助剂对球形Cu/SiO_(2)催化剂甲醇脱氢制甲酸甲酯反应性能的影响  

Influence of additives on catalytic performance of spherical Cu/SiO_(2) catalyst for dehydrogenation of methanol to methyl formate

作　　者：靳钰婷 郭宇伟 权燕红[1,2] 赵金仙 任军 JIN Yuting;GUO Yuwei;QUAN Yanhong;ZHAO Jinxian;REN Jun(State Key Laboratory of Clean and Efficient Coal Utilization,Taiyuan University of Technology,Taiyuan 030024,Shanxi,China;College of Chemical Engineering and Technology,Taiyuan University of Technology,Taiyuan 030024,Shanxi,China;Shanxi Lu’an Tanyi Chemical Co.,Ltd.,Changzhi 046100,Shanxi,China)

机构地区：[1]太原理工大学省部共建煤基能源清洁高效利用国家重点实验室,山西太原030024 [2]太原理工大学化学工程与技术学院,山西太原030024 [3]山西潞安碳一化工有限公司,山西长治046100

出　　处：《低碳化学与化工》2024年第2期17-25,共9页Low-Carbon Chemistry and Chemical Engineering

基　　金：国家自然科学基金(22108191,22179091);中国博士后科学基金(2022M712335)。

摘　　要：甲醇脱氢制甲酸甲酯是实现甲醇下游产品多元化利用的绿色高效途径,使用助剂对SiO_(2)催化剂进行改性已成为提高目标产物甲酸甲酯收率的有效策略。首先通过溶胶-凝胶法制备了球形SiO_(2)负载Cu催化剂(Cu/SiO_(2)),然后采用旋蒸法引入助剂制得CuM/SiO_(2)(M=Ce或Al)催化剂,借助N2吸/脱附、扫描电子显微镜(SEM)、H_(2)-N_(2)O滴定和X射线衍射(XRD)等手段对催化剂进行了表征,并将催化剂用于甲醇脱氢制甲酸甲酯反应评价了其催化性能。结果表明,助剂可改变催化剂中活性Cu^(0)物种的含量和表面酸碱性。与Cu/SiO_(2)催化剂相比,CuCe/SiO_(2)催化剂表面Cu颗粒的分散度提高,这促进了活性物种Cu^(0)的形成,同时表面碱性位点减少,抑制了副反应发生,因而CuCe/SiO_(2)催化剂表现出最高的活性。在300℃、0.2 MPa的反应条件下,CuCe/SiO_(2)催化剂的甲醇转化率、甲酸甲酯选择性分别为29.2%、86.3%,甲酸甲酯收率为25.2%,均明显优于文献报道的Cu基催化剂。Methanol dehydrogenation to methyl formate is a green and efficient way to diversify methanol downstream products.The modification of Cu/SiO_(2) catalyst with additive has become an effective strategy to increase the yield of the target product methyl formate.Firstly,spherical SiO_(2) supported Cu catalyst(Cu/SiO_(2))was prepared by the sol-gel method,and then a series of CuM/SiO_(2)(M=Ce or Al)catalysts were obtained through the introduction of additive to Cu/SiO_(2) via the rotary evaporation method.The catalysts were characterized by N2 absorption/desorption,scanning electron microscopy(SEM),H_(2)-N_(2)O titration,X-ray diffraction(XRD)and so on,and their catalytic performances were evaluated for the reaction of methanol dehydrogenation to methyl formate.The results show that the additive can change the content of active Cu^(0) species and the surface acidity of the catalysts.Compared with the Cu/SiO_(2) catalyst,the dispersion of Cu particles on the surface of CuCe/SiO_(2) catalyst is increased,which promotes the formation of the active species Cu^(0),while the surface alkaline site is reduced,which inhibits the occurrence of side reactions,and thus exhibits the highest activity.Under the reaction conditions of 300℃ and 0.2 MPa,the methanol conversion rate and the selectivity of methyl formate of CuCe/SiO_(2) catalyst are 29.2%and 86.3%,respectively,and the yield of methyl formate is 25.2%,which are obviously better than that of Cu-based catalysts reported in the literature.

关 键 词：甲醇脱氢 Cu基催化剂 球形SiO2 甲酸甲酯 助剂 

分 类 号：TQ426.98[化学工程]