5.1.2.

5 Carbonate Stress Corrosion Cracking (ACSCC)

5.1.2.5.1 Description of Damage
Carbonate stress corrosion cracking (often referred to as carbonate cracking) is the term applied to
surface breaking cracks that occur adjacent to carbon steel welds under the combined action of tensile
stress in systems containing a free water phase with carbonate, where some amount of H2S is also
present. It is a form of Alkaline Stress Corrosion Cracking (ACSCC).
This type of damage has also been observed in other environments which are outside the scope of this
discussion. Those environments include the outside surface of buried pipelines; and piping and
equipment containing aqueous carbonate solutions (e.g., potassium carbonate) used in the carbon
dioxide (CO2) removal facilities associated with hydrogen reformers.
5.1.2.5.2 Affected Materials
Carbon steel and low alloy steels.
5.1.2.5.3 Critical Factors
a) The residual stress level of carbon steel and the water chemistry are the critical factors that
determine the likelihood of carbonate cracking.
b) Carbonate stress corrosion cracking can occur at relatively low levels of residual stress but usually
occurs at welds or cold worked areas that have not been stress relieved.
c) Additional details of water chemistry affecting susceptibility in FCC units are outlined below. More
detailed information can be found in a NACE industry review published in 2008 (Reference 4).
1) Water - In all areas in which ACSCC has been reported, there has been a separate liquid water
phase present.
2) pH - The pH of the sour water is a critical factor; most failures have occurred in the range of pH
8 to 10.
3) H2S – Cracking occurs where alkaline water is present. Although H2S is often present, no
threshold level has been established.
4) Ammonia - NH3 in the sour water is usually higher in cases where ACSCC has been observed
than in cases with no ACSCC (e.g., 4,800 ppmw vs. 2,500 pmmw). Increasing NH3 and
decreasing H2S together increase the likelihood of ACSCC.
5) Carbonate ion concentration – Cracking occurs above a certain threshold concentration. It has
been suggested that levels above 100 ppmw can cause ACSCC, depending on the pH of the
system. However, specific guidelines are difficult to define, largely as a result of the difficulty of
sampling for carbonate ions and the lack of available data.
6) Cyanides – Cracking can occur with or without the presence of cyanides.
7) Polysulfides - There is no evidence to suggest that ammonium polysulfide injection increases
or decreases the potential for ACSCC.
d) FCCU feed quality and unit operation appear to have an effect on cracking susceptibility:
1) Feed Nitrogen - The total nitrogen in FCCU feed is usually higher in cases where ACSCC
has been observed than in cases with no ACSCC (e.g., 2,645 ppmw vs. 940 ppmw).
2) Feed Sulfur – In general, cracking is associated with low sulfur FCCU feeds as opposed to high
sulfur feeds. Susceptibility to cracking appears to be much more likely with hydrotreated feed.
3) N to S ratio – Most cases of ACSCC have been associated with N/S ratio in the FCCU feed of 0
to 70
4) Full burn vs. partial burn – The likelihood of cracking occurring in the FCC Regenerator partial-
burn mode is approximately the same as full burn mode.
e) In CO2 removal units, cracking may occur when the CO2 content is above 2% and temperatures
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exceed 200 F (93 C).
5.1.2.5.4 Affected Units or Equipment
a) Carbonate cracking has been most prevalent in the fluid catalytic cracking unit main fractionator
 overhead condensing and reflux system, the downstream wet gas compression system, and the sour
water systems emanating from these areas. Both piping and vessels are affected. See Figure 5-44
and 5-45 for typical locations where cracking has occurred.
b) Carbonate cracking has also been observed in SWS units of the side-pumparound type in the
pumparound return line to the SWS tower; on the OD (process side) of highly cold worked SA179
condenser tube u-bends; and in the floor of tank storing sour water from an FCC unit.
c) Carbonate cracking has also occurred in piping and equipment in potassium carbonate in Catacarb
and CO2 removal facilities of hydrogen manufacturing units.
5.1.2.5.5 Appearance or Morphology of Damage
a) Carbonate cracking typically propagates parallel to the weld in the heat-affected zone, or adjacent
base metal within 2 inches (50 mm) of the weld. At least two cases have been reported to occur
more than 3 inches away (80 mm) in highly cold worked fittings including an elbow and reducer.
b) Cracking can also occur in the weld deposit.
c) The pattern of cracking observed on the steel surface is sometimes described as a spider web of
small cracks, which often initiate at or interconnect with weld-related flaws that serve as local stress
raisers.
d) These cracks may be easily mistaken for SSC or SOHIC, however, the carbonate cracks are usually
further from the toe of the weld and have multiple parallel cracks (Figure 5-46 to Figure 5-47).
e) Carbonate cracks are surface breaking flaws that are predominantly intergranular in nature and
typically occur in as-welded carbon steel fabrications as a network of very fine, oxide-filled cracks
similar in appearance to caustic stress corrosion cracking and amine stress corrosion cracking. See
Figures 5-48 to Figure 5-55.
5.1.2.5.6 Prevention / Mitigation
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a) Application of a post-fabrication stress-relieving heat treatment of 1200 F to 1225°F (649 C to
o
663 C) in accordance with WRC 452 (Reference 8) is a proven method of preventing carbonate
cracking. Heat treatment requirements apply to repair welds as well as internal and external
attachment welds.
b) Cracking can be eliminated through the use of effective barrier coatings, solid or clad 300 Series SS,
Alloy 400 or other corrosion resistant alloys in lieu of carbon steel.
c) Water wash non-PWHT piping and equipment prior to steamout or heat treatment in hot carbonate
systems.
d) A metavanadate inhibitor can be used in hot carbonate systems in CO2 removal units in hydrogen
manufacturing units to prevent cracking. Proper dosing and oxidation of the inhibitor must be
maintained.
5.1.2.5.7 Inspection and Monitoring
a) Monitoring the pH of FCC sour waters is the fastest and most practical and cost effective method to
locate areas where there is a potential for ASCC to occur.
b) The cracking can involve sporadic and rapid growth, depending on subtle changes in the process.
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Periodic monitoring of CO3 concentration in FCC sour waters should be done to determine
cracking susceptibility.
c) Although cracks may be seen visually, crack detection is best performed with WFMT or ACFM
techniques. Surface preparation by grit blasting, high pressure water blasting or other methods is
usually required for WFMT. PT usually cannot find tight or scale filled cracks and should not be
used.
d) There is usually much branching so crack depths may be measured with a suitable UT technique
including external SWUT. Electrical resistance type instruments that measure crack depth are not
effective because the cracks typically contain magnetic iron oxide.
e) This cracking is not susceptible to extension by grinding. Grinding out the cracks is a viable method
of crack depth determination.
f) AET can be used for monitoring crack growth and locating growing cracks.
5.1.2.5.8 Related Mechanisms
Carbonate cracking is more properly termed carbonate stress corrosion cracking and is a form of Alkaline
Stress Corrosion Cracking (ASCC). Amine cracking (see 5.1.2.2) and caustic stress corrosion cracking
(see 4.5.3) are two other similar forms of ASCC.
5.1.2.5.9 References
1. J.H. Kmetz and D.J. Truax, “Carbonate Stress Corrosion Cracking of Carbon Steel in Refinery FCC
Main Fractionator Overhead Systems,” CORROSION/90, Paper No. 206, NACE International,
Houston, TX, 1990.
2. H.U. Schutt, “Intergranular Wet Hydrogen Sulfide Cracking,” CORROSION/92, Paper No. 454, NACE
International, Houston, TX, 1992.
3. E. Mirabel et al, “Carbonate-type Cracking in an FCC Wet Gas Compressor Station,” Materials
Performance, July, 1991, pp. 41-45.
4. NACE Standard RP0296, “Guidelines for Detection, Repair and Mitigation of Cracking of Existing
Petroleum Refinery Pressure Vessels in Wet H2S Environments, NACE International, Houston, TX.
5. NACE Publication 34108, Review and Survey of Alkaline Carbonate Stress Corrosion Cracking in
Refinery Sour Water, NACE International, Houston, TX, 2008.
6. M. Rivera et al., “Carbonate Cracking Risk Assessment for an FCCU Gas Plant”, Paper #04639,
NACE International, Houston, TX, 2004.
7. D. Milton et al., , FCCU Light Ends Plant Carbonate Stress Corrosion Cracking Experience, Paper
#07564, NACE International, Houston, TX, 2007.
8. WRC Bulletin 452, “Recommended Practices for Local Heating of Welds in Pressure Vessels”
9. Welding Research Council (WRC), Shaker Heights, OH.
Figure 5-44 – Simplified PFD of an FCCU gas plant showing where ACSCC has been reported
Reference 5).
Figure 5-45 – In a span of 7 months, a refinery experienced 23 leaks in piping in the Fractionator
Overhead and the Wet Gas Compressor sections. Follow-up with SWUT located 73 more
indications (Reference 6)

