Natech Accident
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Type
Natech Accident
Date
2002/12/17
Duration
30 hour(s)
Status
Published

Units Involved

  1. Name
    Cyclohexane pipe and manifold
    Type
    Auxiliary: Pipes and pipework
    Description
    A ND 50 mm half-buried manifold supplies cyclohexane to the adiponitrile production facility (ADN). This pipe is connected to a ND 100 mm pipeline that joins the 10,000 m3 cyclohexane storage tank to the OLONE production shop.

Event Sequences

  1. Name
    Cyclohexane leak
    Unit
    1. Cyclohexane pipe and manifold
    Description
    Low outside temperatures in early December resulted in the solidification of cyclohexane in the manifold. Due to temperature variations over the weekend of 15-16 December, which led to the expansion and contraction of the cyclohexane, the manifold broke near the expansion loop. The resulting hole was oblong and sized like the palm of a hand.
    Substances Involved
    1. Name
      Cyclohexane
      CAS No
      110-82-7
      Involved Quantity
      1200 ton
      Potential Quantity
      10000 m³
      Description
      Melting/freezing temperature 6.5°C
    Initiating EventCritical EventMajor Event
    Lifeline: Loss of heating
    Since the steam tracing which kept the cyclohexane liquid had been turned off and with the low outside temperatures, the temperature dropped under 6.5°C which is the melting point of cyclohexane. This caused cyclohexane solidification at the manifold.
    Contributing Factors
    Human: Operator error: Non-existent
    The steam tracing had been turned off for unknown reasons and for an unknown period of time.
    Release: Liquid release to ground
    The ND 50 mm manifold broke near the expansion loop due to the solidification, expansion and contraction of the cyclohexane caused by temperature variations.
    Contributing Factors
    Equipment: Blockage:
    Due to the switched off steam tracing and the low outside temperatures, the cyclohexane solidified in the pipe.
    Equipment: Component failure:
    Outside temperature variations caused expansion and contraction of the cyclohexane in the pipe.
    Release: Liquid release to ground
    The leak occurred from the rupture due to the dilation of liquid cyclohexane. Liquid cyclohexane was released underground, eventually reaching the aquifer underneath the installation.
    Contributing Factors
    Measure: Instrument / control / monitoring devices: Non-existent
    As the piping was not yet equipped with a device for rapid leak detection, it took 30 hours to determine the cause of the pressure anomaly. Eventually, the leak was traced due to its odour.
    Measure: Emergency shut off / safety valves: Unavailable
    The outlet valve of the ND 50 mm manifold was permanently switched to open.
    Release: Gas, vapour, mist, or smoke release to air
    A fraction of gaseous cyclohexane was released into the atmosphere.
    Dispersion: Substance in / on ground
    Dispersion: Substance in groundwater

Weather Conditions

Temperature
0 °C

Emergency Response

Response Planning Activities
Since the cyclohexane released did not ignite or explode, the internal contingency plan was not activated.
Difficulties in Response to the Natech Event
Insufficient personnel and equipment to respond to both emergencies: No
Damage to lifelines (e.g. water, power, communication, transportation): No
Response to the Natech Event
On December 16, plant personnel noted disruptions of the cyclohexane supply. As a consequence, systems were checked but no problem could be found. With the supply irregularities continuing, the manifold was inspected on the next day, and a cyclohexane leak was discovered based on the odour the leak emanated. Once the origin of the leak had been isolated, the manifold's outlet valve was closed, thereby stopping the release.

A network of 25 existing wells distributed around the chemical platform was adapted to create a hydraulic barrier. This measure confined the pollution to the industrial site and prevented the migration downstream.

Consequences

Human Health Impacts
Offsite samples of the water showed no contamination with cyclohexane that would have been above the consumption threshold.
Environmental Zones Impacted
Freshwater (e.g. pond, lake, stream)
Environmental Impacts
The released cyclohexane entered the soil and infiltrated the underground aquifer. Most of the substance spread out at the top of the underground water table, and 1% of the released quantity dissolved in the water.

The pollution resulted in a large risk of contamination of the community's drinking water reservoirs and agricultural pumping stations located downstream in the region.

With the pollution spreading under the site, in August 2003 remedial activities were taken that limited the expansion of the pollution under the site to an area of 600 m by 300 m. The thickness of the supernatant cyclohexane layer reached a maximum of about 10 centimetres.
Economic Impacts
The overall cost of this leak and the resulting actions was estimated at 2 million Euros.

Remedial Activities

Remediation Activities
In August 2003, piezometres were drilled (special precautions to prevent the risk of explosion) to determine the extent of the pollution, to pump the supernatant cyclohexane, to draw off the gases (venting), and to perform additional analyses. Two cyclohexane fixation wells with a water table barrier and four control piezometres were drilled. A sparging barrier (300 m) was set up along the site's northern limit to reinforce the existing hydraulic barrier. These actions limited the expansion of the pollutant and kept it confined to the industrial site.

In July 2004, 590 tons of cyclohexane had been recovered from the ground by skimming of the supernatant, venting, and sparging. Since the amount of recovered substance was, however, saturating, a long-term remediation strategy was required.

A prefectural order was issued that requested that risk analysis be conducted within the scope of a remediation plan.

Lessons Learned

Lessons Learned on Equipment
There is a need for real-time output measurements on all lines. This information should be reported to the control room and trigger an alarm in case of supply irregularities.

There is also a need for leak detection systems to quickly identify the source of the release.
Lessons Learned on Human Health Aspects
Personnel should consider that a release might have occurred in case supply irregularities on a line is detected.
Lessons Learned on Organisational Aspects
The accident highlighted several organisational issues that should be addressed. More specifically:
- Inspection programmes are needed to check the status of equipment (e.g. steam tracing, pipeway). This also includes the designation of personnel in charge of carrying out these verification actions.
- Personnel should be trained to allow them to quickly identify and react to solve problems quickly and effectively.
- Procedures should be established to give instructions on how to react in case of a release. Procedures should also be set up for lines that are not used (e.g. draining the line, closing valves, etc.)
- Effective communication is needed between the operator (or operators in case responsibilities are shared between several departments), authorities and communities around the site. This includes the sharing of complete information about the accident and its evolution.
Lessons Learned on Mitigation Measures
Response to the leak confirmed the efficiency of the hydraulic barrier installed in the 1980s following a severe pollution accident.
ID: 25, Created: Bogdan DORNEANU, 2013-10-21 11:35:21 – Last Updated: Amos NECCI, 2021-01-15 09:48:12

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