Catalysts copper chloride

Benzene Oxychlorin tion. In the benzene oxychlorination process, also known as the Raschig Hooker process, benzene is oxychlorinated with hydrogen chloride, air, and with the presence of iron and copper chloride catalyst to form chlorobenzene. The reaction occurs at 200—260°C and atmospheric pressure. The chlorobenzene is hydrolyzed at 480°C in the presence of a suitable catalyst to produce phenol and chloride. The yield of phenol is - 90 mol% of theoretical. These plants have been shut down for environmental and economic reasons. 

Significant quantities of ethyl chloride are also produced as a by-product of the catalytic hydrochlorination over a copper chloride catalyst, of ethylene and hydrogen chloride to produce 1,2-dichloroethane, which is used as feedstock in the manufacture of vinyl choride (see Vinyl polymers). This ethyl chloride can be recovered for sale or it can be concentrated and catalyticaHy cracked back to ethylene and hydrogen chloride (25). As the market for ethyl chloride declines, recovery as an intermediate by-product of vinyl chloride manufacture may become a predominant method of manufacture of ethyl chloride. 

Oxychl orin ation of ethylene has become the second important process for 1,2-dichloroethane. The process is usually incorporated into an integrated vinyl chloride plant in which hydrogen chloride, recovered from the dehydrochlorination or cracking of 1,2-dichloroethane to vinyl chloride, is recycled to an oxychl orin a tion unit. The hydrogen chloride by-product is used as the chlorine source in the chlorination of ethylene in the presence of oxygen and copper chloride catalyst ... 

Hexachloroethane is formed in minor amounts in many industrial chlorination processes designed to produce lower chlorinated hydrocarbons, usually via a sequential chlorination step. Chlorination of tetrachloroethylene, in the presence of ferric chloride, at 100—140°C is one convenient method of preparing hexachloroethane (142). Oxychlorination of tetrachloroethylene, using a copper chloride catalyst (143) has also been used. Photochemical chlorination of tetrachloroethylene under pressure and below 60°C has been studied (144) and patented as a method of producing hexachloroethane (145), as has recovery of hexachloroethane from a mixture of other perchlorinated hydrocarbon derivatives via crystalH2ation in carbon tetrachloride. Chlorination of hexachlorobutadiene has also been used to produce hexachloroethane (146). 

Alkyl chlorides. Olefins are chlorinated to alkyl chlorides in a single fluidized bed. HCl reacts with O9 over a copper chloride catalyst to form chlorine. The chlorine reacts with the olefin to form the alkyl chloride. The process developed by the Shell Development Co. uses a recycle of cat yst fines in aqueous HCl to control the temperature [Chem. Proc., 16, 42 (1953)]. 

Today most dimethyl carbonate is made by methanol carbonylation (Equation 3.2) using a copper chloride catalyst with a very long life. This process produces pure dimethyl carbonate, which is not now classified as harmful, and water as a by-product. 

Oxyhydrochlorination A two-stage process for making gasoline from lower paraffinic hydrocarbons, especially methane. The methane, mixed with oxygen and hydrogen chloride, is passed over a supported copper chloride catalyst, yielding a mixture of chloromethanes ... 

The oxychlorination reactor is packed with cupric (copper) chloride catalyst. Three feeds, gaseous hydrogen chloride, pure oxygen or oxygen in the form of air, and ethylene are reacted at 600-800°F and 60-100 psi, to form EDC, and water, as in Reaction Three in Figure 9-1. The reaction effluent is then piped over to the cleanup fractionator, where it commingles with the EDC stream from Reaction One and the recycle stream from VC fractionator. 

A route not yet commercialized is the reaction of ethylene, carbon monoxide, and air to give AA. The ethylene is dissolved in acetic acid. The process talces place at 270°F and 1100 psi in the presence of palladium chloride-copper chloride catalyst. Yields are 80—85%. If the by-product and corrosion problems can be licked, the process will probably catch on. 

Benzoxepins are frequently synthesized by cyclization of alkyl aryl or diaryl ether precursors. An intramolecular Wittig reaction (equation 48) is used to provide the ring closure step in the synthesis of 1-benzoxepin (28) (68JOC2591). An internuclear cyclization reaction of an aromatic sulfonyl chloride (equation 49) occurred upon heating (250 °C) in the presence of a copper chloride catalyst to yield tribenz[6,d,/]oxepin (175). The analogous thiepin (see equation 71) may also be synthesized by this route (65T1299). 

All-Ethylene Route. In the early 1960 s an all-ethylene route (6, 10, 11, 12, 13, 14, 15, 16, 17, 18) to VCM, as shown in Figure 8, was made possible by development of the oxyhydrochlorination process. In this process, which replaced the acetylene-HCl part of the balanced route, the by-product HCI from EDC cracking reacts with ethylene and oxygen in the presence of a copper chloride catalyst to produce EDC. 

