磷改性对K-Mo催化剂催化合成气制甲硫醇的影响  

Effect of Phosphorus Modification on Methanethiol Synthesis from H_2S-rich Syngas Catalyzed by K-Mo Catalysts

作　　者：郭红彦[1,2] 王琪[1] 王静 赵星[3] 柴翠元[2] GUO Hong-yan;WANG Qi;WANG Jing;ZHAO Xing;CHAI Cui-yuan(School of Chemical Engineering, Hefei University of Technology, Hefei Anhui 230009, China;Department of Chemical Engineering, Huainan Union University, Huainan Anhui 232038, China;School of Chemical and Material Engineering,Huainan Normal University, Huainan Anhui 232038, China)

机构地区：[1]合肥工业大学化学工程学院,安徽合肥230009 [2]淮南联合大学化学工程系,安徽淮南232038 [3]淮南师范学院化学材料学院,安徽淮南232038

出　　处：《安徽理工大学学报（自然科学版）》2018年第6期31-35,共5页Journal of Anhui University of Science and Technology:Natural Science

基　　金：国家自然科学基金资助项目(21106027);安徽省自然科学研究重点基金资助项目(KJ2015A356);安徽省高校优秀青年人才支持计划基金资助项目(gxyqZD2016553);淮南联合大学校级产学研基金资助项目(LCY1405)

摘　　要：甲硫醇作为一种重要化工原料和有机中间体,被广泛用于食品、饲料添加剂和农药等领域。采用等体积浸渍法分别制备了不同磷负载量的K-Mo-P/SiO_2催化剂,并在固定床反应装置上考察其对高硫合成气制备甲硫醇反应的催化性能。通过程序升温还原技术(H_2-TPR)、激光拉曼分析(LRS)以及电子顺磁(ESR)等表征手段对催化剂进行了表征。结果表明,磷与活性组分相互作用,增加了八面配位的钼物种"Mo^(6+)(Oh)"的含量,促进催化剂的低温还原性增强。磷的引入还提高了活性钼物种的分散度和硫化度,有利于催化剂活性Mo物种向MoS_2物种转化,增加了CO的吸附活性中心位,促进了催化剂的加氢性能,使得催化剂具有更高的催化活性和甲硫醇的选择性。Methanthiol is widely used in food, feed additive, pesticides as an important chemical raw material and organic intermediate. In this work, a series of K-Mo-P/SiO 2 catalysts were prepared through incipient wetness co-impregnation method, and characterized by H2 temperature-programmed reduction (H2-TPR), laser Raman spectroscopy (LRS), electron paramagnetic resonance (EPR) and catalytic performance for methanethiol synthesis from H 2S-rich syngas. The results indicated that addition of phosphate into the catalyst resulted in the increase of octahedral coordinated Mo species, and the decrease of tetrahedral coordination Mo species, as evidenced by the LRS and EPR characterizations. Simultaneously, the interaction between phosphorus and active components increases the content of octahedral molybdenum species “Mo 6+(oh)” and promotes the reduction of catalyst at low temperature. The introduction of phosphate also improved the dispersion and vulcanization of active molybdenum species. Conversion of active Mo species to MoS2 species, and the active sites of CO adsorption were increased,which was able to active hydrogen, thus improving selectivity to methanethiol.

关 键 词：磷改性 K-Mo催化剂 合成气 甲硫醇 

分 类 号：TQ032.41[化学工程]