高硫合成气制甲硫醇钼基催化剂ESR和XPS表征  

The ESR and TPR characterization of the Mo-based catalysts for methanthiol synthesis from high H_2S-containing syngas

作　　者：杨意泉[1] 王琪[1] 杨华 袁友珠[1] 于腊佳 戴深峻[1] 

机构地区：[1]厦门大学化学系物理化学研究所,固体表面物理化学国家重点实验室,厦门361005

出　　处：《天然气化工—C1化学与化工》2001年第3期23-26,共4页Natural Gas Chemical Industry

基　　金：国家自然科学基金资助项目! (2 96 730 34 )

摘　　要：研究以 (NH4 ) 6Mo7O2 4 ·4H2 O为前驱物料所制得的MoO3 /K2 CO3 /SiO2 催化剂对高硫化氢合成气一步法合成甲硫醇的催化活性 ,考察K2 CO3 助剂对钼基催化剂催化行为的影响。ESR表征结果显示 ,工作态催化剂观测到氧包围的“oxo -Mo(V)”(g =1.93)、硫包围的“thio -Mo(V)”(g =1.98)和S(g =2 .0 1,g =2 .0 4)等信号 ,随着K2 CO3 添加量的增加 ,oxo -Mo(V)含量增加 ,thio -Mo(V)含量减少 ;XPS表征显示 ,钼包含了Mo4 + 、Mo5+ 和Mo6+ 的混合价态 ,硫包含了S2 -(16 1.5eV)、(S -S) 2 -(16 2 .5eV)和S6+ (16 8.5eV)等 3种物种 ,Mo5+ /Mo4 + 摩比为 0 .4和S2 -/ (S -S) 2 -比接近The catalytic activity of MoO 3/K 2CO 3/SiO 2 prepared with precursor (NH 4) 6Mo 7O 24 for the methantiol directly synthesis from syngas blending with high H 2S content and the effects of promoter K 2CO 3 on the catalytic behavior of molybdenum based catalyst were studied.The results of ESR characterization show that the signals of O surrounded “oxo Mo(V)”( g =1.93),S surrounded“thio Mo(V)”( g =1.98),and S( g = 2.01 and 2.04)in functioning catalyst can be detected.The content of oxo Mo(V) was found to increase with the added K 2CO 3 content increasing,while thio Mo(V) was found to decrease.The XPS characterization indicated that Mo 4+ ,Mo 5+ and Mo 6+ are main species included in the Mo content,and that S 2- (161.5eV),(S-S) 2- (162.5eV) and S 6+ (168.5eV) species are included in the S content.

关 键 词：甲硫醇 钼基催化剂 高硫合成气 催化活性 制备 碳酸钾 助剂 ESR XPS 

分 类 号：TQ223.2[化学工程—有机化工] TQ426.81