbury4 did not reveal any signs of CSC under typical
produced water conditions. Therefore, it is not presently envisaged that CSC will be a
problem for produced fluids with this family of materials. However, given the limited test data
and service experience, care should be taken in their application in respect of the possibility of
CSC (e.g. check with the supplier/s and/or undertake evaluations if/when necessary). In
addition very recently (i.e. in 1999) there has been a case within BP Amoco of a 95ksialloyed
martensitic 13%Cr steel tubing string suffering from cracking. This initiated from the external
surface, i.e. the surface in contact with the completion brine. This incident is still be
investigated, but at the present the most likely cause is CSC in the calcium chloride high
density completion brine. Therefore, extra care needs to be exercised in the selection of
completion brines for use with this family of materials.
(b) Austenitic Stainless Steels
In principle, the austenitic stainless steels can be prone to CSC in typical downhole
environments. This type of cracking is exacerbated by increasing temperature. It is also known
that such cracking can be exacerbated by the presence of hydrogen sulphide. The possibility of
such cracking has meant that only alloys that are very resistant to it have been selected for
downhole applications in the past. For example, the NIC 32, Sanicro 28, type alloys are often
considered for downhole tubulars in place of the cheaper and more common AISI 300 series
stainless steels. These alloys have not been widely evaluated within BP Amoco. However,
there is some limited information available from the manufacturers. For example, NKK
indicate a temperature limit for NIC-32 (22%Cr, 4.5%Mo, 32%Ni) of 175C, if CSC is to be
avoided. It is recommended that if such alloys are being considered, the relevant specialist
should be consulted.
Downhole Tubulars - Evaluation of the Application Regimes for Super 13%Cr Alloys,
ESR.96.ER.008, January 1996.
February 2000
Page 43
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Appendix B
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Appendix B
Condensed Water - for the case of gas wells. For the purpose of these tests distilled
water with 1000ppm of sodium chloride should be used.
b) Deaerate fully using oxygen free nitrogen prior to specimen immersion. Insert the
specimens, close the autoclave and re-deaerate fully by nitrogen. Purge the test solution using
the CO2 and/or H2S mixture for a period of at least one hour and then add CO2 and/or H2S up
to a suitable pressure such that at the test temperature the partial pressures of these gases
anticipated in service is achieved.
c) Heat to the test temperature (this should represent the anticipated bottom hole
temperature).
(Note: During the immersion, specimens should be kept away from direct contact with the
autoclave wall and other specimens.)
Reagents The reagents shall be high purity grades.
Acidic Gases High purity CO2 and H2S gas shall be used.
Solution Volume This shall be a minimum of 30 cc/cm2 of specimen.
Test Duration Test duration shall be kept to a minimum of 30 days.
Post Exposure Analysis The specimens shall be examined immediately after exposure and
their condition noted. They shall then be mechanically cleaned by scrubbing with a soft brush
under running water followed by the application of an appropriate cleaning solution (e.g.
inhibited acid) to remove any scale (refer to ASTM Standard G1, latest edition). Specimens
shall be dried and re-weighed to identify the weight loss. After weighing the specimens shall
be visually examined for corrosion/pitting with the aid of a stereo microscope at X40. In case
of pitting, all pits which are greater than 0.1mm diameter shall be reported. The report shall
include the number, maximum depth (mm), population per unit area of pits and pitting rate
(mm/yr).
4.2. Stress Corrosion Cracking.
The following test protocol can be used as part of the material pre-qualification process to
determine the suitability of a candidate material for the intended application with regards to
stress corrosion cracking resistance:Test Solution
The test solution shall consist of NaCl (at a concentration to simulate the level of Cl
anticipated in the produced water) + sodium acetate (CH3COONa, at a level sufficient to
buffer the pH, e.g. 0.86g/l has often been used in the past)5 in distilled or de-ionised water.
The procedure for solution preparation shall be as follows:a.
b.
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Appendix B
c.
d.
Introduce the solution into a test vessel, deaerate and saturate with a mixture of
CO2/H2S with the following gas ratios:
H2S at the partial pressure anticipated in the downhole tubulars, with the balance being CO2
up to the ambient test pressure (1 bar)
During the test the pH may alter, but shall not exceed a value 0.2 above the target figure. This
will be achieved through complete exclusion of oxygen and maintaining a sufficient solution
volume to test piece surface area ratio.
Test Temperature
The temperature shall be maintained at ambient (23oC)
Reagents
The reagents shall be in accordance with those specified in NACE TM0177-96 Section 3.
