SPE 156110

Case Study of Chloride Stress Corrosion Cracking at Gas Recycling Plant,

Qatar Petroleum, Dukhan - Theories and Practicality’s
Gopalakrishnan Bharathan & Salem Al Latifi, Qatar Petroleum

Copyright 2012, Society of Petroleum Engineers

This paper was prepared for presentation at the SPE International Production and Operations Conference and Exhibition held in Doha Qatar, 14–16 May 2012.

This paper was selected for presentation by an SPE 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 Society of Petroleum Engineers and are subject to correction by the author(s). The material does not necessarily reflect any position of the Society of Petroleum Engineers, its
officers, or members. Electronic reproduction, distribution, or storage of any part of this paper without the written consent of the Society of Petroleum Engineers is prohibited. Permission to
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 SPE copyright.

Abstract

Chloride stress corrosion cracking (CSCC) on austenitic stainless steel sections of the oil and gas plants has been known to
cause unpredictable failures, introducing high safety risks, and causing severe damage to equipment and loss of revenue.
This paper discusses three cases of CSCC at the Gas Recycling plant, Qatar Petroleum, Dukhan. The incidents have all been
successfully rectified and also mitigated for the future, at a nominal cost.

The article describes the 3 cases in detail, explains the analysis conducted to determine the root cause of the failure. How
evidence of CSCC was confirmed in each case and what mitigation measures were considered, how the most cost effective
solution was identified and implemented. It also highlights the lessons learnt to prevent such failures, in the future.
2 SPE 156110

Introduction:
Chloride stress corrosion cracking (CSCC) on austenitic stainless steel sections of the oil and gas plants has been known to
cause unpredictable failures, introduce high safety risks, and cause severe damage to equipment and lost revenue.

Generally, austenitic stainless steel has great corrosion resistance properties, H2S resistance, in addition to being suitable to
high temperature applications. This relatively new age material is used extensively in oil and gas plants in various sections of
the plant and even as small components in critical equipment/valves. However, Austenitic stainless steel materials are
susceptible to Chloride Stress Corrosion cracking when simultaneously exposed to the following, for long durations:

1. Stress due to pressure, welding

2. Continuous exposure to internal and ambient temperature over 60 deg C
3. Used in areas where chlorides can accumulate either from the process (internal) or from atmosphere
(external).

The most difficult part of this CSCC failure is that there is no appropriate non destructive technology is available to identify
this mode of failure and it is impractical to conduct preventive inspections like radiography (although not highly recommended
due to lack of reliability, but as this is the only viable NDT option available) of all susceptible areas in the plant, making it
impossible to predict and prevent CSCC failure.

Therefore, failures due to CSCC always happen abruptly, further increasing the damage and risks associated with it.

CASE STUDY - A

On 24 July 2007 one 2” 1500 ball valve (99-BV-0801-03960) located at well head DK 497 failed abruptly. The bonnet of the
valve was blown out to a distance of 15 meters during normal operation and one operator had just left the site after opening
this valve. Figure 1 shows the photograph of the damaged valve body. Detailed investigations revealed that the bonnet screws
which were made of austenitic stainless steel had cracked. Figure 3 and 4 shows the corroded and sheared off bonnet screws
with red colour arrows. Figure 5 – 10 confirms the material of construction A2-70 (SS 304), and the fractured surface of the
cap screws. All the components of the valve were sent for detailed failure investigation at the metallurgical laboratory.
Microstructure examination revealed that the main cause of the bonnet bolt failure was CSCC with numerous transgranular
cracks with branching, typical of stress corrosion cracking. Figure 11-14 illustrates the microstructure examination of the
failed screws under different magnification levels confirming CSCC on Austenitic stainless steel.

The conditions at DK497 included all risk factors for CSCC.

These valves were installed during 1996 in the open desert and had been exposed to the elements for over 10 years at the time
of the incident. The line operated at over 160bar causing sufficient stress on the failed component. The surface temperature of
all metallic component exposed to direct sunlight during peak summer was in the region of 80deg C. The chlorides present in
the coastal atmosphere had been accumulating on the valve body over the years till the failure happened. Figure 2 shows the
atmospheric corrosion on the valve with the bonnet kept separately.

