Appendix

Report on the Investigation of the Explosion and Fire Serious Incident at

Resorcinol Production Facility at Iwakuni-Ohtake Works (Summary)

1. Overview of the Accident

・At 23:20 on April 21, 2012, there was a problem with the steam supply system at
Iwakuni-Ohtake Works. At 23:32, workers instituted an emergency shutdown of the
resorcinol production plant. Air supply to the oxidation reactor of resorcinol plant was
terminated and nitrogen replacement while cooling the oxidation reactor commenced.
・ At 0:40 on April 22, the supply of nitrogen was terminated as was the agitator.
Temperature of the oxidation reactor began to rise.
・At 2:15, the oxidation reactor burst causing an explosion and fire. The fire spread to the
cymene plant and the utility piping rack.
・At 8:05, a second explosion occurred at the oxidation reactor.

2. Location
Resorcinol Production Facility, Iwakuni-Ohtake Works, Mitsui Chemicals Inc.
6-1-2 Waki, Waki-cho, Kuga-gun, Yamaguchi

3. Date and Time of Accident

April 22, 2012 at 2:15

4. Damages
(1) Casualties
1 dead, 25 injured
External areas
Residents of local communities: 14 injured
Employees of subcontractors at JX Nippon Oil & Energy Marifu Refinery: 2 injured
Within premises
Employees: 1 dead, 7 injured (2 seriously injured)
Employees of subcontractors: 2 injured

(2) Physical damage

External areas
Damage to buildings/homes: 999
Partial damage to facilities of neighboring companies

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 Within premises
Severe damage to resorcinol production plant around the oxidation reactor
The cymene plant and utilities piping rack were damaged by the force of the
explosion and subsequent fire and flying debris.
15 nearby plants were also damaged from the force of the explosion and flying
debris.

5. Overview of the Resorcinol Production Facility

・The plant started operations in 1980 and the oxidation reactor was installed in 1999.
・Production capability is 7,600 tons annually.
・The main processes of the facility are 1) oxidation, 2) reoxidation, 3) cleavage, and
4) refining processes.

Batch processing Continuous processing

２

４
１

Reoxidation process

Cleavage process

Refining process
Oxidation process

m-DIPB
Product
Oxygen Resorcinol

Figure 1. Block flow of the resorcinol production process

1) Oxidation process: The raw material meta-Diisopropylbenzene (hereinafter referred to

as m-DIPB) is oxidized with oxygen in the air to create an intermediate.
m-DIPB + oxygen →Dihydroxy peroxide (hereinafter referred to as DHP)
+ Hydroxy hydroperoxide (hereinafter referred to as HHP)
2) Reoxidation process: HHP + oxygen → DHP
3) Cleavage process: DHP → Resorcinol + Acetone
4) Refining process: After removing impurities through separation by distillation and
crystallization, flaking is conducted to create products.

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6. Accident investigation structure
・On April 24, 2012, Mitsui Chemicals, Inc. formed a “Accident Investigation Committee” to
investigate the accident at the resorcinol production facility at Iwakuni-Ohtake Works
(hereinafter referred to as the Committee)” which comprised of four members from the
academia and external specialists from relevant organizations functioning as observers.

Committee members:
Dr. Terushige Ogawa Emeritus Professor, Yokohama National University
Executive Director, Research Institute for Safety Engineering
Dr. Kazuhiko Suzuki Professor, Okayama University Graduate School of Natural
Science and Technology
Mr. Jun Nakamura Director, Research Institute for Safety Engineering
Dr. Masayoshi Nakamura Professor, Tokyo University of Agriculture and Technology,
The Graduate School of Technology Management

Observers:
Nuclear Industrial Safety Agency, Ministry of Economy, Trade and Industry
Disaster Prevention & Crisis Management Division, General Affairs Department,
Yamaguchi Prefecture
District Fire Fighters, Iwakuni Fire Department
High Pressure Gas Safety Institute of Japan

・The committee met a total of 6 times (May 1, May 27, June 12, July 5, July 26 and Aug. 15,
2012) to determine the situation in which the accident occurred and the direct cause of the
accident. Additionally, it approved measures to prevent recurrences.

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7. Events leading up to the accident
・As for the events leading up to the accident, based on operation data (DCS data),
testimonies from operators, thermal behavior measurements using adiabatic calorimeters
(ARC test devices), and analysis of flow simulation, we have estimated the following.

