The World Bank

Chlor-Alkali Plants Industry - Pollution Prevention Guidelines


Courtesy of Courtesy of The World Bank


Pollution Prevention Guidelines to provide technical advice and guidance to staff and consultants involved in pollution-related projects. The guidelines represent state-of-the-art thinking on how to reduce pollution emissions from the production process. In many cases, the guidelines provide numerical targets for reducing pollution, as well as maximum emissions levels that are normally achievable through a combination of cleaner production and end-of-pipe treatment. The guidelines are designed to protect human health; reduce mass loadings to the environment; draw on commercially proven technologies; be cost-effective; follow current regulatory trends; and promote good industrial practices, which offer greater productivity and increased energy efficiency.

Table of Contents

  • Industry Description and Practices
  • Waste Characteristics
  • Pollution Prevention and Control
  • Target Pollution Loads
  • Treatment Technologies
  • Emissions Guidelines
  • Monitoring and Reporting
  • Key Issues

Industry Description and Practices

There are three basic processes for the manufacture of chlorine and caustic soda from brine: the mercury cell, the diaphragm cell, and the membrane cell. The membrane cell is the most modern and has economic and environmental advantages. The other two processes generate hazardous wastes containing mercury or asbestos.

In the membrane process, the chlorine (at the anode) and the hydrogen (at the cathode) are kept apart by a selective polymer membrane that allows the sodium ions to pass into the cathodic compartment and react with the hydroxyl ions to form caustic soda. The depleted brine is dechlorinated and recycled to the input stage. The membrane cell process is the preferred process for new plants. Diaphragm processes may be acceptable, in some circumstances, if nonasbestos diaphragms are used. The energy consumption in a membrane cell process is of the order of 2,200–2,500 kilowatt-hours per metric ton (kWh/t), as against 2,400–2,700 kWh/t of chlorine for a diaphragm cell process. The World Bank does not finance mercury cell technology.

Waste Characteristics

The major waste stream from the process consists of brine muds—the sludges from the brine purification step—which may contain magnesium, calcium, iron, and other metal hydroxides, depending on the source and purity of the brines. The muds are normally filtered or settled, the supernatant is recycled, and the mud is dried and landfilled.

Chlorine is a highly toxic gas, and strict precautions are necessary to minimize risk to workers and possible releases during its handling. Major sources of fugitive air emissions of chlorine and hydrogen are vents, seals, and transfer operations. Acid and caustic wastewaters are generated in both the process and the materials recovery stages.

Pollution Prevention and Control

The following pollution prevention measures should be considered:

  • Use metal rather than graphite anodes to reduce lead and chlorinated organics.
  • Resaturate brine in closed vessels to reduce the generation of salt sprays.
  • Use noncontact condensers to reduce the amount of process wastewater.
  • Scrub chlorine tail gases to reduce chlorine discharges and to produce hypochlorite.
  • Recycle condensates and waste process water to the brine system, if possible.
  • Recycle brine wastes, if possible.

For the chlor-alkali industry, an emergency preparedness and response plan is required for potential uncontrolled chlorine and other releases. Carbon tetrachloride is sometimes used to scrub nitrogen trichloride (formed in the process) and to maintain its levels below 4% to avoid explosion. Substitutes for carbon tetrachloride may have to be used, as the use of carbon tetrachloride may be banned in the near future.

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