Aqueous-phase furfural-acetone aldol condensation over basic mixed oxides

被引:184
作者
Faba, Laura [1 ]
Diaz, Eva [1 ]
Ordonez, Salvador [1 ]
机构
[1] Univ Oviedo, Dept Chem Engn & Environm Technol, Fac Chem, E-33006 Oviedo, Spain
关键词
Aldol reaction; Basic catalysis; Biomass upgrading; C-C coupling; SOLID BASE; CATALYSTS; ALKANES; HYDROGEN; MGO;
D O I
10.1016/j.apcatb.2011.11.039
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
Catalytic aqueous-phase aldol-condensation of acetone and furfural has been studied in this work. Three different mixed-oxides catalysts (Mg-Zr, Mg-Al and Ca-Zr, with different basic sites distribution) were studied, their activity and selectivity being correlated with their physico-chemical properties. Catalysts with the highest concentration of basic sites (especially medium-strength basic sites) are the most active and selective for the C13 fraction, whereas molar ratios of 1:1 yield the highest selectivities for C13 fraction (more than 60% atomic yield for the Mg-Zr mixed oxide). Concerning to reaction mechanism, as isomers are the first ones formed, whereas trans isomers are the most abundant at higher reaction times. The main causes of catalysts deactivation are the modification of the physico-chemical properties of catalysts - because of the interaction with water - and in minor extent, the leaching effect; although homogeneous catalytic effects are discarded at studied conditions. The products formed, and the kinetic dependence on reactant concentration, are consistent with a catalytic mechanism in which the rate-determining step is the formation of the enolate species. The model considers consecutive reversible reactions yielding C8, in the first step, and C13, in the second step; with a first-order dependence on the species with a-hydrogen (acetone and C8), and zero-th order on those species without it (furfural and C13). (C) 2011 Elsevier B.V. All rights reserved.
引用
收藏
页码:201 / 211
页数:11
相关论文
共 35 条
[1]   Aldol condensation of campholenic aldehyde and MEK over activated hydrotalcites [J].
Abello, S. ;
Medina, F. ;
Tichit, D. ;
Perez-Ramirez, J. ;
Sueiras, J. E. ;
Salagre, P. ;
Cesteros, Y. .
APPLIED CATALYSIS B-ENVIRONMENTAL, 2007, 70 (1-4) :577-584
[2]   Catalytic conversion of biomass to biofuels [J].
Alonso, David Martin ;
Bond, Jesse Q. ;
Dumesic, James A. .
GREEN CHEMISTRY, 2010, 12 (09) :1493-1513
[3]   Magnesium-containing mixed oxides as basic catalysts:: base characterization by carbon dioxide TPD-MS and test reactions [J].
Aramendía, MA ;
Borau, V ;
Jiménez, C ;
Marinas, A ;
Marinas, JM ;
Ruiz, JR ;
Urbano, FJ .
JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL, 2004, 218 (01) :81-90
[4]   A characterization study of the surface acidity of solid catalysts by temperature programmed methods [J].
Arena, F ;
Dario, R ;
Parmaliana, A .
APPLIED CATALYSIS A-GENERAL, 1998, 170 (01) :127-137
[5]   Single-reactor process for sequential aldol-condensation and hydrogenation of biomass-derived compounds in water [J].
Barrett, C. J. ;
Chheda, J. N. ;
Huber, G. W. ;
Dumesic, J. A. .
APPLIED CATALYSIS B-ENVIRONMENTAL, 2006, 66 (1-2) :111-118
[6]   Allylic alcohol synthesis by gas-phase hydrogen transfer reduction of unsaturated ketones [J].
Di Cosimo, JI ;
Acosta, A ;
Apesteguía, CR .
JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL, 2005, 234 (1-2) :111-120
[7]   Enhancement of the CO2 retention capacity of Y zeolites by Na and Cs treatments:: Effect of adsorption temperature and water treatment [J].
Diaz, Eva ;
Munoz, Emilio ;
Vega, Aurelio ;
Ordonez, Salvador .
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH, 2008, 47 (02) :412-418
[8]   Aldol condensation of citral with acetone on MgO and alkali-promoted MgO catalysts [J].
Diez, V. K. ;
Apesteguia, C. R. ;
Di Cosimo, J. I. .
JOURNAL OF CATALYSIS, 2006, 240 (02) :235-244
[9]   Performance of bifunctional Pd/MxNyO (M = Mg, Ca; N = Zr, Al) catalysts for aldolization-hydrogenation of furfural-acetone mixtures [J].
Faba, Laura ;
Diaz, Eva ;
Ordonez, Salvador .
CATALYSIS TODAY, 2011, 164 (01) :451-456
[10]  
Fogler H.S., 2008, ELEMENTS CHEM REACTI