Rh-TPPTS/CTAB-MMT催化剂的制备及其催化长链烯烃氢甲酰化反应性能研究

通过浸渍法将水溶性铑膦配合物(Rh-TPPTS)负载到由十六烷基三甲基溴化铵(CTAB)修饰的蒙脱土(MMT)上,制备出Rh-TPPTS/CTAB-MMT负载型催化剂.采用XRD,FTIR,TG,BET,31P CP-MAS NMR和分散性实验对催化剂进行了表征.结果表明:水溶性铑膦配合物成功地负载到有机MMT上,并且该催化剂在有机溶剂中具有很好的分散性.该催化剂对于1-癸烯的氢甲酰化反应具有好的催化活性.在100℃、4 MPa、甲苯为溶剂的条件下,催化1-癸烯氢甲酰化可获得93.0%的转化率,95.8%的醛的选择性,2.1的正异比,137 h-1的TOF值.并对不同链长烯烃底物进行了考察.随着烯烃碳链的增加,醛的选择性下降,但是正异比有所增加.

Preparation of Rh-TPPTS/CTAB-MMT catalysts and their catalytic performance of long chain olefin hydroformylation

A supported Rh-TPPTS/CTAB-MMT catalyst was prepared by impregnating water-soluble rhodium phosphine complex (Rh-TPPTS) with montmorillonite (MMT) modified with cetyltrimethylammonium bromide (CTAB). The as-prepared catalyst was characterized by XRD, FTIR, TG, BET, 31P CP-MAS NMR, and dispersibility measurement. The results show that the water-soluble rhodium phosphine complex has been supported on the organic MMT successfully and this catalyst can be well dispersed in organic solvents. Moreover, this catalyst exhibits high activity in the hydroformylation of 1-decene. In the optimal reaction conditions (100 oC, 4 MPa syngas and toluene as solvent), the conversion of 1-decene was 93.0%, the selectivity and TOF (turnover frequency defined as the moles of aldehyde per mole Rh per hour) was 137 h-1.