Steam reforming of methanol over a Cu/ZnO/Al2O3 catalyst:: a kinetic analysis and strategies for suppression of CO formation

被引:291
作者
Agrell, J [1 ]
Birgersson, H [1 ]
Boutonnet, M [1 ]
机构
[1] Royal Inst Technol, KTH, Dept Chem Engn & Technol, SE-10044 Stockholm, Sweden
关键词
hydrogen production; methanol; steam reforming; Cu/ZnO/Al2O3; catalyst; carbon monoxide; PEM fuel cell vehicles;
D O I
10.1016/S0378-7753(01)01027-8
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
Steam reforming of methanol (CH3OH + H2O --> CO2 + 3H(2)) was studied over a commercial Cu/ZnO/Al2O3 catalyst for production of hydrogen onboard proton exchange membrane (PEM) fuel cell vehicles. A simple power-law rate expression was fitted to experimental data in order to predict the rates Of CO2 and H-2 formation under various reaction conditions. The apparent activation energy (E-a) was estimated to be 100.9 kJ mol(-1), in good agreement with values reported in the literature. Appreciable amounts of CO by-product were formed in the reforming process at low contact times and high methanol conversions. Being a catalyst poison that deactivates the electrocatalyst at the fuel cell anode at concentrations exceeding a few ppm, special attention was paid to the pathways for CO formation and strategies for its suppression. It was found that increasing the steam-methanol ratio effectively decreases CO formation. Likewise, addition of oxygen or air to the steam-methanol mixture minimises the production of CO. By shortening the contact time and lowering the maximum temperature in the reactor, CO production can be further decreased by suppressing the reverse water-gas shift reaction. (C) 2002 Elsevier Science B.V. All rights reserved.
引用
收藏
页码:249 / 257
页数:9
相关论文
共 32 条
[1]   Production of hydrogen by partial oxidation of methanol over Cu/ZnO catalysts prepared by microemulsion technique [J].
Agrell, J ;
Hasselbo, K ;
Jansson, K ;
Järås, SG ;
Boutonnet, M .
APPLIED CATALYSIS A-GENERAL, 2001, 211 (02) :239-250
[2]   Partial oxidation of methanol to produce hydrogen over Cu-Zn-based catalysts [J].
Alejo, L ;
Lago, R ;
Pena, MA ;
Fierro, JLG .
APPLIED CATALYSIS A-GENERAL, 1997, 162 (1-2) :281-297
[3]   HYDROGEN-PRODUCTION BY THE CATALYTIC STEAM REFORMING OF METHANOL .2. KINETICS OF METHANOL DECOMPOSITION USING GIRDLER G66B CATALYST [J].
AMPHLETT, JC ;
EVANS, MJ ;
MANN, RF ;
WEIR, RD .
CANADIAN JOURNAL OF CHEMICAL ENGINEERING, 1985, 63 (04) :605-611
[4]   Kinetic studies using temperature-scanning: the steam-reforming of methanol [J].
Asprey, SP ;
Wojciechowski, BW ;
Peppley, BA .
APPLIED CATALYSIS A-GENERAL, 1999, 179 (1-2) :51-70
[5]   KINETICS OF CATALYTIC CONVERSION OF METHANOL AT HIGHER PRESSURES [J].
BARTON, J ;
POUR, V .
COLLECTION OF CZECHOSLOVAK CHEMICAL COMMUNICATIONS, 1980, 45 (12) :3402-3407
[6]   Methanol reforming for fuel-cell applications: development of zirconia-containing Cu-Zn-Al catalysts [J].
Breen, JP ;
Ross, JRH .
CATALYSIS TODAY, 1999, 51 (3-4) :521-533
[7]   Mechanistic aspects of the steam reforming of methanol over a CuO/ZnO/ZrO2/Al2O3 catalyst [J].
Breen, JP ;
Meunier, FC ;
Ross, JRH .
CHEMICAL COMMUNICATIONS, 1999, (22) :2247-2248
[8]   Catalytic production of hydrogen from methanol [J].
de Wild, PJ ;
Verhaak, MJFM .
CATALYSIS TODAY, 2000, 60 (1-2) :3-10
[9]  
Fogler H.S., 1999, ELEMENTS CHEM REACTI
[10]   Autothermal methanol reforming for hydrogen production in fuel cell applications [J].
Geissler, K ;
Newson, E ;
Vogel, F ;
Truong, TB ;
Hottinger, P ;
Wokaun, A .
PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 2001, 3 (03) :289-293