INSPECTIONEERING JOURNAL

High Temperature Hydrogen Attack in API RP 581 RBI Methodology: A

Commentary
By Ibrahim Kodssi, Senior Asset Integrity Specialist at Lloyd’s Register Energy Canada Limited, and Hussain Fadhel, Independent
Consultant – Pipeline Integrity. This article appears in the July/August 2020 issue of Inspectioneering Journal.

Introduction and Scope

Risk based inspection (RBI) is implemented by many oil and gas operators around the world.
It is utilized to obtain an understanding of the risk profile of static assets, establish
inspection intervals, and develop inspection plans. RBI methodologies were developed by
industry trade organizations such as API, EEMUA, and ASME, as well as by owner/operator
companies and consulting and technology providers. Despite the similarities in approach,
there are differences in the details of the methodologies. For this reason, it is important to
understand the different methodologies and their respective strengths, weaknesses, and
relevance, before applying one. In this article, the focus is on API Recommended Practice
(RP) 581 Risk-Based Inspection Methodology, 3rd Edition.[1]

Risk is a combination of the probability of failure (POF) and Consequence of Failure (COF).
The damage factor (DF) is one of few factors for the calculation of POF with a focus on
statistical quantification of damage in consideration of time and inspection activities. In
order to calculate relative risks for equipment in the oil and gas and petrochemical
industries which are subject to a large number of damage mechanisms, API RP 581 includes
six damage modes: thinning, stress corrosion cracking, external damage, high temperature
hydrogen attack (HTHA), piping mechanical fatigue, and brittle fracture. This paper explores
API RP 581’s approach to HTHA DF calculations to obtain the POF that subsequently affects
risk assessment and management. Sample calculations are provided to affirm an
understanding of the concept along with reflections on the approach.

A Recap on HTHA
HTHA is a damage mechanism that has been thoroughly covered in Inspectioneering
Journal, so this article will simply provide a brief recap. In short, HTHA affects
hydroprocessing, catalytic reformers, and hydrogen cleanup units where carbon steel and
chromium-molybdenum alloys are exposed to hydrogen at elevated temperature and
pressures as described by API RP 571 3rd edition. API RP 571 also describes the stages of
formation and development of HTHA from bubbles/cavities formations, cracking, fissuring
to blistering. Among listed affected units are hydrotreaters (desulfurizers), hydrocrackers,
catalytic reformers and pressure swing absorption units.[2]

API RP 941, 8th edition states that steel is susceptible to surface or internal decarburization,
fissuring, and cracking due to the rapid diffusion of hydrogen at elevated temperature and
reaction with steel, depending upon the alloy, hydrogen partial pressure, temperature, and
certain other parameters. It also indicates that this damage may be present in different
degrees on base metal, weld heat affected zone, or welds. Moreover, the recommended
practice includes Nelson Curves for different steel grades to determine the susceptibility to
HTHA at certain temperatures and hydrogen partial pressures. The impact of these curves
on POF calculations is discussed in a later section of this article. The recommended practice
indicates that these curves are based on experimental tests and actual data from operating
facilities. However, in some cases, HTHA has been observed at conditions below the curves.
Thus, it is recommended to consider normal operating along with transitional and
startup/shutdown conditions when using the curves in API RP 941.[3]

API RP 581 Calculations of DF and POF for HTHA

API RP 581’s calculations of DF for HTHA rely heavily on the revised Nelson Curves in API RP
941. The material is considered highly susceptible to HTHA if it operates at or above the
applicable curve. Moreover, not only does API RP 581 follow the API RP 941
recommendations to set a margin for susceptibility below the curve, but it also provides
quantification as shown in Figure 1. This need for a safety margin is highlighted by API 941
to be driven by factors such as the uncertainty of the actual operating conditions and the
application of empirical experience to develop the curves as listed in API RP 941.

Read Related Articles

Avoiding HTHA Failures in Existing Equipment

Avoiding HTHA Failures: An Owner-User Perspective of the HTHA Risk Mitigation Process
A New Method for Prioritizing Equipment in HTHA Service for Inspection & Replacement and the
Challenges in Obtaining Process Conditions to be Used in the HTHA Assessment
Avoiding HTHA Failures: An Owner-User Perspective of the HTHA Risk Mitigation Process
Practical HTHA Experience and Time-Based Nelson Curves for Improved Equipment Life
Management
It is important to note that the API RP 581 HTHA module was published based on the seventh
edition of API RP 941, which has since been updated with an eighth edition. Thus, we
recommend using the most current edition of API RP 941.

Figure 1. Susceptibility Quantification and Safety margin for DF calculations

(Source: API RP 581 3rd edition)

The process to calculate the DF can be easily followed in Figure 2 so we will not go through
each step. Instead, we will provide a commentary on a few of the steps. The data required
includes the material of construction, operating temperature, hydrogen partial pressure,
inspection history, repair execution, and replacement performance. For cases where HTHA
was detected, the susceptibility is considered to be high even if the damaged component was
replaced in kind. However, this is not necessarily the same if the material was upgraded.

