Cathode chlor-alkali

Overvoltages for various types of chlor—alkali cells are given in Table 8. A typical example of the overvoltage effect is in the operation of a mercury cell where Hg is used as the cathode material. The overpotential of the H2 evolution reaction on Hg is high hence it is possible to form sodium amalgam without H2 generation, thereby eliminating the need for a separator in the cell. 

Electrolytic Preparation of Chlorine and Caustic Soda. The preparation of chlorine [7782-50-5] and caustic soda [1310-73-2] is an important use for mercury metal. Since 1989, chlor—alkali production has been responsible for the largest use for mercury in the United States. In this process, mercury is used as a flowing cathode in an electrolytic cell into which a sodium chloride [7647-14-5] solution (brine) is introduced. This brine is then subjected to an electric current, and the aqueous solution of sodium chloride flows between the anode and the mercury, releasing chlorine gas at the anode. The sodium ions form an amalgam with the mercury cathode. Water is added to the amalgam to remove the sodium [7440-23-5] forming hydrogen [1333-74-0] and sodium hydroxide and relatively pure mercury metal, which is recycled into the cell (see Alkali and chlorine products). 

Sodium was made from amalgam ia Germany duriag World War II (68). The only other commercial appHcation appears to be the Tekkosha process (74—76). In this method, preheated amalgam from a chlor—alkali cell is suppHed as anode to a second cell operating at 220—240°C. This cell has an electrolyte of fused sodium hydroxide, sodium iodide, and sodium cyanide and an iron cathode. Operating conditions are given ia Table 6. 

There have been a number of cell designs tested for this reaction. Undivided cells using sodium bromide electrolyte have been tried (see, for example. Ref. 29). These have had electrode shapes for in-ceU propylene absorption into the electrolyte. The chief advantages of the electrochemical route to propylene oxide are elimination of the need for chlorine and lime, as well as avoidance of calcium chloride disposal (see Calcium compounds, calcium CHLORIDE Lime and limestone). An indirect electrochemical approach meeting these same objectives employs the chlorine produced at the anode of a membrane cell for preparing the propylene chlorohydrin external to the electrolysis system. The caustic made at the cathode is used to convert the chlorohydrin to propylene oxide, reforming a NaCl solution which is recycled. Attractive economics are claimed for this combined chlor-alkali electrolysis and propylene oxide manufacture (135). 

H. Y. Castner (US/UK) and C. Kellner (Vienna) independently developed commercial mercury-cathode cell for chlor-alkali production... 

When chlor-alkali electrolysis is conducted in an undivided cell with mild-steel cathode, the chlorine generated anodically will react with the alkali produced cathodically, and a solution of sodium hypochlorite NaClO is formed. Hypochlorite ions are readily oxidized at the anode to chlorate ions this is the basis for electrolytic chlorate production. Perchlorates can also be obtained electrochemically. 

Tekkosha An electrolytic process for obtaining sodium from the sodium amalgam formed in the chlor-alkali process. The electrolyte is a fused mixture of sodium hydroxide, sodium iodide, and sodium cyanide. The sodium deposits at the iron cathode. Developed by Tekkosha Company, Japan, in the 1960s and commercialized in 1971. 

Encouraging laboratory experiments since 1994 with oxygen-depolarised cathodes (ODC) in chlor-alkali as well as hydrochloric acid electrolysis motivated the development of this technique up to the industrial scale. Based on the predictions of the theory, the reduction of cell voltage could be expected up to 1 V (Fig. 4.1) for both applications. Early on, the proper choice and improvement of ODC, deriving mainly from the DeNora group, led to results with voltages as predicted in short tests as well as in endurance tests conducted over dozens of months at the Bayer endurance test facilities. 

The flow-through cathode is the result of a tailored-to-the-process evolution of the GDE structure, which is available also in two additional configurations double-sided (originally developed for fuel cell servicing) and single-sided (see Fig. 9.7). The double-sided type is particularly suited for the electrochemical process where the product should not be released on to the back surface of the cathode, as in the case of oxygen-depolarised chlor-alkali electrolysis, discussed in Section 9.3. 