Fig 1 – 99-BV-801-0396 – Valve body with blew out stem Fig 2 – 99-BV-801-0396 – Valve body Red coloured stain
marks indicated with yellow arrow shows active
atmospheric corrosion.
SPE 156110 3

Fig 3 – 99-BV-801-0396 – Red coloured arrows indicate Fig 4 – 99-BV-801-0396 – Red coloured arrows indicate
corroded and broken cap screws. corroded and broken cap screws.

Fig 5 – 99-BV-801-0396 – Bonnet cap screw - Fractured Fig 6 - 99-BV-801-0396 – Bonnet cap screw –
surface indicate failure occurred over a period of long time. Manufacturers material specification (SS – 304)

Fig 7 – 99-BV-801-0396 – Bonnet cap screw 1 - Fractured Fig 8 – 99-BV-801-0396 – Bonnet cap screw 2 - Fractured
surface surface
4 SPE 156110

Fig 9 – 99-BV-801-0396 – Bonnet cap screw 3 - Fractured Fig 10 – 99-BV-801-0396 – Bonnet cap screw 4 - Fractured
surface surface

Figure 11 & 12 – Ball valve – Cap Screw Magnification 50 & 100X – The Un-etched micrograph showing branched
cracking in the perpendicular direction to the tensile axis. Sample selected near the fractured surface.

Figure 13 & 14 – Ball valve -Cap screw - Magnification 50 X – The micrograph near the fracture surface in etched
condition consists of austenitic structure with numerous cracks. The cracks are branched and transangular in nature.
Pronounced twinning in the austenitic grains indicates extensive cold working.
SPE 156110 5

CASE STUDY – B

The acid gas compression unit was commissioned in 2003 as a part of the plant upgrade project. Couple of Pin hole leaks
developed suddenly during June 2007 on the acid gas pipe lines to the safety relief valves on the acid gas compressors. It was
observed that all these leaks were only on Stagnant SS316L pipe lines, very close to a weld joint and ended up releasing high
concentration H2S gas to the atmosphere. Figure 15 – shows the location of the failure.

Figure 15 – Photograph showing the location of the leak – Figure 16 – showing the crack in the weld support joint
marked in a yellow circle. indicated with a yellow arrow.

The above leaks were soon followed up with 10-15 more leaks within a period of 2 months on the same pipelines, again
adjoining the weld joints as shown in Figure 16. Figure 17 indicates the cut section of the pipe highlighting the crack on the
weld support joint.

Figure 17 – showing the cut section of the pipe showing the Figure 18 – showing the CSCC crack under 200X
weld joints adjoining the pin hole leak. magnification.

Emergency repairs and pipeline replacement projects had to be taken up on top priority, to continue operating the plant.

The conditions at these pipes contained all risk factors for CSCC.

The failed pipes were sent for detailed failure investigations and microstructure examination revealed chloride stress corrosion
cracking, as displayed in Figure 18 under 200X magnification. The powdered debris collected from inside the pipeline showed
strong presence of chlorides refer Figure 19 below. Chlorides were carried forward to this section of the plant from the
Demineralization water plant. The chlorides did not get carried forward due to the pipeline content being stagnant, unlike other
flowing pipelines. This also explains why these failures were not observed in the flowing lines.

Figure 19 – showing the Chemical analysis of the residue showing high chloride content.
6 SPE 156110

These pipelines were subjected to high stresses and vibration as they were connected to reciprocating compressors. The
discharge temperatures of the gases before the coolers increases as the reciprocating compression stage increases. These SRV
lines are connected to the compressor discharge prior to the gases being cooled at the coolers, and this explains why failures
were always observed first on the 5th stage pipelines, followed by the preliminary stages.

The pin hole leaks caused severe safety hazards due to high concentration H2S gas being leaked to atmosphere. High level
safety precautions were required to repair the leaks and replace the pipelines, while the plant kept operating.

Preventive radiography attempted to identify cracks on all weld joints of the stagnant lines of the acid gas compressors. The
Radiography results were in line with the predicted CSCC theory.

Since it was extremely difficult to conduct a metallurgical review and upgrade the material of the pipeline to prevent
recurrence of the failure, it was decided that only like for like replacement shall be taken up during the emergency repairs. All
these pipelines were replaced with same SS316 materials during 2008-09, as a temporary measure.

