固体酸和固体超强酸负载Cu~Ⅰ的催化剂制备与催化合成碳酸二甲酯  

Preparation and Catalytic Synthesis Dimethyl Carbonate of Cu~Ⅰ-based Catalysts Carried by SO_4^(2-)/M_xO_y and S_2O_8^(2-)/M_xO_y

作　　者：黄海彬[1] 孟凡会[1] 李威渊[1] 阴丽华[1] 李忠[1] 

机构地区：[1]太原理工大学煤科学与技术教育部和山西省重点实验室,山西太原030024

出　　处：《太原理工大学学报》2008年第4期343-346,共4页Journal of Taiyuan University of Technology

基　　金：国家自然科学基金资助项目(20576085);国家重点基础研究发展计划项目(2005CB221204)

摘　　要：用含SO42-和S2O82-离子溶液对未定型MxOy(M=Al,Zn,Fe)金属氧化物和γ-Al2O3浸渍法处理后经过热处理制备了多种SO42-/MxOy,S2O82-/MxOy固体酸,并以其为载体采用固体离子交换法制备了CuⅠ/SO42-/MxOy和CuⅠ/S2O82-/MxOy催化剂。该系列催化剂在CH3OH液相氧化羰基化合成碳酸二甲酯(DMC)反应中表现出良好的催化活性。其中,CuI/S2O82-/γ-Al2O3催化剂的甲醇转化率高达17.46%,DMC选择性和时空产率也分别达到98.65%和3.02 g.g-1.h-1,明显高于传统的CuCl催化剂。py-FTIR和XRD表征分析证明,SO42-/γ-Al2O3和S2O82-/γ-Al2O3固体酸上具有Bronsted酸位,通过固体离子交换实现了载体对活性金属组分的负载和锚定,同时保持了载体原有的结构。XPS表征表明,催化剂内的Cu主要以CuⅠ形式存在,为催化剂的活性中心。More than one kind of SO4^2-/MxOy and S2O8^2-/MxOy solid acids were prepared by heat treating the unshaped metal oxide MxOy（M=Al,Zn,Fe） and 7-Al2O3, which had been impregnated by SO4^2- and S2O8^2- ion solution respectively. Then Cu^Ⅰ/SO4^2-/MxOy and Cu^Ⅰ / S2O8^2-/MxOy catalysts were obtained using copper chlorid and the carriers of SO4^2-/MxOy and S2O8^2-/MxOy through solid-state ion-exchange. The evaluation result of all the prepared catalysts in slurry reactor showed excellent activity in the oxidative carbonylation of methanol to dimethyl carbonate （DMC）, the best activity was gotted from the catalyst Cu^Ⅰ/S2O8^2-/γAl2O3 ： the molar conversion and selectivity which were based on methanol to DMC can reach to 17.46% and 98.65% respectively, as well as space-time yields of DMC reaches to 3.02 g · g^-1 · h^-1 , it is higher obviously than the traditional catalyst CuCl on conversion, selectivity and space-time yields in the same reaction condition. The combined characterization of py-FTIR, XRD and XPS show that the Bronsted acid sites are formed on the surface of SO4^2-/γ-Al2O3 and S2O8^2-/γ Al2O3 solid acids, and the active metal ingredient can be fixed on the solid acids from metal chloride and the Bronsted acid sites by solid-state ion-exchange method as well as the intact structure of carrier is maintained in catalyst. Furthermore, the active component of copper in catalyst lies in the type of Cu^Ⅰ.

关 键 词：固体酸 多相催化 铜催化剂 固体离子交换 

分 类 号：TQ225.52[化学工程—有机化工]