制备参数对CaO-ZrO_2结构及CuO/CaO-ZrO_2催化剂合成甲酸甲酯性能的影响  

Influences of Preparation Conditions on Structure of CaO-ZrO_2 and Catalytic Performances of CuO/CaO-ZrO_2 for Synthesis of Methyl Formate

作　　者：赵海军[1,2] 林明桂[1] 房克功[1] 李文斌[1] 孙予罕[3] 

机构地区：[1]中国科学院山西煤炭化学研究所,山西太原030001 [2]中国科学院大学,北京100049 [3]中国科学院上海高等研究院,上海201203

出　　处：《石油化工》2015年第5期572-580,共9页Petrochemical Technology

基　　金：国家自然科学基金青年项目(21103217)

摘　　要：采用溶胶-凝胶法制备介孔Ca O-Zr O2固体碱,考察了制备参数对Ca O-Zr O2固体碱结构的影响,用TEM和CO2-TPD方法表征了固体碱的结构和碱性。采用浸渍法在Ca O-Zr O2固体碱上引入活性组分Cu O,制备Cu O/Ca O-Zr O2双功能催化剂。该催化剂用于合成气在浆态床反应器中合成甲酸甲酯(MF)的反应时,Ca O-Zr O2固体碱的制备参数对Cu O/Ca O-Zr O2催化剂合成MF的性能有重要影响。Ca O-Zr O2固体碱的最佳制备条件为:溶液p H=6.4,n(P123)∶n(Zr)=0.02,晶化温度60℃,晶化时间24 h,后处理介质为0.5 mol/L的Na OH溶液。以最佳条件下制备的Ca O-Zr O2固体碱为载体制备的Cu O/Ca O-Zr O2催化剂,在170℃、5.0 MPa、n(H2)∶n(CO)=2.0下进行合成MF的反应,MF的时空产率和选择性分别可达89.4 g/(L h)和27.4%。Mesoporous CaO-ZrO2 solid bases were prepared by sol-gel method and were characterized by means of TEM and CO2-TPD. The influences of preparation conditions on the structure of CaO-ZrO2 solid bases were investigated. And difunctional CuO/CaO-ZrO2 catalysts were prepared by impregnation. Their catalytic performances for the synthesis of methyl formate （MF） by the hydrogenation of CO were studied in a batch slurry reactor. It was found that the preparation conditions significantly affected the structures of the solid bases and the hydrogenation over the CuO/CaO-ZrO2 catalyst. The optimal conditions for the preparation of the solid base were pH 6.4, n （surfactant （P123）） ： n （Zr） 0.02, crystallization temperature 60 ℃, crystallization time 24 h and NaOH solution as post-treatment solution 0.5 mol/L. Under the conditions of CuO/CaO-ZrO2 as catalyst with the above solid base as support, 170 ℃, 5.0 MPa and n（H2） ： n（CO） 2.0, the yield and selectivity of MF were 89.4 g/（L · h） and 27.4%, respectively.

关 键 词：氧化钙-氧化锆固体碱 双功能催化剂 合成气 一氧化碳加氢 甲酸甲酯 

分 类 号：TQ426.82[化学工程]