OTC 20995

Material Assessment for Souring Subsea Systems

R.T. Hill, F.A. Ramirez, and S. Martinez, UniversalPegasus

Copyright 2010, Offshore Technology Conference

This paper was prepared for presentation at the 2010 Offshore Technology Conference held in Houston, Texas, USA, 36 May 2010.
This paper was selected for presentation by an OTC program committee following review of information contained in an abstract submitted by the author(s). Contents of the paper have not been
reviewed by the Offshore Technology Conference and are subject to correction by the author(s). The material does not necessarily reflect any position of the Offshore Technology Conference, its
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reproduce in print is restricted to an abstract of not more than 300 words; illustrations may not be copied. The abstract must contain conspicuous acknowledgment of OTC copyright.

Abstract
Material selection for subsea pipelines and equipments for the cases where the well fluid analysis shows
elevated levels of H2S (sour service) has been extensively studied and documented during the past years.
However, several cases have been reported where the fluid analysis at the start up stage does not show
evidence of H2S but the risk of sour production is still present. There are two main causes for this to occur:
1) typically, the resolution of the gas composition measurement is only valid down to 0.01 mole% (100 ppm)
leaving the possibility of H2S being present in amounts between 0-99 ppm presenting potential sour
conditions for high pressure systems. 2) The H2S contents can increase during production when water
injection systems are used to pressure-support the production reservoir. Seawater injection increases the
H2S levels on the fluid due to microbial activity.
This paper addresses the risk associated with sour systems which were not designed for such service. The
paper presents a project specific study where the presence of H2S was determined after the system was
built. A material risk assessment was performed to determine the suitability of the system. The purpose is to
share the lessons learned and to provide guidelines for the material assessment of souring production
systems.

Introduction
Corrosion produced by hydrogen sulfide (H2S) in oil and gas production, referred to as sour corrosion, has
been recognized and extensively studied for several years. The presence of H2S in the produced fluids not
only generates general corrosion but also can lead to hydrogen embrittlement and cracking making the
material prone to catastrophic failure. When the produced fluid is regarded as sour, the risk of hydrogen
embrittlement failures due to sulfide stress cracking (SSC) or hydrogen induced cracking (HIC) may support
the selection of highly priced materials reflected in abundant cost penalty on the initial capital expenditure
(CAPEX) [1,2].
Several systems on the North Sea and Gulf of Mexico have been designed for sweet service (i.e. H2S is not
present) since the fluid analysis at the start up stage did not show evidence of H2S. However, it has been
reported that several of these systems have experienced the presence of H2S afterwards [2-5]. There are
two main reasons for this to occur:
1) Usually, the gas composition measurement resolution is only valid down to 0.01 mole% (100 ppm) and,
therefore, there is the possibility of H2S being present in amounts between 0-99 ppm presenting potential
sour conditions for high pressure systems.

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2) When water is injected into the production reservoir to pressure support it and extend its productivity life,
the reservoir can sour. Water injection may support the reservoir souring as follows: introducing abundant
source of sulfate from seawater, supplying nutrients from seawater or produced water if it is re-injected, and
reducing the salinity of the reservoir (since salinity represents a difficult environment for bacterial growth)
[6]. In the last years, a number of potential souring mitigation and prevention tools have been analyzed
including sulfate removal units, biocide injection treatments, and nitrate/nitrite injection treatments [4].
The purpose of this paper is to address the risk associated with sour systems which are not designed for
such environments. The paper presents a project specific study where the presence of H2S was determined
after the system was built and therefore, the system was designed based on sweet service. A material risk
assessment was performed to determine the suitability of the system.