Acidic Gases
High purity H2S/CO2 gas mixtures shall be used. The test solution shall be purged with the gas
mixture throughout the test period.
Test pieces
All test pieces shall be machined from the pipe wall in the longitudinal direction
Test Vessels and Solution Volume
These shall be in accordance with those specified in NACE TM0177-96 and ISO 7539-1:
1987.
Number of Tests
A set shall comprise duplicate tests.
SSC Test Method
A smooth test piece tensile test shall be carried out in accordance with the procedures
specified in NACE TM0177-96 (Method A) and the additional requirements described in this
document.
Both types of stress fixtures and test containers used for stress corrosion testing are
acceptable; namely, constant load devices or sustained load (proof ring of spring loaded)
devices (ASTM G49-76).
Failure Appraisal
Total fracture of a test piece during the 720 hour test period shall be considered a failure.
To be considered a pass, the gauge length of the test piece shall be free from any signs of
fissure and/or cracks, after the exposure period. This may be assessed through visual
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Appendix B
examination of the gauge length (at a magnification of x10) plus one of the following
procedures: Metallographic examination of the gauge length by longitudinal sectioning and
polishing.
Fast fracturing of the test piece using a tensile test machine. Subsequent
visual examination of the gauge length for cracks. Analysis of the tensile test data and
fracture surfaces for evidence of embrittlement and/or brittle fracture.
Alternative methods may be offered for approval by BPX.
Applied Stress
The applied stress shall be 90% of the measured (actual) yield strength. The yield strength
shall be determined on a round bar test piece (Figure 4 of ASTM A370-94) using the 0.2%
offset method in ASTM A370-94.
Test pieces
The standard tensile test pieces shall be in accordance with those recommended in NACE
TM0177-96 (Method A). Where full-size test pieces can not be achieved then sub-size test
pieces in line with NACE TM-0177-96 may be used.
Test Duration
The test duration shall be 720 hours
Data Reporting
Data reporting shall include test piece geometry, test solution and conditions (temperature, gas
mixture), pH (initial and final), loading device used, test duration, test result (failure/pass) and
test piece surface appearance subsequent to test termination.
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Appendix B
TABLE B1. MAXIMUM SERVICE TEMPERATURE LIMITS FOR CORROSIONRESISTANT ALLOYS TO AVOID LOCALISED CORROSION
(a) 13% Chromium Steel
MATERIAL
13%Cr steel
13%Cr steel
13%Cr steel
13%Cr steel
13%Cr steel
13%Cr steel
13%Cr steel
13%Cr steel
13%Cr steel
WELL
CONDITIONS
6,000ppm Chloride
pH = 4.5*
pH2S = 0.001 bara
30,000ppm Chloride
pH = 4.5*
pH2S = 0.001 bara
120,000ppm Chloride
pH = 4.5*
pH2S = 0.001 bara
6,000ppm Chloride
pH = 4.5*
pH2S = 0.01 bara
30,000ppm Chloride
pH = 4.5*
pH2S = 0.01 bara
120,000ppm Chloride
pH = 4.5*
pH2S = 0.01 bara
6,000ppm Chloride
pH = 4.5*
pH2S = 0.1 bara
30,000ppm Chloride
pH = 4.5*
pH2S = 0.1 bara
120,000ppm Chloride
pH = 4.5
pH2S= 0.1bara
MAXIMUM
TEMPERATURE LIMITS
(oC)
Onset of
Pitting
Pit
Propagation
100
140 (GC**)
110
140 (GC**)
120
140 (GC**)
120
130 (P)
120
130 (P)
120
130 (P)
120
120 (P)
120
120 (P)
120
120 (P)
* Note that at pH levels lower than 4.5 13%Cr steels are liable to general corrosion over the
whole temperature range. In the case of general corrosion the likely rate of attack can be
assessed using the methodology outlined in Section 1 of Appendix B.
** For 13%Cr steel "significant attack" is likely to occur either as pitting corrosion (P) or
general corrosion (GC). The likely rate of general corrosion attack can be assessed using the
methodology outlined in Section 1 of Appendix B.
