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Summary
Hydrogen-induced cracking (HIC) is a materials- and corrosion-related problem that occurs in surface production systems. Steels used
to construct sour-gas production facilities and flowlines may corrode from wet hydrogen sulfide (H2S) gas in the production stream.
The corrosion process generates hydrogen that may damage the
steel, resulting in HIC and other forms of damage from hydrogen.
HIC control and prevention are an important consideration in operating surface-facility equipment in a safe and efficient manner. By
effectively controlling or preventing HIC damage in surface-facility
equipment, operating costs are reduced, potential costly downtime
from equipment failure is avoided, and a safe work environment is
more easily realized.
We developed an overall approach to understand and deal with
the HIC problem in sour-surface production facilities. The approach
dealt with understanding the mechanism in steel materials used in
surface-facility equipment; implementing state-of-the-art inspection techniques; fitness-for-service (FFS) evaluation to assess damage effect on performance; repair procedures on existing equipment; and finally, establishing steel performance and fabrication
requirements to eliminate or reduce HIC damage risk for newly fabricated equipment.
This paper presents the results of laboratory examinations of over
40 steels covering both new and existing equipment, leading to the
approaches developed for controlling HIC in existing equipment
and for controlling or preventing HIC in new construction. We also
present the basis for the approaches developed to deal with HIC in
surface production facilities.
Introduction
Wet H2S- or cyanide- (CN-) cracking in surface production process
equipment, such as pressure vessels, is now a major concern in the
industry. Industry attention turned to this potential cracking problem in the mid-1980s, following the catastrophic rupture of an
amine contactor at the Union Oil refinery in Lemont, IL.1
Two steps were taken to address this concern in production operations: 1) special requirements were placed on steel, vessel fabrication, and operation to avoid process equipment and vessel cracks after understanding the steel-cracking mechanism, and 2) a sour-gas
plant inspection/maintenance program was initiated2 in the operating plants with an FFS capability developed to assess cracking significance on equipment service ability. This overall approach has an
industry-wide impetus.
To address materials performance in hydrogen-charging environments for new construction, we initiated an effort to study the performance of pressure vessel steels in wet H2S/CN environments.
From these studies, recommendations about the benefit of specialized chemistry control, normalization after rolling, special metallurgical processing techniques, and other controllable variables
were determined. These recommendations were then incorporated
into a material-purchase specification.
Wet H2S/CN Cracking Mechanisms in Process Equipment. Wet
H2S- or CN- assisted hydrogen cracking (HC)often known as
Copyright 1996 Society of Petroleum Engineers
Original SPE manuscript received for review June 1, 1993. Revised manuscript received July
13, 1995. Paper peer approved Aug. 15, 1995. Paper (SPE 25583) first presented at the 1993
SPE Middle East Oil Technical Conference & Exhibition held in Bahrain, April 36.
found in the pearlite colonies and forms methane that produces intergranular fissuring, cracking, and severe loss of ductility.
Hydrogen blistering is not necessarily considered critical to the
pressure integrity of a vessel or pipe; often the blisters do not link
from one plane to another or break the surface. This influences vessel FFS assessments and leads to extended service life. Typically,
blisters are observed on the internal surface of the vessel and may
be drilled to relieve pressure and reduce further deformation.
SSC. SSC has been extensively studied in carbon manganese,
low-alloy high-strength, and microalloyed steels (Ref. 6). SSC is a
specific form of hydrogen embrittlement that occurs in highstrength steels and hard-weld heat-affected-zones (HAZ). Other research characterizes cracking for steels as dependent on hardness,
temperature, H2S concentration, cold work, and alloy content. Alloys with higher alloying content, called corrosion resistant alloys
(CRAs), can still be susceptible to SSC. SSC in CRAs is influenced
by the same parameters. SSC is mostly observed in surface production equipment at internal attachment clip welds where a hard HAZ
can be developed.
HIC. HIC is a hydrogen-damage mechanism that occurs in soft,
low-strength steels (yield strength less than 80 ksi). Cracking occurs
by the linking of small inclusions that have blistered. The linking
mechanism proceeds from one blistered inclusion to another in anisotropic planes developed from the rolling process in plate manufacture. The linking is sometimes called stepwise cracking because
the cracking morphology appears as steps in a metallurgical section
(Fig. 1). Another common term that is applied is blister cracking.
HIC or blister cracking is differentiated from simple blistering by
the linking or cracking of the steel from one blister to another.
