[1]李国儒,李 工,周书喜,等.Cu/MCM-41和Cu-ZnO/MCM-41的制备及对甲醇脱氢制甲酸甲酯的催化性能[J].常州大学学报(自然科学版),2012,(02):22-27.
　LI Guo-ru,LI Gong,ZHOU Shu-xi,et al.Preparation and Catalytic Performance of Cu/MCM-41 andCu-ZnO/ MCM-41 for Dehydrogenation of Methanol to Methyl Formate[J].Journal of Changzhou University(Natural Science Edition),2012,(02):22-27.
点击复制

Cu/MCM-41和Cu-ZnO/MCM-41的制备及对甲醇脱氢制甲酸甲酯的催化性能()
分享到：

常州大学学报(自然科学版)[ISSN:2095-0411/CN:32-1822/N]

卷:
期数:
2012年02期
页码:
22-27
栏目:
出版日期:
2012-03-30

文章信息/Info

Title:
Preparation and Catalytic Performance of Cu/MCM-41 andCu-ZnO/ MCM-41 for Dehydrogenation of Methanol to Methyl Formate
作者:
李国儒; 李 工; 周书喜; 佟惠娟
常州大学 石油化工学院,江苏 常州 213164
Author(s):
LI Guo-ru; LI Gong; ZHOU Shu-xi; TONG Hui-juan
School of Petrochemical Engineering,Changzhou University,Changzhou 213164,China
关键词:
MCM-41载体;  铜基催化剂;  浸渍法和研磨法;  甲醇脱氢;  甲酸甲酯
Keywords:
MCM-41 support;  Cu-based catalysts;  impregnation and grinding methods;  dehydrogenation of methanol;  methyl formate
分类号:
TQ 225
文献标志码:
A
摘要:
以MCM-41介孔分子筛为载体,通过浸渍法和研磨法制备了Cu/MCM-41和Cu-ZnO/MCM-41催化剂。采用XRD、N2吸附-脱附、TPR、NH3-TPD等方法对催化剂进行表征。结果表明,催化剂均保留了MCM-41有序的六方介孔结构,ZnO和CuO存在着相互作用,研磨法制备的催化剂其酸性比浸渍法制备的略强。在连续流动式常压微型反应器上评价了催化剂对甲醇脱氢制甲酸甲酯反应的催化活性。浸渍法和研磨法相比,浸渍法制备的催化剂对甲酸甲酯的选择性较高,但对甲醇的转化率较低; 研磨法制备的催化剂对甲酸甲酯的选择性较低,但甲醇的转化率较高,添加助剂ZnO能提高甲酸甲酯的选择性。浸渍法制备的Cu-ZnO/MCM-41-I在250 ℃对甲醇的转化率和对甲酸甲酯的选择性分别为15.28%和81.31%,在相同条件下,研磨法制备的Cu-ZnO/MCM-41-G对甲醇的转化率和对甲酸甲酯的选择性分别为18.83%和75.32%。
Abstract:
Cu-ZnO/MCM-41 and Cu/MCM-41 catalysts were prepared usingimpregnation and grinding methods with MCM-41 molecular sieves as the support.The catalysts were characterized by XRD,N2 adsorption-desorption, TPR and NH3-TPD methods. The results showed that the catalysts retain the ordered mesoporous hexagonal structure of MCM-41,and that there was interaction between ZnO andCuO in the catalysts and the catalysts prepared by grinding had slightly stronger acidity than the catalysts prepared by impregnation. The catalytic activity ofthe dehydrogenation of methanol to methyl formate(MF)was evaluated using theflow microreactor under atmospheric pressure. The catalyst prepared by impregnation has a better selectivity for the MF, but a lower methanol conversion rate than the catalyst prepared by grinding. The MF selectivity could be improved by ZnO additive while the methanol conversion rate was reduced. For Cu/MCM-41 prepared by impregnation and grinding, the methanol conversion was 20.18% and 24.13%respectively and the MF selectivity was 73.75% and 67.35% at 250 ℃ respectively. Likewise for Cu-ZnO/MCM-41 prepared by impregnation and grinding, themethanol conversion rate was 15.28% and 18.83% respectively and the MF selectivity was 81.31% and 75.32% at 250 ℃ respectively.

参考文献/References:

[1]He Ling,Liu Haichao,Xiao Chaoxian,et al. Liquid-phase synthesis ofmethyl formate via heterogeneous carbonylation of methanol over a soluble copper nanocluster catalyst[J].Green Chem,2008,10:619-622.
[2]Wittstock A,Zielasek V,Biener J,et al. Nanoporous gold catalysts for selective gas-phase oxidative coupling of methanol at low temperature[J].Science,2010,327:319-322.
[3]Lichtenberger J,Lee D,Iglesia E. Catalytic oxidation of methanol on Pd metal and oxide clusters at near-ambient temperatures[J].Phys Chem,2007,9(35):4902-4906.
[4]王乐夫,谭凤仙,张映珊,等.甲醇脱氢制甲酸甲酯的催化剂和反应性能研究[J].化学反应工程与工艺,1994,10(4):403-407.
[5]Guo Yanglong,Lu Guanzhong,Mo Xunhua,et al. Vapor phase dehydrogenation of methanol to methyl formate in the catalytic membrane reactor with Cu/SiO2/ceramic composite membrane[J]. Catalysis Letters,2005,99(1-2):105-108.
[6]刘说,吴静,汪海滨,等.甲醇脱氢制甲酸甲酯催化剂的研究[J].沈阳化工学院学报,2005,19(4):266-269.
[7]郑振涛,佟惠娟,李工.Cu-CFG和Cu-MCM-41催化合成2,2-二甲基环丙烷甲酸乙酯[J].江苏工业学院学报,2008,20(3):6-9.
[8]Kresge C T,Leonowicz M E,Roth W J,et al. Ordered mesoporous molecular sieves synthesized by liquid-crystal template mechanism[J]. Nature,1992,359:710-712.
[9]Lin Wenyong,Wen QiangCai,Pang qin,et al. New mineralization agents for the synthesis of M CM-41[J]. Micorporous and Mesoporous Materials,1999,33(1):187-196.
[10]邱永福.催化剂Au/CeO2/MCM-41的制备及其活性研究[J].广东化工,2011,38(3):49-51.
[11]Cai Chao,Wang Hua,Han Jinyu. Synthesis and characterization of ionic iquid-functionalized alumino-silicate MCM-41 hybrid mesoporous materials[J]. Applied Surface Science,2011,257(33):9802-9808.
[12]田部浩三.固体酸碱及其催化性质[M].赵君生,张嘉郁,译.北京:化学工业出版社,1979:76-77.

备注/Memo

备注/Memo:
基金项目:江苏省高校自然科学基金(08KJD150013) 作者简介:李国儒(1985- ),男,山西应县人,硕士生; 通讯联系人:李工。
更新日期/Last Update: 2012-03-30