| In the thesis, it was studied that the properties of three catalysts, Cu(L)Cl(L= n-butylamine) and RuCl2(PPh3)3, which were used in the coupling reactions of C1-C2 chlorinated hydrocarbons, and investigated the influence of different reaction conditions on the catalytic activities. Because of the dehydrochlorination activity of the FeCl3-AlCl3-TiCl4/AC catalyst, it could be tried to apply to acetylene hydrochlorination. The conversion rate of raw material and product selectivity evaluated the performance of the catalyst, and catalysts were characterized by XRD, BET and SEM methods.1. chlorinated hydrocarbon coupling reactionThe FeCl3-AlCl3-TiCl4/AC catalyst, selected from four kinds of catalysts by chloroform and trans-1,2-dichloroethylene coupling reaction as probe reaction, had a relatively highly activity. It was characterized by XRD, SEM, and BET methods. The XRD and SEM results showed that the metal chlorides were equably loaded to the surface of activated carbon, and the graphite structures of activated carbon were not damaged. The BET results showed that the specific surface area was 1081.4 m2/g, pore volume was 0.23 cm3/g, and there existed mesopores and the major part of micropores.The FeCl3-AlCl3-TiCl4/AC catalyst was further probed by coupling reaction of carbon tetrachloride and trans-1,2-dichloroethylene, carbon tetrachloride and 1,2-dichloroethane, chloroform and tetrachloroethane. The results showed that the catalyst had good activity in the three kinds of reactions, especially in chloroform and tetrachloroethane coupling reaction. The conversion of chloroform and tetrachloroethane respectively reached 95% and 100%, the total selectivity of trichloroethylene and tetrachloroethylene was more than 95%. And it was found that the catalyst had good activity in the dehydrochlorination and the hydrochlorination. But only the C2 compounds, no C3 compounds, were produced in the reactions, which is only a single coupling reaction between C1 and C1 chlorohydrocarbons.In order to get C3 compounds or higher carbon number of chlorinated hydrocarbons, the activities of Cu(L)Cl(L=n-butylamine) and RuCl2(PPh.3)3 catalysts were investigated. The study found that two kinds of catalysts for the generation of C3 compounds had certain activity. Cu(n-butylamine)Cl had good catalytic activity in the coupling reaction between carbon tetrachloride and trans-1,2-dichloroethylene. The trans-1,2-dichloroethylene conversion rate reached 36% and the C3 product selectivity reached 51%, at 120℃. However the activities of two kinds of catalysts were lower in chloroform and trans-1,2-dichloroethylene coupling reaction.In the coupling reaction, FeCl3-AlCl3-TiCl4/AC catalyst had high catalytic activity in mild reaction conditions, so it had the high application value. Its application was further investigated in the acetylene hydrochlorination.2. The acetylene hydrochlorinationThe FeCl3-AlCl3-TiCl4/AC catalyst was investigated by acetylene hydrochlorination in fixed bed reaction device, where chloroform or tetrachloroethane was the chlorine source and acetylene was the carbon source. And the influence of reaction temperature, mole ratio and reaction run time on the catalyst activity were studied. Results showed that when the reaction conditions were 0.69h-1 as quality airspeed of Chloroform, CHCl3/C2H2=2:1 as feed mole ratio, 290℃ as reaction temperature, acetylene conversion rate reached 92%, the selectivity of vinyl chloride reached 90%. With the increasing of temperature, acetylene conversion rate remained stable, and selectivity of vinyl chloride began to drop. When the feed molar ratio of chloroform and acetylene was 3:1, the selectivity of vinyl chloride was best, which is 94%, and acetylene conversion rate was 76%. When tetrachloroethane was chlorine source, the tetrachloroethane conversion rate was always close to 100% in different temperatures, and the trichloroethylene selectivity remained at around 95%. The above datas further illustrated that the catalyst had good activity in the dehydrochlorination. Acetylene conversion rate reached 55% at 270℃, which was higher than other reaction temperature. The selectivity of vinyl chloride increased slowly with temperature rise, the highest to 90% at 300℃. This feed molar ratio had a small effect on the activity of catalyst in C2H2Cl4:C2H2=(1-3):1. |
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