The substitution of conventional hydrogen-evolving cathodes with oxygen-consuming gas-diffusion electrodes (GDE), often referred to as oxygen-depolarised cathodes (ODC), also allows a substantial reduction in the energy consumption of the chlor-alkali process. 

Ion-exchange membranes for chlor-alkali electrolysis generally contain a sulphonic layer which faces the anode and a carboxylic layer which faces the cathode, joined by lamination. The Na+ transport number is higher in the carboxylic layer than in the sulphonic layer, and a region of low Na+ concentration therefore tends to form at the interface between the two layers during electrolysis, as shown in Fig. 17.5. 

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. 

Scott et al. [33] designed a DMFC with stainless steel mesh as the anode FF plate that was able to remove the carbon dioxide gas effectively. Later, the same research group was able to demonstrate that using similar meshes as DLs in the anode side also improved the overall gas removal [26,34] (wet-proofed CFP was used as the DL on the cathode side). These meshes were used on the anode side and were made out of catalyzed Ti because similar meshes have been used extensively as catalyzed electrodes in other industries, such as the chlor-alkali industry [26]. 

The high overpotential for O2 evolution could be avoided if the reaction were replaced with a different anodic reaction. This replacement could in turn reduce AE, the minimum cell potential difference, which depends on the nature of the electrode reactions. Such a strategy has already been applied with success in the chlor-alkali industry, where the CI2-H2 couple (A = 1.35 V) has been replaced with CI2-O2 (A ri0.90 V) (O2 is reduced at the so-called air cathode). 

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. 

Mild steel cathodes are used extensively in chlor-alkali and chlorate cells. Newer activated cathode materials have been developed that decrease cell voltages about 0.2 V below that for cells having mild steel cathodes. Some activated cathodes have operated in production membrane cells for three years with only minor increases in voltage (17). Activated cathodes can decrease the energy consumption for chlorine—caustic production by 5 to 6.5%. 

Mercury is directly below cadmium in the periodic table, but has a considerably more varied and interesting chemistry than cadmium or zinc. Elemental mercury is the only metal that is a liquid at room temperature, and its relatively high vapor pressure contributes to its toxicological hazard. Mercury metal is used in electric discharge tubes (mercury lamps), gauges, pressure-sensing devices, vacuum pumps, valves, and seals. It was formerly widely used as a cathode in the chlor-alkali process for the manufacture of NaOH and Cl2, a process that has been largely discontinued, in part because of the mercury pollution that resulted from it. 

Castner, Hamilton Young — (Sep. 11, 1858, Brooklyn, New York, USA - Oct. 11,1899, Saranac Lake, New York, USA) Castner studied at the Brooklyn Polytechnic Institute and at the School of Mines of Columbia University. He started as an analytical chemist, however, later he devoted himself to the design and the improvement of industrial chemical processes. He worked on the production of charcoal, and it led him to investigate the Devilles aluminum process. He discovered an efficient way to produce sodium in 1886 which made also the production of aluminum much cheaper. He could make aluminum on a substantial industrial scale at the Oldbury plant of The Aluminium Company Limited founded in England. However, - Hall and - Heroult invented their electrochemical process which could manufacture aluminum at an even lower price, and the chemical process became obsolete. Castner also started to use electricity, which became available and cheap after the invention of the dynamo by - Siemens in 1866, and elaborated the - chlor-alkali electrolysis process by using a mercury cathode. Since Karl Kellner (1851-1905) also patented an almost identical procedure, the process became known as Castner-Kellner process. Cast-... 

A chlor-alkali membrane designed to produce 30-35 percent NaOH consists of at least two distinctly different polymer layers, as shown in Fig. 26.9. The anode side of the membrane is about a 0.1-mm film of sulfonic acid polymer, whereas the cathode side is... 

Figure 6.1 Schematic of a chlor-alkali cell in which an electric current is passed through a sodium chloride solution (hrine). Chlorine gas is produced at the anode (note the paddle-like electrodes with the positive charge at the top), and sodium dissolves in the cathode (note the negative charge at the bottom). In this case, the cathode is a pool of elemental mercury, and the sodium amalgam is later hydrolyzed to produce sodium hydroxide.

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