J Fail. Anal. and Preven.

(2012) 12:624–627
DOI 10.1007/s11668-012-9605-x

LESSONS LEARNED

Reducing the Risk of High Temperature Hydrogen Attack

(HTHA) Failures
Daniel J. Benac • Paul McAndrew

Submitted: 23 July 2012 / Published online: 14 August 2012

Ó ASM International 2012

Abstract The objective of this article is to provide les- HTHA Phenomenon

sons learned from materials, structure, and equipment
failures so that costly failures can be prevented through High-temperature exposure of the carbon and low-alloy
good design, maintenance, and inspection practices, thus steels used for piping and pressure vessels (Fig. 1) used in
increasing safety, equipment reliability, and integrity of high-pressure hydrogen service leads to a special form of
designs. degradation known as HTHA, sometimes called hydrogen
attack. Note that this is not the same as hydrogen embrit-
Keywords Hydrogen damage
High temperature
tlement which degrades toughness at low temperatures.
Failure mechanism
Ferrous metals
HTHA HTHA leads to degradation of material properties at ele-
vated operating temperatures, but like hydrogen
embrittlement, HTHA can result in sudden and catastrophic
Introduction brittle failure.
Some equipment involves the use of, or production of,
Has equipment been deteriorated by elevated temperature hydrogen at pressures greater than 0.8 MPa (100 psig) and
exposure and hydrogen? This question is frequently asked at temperatures of 230 °C (450 °F) or above. These service
by those in ammonia, refinery, and chemical plants, who conditions can lead to deterioration of carbon steel com-
use piping, heat exchangers, and pressure vessels contain- ponents and result in equipment failure, notably of pressure
ing hydrogen at elevated temperatures. Beginning with vessels and piping.
research performed in the 1940s [1], equipment exposed to Under the influence of certain temperature conditions
hydrogen at elevated temperatures is known to potentially and hydrogen partial pressure, atomic hydrogen permeates
degrade over time in a phenomenon called high-tempera- the steel and reduces iron carbide (Fe3C) in the steel to
ture hydrogen attack (HTHA). Failures of hydrogen- form methane (CH4). Note that the methane does not dif-
containing equipment can result in fires, fatal accidents, fuse from the metal, and its pressure may exceed the
loss of production, and leaking of hydrocarbon products cohesive strength of the metal, causing fissuring between
that can ignite, resulting in an explosion. This article dis- grains (Fig. 2). When fissuring occurs, the ductility of the
cusses some of the necessary safety considerations and metal is significantly and permanently lowered. The
controls used by plant designers and operators to reduce the severity of hydrogen attack increases with increasing
risk of failure of such equipment. temperature and hydrogen partial pressure.
Usually, hydrogen attack occurs in three stages:
1. Atomic hydrogen diffuses into the metal,
2. Decarburization occurs (in steel), and
D. J. Benac (&)
P. McAndrew 3. Intergranular fissuring occurs [2].
Baker Engineering and Risk Consultants, Inc., 3330 Oakwell
Court, Suite 100, San Antonio, TX 78218, USA A metal in the first stage of hydrogen attack suffers only
e-mail: dbenac@BakerRisk.com a temporary loss in ductility, since the ductility of the metal

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J Fail. Anal. and Preven. (2012) 12:624–627 625

Fig. 1 Pressure vessels, heat exchangers, and piping equipment,

which are often exposed to high-temperature hydrogen attack
(HTHA) conditions

can be restored by heating. During stage two of decarbu-

rization, an attack can be confined to the surface in a
surface attack, or it can occur internally, where the resul-
tant product—methane—is unable to escape, leading to
permanent internal damage. Methane bubbles nucleate as
the carbides grow under methane pressure and can then
Fig. 2 (a) Undamaged carbon steel refinery line. (b) Hydrogen-
link up to form fissures, cracks, and/or blisters. damaged carbon steel refinery line. Decarburization and fissuring
If the internal pressure generated by entrapped methane region caused by hydrogen depleting the iron carbides. Nital etch
exceeds the strength of the metal and fissuring occurs, then
the result is permanent, irreversible embrittlement. Con-
sequently, permanent embrittlement occurs during the
second and third stages of a HTHA.

