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Table 1.2: Typical conditions for chlor-alkali production in membrane processes [3, 4, 8]. Temperature / ◦C 90 NaCl concentration in the anolyte / g dm−3 200 Anolyte pH 2-4 NaOH concentration in the catholyte / wt-% 32 Table 1.3: Typical operating conditions in sodium chlorate production [5, 9, 10]. 3 Cell voltage / V Current density / kAm−2 2.4-2.7 1.5-7 Cell voltage / V Current density / kAm−2 Temperature / ◦C NaCl concentration / gdm−3 NaClO3 concentration / gdm−3 NaOCl concentration / gdm−3 Na2Cr2O7 concentration / gdm−3 Electrolyte pH 2.9-3.7 1.5-4 65-90 70-150 450-650 1-5 1-6 5.5-7 whereas in undivided (sodium chlorate) cells the overall reaction is NaCl + 3 H2O NaClO3 + 3 H2 (1.7) The type of “divider” used separates the different chlor-alkali processes into three subtypes: the mercury cell process, the diaphragm process and the membrane pro- cess. Only the last type is currently acceptable from the environmental and eco- nomic points of view[7], and the other processes are to be discontinued in the European Union. Due to the high yearly production rates of both chemicals, with chlor-alkali production alone consuming an estimated 150 TWh of electricity per year[4], it is clear that high selectivity and energy efficiency in both processes is required.[1] Typical operating conditions for the membrane chlor-alkali and sodium chlorate processes are found in Tables 1.2 and 1.3, respectively.[3–5, 8–10] A challenge in both processes is parasitic oxygen evolution. The possible pathways for this oxygen evolution include direct anodic water oxidation, competing with reaction 1.1, 2H2O → O2 + 4H+ + 4e−, (1.8) direct anodic chlorate formation 6ClO−+3H2O→2ClO−3 +4Cl−+6H++1.5O2+6e−, (1.9)PDF Image | Studies of Electrode Processes in Industrial Electrosynthesis
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