Chlorine Commercial process

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. 

The cumene oxidation route is the lea ding commercial process of synthetic phenol production, accounting for more than 95% of phenol produced in the world. The remainder of synthetic phenol is produced by the toluene oxidation route via benzoic acid. Other processes including benzene via cyclohexane, benzene sulfonation, benzene chlorination, and benzene oxychl orin ation have also been used in the manufacture of phenol. A Hst of U.S. phenol production plants and their estimated capacities in 1994 are shown in Table 2, and worldwide plants and capacities are shown in Table 3. 

Three significant, commercial processes for the production of amyl alcohols include separation from fusel oils, chlorination of C-5 alkanes with subsequent hydrolysis to produce a mixture of seven of the eight isomers (Pennsalt) (91), and a low pressure 0x0 process, or hydroformylation, of C-4 olefins followed by hydrogenation of the resultant C-5 aldehydes. 

After World War I, other chlohne-based bleaches were developed. In 1921 the use of chlorine dioxide for bleaching fibers was reported followed by the development of the commercial process for large-scale production of sodium chlorite. In 1928 the first dry calcium hypochlorite containing 70% available chlorine was produced in the United States. This material largely replaced bleaching powder as a commercial bleaching agent. 

Two cocrystallization processes employ dibasic crystals as intermediates. The PPG process (199—202) is discussed under commercial processes. The PPC process (203) forms dibasic crystals from lime and recovered filtrates. The dibasic crystals are separated from thek mother liquor by decantation, slurried in caustic solution and chlorinated to produce a cocrystalline slurry of Ca(OCl)2 and NaCl. The slurry is sent to a flotation cell where the larger salt crystals settle out and the smaller hypochlorite crystals float to the top with the aid of ak and flotation agent. The hypochlorite slurry is centrifuged the cake going to a dryer and the centrate to the flotation cell. The salt-rich bottoms from the flotation cell are centrifuged and washed with dibasic mother Hquor. The centrates are recycled to the precipitation step. 

Commercial Processes. Olin s earlier triple salt process, originally commercialized in 1928, was modified in 1983. In the patented process, a slurry of dibasic calcium hypochlorite is mixed with a strong, low salt sodium hypochlorite solution and hypochlorite Hquors and chlorinated. The resultant Ca(OCl)2 2H20 slurry is filtered, the cake going to the dry-end and the filtrate to the dibasic precipitation step where it reacts with lime. 

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. 

Addition Chlorination. Chlorination of olefins such as ethylene, by the addition of chlorine, is a commercially important process and can be carried out either as a catalytic vapor- or Hquid-phase process (16). The reaction is influenced by light, the walls of the reactor vessel, and inhibitors such as oxygen, and proceeds by a radical-chain mechanism. Ionic addition mechanisms can be maximized and accelerated by the use of a Lewis acid such as ferric chloride, aluminum chloride, antimony pentachloride, or cupric chloride. A typical commercial process for the preparation of 1,2-dichloroethane is the chlorination of ethylene at 40—50°C in the presence of ferric chloride (17). The introduction of 5% air to the chlorine feed prevents unwanted substitution chlorination of the 1,2-dichloroethane to generate by-product l,l,2-trichloroethane. The addition of chlorine to tetrachloroethylene using photochemical conditions has been investigated (18). This chlorination, which is strongly inhibited by oxygen, probably proceeds by a radical-chain mechanism as shown in equations 9—13. 

Liquid-phase chlorination of butadiene in hydroxyhc or other polar solvents can be quite compHcated in kinetics and lead to extensive formation of by-products that involve the solvent. In nonpolar solvents the reaction can be either free radical or polar in nature (20). The free-radical process results in excessive losses to tetrachlorobutanes if near-stoichiometric ratios of reactants ate used or polymer if excess of butadiene is used. The "ionic" reaction, if a small amount of air is used to inhibit free radicals, can be quite slow in a highly purified system but is accelerated by small traces of practically any polar impurity. Pyridine, dipolar aptotic solvents, and oil-soluble ammonium chlorides have been used to improve the reaction (21). As a commercial process, the use of a solvent requites that the products must be separated from solvent as well as from each other and the excess butadiene which is used, but high yields of the desired products can be obtained without formation of polymer at higher butadiene to chlorine ratio. 