Wet Hydrogen Sulfide Corrosion and Cracking

Corrosion and Cracking Mechanisms:
The corrosion of steel associated with the presence of wet hydrogen sulfide is referred to as sour corrosion.
In environments with high levels of H2S, the steel reacts with the hydrogen sulfide as follows:
Anodic Reaction
2

(1)

Dissociation Reaction
(2)
(3)
Overall Reaction
(4)

The corrosion mechanism involves the formation of an iron sulfide film on the steel surface, being
mackinawite the predominant film [7]. Compared to CO2 corrosion (or sweet corrosion) which can cause
severe general corrosion of steels, H2S corrosion is more localized and can lead to sulfide stress cracking
(SSC) and hydrogen induced cracking (HIC). H2S may not necessarily be reflected in high corrosion rates
but rather makes materials prone to catastrophic failure.
SSC and HIC are brittle mechanical fractures caused by diffusion and penetration of atomic hydrogen into
the crystal structure of an alloy. The H+ ions present in the acidic solution combine at the cathode with
electrons, released by the steel, to form atomic hydrogen on the steel surface as follows:
2

(atomic hydrogen)

(5)

Normally, the adsorbed hydrogen at the surface of the steel will recombine to form hydrogen gas (H2).
However, the sulfide ions will poison the recombination of hydrogen atoms thus promoting hydrogen atoms
diffusion into the steel. Diffused hydrogen atoms are trapped at sensitive microstructural locations.
This process is most severe at temperatures between 20 F to 120 F. Since diffusion is a thermally
activated process, below 20 F the diffusion rate of the atomic hydrogen is low and the critical concentration
is not achieved. On the other hand, above 120 F the atomic hydrogen diffusion rate is high and therefore
some of the atomic hydrogen is not trapped in the metal making it less susceptible to SSC and HIC.

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The main differences between SSC and HIC are shown in Table 1.

Table 1: Difference between SSC and HIC

FEATURES

SSC

HIC

SSC is a form of hydrogen

embrittlement in which cracking is
caused by the dissolution of hydrogen
into the steel while subject to tensile
stress

HIC is a form of hydrogen

embrittlement in which hydrogen
diffuses into the material and
recombines as gaseous hydrogen and
colects at inclusions, stringers, or
other microstructural defects where it
produces and internal pressure

Stress dependent

Stress independent

Generally, cracking occurs in high

strength materials

Cracking occurs in both high and low

strength material

SUSCEPTIBLE
LOCATIONS /
HYDROGEN
DIFFUSION

In the metal, hydrogen atoms diffuse

and are trapped at regions of high
triaxial tensile stress, high hardness, or
at some microstructural configurations

In the metal, hydrogen atoms diffuse

and are trapped at non-metallic
inclusions, and bands of hard
microstructures

PARAMETERS
AFFECTING SSC AND
HIC

- pH level
- Cl-, CO2, and H2S concentrations
- Chemistry and microstructure
- Hardness of steel
- Applied and residual stresses
- Pressure and temperature
- Flow rate of the solution present

- pH level
- Cl-, CO2, and H2S concentrations
- Chemistry and microstructure
- Pressure and temperature
- Flow rate of the solution present

PREVENTION

Control material hardness, strength and

residual stresses.

Control material quality,

microstructural defects, non-metallic
inclusions, etc.

TYPICAL PREVENTION
AND TESTING
STANDARDS

- NACE TM0177 [8]

- NACE MR0175/ISO 15156 [10]

- NACE TM0284 [9]

DESCRIPTION

STRESS DEPENDENCY

Prevention and Testing Standards:

Sulfide stress cracking is controlled by factors such as: material chemical composition, strength, heat
treatment, and microstructure; environmental hydrogen ion concentration (pH), H2S, CO2, and Cl
concentrations; temperature, total pressure, and applied and residual stresses. Prevention of SSC is
accomplished by selecting the correct material and fabrication practice.

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To prevent SSC damage, criteria have been specified for the manufacture and selection of high strength
alloys by industrial organizations such as NACE and ISO. The level at which a fluid is regarded as sour is
defined by NACE MR0175/ISO 15156 [10]as a partial pressure of H2S of 0.05 psi.
The severity of the sour environment, determined in accordance with NACE MR0175/ISO 15156 with respect
to SSC of a carbon or low alloy steel is assessed using Figure 1 below:

Figure 1: Regions of environmental severity with respect to SSC of

carbon and low alloy steels [10]
SSC Region 0: Generally, no precautions are required regarding corrosion due to H2S.
SSC Region 1-3: These regions represent the severity of the exposure environment, with Region 3 being the
most severe of the environments.
Also, for the evaluation of the metals resistance to SSC, NACE developed the standard test method TM0177
[8] where stressed test specimens are immersed in acidified aqueous environments containing H2S.
To evaluate the resistance of pipeline and pressure vessel plate steels to HIC, NACE has developed the
standard test method MT0284 [9]. The test method consists of exposing unstressed test specimens to one of
the two standard solutions, either solution A, a sodium chloride, acetic acid solution saturated with H2S at
ambient temperature and pressure, or Solution B, a synthetic seawater solution saturated with H2S at ambient
temperature and pressure. After the specified time, the specimens are removed and evaluated against NACE
cracking criteria.