SOHIC. SOHIC is a hydrogen-damage mechanism like HIC. The
damage mechanism, however, is driven not only by the high pressures that are generated by the hydrogen at the inclusion to steel interface, but also by the external applied stress.4 These stresses cause
the crack path between inclusions to move more directly through the
plate. The cracking morphology is more reminiscent of a ladder than
a stair step; the inclusions link not as stair steps, but more in a vertical direction like the rungs on a ladder (Fig. 1). Another common
term that is used to describe this phenomenon is ladder cracking.
Corrosion Process: Hydrogen Generation and Transport. To
produce HC-blistering, SSC, HIC, or SOHIC, hydrogen must be
present at the steel surface and then be adsorbed into the metal. The
corrosion process generates hydrogen and involves the production
of iron at the anode that goes into aqueous solution as
FeFe+2)2e, . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (1)
and at the cathode hydrogen is produced and either enters the steel
or forms hydrogen gas and bubbles off. When H2S is present,
2H+)2e H)H. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (2)
When H2S is not present,
H)H H2 (gas). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (3)
Hydrogen enters the steel first by adsorption onto the steel at the
water to steel interface and then by being absorbed into the steel as
hydrogen. The amount of hydrogen absorption depends on the cor50
rosion rate of the steel surface and the concentration of anions, such
as CN or HS, that reduce the tendency to produce hydrogen gas,
shown in Eq. 2. CN and HS also promote hydrogen, H, entry into
the steel. Fig. 2 shows that in a strictly acid environment without
H2S present, HIC, SOHIC, and SSC would not occur.
Produced wet sweet-acid gas (CO2) environments are an example
of the criticality of HS in the HC mechanisms. General weight loss
corrosion occurs, but HIC, SOHIC, SSC, and blistering in steels
does not occur when HS and CN are not present. Introduction of a
sour environment allows this to occur and these damage mechanisms become active given a susceptible steel microstructure.
Acid-concentration, typically related to pH, has an influence on
damage. An example is acidizing to clean Fe2S-scaled carbon-steel
vessels or piping. Acidizing with a Fe2S scale present produces an
acidic environment with HS present. At pHu4,
Fe2S)acidFe+2)H+)HS. . . . . . . . . . . . . . . . . . . . . . . (4)
At pHt4,
Fe2S)acidFe+2)H+)H2S, . . . . . . . . . . . . . . . . . . . . . . (5)
which then leads to either hydrogen charging of the steel with hydrogen or hydrogen gas evolution.
2H+)2eH)H , . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (6)
and H)HH2 (gas). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (7)
The presence of the HS promotes the transfer of hydrogen into the
steel (Eq. 6). Normally, acidizing is accomplished with acids with
a pH of 4 to 6, producing high fluxes of hydrogen and the risk of blistering, HIC, or SOHIC from the acidizing alone.
Conditions for Blistering, HIC, and SOHIC. Blistering, HIC,
and SOHIC are interrelated and depend heavily on hydrogen entry
into the steel microstructure. Blistering occurs when the hydrogen
concentration, CH , at a discontinuity exceeds the critical threshold
hydrogen concentration, Cth . The internal discontinuity is usually
an inclusion, but can be produced by SSC of a hardened area where
high Mn segregation has occurred. The condition is expressed as
CH uCth , . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . (8)
and Cth is related to the material resistance to the hydrogen gas that
has recombined to produce a pressure on the inclusion nucleated
void. The pressure available for causing the inclusion to disbond
from the metal matrix is related to CH at the point where the inclusion is located. Fig. 3 shows a typical profile of CH through thickness in a pressure vessel steel wall, illustrating the conditions for
blistering, HIC, or SOHIC.
Blistering, HIC, or SOHIC damage conditions are determined by
the following critical variables: (1) pressure, pc , (2) steel matrix to
inclusion resistance or fracture-toughness, KIC , and (3) the length
SPE Production & Facilities, February 1996
Fig. 3Condition for HIC in a steel plate based on CH and Cth required for HIC or blister formation.
Cracking-Cause
Mechanism/Source
Weld Fabrication
Blistering or HIC
Sulfide Stress
Alkaline Stress Cracking
Total
Number of
Vessel
Instances
Total Vessels
Inspected
(%)
185
64
29
15
293
17
10
5
3
. . . . . (12)
SPEPF
Nomenclature
a+ characteristic inclusion or crack length
a+ fraction of hydrogen absorbed into steel at interface
of steel and corrosive environment
CH + hydrogen concentration
SPE Production & Facilities, February 1996
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