Ballot: 581-XXXX-XXX

Modifications to Carbonate Cracking Module (Section 11 of Part 2)

Title:
Date:
Contact:

April 15, 2011

Source:

Name: Kim Galante

Company: Equity Engineering
Phone:
484-442-8030
E-mail:
kkgalante@equityeng.com
This ballot is to update the Carbonate cracking module for calculation of
damage factor based on the latest technology. Also, have added a VERY
LOW susceptibility category
Action Log

Revision:

Impact:

The addition of the VERY LOW susceptibility provides better flexibility

for inspection planning.

Rationale:

This ballot is to update the Carbonate cracking module for calculation of

damage factor based on the latest technology.

Purpose:

Changes: See attached red-lined version of Section 11.0

11 SCC DAMAGE FACTOR CARBONATE CRACKING
11.1 Scope
The damage factor calculation for components subject to alkaline carbonate stress corrosion cracking
(ACSCC) is covered in this paragraph.
11.2 Description of Damage

Carbonate cracking is a the common term applied to surface-breaking cracksing of a metal that occur at
or near carbon steel welds under the combined action of tensile stress and corrosion in the presence of
an alkaline sour water containing moderate to high concentrations of carbonate (CO 3). On a macroscopic
level, carbonate cracking typically propagates parallel to the weld in the adjacent base metal, but can also
occur in the weld deposit or heat-affected zones. At times, ACSCC may be mistaken for SSC or SOHIC,
but further review will show that carbonate cracking is usually located further from the toe of the weld and
contains multiple, parallel cracks. TAt times, the pattern of cracking observed on the steel surface is
sescribed as a spider web of small cracks, which often initi or interconnect with weld-related flaws that
serve as local stress risers. Finally, from the microscopic perspective tThe cracking is predominantly
intergranular, in nature, and typically occurs in as-welded carbon steel fabrications as a network of very
fine, oxide-filled cracks are similar in appearance to caustic stress corrosion cracking and amine cracking.
Carbonate cracking typically propagates parallel to the weld in adjacent base metal, but can also occur in
the weld deposit or heat-affected zones. 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 weldrelated flaws that serve as local stress risers.
Historically, cCarbonate cracking has been most prevalent in the fluid catalytic cracking unit (FCCU) main
fractionator overhead condensing and reflux systems, the downstream wet gas compression system, and
the sour water systems emanating from these areas. Based upon recent survey results, sour water
strippers with side-pumparound designs, Catacarb/CO2 removal facilities for hydrogen manufacturing
units and delayed coker light ends units have been added to the list of affected units. In all instances,
both piping and vessels are affected.
Assuming the presence of a sour free water phase containing H2S, three key parameters are used to
assess the susceptibility of steel fabrications to carbonate cracking; pH of the sour water, carbonate
concentration of the sour water, and level of tensile stressthe residual stress level of the exposed carbon
steel. Typical pHs are in the 8-10 range. Regarding contaminant/additive concentrations, no threshold
for H2S has been identified; no evidence exists to indicate cyanides or polysulfides have any impact; and
increased ammonia (NH3) concentrations will directionally increase ACSSS likelihood. As for residual
stress levels, they typically emanate from welding, but can be associated with cold worked areas.
Studies have concluded that the sour waters corrosion electrochemical potential can be used to assess
the likelihood of the crackingACSCC. occurs in a narrow range of electrochemical potential, which is
very dependent upon the sour water composition. The presence of moderate to high levels of carbonates
in alkaline sour water often produces an electrochemical potential of steel which is in this narrow range
where carbonate cracking is likely to occur. Another common contaminant in these sour waters,
cyanides, has been shown to influence cracking susceptibility.
Despite this mechanistic
understandingHowever, accurate measurement in a field environment is difficult. Therefore, further
discussion of the electrochemical potential of in-service components may not be readily availableis
outside the scope of this document.. Therefore, pH and carbonate concentration of the sour water are
judged to be the key environmental parameters influencing the susceptibility of steel fabrications to
carbonate cracking. Based on a survey of many process units reported in Reference [30], cracking
susceptibility increases with increasing pH and carbonate concentration.
With regard to mitigation techniques, the level of tensile stress, as-welded or as-bent carbon steel
fabrications are susceptible to carbonate cracking because of the high level of residual stress remaining
after fabrication by these methods. Aapplication of a post fabrication stress-relieving heat treatment (e.g.
postweld heat treatment) is a proventhe most commonly used method of preventing carbonate cracking.
A heat treatment of about 621649C - 663C [11501200F-1225F] for one hour per inch of thickness (one
hour minimum) in accordance with WRC 452 is considered an effective. The heat treatment requirements
apply to all exposed welds as well as any external welds with heat affected zones (HAZ) in contact with
the service environment. Other mitigation techniques include: process barriers (either organic or
metallic), alloy upgrades (solid or clad 300SS, Alloy 400 or other CRA), effective water washing and
inhibitor injection. stress-relieving heat treatment to prevent carbonate cracking of carbon steel.
11.3 Screening Criteria

