物理化学学报 >> 2014, Vol. 30 >> Issue (6): 1148-1154.doi: 10.3866/PKU.WHXB201404181

催化和表面科学 上一篇    下一篇

过渡金属改性的ZSM-5催化剂应用于甲硫醚转化制甲硫醇

陈世萍1, 王伟明1, 刘迎伟2, 魏育才2, 袁成龙1, 方维平1, 杨意泉2   

  1. 1 厦门大学化学化工学院化学工程与生物工程系, 福建厦门361005;
    2 厦门大学化学化工学院化学系, 福建厦门361005
  • 收稿日期:2014-02-26 修回日期:2014-04-17 发布日期:2014-05-26
  • 通讯作者: 杨意泉 E-mail:yyiquan@xmu.edu.cn

Transition Metal Promoted ZSM-5 Catalysts for the Conversion of Dimethyl Sulfide into Methanethiol

CHEN Shi-Ping1, WANG Wei-Ming1, LIU Ying-Wei2, WEI Yu-Cai2, YUAN Cheng-Long1, FANG Wei-Ping1, YANG Yi-Quan2   

  1. 1 Department of Chemical and Biochemical Engineering, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, Fujian Province, P. R. China;
    2 Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, Fujian Province, P. R. China
  • Received:2014-02-26 Revised:2014-04-17 Published:2014-05-26
  • Contact: YANG Yi-Quan E-mail:yyiquan@xmu.edu.cn

摘要:

负载过渡金属的ZSM-5 催化剂用于催化甲硫醚(DMS)转化成甲硫醇(MT)的反应. 实验结果表明,催化剂的甲硫醚转化率提高和甲硫醇选择性降低的趋势一样,都是以下顺序:Co/ZSM-5>Mo/ZSM-5>Ni/ZSM-5>W/ZSM-5. 表征结果表明,由于过渡金属阳离子(W6+、Ni2+、Co3+、Mo6+)比Al3+活泼,而改性过程中W6+、Ni2+、Co3+、Mo6+分别代替了部分Al3+,使得改性催化剂对DMS和MT的化学吸附作用更强. 过渡金属的引入使得ZSM-5总酸度增强,提高了C―S键的裂解能力,从而改进了催化转化DMS的能力. 研究结果发现,在转化DMS的过程中,金属活性位和酸性位之间通过强的协同效应起作用.

关键词: ZSM-5, 过渡金属, 甲硫醚, 甲硫醇

Abstract:

ZSM-5-supported transition metal catalysts were prepared and used to catalyze the conversion of dimethyl sulfide (DMS) into methanethiol (MT). Test results indicated that the activities of the catalysts for the conversion of DMS increased as follows: Co/ZSM-5>Mo/ZSM-5>Ni/ZSM-5>W/ZSM-5. The decrease in MT selectivity followed the same trend. The characterization results showed that transition metal cations (W6+, Ni2+, Co3+, Mo6+) replaced some Al3+ sites leading to more active in chemiadsorption of DMS and MT since transition metal cations are more active than Al3+. The incorporation of transition metals into ZSM-5 enhances the total acidity of ZSM-5 and increases its capacity to rupture C―S bonds. This subsequently improves its catalytic behavior in the conversion of DMS. We found that the metal active sites and closely situated acidic sites have a strong synergistic effect when converting DMS.

Key words: ZSM-5, Transition metal, Dimethyl sulfide, Methanethiol

MSC2000: 

  • O643