Chlorinations copper chloride

Another attractive commercial route to MEK is via direct oxidation of / -butenes (34—39) in a reaction analogous to the Wacker-Hoechst process for acetaldehyde production via ethylene oxidation. In the Wacker-Hoechst process the oxidation of olefins is conducted in an aqueous solution containing palladium and copper chlorides. However, unlike acetaldehyde production, / -butene oxidation has not proved commercially successflil because chlorinated butanones and butyraldehyde by-products form which both reduce yields and compHcate product purification, and also because titanium-lined equipment is required to withstand chloride corrosion. 

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)]. 

With the growing prominence of the petrochemicals industry this technology was, in turn, replaced by direct air oxidation of naphtha or butane. Both these processes have low selectivities but the naphtha route is still used since it is a valuable source of the co-products, formic and propanoic acid. The Wacker process, which uses ethylene as a feedstock for palladium/copper chloride catalysed synthesis of acetaldehyde, for which it is still widely used (Box 9.1), competed with the direct oxidation routes for a number of years. This process, however, produced undesirable amounts of chlorinated and oxychlorinated by-products, which required separation and disposal. 

Westvaco (2) A process proposed for making chlorine by electrolyzing aqueous copper chloride. Invented in 1928 by F. S. Low at Chlorine Products, New York. Piloted by Westvaco in the 1940s, but not commercialized. 

Only a minor amount of chlorinated copper phthalocyanine, for instance, especially in the 4-position of the copper phthalocyanine molecule, prevents a change of modification from a to (3. Approximately 3 to 4% chlorine is commonly used, which corresponds to the formula CuPc-Cl0.5, also referred to as semi-chloro-CuPc . The phthalic anhydride/urea synthesis, for instance, affords a partially chlorinated product if 4-chlorophthalic anhydride is added to the reaction mixture. Copper chlorides in the phthalonitrile process have the same effect. 

TAT, Nitric acid, Phosphorus pentoxide Resorcinol, Nitric acid, Sodium nitrite Resorcinol, Nitric acid, Sodium nitrite. Sulfuric acid Benzene, Sulfur chloride, Ammonia Toluene, Sulfur chloride, Ammonia Toluene, Sulfur, Ammonia, Chlorine Picryl chloride, Methanol, Potassium hydroxide Hydrogen cyanide, Sodium azide, Copper-II-sulfate pentahydrate, Hydrogen peroxide, Formic acid, Ammonium chloride... 

The reaction is exothermic (see Exercise 12.1), but, since it is very slow, a catalyst is necessary. Nitric oxide, once again, can serve as an oxygen carrier, as in the lead chamber process (Section 10.2) and in reaction 10.8, where (CH3)2S generated in the kraft process is converted to DMSO. Even so, at the elevated temperatures required, reaction 12.1 needs to be forced to completion by absorption of the steam in concentrated sulfuric acid or some other desiccant. In variants of the Deacon process, copper chloride acts as the catalyst or as an intermediate for chlorine regeneration. 

By passing chlorine through a suspension of basic copper carbonate in aqueous selenious acid, copper selenate and copper chloride pass into solution ... 

Chlorobiphenyts. These compounds can be synthesized by direct chlorination of biphenyl in [he presence of iron or other calalysts. Other means of preparation include reaction of diazotized aminobiphenyl with copper chloride. Treatment of chlorobiphenyls at elevated temperatures (300—400°C] with strong caustic yields hydroxybiphenyls. Various reactions, normal to aromatic systems, will occur—usually on the unsubstlluted ring. 

Electrolysis as decomposition, for example of copper chloride solution, zinc bromide solution, hydrochloric acid and acidified water. Include tests for chlorine, oxygen and hydrogen. R... 

Selenic Acid.—Selenic Acid, H2Se04, is also a il colourless syrupy liquid it can be produced by direct oxidation of selenium by chlorine water, but on concentra-I tion the resulting hydrochloric acid reduces the selenic acid I to selenious acid, as hydriodic acid reduces sulphuric acid. It is best prepared by addition of copper carbonate to the mixture of selenic and hydrochloric acids obtained in that way selenate and chloride of copper are formed the 1 mixture is evaporated to dryness, and the copper chloride is dissolved out with alcohol, leaving the insoluble selenate 1 behind. The selenate is dissolved in water, and on treatment with sulphuretted hydrogen, copper sulphide is precipitated, and removed by filtration the selenic acid is then concentrated if it contains a trace of water, it is a heavy liquid 5 but if quite anhydrous, it forms a solid, melting at 58°. 

The purpose of this article is to study the viability of the copper chloride thermochemical cycle by studying the hydrolysis reaction of CuCl2 which is not favoured thermodynamically. To better understand the occurrence of possible side reactions, together with a good control of the kinetics of the hydrolysis reaction, the use of optical absorption spectrometries, UV visible spectrometry to detect molecular chlorine which may be formed in side reactions, FTIR spectrometry to follow the concentrations of H20 and HCl is proposed. 

To assess the viability of the copper-chloride cycle, a dedicated experimental programme is proposed the study of the occurrence of possible side reactions. In order not to change the speciation of the vapour phase, the use of optical absorption spectrometry is proposed UV visible spectrometry to detect the possible presence of molecular chlorine, product of side reactions. 

Oxychlorination of ethylene. Knowledge of the role of copper chloride and the mechanism of oxychlorination has evolved. Current theory suggests that Cu(II) chloride chlorinates ethylene, which is chemisorbed on the catalyst. 

Cyclohexene is chlorinated to yield 1,2-mms-dichlorocyclohexane977. CuCl+ has been found to be the reactive species in the chlorination process. Copper chloride chlorinates malonate carbanions (equation 152)978. 

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