Figure 5-46 – Overhead interstage knockout drum vapor outlet nozzle.

 Figure 5-47 – Carbonate cracking adjacent to a weld (Reference 6).

Figure 5-48 – Metallographic sample showing intergranular carbonate cracking developed after 6
months service (Reference 6).
Figure 5-49 – Most cracks originate in base metal but this weldment contained a crack that
originated at the root and propagated through the weld metal. Other cracks appear to have
initiated in the HAZ (Reference 7).

Figure 5-50 – Photomicrograph of a cross-section of carbonate cracking in the base metal.

Cracks initiate from the I.D. surface (left side). Unetched.
Figure 5-51 – Photomicrograph of a cross-section of carbonate cracking in the base metal,
initiating at a corrosion pit on the ID surface. Unetched.

Figure 5-52 – Photomicrograph of a cross-section of carbonate cracking in the base metal,

showing the branched nature of the cracking. Etched.
Figure 5-53 – Photomicrograph of a cross-section of a weld from a 4 inch (100 mm) ASTM A53
reflux line on the Main Fractionator that leaked after 52 years service.
 Figure 5-54 – An 18 inch (460 mm) diameter API 5L Grade B pipe section with two 1 in (25 mm)
water wash injection nozzles at the inlet to the 2nd stage compressor. Note the cracks on the ID
of the two injection nozzles after blast cleaning. The line leaked after 21 years service.
 Figure 5-55 – A 3 in x 4 in (76 mm x 100 mm) diameter tee in a hydrocarbon line off a water
knockout pot in the FCC light ends recovery section. Cracking developed after 6 months service.