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采用共沉淀法制备系列铁磁性氧化物负载的钴、铑及钴铑双金属催化剂。研究以三苯基膦改性的Co/Fe3O4、Rh/Fe3O4和Co-Rh/Fe3O4催化剂对双环戊二烯氢甲酰化合成三环癸烷二甲醛的催化性能,并对催化剂进行XRD、FT-IR和TPR等表征。结果表明,Co-Rh/Fe3O4催化剂对双环戊二烯氢甲酰化合成三环癸烷二甲醛具有最高的选择性。双环戊二烯氢甲酰化合成三环癸烷二甲醛的过程与反应压力、催化剂与双环戊二烯的质量比、反应温度和溶剂的种类有关。增加催化剂与双环戊二烯质量比和升高温度及压力有利于双环戊二烯的转化和三环癸烷二甲醛选择性,采用极性相对较小的溶剂有利于三环癸烷二甲醛的形成。催化剂重复使用5次,催化活性几乎不变。在催化剂与双环戊二烯质量比为2∶15、Rh的负载量为1∶100、反应温度140℃、反应压力7 MPa和反应时间5 h条件下,双环戊二烯转化率达99%以上,三环癸烷二甲醛选择性达60%以上,进一步延长反应时间至12 h,三环癸烷二甲醛选择性超过90%。
A series of ferromagnetic oxide supported cobalt, rhodium and cobalt rhodium bimetallic catalysts were prepared by coprecipitation method. The catalytic performance of tricyclodecane dicarboxaldehyde for hydroformylation of dicyclopentadiene with triphenylphosphine-modified Co / Fe3O4, Rh / Fe3O4 and Co-Rh / Fe3O4 catalysts was investigated. The catalysts were characterized by XRD, FT -IR and TPR characterization. The results show that the Co-Rh / Fe3O4 catalyst has the highest selectivity for the synthesis of tricyclodecane-2-carboxaldehyde by hydroformylation of dicyclopentadiene. Dicyclopentadiene hydroformylation of tricyclodecanedicarboxaldehyde process and reaction pressure, the mass ratio of catalyst and dicyclopentadiene, the reaction temperature and the type of solvent. Increasing the mass ratio of the catalyst to dicyclopentadiene and increasing the temperature and pressure favor the conversion of dicyclopentadiene and the selectivity of tricyclodecane dicarbaldehyde. The use of a less polar solvent favors tricyclodecane dicarboxaldehyde form. Reuse of catalyst 5 times, almost unchanged catalytic activity. The conversion of dicyclopentadiene was above 99% at a mass ratio of catalyst to dicyclopentadiene of 2:15, Rh loading of 1: 100, reaction temperature of 140 ℃, reaction pressure of 7 MPa and reaction time of 5 h , Tricyclodecane dicarbaldehyde selectivity of more than 60%, to further extend the reaction time to 12 h, tricyclodecane dicarbaldehyde selectivity of more than 90%.