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Corrosion Wet H2 S
Corrosion Wet H2 S
ABSTRACT
Operating an Oil refinery today means searching for methods to reduce risk to personnel and
plant equipment. There are so many deterioration processes active on refinery equipment /
piping etc. But this paper will concentrate on material selection and operational control issues
related to Wet H2S Cracking in refinery process environment. This paper will also address
operational control like wash water injection, corrosion inhibitor dosing and APS dosing for
substantial reduction of
Wet H2S related damages in operating equipment / piping.
Inspection methods (WFMT etc) & its priorities, intervals and extent of inspection are also
covered in the papers.
Keywords: Wet H2S, SSC, HIC, Blistering and WFMPI
INTRODUCTION
The Wet H2S cracking problem in oil industry was first recognized in the 1970s and guidance
on material requirements to avoid SSC was published at that time by NACE as MR0175. In
earlier days, it was hoped that the blistering and hydrogen induced cracking (HIC) observed in
many refinery process vessel were isolated occurrences. The findings of NACE international
task group T-8-16 survey during 1990 i.e cracking of existing carbon steel pressure vessel in wet
H2S process environment had also raised significant concern in the petroleum refining industry.
And the survey in 1988-1990 had revealed cracking incident in Wet H2S environment varied
from a low of 18 to 19 % in Crude units and Coker fractionation units to a high of 45 % in Fluid
Catalytic Cracking (FCC) Light ends units. High cracking incident was also reported in other
process units include FCC fractionation (41%), liquefied petroleum gas (LPG) (41%).
Presently, a better appreciation of the consequences of wet H2S damages has been ascertained
because handling of H2S rich process streams in oil industry has a safety consequence also and
its mitigation methods are getting prime importance and selection of wet H2S cracking
resistance material for various process units like FCCU, DHDS, COKER continues to be the
thrust areas in future The safety issue is inescapable and can only be addressed by ensuring the
proper facilities like proper material, suitable inspection frequency and timely replacement and
this a also link up with economic consideration.
Presence of cyanides in FCCU overhead section will increase probability and severity of Wet
H2S damages.
Entire vapor recovery section of delayed coking unit is vulnerable for potential Wet H2S
damage and presence of cyanides will significantly increase the probability and severity of
blistering, HIC damage.
Sour water stripper overhead systems are especially prone to Wet H2S corrosion problem and
this will increase if cyanides are also present like sour water of FCCU. Amine regenerators over
head systems are also prone to Wet H2S damage and cyanide has also similar effect. In hydro
processing units increasing concentration of ammonium bisulfide increases the potential for
blistering, HIC. Acid gas rich amine flash drum is also vulnerable for severe hydrogen
blistering.
Hydrogen absorption of carbon steels equipments due to result of wet ammonium bisulfide
(NH4HS) corrosion in effluent condensers of hydro processing / hydro cracking units in
refineries and in stripper column over head systems of hydro treating units are well known and
thus blistering and HIC is also likely in the same sections.
Carbonate cracking may be prevalent in the main fractionators overhead and wet gas
compression system of Fluidized catalytic cracking units, sour water strippers and delayed
coking unit.
Failure of CS weld in HCO recycle circuit of RFCCU was observed at stresses considerably below
the yield of hard metal due to sulfide stress cracking while processing wild naphtha of DHDS.
The wild naphtha was having H2S content around 20,000-ppm wt and operating temperature was
40 degree C and operating pressure was at 5.0 Kg/ Cm2g pressure. The line originally was not
PWHT and hardness was above 200 BHN.
in near natural pH solutions (pH 5.5-7.5). The hydrogen flux resulting from wet sulfide corrosion
increases both as the pH increases and as the pH decreases from this near neutral range.
Corrosion at the lower (more acidic) pH values is caused by higher concentrations of dissolved
H2S in the water whereas corrosion at the higher (more alkaline) pH values is caused by higher
concentrations of the bisulfide ion in the water.
The sulfide content of the water is generally related to the H2S partial pressure in the gas
phase associated with the water. In acidic sulfide environments, SSC is likely to occur when the
H2S partial pressure exceeds 0.0003 MPa absolute or 3 mbara (0.05 psia). This corresponds to
approximately 1-3 ppm of H2S dissolved in the water. The likelihood of SSC increases with
increasing sulfide application in the water. At sulfide to concentrations greater than 1,000 ppm
the likelihood of SSC is considered to be high. Presence of significant levels of cyanides (>20
ppm) in the water at pH values above 7.5 increases the hydrogen charging of the steel and can
produce a high likelihood of SSC at lower sulfide concentrations.
Susceptible material parameters for SSC
Susceptibility to SSC is related to two materials parameters- hardness and tensile stress level.
The hardness of the base metal is its strength level. Materials with a high hardness are more
susceptible to SSC is generally considered a concern for materials with a tensile strength that
exceeds 620 MPa (90 ksi). Therefore, SSC is highly likely to occur in the low- alloy steel and
other more highly alloyed materials whose tensile strengths exceed this level. SSC of the
typical carbon steel base metals used for pressure vessels and piping in wet H2S service in
oilfield, gas and refining facilities is not a concern because of their low hardness levels.
