5/29/2021 High Temperature Hydrogen Attack (HTHA) - TWI

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HIGH TEMPERATURE HYDROGEN

ATTACK (HTHA)

  

Di ering levels of HTHA damage in a specimen generated in TWI laboratory

Risks and Mitigation in light of the U.S. Chemical Safety

Board (CSB) investigation into the Tesoro Re nery
industrial accident

Summary:

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5/29/2021 High Temperature Hydrogen Attack (HTHA) - TWI

The Tesoro Re nery industrial accident in 2010 resulted from damage due to high
temperature hydrogen attack (HTHA).

The risk of related failures was assessed using API RP 941 Nelson curves.

The U.S. Chemical Safety Board (CSB) concluded that the carbon steel Nelson curve
methodology is inaccurate, cannot be depended on to prevent equipment failures due
to HTHA, and cannot be reliably used to predict the occurrence of damage due to HTHA
.

The CSB has identi ed at least eight incidents of HTHA occurrence below the carbon
Nelson curve; i.e. which did not indicate high risk of HTHA. The 2016 edition of API RP
941 reports 13 new failures below  the carbon steel Nelson curve.

CSB recommendation: For existing equipment operating at risk, all carbon steel
equipment in hydrogen service should be identi ed. Those operating at elevated
temperatures and greater than 50 psia should be replaced with inherently safer
materials (see above).

The most e ective safeguard is better design against HTHA; including the application of
high chromium steels with greater resistance to HTHA.

An alternative approach to replacing all equipment with higher performance materials

would be to improve detectability of defects at an early stage and focus replacement
where the risk is greatest.

The e ectiveness of Risk Based Inspection (RBI) is limited by current technology and the
e ectiveness of operator skill.

Advances in inspection system capability combined with e ective training of operators

coupled with e ective RBI could mitigate the risk for existing carbon-steel plant.

Early Friday morning, April 2, 2010, an explosion and re in the Naphtha Hydro-treater Unit

at the Tesoro Re nery in Anacortes, led to the death of seven re nery workers in the

immediate vicinity of the heat exchangers being returned to operation following

maintenance. The subsequent investigation of the incident by the U.S. Chemical Safety

Board found that the root technical cause  “was the result of the carbon steel heat

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5/29/2021 High Temperature Hydrogen Attack (HTHA) - TWI

exchanger being severely weakened by a damage mechanism known as HTHA” (Ref “CSB

report 2010-08-I-WA”). High temperature hydrogen attack (HTHA), also called hot hydrogen

attack, is a problem which a ects steels operating at elevated temperatures in hydrogen

environments, in re nery, petrochemical and other chemical facilities and, possibly, high

pressure steam boilers (TWI FAQ).

Whilst the cause of the failure was linked to de ciencies in safeguards and hazard

identi cation/control adopted by the operator, the CSB Report also called into question the

e cacy of the use of Nelson curves for evaluation of design operating conditions. API RP

941 provides industry guidance to predict the occurrence of HTHA in various materials of

construction by using the Nelson curves; which delineate the region of safe use for carbon

steels, 1.25Cr-0.5Mo steels etc. within high temperature ranges. The report stated:

“The Nelson curves are predicated on past equipment failure incidents and are plotted

based on self-reported process conditions that are ill-de ned and lack consistency”

“The CSB has learned of at least eight recent re nery incidents where HTHA reportedly

occurred below the carbon steel Nelson curve”.

“The CSB found that the carbon steel Nelson curve is inaccurate and cannot be relied on to

prevent HTHA equipment failures or accurately predict HTHA equipment damage” (Ref: CSB

report 2010-08-I-WA Section 1.2.3).

Corresponding recommendations by the CSB (Ref: CSB report 2010-08-I-WA Section 8.4)

included the revision of API RP 941 to prohibit the use of carbon steel equipment in HTHA-

susceptible service i.e. those operating above elevated temperatures and greater than 50

psia. API revised RP 941 and published the 8th edition of the RP in February 2016. The

original recommendations together with API’s actions for each subpart are detailed in the

“ CSB Status Change Summary 2010-8-I-WA-R10”, issued on 13 July 2016. The report noted

that new API “design margins” are for the design of new equipment. Existing equipment

that operates near the Nelson curves do not require an operating margin safety factor. This

is a major ageing equipment issue, as older equipment is much more susceptible to

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5/29/2021 High Temperature Hydrogen Attack (HTHA) - TWI

catastrophic failure from HTHA than the new equipment to which this design margin would

apply. All existing equipment is not required to incorporate a 50 °F safety margin. “CSB

concluded that API took insu cient action on all parts of the recommendation”. In light of

this, in August 2016 the CSB issued a “Safety Alert: Preventing High Temperature Hydrogen

Attack (HTHA)”, which gives the following guidance to prevent HTHA Equipment Failure:

1. Identify all carbon steel equipment in hydrogen service that has the potential to
harm workers or communities due to catastrophic failure;

2. Verify actual operating conditions (hydrogen partial pressure and temperature)

for the identi ed carbon steel equipment;

3. Replace carbon steel process equipment that operates at elevated

temperatures and greater than 50 psia hydrogen partial pressure; and

4. Use inherently safer materials, such as steels with higher chromium and
molybdenum content

The CSB also pointed out that HTHA is a damage mechanism that takes years to form cracks

that severely weaken vessels.

These recommendations to replace rather than monitor structures are driven by di culties

associated with inspection for microscopic cracks resulting from HTHA, also highlighted in

the CSB report. This inspection is highly dependent on the speci c techniques employed

and the skill of the inspector.  TWI is looking to develop an alternative approach to reduce

the risk associated with this failure mechanism by developing improved inspection

techniques.

For more information, please contact us.

For more information please email:

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5/29/2021 High Temperature Hydrogen Attack (HTHA) - TWI

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