Fe3O4负载催化剂上双环戊二烯氢甲酰化

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%。

Hydroformylation of dicyclopentadiene on Fe3O4 based catalysts

A series of the catalysts of magnetic iron oxide containing Co and Rh was prepared by co-precipitation method and was tested in the hydroformylation of dicyclopentadiene (DCPD).The as-prepared catalysts were characterized by XRD,TPR,and FTIR. The effects of catalysts/DCPD mass ratio,reaction pressure,reaction temperature and different solvents were investigated.The results showed that Co-Rh/Fe₃O₄ catalysts had the best catalytic activity for hydroformylation of DCPD to diformyltricyclodecanes (DFTD).Increasing the catalyst/DCPD mass ratio,reaction pressure and reaction temperature was beneficial to the enhancement of DCPD conversion and the selectivity to DFTD.The solvent with relatively smaller polarity favored the formation of DFTD.The conversion of DCPD and the selectivity to DFTD reached over 99% and 60%,respectively under the condition as follows:Rh loading 1∶100,catalyst/DCPD mass ratio 2∶15,reaction temperature 140 ℃,reaction pressure 7 MPa,and reaction time 5 h.When the reaction time was prolonged to 12 h,the selectivity to DFTD of over 90% was attained.A higher selectivity to DFTD was achieved with 1-hexane as the solvent,the possible reason was that 1-hexane has low polarity.The catalyst had a little loss of the activity when it was reused for 5 times.