36 hours into batch oxidation reaction

(1 batch take 40 hours)
Operators instructed to stop
plants using steam due to 23:32 Emergency shutdown of resorcinol plant
trouble with steam supply
system within Iwakuni- Interlock triggered
Ohtake Works Emergency cooling by adding nitrogen and emergency cooling water

Interlock was released in

order to switch from 0:40 Release of interlock causes flow of nitrogen for agitation to stop
emergency cooling water
to circulating water Liquid phase flow drops

Temperature rises at upper liquid phase Temperature does not rise

(where there was no cooling coil) in lower liquid phase
(where there was a cooling coil)
Rise in temperature accelerates
decomposition of organic peroxide

Temperature and pressure rise accelerates

Safety valve triggered but
pressure continues to rise

2:15 Oxidation reactor bursts Flammable substances such as organic

peroxide and cracked gas ignite causing
explosion and fire

Figure 2. Events leading up to explosion and fire

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 Gases

Gas
separator
Oxidation
reactor

Circulating
water
Air
Air compressor Emergency cooling water

Nitrogen Holding tank

Extraction line

Figure 3. Flow sheet of resorcinol oxidation reactor

・The following events leading up to the accident have been summarized in two parts. The
first starts with the emergency shutdown to release of the interlock. The second starts
with the release of the interlock to the explosion and fire.

(1) Emergency shutdown to release of interlock

・At 23:20 on April 21, there was a problem with the steam supply system and were ordered
to shut down all plants using steam.
・At 23:32, the emergency shutdown triggered the interlock and emergency shutdown was
instituted for all processes at the resorcinol production plant.
・With triggering of the interlock, the valves ware operated automatically and air supply to
the oxidation reactor was replaced with nitrogen. Cooling water was switched from
circulating water to emergency cooling water.
・Air in the oxidation reactor was replaced with nitrogen and agitation continued resulting in
a gradual drop in temperature.
・At 0:40 on April 22, it was determined that temperature of the oxidation reactor had not
dropped so the interlock was released to switch cooling water from emergency cooling
water to circulating water.

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 (2) Release of interlock to explosion and fire
・With release of the interlock, the valve was automatically operated and nitrogen supply
and agitation in the oxidation reactor was stopped. At the same time, cooling water was
switched from emergency cooling water to circulating water.
・ The upper liquid phase of the oxidation reactor did not have a cooling coil and
decomposition heat from the organic peroxide could not be removed resulting in a gradual
rise in temperature. (Temperature continued to drop for the lower liquid phase where
there was a cooling coil.)
・Operators did not recognize the rise in temperature in the upper liquid phase. Organic
peroxide continued to generate decomposition heat and temperatures continued to rise.
・At around 2:10, the decomposition reaction of the organic peroxide accelerated,
temperatures rose and decomposition gas was also generated resulting in an increase in
pressure.
・The safety valve was triggered but pressure continued to increase.
・At 2:15, the oxidation reactor burst, ignited, and exploded, causing a fire..

8. Determining the Cause of the Accident

・ Using the cause analysis method, we determined the possible direct cause and
reorganized factors into three primary causes and extracted secondary causes.

(1) Direct cause

・During the emergency shutdown of the oxidation reactor that produces organic peroxide,
the interlock was released. This stopped nitrogen supplies to the oxidation reactor and
stopped agitation of the liquid phases. As a result, decomposition heat of the organic
peroxide could not be removed from the upper liquid phase where there was no cooling
coil and temperatures rose. This rise in temperature accelerated the decomposition
reaction of the organic peroxide, pressure increases in the oxidation reactor, and the
reactor burst, causing an explosion and fire.

(2) Primary cause

a. Operator decided that it would be better to release the interlock.
b. The interlock is easily released.
c. By releasing the interlock, nitrogen supply was terminated for an extended period of
time and agitation was stopped causing temperatures to rise.

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(3) Secondary cause
a. Operator decided that it would be better to release the interlock.
・In order to secure the flow rate of emergency cooling water necessary to cool the reactor,
it is necessary to raise source pressure, however this is not automatic and is done on
request by resorcinol plant operators.
・Even after pressure of emergency cooling water was increased and the flow rate of the
emergency cooling water was secured, the temperature drop was very slow.
・The target temperature for maintaining stable conditions after an emergency shutdown
and target speeds for temperature drops were not provided in the operating manual.
・Based on operator’s experience with cooling after an oxidation reaction in normal
operation, operator decided that it would be better to switch from emergency cooling
water to circulating water.
・Conditions are confirmed by digital displays on the DCS main screen so it was difficult to
determine trends in temperature drops.

b. The interlock is easily released.

