Asbestos diaphragm cells

For over a hundred years the chlor-alkali industry has used the mercury cell as one of the three main technologies for the production of chlorine and caustic soda. For historical reasons, this process came to dominate the European industry - while in the United States the asbestos diaphragm cell took the premier position. Over the last two decades developments in membrane cells have brought these to the forefront, and membrane cells of one kind or another now represent the technology of choice worldwide. 

The anionic groups almost completely inhibit transport of hydroxide ions from the cathode, at the same time letting current flow in the form of sodium ions. The resulting caustic is purer and more concentrated while still avoiding the potential pollution of mercury cells. These cells have larger power requirements than asbestos diaphragm cells. 

In the obsolescent asbestos diaphragm cell, the product on the cathode side is typically 11% in NaOH and 16% NaCl (i.e., about 2.7 mol of each per kilogram of solution). Evaporation to about 50% NaOH causes most of the NaCl to crystallize, leaving about 1% NaCl in solution this caustic soda is sufficiently pure for many industrial uses. The Si-0 links in the asbestos are attacked by the alkali (Section 3.5 and Chapter 7), and the diaphragm soon deteriorates. 

Other remaining technical concerns with membrane cells relate to somewhat lower current efficiencies and to relatively short membrane lifetimes. At present, this is limited to 2-3 year of operation when coupled to much more careful brine pretreatment than is required for conventional asbestos diaphragm cells. A combination of mercury cell and membrane cell technologies has been recently tested for commercial feasibility [19]. The economics of the three primary chloralkali technologies have also been reviewed [20]. 

Separation of the anode and cathode products in diaphragm cells is achieved by using asbestos [1332-21 -4] or polymer-modified asbestos composite, or Polyramix deposited on a foraminous cathode. In membrane cells, on the other hand, an ion-exchange membrane is used as a separator. Anolyte—catholyte separation is realized in the diaphragm and membrane cells using separators and ion-exchange membranes, respectively. The mercury cells contain no diaphragm the mercury [7439-97-6] itself acts as a separator. 

The toxicological problems associated with asbestos have been widely pubHshed and asbestos has been banned from most uses by the EPA. However, modem diaphragm cell chlorine plants have not had difficulty meeting the required exposure limits for asbestos fibers, and, as of 1990, the chlorine industry had an exemption allowing the continued use of asbestos as a diaphragm material. 

Fig. 9. Dow diaphragm cell, section view a, perforated steel back plate b, cathode pocket c, asbestos diaphragm d, DSA anode e, copper back plate f,...

In the diaphragm-cell process, a solid cathode (iron) is used where hydrogen is evolved [reaction (15.4)]. Porous asbestos diaphragms are used to prevent mixing of the catholyte and anolyte, but owing to the finite permeability of these diaphragms, the alkaline solution that is produced near the cathode stiU contains important levels of chloride ions as an impurity. 

The diaphragm cell consists of multiple electrolytic cells having the anode plates and cathodes mounted vertically and parallel to each other. The cathodes, often flat hollow perforated steel structures that are covered with asbestos fibers, serve as the diaphragm that prevents the mixing of hydrogen and chlorine and back diffusion of hydroxide (OH) ions from the cathode to the anode. Brine fed into the cell is decomposed to approximately half of its original concentration to produce chlorine gas at the anode and hydrogen and sodium hydroxide at the cathode. 

The wastewater generated in the membrane cell and other process wastewaters in the cell are generally treated by neutralization.28 Other pollutants similar to those in mercury and diaphragm cells are treated in the same process stated above. Ion exchange and xanthate precipitation methods can be applied in this process to remove the metal pollutants, while incineration can be applied to eliminate some of the hydrocarbons. The use of modified diaphragms that resist corrosion and degradation will help in reducing the amount of lead, asbestos, and chlorinated hydrocarbon in the wastewater stream from the chlor-alkali industry.28... 

If mercury shutdowns were to occur without replacement then Europe would be forced into importing chlorine derivatives such as EDC to compensate. The future of asbestos in diaphragm cells is also an issue, but with a much lower profile in Europe this has attracted less attention apart from in France. In the USA there are pressures on the industry too, which could be more acute depending on who occupies the White... 

Recently, diaphragm cells have been coming under increased pressure both environmentally, by their use of asbestos in the diaphragm, and also in marketing, owing to the presence of salt in the caustic soda. SHE pressure has led to an increased awareness and use of synthetic diaphragms, of which there are several in the market. 

The chlor-alkali cell in this diagram electrolyzes an aqueous solution of sodium chloride to produce chlorine gas, hydrogen gas, and aqueous sodium hydroxide. The asbestos diaphragm stops the chlorine gas produced at the anode from mixing with the hydrogen gas produced at the cathode. Sodium hydroxide solution is removed from the cell periodically, and fresh brine is added to the cell. 

In chlor-alkali diaphragm cells, a diaphragm is employed to separate chlorine hberated at the anode from the sodium hydroxide and hydrogen generated at the cathode. Without a diaphragm, the sodium hydroxide formed will combine with chlorine to form sodium hypochlorite and chlorate. In many cells, asbestos diaphragms are used for such separation. Many types of diaphragm cells are available. 

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