非均相催化一步合成碳酸二苯酯的研究Ⅰ.载体制备方法对催化剂性能的影响  

Study on Direct Synthesis of Diphenyl Carbonate through Heterogeneous CatalysisⅠ. Effect of Preparation Method of Supports on Catalyst Activity

作　　者：张光旭[1] 吴元欣[2] 马沛生[1] 吴广文[2] 李定或[2] 

机构地区：[1]天津大学化工学院一碳化学与化工国家重点实验室,天津300072 [2]武汉化工学院化工系,湖北武汉430074

出　　处：《催化学报》2002年第2期130-132,共3页

基　　金：国家自然科学基金资助项目 (2 0 0 760 3 6)

摘　　要：采用溶胶 凝胶法、共沉淀法和冷冻干燥法 ,制备了LaxMnyPbzO复合型金属氧化物载体 ,并以PdCl2 或Na2 PdCl4的水溶液为浸渍液 ,通过浸渍方法制得固相催化剂 ,用于一步合成碳酸二苯酯 .用XRD ,TEM及SEM对载体及催化剂进行了表征 .结果表明 ,三种载体的主要物相皆为La0 .3 Mn0 .5PbO ,溶胶 凝胶法制得的载体及催化剂的粒径分布较好 ,空隙率较大 ,活性组分分散度较高 ;溶胶 凝胶法制得的催化剂的催化性能较好 ,碳酸二苯酯选择性可高于 99 5 %The compound metal oxides La x Mn y Pb z O used as Pd catalyst supports for direct synthesis of diphenyl carbonate (DPC) through heterogeneous catalytic reaction were prepared by sol gel, co precipitation and freeze drying methods and calcined at 700～800 ℃. The catalyst samples were prepared by impregnation of the supports with PdCl 2 or Na 2PdCl 4 solution. The supports and the catalyst samples were characterized by XRD, TEM and SEM techniques. The results showed that the main crystal phase in the supports is La 0.3 Mn 0.5 PbO, and that the particle and pore size distribution of the support prepared by sol gel method is better than by the others. The synthesis of DPC was carried out in a high pressure reactor under the conditions of m (cat)=2 g, m (PhOH)=50 g, m (C 16 H 36 BrN)=0 986 g, p =8 MPa, p (CO)/ p (O 2)=100, θ =80 ℃ and t =5 h. It was found that the performance of the catalyst with the support prepared by sol gel method is better than by the others, and the selectivity for DPC can be greater than 99 5%.

关 键 词：溶胶-凝胶法 共沉淀法 冷冻干燥法 金属复合氧化物 碳酸二苯酯 载体 催化剂 氧化羰基化法 非均相催化 一步法合成 

分 类 号：O643.3[理学—物理化学] O623.624[理学—化学]