Petrotech-2010

31 October-3 November 2010, New Delhi, India

Paper ID : 20100265
Wet - H2S Corrosion Mechanism and Control Strategies in Refining
Industry
B. S. Negi
Chief Inspection Manager, Indian Oil Corporation Limited, Refineries Division, Maintenance &
Inspection Dept., Indian Oil Bhawan, A-1, Udyog Marg, Sector-1, NOIDA Uttar Pradesh, INDIA
Email : bnegi@iocl.co.in
Abstract
Carbon steels are the predominant materials for equipment and piping in the refining industry.
Refinery operation involves exposure to aqueous environments containing hydrogen sulphide. This
wet- H2S environment is mild corrosive to carbon steels. However, hydrogen liberated during
corrosion reaction, in presence of sulphide scale, penetrates into steels and causes hydrogen
blistering and cracking. As a result, the mechanical properties of the steel are deteriorated and
reliability and integrity of equipment is reduced. The welded pressure containing components are
more susceptible to wet-H2S corrosion. The extent and types of damages depend upon H2S
concentration, pH, contaminants, temperature, steel quality, fabrication practice and corrosion control
practices. The damages are surface and sub surface oriented. Visual inspection, wet fluorescent
magnetic particle testing and ultrasonic flaw detection are the common non destructive testing (NDT)
methods for detection and evaluation of damages. The correct evaluation of these damages and
using suitable repair procedures, integrity of equipment can be restored. This paper focuses on the
wet-H2S corrosion mechanism, repair procedures and control strategies to be followed for enhancing
the reliability and integrity of equipment.
Keywords: Wet-H2S, SSC, HIC, SOHIC, WFMT, Blistering, SWC, HAZ, PWHT, UT, NDT
Introduction
Wet- H2S corrosion is caused by the generation of atomic hydrogen and subsequent diffusion of the
atomic hydrogen into the steel during corrosion reaction in presence of sulphide scale. Hydrogen
blistering, hydrogen induced cracking (HIC), stress oriented hydrogen induced cracking (SOHIC) and
sulphide stress corrosion cracking (SSC) are common to refinery equipment that contains greater
0
than 50 ppm H2S in water, between ambient temperatures and 150 C. The extent and types of
damages depend upon H2S concentration, pH, contaminants, temperature, steel quality, fabrication /
manufacturing process and corrosion control practices. Visual inspection of welding joints and
pressure boundary surface is the best technique for detection of blisters and surface cracks. Wet
fluorescent magnetic particle testing (WFMT) and ultrasonic testing (UT) are to be done for surface
and sub-surface crack detection and sizing.
Evaluation of blisters and cracks are to be done in accordance with API 579 for assessing the
equipment integrity for further service. Surface blisters less than 50 mm in diameter can be drilled to
relieve the internal pressure. Cracks may be removed by grinding or gouging. Cracks deeper than
corrosion allowance can be repaired by weld buildup. The repair area to be re-inspected after welding
& post weld heat treatment (PWHT).
Hydrogen blistering and HIC can be controlled by using clean steels with minimum inclusion,
restricting trace elements, such as sulfur, phosphorus, cyanides and controlling manufacturing
variables. PWHT, which reduces residual stresses and tempers the microstructure along with
controlling welding parameters to achieve hardness below 200 HBW are the best approaches to
mitigating SOHIC and SSC. Injection of good film forming amine, polysulfide inhibitor, wash water
and pH can help in reducing wet- H2S corrosion.

Petrotech-2010
31 October-3 November 2010, New Delhi, India

Corrosion Mechanism
Hydrogen damage in wet H2S service is caused by the generation of atomic hydrogen during
corrosion reaction and the subsequent diffusion of the atomic hydrogen into the steel. Atomic
hydrogen (H) and molecular hydrogen (H2) are produced in the corrosion reaction of steel with
aqueous H2S as illustrated below.
Fe + H2S

FeS + 2 H

(1)

2H

H2

(2)

