Sabp A 001
Sabp A 001
Sabp A 001
1 Scope.......................................................................... 3
2 Use of Best Practice.................................................... 3
3 References.................................................................. 4
4 Definitions and Abbreviations...................................... 5
5 Polythionic Acid Stress Corrosion
Cracking (PASCC).............................................. 6
6 Criteria for Soda Ash Washing
(Decision Tree).................................................. 10
7 Guidelines for Soda Ash Washing.............................. 11
8 Material Selection Guidelines for New
Projects and Upgrades...................................... 13
9 Other PASCC Mitigation Measures............................ 15
10 Health and Safety....................................................... 15
Page 2 of 20
Document Responsibility: Materials and Corrosion Control SABP-A-001
Issue Date: 31 July 2005 Polythionic Acid SCC Mitigation - Materials Selection and Effective
Next Update: 1 August 2010 Protection of Austenitic Stainless Steels and other Austenitic Alloys
1 Scope
• Criteria to determine the need for soda ash washing of existing austenitic stainless
steel equipment and piping during plant downtime.
Its purpose is to prevent polythionic acid stress corrosion cracking (PASCC) caused by
the reaction of sulfide corrosion products, oxygen (air) and water/moisture during
shutdowns. Refineries shall adopt this Best Practice to formulate or revise PASCC
mitigation strategies, which are normally documented as RIMs.
Optimized materials selection for new projects or upgrades is the key to equipment
reliability. Significant potential cost savings may be achieved when protection by soda
ash washing is determined to be unnecessary.
Commentary Note:
2.1 Disclaimer
In the event of a conflict between this Best Practice and other Mandatory Saudi
Aramco Engineering Standards or Specifications, the matter shall be referred to
the Coordinator of ME&CCD/CSD for resolution.
Page 3 of 20
Document Responsibility: Materials and Corrosion Control SABP-A-001
Issue Date: 31 July 2005 Polythionic Acid SCC Mitigation - Materials Selection and Effective
Next Update: 1 August 2010 Protection of Austenitic Stainless Steels and other Austenitic Alloys
3 References
This Best Practice is based on the latest edition of the references below, unless
otherwise noted.
Other Documents
BI-3789 Project Specification for Material Specification
and Corrosion Control – Rabigh Refinery 1997
Upgrade Project
NACE 02478-2002 Thick-Wall Stainless Steel Piping in
Hydroprocessing Units – Heat Treatment
Issues
NiDI Publication The Role of Stainless Steels in Petroleum Refining
9021 (1977)
R. L. Piehl Stress Corrosion Cracking by Sulfur Acids –
Proceedings API, Refining Division, 1964
C. H. Samans Stress Corrosion Cracking Susceptibility of
Stainless Steels and Nickel-base Alloys in
Polythionic Acids and Copper Sulfate Solution,
Corrosion 20, 8 (1964)
NACE 541-1993 Performance of High Nickel Alloys in Refinery
and Petrochemical Environments
Page 4 of 20
Document Responsibility: Materials and Corrosion Control SABP-A-001
Issue Date: 31 July 2005 Polythionic Acid SCC Mitigation - Materials Selection and Effective
Next Update: 1 August 2010 Protection of Austenitic Stainless Steels and other Austenitic Alloys
4.1 Definitions
Austenitic Stainless Steels are 300 series stainless alloys with an austenitic
microstructure, such as 304, 316, 321 and 347.
Chemical Stabilization involves the addition of titanium (Ti) and niobium (Nb)
to minimize sensitization.
Neutralization is the use of alkali to neutralize acid, or vice versa. In this Best
Practice, it primarily refers to soda ash solution which is used to neutralize
polythionic acids.
Polythionic Acids are sulfur acids with the formula H2SxO6; where x ranges
from 3 – 6. Such acids can form on plant shutdown in certain refinery
equipment, especially in units operating in H2/H2S service.
Page 5 of 20
Document Responsibility: Materials and Corrosion Control SABP-A-001
Issue Date: 31 July 2005 Polythionic Acid SCC Mitigation - Materials Selection and Effective
Next Update: 1 August 2010 Protection of Austenitic Stainless Steels and other Austenitic Alloys
4.2 Abbreviations
• PASCC is a type of stress corrosion cracking which can occur rapidly under
shutdown or T&I conditions. Cracking is due to sulfur acids forming from
sulfide scale, air and moisture acting on sensitized austenitic stainless steels.
