MANUFACTURE OF VINYL CHLORIDE

Abstract: A process for the manufacture of vinyl chloride com­ prises reacting 1,1,2-trichloroethane with hydrogen in the vapour phase at elevated temperature in the presence of a supported catalyst comprising a chloride of a noble metal, a chloride of an alkali metal and a chloride of iron.

Description: MANUFACTURE OF VINYL CHLORIDE This invention relates to a process for the manufacture of vinyl chloride by the hydrodechlorination of 1,1,2-trichloroethane and to catalysts for use therein. In Japanese Patent Publication No 77/31005 there is described a process for the manufacture of vinyl chloride by reacting 1,1,2-trichloroethane with hydrogen in the presence of a supported catalyst consisting of palladium chloride, copper chloride and an alkali metal chloride; however in this process the conversion of 1,1,2trichloroethane to vinyl chloride (i.e. the number of moles of vinyl chloride produced per mole of 1,1,2-trichloroethane fed) is below 60%. We have now found that relatively high conversions to vinyl chloride may be obtained by use of a catalyst comprising a chloride of a noble metal and an alkali metal chloride together with a chloride of iron. The said catalysts also have a long active life. Thus according to the present invention there is provided a process for the manufacture of vinyl chloride by reacting 1,1,2-trichloroethane with hydrogen in the vapour phase at elevated temperature in the presence of a supported catalyst comprising a chloride of a noble metal and an alkali metal chloride, characterized in that the catalyst also contains a chloride of iron. The noble metal chloride is preferably a chloride of platinum, palladium or rhodium; the chlorides of'palladium and rhodium are especially preferred. Mixtures of the chlorides of two or more noble metals may be used if desired. The preferred alkali-metal chlorides are potassium chloride and cesium chloride; mixtures of two or more alkali-metal chlorides may be used if desired. Other components which may optionally be included in the catalyst are chlorides of copper and/or chlorides of rare-earth metals (for example cerium chloride). The defined chlorides may be introduced as such during the preparation of the catalyst; alternatively, the metals may be introduced in the form of salts which are at least partially converted into the corresponding chlorides under the conditions of preparation or use of the catalyst. The proportion of iron in the catalyst is preferably from 0.5 to 20 gram atoms per gram atom of noble metal, for example from 1 to 10 gram atoms of iron per gram atom of noble metal. When the catalyst also contains copper chloride, the preferred proportion of iron is towards the lower end of the said range; thus, for example, the catalyst may contain from 2 to 10 gram atoms of copper and from 0.5 to 5 gram atoms of iron per gram atom of noble metal. The proportion of alkali metal is preferably from 1 to 25 gram atoms per gram atom of noble metal, for example from 2 to 12 gram atoms of alkali metal per gram atom of noble metal. When the catalyst also contains a rare-earth metal chloride, the preferred proportion of alkali metal is towards the lower end of the said range; thus, for example, the catalyst may contain from 2 to 10 gram atoms of rare-earth (for example cerium) and from 2 to 10 gram atoms of alkali metal per gram atom of noble metal. The total proportion of metal chlorides is preferably at least 2% by weight (for example from 2% to 15%, especially from 5% to 10%) of the total weight of metal chlorides and support. The metal chlorides may be supported upon conventional carrier materials, for example silica or alumina. Suitable carriers include aluminas having surface areas in the range from 10 m2/g to 150 m2/g. The catalyst may be employed in fixed, moving or fluidised beds. The reaction temperature is preferably in the range from 2000C to 3500C. The preferred reaction temperature is dependent to some extent upon the composition of the catalyst. With a catalyst composition containing iron but containing no copper (or containing less than 2 gram atoms of copper per gram atom of noble metal) the preferred temperatures are in the range from 3000C to 3500C. With a catalyst containing 2 or more gram atoms of copper per gram atom of noble metal the reaction temperatures are somewhat lower, preferably in the range from 2500C to 3000C. Preferably there is employed at least the stoichiometric amount of hydrogen, that is, at least one mole of hydrogen per mole of 1,1,2-trichloroethane. Excess hydrogen, for example, up to two moles of hydrogen per mole of 1,1,2-trichloroethane may be employed but higher proportions of hydrogen are undesirable since there is increasing formation of ethylene as the proportion of hydrogen is increased. Atmospheric, subatmospheric or superatmospheric pressures may be employed. Contact times are conveniently in the range from 2 to 30 seconds. The 1,1,2-trichloroethane may be introduced into the reaction system, for example, by passing it into a flash vaporiser together with a diluent gas such as nitrogen which acts as a carrier gas. Alternatively hydrogen may be used both as reactant and carrier gas. Vinyl chloride and hydrogen chloride formed in the process may be recovered by conventional means. For example the reaction product may be cooled to condense the organic product while hydrogen chloride passes through the condensing system. The organic product can be fractionally distilled to give pure vinyl chloride. The following Examples illustrate the invention: EXAMPLE 1 Catalyst (A) was made as follows: The support for the catalyst was a gamma 2 alumina of approximate surface area 60 m /g and was in the form of cylindrical pellets of length 0.32 cm. To a weak solution of hydrochloric acid were added: (i) 0.5 g palladous chloride (ii) 1.9 g cupric chloride dihydrate (iii) 0.45 g ferric chloride and (iv) 4.7 g cesium chloride 100 g of the support were added to the solution containing the metal chlorides. The mixture was stirred continuously at 800C to 1200C for a period of approximately 4 hours by which time the catalyst (A) was dry. This catalyst was for use in a fixed bed process. Other supported catalysts (B) and (C) were prepared from metal chlorides as shown in Table 1 by a similar procedure except that the gamma alumina was replaced by alpha alumina of surface area of approximately 35 m2/g and of particle size 150 to 250 microns. These two catalysts were for use in a fluid bed process. In Table 1 11% total chlorides11 is the proportion of total metal chloride impregnants expressed as a percentage by weight of total metal chloride plus carrier. TABLE 1 EMI5.1 <tb> Catalystl <SEP> Atomic <SEP> Ratios <SEP> of <SEP> Metals <SEP> | <SEP> % <SEP> total <tb> <SEP> Pd <SEP> Rh <SEP> Fe <SEP> Cu <SEP> K <SEP> Cs <SEP> Ce <SEP> chlorides <tb> (A) <SEP> 1 <SEP> nil <SEP> 1 <SEP> 4 <SEP> nil <SEP> 10 <SEP> nil <SEP> 6.7 <tb> (B) <SEP> nil <SEP> 1 <SEP> 4 <SEP> nil <SEP> nil <SEP> 5 <SEP> 5 <SEP> 7.8 <tb> (C) <SEP> , <SEP> 1 <SEP> nil <SEP> 4 <SEP> nil <SEP> 5 <SEP> nil <SEP> nil <SEP> 3.2 <tb> EXAMPLE 2 The apparatus comprised a vertical heat resistant glass tube 30 cms long and 2.5 cms internal diameter surrounded by an electric furnace. The tube contained 90 g of the supported catalyst occupying 18 cm of the height of the tube. 1,1,2-trichloroethane was vaporised by passing it to a heated glass vessel containing porcelain particles held at a temperature of approximately 1800 C. Nitrogen was passed through the vessel in such proportion that the volume of nitrogen was twice the volume of the vaporised 1,1,2-trichloroethane. Hydrogen was also mixed with the 1,1,2trichloroethane and the resulting gaseous mixture was passed over the fixed bed catalyst (A) and through catalysts (B) and (C) maintaining the latter two catalysts in the fluidised state. The molar ratio of hydrogen to 1,1,2-trichloroethane was 1:1 in all runs. The contact time in all runs was approximately 4 seconds. The reaction temperatures and results obtained were as shown in Table 2. The product was recovered and analysed by conventional means. TABLE 2 EMI6.1 <tb> <SEP> Catalyst <SEP> Temp <SEP> $ <SEP> Conversion <SEP> to <tb> <SEP> OC <SEP> specific <SEP> products <tb> <SEP> chloroethane <tb> <SEP> reacted <tb> <SEP> VC <SEP> Ethylene <SEP> -DCE <tb> <SEP> (A) <SEP> ¯ <SEP> <SEP> 265 <SEP> <SEP> 88 <SEP> 80 <SEP> 1 <SEP> 4.5 <SEP> 4.5 <tb> <SEP> (B) <SEP> 290 <SEP> 90 <SEP> 82 <SEP> Nil <SEP> 6 <tb> - <SEP> (B) <SEP> 290 <SEP> 90 <SEP> 82 <SEP> 0.5 <SEP> 3 <tb> <SEP> (C) <SEP> L <SEP> 320 <SEP> 93 <SEP> 86 <SEP> 0.5 <SEP> 3 <tb> VC denotes vinyl chloride DCE denotes dichloroethylenes "Conversion" denotes moles of specific product per 100 moles of 1,1,2-trichloroethane fed.