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Appendix B
MATERIAL
25%Cr/7%Ni
duplex stainless
steel
25%Cr/7%Ni
duplex stainless
steel
25%Cr/7%Ni
duplex stainless
steel
25%Cr/7%Ni
duplex stainless
steel
25%Cr/7%Ni
duplex stainless
steel
25%Cr/7%Ni
duplex stainless
steel
25%Cr/7%Ni
duplex stainless
steel
25%Cr/7%Ni
duplex stainless
steel
25%Cr/7%Ni
duplex stainless
steel
February 2000
WELL
CONDITIONS
6,000ppm Chloride
pH = 3.5
pH2S = 0.001 bara
30,000ppm Chloride
pH = 3.5
pH2S = 0.001 bara
120,000ppm Chloride
pH = 3.5
pH2S = 0.001 bara
6,000ppm Chloride
pH = 3.5
pH2S = 0.01 bara
30,000ppm Chloride
pH = 3.5
pH2S = 0.01 bara
120,000ppm Chloride
pH = 3.5
pH2S = 0.01 bara
6,000ppm Chloride
pH = 3.5
pH2S = 0.1 bara
30,000ppm Chloride
pH = 3.5
pH2S = 0.1 bara
120,000ppm Chloride
pH = 3.5
pH2S = 0.1 bara
MAXIMUM
TEMPERATURE LIMITS
(oC)
Onset of
Pitting
Pit
Propagation
180
200
160
200
140
200
170
200
140
180
140
180
140
180
130
170
130
170
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Appendix C
Partial Pressure of
Hydrogen Sulphide (psia)
Sour Environment
(YES/NO)
<65
<0.05
NO
<65
>0.05
NO
>65
<0.05
NO
>65
>0.05
YES
Partial Pressure of
Hydrogen Sulphide
in the gas phase
(psia)
Sour Environment
(YES/NO)
<265
<0.05
<15
NO
<265
>0.05, <10
<15
NO
>265
<0.05
<15
NO
>265
>0.05
YES
>10
YES
>15
YES
From the Tables, 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 Tables
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 firstly a gas well, the information required is the bottom hole pressure and the
mole (or volume) fraction of hydrogen sulphide in the gas. The partial pressure is then
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Appendix C
calculated simply by multiplying the mole fraction of hydrogen sulphide in the gas by the
bottom hole pressure. For example, for a 5500m deep gas well with a bottom hole pressure of
14,000 psi and a hydrogen sulphide content of 5 ppm mole, the partial pressure of hydrogen
sulphide would be 0.07 psia (5/1,000,000 * 14,000), i.e. 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.
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Appendix D
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Appendix D
For operating
temperatures 65oC
or greater (2)
For operating
temperatures
80oC or greater
(2)
For operating
temperatures
107oC or
greater (2)
Proprietary grades
Per NACE MR-0175
Section 10.2.
Proprietary Q + T
grades with 110ksi or
less maximum yield
strength
Proprietary Q + T
grades with 140ksi
or less maximum
yield strength.
February 2000
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Appendix D
applicable to all likely operating temperatures (Note: This methodology need not be applied to
the traditional sour-resistant grades in API 5CT [i.e. L80, C90, T95] which it is assumed are
suitable for all sour conditions on the basis of past experience and test data).
To apply the BP AMOCO methodology, it is necessary to know certain information about the
proposed well, i.e. the partial pressure of hydrogen sulphide in the gas phase, and the in-situ
pH of the water associated with the produced fluids. As an in-situ pH is not usually available,
the methodology outlined in Appendix A 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. If the operating conditions fall within the acceptable domain then the material can be
considered to have an acceptable resistance to SSC under the prevailing conditions. However,
if the operating conditions fall within the unacceptable domain then it will be necessary to
consider a material with greater SSC resistance.
Domain diagrams are included for 95ksi alloyed martensitic 13%Cr steels (e.g. Super 13Cr;
Hyper 13Cr). These alloys do not represent a distinct chemical composition, but rather are
comprised of a family of alloys with differing chemical compositions (varying between
manufacturers) and hence often having differing sour resistance. For this reason, it has not
been possible to develop a simple go no go domain chart. Therefore, for ease of
interpretation, charts with three domains have been developed. These three domains represent:
Acceptable (Green for go) - the material is satisfactory for the proposed
application.
Unacceptable (Red for no go) - the material is unsuitable for the proposed
application and an alternative material with greater SSC resistance should be
considered.
Further Assessment Required (Yellow for caution) - to assess whether the
material is suitable for the intended application or not, further assessment is required
in the form of consideration of specific pre-qualification data for the
alloy/manufacturer being considered, reference to relevant past test data (e.g. for a
similar application), application specific testing.
