Valorization of bio-glycerol: New catalytic materials for the synthesis of glycerol carbonate via glycerolysis of urea

被引:206
作者
Aresta, Michele [1 ,2 ]
Dibenedetto, Angela [1 ,2 ]
Nocito, Francesco [1 ,2 ]
Ferragina, Carla [3 ]
机构
[1] Univ Bari, Dipartimento Chim, I-70126 Bari, Italy
[2] Univ Bari, CIRCC, I-70126 Bari, Italy
[3] CNR Roma 1, IMIP, I-00016 Monterotondo, Roma, Italy
关键词
Glycerolysis of urea; Reaction mechanism; Glycerol carbonate; Heterogeneous catalysis; ZEOLITES; DIOXIDE; ACIDITY;
D O I
10.1016/j.jcat.2009.09.008
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
The glycerolysis of urea plays an important role in the conversion of glycerol into glycerol carbonate because it is a phosgene-free process that uses easily available and low-cost raw materials that have a low toxicity. gamma-Zirconium phosphate shows a good activity as catalyst as it affords 80% of conversion of glycerol under mild reaction conditions. The catalyst is easily recoverable and reusable in subsequent cycles of reaction. The kinetics of the reaction has been studied considering the full parameter space. The best temperature is 418 K, with 3 h of reaction using an equimolar amount of the two reagents (glycerol and urea) with a catalyst load of 0.6-1.5% w/w with respect to glycerol. The behaviour of the catalyst has been investigated by using the TPD technique. Multinuclear H-1 and C-13 NMR and FTIR have been used for the characterization of intermediates and by-product. The reaction mechanism is fully elucidated. (C) 2009 Elsevier Inc. All rights reserved.
引用
收藏
页码:106 / 114
页数:9
相关论文
共 37 条
[1]   INTERACTION OF CARBON-DIOXIDE WITH COORDINATIVELY UNSATURATED RHODIUM(I) COMPLEXES WITH THE LIGAND 1,2-BIS(DIPHENYLPHOSPHINO)ETHANE [J].
ALBANO, P ;
ARESTA, M ;
MANASSERO, M .
INORGANIC CHEMISTRY, 1980, 19 (04) :1069-1072
[2]   PREPARATION AND ION-EXCHANGE PROPERTIES OF A NEW PHASE OF CRYSTALLINE TITANIUM PHOSPHATE, TI(HPO4)2.2H2O [J].
ALLULLI, S ;
FERRAGINA, C ;
LAGINESTRA, A ;
MASSUCCI, MA ;
TOMASSINI, N .
JOURNAL OF INORGANIC & NUCLEAR CHEMISTRY, 1977, 39 (06) :1043-1048
[3]  
Aresta M, 2004, STUD SURF SCI CATAL, V153, P213
[4]  
ARESTA M, 2009, CATALYSTS SUSTAINABL
[5]  
ARESTA M, 2008, Patent No. 083056531
[6]   A study on the carboxylation of glycerol to glycerol carbonate with carbon dioxide: The role of the catalyst, solvent and reaction conditions [J].
Aresta, Michele ;
Dibenedetto, Angela ;
Nocito, Francesco ;
Pastore, Carlo .
JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL, 2006, 257 (1-2) :149-153
[7]  
BONDIOLI D, 2004, CHIM IND MAR, P46
[8]   X-RAY-POWDER DIFFRACTION STUDY OF LAYER COMPOUNDS - THE CRYSTAL-STRUCTURE OF ALPHA-TI(HPO4)2.H2O AND A PROPOSED STRUCTURE FOR GAMMA-TI(H2PO4)(PO4).2H2O [J].
CHRISTENSEN, AN ;
ANDERSEN, EK ;
ANDERSEN, IGK ;
ALBERTI, G ;
NIELSEN, M ;
LEHMANN, MS .
ACTA CHEMICA SCANDINAVICA, 1990, 44 (09) :865-872
[9]   NEW CRYSTALLINE PHASES OF ZIRCONIUM PHOSPHATE POSSESSING ION-EXCHANGE PROPERTIES [J].
CLEARFIELD, A ;
BLESSING, RH ;
STYNES, JA .
JOURNAL OF INORGANIC & NUCLEAR CHEMISTRY, 1968, 30 (08) :2249-+
[10]  
COOPER B, 1990, Patent No. 4900668