CASE STUDY – C

During the middle of 2011, similar cracks as explained above in Case Study - B, reappeared on the 5th stage acid gas
compressor stagnant SRV line on all the 3 compressors. Considering the fact that these failures have appeared on many of the
above newly replaced pipelines within 3 years of operation, urgent action was initiated to replace the pipelines with improved
metallurgy.
These multiple and repeated failures confirmed that chloride stress corrosion cracking CSCC is a serious menace and needs to
be addressed quickly and permanently.

THEORY OF CSCC AND EVALUATION OF ALTERNATE OPTIONS.

Chloride Stress corrosion cracking (CSCC) of stainless steel is a well known mode of corrosion failure. Cracks initiated during
operation over a period of time gradually leads to catastrophic failure. CSCC can either occur externally as happened in the
fracture of cap screws or internally from process fluids e.g. cracking of 2” pipe elbow.

The Basic Parameters leading to CSCC in stainless steel is represented below in Figure 20.

Figure 20 – The basic parameters under the influence of which CSCC can occur.

The operating parameters under which the pipelines were working were : Temperature – inlet 570C and discharge 1400C,
Pressure - Maximum 73 barg, Composition: (mole%), H2S - 5.0% (Regenerator O/H) to 23.9 % (at 5th Stage Acid Gas
Compressor (AGC) Inlet to knock out drum (KOD)), CO2 - 18.3% (Regenerator Overhead(O/H)) to 74.6% (at 5th Stage AGC
Inlet to KOD), Water - 76.5% (Regenerator O/H) to 0.7% (at 5th Stage AGC Inlet to KOD), Hydro carbon - 0.2%
(Regenerator O/H) to 0.8% (at 5th Stage AGC Inlet to KOD) and chlorides 45ppm in the 1st stage AGC - KOD.

Hence all the required parameters for CSCC of the pipelines were present.
SPE 156110 7

OPTIONS AVAILABLE TO PREVENT FAILURE - CONTROLLABLE FACTOR – Material of construction (MOC)

The options considered to prevent such failures are

1. Usage of Corrosion Resistant Alloys (CRA) like Duplex stainless steel, Super austenitic stainless steel 254
SMO, 904L, Incoloy 825, Incoloy 625 or
2. Complete elimination i.e 0 ppm chloride renders austenitic SS (316L) non susceptible therefore change in
MOC is not required,

However since 0 ppm chloride content is not practically achievable, this option was not pursued further.

In order to asses and select the most suitable material of construction, the crevice and pitting corrosion resistance and the
susceptibility to CSCC of various material options above was compared. Figure 21 illustrates the temperatures at which
different material options above, looses their resistance to crevice and pitting corrosion and Figure 22 shows the susceptibility
to CSCC

CREVICE & PITTING CORROSION RESISTANCE

CCT – Critical Crevice Temperature Figure 22 – displays the susceptibility to CSCC of various
CPT – Critical Pitting Temperature materials of construction – options considered.

Figure – 21 – Graph showing the corrosion and pitting

resistance of different material options considered.

Finally the advantages and disadvantages of using the various options (MOC) based on the above properties were analysed and
a final choice of Incoloy 825 made as below.

Duplex stainless was found to be more resistant to CSCC than 316L SS. However there have been cases of failure in presence
of high concentration of chlorides and at higher levels of temperature. This material was also found to be more susceptible to
cracking in H2S environments than 316L SS. Hence this option was not considered.

Super austenitic stainless steel (SMO 254 & 904L) material was found to posses good resistance against CSCC, but was found
to be susceptible to crevice and pitting corrosion at 900 C in high chloride environments. However since the sourcing of this
material was very difficult due to supply constraints in addition to many fabrication difficulties, this MOC was not considered
a viable option.

INCOLOY 825 was found to be Immune to pitting and crevice attack, the Immunity of cold worked Incoloy 825 in saline 20
bar ppCO2, 10 bar ppH2S at 2000 C, to CSCC was excellent. The higher nickel content is responsible for excellent resistance to
CSCC. Hence this material was selected as the best alternative option to prevent CSCC.
8 SPE 156110

MITIGATION MEASURES.