• 300 series stainless steels, Alloy 600/600H, Alloy 625, Alloy 800/800H and
Alloy 825.
Commentary Note
It is noted that Alloy 625 and 825 are much more sensitization-resistant than the
300 series stainless steels, with a sensitization threshold at about 650°C
(1200°F).
Page 6 of 20
Document Responsibility: Materials and Corrosion Control SABP-A-001
Issue Date: 31 July 2005 Polythionic Acid SCC Mitigation - Materials Selection and Effective
Next Update: 1 August 2010 Protection of Austenitic Stainless Steels and other Austenitic Alloys
• The carbon content and the thermal history of the alloy have a significant
effect on sensitization susceptibility. Regular and controlled carbon grades
of stainless steels such as types 304/304H and 316/316H are particularly
susceptible to sensitizing in the weld HAZ. Low carbon "L" grades
(< 0.03% C) are less susceptible and usually can be welded without
sensitizing. The L grades will not sensitize provided long term operating
temperatures do not exceed 400°C (750°F). Time - Temperature
sensitization curves have generally been adopted by industry for 304, 304L,
321 and 347 grades (Figure 1).
• All units where alloys that may become sensitized are used in sulfur-
containing environments. Commonly damaged equipment includes but is
not limited to heat exchanger tubes, furnace tubes and piping.
• FCC units (air rings, plenums, slide valves, cyclone components, expansion
joint bellows and piping).
Page 7 of 20
Document Responsibility: Materials and Corrosion Control SABP-A-001
Issue Date: 31 July 2005 Polythionic Acid SCC Mitigation - Materials Selection and Effective
Next Update: 1 August 2010 Protection of Austenitic Stainless Steels and other Austenitic Alloys
Commentary Note
At the time of developing this Best Practice, no austenitic stainless steel type 300
components exist in Saudi Aramco Crude/Vacuum units.
• Typically occurs next to welds, but can also occur in the base metal (Figures
2, 3). It is usually quite localized and may not be evident until a leak
appears during start-up or, in some cases, operation.
Material Factors
Page 8 of 20
Document Responsibility: Materials and Corrosion Control SABP-A-001
Issue Date: 31 July 2005 Polythionic Acid SCC Mitigation - Materials Selection and Effective
Next Update: 1 August 2010 Protection of Austenitic Stainless Steels and other Austenitic Alloys
• However, for thicker wall piping (>1 inch) or equipment operating below
427°C, thermal stabilization is not recommended. Experience has shown
that the risks of reheat cracking and sigma phase embrittlement outweigh the
benefits of thermal stabilization of thicker wall material.
Process factors:
• Penetrant Testing (PT) examination can be used to detect PASCC (Figure 2).
However, because the cracks are filled with a tight deposit, flapper disc
sanding may be needed to improve the PT sensitivity.
• PASCC can be an inspection challenge because the cracking may not occur
until well into a turnaround.
Page 9 of 20
Document Responsibility: Materials and Corrosion Control SABP-A-001
Issue Date: 31 July 2005 Polythionic Acid SCC Mitigation - Materials Selection and Effective
Next Update: 1 August 2010 Protection of Austenitic Stainless Steels and other Austenitic Alloys
A decision tree for soda ash washing for existing equipment and piping is presented in
Figure 6. Requirements for new equipment/upgrades are addressed in Section 8.
The key points to consider in applying this decision tree are as follows:
• Alloy verification to confirm austenitic material type and stabilization ratios for 321
and 347 grades. Specifically, stabilization ratios shall be as follows:
For fired equipment, the metal temperature is usually derived from skin
thermocouple records. Accordingly, such equipment must be fitted with reliable
skin thermocouples. For other equipment, e.g. exchangers, the process
temperature is regarded as representative of the metal temperature.
o For non-stabilized grades, i.e. 304/316, a soda ash wash is required at every
shutdown. It is noted that at temperatures below 370°C sensitization is not
anticipated for these grades.
