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This data is from the European Hydrogen Incidents and Accidents database HIAD 2.1, European Commission, Joint Research Centre.

High-Pressure Reactor Rupture During Wax Isomerization, Igniting Hydrogen Gas
During the isomerization of wax in a lube oil plant, the high pressure reactor ruptured, releasing its contents. The released gas ignited and a fire developed in the plant area where operators and engineers were working.The release gas had a temperature above 400 C and consisted of hydrogen (ca. 70%) and gaseous hydrocarbons (ca. 30%, among which methane and ethane), but eh total quantity remained unknown.
Event Date
May 22, 1994
Record Quality Indicator
Event Initiating System
Classification of the Physical Effects
Nature of the Consequences
Cause Comments
The accident occurred because operating outside the design specifications. The temperature indicators on reactor had maximum readings below expected temperatures and, besides, no high temperature trips were available.Contributing causes were presence of manufacturing defects or corrosion of the reactor. The root causes are multiple, and point at one organization-related common root cause : of the incident can be summed up as follows:(1) Failure to understand the processes occurring in the reactor and the effect of an increase in temperature on the rate of exothermic reactions.(2) Inadequate cooling facilities.(3) An inadequate control system and the absence of a high temperature trip device.(4) Inadequate operational procedures and training of managers, engineers and operators.
Facility Information
Application Type
Specific Application Supply Chain Stage
Components Involved
de-wax isomerization high pressure reactor
Storage/Process Medium
Location Type
Location description
Industrial Area
Operational Condition
Pre-event Summary
The unit affected by this event consisted in a dewaxing process aiming at lowering the pour point of an oil by catalytic isomerizing the paraffinic waxy components.The incident occurred during the activation of a platinum catalyst using refinery treat gas. The component involved was a wax isomerization reactor of the following dimension: 23 m high, 1 m diameter, wall thickness walls of 55 mm. Operating conditions: 64 barg and 430-480C.
Consequences
Number of Injured Persons
5
Currency
Lessons Learned
Lessons Learned
According to the eMARS report (see references), the accident investigation identified several causes, mostly related to the inadequacy of the operational measures to early spot anomalies and to learn from them. The findings can be cluster as follows. DESIGN SHORTCOMING(1) Catalyst activation was not taken into account during the reactor design: (2) There was no automatic trip in case of trespassing of the maximal reactor temperature. NEAR MISSES which were not taken into account (1)During initial plant start-up in 1991 and catalyst activation at 400 degrees Celsius an exothermic was experienced. Its cause was identified as a hydro cracking reaction of the paraffins in the treat gas, but no further action was taken; (2)In 1994 during a preliminary hot de-waxed treatment at 430 degrees Celsius, temperature indicators were seen to be out of range. No investigation was made. The settings of the temperature indicators was 410 and 450 Celsius although the instruments had a potential maximum of 1000 Celsius. All alarms were set at 405 Celsius. RISK ASSESSMENT SHORTCOMING(1)The original risk assessment did not consider the catalyst activation stage and dismissed the possibility of a runaway exothermic reaction.(2)The reactor installation was provided with an emergency shut-down control which was manually activated and required operators to respond correctly to the situation. (3)In May 1994 a new catalyst had to be activated. A temperature 430 Celsius was planned, instead of the 400 C originally used, but there was no risk assessment on this change in operating conditions. (4)During the activation stage 3 people went out onto the reactor ladders and platforms at various times, if they had been present when the reactor ruptured they would have been caught by the fire.LESSON LEARNED - ORGANISATION: A.Near misses are an important indicator of the potential for accidents. The plant organization has to record and assess them, and act upon. B.Operation process parameters cannot be changed without performing a new (partial) risk assessment C.Management of changes is a critical tool which should be adopted. It was not in the present case. LESSON LEARNED TECHNICAL KNOWLEDGE: At the time of the accidents, very little published information on runaway exothermic in continuous reactors was available. A case report in Safety Digest of American Petroleum institute, Publication 758 Section 2 1979 Chapter 5 is similar to this incident. Also "Chemical Reaction Hazards - A Guide" Editors Barton and Rogers published by IChemEng 1993 and IChemSymposium Series No. 85 "Protection of Exothermic Reactors and Pressurized Storage Vessels" could have been used to identify the chemical process on going in the reactor.Since then, hydro cracking and thermal cracking of paraffins at the temperatures experienced in this reactor are widely reported in standard text books.
Event Nature
Emergency Action
INTERNAL TO THE ESTABLISHMENT: Operators shut-down the plant and shut-off the fuel supply. Four people of the company fire brigade extinguished the fire, after which a decontamination of the plant was performed
Release Type
Hole Shape
Ignition Source
Detonation
No
Deflagration
No
High Pressure Explosion
No
High Voltage Explosion
No
Flame Type
Source Category
References
References

Event description in the European database eMARS
https://emars.jrc.ec.europa.eu/en/eMARS/accident/search?bfd=1#
(accessed December 2020)

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