Fit for Purpose Assessment

This section presents a project specific case where the subsea system was not designed and built for sour
service but the possible presence of H2S was noticed afterwards. A material/risk assessment criterion was
addressed for this case study.
The project was developed in the Gulf of Mexico at a water depth of 4,000 ft. In the current phase, a single
subsea well tie-back produces to an existing platform using a 4-inch nominal size rigid pipeline and a 4-inch
I.D. flexible riser. The pipeline route length from the well to the platform location is around 10 miles and the
flexible riser length is approximately 1.9 miles. The system maximum allowable operating pressure (MAOP)
is 11,500 psi.

OTC 20995

During the design phase, the analysis of the fluid composition for the project did not show evidence of H2S.
Nevertheless, the resolution of the gas composition measurement was only valid down to 0.01 mole % (100
ppm). Therefore, there is the possibility of H2S being present in amounts between 0-99 ppm. The shut-down
pressure of the system is 11,500 psi and the operation pressure is 5,000 psi. However, the assessment of H2S
corrosion should be based on a liquid phase wherein the partial pressure of H2S is based on the bubble point
pressure at the operating temperature, i.e. 4,800 psi at 175 F. Due to the high, pressure the possibility of
having sour service is present (i.e. per NACE MR0175/ISO 15156 [10] if the H2S partial pressure is greater
than 0.05 psi, the environment is considered sour).
The parameters considered for this case are shown in Table 2.

Table 2: Parameters for H2S corrosion assessment.

PARAMETER

VALUE

Pressure (psi)
@ 175 F

4,850

H2S (%)

0.0099

pp H2S (psi)

0.48

CO2 (%)

0.07

pp CO2 (psi)

3.4

Bicarbonate (mg/L)

376

pH

6.5

Based on the information provided in Table 2, the project studied can be considered sour service. In fact,
due to the high pressure, H2S contents as low as 0.0010% (10 ppm) will be reflected in sour conditions.
Since all the components (e.g. pipeline, riser, valves, connectors, etc.) were fabricated and purchased
based on sweet (no H2S) conditions, a risk evaluation was performed to determine the suitability of those
components for sour service as outlined below. It is a company standard to request and keep all relevant
documents and procedures pertaining to the purchased components. This information indicates material
parameters such as hardness, welding procedures, heat treatments, etc. that were used for the
assessment. Due to the current manufacturing practices and specified quality control programs, the risk of
SSC takes precedence over HIC.
After the evaluation of all the documentation for the components, it was concluded that the system, initially
designed for sweet service, was suitable for the possible sour conditions as indicated below.

Carbon Steel Pipeline:

Purchased Material
Seamless carbon steel: 5.563 O.D x 0.750 W.T. Grade X65
Material Suitability
Per NACE/ISO [10] criteria (Figure 1), the SSC severity for carbon steel is defined by region 1.
these conditions, the requirements for carbon steel are:

Under

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- Carbon steel requires appropriate restricted chemistry to ensure good weldability.

- SMYSs of up to 80 ksi have proven acceptable.
- Fabrication and field weld hardness should not exceed 300 HV10.
The purchased carbon steel pipeline and girth welding process is suitable for sour service as indicated
below:
- The product chemistry reported on the material test reports (MTRs) satisfies the requirements of API
5L/ISO 3183 (Appendix H) [11] for sour service. The reported sulfur content, 0.0006 %, is much lower than
the specified by the mentioned standards, 0.003 %.
- The flowline welding procedure was qualified using project pipe and no problems were encountered during
welding qualification and production. The maximum reported hardness for the base metal, weld, and heat
affected zone was 250 HV10.

