PREVENTION OF POLYTHIONIC ACID STRESS CORROSION CRACKING OF AUSTENITIC STAINLESS STEEL EQUIPMENT

(This practice is appropriate for attachment to Inquiry or Purchase Document)

EG 19-7-1.2
Page 1 of 2 Rev. 0 June, 1996

SCOPE 1.1 The purpose of this Engineering Guide is to provide information to prevent polythionic acid stress corrosion cracking (PSCC) of stainless steel equipment. Both lined (weld overlayed or clad) and solid stainless components are addressed. DEFINITION 2.1 Polythionic acid stress corrosion cracking is a form of intergranular corrosion which takes place during unit downtimes when stainless steel equipment, which has previously been subjected to a high temperature sulfur bearing environment, is exposed to moisture. In order to be susceptible to cracking the alloy must be in the sensitized condition (see Par. 3.2). Polythionic acid (H2SxO6) forms when the moisture reacts with any iron sulfide (FeS) present on the surface of the equipment. This acid then attacks the grain boundaries of the alloy causing cracking. Note that the FeS may have been produced by either corrosion of the stainless steel itself or by corrosion of upstream equipment. MATERIALS 3.1 The austenitic forms of stainless steel (i.e., 300 series) are susceptible to stress corrosion cracking from polythionic acid. Other grades such as martensitic or ferritic stainless (e.g., 400 series) are not susceptible. Duplex stainless steels are resistant to PSCC under most conditions. Certain higher alloy materials are also vulnerable to cracking. It has been found that some fully austenitic high alloys (e.g., Inconel 600 and Incoloy 800) can crack in polythionic acid if they do not contain stabilizing elements (see Par. 3.2). 3.2 Stainless steel must be in the sensitized condition to be susceptible to PSCC. Sensitization refers to the depletion of chromium at the grain boundaries of the alloy due to chromium carbide precipitation. It occurs only after prolonged exposure to high process operating temperatures, from the heat of welding, or from manufacturing practices. Certain grades of stainless have been stabilized in order to minimize chromium depletion. These grades have special additions of titanium (Type 321) or niobium (Type 347) which form very stable carbides that minimize chromium carbide formation. Low carbon grades of stainless (e.g., Type 304L or 316L) are also commonly used to prevent sensitization. These alloys limit the amount of carbon to 0.03% to reduce the extent of chromium carbide precipitation. a. The stabilized and low carbon grades of stainless steel do not sensitize during welding, but can sensitize after long term service above 850_F. All other grades, particularly the high carbon versions (usually > 0.04% carbon) like Type 304H, will sensitize after service above 750_F, or by welding. It has been found that certain mill applied heat treatments may result in Type 321 being susceptible to sensitization and PSCC. Consequently, any purchases of Type 321 should stipulate that the material pass the testing requirements of ASTM A262 Practice E. Most common grades of stainless steel used for weld overlays (e.g., Types 308, 308L, 309, 347) are extremely resistant to sensitization at typical operating and post weld heat treatment temperatures. In general, overlays are considered resistant to PSCC; however, heating an overlay to temperatures above 1500_F will cause sensitization and should be avoided. It has been found that PSCC can occur when the outer layer(s) of a multi-pass overlay are machined away, exposing the earlier passes. Most austenitic heat exchanger bundles that have rolled tubes, without any strength or seal welds at the tubesheet, are resistant to PSCC provided operating temperatures comply with Par. 3.2 a. above. PREVENTION OF PSCC 4.1 In order to prevent PSCC it is possible to wash equipment with an alkaline solution (typically soda ash) which both neutralizes polythionic acid and passivates the stainless steel. SODA ASH SOLUTION PREPARATION Soda ash solution is defined as follows: 2 wt% soda ash (Na2CO3), 0.05 wt% sodium nitrate, 0.05 wt% wetting agent, balance water. The chloride content must not exceed 50 ppm in the water or 500 ppm in the soda ash, and in no case should the final solution contain more than 150 ppm chloride. Mixing of the solution should be done with the water at approximately 100_F. Further details about alkaline wash solutions can be found in NACE RP0170-93.

b.

c.

d.

