ZSM-5催化高硫合成气制备甲硫醇的影响.pdf

石油化工
1014
PETROCHIEMCAL TECHNOLOGY
2014年第43卷
硅铝比对K2MoO4- NO//SV-5催化高硫
合成气制备甲硫醇的影响
王琪23,鲁骥,陈亚中,郭红彦,崔鹏
(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上后工作站,安徽铜陵244021)
[摘要]考察了不同硅铝比ZSM-5分子筛负载的K2MoO4- 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,H2-TPR,NH3-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MoS2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0.2MPa、气态空速30005时,CO转化率达34.51%;CHSH,CO2,COS的选择性分别为
49.17%,24.52%,23.21%;副产物甲烷的选择性为
关键词]ZSM-5分子筛;硅铝比;钼基催化剂:;高硫合成气;甲硫醇
L文章编号]1000-8144(2014)09-1014-06
L中图分类号]TQ426.82
文献标志码]A
Effect of Silica-alumina Ratio on the Performance of K Moo -Nio/ZSM-5 in
Synthesis of Methyl Mercaptan from High Hs-containing Syngas
Wang Qi", Lu i, Chen Yazhong, Guo Hongyan, Cui Peng
(1. Anhui Key Laboratory of Controllable Chemical Reaction and Material Chemical Engineering, School of Chemical Engineering
Hefei University of Technology, Hefei Anhui 230009, China; Ma erial Science and Engineering Post-doctoral Research Station
Hefei University of Technology, Hefei Anhui 230009, China; 3. Post-doctoral Work Station
Anhui Liuguo Chemical Company Limited, Tongling Anhui 244021, China
Abstract]K, Moo -Nio/ZSM-5 catalysts with different silica-alumina ratio were prepared and
characterized by means of XRD, H-TPR, NH -TPD and LRS. The performances of the catalysts in the
synthesis of methyl mercaptan from high H S-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 Mos, more
easily, which was beneficial to increasing the CO conversion. Furthermore, with increasing the acidity
of ZSM-5, the selectivity to by-product CH, increased rapidly. When the silica-alumina ratio was 25, the
catalyst exhibited the best performance. Under the conditions of360 C, 0.2 Mpa and GSHV of3000 h
the conversion of CO and the selectivities to CH SH, CO, COS and by-product CH reached 34.51%
49.179%,24.52%,23.219%and3.10%, respectively.
L Keywords ZSM-5 zeolite; silica-alumina ratio; molybdenum-based catalyst; high hydrogen sulfide-
containing syngas; methyl mercaptan
甲硫醇是合成蛋氨酸所需的重要化工中间硫醇催化效果较好的是钾钼系催化剂,载体一般选
体,目前工业上主要采用甲醇一-硫化氢法合成;但
甲醇是由合成气制得,因此由含硫化氢合成气一步
收稿日期]2014-03-26;[修改稿日期]2014-06-1
法制备甲硫醇可减少合成气制甲醇步骤,具有很好
[作者简介]王琪(1978-),男,安徽省蚌埠市人,博士,副研
究员,电话0551-62901458,电邮mangal(@hfut.edu.cn
的工业应用前景。对于含硫化氢合成气一步法制甲[基金项目1国家自然科学基金项目(21107)