・ Conditions for determining “stable conditions” for releasing the interlock were not
provided in the manual for emergency shutdown.
・Proper procedures were not taken when releasing the interlock.
・Operators lacked awareness of the significance of releasing the interlock.

c. By releasing the interlock, nitrogen supplies were terminated for an extended period of
time and agitation stopped causing temperature to rise.
<Regarding stopping agitation>
・The system was such that if the interlock is released, nitrogen is stopped.
<Regarding rising temperature>
・Once agitation stopped, the upper liquid phase could not be cooled.
・The thermometer that triggers the interlock was only in the lower part of the oxidation
reactor and not in the upper part.
<Regarding stopping agitation and delay in noticing temperature was rising>
・There was no alarm to detect that gas for agitation had stopped.
・The main screen of the DCS did not show nitrogen flow rate.
・If agitation is stopped, it was difficult to determine temperature distribution in the
oxidation reactor by DCS screen.
・Operators did not recognize that the position of the thermometer failed to show
temperature rises in all parts of the oxidation reactor and as a result they failed to
recognize the abnormal rise in temperature.
・The operating manual and training materials did not state that nitrogen supply would be
stopped when the interlock is released.

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 ・Operators were not aware of the importance of agitation so though they knew nitrogen
would stop when the interlock is released, they did not realize that it would affect
agitation.
・Temperature at which organic peroxide would start to decompose was not clearly
known to all workers resulting in a failure to notice rises in temperature.
・There was insufficient technical knowledge regarding heat decomposition behavior of
organic peroxide.

9. Measures to prevent recurrence of similar accidents

・To prevent the recurrence of similar accidents, (1) fundamental measures to prevent
accidents and (2) management of emergency operations and improvements in
technology were established considering measures for hardware (equipment, devices,
etc.) and software (procedures, rules, methods, etc.).

(1) Fundamental measures to prevent accidents

a. Secure necessary abilities for cooling oxidation reactor during emergency shutdown.
1) Cooling ability necessary for a pronounced drop in temperature (increase
heat-transfer area of cooling coil and expand installation range)
2) System whereby pressure of emergency cooling water can be increased swiftly and
strengthening of monitoring
3) Maintain agitation in oxidation reactor

b. Clarify conditions for releasing interlock

1) Set standards for “stable condition” at which the interlock can be released during
emergency shutdown.
2) Compile and utilize a checklist for release of interlocks
・Confirmation of stable conditions
・Authorization from superiors

c. Review temperature management based on data on heat decomposition behavior of

organic peroxide using latest methods (such as an adiabatic calorimeter) and educate all
workers
1) Collect data on heat decomposition of organic peroxide
2) Reflect data on safety design philosophy
3) Educate workers regarding hazards of organic peroxide and hand down skills

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(2) Management of emergency operations and improvements in technology
a. Install multiple thermometers for triggering interlock in oxidation reactors

b. Create a DCS screen that makes it easier to notice abnormalities during emergency
shutdown and review alarms
・Agitation condition (display nitrogen flow rate, alarm for stopped agitation gas)
・Temperature distribution (improve display, alarm sound, etc.)
・Temperature trends

c. Compile training material regarding interlocks and conduct education and training
・Importance of agitation in oxidation reactor
・Rules within section and authorization for releasing interlocks
・Details of process operation after interlock is released

d. Review risks of operation procedures for emergency shutdown of oxidation reactor and
equipment

・Note that when resuming operations at the meta/para cresol (MPCR) and hydroquinone
(HQ) production plants, which are similar to the resorcinol plant, measures will be
securely implemented for the issues extracted in accordance with the characteristics of
each production plant and approval will be obtained from supervisory agencies.

10. Consider underlying causes of the accident

・In the future, the Committee will continue to extract issues and consider measures
regarding the underlying causes that led to the direct causes of this accident, such as
work climate and corporate culture.

11. Our future

・Our company has implemented various safety activities under the management policy,
“Safety is our top priority”. However, unfortunately this tragic accident, which had a
significant effect on society, occurred. We are strongly aware that we must thoroughly
review the problems with safety at MCI through a companywide structure and consider
and implement fundamental measures for safety. To this end, on June 19, 2012, we
formed the Fundamental Safety Committee with the President of MCI as the
chairperson.
・Through a team consisting of external advisors and members from various parts of the
company, this committee will investigate the root causes in the people, organization,
technology, and culture of the company and propose and implement strengthening
measures for the fundamental aspects of safety at MCI.