However, weld deposits and heat affected zones (HAZs) in welded carbon steel may contain
local areas of high hardness due to the presence of non- tempered martensite and high residual
stresses associated with the welding that could increase susceptibility to SSC.
Guidance on environmental conditions leading to SSC of Carbon Steels
Sulfide stress cracking (SSC) is especially dangerous because of the speed of cracking if
susceptible steel is exposed to a H2S- containing environment whilst under some level of tensile
stress; potentially causing a crack within hours. This was recognized in the 1970's and the
National Association of Corrosion Engineers (NACE) in the USA (Materials Recommendation,
MR0175) published the first document giving guidance on materials requirements to avoid SSC
at that time. That document defined a specific environmental condition, which was termed "sour
service within which there is a risk of SSC of materials that are susceptible. Sour conditions
were defined from the total pressure of the system and the concentration of H2S in the gas
phase.
In the mid 1990's the European Federation of Corrosion (EFC) published two European
documents. EFC publication 16 was concerned with carbon and low alloy steels and EFC
publication 17 was concerned with corrosion resistant alloys. EFC 16 defined sour service in
terms of the partial pressure of H2S and the pH of the environment.
Most recently (2003), the above-mentioned two approaches were combined in a new ISO
standard, drawing together the American and European work in an ISO standard, ISO 15156.
This allows the user to select the definition of sour service based on the NACE approach
(considering only the partial pressure of H2S), or the EFC approach (considering the partial
pressure of H2S and the pH of the environment).
Guidance on environmental conditions leading to SCC of Stainless Steels
Early versions of MR 0175 probably did not give any guidance on the conditions within which
stainless steels could be safely used in sour service as they originally concentrated on carbon
steels. However, later versions incorporated advice on a range of materials including 300- series
stainless steels. The following text quotes section 3.5.1 from the 1995 version of MR 0175:
Austenitic stainless steels with chemical compositions as specified in accordance with the
standards listed in Table 1, either cast or wrought, are acceptable at a hardness of 22 HRC
maximum in the annealed condition, provided they are free of cold work designed to
enhance their mechanical properties".
However, it is now recognized that stainless steels have a risk of chloride stress cracking in
sour environments, which contain chloride ions. The exact combinations of conditions, which are
most likely to result in cracking, are not fully defined for every combination of chloride ion
concentration, partial pressure, pH and temperature. However, the new ISO 15156 document
has fixed some guidelines for solution annealed (i.e. without cold work) 300 series stainless
steels at a maximum hardness of 22HRC.
This states two separate limiting conditions, one for low chloride ion concentration and one for
unlimited chloride ion concentration as quoted below.
Temperature
0
C
Partial pressure
of H2S (psi)
60
15
Chloride
concentration
(ppm)
Any
60
50
50
Comments
Specifically for instrument tubing and associated compression fittings the document states in
Table A.4 that S31600 (AISI 316) stainless steel has been used to date without environmental
restriction and so no limits are set on its use in sour service. A comment is added that "some
combinations" of temperature, in- situ pH, partial pressure of H2S and chloride ion
concentration may not be acceptable.
Manufacturing Route
Cast
Forged
Seamless
Rolled plate steel
Even continuously inhibited equipment may suffer HIC if made of susceptable material. But
Inhibitor dosing will reduce the rate of corrosion. The rate of HIC damage accumulation will be
lowered and this will have some impact upon the frequency of inspection for HIC. But inhibitor
may introduce some operational problems.
Evaluation of risk of hydrogen blistering / HIC / SWC
Thus the recommended approach is to inspect equipment to detect the onset and early stages of
growth of cracking. With time passes, the HIC damage may gradually build up and crack linking
may arise, at which stage it may become necessary to replace equipment. The frequency of
inspection is determined by the anticipated rate of accumulation of HIC/ SWC damage and its
severity:
The risk of HIC in forgings and castings is considered to be so low that these need not
be inspected for HIC.
Seamless pipe is very resistant to HIC, and an inspection period of 6 years is considered
safe. It is also considered that inspection of seamless pipe need only commence once HIC
has been positively identified in welded pipe. That is, the welded pipe in the plant can be
used as a 'tell-tale" to indicate the increase in HIC risk.
A 6- yearly inspection has been assigned to welded items (including vessels made from
plate steel) which are internally., coated and to welded items without internal coating,
but exposed to H2S partial pressures less than 0,05 psi.
A 3- yearly inspection has been assigned to welded items (made from plate steel), which
are & exposed to H2S partial pressures greater than 0.06 psi.
The above inspection frequency guidance is used to consider the HIC inspection approach for all
items of equipment considered in the plants. By contrast, steels fully meet the limiting Sulfur
levels as they were purchased to HIC requirements. Thus, these carbon steels may not be
provide total resistant to HIC in actual refining condition and so periodical inspection is also to
be considered for HIC resistant steel.
However, blisters shall be inspected (dia, projection, min thickness, crack etc) and evaluated as
per API 579 guidelines for their acceptance / rejection in different level of assessment. If
Blisters are present to the extent that repairs are necessary then venting of entrapped
hydrogen is to be considered with appropriate caution and safety.