In order to assure control of the reaction, the vapor-phase inhibitor concentration must be closely controlled in the ppm range. Although several compounds have been claimed to be useful, it is likely that commercial processes use only ethylene dichloride or some of the simpler chlorinated aromatics (102). In general, the choice between inhibitors is not based on their differences in performance, but rather on the designers preference for dealing with the type of control problems each inhibitor system imposes (102). 

Chlorine dioxide, discovered in 1811 by Davy, was prepared from the reaction of potassium chlorate with hydrochloric acid. Early experimentation showed that chlorine dioxide exhibited strong oxidizing and bleaching properties. In the 1930s, the Mathieson Alkali Works developed the first commercial process for preparing chlorine dioxide from sodium chlorate. By 1939, sodium chlorite was established as a commercial product for the generation of chlorine dioxide. 

Wendell Dunn A family of chlorine beneficiation processes based on selective chlorination of ores in a fluidized bed. Developed by W. E. Dunn of Chlorine Technology in Australia in the 1970s, primarily for beneficiating ilmenite. The first such commercial ilmenite beneficiation plant, completed in 1991, was that of Bene-Chlor Chemicals Private, Madras. 

Hydrazine may he produced by several methods. The most common commercial process is the Raschig process, involving partial oxidation of ammonia or urea with hypochlorite. Other oxidizing agents, such as chlorine or hydrogen peroxide may he used instead of hypochlorite. The reaction steps are as follows. 

Although many commercial processes have heen developed since the first electrolytic isolation of Mg metal hy Davy and Faraday, and Bussy, hy chemical reduction, the principles of the manufacturing processes have not changed. At present, the metal is most commonly manufactured by electrolytic reduction of molten magnesium chloride, in which chlorine is produced as a by-product. In chemical reduction processes, the metal is obtained by reduction of magnesium oxide, hydroxide, or chloride at elevated temperatures. 

The formation of epoxides is synthetically a very important transformation. The indirect epoxidation of olefins (see Eq. 7) in the presence of electrogenerated chlorine (or bromine) [95] is a commercial process in which chlorine is recycled and not part of the product. The products such as propylene oxide are key intermediates in many further chemical processes. 

Dichloromethane was first prepared by Regnault in 1840 by the chlorination of methyl chloride in sunlight. It became an industrial chemical of importance during the Second World War. Two commercial processes are currently used for the production of dichloromethane—hydrochlorination of methanol and direct chlorination of methane (Rossberg etal., 1986 Holbrook, 1993). 

The catalyst modified with selenium is most suitable for the studies of reaction kinetics since this element, in contrast to chlorine usually used as promoter in the commercial processes, does not volatilize from the surface of silver under the reaction conditions. We studied the kinetics of ethylene oxidation under gradientless conditions (Section II) using a circulation flow system in the experiments at atmospheric pressure (59-61) and a reactor with rotating baskets for the catalyst (5) at elevated pressures (62). 

The second example also involves catalysts development. The goal of this project, headed by Leo E. Manzer and Walter Cicha at the DuPont Central Research Station, was charged with developing a new highly selective catalyst for the manufacture of phosgene while reducing the amount of the undesired by-product, carbon tetrachloride. As a result of basic studies by the DuPont catalysts research team, it was recognized that carbon tetrachloride formation arose from chlorination of the carbon catalyst that is used in the commercial process to promote the reaction of carbon monoxide and chlorine. 

PO is produced by one of two commercial processes the chlorohydrin process or the hydroperoxide process. The chlorohydrin process involves reaction of propylene and chlorine in the presence of water to produce the two isomers of propylene chlorohydrin. This is followed by dehydrochlorination using caustic or lime to produce PO and salt. The hydroperoxide process involves oxidation of propylene to PO by an organic hydroperoxide. 

Cationic polymerization of 3,3-bis(chloromethyl)oxetane (BCMO) was in the past employed in the commercial process for making chlorinated polyether-Penton , polymer having very good chemical resistance toward aggressive media (e.g., cone. H2S04 up to 120° C). Relatively high price, due to the difficult monomer synthesis, was the reason, that Penton... 

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