CSCC on Valves (Case Study A)

15,275 at-risk valves were identified in the plant. The valves were short-listed to meet the following conditions:
1. Contained components prone to chloride stress cracking.
2. Exposed to high pressure application,
3. Exposed to direct sunlight where surface temperatures can reach over 60 deg C
4. Exposed to high process temperatures
5. Un-insulated, which might otherwise prevent exposure to atmospheric chlorides

The final list of 2,934 valves met all the above consideration. All valves of 2” size and predominantly 1500# rating were
replaced completely. For bigger valves, the body and bonnet screws were replaced. The body and bonnet screws for the
repaired / replaced valves were all made of A320 L7M, which is not susceptible to chloride stress corrosion cracking, but was
also a cheaper option and suitable for the service requirement.

Simultaneously, an online contract was also initiated to clean and grease all 15,275 valves in the plant every 6 months and to
apply grease on the body / bonnet screws to prevent accumulation of chlorides in the vicinity. This contract has been in
operation for the past 3 years. We have not experienced another failure on valves due to the above actions.

CSCC on pipelines (Case Studies B &C)

The pipelines of the acid gas compressors and all other stagnant lines in the acid gas removal unit are in the process of being
replaced with the material, Incoloy 825. Incoloy 825 is not susceptible to chloride stress corrosion cracking. Even though the
cost of Incoloy is approximately 50% more than SS316, the solution is more prudent considering the risks that are avoided.

The CSCC experience gained in operating the acid gas removal unit has been also utilized to change the metallurgy in the new
Acid Gas Removal Project (AGRP), currently under construction. The project engineering team from EPIC contractor
conducted many audits, independent analysis, and their own surveys and produced a study report. Extract from the study report
item 7.1, states the following.

“Stainless steels are selected for service in oil and Gas environment because of their high level of corrosion resistance in
typical producing environments. Unfortunately these materials, particularly 300- series austenitic stainless steel are not totally
resistant to corrosion in certain environments. In particular they are sensitive to pitting and crevice c orrosion in aerated water
environments with chloride ions present at certain temperature conditions. More dangerously pitting corrosion may lead to
Chloride stress corrosion cracking under the influence of residual stresses and higher temperatures with catastrophic results to
the plant.”

Although many in the oil and gas industry have set the limit of 50ppm chloride concentration at a temperature of 60deg C for
restricting use of austenitic stainless steel, it may be noted that in the presence of H2S as in this case the likelihood of CSCC
increases.

Due to the above factors the EPIC contractor has agreed to replace the SS316L lines with Incoloy 825, and the item 13 of the
study report states the following:

“Conclusion and Recommendations.

The proposed austenitic stainless steel MOC for the lines and equipments in the AGC plant is a good material only when
resistance against wet CO2 is required, however it has significant disadvantage in its inherent susceptibility to damage in
chloride containing environment as clearly shown in the case of QP SS316L failure due to chloride stress corrosion cracking.
The new AGC unit will be operating under very severe conditions of high levels of hydrogen sulphide gas, possibility of
detrimental concentrations of chlorides high pressures and temperatures in mostly wet environment.
Based on the above mentioned corrosion mechanism in SS316L, corrosion threats in AGC unit and advantages of Incoloy 825
over SS316L, PIL concludes overall benefits of Incoloy 825 over SS316L in places where fluid is stagnant as follows.
 Safe Plant operation can be ensured
 Integrity of the plant can be increased
 The possibility of material fracture can be reduced/avoided
 Unexpected H2S leakages into the environment can be avoided.”
SPE 156110 9

Conclusion:

Chloride stress corrosion cracking presents a major safety risks to oil and gas plants. The fact that this type of failure cannot be
practically identified and mitigated in advance makes prevention the best mode of mitigating the risk. The use of Austenitic
stainless steel (Stainless steel in 300 series) has to be curtailed during material selection in project design engineering,
whenever exposure to chlorides + H2S + Temperature + stress in various combinations, is considered unavoidable.

Adopting the above strategy will:

 Prevent unpredictable metallurgical failures

 Increase the safety of plant operations
 Avoid rectification of the failure in potentially dangerous environments
 Avoid revenue loss due to curtailed or reduced operations.

Acknowledgement

We thank Qatar Petroleum, Dukhan Operations - for providing an opportunity to present the paper on chloride stress cracking.

References.

1. Various failure analysis reports generated by QP HSE and Inspection departments.

2. Study report for the replacement of austenitic stainless steel 316L with Incoloy 825 – by Petrofac –
Document number 2971-5-17-2503 dated 16-12-2010. The study was initiated based on QP requirements
to change the materials of construction designed during FEED of the project.