In the conventional corrosion process, under ordinary acidic conditions, molecular H2 forms at the
surface of the steel and, if produced slowly at low corrosion rates, it harmlessly dissipates. However,
when sulfide scale is present, the sulfide acts as a negative catalyst and discourages the reaction (2).
As a result, the atomic hydrogen penetrates the steel, accumulating in the crystal structure and
affecting the steels mechanical properties.
Other compounds, such cyanide (HCN), phosphorus, antimony, selenium and arsenate ions, which
are called recombination poisons or catalyst poisons, also interfere with the conversion of atomic
hydrogen to molecular hydrogen. In the presence of a catalyst poison, the surface concentration of
atomic hydrogen rises and a corresponding increase occurs in the amount of hydrogen diffusing into
the metal.
The types of damages depend upon H2S concentration, pH, contaminants, temperature and steel
quality. The favourable environmental conditions for promoting the wet- H2S corrosion are free water
containing with more than 50 ppm of H2S, pH above 7.6 or below 4.0 and temperature between
0
ambient to 150 C. High strength and high hardness steels are prone to SSC.
Types Of Damages
Hydrogen Blistering
The blister results from hydrogen atoms that originate during the sulfide corrosion process at the steel
surface. They diffuse into steel and form hydrogen molecules at inclusion or lamination sites present
in steel. The hydrogen molecules so formed, exert pressure to cause local deformation and blistering.
Blisters may appear on either or both surfaces of a plate or on top of one another, depending on the
location of the lamination. They vary in size and appearance from small protrusions to swellings
several feet or more in diameter. Increasing blister growth can produce tears in the surface and result
in loss of the pressure retaining capability of the equipment. Figure-1 Illustrates the hydrogen
blistering observed in LPG caustic wash vessel.

Figure-1: Hydrogen Blistering observed in LPG caustic wash vessel

Petrotech-2010
31 October-3 November 2010, New Delhi, India

Hydrogen Induced Cracking (HIC)

It is manifested as blister cracks oriented parallel to the plate surface. HIC occurs due to the stresses
generated by hydrogen gas collected in the planar stringer inclusions in steel. Non-homogenous,
elongated sulfide or oxide inclusions occurring parallel to the plate rolling direction are typically
associated with HIC. These inclusions serve as sites for formation of microscopic hydrogen blisters
that grow and eventually connect via stepwise cracks. Interconnecting cracks between the blisters
often have a stair step appearance and so HIC is sometimes referred to stepwise cracking (SWC).
Figure-2 shows the crack orientation in HIC. Since, HIC is not stress dependent or associated with
hardened microstructures, post weld heat treatment is of little significance.

Figure-2: HIC & SOHIC cracking in LPG caustic wash vessel

Stress Oriented Hydrogen Induced Cracking (SOHIC)
SOHIC is similar to HIC but have arrays of cracks linked in the through thickness direction by
transgranular cleavage cracks. It is driven by high levels of residual or applied stress and usually
appears in the base metal adjacent to the weld heat affected zones (HAZ). Since stress is involved in
crack development and propagation, post weld heat treatment is somewhat effective in reducing
SOHIC. Controlling manufacturing variables and trace elements is also effective. Figure-2 shows the
crack orientation in SOHIC.
Sulfide Stress Cracking (SSC)
Sulfide stress cracking is defined as cracking of metal under the combined action of tensile stress and
corrosion in the presence of moisture and H2S. SSC can initiate in high hardness zones of high
strength steels. Susceptibility of steel to SSC is highly dependent on its composition, microstructure,
strength, residual stress and applied stress levels. Steel composition and microstructure influence the
threshold hardness of steel to SSC. Figure-3 shows the surface crack observed during wet
fluorescent magnetic particle inspection (WFMPI) of LPG storage vessel fabricated from ASTM A537
plates.

Petrotech-2010
31 October-3 November 2010, New Delhi, India

Figure-3: Linear indication observed in WFMT

Inspection Methodology
Thorough internal visual inspection of weld joints, HAZ and pressure boundary of vessel shall be
carried out. If blisters are observed, UT is to be used to detect subsurface cracks, lamination and
blisters. UT is most frequently used method for sizing cracks, mapping of blisters and laminations for
fitness for service evaluation. For detection of surface breaking cracks WFMT is to be done. The
surface of the weld and about 150 mm base metal on both sides of welding should be cleaned for
WFMT using AC yoke. It is one of the most commonly used methods for internal pressure vessel
inspection in wet- H2S service. Some indications may be irrelevant. A representative number and type
of indications are be evaluated to determine their relevance and severity with respect to code
requirement.
Inspection for SSC is to be considered in the process units and storage facilities using pressure
vessels made of high strength steel. Generally, 100 percent wet fluorescent magnetic particle testing
of all the weld seams shall be carried out internally. In addition to this, cleat, arc strike locations and
support location shall also to be tested with WMFT. About 20-25 percent of weldments including all
tee joints should be tested using shear wave ultrasonic testing.
Blistering, HIC, SOHIC and SSC damages can occur throughout the refinery wherever there is a wet
H2S environment present. Area prone to wet- H2S corrosion includes LPG and sour water treating
units, LPG storage vessel, fractionator overhead drums, fractionation towers, absorber and stripper
towers, compressor interstate separators and knockout drums and various heat exchangers,
condensers, and coolers. Sour water stripper and amine regenerator overhead systems are especially
prone to wet H2S damage because of generally high ammonia bisulfide concentrations and cyanides
presence. SSC is most likely found in hard weld and heat affected zones and in high strength
components including bolts, relief valve springs, 400 series SS valve trim, compressor shafts, sleeves
and springs.