If the components material of construction is carbon or low alloy steel and the process environment
contains free sour water at pH > 7.58 in any concentration, then the component should be evaluated for
susceptibility to carbonate cracking.
11.4 Required Data
The basic component data required for analysis is given in Table 5.1 and the specific data required for
determination of the carbonate cracking damage factor is provided in Table 11.1.

11.5 Basic Assumptions

The main assumption in determining the damage factor for carbonate cracking is that the damage can be
characterized by a susceptibility parameter that is designated as high, medium, or low based on process
environment, material of construction, and component fabrication variables (i.e. heat treatment). Based
on a susceptibility, a Severity Index can be determined that a measure of the susceptibility of the
component cracking (or the probability of initiating cracks) and the probability of a crack resulting in a
leak.
If cracks are detected in the component during an inspection, the susceptibility is designated as High, and
this will result in the maximum value for the Severity Index. Cracks that are found during an inspection
should be evaluated using Fitness-For-Service methods in API 579 [10].
11.6 Determination of the Damage Factor
11.6.1 Overview
A flow chart of the steps required to determine the damage factor for carbonate cracking is shown in
Figure 11.1. The following paragraphs provide additional information and the calculation procedure.
11.6.2 Inspection Effectiveness
Inspections are ranked according to their expected effectiveness at detecting carbonate cracking and
correctly predicting the rate of damage.
Examples of inspection activities for carbonate cracking that are both intrusive (requires entry into the
equipment) and non-intrusive (can be performed externally), are provided in Table 11.2.
The effectiveness of each inspection performed within the designated time period must be characterized
in accordance with Table 11.2. The number and category of the highest effective inspection will be used
to determine the damage factor. If multiple inspections of a lower effectiveness have been conducted
during the designated time period, they can be equated to an equivalent higher effectiveness inspection in
accordance with paragraph 4.4.3.
11.6.3 Calculation of the Damage Factor
The following procedure may be used to determine the damage factor for carbonate cracking, see Figure
11.1
a) STEP 1 Determine the number of inspections, and the corresponding inspection effectiveness
category using paragraph 11.6.2 for all past inspections. Combine the inspections to the highest
effectiveness performed using paragraph 4.4.3.

c)

STEP 2 Determine the time in-service, age , since the last Level A, B, C or D inspection was
performed.
STEP 3 Determine the susceptibility for cracking using Figure 11.1 and Table 11.3 based on the pH
of the water and CO3 concentration, and knowledge of whether the component was subject to
PWHT. Note that a HIGH susceptibility should be used if cracking is known to be present.

d)

STEP 4 Based on the susceptibility in STEP 3, determine the severity index,

e)

STEP 5 Determine the base damage factor for carbonate cracking,

b)

SVI , from Table 11.4.

D carbonate
, using Table 7.4
fB

based on the number of, and the highest inspection effectiveness determined in STEP 1, and the
severity index, SVI , from STEP 4.

f)

STEP 6 Calculate the escalation in the damage factor based on the time in-service since the last
inspection using the age from STEP 2 and Equation (2.21). In this equation, it is assumed that the
probability for cracking will increase with time since the last inspection as a result of increased
exposure to upset conditions and other non-normal conditions.

D carbonate
D carbonate
age
f
fB

1.1

11.7 Nomenclature

age

is the in-service time since the last Level A, B, C or D inspection was performed

carbonate
f

is the damage factor for carbonate cracking

carbonate
fB

is the base value of the damage factor for carbonate cracking

SVI

is the severity index

11.8 References
1. R. D. Merrick, Refinery Experiences with Cracking in Wet H 2S Environments, Materials
Performance 27, 1 (1988), pp. 3036.
2. J. H. Kmetz and D. J. Truax, Carbonate Stress Corrosion Cracking of Carbon Steel in Refinery FCC
Main Fractionator Overhead Systems, NACE Paper #206, CORROSION/90.
3. H. U. Schutt, Intergranular Wet Hydrogen Sulfide Cracking, NACE Paper #454, Corrosion/92 (see
also Stress Corrosion Cracking of Carbon Steel in Amine Systems, NACE paper #187,
Corrosion/87) (see also Materials Performance 32, 11 (1993), pp. 55-60).
4. E. Mirabel et al, Carbonate-type Cracking in a FCC Wet Gas Compressor Station, Materials
Performance, July, 1991, pp.41-45.
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 Cracking Experience, Paper #07564, NACE
International, Houston, TX 2007.
8. WRC Bulletin 452, Recommended Practices for Local Heating of Welds in Pressure Vessels,
Welding Research Council (WRC), Shaker Heights, OH.

