应用化学 ›› 2016, Vol. 33 ›› Issue (9): 1079-1084.DOI: 10.11944/j.issn.1000-0518.2016.09.160021

• 研究论文 • 上一篇    下一篇

钾对高硫合成气制甲硫醇磷钼基催化剂的影响

周布康a,王琪abc*(),陈亚中a,崔鹏a,沈泽斌d,张庆红d,王野d   

  1. a合肥工业大学 化学与化工学院,可控化学与材料化工安徽省重点实验室 合肥 230009
    b合肥工业大学 材料科学与工程博士后流动站 合肥 230009
    c安徽六国化工股份有限公司博士后工作站 安徽 铜陵 244021
    d厦门大学化学化工学院,固体表面物理化学国家重点实验室 福建 厦门 361005
  • 收稿日期:2016-01-13 接受日期:2016-05-04 出版日期:2016-08-23 发布日期:2016-08-23
  • 通讯作者: 王琪
  • 基金资助:
    国家自然科学基金(21106027)固体表面物理化学国家重点实验室开放基金(201412)资助项目

Effect of Potassium on the Performance of MoP-based Catalysts in Methyl Mercaptan Synthesis from High H2S-Containing Syngas

ZHOU Bukanga,WANG Qiabc*(),CHEN Yazhonga,CUI Penga,SHEN Zebind,ZHANG Qinghongd,WANG Yed   

  1. aAnhui Key Laboratory of Controllable Chemical Reaction and Material Chemical Engineering,School of Chemistry and Chemical Engineering,Hefei University of Technology,Hefei 230009,China
    bMaterial Science and Engineering Post-Doctoral Research Station,Hefei University of Technology,Hefei 230009,China
    cPost-Doctoral Work Station,Anhui Liuguo Chemical Company Limited,Tongling,Anhui 244021,China
    d State Key Laboratory of Solid Surface Physical Chemistry,College of Chemistry and Chemical Engineering,Xiamen University,Xiamen,Fujian 361005,China
  • Received:2016-01-13 Accepted:2016-05-04 Published:2016-08-23 Online:2016-08-23
  • Contact: WANG Qi
  • Supported by:
    Supported by the National Natural Science Fundation of China(No.21106027), State key Laboratory of Solid Surface Physical Chemistry(No.201412)

摘要:

采用等体积共浸渍法,制备了一批不同钾含量的KxMoP/Al2O3(x表示K与Mo摩尔比,0≤x≤3)催化剂,考察其对高硫合成气制甲硫醇性能的影响,并采用X射线衍射分析(XRD)、程序升温还原法(TPR)和激光拉曼光谱(LRS)等技术手段对催化剂进行了表征。 结果表明,氧化铝负载的磷钼氧化物前驱体在850 ℃经H2气还原制备出了MoP/Al2O3催化剂,少量添加钾催化剂有较高的甲烷选择性,大量添加钾助剂促进了催化剂表面活泼钼硫物种的生成,使得磷化钼基催化剂有较好的甲硫醇选择性,而过量添加钾又会阻碍了甲硫醇的生成。 当n(K)/n(Mo)比在2~2.5之间时,磷化钼基催化剂对该反应有较好的催化活性。

关键词: 钾助剂, 磷化钼, 高硫合成气, 甲硫醇

Abstract:

A series of KxMoP/Al2O3(x is K/Mo molar ratio, 0≤x≤3) catalysts with different K/Mo molar ratios was prepared through co-impregnation and characterized using X-ray diffraction(XRD), temperature-programmed reduction(TPR) and laser Raman spectroscopy(LRS). The effects of different potassium content of the catalysts for the synthesis of methyl mercaptan from high H2S-containing syngas were investigated. The results indicate that MoP/Al2O3 catalysts are formed by hydrogen reduction at 850 ℃ from phosphorus molybdenum oxide precursor. With a small amount of potassium, the catalysts show higher methane selectivity. Further increase of potassium content promotes the generation of activity molybdenum sulfur phase, showing good methyl mercaptan selectivity. Excessive potassium hinders the generation of methyl mercaptan. When K/Mo molar ratio is between 2 and 2.5, MoP-based catalysts shows good catalytic activity and selectivity.

Key words: potassium, molybdenum phosphide, high H2S-containing syngas, methyl mercaptan synthesis