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Clean Hydrogen Partnership

Explosion in the chlorine line of a sodium hydroxide electrolysis unit

Event

Event ID
634
Quality
Description
The incident occurred at a caustic soda electrolysis plant.
A chlorine suction pump failed on a sodium hydroxide electrolysis unit. The arrest of the pump caused the stop of the electrolysis current.
Recovery operations were carried out including nitrogen purging of hydrogen piping and air purging of chlorine piping before starting to add chlorine into the electrolysis vessel. A sudden explosion occurred about 40 minutes later at a chlorine chilling tower and chlorine transfer pipeline.

The cause of the incident was a leak through the valve on the chlorine pipeline. This valve had been correctly closed after the injection of air, but it was leaking. Since the fume removing equipment continued to operate, it created a negative pressure in the chlorine compartment. Therefore, residual hydrogen gas in the cathode cell went into the chlorine pipeline, forming a hydrogen-air explosive gas mixture.
Event Initiating system
Classification of the physical effects
Hydrogen Release and Ignition
Nature of the consequences
Macro-region
Asia
Country
Japan
Date
Main component involved?
Valve (Generic)
How was it involved?
Leak & Formation Of A Flammable H2-Cl2-Air Mixture
Initiating cause
Material Degradation (Generic)
Root causes
Root CAUSE analysis
The INITIATING CAUSE was the failure of an isolation on the chlorine compartment, which allowed hydrogen to access the chlorine compartment crating a hydrogen-air explosive mixture.
This incident occurred during the recovery work followed a non-hydrogen related emergency.
A contributing factor has been breaking of one of the exchange membranes, due to pressure fluctuations during the shutdown. This was due to the fact the discharge capacity of the water-sealed relief valve was insufficient, causing the pressure inside the electrolysis cell to fluctuate rapidly.

Despite the operational steps undertaken, material failures and lack of diagnostics allowed the occurrence of the explosion. The ROOT CAUSE can be attributed to shortcoming in performing the risk assessment and in designing the realted safe procedures.

Facility

Application
Chemical Industry
Sub-application
Chlorine production
Hydrogen supply chain stage
All components affected
hydrogen pipeline, chlorine pipeline, electrolytic cell,
Location type
Unknown
Operational condition
Pre-event occurrences
A recovery action was ongoing, caused by the arrest of a pump.

Emergency & Consequences

Number of injured persons
0
Number of fatalities
0

Event Nature

Release type
gas mixture
Involved substances (% vol)
H2, CL2
Presumed ignition source
Not reported

References

Reference & weblink

High Pressure Gas Accident Cases Database of the KHK (High Pressure Gas Safety Association): <br />
https://www.khk.or.jp/public_information/incident_investigation/hpg_inc… />
(accessed May 2025)

The first entry in HIAD was comingfrom RISCAD, which is now closed.<br />

JRC assessment