• For stabilized materials operating above 455°C, soda ash washing must be applied
at the first shutdown. This should be immediately followed by a field sensitization
test to check degree of sensitization. If the material is not sensitized, then the soda
ash wash can be skipped at the next shutdown, but re-applied at the subsequent
shutdown. The cycle of monitoring sensitization (repeating sensitization test) and
skipping soda ash wash at subsequent shutdowns can be repeated (Figure 6, Pale
Page 10 of 20
Document Responsibility: Materials and Corrosion Control SABP-A-001
Issue Date: 31 July 2005 Polythionic Acid SCC Mitigation - Materials Selection and Effective
Next Update: 1 August 2010 Protection of Austenitic Stainless Steels and other Austenitic Alloys
Blue Cycle). This approach shall be followed regardless of the operating interval
between shutdowns.
Plants shall develop a RIM based on process licensor's guidelines. This RIM
shall include the following key points:
2) Monitor and record solution pH (> 9) and chlorides (< 250 mg/L
[250 ppmw]), on an hourly basis.
3) A protective residual film of soda ash will remain after draining, even after
the equipment has dried. Do not rinse or wash off the residual film before
putting equipment back in service.
4) This equipment should then be kept dry and out of the weather to the
greatest practical extent to avoid washing away of the protective film.
6) It is generally not necessary to re-apply the film unless the protective film
was been washed-off or mechanically removed or damaged.
7) Care should be taken during startup and shutdown to avoid washing away
a film and exposing equipment to air and water (e.g., hydrotesting, steam
out. Refer Section 7.2.2).
Page 11 of 20
Document Responsibility: Materials and Corrosion Control SABP-A-001
Issue Date: 31 July 2005 Polythionic Acid SCC Mitigation - Materials Selection and Effective
Next Update: 1 August 2010 Protection of Austenitic Stainless Steels and other Austenitic Alloys
• For long term outage (> 2 weeks) the tubes should be blown dry with
air or inert gas and sealed with a slight positive pressure of dry inert
gas.
During cool down after decoking, condensed steam and air can coexist
and could result in PASCC. To prevent this, 5000 ppm NH3 should be
injected into the steam during the final phase of steaming-out or
decoking. This ammoniated steam can then be displaced with soda ash
as required. Alternatively, nitrogen purging (9.1) can be used.
7.2.4 Reactors
Page 12 of 20
Document Responsibility: Materials and Corrosion Control SABP-A-001
Issue Date: 31 July 2005 Polythionic Acid SCC Mitigation - Materials Selection and Effective
Next Update: 1 August 2010 Protection of Austenitic Stainless Steels and other Austenitic Alloys
• Due to their large volume and presence of catalyst, soda ash washing
of reactors is often impractical. Additionally, sodium is a catalyst
poison. Therefore, the most practical means of protecting reactors is
by inerting or keeping dry.
• Note dry air can be used only if the catalyst has been regenerated to
convert the bulk of the pyrophoric iron sulfide which is usually
present. However, soda ash wash can be used for protecting reactors
after the catalyst has been dumped or even for wet dumping catalyst
when replacement is planned.
• Both filling and hosing down the walls with soda ash have been used.
Recirculating the soda ash solution is acceptable for hosing purposes
provided the alkalinity is maintained.
Therefore, when the risk of PASCC is judged to be low, based on optimum material
selection, alloy verification (PMI), fabrication practices and process design parameters,
the Materials Engineering Unit of CSD shall be consulted to determine the need for
soda ash washing. Since PASCC is time - temperature dependent, this approach:
• Is valid for a limited service period, e.g. up to 2nd Turnaround or 7 years maximum.
Subsequent service beyond the 2nd Turnaround requires full re-evaluation based on
criteria given in Section 5.
Page 13 of 20
Document Responsibility: Materials and Corrosion Control SABP-A-001
Issue Date: 31 July 2005 Polythionic Acid SCC Mitigation - Materials Selection and Effective
Next Update: 1 August 2010 Protection of Austenitic Stainless Steels and other Austenitic Alloys
Accordingly, for new Saudi Aramco projects and upgrades with potential PASCC risk,
optimum material specification and heat treatments (for base materials and welds during
manufacture) shall include the following requirements, to enhance PASCC and Cl-SCC
resistance:
3) For 321 stainless steels, the Ti:C stabilization ratio shall be greater than or equal to
8.
