Chlor-alkali diaphragm cell process

A newer chlor-alkali membrane-cell process, in which the diaphragm is replaced by a polymeric membrane to separate the cell compartments, has been adopted in much of the industrialized world. The membrane allows only cations to move through it and only from anode to cathode compartments. Thus, as CF ions are removed at the anode through oxidation to CL, Na ions in the anode compartment move through the membrane to the cathode compartment and form an NaOH solution. In addition to forming purer NaOH than the older diaphragmcell method, the membrane-cell process uses less electricity. 

Summary of Raw Waste Loadings Found in Verification Sampling of Unit Product of Chlor-Alkali (Mercury Cell and Diaphragm Cell Processes)... 

In 1800, Cruickshank was the first to prepare chlorine electrochemically [38] however, the process was of little significance until the development of a suitable generator by Siemens and of synthetic graphite for anodes by Acheson and Castner in 1892. These two developments made possible the electrolytic production of chlorine, the chlor-alkali process, on an industrial scale. About the same time, both the diaphragm cell process (1885) and the mercury cell process (1892) were introduced. The membrane cell process was developed much mpre recently (1970). Currently, more than 95 % of world chlorine production is obtained by the chlor-alkali process. Since 1970 graphite anodes have been superseded by activated titanium anodes in the diaphragm and mercury cell processes. The newer membrane cell process uses only activated titanium anodes. 

Figure 12.14 is a simplified flow sheet for a typical diaphragm cell chlor-alkali plant. The process begins with brine treating, in which... 

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... 

FIGURE 22.6 General wastewater treatment process flow diagram at a diaphragm cell plant for production of chlor-alkali. 

Diaphragm cell A family of electrochemical chlor-alkali processes using cells with semi-permiable membranes which minimize diffusion between the electrodes. The overall reaction is 2NaCl + 2H20 = 2NaOH + H2 +C12... 

Glanor A Chlor-Alkali process using a bipolar diaphragm cell. Developed by PPG Industries and Oronzio de Nora Impianti Elettrochimic in the early 1970s. 

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. 

In the last twenty-five years a new process has been developed in the chlor-alkali industry that uses a membrane to separate the anode and cathode compartments in brine electrolysis cells. The membrane is superior to the diaphragm used in diaphragm cells because the membrane is impermeable to anions. Only cations can flow through the membrane. Because neither Cl- nor OH- ions can... 

Chlorine gas, CI2, is prepared industrially by the electrolysis of molten NaCl (see Section 19.8) or by the chlor-alkali process, the electrolysis of a concentrated aqueous NaCl solution (called brine). Chlor denotes chlorine and alkali denotes an alkali metal, snch as sodium.) Two of the common cells nsed in the chlor-alkali process are the mercnry cell and the diaphragm cell. In both cells the overall reaction is... 

The choice of technology, the associated capital, and operating costs for a chlor—alkali plant are strongly dependent on local factors. Especially important are local energy and transportation costs, as are environmental constraints. The primary difference in operating costs between diaphragm, mercury, and membrane cell plants results from variations in electricity requirements for the three processes (Table 25) so that local eneigy and steam costs are most important. 

Figure 21.26 A diaphragm cell for the chlor-alkali process. This process uses concentrated aqueous NaCI to make NaOH, CI2, and H2 in an eiectrolytic celi. The difference in iiquid ievei between compartments keeps a net movement of solution into the cathode compartment, which prevents reaction between OH" and Ci2. The cathode eiectroiyte is concentrated and fractionaiiy crystallized to give industrial-grade NaOH.

The unit operations in a commercial chlor-alkali plant can be generally classified as follows (1) brine purification, (2) electrolytic cells, (3) H2 and Cl2 collection, and (4) caustic concentration and salt removal. In this section, the general process flowsheets for diaphragm, membrane, and mercury cell technologies are discussed with emphasis on the need for brine purification and the manner in which it is carried out. 

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