Acidic mesoporous silica for the acetylation of glycerol: Synthesis of bioadditives to petrol fuel

被引:226
作者
Melero, Juan A. [1 ]
van Grieken, Rafael [1 ]
Morales, Gabriel [1 ]
Paniagua, Marta [1 ]
机构
[1] Rey Juan Carlos Univ, Dept Chem & Environm Technol, Madrid 28933, Spain
关键词
D O I
10.1021/ef060647q
中图分类号
TE [石油、天然气工业]; TK [能源与动力工程];
学科分类号
0807 ; 0820 ;
摘要
Expected increasing biodiesel production during the next few years will lead to an overproduction of glycerol, which is the main byproduct. The use of glycerol-based additives to improve petrol fuel properties is one of the possibilities currently being explored to utilize this renewable feedstock. In this context, sulfonic acid functionalized mesostructured materials have demonstrated an excellent catalytic behavior in the esterification of glycerol with acetic acid to yield acetylated derivates. Diacetylglycerol (DAG) and triacetylglycerol (TAG, also called triacetin) have been shown to be valuable petrol fuel additives leading to either enhanced cold and viscosity properties when blended with diesel fuel or antiknocking properties when added to gasoline. The activities and selectivities achieved using sulfonic acid functionalized mesostructured materials as catalysts are comparable or even superior to those displayed by conventional acid catalysts, providing values up to 90% of glycerol conversion and over 80% of combined selectivity toward DAG and TAG after 4 h of reaction. The acid strength of the sulfonic acid site has also been found to be an important factor affecting the catalytic performance of these materials. Moreover, these sulfonated mesostructured materials have been reused in repeated catalytic runs after a mild solvent-washing regeneration step yielding similar catalytic performance to that of the fresh catalyst. Expected increasing biodiesel production during the next few years will lead to an overproduction of glycerol, which is the main byproduct. The use of glycerol-based additives to improve petrol fuel properties is one of the possibilities currently being explored to utilize this renewable feedstock. In this context, sulfonic acid functionalized mesostructured materials have demonstrated an excellent catalytic behavior in the esterification of glycerol with acetic acid to yield acetylated derivates. Diacetylglycerol (DAG) and triacetylglycerol (TAG, also called triacetin) have been shown to be valuable petrol fuel additives leading to either enhanced cold and viscosity properties when blended with diesel fuel or antiknocking properties when added to gasoline. The activities and selectivities achieved using sulfonic acid functionalized mesostructured materials as catalysts are comparable or even superior to those displayed by conventional acid catalysts, providing values up to 90% of glycerol conversion and over 80% of combined selectivity toward DAG and TAG after 4 h of reaction. The acid strength of the sulfonic acid site has also been found to be an important factor affecting the catalytic performance of these materials. Moreover, these sulfonated mesostructured materials have been reused in repeated catalytic runs after a mild solvent-washing regeneration step yielding similar catalytic performance to that of the fresh catalyst.
引用
收藏
页码:1782 / 1791
页数:10
相关论文
共 38 条
[1]   Nafion-functionalized mesoporous MCM-41 silica shows high activity and selectivity for carboxylic acid esterification and Friedel-Crafts acylation reactions [J].
Alvaro, M ;
Corma, A ;
Das, D ;
Fornés, V ;
García, H .
JOURNAL OF CATALYSIS, 2005, 231 (01) :48-55
[2]   Single-step preparation and catalytic activity of mesoporous MCM-41 and SBA-15 silicas functionalized with perfluoroalkylsulfonic acid groups analogous to Nafion® [J].
Alvaro, M ;
Corma, A ;
Das, D ;
Fornés, V ;
García, H .
CHEMICAL COMMUNICATIONS, 2004, (08) :956-957
[3]  
Biofuels for Transport, 2004, BIOF TRANSP INT PERS, P169
[4]  
Box G.E., 1978, STAT EXPT
[5]  
Bradin, 1996, Patent No. [US 5578090, 5578090]
[6]  
Delfort B., 2004, FR Patent, Patent No. 2866654
[7]  
Delgado J, 2002, SP Patent, Patent No. [2,201,894, 2201894]
[8]   Combined alkyl and sulfonic acid functionalization of MCM-41-Type silica -: Part 2.: Esterification of glycerol with fatty acids [J].
Díaz, I ;
Márquez-Alvarez, C ;
Mohino, F ;
Pérez-Pariente, J ;
Sastre, E .
JOURNAL OF CATALYSIS, 2000, 193 (02) :295-302
[9]   Influence of the alkyl chain length of HSO3-R-MCM-41 on the esterification of glycerol with fatty acids [J].
Díaz, I ;
Mohino, F ;
Blasco, T ;
Sastre, E ;
Pérez-Pariente, J .
MICROPOROUS AND MESOPOROUS MATERIALS, 2005, 80 (1-3) :33-42
[10]   Design of heterogeneous catalysts via multiple active site positioning in organic-inorganic hybrid materials [J].
Dufaud, V ;
Davis, ME .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2003, 125 (31) :9403-9413