Wise BoM te (eh cH HR 199s Vol. 16 No. 6 — Chinese Journal of Catalysis (CUIHUA XUEBAO) November 1995 VAPOR-PHASE ALKYLATION OF BENZENE WITH PROPYLENE OVER SiW,;/C CATALYST Chu, Wen-ling; Yang, Xiang-guang; Ye, Xing-kai and Wu, Yue* (Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022) Key words alkylation, benzene. propylene, supported heteropolyacid catalyst Alkylation of benzene with propylene to cumene has attracted much at- tention in recent years. Postwar production of phenol and acetone by oxida- tion of cumene initiated the large-scale production of cumene. Up to now, phosphoric acid!!, aluminium chloride? and zeolite"! have been used for alkylation of benzene with propylene. But it is unsatisfied that these cata- lysts gave a variety of undesired by-products. In this communication. the use of heteropolyacid (HPA) supported on activated carbon for the first time as catalyst in the vapor phase alkylation of benzene with propylene was test- ed and proved to be an excellent alkylation catalyst with very high catalytic activity under lower temperature. especially, the selectivity for cumene is up to 100%. The supported catalyst was prepared by adsorbing dodecatungstosilicic acid (SiW,,) with the commercial coal based active carbon in aq. solution. Catalytic tests were performed in a flow fixed-bed reactor operating at atmo- spheric pressure. 2 ml of catalyst was placed at the center of the reactor and covered with a preheating zone of quartz sand. The products were analyzed by GC. Table 1 showed that the conversion of starting material is dependent on reaction temperature. At the lower temperatures, 150 and 190C. the con- version of propylene was low. With the increase of reaction temperature, the conversion of C3H,g increases and the activity of SiW,./C catalyst reaches a maximum at 230 C. At higher temperature, 250 C. decrease in C3Hs conver- sion was observed, because the active sites of the catalyst would be occupied by the product of polymerization of propylene itself. It is important to notice Received 1995-07- + To whom correspondence should be addressed.432 to tk 16 & Table 1 The effect of reaction condition on the alkylation Temperature (C) LHSV (h-") Benzene/propylene Condition ae - ————— 150 170 190 205 230 250 46 8 2 4 6 86 230 230 230 230 230 230 230 Temperature CC) LHSV (ho) $4 4 4 4 4 144 4 Benzene/propylene «8.6 8.6 8.6 8&6 86 86 86 8.6 86 86 Conversion of CsHa(%) 49.8 53.5 62.0 70.1 97.6 90.2 98.9 97.6 86.1 51.6 7.4 33.6 73.0 97.6 Selectivity for cumene (%) 100 100 100 100 100 <100 100 100 100 100 100 100 100 100 that no by-products were detected even at higher temperatures for the SiW,2/C catalyst, which showed that it is superior to H;PO,, AICI; and zeo- lite. The high selectivity can be ascribed to the stronger acidity of the SiWi2. which is favorable to the production of cumene. In addition, this also sug- gests that the isopropyl cation, produced more easily by protonation of propylene in the presence of heteropolyanion which exhibits speciality to co- ordinate with propylene’, is the active alkylation species. The conversion of CH, increased with the increase of benzene/propy- lene wt ratio, and at a ratio of 8.6/1, all of the propylene was virtually con- verted to product at 230. and the selectivity for cumene was up to 100%. It of benzene/propylene are favorable to the production of cumene. For exam- ple, about 98.9% cumene was produced at a lower LHSV of 2 h7!. The lit- erature has reported" that the velocity of alkylation of benzene or isopropyl- found from LHSV tests that the decrease of LHSV and the increase benzene with propylene is faster than that of disproportionation reaction of diisopropylbenzene with benzene. and thus suggested that the decrease of LHSV would be favorable to the disproportionation reaction to improve the selectivity for cumene. In our study, this possibility is excluded because no by-product, diisopropylbenzene, was detected. From above, the results ob- tained present that SiW,./C catalyst has a potential use in practice. References 1 McAllister SH, Anderson J, Bullard EF. Chem Eng Prog, 1947, 43: 189 Canfield RD, Unruh TL. Chem Eng, 1983, 32: 21 Warren WK, Robert EH. «J Caral, 1988, 109: 212 Misono M. et al, Appl Catal, 1990, 64: 1