Petrotech-2010
31 October-3 November 2010, New Delhi, India

Repair Procedures
Blisters and cracks are to be evaluated in accordance with API 579. In case integrity of the pressure
vessel is found to be unreliable, replacement in full or part should be considered. For in situ part
replacement, welding procedure specification shall be developed and qualified for each application.
Hydrogen bake-out treatment (HBT) shall be carried out to flush out hydrogen and also to facilitate
welding. Local post weld heat treatment of welded joints shall be carried out as per original code of
construction.
API 579 suggests three level of assessment for determining the acceptability of blister for reliability of
equipment. Level-1 & level-2 considers the acceptability on various criteria related to size density and
distribution of blister, localized thinning assessment. Level-3 analysis needs detail fracture
mechanics approach if the blister result in crack like defects in thickness direction. Surface blisters
less than 50 mm in diameter may be drilled to relieve the internal pressure. However, the remaining
net sections of metal to be capable withstanding the internal design pressure.
Cracks may be removed by grinding or gouging. The tip of the cracks is to be made blunt to arrest its
propagation during grinding. The cavities formed by removing the cracks are to be made smooth with
boat shape contour and to be inspected with WFMT to ensure that all cracks are removed. Cracks
deeper than corrosion allowance can be repaired by weld buildup. The weld repair can be carried out
in accordance with industry recommended practice such as API 510. Controlled-deposition welding
method can be adopted to avoid PWHT. Sharp edges of welding and arc strikes are to be removed
by blend grinding. Repair welds hardness control to be in-accordance with the NACE RP 0472. The
repaired area is to be re-inspected after welding & post weld heat treatment.
Control Strategies
Material selection

Selection of correct material manufacturing process to produce material free of blow holes,
laminations, porosity and inclusion. Silicon killed steels are preferable than rimmed and
semiskilled steels. Killed and normalized steel with grain refinement microstructure possess
superior resistance to brittle fracture and crack propagation. Calcium treated steels offer better
resistance due to inclusion morphology control.
Material chemistry control also play important role in mitigation of wet-H2S corrosion. Restricting
trace elements, such as sulfur, phosphorus and controlling manufacturing variables for steel
provide HIC resistance.
Use of low strength steel containing low sulfur and low phosphor for fabrication of vessel and
seam pipes and adherence to NACE MR 0103 to be considered.

Fabrication Practices

Welding of fabrication cleats with preheat , avoiding frequent arc strike on the metal surface,
grinding off sharp edges and smoothening of weld contour reduces the chances of crack initiation.
Post weld heat treatment, which reduces residual stresses and tempers the microstructure, along
with controlling welding parameters are the best approaches to mitigating SSC. .
Post weld heat treatment (PWHT) and controlling weld and HAZ hardness below 200 BHN and
adherence to NACE- RP 0472 practice to be followed.

Linings and Coatings

Wet H2S corrosion can be controlled and mitigated by reducing or eliminating the hydrogen
activity. This can be accomplished by using alloy or alloy clad materials of more corrosion
resistant metal. Application of fiber reinforced plastic (FRP) lining, thick epoxy coating or gunnite
lining on vessel internal surface helps in the mitigation of wet H2S corrosion.

Petrotech-2010
31 October-3 November 2010, New Delhi, India

Operation Monitoring

Corrosion at the lower pH is caused by higher concentrations of dissolved H2S in water and at the
higher pH is caused by higher concentrations of the bisulfide ion in the water. Monitoring pH
within 5.5 to 7.5 will result in minimum corrosion
There are varieties of approaches like water washing, polysulfide addition, as well as the use of
organic filming inhibitors for prevention of both corrosion and hydrogen blistering. It forms a
protective layer at the surface and controls corrosion.

Conclusion
The integrity of pressure vessel in Wet H2S service can be enhanced by proper material selection,
fabrication practice & operational monitoring. Periodic internal inspection and proper damage
assessment and adopting repair procedure, the vessel serviceability and reliability can be increased.
References
1. API RP 571 Damage Mechanisms Affecting Fixed Equipment in the Refining Industry, First
Edition, December 2003, p.5-41.
2. API Recommended Practice 579 Fitness for Service, Jan2000.
3. NACE Standard MR0103-2005, Item No.21305 Material Resistant to Sulfide Stress Cracking in
Corrosive Petroleum Refining Environments".
4. NACE Standard RP 0472-2005, Item No.21006 Methods and Controls to Prevent In-service
Environmental Cracking of Carbon Steel Weldments in Corrosive Petroleum Refining
Environments".
5. NACE Standard RP 0296-2004, Item No.21078 Guidelines for Detection, Repair, and Mitigation
of Cracking of Existing Petroleum Refinery Pressure Vessel in Wet H2S Environments.