Riser:
Purchased Material
4.0 I.D Flexible Riser rated for 15,000 psi
- Carcass: Duplex 2304
- Inner Layer: PA 11 Polymer
- High Strength Wires: carbon steel 145 ksi and 203 ksi
- Outer Layer: Proprietary polymer
Material Suitability
There is a high risk failure on risers since the fatigue resistance of the steel is significantly degraded in the
presence of H2S. As a result of SSC the endurance limit decreases and the fatigue crack growth rate
increases. These knock-down factors need to be considered in the riser design.
Some studies [12-14] have reported the effects of sour environments on crack propagation rates for
carbon steel pipelines. Reference [12] compares crack propagation rates over a range of different stress
intensity factors for tests carried out in air to those carried out in a sour environment (1 psi H2S partial and
a pH of 3.5). For the test carried out in sour environment, crack growth rates were typically a factor of 30
higher than in air.
Reference [12] compares crack propagation rates for a constant stress intensity factor (approx. 8 ksi
(in)0.5). For the test carried out in sour environments, the crack propagation rate was initially (when the
falw size is from78 to 157 mils) a factor of between 30 to 130 times higher than in air, but was reduced to
a factor of between 5 to 12 times higher than in air by the end of the test (when the flaw size is from 236
to 394 mils).
Regarding SSC and HIC, flexible risers present advantages over steel catenary risers (SCR). The main
advantage of the flexible riser is that only a small portion of the H2S gas permeates through the inner
polymer layer and, therefore, the high strength wires, which are the load carrying members, experience
lower H2S concentration than the SCRs.
The flexible riser manufacturer for this project validated and confirmed that the flexible riser is suitable for
sour service region 1 based on modeling the H2S permeation through the inner layer, and performing HIC
and SSC testing of the high strength wires under this environment.

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Valves
Purchased Material
2.0 and 4.0 gate valves rated to 15,000 psi.
- Body: 4130 Cr-Mo low alloy steel (75 ksi SMYS)
- Gate: 410 stainless steel
- Stem: 17-4PH stainless steel
- Seat: 410 stainless steel

Material Suitability
- Per NACE/ISO [10] criteria for region 1 (Figure 1), the AISI 41XX Cr-Mo low alloy steel (4130 and 4140)
should be in the quenched anf tempered condition, the SMYS should be 110 ksi, the maximum yield
strength should be 130 ksi, and the maximum hardness should be 30 HRC (or approximately 300 HV10).
The MTR for the 4130 material indicates that the material is suitable for sour service since it satisfies the
parameters given above.
- NACE/ISO [10] acceptance criteria for the 410 SS material used for the gate and seat is as follows: the
410 SS shall have a maximum hardness of 22 HRC under any combination of temperature, H2S partial
pressure, and chloride concentration. Additionally, the material shall be heat treated following the code
recommendations (i.e. double tempering process). The documentation submitted by the valve vendor
indicated that the material complies with code requirements.
- NACE/ISO [10] acceptance criteria for the 17-4PH used for the steam is as follows:
The H2S partial pressure should be maximum 0.5 psi. Additionally, the precipitation hardening martensitic
steel shall have a maximum hardness of 33 HRC and shall be heat treated following NACE/ISO [10]
standard requirements (i.e. double age-hardening process). Again, the documentation submitted by the
valve vendor indicated that the material complies with the code requirements.

Flowline Connectors:
Purchased Material
4 clamp type flowline connectors rated to 15,000 psi.
- Body: 4130 Cr-Mo low alloy steel (75 ksi SMYS)
- Ball: 4140 Cr-Mo low alloy steel (90 ksi SMYS)
- Seal: 17-4PH stainless steel

Material Suitability
- The documentation provided by the flowline connectors showed that the 4130, 4140, and 17-4PH
materials used in the project satisfied the code requirements [10] (see section 3.3)

Other Materials and Components

The material selection for the well casings, tubular, etc was not part of the company scope. However, the
responsible company has performed an assessment to ensure the suitability of these materials under the
possible sour conditions.