11.9 Tables
Table 11.1 Data Required for Determination of the Damage Factor Carbonate Cracking
Required Data

Comments

Susceptibility
(Low, Medium, High)

The susceptibility is determined by expert advice or using the

procedures in this paragraph. This type of cracking may be sporadic
and may grow rapidly depending on subtle changes in the process
conditions. Periodic monitoring of process pH and CO3-2 in FCC sour
waters should be done to determine cracking susceptibility.

Presence of Water
(Yes or No)

Determine whether free water is present in the component. Consider

not only normal operating conditions, but also startup, shutdown,
process upsets, etc.

Presence of 50 ppm or more H2S

in the Water
(Yes or No)

Determine whether 50 ppm or more H2S is present in the water

phase in this component. If analytical results are not readily
available, it should be estimated by a knowledgeable process
engineer.

pH of Water

Determine the pH of the water phase. If analytical results are not

readily available, it should be estimated by a knowledgeable process
engineer.

CO3 Concentration in Water

Determine the carbonate concentration of the water phase present in

this component. If analytical results are not readily available, it
should be estimated by a knowledgeable process engineer.

Age
(years)

Use inspection history to determine the time since the last SCC
inspection.

Inspection Effectiveness Category

The effectiveness category that has been performed on the

component.

Number of Inspections

The number of inspections in each effectiveness category that have

been performed.

Table 11.2 Guidelines for Assigning Inspection Effectiveness Carbonate Cracking

Inspection
Category

Inspection
Effectiveness
Category

Intrusive Inspection Example

None

Highly
Effective

Wet fluorescent magnetic particle

testing (WFMT) of 100% of repair
welds and 50-100% of other
welds/cold bends. Alternating
Current Field Measurement
(ACFM) can also be used to
detect and size surface breaking
cracks.
See Notes below.

Usually
Effective

WFMT or ACFM et fluorescent

magnetic particle testing of 2049% of welds/cold bends.
See Notes below.

Shear wave ultrasonic testing of 50100% of welds/cold bends; or Acoustic

Emission testing with follow-up shear
wave UT.
Shear wave ultrasonic testing of 20-49%
of welds/cold bends.

Fairly Effective

WFMT or ACFM et fluorescent

magnetic particle testing of less
than 20% of welds/cold bends; or
Dry magnetic particle testing of
50-100% of welds/cold bends; or
Dye penetrant testing of 50-100%
of welds/cold bends.

Poorly
Effective

Dry magnetic particle testing of

less than 50% of welds/cold
bends; or Dye penetrant testing of
less than 50% of welds/cold
bends.

Shear wave ultrasonic testing of less

than 20% of welds/cold bends; or
Radiographic testing; or Visual
inspection for leaks.
No inspection

Ineffective

Visual inspection. Although

cracks may be seen visually in
more progressed damage, WFMT
or ACFM is best for crack
detection.

Non-intrusive Inspection Example

NOTES:
1. When cracking is identified, it is suggested that metallographic techniques, in-situ or destructive,
be used to confirm the cracking mechanism.

Table 11.3 Susceptibility to Cracking Carbonate Cracking

Susceptibility to Cracking as a Function Residual Stress
and of CO3 Concentration in Water
Effective PWHT,
possible cold working

pH of Water

CO3 < 100 ppm

7.6 to 8.3< 8.0

LowVery Low

Unknown or Ineffective PWHT,

possible cold working

CO3 100
ppm100 - 500
ppm

CO3 < 100 ppm500

- 1000 ppm

CO3 > 1000 ppm

Very LowLow

Low

Medium

> 8.3 to < 9.0

Low

Low

Medium

High

=> 89.0

Very LowLow

MediumLow

MediumHigh

High

Table 11.4 Determination of Severity Index Carbonate Cracking

Susceptibility

Severity Index

High

1000

Medium

100

Low

10

Very Low

None

SVI

11.10 Figures

Figure 11.1 Determination of the Carbonate Cracking Damage Factor