Chlorine production processes

Other Chlorine Production Processes. Although electrolytic production of CI2 and NaOH from NaCl accounts for most of the chlorine produced, other commercial processes for chlorine are also in operation. 

A Survey of Potential Chlorine Production Processes, Contract 31-109-38-2411 by Versar Inc., ANL/OEPM-79-1, Argonne National Laboratory, Argonne, HI., April, 1979. 

To ensure a safe, uninterrupted, and smooth operation of chlorine production plants, it is vital to prevent the formation of explosive gas mixtures. Continuous monitoring of the hydrogen concentration in chlorine gas in several stages of the chlorine production process can help in identifying the formation of such explosive mixtures in an early stage. 

A mixture of hydrogen and chlorine gas, eventually in combination with air, can be very explosive if one of the components exceeds certain limits. In chlorine production plants, based on the electrolysis of sodium chloride solutions, there is always a production of hydrogen. It is, therefore, essential to be aware of the actual hydrogen content of chlorine gas process streams at any time. There are several places in the chlorine production process where the hydrogen content in the chlorine gas can accumulate above the explosion limits. Within the chloralkali industry, mainly two types of processes are used for the production of chlorine—the mercury- and the membrane-based electrolysis of sodium chloride solutions (brine). 

Table 1.7-lS, Contributions of the Chlorine Production Processes in Europe in %. 

J.S. Robinson (Ed.), Chlorine Production Processes, Chemical Technology Review No. 185, Noyes Data Corp, NJ, 1981. 

Chlorine production processes Recent and energy saving developments, Ed. by J. S. Robinson, Noyes Data Corporation, New Jersey, 1981. 

Robinson J.S. In Chlorine Production Processes Recent and Energy Saying Deyelooments Noyes Data, New Jersey, 1981. 

J. S. Robinson Chlorine Production Processes, Noyes Data Corp., Park Ridge, N.J., 1981. 

Chlorine production processes Recent and energy saving developments, Ed. by... 

Electrolytic Cell Operating Characteristics. Currently the greatest volume of chlorine production is by the diaphragm ceU process, foUowed by that of the mercury ceU and then the membrane ceU. However, because of the ecological and economic advantages of the membrane process over the other systems, membrane ceUs are currently favored for new production facHities. The basic characteristics of the three ceU processes are shown in Eigure 5. 

Sodium Hydroxide. Before World War 1, nearly all sodium hydroxide [1310-93-2], NaOH, was produced by the reaction of soda ash and lime. The subsequent rapid development of electrolytic production processes, resulting from growing demand for chlorine, effectively shut down the old lime—soda plants except in Eastern Europe, the USSR, India, and China. Recent changes in chlorine consumption have reduced demand, putting pressure on the price and availabiHty of caustic soda (NaOH). Because this trend is expected to continue, there is renewed interest in the lime—soda production process. EMC operates a 50,000 t/yr caustic soda plant that uses this technology at Green River it came onstream in mid-1990. Other U.S. soda ash producers have aimounced plans to constmct similar plants (1,5). 

Sodium bicarbonate may be prepared by the ammonia-salt (Solvay) process. Carbon dioxide is passed through a solution of sodium chloride in ammonia water. Sodium bicarbonate is precipitated and the ammonium chloride remains in solution. The ammonium chloride is heated with lime to regenerate ammonia (see Alkali AND CHLORINE PRODUCTS). 

Specifications and Standards, Shipping. Commercial iodine has a minimum purity of 99.8%. The Committee of Analytical reagents of the American Chemical Society (67) and the U.S. Pharmacopoeia XXII (68) specify an iodine content not less than 99.8%, a maximum nonvolatile residue of 0.01%, and chlorine—bromine (expressed as chlorine) of 0.005% (ACS) and 0.028% (USP), respectively. In the past these requirements were attained basicaHy only by sublimation, but with processing changes these specifications can be met by direct production of iodine. Previously the impurities of the Chilean product were chiefly water, sulfuric acid, and insoluble materials. Improvements in the production process, and especiaHy in the refining step, aHow the direct obtainment of ACS-type iodine. Also, because of its origin and production process, the Chilean iodine has a chlorine—bromine impurity level of no more than 0.002%. 

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). 

HCIO4, one of the strongest of the mineral acids. The perchlorates are more stable than the other chlorine oxyanions, ie, chlorates, CIO chlorites, CIO or hypochlorites, OCf (3) (see Chlorine oxygen acids and salts). Essentially, all of the commercial perchlorate compounds are prepared either direcdy or indirectly by electrochemical oxidation of chlorine compounds (4—8) (see Alkali and chlorine products Electrochemical processing). 

The most innovative photohalogenation technology developed in the latter twentieth century is that for purposes of photochlorination of poly(vinyl chloride) (PVC). More highly chlorinated products of improved thermal stabiUty, fire resistance, and rigidity are obtained. In production, the stepwise chlorination may be effected in Hquid chlorine which serves both as solvent for the polymer and reagent (46). A soHd-state process has also been devised in which a bed of microparticulate PVC is fluidized with CI2 gas and simultaneously irradiated (47). In both cases the reaction proceeds, counterintuitively, to introduce Cl exclusively at unchlorinated carbon atoms on the polymer backbone. 

A.mmonia-Soda Process. Ammonium chloride is made as a by-product of the classic Solvay process, used to manufacture sodium carbonate (12,13) (see Alkali and chlorine products, sodium carbonate). The method iuvolves reaction of ammonia, carbon dioxide, and sodium chloride ia water... 

Process Raw Material. Industrial solvents are raw materials in some production processes. Eor example, only a small proportion of acetone is used as a solvent, most is used in producing methyl methacrylate and bisphenol A. Alcohols are used in the manufacture of esters and glycol ethers. Diethylenetriamine is also used in the manufacture of curing agents for epoxy resins. Traditionally, chlorinated hydrocarbon solvents have been the starting materials for duorinated hydrocarbon production. 

In oxychlorination, ethylene reacts with dry HCl and either air or pure oxygen to produce EDC and water. Various commercial oxychlorination processes differ from one another to some extent because they were developed independentiy by several different vinyl chloride producers (78,83), but in each case the reaction is carried out in the vapor phase in either a fixed- or fluidized-bed reactor containing a modified Deacon catalyst. Unlike the Deacon process for chlorine production, oxychlorination of ethylene occurs readily at temperatures weU below those requited for HCl oxidation. 

Chlorate. Conversion to metal anodes has also taken place in this process. Sodium hydroxide, which is formed at the cathode, reacts to form the sodium chlorate product (see Alkali and chlorine products). 

Chlorine dioxide produced from the methanol reductant processes contains carbon dioxide and small amounts of formic acid. For this reason, sulfur dioxide and chloride-based chlorine dioxide processes are stih used for sodium chlorite production. This problem has been addressed by recycling a portion of the vapor from methanol-based generators so that formic acid further reacts to carbon dioxide ... 

Chlorine atoms obtained from the dissociation of chlorine molecules by thermal, photochemical, or chemically initiated processes react with a methane molecule to form hydrogen chloride and a methyl-free radical. The methyl radical reacts with an undissociated chlorine molecule to give methyl chloride and a new chlorine radical necessary to continue the reaction. Other more highly chlorinated products are formed in a similar manner. Chain terrnination may proceed by way of several of the examples cited in equations 6, 7, and 8. The initial radical-producing catalytic process is inhibited by oxygen to an extent that only a few ppm of oxygen can drastically decrease the reaction rate. In some commercial processes, small amounts of air are dehberately added to inhibit chlorination beyond the monochloro stage. 

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