In the process section / equipments having potential for damages, inspection for HIC is to be
considered and generally, Wet fluorescent magnetic particle testing of 50- 100% of weldments,
plus additional shear is considered to be a highly effective intrusive inspection method whereas
no non-intrusive method is considered to be highly effective.
PREVENTION / MITIGATION OF CARBONATE CRACKING
The prevention of carbonates cracking mainly accomplished by application of a post- fabrication
stress- relieving heat treatment (e.g. post weld heat treatment) for susceptible equipment and
piping. A heat treatment of about 620o C (1150o F) for one hour per 25 mm (1 inch) of thickness
(one hour minimum) each considered and effective stress- reliving heat treatment to prevent
carbonate cracking of carbon steel.
Evaluation of risk of carbonate cracking
Inspection for carbonate cracking is to be considered in the process units those are having
potential for same and generally, wet fluorescent magnetic particle testing of 100% of repair
welds and 50- 100% of other welds/ cold bends is considered to be a highly effective intrusive
inspection method. Evaluation of risk of carbonate cracking shall be reassessed in totality for
any major process chances like de-sulphurisation of FCCU feed. This de-sulphurodation will
reduce the H2S level in the overhead system of FCCU and will increase the pH level (relatively)
even may be upto 10 and thus requires Post weld heat treatment to avoid cracking in future.
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Controlling of cyanides is the most important aspect for controlling blistering and HIC related
problem. By wash water injection, dilution of the amount of contaminants, among them cyanides
also, present in the water separated in plant. The generally accepted industry norms for
cyanides in the water solution is between 10- 20 ppm as because this limit allow the FeS layer to
formed on the steel and for the existing layer to remain intact. But there is some limitation;
dilution method for controlling cyanides problem is generally acceptable practice upto the level
of 1500 ppm nitrogen level in the crude oil.
Polysulfide injection along with wash water is producing protective layer and controlling
corrosion. But polysulfide being a very unstable, its supply chain system is highly complicated.
Some times it precipitates as free sulfur and causing dosage lines and pumps to clog up. On site
polysulfide generation systems by peroxide injection is found to be the most suitable method
for cyanide control.
Injection of filming inhibitor has been researched in laboratory but its efficacy in process plant
still
in
question
technically
as
well
as
economically.
Treatment of overhead condensates of FCCU with carbohydrazide is also a suggested method
for prevention of blistering problem in FCCU. The amount of carbohydrazide used to treat
these overheads may vary from as little as 0.5 ppm, up to as much as 100-200 ppm.
CONCLUSIONS
For wet H2S system, low sulphur steel is to be used with qualified HIC resistant properties
(CSR, CLR, CTR). During fabrication, recommended weld hardness with PWHT shall be
maintained for SSC resistant steel. Wet H2S system is to be periodically re-inspected even if
made of HIC resistant steel because these steel may not be total resistant in actual refinery
operation. For any major operational changes, total system shall be critically reviewed with
respected to Carbonate cracking also.
1. ISO 15156/ NACE MR0175 Petroleum and Natural Gas Industries - Materials for Use in
H2S- Containing Environments in Oil and Gas Production. Published by ISO, Dec 2003
2. EFC16 "Guidelines On Materials Requirements For Carbon And Low Alloy Steels For H2S
Containing Environments In Oil And Gas Production", published by The Institute of
Materials, London 1995
3. EFC17 "Corrosion Resistant Alloys For Oil And Gas Production: Guidelines On General
Requirements and Test Methods For H2S Service.", published by The Institute of
Materials, London 1996
4. NACE MR 0103: Materials Resistant to Sulfide Stress Cracking in Corrosive Petroleum
Refining Environments (2003).
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5. Sulfide Stress Cracking in API Publication 581, Risk- Based Inspection Base Resource
Document, 1st Edition, May 2000.
6. Hydrogen- Induced Cracking and Stress- Oriented Hydrogen Induced Cracking in
Hydrogen Sulfide Services (HIC/ SOHIC- H2S) in API Publication 581, Risk- Based
Inspection Base Resource Document, 1st Edition, May 2000.
7. Carbonate Cracking in API Publication 581, Risk- Based Inspection Base Resource
Document, 1st Edition, May 2000.
8. NACE RP 0472: Methods and Controls to Prevent In- Service Environmental Cracking of
Carbon Steel Weldments in Corrosive Petroleum Refining Environments (2000).
9. NACE RP 0296: Guidelines for Detection, Repair, and Mitigation of Cracking of Existing
Petroleum Refinery Pressure Vessels in Wet H2S Environments (2004).
10. J. H. Kmetz and D.J. Truax, Carbonate Stress Corrosion Cracking of Carbon Steel in
Refinery FCC Main Fractionator Overhead Systems, NACE paper # 2006.
11. R.R. Petrie and E.M. Moore, Jr. Determining the Suitability of Existing Pipelines and
Producing Facilities for Wet South Service, Materials Performance 28, 6 (June 1989), pp.
59-65.
12. Singh, V, "Performance of Austenitic Stainless Steels in Wet Sour Gas - Parts 1 and 2
Materials Performance, August and September 2004
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