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Conclusions
Systems that initially were not believed to be sour can be or become sour. There are two main reasons
for this to occur: 1) Frequently, the resolution of the gas composition measurement is only valid down to
0.01 mole% (100 ppm) and therefore H2S can bepresent in amounts between 0-99 ppm presenting
potential sour conditions for high pressure systems. 2) The H2S contents can increase during production
when water injection systems are used to pressure-support the production reservoir. Seawater injection
increases the H2S levels on the fluid due to microbial activity.
In order to avoid risky and colstly issues under souring scenarios, the following precautions should be
taken during the design stages:
- During the initial stages of the design of high pressure systems, the tool use to determine the fluid
composition should be able to measure down to, at least, 0.001 mole% (10 ppm). This will avoid
misleading interpretations of the fluid corrosiveness and, therefore, will avoid unnecessary risky or costly
decisions.
- If the need of water injection for secondary recovery is foreseen, the impact of reservoir souring should
be made during the design phases. This will involve the material selection and/or mitigation plans such as
sulfate removal units, biocide injection treatments, and nitrate/nitrite injection treatments.
However, for systems designed for sweet service where the H2S presence becomes evident afterwards, a
risk/benefit assessment can be performed to determine the actual suitability of the system. This analysis
provides two main conclusions, as follows:
- In order to determine the suitability of existing components and system, designed for sweet service only,
to handle sour fluids, detailed information on material specifications, fabrication, test reports, etc. is
required. Therefore, the engineering companies should require the proper documentation for every
purchased/fabricated item.
- Due to current manufacturing processes and quality control programs, many materials qualify for sour
service based on NACE/ISO requirements even though they were not engineered for such service.
References
[1]

Kermani, B., Material Optimisation for Oil and Gas Sour Production, Corrosion 2000 -00156.

[2]

Jordan, L. C., The Impact of Reservoir Souring Upon Decision Processes Made During the
Design of New Deepwater Developments, Corrosion 2005 05633.

[3]

Larsen, J., Downhole Nitrate Applications to Control Sulfate Reducing Bacteria Activity and
Reservoir Souring, Corrosion 2002- 02025.

[4]

Jordan, L. C., Selection of an Active Souring Management Solution for a Gulf of Mexico
Waterflood, Corrosion 2004 04759.

[5]

Larsen, J., Rod, M. H., Zwolle, S., Prevention of Reservoir Souring in the Halfdan Field by Nitrate
Injection, Corrosion, 2004 04761.

[6]

Farquhar, G.B., Review and Update of Technology Related to Formation Souring, Corrosion 97
210.

[7]

Wikjord, A.G., Rummery, T.E., Doewn, F.E., Owen, D.G., Corrosion and Deposition During the
Exposure of Carbon Steel to Hydrogen Sulfide Water Solutions, Corrosion Science 20, 1980.

[8]

NACE TM0177, Laboratory Testing of Metals for Resistance to Sulfide Stress Cracking in
Hydrogen Sulfide (H2S) Environments, 2005.

[9]

NACE TM 0284, Standard Test Method of Pipeline and Pressure Vessel Steels for Resistance to
Hydrogen-Induced Cracking, 2003.

[10]

NACE MR0175/ISO 15156, Petroleum and Natural Gas Industries Materials for Use in H2S
Containing Environments in Oil and gas Production, 2003.

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[11]

API 5L/ISO 3183, Specification for Line Pipe, 44th Edition, 2009.

[12]

Holtam, C.M., Baxter, D.P., Aschcroft, I.A., Thomson, R.C., Effect of Crack Depth on Fatigue
Crack Growth Rates for C-Mn Pipeline Steel In Sour Environment, International Journal of
Fatigue, 32, 2010.

[13]

Buitrago, J., Weir, M.S., Experimental Fatigue Evaluation of Deepwater Risers in Mild Sour
Service, Deep Offshore Technology Conference, New Orleans, 2002.

[14]

McMaster, F., Thomson, H., Zhang, M., Walters, D., Bowman, J., Sour Service Corrosion Fatigue
Testing of Flowline Welds, Proceeding of OMAE2007 26th Annual Conference of Offshore
Mechanics and Arctic Engineering, San Diego, 2007.