When either an alcohol or an amine function is present in the alkene, the possibility for lactone or lactam formation exists. Cobalt or rhodium catalysts convert 2,2-dimethyl-3-buten-l-ol to 2,3,3-trimethyl- y-butyrolactone, with minor amounts of the 8-lactone being formed (equation 51).2 In this case, isomerization of the double bond is not possible. The reaction of allyl alcohols catalyzed by cobalt or rhodium is carried out under reaction conditions that are severe, so isomerization to propanal occurs rapidly. Running the reaction in acetonitrile provides a 60% yield of lactone, while a rhodium carbonyl catalyst in the presence of an amine gives butane-1,4-diol in 60-70% (equation 52).8 A mild method of converting allyl and homoallyl alcohols to lactones utilizes the palladium chloride/copper chloride catalyst system (Table 6).79,82 83... 

Description The exothermic reaction is catalyzed by a copper chloride catalyst in a single-step, fluidized-bed reactor at temperatures of 220°C. Heat of reaction is recovered by producing 10 bar g steam or heating other heat-transfer fluids. 

Two oxidative carbonylation processes to DMC have been commercialized, one by EniChem uses a copper chloride catalyst the other, developed by Ube and Bayer uses methyl nitrite (from methanol, NO and oxygen). 

Chlorobenzene is an important commercial solvent, although it is less used nowadays because of environmental concerns. It is produced commercially by the Raschig process, in which a mixture of benzene vapour, air and hydrogen chloride is passed over a copper chloride catalyst. 

In combination with the incremental advances concerning reaction conditions in recent years, especially for low-pressure carbonylations, there is a trend toward increasing use of this chemistry to synthesize advanced building blocks. In this respect carboxylation of alkenes with an appropriate alcohol or amine function leads to the formation of lactones or lactams. Thus, cobalt, rhodium, or palladium chloride/copper chloride catalysts convert allyl and homoallyl alcohols or amines to the corresponding butyrolactones or butyrolactams, respectively [15]. 

Oxychlorination of hydrocarbons refers to a chemical reaction in which oxygen and hydrogen chloride react with a hydrocarbon in the vapor phase over a supported copper chloride catalyst to produce a chlorinated hydrocarbon and water. The oxychlorination of ethylene to produce 1, 2-dichloroethane (commonly, ethylene dichloride (EDC)) is of the greatest commercial importance. EDC is the precurser for vinyl chloride monomer, which when polymerized to polyvinyl chloride (PVC), becomes one of the most conunonly used commercial plastics. The overall oxychlorination reaction of ethane is given by... 

Modification of the copper chloride catalyst has been sought by different research groups in the effort to improve the catalyst performance examples are ... 

Because of its relatively poor selectivity to individual components, methane is not the preferred feedstock for the production of chloromethanes. " Methyl chloride, for example, is best obtained by the reaction of methanol with hydrogen chloride, and methylene dichloride can be obtained by the chlorination of methyl chloride. Methane is difficult to chlorinate. Because methyl chloride is easier to chlorinate than methane, a large excess of methane is required if a reasonable yield of methyl chloride is desired. For example, a mol ratio of 0.1/1 for chlorine to methane at about 450°C over a copper chloride catalyst will yield mostly methyl chloride ... 

Copper chloride catalysts are used to operate at lower temperature, and to improve selectivity. Their action mechanism can be explained by the formation of a complex with ethylene, which is then capable of being converted to ethylene dichloride. In these conditions, the usual reaction scheme is as follows ... 

Ethyl chloride will be produced by the gas-phase reaction of HCl with ethylene over a copper chloride catalyst supported on silica as... 

Deacon process A former process for making chlorine by oxidizing hydrogen chloride in air at 450°C using a copper chloride catalyst. It was patented in 1870 by Henry Deacon (1822-76). 

Bromo and 3-chloroquinolines were prepared unexpectedly when the synthesis of quinolines via the addition of an alkyl Grignard to an o-trifluoroacetylaniline was quenched with hydrohalic acid (Scheme 53). The reaction requires a copper chloride catalyst. Interestingly, both cuprous and cupric chloride worked to form the 3-chloroquinolines when mixed with 1.5 equivalents of hydrochloric acid. Anilines with different groups were tolerated well under these reaction conditions. The electronic nature... 

The most recent development in this story brings us to the currently used route, the oxychlorination route. The start of this part of the story provides a valuable lesson for all chemists and particularly research chemists. This is the importance of searching that immense treasure house, the chemical literature. As a result it was discovered that disposal of by-product HCl (from substitutive chlorination reactions) was nothing new, since Deacons in 1868 had overcome this by patenting a process for converting it into the much more valuable chlorine by oxidation with air over a copper chloride catalyst at 450°C. However, just adding this on to an existing VCM process... 

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