硅铝比对K_2MoO_4-NiO/ZSM-5催化高硫合成气制备甲硫醇的影响  

Effect of Silica-Alumina Ratio on the Performance of K_2MoO_4-NiO/ZSM-5 in Synthesis of Methyl Mercaptan from High H_2S-Containing Syngas

作　　者：王琪[1,2,3] 鲁骥[1] 陈亚中[1] 郭红彦[1] 崔鹏[1] 

机构地区：[1]合肥工业大学化工学院可控化学与材料化工安徽省重点实验室,安徽合肥230009 [2]合肥工业大学材料科学与工程博士后流动站,安徽合肥230009 [3]安徽六国化工股份有限公司博士后工作站,安徽铜陵244021

出　　处：《石油化工》2014年第9期1014-1019,共6页Petrochemical Technology

基　　金：国家自然科学基金项目(21106027)

摘　　要：考察了不同硅铝比ZSM-5分子筛负载的K_2MoO_4-NiO/ZSM-5催化剂对高硫合成气制备甲硫醇性能的影响;并采用XRD,H_2-TPR,NH_2-TPD,LRS等手段对催化剂的物化性能进行了表征。实验结果表明,随ZSM-5分子筛硅铝比的减小,载体的酸性增强,促进了Mo物种在载体上的分散,使其更易被还原硫化成MoS_2物种,而此物种对提高CO转化率有促进作用。但随ZSM-5分子筛酸性的增强,副产物甲烷的选择性迅速增大。当ZSM-5分子筛的硅铝比为25时,催化剂的活性最高,在反应温度360℃、反应压力0.2 MPa、气态空速3 000 h^(-1)时,CO转化率达34.51%;CH_3SH,CO_2,COS的选择性分别为49.17%,24.52%,23.21%;副产物甲烷的选择性为3.10%。K2MoO4-NiO/ZSM-5 catalysts with different silica-alumina ratio were prepared and characterized by means of XRD,H2-TPR,NH3-TPD and LRS.The performances of the catalysts in the synthesis of methyl mercaptan from high H2S-containing syngas were investigated.The results showed that with the decrease of the silica-alumina ratio,the acidity of ZSM-5 increased,which could promote the dispersion of Mo species on the zeolite support,so the Mo species could be sulfurized into MoS2 more easily,which was beneficial to increasing the CO conversion.Furthermore,with increasing the acidity of ZSM-5,the selectivity to by-product CH4 increased rapidly.When the silica-alumina ratio was 25,the catalyst exhibited the best performance.Under the conditions of 360 ℃,0.2 MPa and GSHV of 3 000 h-1,the conversion of CO and the selectivities to CH3SH,CO2,COS and by-product CH4 reached 34.51％,49.17％,24.52％,23.21％and3.10％,respectively.

关 键 词：ZSM-5分子筛 硅铝比 钼基催化剂 高硫合成气 甲硫醇 

分 类 号：TQ426.82[化学工程]