HTHA Industry Standard

The operating limits for steels can be empirically described

using the operating temperature and the hydrogen partial
pressure, as originally discussed by Nelson in 1949 and in
API recommended practice 941, ‘‘Steels for Hydrogen
Fig. 3 Illustration of API 941 (Nelson) curve—material selection for
Service at Elevated Temperatures and Pressures in Petro- equipment exposed to hydrogen at elevated temperature and pressures
leum Refineries and Petrochemical Plants.’’ should follow API 941 guidelines
Since the 1970s, empirical data have been collected
from operating plants and tests to establish operating limits For example, if the normal operating conditions are a
of carbon steel and low alloy steel equipment in hydrogen temperature of 288 °C (550 °F) and 13.79 MPa (2,000
service at elevated temperatures. API 941 provides guid- psig) hydrogen partial pressure, as illustrated in Fig. 3, then
ance on those limits. the carbon steel in this case is not suitable for service under
Using API 941, if a piece of equipment or piping is those conditions. There would be a high risk of premature
operated above the API 941 (Nelson) curve, then the failure in a relatively short time of exposure. Either the
material is not suitable for service under those conditions. temperature or the pressure would have to drop below the

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carbon steel curve, or chromium alloyed steel should be 7. Providing definite safe operating limits with necessary
considered for use instead. The selection of a 1 Cr–‘ Mo process alarms and a response plan when those limits
material would be the preferred choice. are exceeded.
Using API 941, the following practices should be
considered:
1. Selecting the proper material for the operating condi- Lined Equipment
tions, and for increased temperatures, considering the
use of alloys with higher weight percents of chromium For corrosion purposes, sometimes vessels are clad, lined,
and molybdenum. or weld overlaid to protect the vessel surface. This can
2. Using actual operating temperatures for assessing provide initial protection, provided hydrogen does not
HTHA susceptibility and validating that the actual diffuse through the liner or migrate behind the lining or
operating temperatures and pressures are below API cladding. If that occurs, then the vessel wall may be sus-
941 curve by a defined amount. ceptible to HTHA.
3. Employing experienced individuals who understand the Refractory lining is often used to insulate a pipe or
HTHA phenomenon as well as the API 941 recom- vessel to lower the metal wall temperature and is an
mended practices. effective way to reduce the effects of HTHA. However, the
refractory can degrade, crack, or deteriorate due to oper-
ating conditions or even flexure of the refractory, allowing
hot spots to form, which would elevate the metal wall
Operating Conditions
temperature and possibly result in exceeding the HTHA
operating limits of the equipment. Figure 4 illustrates
To perform an adequate assessment of HTHA suscepti-
how a degraded refractory and hot spot could result in
bility, the operating conditions of the equipment must be
exceeding the operating temperature limit for a carbon steel
known. Typical or possible design limits are not suffi-
line.
cient. A good HTHA assessment requires validation of
One way to monitor the condition of the refractory is to
data with process engineering involvement and actual
perform regular infrared imaging of the equipment. (An
field data. The key parameter is that the actual conditions
example is illustrated in Fig. 5.)
to which the metal wall has been exposed must be
For clad, lined, or overlaid equipment the following
known.
practices should be considered:
In determining the actual conditions, the placements of
temperature and pressure indicators are important, as well 1. Ensuring that proper foundation support for refractory-
as knowing whether excursions and process creep condi- lined equipment is in place to reduce flexure of the
tions have occurred over a period of time. Once the HTHA refractory.
limits are determined, safe operating limits with necessary 2. Performing regular infrared inspections, especially on
process alarms should be established, and a response plan refractory-lined equipment.
should be implemented for safe operations when those 3. Ensuring that the operating limit is understood, and
limits are exceeded. Plant operations should consider the appropriate actions are taken if the limit is exceeded.
following practices:
1. Performing regular process hazard assessment of the
operating conditions including changes in pressure,
temperatures or partial pressure of hydrogen.
2. Verifying the actual operating conditions that
the equipment experiences through good field data.
3. Installing pressure and temperature indicators at loca-
tions that measure the actual operating conditions of
equipment that could be susceptible to HTHA.
4. Determining whether process creep that may affect the
metal has occurred.
5. Evaluating material or operating changes using a
management of change (MOC) process. Fig. 4 Illustration of API 941 (Nelson) curve—damaged refractory
6. Evaluating whether temperature excursions and regener- can result in an increase in the metal wall temperature which if above
ation operations have an effect on HTHA susceptibility. the recommended limits could result in HTHA failure