EXXON REGIONAL ENGINEERING GUIDE

EG 19-7-1.2
Page 2 of 2 Rev. 0 June, 1996

(This practice is appropriate for attachment to Inquiry or Purchase Document)

PREVENTION OF POLYTHIONIC ACID STRESS CORROSION CRACKING OF AUSTENITIC STAINLESS STEEL EQUIPMENT
PREVENTION OF PSCC (Cont)

4.2

Generally, vessels require only a single wash immediately after opening (or catalyst removal). However, it has been noted that sweating of vessel walls can wash off the protective solution and lead to subsequent cracking. If such conditions are present, re-washing or dehumidification may be required. Methods employing a spraying device are usually more convenient for vessels, but are generally less effective than circulating the solution through the equipment. Equipment not depressured, steamed out, or opened during downtime does not require special precautions for protection against PSCC. Equipment depressured but not opened during unit downtime shall be held under a slightly positive pressure (2 3 psig) using a dry nitrogen purge to prevent moisture and oxygen from entering. If use of dry nitrogen is not possible, dry air may be used as long as the dew point remains lower than 5_F. Steaming out of austenitic stainless steel equipment should be avoided. If the equipment is steamed out, a nitrogen purge should be started as soon a possible before the equipment is allowed to cool. Equipment that is to be opened during the unit downtimes will require the following to prevent moisture ingress and to maintain a film of the soda ash solution on the equipment for the duration of the downtime. a. b. c. d. e. Following depressuring and before air or moisture can enter, the equipment shall be purged with dry nitrogen and held at a slightly positive pressure. The equipment shall be blinded under nitrogen purge. Still under a nitrogen purge at a slightly positive pressure, the equipment shall be filled with soda ash solution (the equipment may be warm but should not be above about 150_F). Soak, flush, or circulate through the equipment with the solution for a minimum of 2 hours. Circulation is recommended over soaking to obtain better coverage. A pH of 7 or greater shall be maintained. Drain equipment but do not wash off the remaining film or allow the film to weather off (due to rain, snow, or heavy dew). Care must be taken to ensure that the film left from the soda ash solution remains on the equipment to neutralize any acids which could develop later during the downtime. Therefore, equipment should never be washed down subsequent to the alkaline wash. Also, water ingress from rain or sweating due to humid conditions must be prevented from washing the solution off the equipment.

4.3 4.4

4.5 4.6

4.7

Reactors: soda ash washing of reactors filled with catalyst is not recommended, as it is detrimental to the catalyst. If opening is required, keep the reactor dry with a nitrogen purge. After the catalyst has been removed, neutralization with soda ash solution is recommended if the solution residue is not detrimental to the catalyst. Furnaces: whenever possible, furnace coils should remain unopened and be kept under a dry nitrogen purge during downtimes in preference to alkaline washing. There are two reasons for this: a. b. It is usually impossible to effectively drain all the water/solution from furnace coil return bends. Furnaces which have a heavy coke build up (and have not been decoked prior to shut down) can not be effectively soda ash washed since the solution will not penetrate the sulfur bearing coke.

4.8

When opening of the furnace coil is required, the soda ash solution should be circulated in a turbulent fashion to promote as much wetting of the stainless steel surface as possible. For furnaces highly susceptible to coking (e.g., lubes extract furnaces) decoking prior to shut down is recommended if the furnace coil must be opened. The solution may be removed by displacing with air, nitrogen, or process fluid. When practical, the coil should remain full of solution during the downtime. CLEANING 5.1 When high pressure water cleaning is used on equipment susceptible to polythionic acid stress corrosion cracking, a soda ash solution should be used in place of water. When other than soda ash is used, a soda ash film should be re-established by coating the equipment with a soda ash solution when cleaning is complete or when the equipment is to be left for a period longer than one hour. When hydrotesting is required, soda ash solution should be used instead of water.

6/96

Revision Memo Rev. 0 Original Issue of Engineering Guide

E Exxon Company, U.S.A., Exxon Chemical Americas, 1996

EXXON REGIONAL ENGINEERING GUIDE