Synthesis, characterization and activity pattern of Cu-ZnO/ZrO2 catalysts in the hydrogenation of carbon dioxide to methanol

被引:465
作者
Arena, Francesco
Barbera, Katia
Italiano, Giuseppe
Bonura, Giuseppe
Spadaro, Lorenzo
Frusteri, Francesco
机构
[1] Univ Messina, Dipartimento Chim Ind & Ingn Mat, I-98166 Messina, Italy
[2] Ist CNR ITAE Nicola Giordano, I-98126 Messina, Italy
关键词
Cu-ZnO/ZrO2; catalysts; CO2; hydrogenation; CH3OH synthesis; physicochemical characterization; dispersion; reducibility; catalytic pattern; structure sensitivity;
D O I
10.1016/j.jcat.2007.04.003
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
A novel synthesis route based on reverse co-precipitation under ultrasound irradiation has led to Cu-ZnO/ZrO2 catalysts (Zn-at/Cu-at, 0-3; ZrO2, 42-44 wt%) with a remarkable development of total surface area (SABET, 120-180 m(2)/g) and very high dispersion (3-58%) and exposure (MSA 9-63 m(2)/g) of the active Cu phase. The activity pattern in the hydrogenation of CO2 to CH3OH (T-R, 433-533 K; P-R, 1.0-3.0 MPa) was addressed in comparison with a commercial Cu-ZnO/Al2O3 methanol synthesis catalyst. Volcano-shaped trends in total and metal surface area signal an optimum zinc loading (Zn/Cu, 0.3-0.7), ensuring higher concentration of active sites and methanol productivity values, whereas the basic relationships among dispersion, reducibility, and TOF indicate a structurally sensitive character of the title reaction and a superior reactivity of poorly dispersed Cu particles. Thermodynamic analysis of the reaction stream revealed that methanol formation proceeds along a parallel path, whereas a stronger "water affinity" accounts for the poorer performance of the conventional alumina-based catalyst compared with zirconia-based ones. (c) 2007 Elsevier Inc. All rights reserved.
引用
收藏
页码:185 / 194
页数:10
相关论文
共 65 条
[1]   Production of hydrogen from methanol over Cu/ZnO catalysts promoted by ZrO2 and Al2O3 [J].
Agrell, J ;
Birgersson, H ;
Boutonnet, M ;
Melián-Cabrera, I ;
Navarro, RM ;
Fierro, JLG .
JOURNAL OF CATALYSIS, 2003, 219 (02) :389-403
[2]   METHANOL SYNTHESIS FROM CO2+H2 .2. COPPER-BASED BINARY AND TERNARY CATALYSTS [J].
AMENOMIYA, Y .
APPLIED CATALYSIS, 1987, 30 (01) :57-68
[3]  
Arena F, 2004, STUD SURF SCI CATAL, V147, P385
[4]   Modelling the activity-stability pattern of Ni/MgO catalysts in the pre-reforming of n-hexane [J].
Arena, F ;
Trunfio, G ;
Alongi, E ;
Branca, D ;
Parmaliana, A .
APPLIED CATALYSIS A-GENERAL, 2004, 266 (02) :155-162
[5]   Activity and resistance to leaching of Cu-based catalysts in the wet oxidation of phenol [J].
Arena, F ;
Giovenco, R ;
Torre, T ;
Venuto, A ;
Parmaliana, A .
APPLIED CATALYSIS B-ENVIRONMENTAL, 2003, 45 (01) :51-62
[6]   A KINETIC-MODEL OF METHANOL SYNTHESIS [J].
ASKGAARD, TS ;
NORSKOV, JK ;
OVESEN, CV ;
STOLTZE, P .
JOURNAL OF CATALYSIS, 1995, 156 (02) :229-242
[7]  
BAIKER A, 1993, STUD SURF SCI CATAL, V75, P1257
[8]  
Bart J. C., 1987, CATAL TODAY, V2, P1
[9]   Methanol production from biomass and natural gas as transportation fuel [J].
Borgwardt, RH .
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH, 1998, 37 (09) :3760-3767
[10]   Synergism between Cu and Zn sites in Cu/Zn catalysts for methanol synthesis [J].
Chen, HY ;
Lau, SP ;
Chen, L ;
Lin, J ;
Huan, CHA ;
Tan, KL ;
Pan, JS .
APPLIED SURFACE SCIENCE, 1999, 152 (3-4) :193-199