Following step 2 in the flow chart, for cases where damage was observed but no replacement
took place, the chart has a redundant box showing “Damage Observed” which then flows to
step 4. The latter then directs the user to use table 19.2 of API RP 581 (provided for your
reference as Table 1 in this article). By examining this table of this article, the value of DF is
the same for both cases of “High Susceptibility” and “Damage Observed.” Accordingly, to
simplify the flow chart, “High Susceptibility” should be assigned to cases where damage was
observed and no replacement to upgrade material took place; this would eliminate the
subsequent steps leading to step 4.

In the authors’ opinions, step 3.1 seems to be serving as a conservative fast approach to
determine susceptibility when compared to Nelson curves of API RP 941. In fact, it eliminates
the need for the use of curves for the stated conditions by directly assigning a high
susceptibility. We assume it is the section where API RP 581 refers to conservatism in the
approach until a more quantitative risk assessment is developed based on new editions of
API RP 941.

Another interesting observation is that for levels of inspection effectiveness, API RP 581
indicates that they do not exist currently for HTHA. This is primarily due to the difficulties in
the inspection as discussed later in this article.

An asset with an internal metallic lining that is different from the base metal may pose a
challenge to some operators during the calculations of POF for HTHA. For those cases, the
authors did not locate guidance in API RP 581 on which material to be used for the
calculation of susceptibility and DF. Our concern is that this may lead to underestimation of
risk. Further information on stainless steel lining on HTHA DF is provided later in the
mitigations section of this article.

A remark is that the calculation is based on the component level. We believe that this allows
for a more accurate risk estimation for an asset where dissimilar materials of construction
are used for the temperature range or gradient such as large reformers. However, operators
are cautioned that this calculation is considering HTHA only and does not account for other
possible damage mechanisms (such as including but not limited to creep and temper
embrittlement) that may arise due to the utilization of different material of construction.
Figure 2. Flow chart for HTHA DF calculation (Source: API RP 581 3rd edition).
Note: On figure 2, the listed figure 19.1 and Table 19.2 coincide with figure 1
and table 1 on this article.

Table 1. HTHA DM Values (Source: API RP 581 3rd edition)

It is worthwhile to explain that susceptibility and POF are not always the same.
Susceptibility is only one of the contributing factors to the calculations of POF and thus the
risk. For simplicity, we will use Table 2 and ignore other factors that are listed on API RP 581
such as management system factor and generic failure frequency. The examples in the next
section of this article show simplified calculations.

Numerical values for POF are shown in Table 2. The columns “Category” on the far left and
“DF Range” are included as part of the scope of this article, which affects the POF for HTHA.
Please note that Category 1 reflects the lowest POF while 5 reflects the highest. As additional
information, COF on the right side of Table 2 is arranged in increasing gradient from A to E.

Table 2. Numerical values associated with POF and area-based consequence

of failure. (Source: API RP 581 Third Edition)

Sample Calculations
Sample calculations are provided in Table 3 to show several cases with different conditions
and the outcome DF obtained by following the steps as explained earlier in this article. Due
to its simplicity, the examples do not include situations where previous damage was detected
on a component.

Table 3. Sample calculations for HTHA POF

Situation Material of Operating Hydrogen Susceptibility DF POF

# Construction Temperature (F) Partial Category
Pressure
(psia)

1 CS (no 400 60 High 5000 5

PWHT)
 2 3Cr – 1 Mo 925 2500 Medium 2000 5

3 3Cr – 1 Mo 875 2500 Low 100 3

4 3Cr – 1 Mo 600 2500 None 0 1

As observed, although situations 1 and 2 have different susceptibility, they still share the
same POF category. However, the value of risk may be different depending on the
calculation of the COF. Moreover, situation 1 shows the conservatism in step 3.1 in Figure 2
as discussed earlier.

Although outside the scope of this article, this is a commentary on COF and total risk of
HTHA for processing equipment in oil and gas facilities. Generally, the COF is at the higher
end of the COF category scale considering the service and the representative fluid (hydrogen
and hydrocarbons at high pressures and temperatures). This depends on the calibration of
the risk matrix zones which may vary from one establishment to another. Thus, it could be
assumed that the total risk for situations 1 and 2 may be at least moderate-high. This also
highlights the benefits of using discreet risk numbers such as those found in quantitative RBI
methodologies like API RP 581 to better compare the equipment by risk values (e.g. feet/year
or meters/year) rather than a risk matrix category or within a color band on an iso-risk plot.

