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WET H2S SERVICE – WHAT ARE THE TYPICAL REQUIREMENTS FOR STEEL PLATE?
JULY 16, 2014 BY DENIS OAKLEY 1 COMMENT
Pressure Vessel made with Dillinger Dicrest HIC Resistant Steel for Wet H2S service
Many petrochemical refineries have Hydrogen Sulphide (H2S) present in the their process
streams. Famous for it’s smell of rotten eggs H2S when mixed with liquid water in a refinery
is known as Wet H2S.
In most refineries carbon steel boiler plates are used in this environment but they are subject
to degradation depending on the a number of key factors
pH – acidity
H2S Level
Temperature
Duration of Exposure
Nature of the material.
Normally the key issue is not thickness loss in the plate but rather it is the hydrogen in the
H2S that is a major concern. Hydrogen is involved in many corrosion mechanisms but the
presence of H2S enables there to be a high atomic hydrogen penetration of the steel.
The consequence of this is that the steel becomes embrittle and the atomic hydrogen can
recombine to form hydrogen molecules as inclusions in the steel. High hydrogen pressure
can then cause high stresses within the steel plate.
DEGRADATION OF STEEL IN WET H2S SERVICE
The main types of degradation are:
HIC – Hydrogen Induced Cracking.
Hydrogen Induced Cracking is a form of planar cracking when atomic hydrogen diffuses into
the carbon or low alloy steel plate. this then combines back into hydrogen molecules at trap
sites in the steel. Hydrogen pressure, assisted by hydrogen embrittlement then can cause
cracks to appear without the requirement for any external stresses.
The main risk factors are the cleanliness of the steel and the size and shape of inclusions in
the steel. Cracks occur in the X-Y axis of the plate and can be identified by characteristics
bulges in the plate surface.
SSC – Sulphide Stress Cracking
Sulphide Stress Cracking a different form of cracking which occurs through a combination of
stresses on the plate am the presence of atomic hydrogen. in this case the cracks are
perpendicular to the the stresses. One of the key risk factors is the hardness of the plate
used. It’s possible to get plate resistant to SSC
SWC – Stepwise Cracking
This is a variation of of HIC. In this case there are multiple hydrogen induced cracks in the
metal at different depths. However there are additional perpendicular cracks that then link
these planar cracks to form the characteristic stair pattern. Risk factors are the hydrogen
embrittlement and the additional stresses caused by the bulging caused by HIC. Applied
stresses can also have a contributory effect.
SOHIC – Stress Oriented Induced Cracking
SOHIC cracks occur in plate already subject to HIC cracking. In this case there is stress in
the plate – either applied or residual. The cracks appear perpendicular to the principal stress
and tend to link pre-existing HIC cracks in a ladder like array. Plates with SOHIC
resistance aren’t produced.
SEVERITY OF WET H2S SERVICE
The severity of the Wet H2S Environment is dependent on the H2S content and the pH of
the water in contact with the boiler plates. Normally steam composition is used as the
primary determinant of severity, but this needs to be reviewed in light of unusual process
operations or brief events that aren’t covered by normal operation procedures.
pH H2S ppm
10 to <50 ≥50 to ≤2000 >2000 to ≤10000 >10000
<5 Low Severe Severe Severe
≥5 to ≤7.8 Low Moderate Moderate Severe
> 7.8 Low Moderate Severe Severe
If there is a presence of cyanide groups (CN) with a concentration of more than 20 ppm then
many cases will be upgraded to high severity
STEEL PLATE SPECIFICATIONS FOR WET H2S SERVICE
Generally carbon steel plates can be used for sour service at all levels – low, moderate
and severe, with a corrosion allowance. This is typically 3 – 6mm depending on plates
thickness and other factors. However the plates (and other carbon steel components such a
forged parts, flanges and pipes) have to meet demanding specifications and these are
usually called HIC resistant steel or HIC resistant plate.
The specifications issued by oil and gas companies for HIC plate are designed to
reduce the hardness and limiting the tensile stress in the steel. This is done by
limiting the residual elements that can increase the hardness of the steel.
reduce HIC susceptibility. This is done by restricting he amount of sulphur
and controlling the shape of inclusions
Limiting crack propagation. This is done by restricting phosphorous in the
steel and segregating element content.
Plates for HIC use are fully killed and normalised. They are also vacuum degassed,
deoxidised and produced with a fine grain structure. The process also has to be focused on
delivering steel with a very low phosphorous and sulphur content.
Steels for use in Wet H2S environments ate produced by:
desulphurisation
dephosphorisation
deoxidising
Calcium treatment can be used to manage inclusion shape if the steel is not particularly
clean. Generally calcium treatment is used where sulphur content in the plate is above
0.002% but it is limited to 3 times the sulphur content.
Normally a yield strength of 415 MPa is the maximum allowed (meaning that HIC plates
cannot be quenched and tempered) and hardness has to be lower than 200 HB (which also
helps with the risk of SSC).
WET H2S IN REFINERIES
Whilst many refineries are concerned with the effects of wet H2S few oil fields produce crude
with a high h2S content. Instead most H2S in refinery process steams occurs as a by
product of other processes within the refiner. These include
Thermal degradation of the feed
Catalytic cracking
Hydrodesulphurisation
Breaking this down a bit:
The pure crude feed has little H2S in it. However thermal cracking adds H2S
as does hydrodesulphurisation (HDS) and coking when cuts are fed back into
the feed for reprocessing.
Distillation overhead is normally moderate sour service whilst some of the
waste gases normally flared can fall under the severe classification
When light cuts are hydrotreated wet H2s can result and the low temperature
areas of hydrotreatment units are often classified as moderate H2S service.
HDS units and hydrocracker units generally have high concentrations of H2S
and consequently low temperature downstream areas with water present tend
to be classified as server service. Amine absorbers and the overhead of
downstream separators is also severe.
Cyanides can strongly impact the severity of HIC corrosion in thermal
cracking units such visbreakers and cokers; also fluid catalytic converters
(FCC) can be severe at the cold light end cut (mainly for LPG).
Amine processing units (absorbers and regeneration units are severe service
Examples of units that are not concerned with West H2S service are reforming,
alkylation, isomerisation and propylene. Generally anything that is
downstream of a hydrotreatment unit or amine absorber does not need HIC
resistant steel
Oakley Steel sells Dicrest HIC resistant steel from Dillinger Hutte thats meets the
requirements of all major oil companies including – Total, Exxon, Shell, Petronas and
Pertamina
This article is based on a paper by Richez and Zanoncelli at the Dillinger Pressure Vessel
Colloquium in 2009. Any mistakes or misinterpretations are of course my own!
≤≥
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COMMENTS
1. Jorge Guerra says
March 17, 2017 at 03:44
I’m quotating a Oil Refinery Reactor specificated with this material composed so I want to
know what it means..
Reply
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