In addition, tests in BP Amoco have demonstrated that the level of chloride is very important,
as increased chloride levels significantly reduces the sulphide stress cracking resistance of the
materials. Therefore domain diagrams have been developed for both high chloride (typical of
produced water in oil/gas wells) and low chloride (typical of condensing water in gas wells)
conditions. For intermediate chloride levels two courses of action are available:
Default to the high chloride domain diagram
Produce/use test data (pre-qualification) for the specific application that
demonstrates acceptability.
With regards to the effect of chloride content, the present domain diagrams seem to infer that
the 110ksi materials perform better in condensing water conditions. This most probably
reflects the improvements in material chemistry and manufacturing methods between the two
sets of tests (the 95ksi materials were tested in 1995 and the 110ksi materials were tested in
1998, a time period which saw significant improvements in the manufacturing methods,
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Appendix D
control of chemistry for these materials). Instinctively, if anything, the 95ksi material should
outperform the 110ksi material. Therefore, it is recommended that manufacturers are
requested to retest the 95ksi materials in low (1000ppm) chloride conditions if intended for
use in gas wells where only condensing water will be present and where the partial pressure of
H2S is such that it would be in an acceptable regime on the attached Regime charts for the
110ksi material but not for the 95ksi material.
Given the wide range of proprietary 'super 13Cr alloys' now available on the market, it has not
been possible to test all those available. Rather, a few representative materials have been
tested. A Qualification Procedure has been developed on the basis of the present results6. It is
recommended that all manufacturers are requested to qualify their material using this
Qualification Procedure prior to using the material in BP Amoco. This will ensure that, as a
minimum, their material conforms with the attached Domain Diagrams. If uncertain whether
the prospective manufacturers material has already been pre-qualified contact the relevant
specialist within BP AMOCO.
It should be noted that the domain diagrams are not all encompassing, but only deal with
resistance to SSC. Before making the final selection of production tubular material, it will be
necessary to consider many other corrosion-related factors. For example, resistance to
general/localised corrosion, stress corrosion cracking resistance, etc. under the prevailing
conditions. These aspects are covered elsewhere in these Guidelines.
In addition, it should be noted that the assessment of the resistance of duplex stainless steels to
SSC and stress corrosion cracking (SCC) is considered further in Appendix B. As a result of
their unique duplex structure consisting of a combination of austenite and ferrite in
approximately equal volume fractions, they are prone to a number of unique cracking
mechanisms. These can consist of either a combination of sulphide stress corrosion cracking
(of the ferrite phase) and chloride stress corrosion cracking (of the ferrite and austenite
phases) or selective corrosion of the ferrite phase leading to crack-like defects.
4. Simplified Test Protocol.
The following test protocol can be used as part of the material pre-qualification process to
determine the suitability of a candidate material for the intended application with regards to
sulphide stress cracking resistance:Test Solution
The test solution shall consist of NaCl (at a concentration to simulate the level of Cl
anticipated in the produced water) + sodium acetate (CH3COONa, at a level sufficient to
buffer the pH, e.g. 0.86g/l has often been used in the past)7 in distilled or de-ionised water.
The procedure for solution preparation shall be as follows:a.
b.
Super 13%Cr Alloy Seamless Tubing Pre-qualification Assessment, J W Martin & R G MacCuish,
April 1999.
7
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Appendix D
c.
d.
Introduce the solution into a test vessel, deaerate and saturate with a mixture of
CO2/H2S with the following gas ratios:
H2S at the partial pressure anticipated in the downhole tubulars, with the balance being CO2
up to the ambient test pressure (1 bar)
During the test the pH may alter, but shall not exceed a value 0.2 above the target figure. This
will be achieved through complete exclusion of oxygen and maintaining a sufficient solution
volume to test piece surface area ratio.
Test Temperature
The temperature shall be maintained at ambient (23oC)
Reagents
The reagents shall be in accordance with those specified in NACE TM0177-96 Section 3.
Acidic Gases
High purity H2S/CO2 gas mixtures shall be used. The test solution shall be purged with the gas
mixture throughout the test period.
Test pieces
All test pieces shall be machined from the pipe wall in the longitudinal direction
Test Vessels and Solution Volume
These shall be in accordance with those specified in NACE TM0177-96 and ISO 7539-1:
1987.
Number of Tests
A set shall comprise duplicate tests.
SSC Test Method
A smooth test piece tensile test shall be carried out in accordance with the procedures
specified in NACE TM0177-96 (Method A) and the additional requirements described in this
document.
Both types of stress fixtures and test containers used for stress corrosion testing are
acceptable; namely, constant load devices or sustained load (proof ring of spring loaded)
devices (ASTM G49-76).
Failure Appraisal
Total fracture of a test piece during the 720 hour test period shall be considered a failure.
