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Sabp A 001
Sabp A 001
Sabp A 001
SABP-A-001
31 July, 2005
Polythionic Acid SCC Mitigation - Materials Selection and Effective
Protection of Austenitic Stainless Steels and other Austenitic Alloys
Materials and Corrosion Control Standards Committee
Scope.......................................................................... 3
Use of Best Practice.................................................... 3
References.................................................................. 4
Definitions and Abbreviations...................................... 5
Polythionic Acid Stress Corrosion
Cracking (PASCC).............................................. 6
Criteria for Soda Ash Washing
(Decision Tree).................................................. 10
Guidelines for Soda Ash Washing.............................. 11
Material Selection Guidelines for New
Projects and Upgrades...................................... 13
Other PASCC Mitigation Measures............................ 15
Health and Safety....................................................... 15
Page 2 of 20
Scope
This Saudi Aramco Best Practice supplements NACE RP0170-2004 "Protection of
Austenitic Stainless Steels and other Austenitic Alloys from Polythionic Acid Stress
Corrosion Cracking during Shutdown of Refinery Equipment". It specifically provides
the following:
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:
In case of discrepancy between this document and NACE RP0170-2004, resolve
discrepancy through the Coordinator ME&CCD.
Disclaimer
This Best Practice provides PASCC mitigation guidelines based on current
industry practices. Its primary purpose is to provide Saudi Aramco Refineries
with strategies to minimize risk of PASCC during plant shutdowns. It is
intended for Saudi Aramco internal use only.
Saudi Aramco is a registered trademark of the Saudi Arabian Oil Company,
Copyright, Saudi Aramco, 2004.
2.2
References
This Best Practice is based on the latest edition of the references below, unless
otherwise noted.
3.1
SAES-L-133
SAEP-325
SAEP-355
Other Documents
BI-3789
NACE 02478-2002
NiDI Publication
R. L. Piehl
C. H. Samans
NACE 541-1993
Page 4 of 20
3.2
API RP571-2003
ASTM A262-2002
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.
Positive Material Identification is a chemical analysis that includes all alloying
elements, including C, Ti and Nb, to determine stabilization ratios.
Sensitization refers to the composition / time / temperature dependent formation
of chromium carbides along the grain boundaries of austenitic stainless alloys.
Sensitization causes a dramatic loss in corrosion resistance along the grain
boundaries and generally occurs in the temperature range 370C to 815C
(700F to 1500F).
Sigmatization or Sigma Phase Embrittlement refers to the formation of an ironchromium phase, affecting austenitic stainless steels. It generally forms with
long-time exposure in the range of 565 to 980C (1050 to 1800F).
Soda Ash is a sodium carbonate solution, normally used at 1 5 %
concentration.
Page 5 of 20
Abbreviations
Cl-SCC
HAZ
PASCC
PMI
PT
= Penetrant Testing
RIM
5.2
Damage Description
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.
Susceptible Materials
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 650C
(1200F).
Page 6 of 20
5.3
Principal Factors
5.4
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 400C (750F). 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 sulfurcontaining 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
5.5
5.6
PASCC Characteristics
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.
PASCC Mitigation
Effective mitigation involves both material selection and control of process
parameters. Material selection is used to specify sensitization-resistant alloys
and heat treatments. Process aspects address shutdown procedures to control
the environment, by preventing polythionic acid formation or including a soda
ash wash neutralization step.
Material Factors
Page 8 of 20
However, for thicker wall piping (>1 inch) or equipment operating below
427C, 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:
5.7
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
Alloy verification to confirm austenitic material type and stabilization ratios for 321
and 347 grades. Specifically, stabilization ratios shall be as follows:
o Greater than 8 for Ti:C and
o Within the range 10 to 12 for Nb:C
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 370C sensitization is not
anticipated for these grades.
For stabilized materials operating above 455C, 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
Blue Cycle). This approach shall be followed regardless of the operating interval
between shutdowns.
7
Key Requirements
Plants shall develop a RIM based on process licensor's guidelines. This RIM
shall include the following key points:
1)
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.
5)
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).
8)
Page 11 of 20
7.2
7.2.2
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.
7.2.3
7.2.4
Reactors
Page 12 of 20
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.
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
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:
1)
2)
b)
c)
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
Sigmatization is promoted by the presence of Nb. Accordingly, an upper limit of 12
is imposed on Nb:C ratio.
5)
6)
7)
For fired heater tubing or other components operating above 455C (metal
temperature), items 1 to 4 above are required. However, for thicker wall piping
(>1 inch) or equipment operating below 427C, 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
8)
For heat exchanger U-bends made of unstabilized grades, e.g. 304L, solution
anneal the entire tube at 1070C 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 - 900C 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.
9
Nitrogen Purging
Nitrogen purging is an alternative to neutralization. The nitrogen should be
pure, dry and oxygen-free.
A positive nitrogen pressure should be maintained. For steam-air decoking
(7.2.2), steam injection should be stopped before the metal temperature cools to
72C above the water dew point. When depressurized, but before further
cooling, the system should be purged with dry nitrogen.
9.2
10
31 July 2005
Revision Summary
New Saudi Aramco Best Practice.
Page 15 of 20
C
650
Time/Temperature-Sensitization
Diagram for Types 304 & 304L
F
Stainless Steels
1200
Type 304
600
1100
550
Type 304L
1000
500
900
450
10
100
1,000
10,000
Time at Heat Treating Temperature
Hours
Source: Piehl
(a)
C
650
Time/Temperature-Sensitization
Diagram for Types 321 & 347
F
Stainless Steels
1200
Type 321
600
1100
550
Type
347
1000
500
900
450
10
100
1,000
10,000
Time at Heat Tre ating Tempe rature
Hours
Source: Piehl
(b)
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Attachment 1
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