负载液膜催化剂催化甲醇气相氧化羰基化合成碳酸二甲酯反应的性能  

Catalytic Performance of Supported Liquid Phase Catalyst in Oxidative Gas Phase Carbonylation of Methanol to Dimethyl Carbonate

作　　者：丁晓墅[1] 岳川[1] 王淑芳[1] 赵新强[1] 王延吉[1] 

机构地区：[1]河北工业大学化工学院河北省绿色化工与高效节能重点实验室,天津300130

出　　处：《石油学报（石油加工）》2014年第6期1010-1015,共6页Acta Petrolei Sinica(Petroleum Processing Section)

基　　金：国家自然科学基金项目(21236001);高等学校博士学科点专项科研基金项目(20121317110009);河北省重大技术创新项目(12275603Z)资助

摘　　要：制备了新型负载液膜催化剂PdCl2-CuCl2-KOAc-EG/AC,并用于甲醇气相氧化羰基化直接合成碳酸二甲酯(DMC),考察了二甘醇、三甘醇和四甘醇及其混合物等不同液膜相,以及制备方法对所制备催化剂在合成DMC反应中催化性能的影响。结果表明,二甘醇作为液膜相,采用高温加压浸渍法制备的催化剂的DMC空时收率比固载型催化剂显著提高。在反应温度160℃、反应压力0.3 MPa、n(CH3OH)∶n(CO)∶n(O2)=3.6∶2.3∶1、原料气体积空速7100h-1条件下,DMC空时收率最高可达921g/(Lcat·h),并且催化剂稳定性也有较大提高。高温加压浸渍法有利于液膜相分散于活性炭孔道中,并保持相对稳定。液膜相的黏度和分子大小是影响负载液膜催化剂反应性能的主要因素。The supported liquid phase catalyst was prepared and used in catalytic synthesized dimethyl carbonate（DMC）from gas-phase oxidative carbonylation of methanol.Diethylene glycol,triethylene glycol and tetraethylene glycol were used as the liquid phases for the supported liquid phase catalyst PdCl2-CuCl2-KOAc-EG/AC,and the influences of the catalyst preparation conditions on its catalytic performance in synthesis of DMC were investigated.The results showed that PdCl2-CuCl2-KOAc-EG/AC catalyst had the higher yield of DMC than the supported catalyst when diethylene glycol was used as the liquid phase and prepared with high temperature and pressure impregnation.The yield of DMC was reached 921g/（Lcat·h）at a reaction temperature of 160℃,reaction pressure of 0.3 MPa,n（CH3OH）∶ n（CO）∶n（O2）=3.6∶2.3∶1and gas hourly space velocity of 7100h-1,simultaneously,the catalytic stability of the catalyst was enhanced.Because the viscosity of the liquid phase decreased and the pressure increased in high temperature and pressure impregnation,the liquid phase was dispersed evenly in the pore and channels of the active carbon and maintained firmly in the supported liquid phase catalyst.The main factors to affect the catalytic performance of the supported liquid phase catalyst were the viscosity and the molecular size of the liquid phase.

关 键 词：负载液膜催化剂 甲醇 碳酸二甲酯 气相合成 高温加压浸渍法 

分 类 号：TQ225.5[化学工程—有机化工] TQ032.4