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Appendix D
To be considered a pass, the gauge length of the test piece shall be free from any signs of
fissure and/or cracks, after the exposure period. This may be assessed through visual
examination of the gauge length (at a magnification of x10) plus one of the following
procedures: Metallographic examination of the gauge length by longitudinal sectioning and
polishing.
Fast fracturing of the test piece using a tensile test machine. Subsequent
visual examination of the gauge length for cracks. Analysis of the tensile test data and
fracture surfaces for evidence of embrittlement and/or brittle fracture.
Alternative methods may be offered for approval by BPX.
Applied Stress
The applied stress shall be 90% of the measured (actual) yield strength. The yield strength
shall be determined on a round bar test piece (Figure 4 of ASTM A370-94) using the 0.2%
offset method in ASTM A370-94.
Test pieces
The standard tensile test pieces shall be in accordance with those recommended in NACE
TM0177-96 (Method A). Where full-size test pieces can not be achieved then sub-size test
pieces in line with NACE TM-0177-96 may be used.
Test Duration
The test duration shall be 720 hours
Data Reporting
Data reporting shall include test piece geometry, test solution and conditions (temperature, gas
mixture), pH (initial and final), loading device used, test duration, test result (failure/pass) and
test piece surface appearance subsequent to test termination.
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Appendix E
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Appendix E
Erosion Guidelines Revision 2.1 (1999), J W Martin, Sunbury Report No. S/UTG/102/99, October
1999)
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Appendix E
Summary guidance for evaluating erosional velocity limits is given in Section 2.1. below.
These indicate the erosional velocity limits for which the rate of erosion will be 0.1mm/yr or
less. Three main categories for solids content are used in these guidelines:
Totally solids free The flow streams are such that there is no risk of solids being
transported in the fluids. It should be noted that even very low levels of solids can cause
significant wastage (erosion or erosion/corrosion) rates. Hence it is very important to be sure
there is no risk of solids entrainment before using these limits.
Nominally solids free less than 1pptb (lbs per thousand barrels) for liquid systems, less
than 0.1lb/mmscf for gas systems; no solids detectable.
Solids present Solids detectable in the system. In this case the levels of solids will need
to be known, or appropriate assumptions made regards their likely level.
2.1. Evaluation of Velocity Limits.
The following criteria indicate the maximum velocity limit to obtain an estimated rate of
erosion of 0.1 mm/yr. or less.
Totally Solids Free Duties:
Non Corrosive
Single Phase (liquid/gas) - no velocity limits for avoidance of erosion
Multiphase - limit velocity to 70m/s to avoid droplet/gas bubble impingement
erosion.
Corrosive
Single Phase Liquid - no velocity limits for avoidance of erosion
Un-inhibited wet gas/multiphase10 - limit velocity to 70m/s to avoid droplet/gas
bubble impingement erosion.
Inhibited carbon steel wet gas/multiphase - use the API RP14e11 equation with
C=200 or 20m/s (whichever is lower).
Nominally Solids Free Duties:
Single Phase Liquid - use the API RP14e7 equation with C=250 for carbon steel;
C=300 for 13Cr steel and C=450 for duplex stainless steel.
Multiphase - use the API RP14e7 equation with C=135 for carbon steel; C=300 for
13Cr steel and C=350 for duplex stainless steel.
10
For carbon steel it is assumed that the fluid has sufficiently low corrosivity to justify its use and is
un-filmed (i.e. no carbonate film). For carbonate filmed carbon steel (see Section ????) use the
inhibited flow velocity limits.
11
API RP14e equation is: Maximum Allowable Velocity (ft/sec) = C/(mixture density in lb/ft3)0.5
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Appendix E
Single Phase Gas - Evaluate using the Erosion Rate models in the Erosion
Guidelines5. Assume a solids production rate of 0.1lb/mmscf if no specific data
available.
Solids Containing Duties:
It is not possible to define a rational flow velocity for all possible operating conditions
below which the rate of erosion will be below 0.1 mm/yr. Therefore, it will be
necessary to undertake an assessment of the likely erosion rate/acceptable flow
velocities on a case by case basis using the relevant erosion rate models from the
Erosion Guidelines5.
If the anticipated maximum flow rate is less than the critical velocity calculated using the
information above, the effect of high fluid flow rates and/or sand erosion need not be
considered further. However, if the maximum flow rate is greater than the critical velocity then
significant wastage may result. In this case further consideration of the likely wastage rates
resulting from erosion/erosion-corrosion will be required. In the first instance reference should
be made to the BP Amoco Erosion Guidelines5.