4) For 347 stainless steels, the Nb:C stabilization ratio shall be within the range 10 to
12.
Commentary Note
7) For fired heater tubing or other components operating above 455°C (metal
temperature), items 1 to 4 above are required. However, for thicker wall piping
(>1 inch) or equipment operating below 427°C, thermal stabilization is not
recommended due to the risks of reheat cracking and sigma phase embrittlement.
Therefore, thermal stabilization is not recommended for thick wall components.
Page 14 of 20
Document Responsibility: Materials and Corrosion Control SABP-A-001
Issue Date: 31 July 2005 Polythionic Acid SCC Mitigation - Materials Selection and Effective
Next Update: 1 August 2010 Protection of Austenitic Stainless Steels and other Austenitic Alloys
8) For heat exchanger U-bends made of unstabilized grades, e.g. 304L, solution
anneal the entire tube at 1070°C after bending (item 2a). Use stabilized grades
321 or 347 if only the U-bends can be heat treated.
9) For drains, where there is a risk of Cl-SCC due to water entrapment during
shutdowns, a stress relief heat treatment at 870 - 900°C for 1 hour per inch
followed by rapid air cooling is required. An alternative is to specify low-point
drains in Cl-SCC resistant alloys, such as Alloy 825 or 625.
10) PASCC failures of Alloy 800 exchanger tubing in Hydroprocessing Units have
been reported; these were attributed to sensitization caused by stress relief heat
treatment or welding. Therefore, where Alloy 800 is specified for such tubing,
this shall be ordered to a maximum carbon content of 0.03%; alternatively, the
stabilized Alloy 801 or Alloy 825 can be used.
The use of dry air is another approach reduce risk of PASCC. The incoming air
dew point must be maintained at a temperature well below internal metal
temperature to prevent water condensation. The recommended temperature
differential (metal temperature minus dew point temperature) is at least 22ºC.
Health and Safety guidelines concerning handling and disposal of soda ash solution are
given in the Chemical Hazard Bulletin (Attachment 1). This states that sodium
carbonate is a severe irritant to the eyes, skin and respiratory tract and hence Personal
Protective Equipment shall include wearing goggles, neoprene gloves and dust mask if
handling solid powder. In addition, operators shall contact Environmental Protection
Department, Dhahran, for safe disposal of the solution.
Revision Summary
31 July 2005 New Saudi Aramco Best Practice.
Page 15 of 20
Document Responsibility: Materials and Corrosion Control SABP-A-001
Issue Date: 31 July 2005 Polythionic Acid SCC Mitigation - Materials Selection and Effective
Next Update: 1 August 2010 Protection of Austenitic Stainless Steels and other Austenitic Alloys
Time/Temperature-Sensitization
Diagram for Types 304 & 304L
C F Stainless Steels
650 1200
Type 304
600
1100
500
900
(a)
Time/Temperature-Sensitization
Diagram for Types 321 & 347
C F
650 1200
Stainless Steels
600
Type 321
1100
550
1000
Type
347
500
900
(b)
Page 16 of 20
Document Responsibility: Materials and Corrosion Control SABP-A-001
Issue Date: 31 July 2005 Polythionic Acid SCC Mitigation - Materials Selection and Effective
Next Update: 1 August 2010 Protection of Austenitic Stainless Steels and other Austenitic Alloys
Page 17 of 20
Document Responsibility: Materials and Corrosion Control SABP-A-001
Issue Date: 31 July 2005 Polythionic Acid SCC Mitigation - Materials Selection and Effective
Next Update: 1 August 2010 Protection of Austenitic Stainless Steels and other Austenitic Alloys
Page 18 of 20
Document Responsibility: Materials and Corrosion Control SABP-A-001
Issue Date: 31 July 2005 Polythionic Acid SCC Mitigation - Materials Selection and Effective
Next Update: 1 August 2010 Protection of Austenitic Stainless Steels and other Austenitic Alloys
Page 19 of 20
Document Responsibility: Materials and Corrosion Control SABP-A-001
Issue Date: 31 July 2005 Polythionic Acid SCC Mitigation - Materials Selection and Effective
Next Update: 1 August 2010 Protection of Austenitic Stainless Steels and other Austenitic Alloys
Attachment 1
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