Claims: CLAIMS 1. A process for the manufacture of vinyl chloride by reacting l,1,2-trichloroethane with hydrogen in the vapour phase at elevated temperature in the presence of a supported catalyst comprising a chloride of a noble metal and a chloride of an alkali metal, characterized in that the catalyst also contains a chloride of iron. 2. A process according to Claim 1 character ized in that the proportion of iron in the catalyst is from 0.5 to 20 gram atoms of iron per gram atom of noble metal. 3. A process according to Claim 2 character ized in that the proportion of iron is from 1 to 10 gram atoms of iron per gram atom of noble metal. 4. A process according to any of the preceding claims characterized in that the proportion of alkali metal is from 1 to 25 gram atoms of alkali metal per gram atom of noble metal. 5. A process according to Claim 4 characterized in that the proportion of alkali metal is from 2 to 12 gram atoms of alkali metal per gram atom of noble metal. 6. A process according to any of the preceding claims characterized in that the catalyst also contains a chloride of copper. 7. A process according to Claim 6 character ized in that the catalyst contains from 2 to 10 gram atoms of copper and from 0.5 to 5 gram atoms of iron per gram atom of noble metal. 8. A process according to any of the preceding claims characterized in that the noble metal is palladium, rhodium or platinum. 9. A process according to any of the preceding claims characterized in that the alkali metal is potassium or cesium. 10. A process according to any of the preceding claims characterized that the support material is alumina having a surface area in the range from 10 m2/g to 150 m2/g. 11. A process according to any of the preceding claims characterized in that the total proportion of metal chlorides is from 2% to 15%, preferably from 5% to 10%, by weight based on the total weight of metal chlorides and support. 12. A process according to any of the preceding claims characterized in that the process is carried out at a temperature in the range from 2000C to 3500C.

Inventors: ALLEN, CHRISTOPHER STORM
Applicants: IMPERIAL CHEMICAL INDUSTRIES PLC
Application year: 1980
Main classification: C07C21
IPC codes: C07C67, C07C21, C07B61, C07C17, B01J27