3. Galvanic Corrosion
This is the preferential corrosion that can occur to one of the metals when two different metals
are electrically coupled in a corrosive environment. In such a couple one of the metals will act
as an anode (i.e. it will corrode at an enhanced rate) and the other will act as a cathode (i.e.
there will be a certain degree of protection). The susceptibility of a material couple towards
galvanic corrosion of the 'anodic' metal 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 magnitude of the potential difference between the two metals in the corrosive
environment.
In general, downhole tubular systems should be designed to eliminate galvanic cells where
possible. For the purposes of downhole materials selection galvanic corrosion should be
considered a potential problem if there is a corrosion-resistant alloy (CRA)/carbon steel
interface. However, if such interfaces do not occur then the problem of galvanic corrosion can
be discounted.
If galvanic corrosion between CRA jewellery and carbon steel tubulars is a concern,
consideration should be given to installing an internally coated CRA between the components.
In general, 9Cr-1Mo or 13%Cr steel against C-steel is not a concern, the major concern is for
the higher metallurgies, e.g. nickel alloys, against carbon steel.
If there is a concern about any material combination that occurs in a downhole tubular design
the relevant specialist/s should be consulted.
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Appendix E
INDIVIDUAL ALLOY "GO/NO GO" CHARTS SULPHIDE STRESS CRACKING AND STRESS CORROSION CRACKING
PERFORMANCE DOMAINS
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Appendix E
Solution pH
6.5
Acceptable
5.5
4.5
Unacceptable
3.5
0.003
0.001
0.01
0.1
1.0
10
pH2S (bara)
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Appendix E
Solution pH
6.5
Suitable
Acceptable
5.5
4.5
Unsuitable
Unacceptable
3.5
0.003
0.001
0.01
0.1
1.0
10
pH2S (bara)
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Appendix E
Solution pH
6.5
Suitable
Acceptable
5.5
4.5
Unsuitable
Unacceptable
3.5
0.003
0.001
0.01
0.1
1.0
10
pH2S (bara)
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Appendix E
6.5
Solution pH
Acceptable
5.5
4.5
Further Assessment
Required
3.5
Unacceptable
0.001
0.01
0.1
1.0
10
pH2S (bara)
Domain diagram for the Sulphide Stress Cracking Limits
of 95ksi Super 13Cr Alloys in low Chloride (1000 ppm Cl-) Waters
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Appendix E
6.5
Solution pH
Acceptable
5.5
4.5
Further Assessment
Required
Unacceptable
3.5
0.001
0.01
0.1
1.0
10
pH2S (bara)
Domain diagram for the Sulphide Stress Cracking Limits
of 95ksi Super 13Cr Alloys in High Chloride (120,000 ppm Cl-) Waters
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Appendix E
Solution pH
6.5
Acceptable
5.5
4.5
Further Assessment
Required
Unacceptable
3.5
0.02
0.001
0.01
0.1
1.0
10
pH2S (bara)
Domain diagram for the Sulphide Stress Cracking Limits
of 22Cr Duplex Stainless Steel
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Appendix E
Solution pH
6.5
5.5
Acceptable
0.5
4.5
Further Assessment
Required
Unacceptable
0.25
3.5
0.001
0.01
0.1
1.0
10
pH2S (bara)
Domain diagram for the Sulphide Stress Cracking Limits
of 25Cr Duplex Stainless Steels
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Appendix E
6.5
Acceptable
Solution pH
Further Assessment
Required
5.5
4.5
3.5
Unacceptable
0.001
0.01
0.1
1.0
10
pH2S (bara)
Domain diagram for the Sulphide Stress Cracking Limits
of 110ksi Super 13Cr Alloys in High Chloride (120,000 ppm Cl) Waters
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Appendix E
Solution pH
6.5
5.5
Further Assessment
Required
Acceptable
4.5
3.5
Unacceptable
0.001
0.01
0.1
1.0
10
pH2S (bara)
Domain diagram for the Sulphide Stress Cracking Limits
of 110ksi Super 13Cr Alloys in Low Chloride (1000 ppm Cl-) Waters
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Appendix E
Solution pH
6.5
Acceptable
5.5
4.5
Further Assessment
Required
Unacceptable
3.5
0.003
0.001
0.01
0.1
1.0
10
pH2S (bara)
Domain diagram for the Sulphide Stress Cracking Limits
of API5CT L80 13Cr Steel
February 2000
Page 72