制备条件对α-Al_(2)O_(3)载体及草酸二甲酯合成催化剂性能的影响  

Effect of preparation conditions on performance of α-Al_(2)O_(3) carrier and dimethyl oxalate synthesis catalyst

作　　者：李凯歌 赵立红 梁旭 谢肥东 蒋元力 刘振峰 谢进军 蔡教民[5] 郑卫 LI Kaige;ZHAO Lihong;LIANG Xu;XIE Feidong;JIANG Yuanli;LIU Zhenfeng;XIE Jinjun;CAI Jiaomin;ZHENG Wei(Research Institute of Henan Energy Industry Group Co.Ltd.,Zhengzhou 450046,Henan,China;Henan Longyu Coal Chemical Co.,Ltd.,Yongcheng 476600,Henan,China;Qianxi Coal Chemical Industry Investment Co.,Ltd.,Bijie 551500,Guizhou,China;Shanxi Woneng Chemical Technology Co.,Ltd,Linfen 041000,Shanxi,China;Zhongyuan Dahua Group Company Limited,Puyang 457000,Henan,China;Xinjiang Zhongkun New Materials Company Limited,Bayingolin 841000,Xinjiang,China)

机构地区：[1]河南能源集团研究总院有限公司,河南郑州450046 [2]河南龙宇煤化工有限公司,河南永城476600 [3]贵州黔希化工有限责任公司,贵州毕节551500 [4]山西沃能化工科技有限公司,山西临汾041000 [5]河南省中原大化集团有限责任公司,河南濮阳457000 [6]新疆中昆新材料有限公司,新疆巴音郭楞841000

出　　处：《工业催化》2025年第2期49-56,共8页Industrial Catalysis

基　　金：河南省重大科技专项(豫科计[2011]7号)。

摘　　要：以偏铝酸钠(NaAlO_(2))为原料,采用硝酸法在不同条件下制备了一系列氧化铝前驱体,经高温煅烧制得α-Al_(2)O_(3)。以α-Al_(2)O_(3)为载体,采用等体积浸渍法制备了负载型钯催化剂,并在固定床反应器上评价了其催化一氧化碳氧化偶联合成草酸二甲酯的性能。通过XRD、BET、SEM、NH_(3)-TPD和H_(2)-TPR等对样品的结构和表面性质进行了表征。结果表明,在成胶温度为55℃、反应终点pH为7.0、NaAlO_(2)物质的量浓度为0.8 mol·L^(-1)的条件下制备得到了氧化铝前驱体,该前驱体经1200℃焙烧处理后制备得到的α-Al_(2)O_(3)载体具有较高的比表面积、合适的表面酸性、适宜的孔径分布和较大的孔隙率。以此为载体制备的钯基催化剂,在空速为3000 h^(-1)、反应温度为130℃、原料气一氧化碳/亚硝酸甲酯(CO/MN)物质的量比为4∶1的反应条件下,亚硝酸甲酯(MN)转化率为87.4%,草酸二甲酯(DMO)选择性为96.1%。A series of alumina precursors were prepared by nitric acid method using NaAlO_(2)as raw material,andα-Al_(2)O_(3)was obtained by calcination at high temperature.The supported palladium catalyst was prepared by incipient impregnation and their performance of CO oxidation coupling to dimethyl oxalate was evaluated on a fixed bed reactor.The texture and surface properties of the samples was characterized by XRD,BET,SEM,NH_(3)-TPD and H_(2)-TPR.The results showed that the precursor was prepared at gelation temperature of 55℃,pH of 7.0,and NaAlO_(2)concentration of 0.8 mol·L^(-1).Theα-Al_(2)O_(3)carrier prepared by the precursor calcined at 1200℃has high specific surface area,suitable surface acidity,suitable pore size distribution and large porosity.On a palladium-based catalyst prepared with this support,the conversion rate of methyl nitrite(MN)was 87.4%and the selectivity of dimethyl oxalate(DMO)was 96.1%at 3000 h^(-1),130℃,and CO/MN ratio of 4∶1.

关 键 词：催化剂工程 硝酸法 α-Al_(2)O_(3) 氧化铝前驱体 孔径分布 草酸二甲酯 

分 类 号：TQ426.65[化学工程] TQ032