Mitigation Measures
There are difficulties in inspection to detect the internal form of the attack. API RP 941 8th
edition indicates that the current nondestructive examination (NDE) techniques and
metallographic technologies cannot detect the attack at its initial stage due to its microscopic
size. Laboratory examination of samples may be able to detect it; however, we assume that
extracting such samples is undesireable for several reasons such as the economic
implications. Considering this challenge, it is recommended to refer to tables E.1 E.2 of API
RP 941 while creating a relevant inspection plan to understand the benefits and limitations
of each inspection technique with regards to HTHA.

Another prevention/mitigation measure is to increase carbide stability to minimize methane

formation by the use of carbide stabilizing elements such as tungsten and vanadium as listed
by API RP 571 3rd edition. Moreover, avoidance of C-0.5 Mo steels was recommended for
new construction targeted for hot hydrogen service. A further measure is the application of
a safety factor approach while using the API RP 941 curves, as reflected in the API RP 581
calculations of the POF and already described in previous sections.
API RP 941 indicates that cold work and thermal stresses may accelerate the attack while
post weld heat treatment (PWHT) improves the resistance to the attack. Thus, avoiding
accelerators and effective application of PWHT may be considered as potential mitigation
options.

The practice of some operators to solely depend on the knowledge of the existence of
stainless steel barriers as an HTHA preventative measure is discouraged by API RP 941. This
applies to situations where the base metal is considered susceptible to HTHA based on
Nelson curves. Instead, API RP 941 highlights factors and methodologies that should be
considered. The factors include base metal thickness, clad/weld build-up thickness, hydrogen
partial pressure, and crystalline structure (especially of the barrier). Moreover, it is
recommended to review the sections in API RP 941 with regards to the calculation of
effective hydrogen partial pressure.

Conclusion
This article discussed the calculation of HTHA damage factor and subsequent POF as per API
RP 581 3rd edition RBI methodology. Exposure to hydrogen at elevated temperature and
pressure may result in an overall loss in strength, a result of HTHA, for carbon steel and
chromium-molybdenum alloys. Examples of affected units include hydrotreaters
(desulfurizers), hydrocrackers, catalytic reformers, and pressure swing absorption units.

The calculation of HTHA damage factor relies on susceptibility which depends on the
proximity of the equipment conditions to the Nelson Curves as listed on API RP 941. The data
required includes the material of construction, operating temperature, hydrogen partial
pressure, inspection history, repair execution, and replacement performance. Among the
observed strengths of the methodology is that it is based on a component level. On the other
hand, we recommend the methodology to explicitly address equipment with an internal
metallic lining such as stainless steel over carbon steel. This is to prevent the inadequate
application of the methodology and underestimation of risk. In certain instances, this article
included commentary on the approach and provided sample calculations to affirm an
understanding of the concept.

References
1. American Petroleum Institute, 2016, “Risk-based Inspection Methodology - API
Recommended Practice 581”, 3rd ed., Washington: API Publishing Services.
2. American Petroleum Institute, 2020, “Damage Mechanisms Affecting Fixed Equipment
in the Refining Industry - ANSI/API Recommended Practice 571”, 3rd ed., Washington:
API Publishing Services.
 3. American Petroleum Institute, 2016, “Steels for Hydrogen Service at Elevated
Temperatures and Pressures in Petroleum Refineries and Petrochemical Plants - API
Recommended Practice 941”, 8th ed., Washington: API Publishing Services.

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About the Authors

Ibrahim Kodssi, Senior Asset Integrity Specialist at Lloyd’s Register Energy Canada Limited
Ibrahim advises on inspection, integrity, reliability, and risk-based inspection (RBI) of static assets. Driven by a passion for
operations' excellence, Ibrahim pursues improvements in quality, speed, flexibility, dependability, and profitability. In addition to
pursing an MBA degree, Ibrahim holds a Bachelor of Science in Mechanical Engineering and he is certified in API 510, API 570,
and API... Read more »

Hussain Fadhel, Independent Consultant – Pipeline Integrity

Hussain advises on in-line inspection analysis, defect assessment, repair decisions, and cathodic protection of pipeline assets.
His experience and interaction with multinational pipeline companies has allowed him to participate in successful pipeline
integrity program development and program execution. Hussain approaches problems with "big picture" thinking and is keen to
integrate AI,... Read more »

Comments and Discussion

Posted by Ravi Bhan on September 17, 2020

my question is for a Reactor in H2 service for along period & operating above the CS line as per latest Nelson curve ( it is
not sure whether PWHT was done for full clad vessel or only the dish ) , anyway it is even operating above CS line with
PWHT .We did Ultrasonic attenuation , velocity ratio , backscatter along with PAUT only found some disbond area of
clad along the long seam near inlet .No bulging , no degradation in micro from outside surface or inside SS surface .
My question is what would be first telltale signs of HTHA happening in the vessel degradation .
What would be reliable method of knowing present health /condition & any way to predict remaining life .
Thanks