Promoting behaviors of alkali compounds in low temperature methanol synthesis over copper-based catalyst

被引:16
作者
Hu, Baoshan [1 ]
Fujimoto, Kaoru [1 ]
机构
[1] Univ Kitakyushu, Dept Chem Proc & Environm, Fac Environm Engn, Kitakyushu, Fukuoka 8080135, Japan
关键词
Methanol synthesis; Low temperature; Sodium compound; Cu/MgO catalyst; Active site; WATER-GAS SHIFT; CU/ZNO CATALYSTS; SLURRY PHASE; LIQUID-PHASE; FORMATE; CONVERSION; KINETICS; SUPPORT; MODEL; CO2;
D O I
10.1016/j.apcatb.2010.01.001
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Hybrid catalyst systems comprised of Na compounds (HCOONa, NaOH, Na2CO3 and NaHCO3) and Cu/MgO catalysts have contributed to a novel high-performance methanol synthesis in ethanol solvent from syngas (CO/H-2 = 1/2) at a low temperature of 433 K and 5 MPa. It is found that Na2CO3 dopant is more beneficial to enhance hydrogenolysis ability of Cu/MgO catalyst than NaOH and HCOONa. Whereas, all the starting Na compounds in ethanol solvent are reversibly converted to HCOONa in alcohol solvent by ex situ observations, revealing that formate alone is the essential species in the catalytic circle. The results unambiguously elucidate that the essence of alkali component in promoting the low temperature methanol synthesis is virtually attributed to the formation of highly reactive alkali-participated active site. It is also proposed that solid Cu/MgO catalyst should play binary roles in successive carbonylation and hydrogenolysis reactions. (C) 2010 Elsevier B.V. All rights reserved.
引用
收藏
页码:208 / 216
页数:9
相关论文
共 42 条
[31]   Methanol technology developments for the new millennium [J].
Tijm, PJA ;
Waller, FJ ;
Brown, DM .
APPLIED CATALYSIS A-GENERAL, 2001, 221 (1-2) :275-282
[32]   Highly effective conversion of CO2 to methanol over supported and promoted copper-based catalysts:: influence of support and promoter [J].
Toyir, J ;
de la Piscina, PR ;
Fierro, JLG ;
Homs, N .
APPLIED CATALYSIS B-ENVIRONMENTAL, 2001, 29 (03) :207-215
[33]   A new method of low-temperature methanol synthesis [J].
Tsubaki, N ;
Ito, M ;
Fujimoto, K .
JOURNAL OF CATALYSIS, 2001, 197 (01) :224-227
[34]  
Tsubaki N., 2001, CATAL COMMUN, V2, P213
[35]   Cu/ZnO aggregates in siliceous mesoporous matrices:: Development of a new model methanol synthesis catalyst [J].
van den Berg, M. W. E. ;
Polarz, S. ;
Tkachenko, O. P. ;
Klementiev, K. V. ;
Bandyopadhyay, M. ;
Khodeir, L. ;
Gies, H. ;
Muhler, M. ;
Gruenert, W. .
JOURNAL OF CATALYSIS, 2006, 241 (02) :446-455
[36]   Dynamical changes in Cu/ZnO/Al2O3 catalysts [J].
Wilmer, H ;
Hinrichsen, O .
CATALYSIS LETTERS, 2002, 82 (1-2) :117-122
[37]   Mechanistic study of a new low-temperature methanol synthesis on Cu/MgO catalysts [J].
Yang, RQ ;
Zhang, Y ;
Iwama, Y ;
Tsubaki, N .
APPLIED CATALYSIS A-GENERAL, 2005, 288 (1-2) :126-133
[38]   In situ DRIFT study of low-temperature methanol synthesis mechanism on Cu/ZnO catalysts from CO2-containing syngas using ethanol promoter [J].
Yang, RQ ;
Fu, YL ;
Zhang, Y ;
Tsubaki, N .
JOURNAL OF CATALYSIS, 2004, 228 (01) :23-35
[39]   A new low-temperature synthesis route of methanol: Catalytic effect of the alcoholic solvent [J].
Zeng, JQ ;
Fujimoto, K ;
Tsubaki, N .
ENERGY & FUELS, 2002, 16 (01) :83-86
[40]  
ZHANG Y, 2002, J FUEL CHEM TECHNOL, V30, P277