Severity
Incident
Leak
Yes
Ignition
Yes

A petroleum refinery experienced a catastrophic rupture at one bank of three heat exchangers in a catalytic reformer/naphtha hydrotreater unit because of high temperature hydrogen attack (HTHA). Hydrogen and naphtha at more than 500F were released from the ruptured heat exchanger and ignited, causing an explosion and an intense fire burned for more than three hours.

The rupture fatally injured seven employees working in the immediate vicinity of heat exchanger at the time of the incident. The workers were in the final stages of a start-up activity to put a parallel bank of three heat exchangers back in service following cleaning. Such start-up activities had resulted in frequent leaks and occasional fires in the past and should have been considered as hazardous and nonroutine.

The damage of the specific heat exchanger was the result of its carbon steel being severly weakened by HTHA, a mechanism that results in fissures and cracking which occurs when the material is exposed to hydrogen at high temperatures and pressures, severely degarding the mechanical properties of the steel. API Recommended Practice 941 (Steels for Hydrogen Service at Elevated Temperatures and pressures in Petroleum Refnieries and Petrochemical Plants) provides Nelson curves to predict the occurrence of HTHA in various materials of construction. These curves are predicated on past equipment failure incidents and are plotted based upon self-reported process conditions. An investigative computer reconstruction of the ruptured heat exchanger estimated that exchanger was operating in a safe region of the Nelson curves where HTHA could not occur. API Recommended Practice 581 (Risk-Based Inspection Technology) allows users to calculate a damage factor to determine HTHA susceptibility of various materials of construction, rather than requiring users to actually verify operating conditions when determining applicable damage mechanisms.

Incident Date
Apr 02, 2010
Setting
Equipment
  • Piping/Fittings/Valves
  • Piping
  • Heating Equipment
  • Heat Exchanger
Damage and Injuries
When Incident Discovered
Lessons Learned

Carbon steel Nelson curve methodology cannot be depended on to prevent HTHA equipment failures and cannot be reliably used to predict the occurrence of HTHA equipment damage. Revisions to recommended practices should be considered regarding the use of carbon steel in HTHA-susceptible service and the verification of actual operating conditions.
Given the difficulty of inspecting for HTHA because the damage might not be detected, inherently safer design is a better approach to prevent HTHA.
Process hazards analysis (PHA) and damage mechanism hazard reviews (DMHRs) need to carefully consider all assumptions, periodically if necessary, to ensure that hazard identification, safeguards and control of hazards to prevent equipment failure are effective.
Effective programs need to be in place to manage and provide oversight for hazardous nonroutine work.

Key:

  • = No Ignition
  • = Explosion
  • = Fire
Hydrogen Incident Summaries by Equipment and Primary Cause/Issue
Equipment / Cause Equipment Design or Selection Component Failure Operational Error Installation or Maintenance Inadequate Gas or Flame Detection Emergency Shutdown Response Other or Unknown
Hydrogen Gas Metal Cylinder or Regulator   3/31/2012
4/30/1995
2/6/2013
4/26/2010 12/31/1969     3/17/1999
11/1/2001
12/23/2003
Piping/Valves 4/4/2002
2/2/2008
5/11/1999
4/20/1987
11/4/1997
12/31/1969
8/19/1986
7/27/1991
12/19/2004
2/6/2008
10/3/2008
4/5/2006
5/1/2007
9/19/2007
10/31/1980
2/7/2009 1/24/1999
2/24/2006
6/8/1998
12/31/1969
2/7/2009

9/1/1992
10/31/1980

10/3/2008  
Tubing/Fittings/Hose   9/23/1999
8/2/2004
8/6/2008
9/19/2007
1/1/1982 9/30/2004
10/7/2005
  10/7/2005  
Compressor   10/5/2009
6/10/2007
8/21/2008
1/15/2019
    10/5/2009 8/21/2008  
Liquid Hydrogen Tank or Delivery Truck 4/27/1989 12/19/2004
1/19/2009
8/6/2004 12/31/1969   1/1/1974 12/17/2004
Pressure Relief Device 7/25/2013
5/4/2012
1/15/2002
1/08/2007
12/31/1969        
Instrument 1/15/2019 3/17/1999
12/31/1969
2/6/2013
    11/13/73    
Hydrogen Generation Equipment 7/27/1999     10/23/2001      
Vehicle or Lift Truck   7/21/2011         2/8/2011
12/9/2010
Fuel Dispenser   8/2/2004
5/1/2007
6/11/2007
9/19/2007
  2/24/2006
1/22/2009
     
Fuel Cell Stack            

5/3/2004
12/9/2010
2/8/2011

Hydrogen Cooled Generator       12/31/1969
2/7/2009
     
Other (floor drain, lab
anaerobic chamber,
heated glassware,
test chamber,
gaseous hydrogen
composite cylinder,
delivery truck)
  11/14/1994
7/21/2011
7/27/1999
6/28/2010
8/21/2008
12/31/1969
3/22/2018
    6/10/2019
  • = No Ignition
  • = Explosion
  • = Fire