Cu基催化剂催化甘油氢解制备丙二醇  

Catalytic hydrogenolysis of glycerol to propanediol over Cu-based catalysts

作　　者：鲍涛[1] 王波[1] 江运良 蔡新兴[1] 计伟荣[1] 

机构地区：[1]浙江工业大学化学工程学院,浙江杭州310014

出　　处：《工业催化》2014年第9期688-693,共6页Industrial Catalysis

摘　　要：在间歇釜式反应器中考察Cu基催化剂在不同酸性条件下的甘油催化氢解反应性能,采用γ-Al2O3、SiO2和SiC酸碱性不同的载体研究催化剂催化活性和选择性的影响,结果表明,3种载体的Cu基催化剂均对1,2-丙二醇的生成有较高的催化活性和选择性,但只有弱酸性SiO2为载体时生成1,3-丙二醇。研究在底物中添加H2SO4(B酸)对甘油氢解反应性能的影响,发现质子酸的存在有利于1,3-丙二醇的生成,但易导致副反应发生,使1,2-丙二醇选择性大幅降低。研究用磷钨酸改性的Cu/SiO2催化剂对甘油氢解反应的催化活性的影响,发现磷钨酸的加入有利于甘油氢解为1,3-丙二醇,且酸性越强,越容易发生副反应。随着Cu/HWP/SiO2催化剂焙烧温度的升高,酸性减弱,丙二醇选择性提高,推测出质子酸作用下Cu基催化剂的甘油氢解反应机理。The performance of Cu-based catalysts for glycerol catalytic hydrogenolysis was studied under different acidic conditions in a batch autoclave reactor. The influence of the supports γ-Al2O3,SiO2 and SiC on the activity and the selectivity of Cu-based catalysts was investigated. The results showed that Cubased catalysts prepared with three supports possessed high catalytic activity and selectivity to 1,2-propanediol,and 1,3-propanediol was obtained by using weak protonic acid SiO2 as the support. By adding H2SO4（B acid） as a substrate solution additive,1,3-propanediol was promoted,but meanwhile some side reactions happened,which resulted in a substantial reduction of the selectivity to 1,2-propanediol. The properties of Cu /SiO2 catalyst modified by phosphate tungstic acid was investigated in glycerol hydrogenolysis. It was found that the addition of phosphate tungstic acid promoted the selectivity to 1,3-propanediol,and the stonger the acidity is,the more easily the side reaction happened. The acidity was weakened and the selectivity to glycerol was enhanced with the increase of Cu /HWP /SiO2 catalyst calcination temperature. The mechanism of glycerol hydrogenolysis reaction over Cu-based catalyst in the presence of proton acid was proposed.

关 键 词：催化化学 甘油 CU催化剂 催化氢解 质子酸 

分 类 号：O643.36[理学—物理化学] TQ426.94[理学—化学]