Wu Yibo, Li Fuxiang, Xue Jianwei, Lv Zhiping
College of Chemistry and Chemical Engineering, Taiyuan University of Technology, Taiyuan China.
Turk J Chem. 2020 Apr 1;44(2):393-408. doi: 10.3906/kim-1909-64. eCollection 2020.
A series of alkylorganotin-based catalysts (Sn-g-CN /AC) was prepared by wet impregnation in ethanol using different g-CN precursors and alkylorganotin compounds. The structure, texture, surface composition, and adsorption properties of the as-prepared catalysts were extensively characterized. Then, the obtained samples were evaluated for their catalytic performance in hydrochlorination of acetylene. The results provided by the X-ray photoelectron spectroscopy, acetylene temperature-programmed desorption, and HCl adsorption confirmed the nature of the active sites (i.e. Sn-N) involved in the reactant adsorption, and hence in the improved catalytic performance. These active sites were also related to the improved lifetime of alkylorganotin-based catalysts in the hydrochlorination of acetylene. At a constant reaction temperature of 200 °C with an acetylene gas hourly space velocity (CH -GHSV) of 30 h , Sn-g -CN /AC-550 exhibited the highest acetylene conversion (~98.0%) and selectivity toward the vinyl chloride monomer (>98.0%). From the catalytic test results, it was reasonably concluded that the hexamethylenetetramine is the most suitable N precursor, as compared to the dicyandiamide and urea, to prepare high-performance catalysts. From the BET specific surface area of fresh and used catalysts, it was suggested that, in contrast to dicyandiamide and urea, hexamethylenetetramine could delay the deposition of coke on alkylorganotin-based catalysts, which is reflected by the extended lifetime.
通过在乙醇中采用不同的g-CN前驱体和烷基有机锡化合物进行湿浸渍法制备了一系列烷基有机锡基催化剂(Sn-g-CN /AC)。对所制备催化剂的结构、织构、表面组成和吸附性能进行了广泛表征。然后,对所得样品在乙炔氢氯化反应中的催化性能进行了评估。X射线光电子能谱、乙炔程序升温脱附和HCl吸附提供的结果证实了参与反应物吸附的活性位点(即Sn-N)的性质,从而证实了催化性能的提高。这些活性位点还与烷基有机锡基催化剂在乙炔氢氯化反应中寿命的延长有关。在200℃的恒定反应温度和30 h的乙炔气体时空速(CH -GHSV)下,Sn-g -CN /AC-550表现出最高的乙炔转化率(~98.0%)和对氯乙烯单体的选择性(>98.0%)。从催化测试结果合理得出,与双氰胺和尿素相比,六亚甲基四胺是制备高性能催化剂最合适的N前驱体。从新鲜催化剂和使用后催化剂的BET比表面积来看,表明与双氰胺和尿素相比,六亚甲基四胺可以延迟焦炭在烷基有机锡基催化剂上的沉积,这通过延长的寿命得以体现。