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welding rod may be used. This is not a common

occurrence, but it happens. Sometimes, visual examina-
tion is performed, but often x-ray inspection is needed.
PMI has also identified incorrect materials in hydrogen
service.
The following inspection practices should be consid-
ered:
1. Selecting inspection methods and establish inspection
frequencies that will detect the initial stages of HTHA.
2. Ensuring that written procedures are in place and
implemented to provide guidance on inspection guide-
lines and intervals.
Fig. 5 Infrared image of a hydrogen-containing line showing a hot
spot (red colors), due to degraded refractory 3. Possessing knowledge of the history of the equipment,
and if unknown, making sure that necessary HTHA
HTHA Inspection Practices inspections are performed.
4. Considering performing PMI on a regular interval,
HTHA inspection requires special inspection techniques. especially during installation of new equipment, weld-
Inspection methods used for corrosion and wall thinning ing of equipment, and during maintenance operations.
are not adequate to detect HTHA, primarily because HTHA 5. Documenting all findings in an inspection program and
is not readily evident on the surface, as it is a subsurface implementing follow-up measures to ensure that find-
phenomenon. The optimum method(s) and frequency of ings are appropriately acted upon.
inspection for HTHA should be specified for specific
equipment.
Accepted HTHA inspection practices include the Summary
following:
Advanced Ultrasonic Backscatter Techniques (AUBT): Failure of hydrogen-containing equipment can be pre-
Ultrasonic waves backscattered from within the metal vented through good material selection, process controls,
are used to evaluate subsurface microstructural features and regular inspection of equipment. Because HTHA is
and the depth of region affected. now better understood and inspections methods are more
Phased Array: Phased Array is an ultrasonic technique reliable, HTHA failures are being avoided. To avoid con-
based on generating and receiving ultrasounds. Instead ditions that could cause HTHA, it is important that actual
of a single transducer and beam, phased arrays use operating conditions are known and monitored, and regular
multiple ultrasonic elements and electronic time delays HTHA inspections performed. When proper safety con-
to create beams by constructive and destructive siderations and controls are established, the risk of HTHA
interferences. failures is greatly reduced in ammonia, refinery, and
In situ metallography: This method evaluates selected chemical plants using tubes, heat exchangers, and pressure
surfaces by polishing, etching, and replicating of the vessels containing hydrogen at elevated temperatures.
microstructure and is limited to small locations and
addresses only the surface of the material.
Positive material identification: Users of equipment are
performing positive material identification (PMI) during References
installation of new equipment, maintenance operations,
or even retro-PMI to ensure that something had not been 1. Nelson, G.A.: Hydrogenation plant steels. In: Proceedings API,
29M (III), p 163 (1949)
altered previously. During installation of new equip- 2. Benac, D.J.: Elevated temperature life assessment for turbine
ment, welding of equipment, and maintenance components, piping and tubing. In: Failure Analysis and Preven-
operations, it is possible that the wrong material or tion, ASM Handbook, vol. 11, pp. 289–311 (2002)

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