Brine electrolysis diaphragm cells

There are two well-established methods for electrolysing brine, the diaphragm cell and the mercury cell. However, recent developments in electrolysis technology, by chemical engineers, have produced the membrane cell (Figure 5.13). This method is now preferred to the other two because it produces a purer product, it causes less pollution and it is cheaper to run. 

Nearly all sodium compounds are soluble in water. Sodium hydroxide is produced commercially by the electrolysis of brine using diaphragm cells or mercury-cathode cells chlorine is a coproduct. 

M. S. Kirchra Electrolysis of Brines in Diaphragm Cells. In J.S. Sconce (ed.). Chlorine Its Manufacture, Properties and Use, Reinhold Publishing Corp., New York (1962), p. 81. 

Kircher, M.S., Electrolysis of brines in diaphragm cells, in Chlorine Its Manufacture, Properties and Uses. Sconce, J.S., Ed., Robert E Krieger Publishing Co., Huntington, NY, 1972, p. 81. 

Recycle and cathodic reduction. The most elegant solution for the Diaphragm Electrolysis Plant (DEP) appears to be recycling of the hypochlorite solution and reduction of the chlorate and bromate on the cathode of the electrolysis cell - the hypochlorite solution is added to the feed brine of the cells and the chlorate and bromate are converted to chloride and bromide at the cathode. 

Figure 19.16. Basic designs of electrolytic cells, (a) Basic type of two-compartment cell used when mixing of anolyte and catholyte is to be minimized the partition may be a porous diaphragm or an ion exchange membrane that allows only selected ions to pass, (b) Mercury cell for brine electrolysis. The released Na dissolves in the Hg and is withdrawn to another zone where it forms salt-free NaOH with water, (c) Monopolar electrical connections each cell is connected separately to the power supply so they are in parallel at low voltage, (d) Bipolar electrical connections 50 or more cells may be series and may require supply at several hundred volts, (e) Bipolar-connected cells for the Monsanto adiponitrile process. Spacings between electrodes and membrane are 0.8-3.2 mm. (f) New type of cell for the Monsanto adiponitrile process, without partitions the stack consists of 50-200 steel plates with 0.0-0.2 ram coating of Cd. Electrolyte velocity of l-2 m/sec sweeps out generated Oz.

In the mercury cell process chlorine is liberated from a brine solution at Ihe anodes which are. today, typically melal anodes (Dimensionally Stable Anodes or DSAl. Collection and processing of the chlorine is similar lo Ihe techniques employed when diaphragm cells are used. However. Ihe cathode is a flowing bed or mercury. When sodium is released by electrolysis it is immediately amalgamated with the mercury The inereury amalgam is then decomposed in a separate cell 10 form sodium hydroxide and Ihe mercury is returned for reuse. 

Chlorine is produced almost entirely by the electrolysis of aqueous solutions of alkali metal chlorides (Fig. 1), or from fused chlorides. Brine electrolysis produces chlorine at the anode and hydrogen along with the alkali hydroxide at the cathode. At present, three types dominate the industry the diaphragm cell, the membrane cell, and the mercury cell, and there are many variations of each type. 

The rapidly growing use of C102 in the pulp and paper industry has led to the rapid growth of sodium chlorate, NaC103, production in recent years. Sodium chlorate is produced by the electrolysis of NaCl brine in a cell that is very similar to a diaphragm chlor-alkali cell, except that it has no diaphragm. The overall reaction is as follows ... 

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... 

Any of the products of brine electrolysis, chlorine, sodium hydroxide, and hydrogen can be hazardous if released. When releases do occur, it is usually from process upsets or breakdowns, which may be minimized by the construction of fail-safe plants, proper maintenance, and by safe transport and storage practices. Probably of greater long-term concern is the mercury loss experienced through the process streams of a mercury cell chloralkali operation. These losses can also carry over to the products of the diaphragm cell, even though this does not use mercury, if a common brine well or common salt dissolver is used for both sets of cells. 

Briefly, how do the brine pretreatment steps required for diaphragm cell electrolysis and mercury cell electrolysis compare, and what are the reasons for these differences ... 

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... 

One of the most common industrial methods for the production of sodium hydroxide depends on the electrolysis of brine in a diaphragm cell. The products of the electrolysis are chlorine, hydrogen, and cell liquor, which is a solution of sodium hydroxide and sodium chloride. A large fraction of the cost of commercial sodium hydroxide results from the concentration, separation, and purification of the alkali. The sodium hydroxide required in the sea water descaling process need... 

Production of CI2 and NaOH by electrolysis of NaCl is a huge industry with annual production capacity in excess of 50 million tons of NaOH per year. Membrane cells are the state-of-the-art technology, but mercury and diaphragm cells are still used because the capital cost for their replacement is substantial. The mercury cell technology is more than a century old and stiU accounts for nearly half of the world s production capacity. Chlorine evolves from a DSA (dimensionally stable anode) situated above a pool of mercury with NaCl brine in between. Mercury reacts with sodium to form sodium amalgam, which is removed and hydrolyzed in a separate reactor. 

---