One-pot synthesis of dimethyl carbonate using ethylene oxide, methanol, and carbon dioxide under supercritical conditions

被引:37
作者
Cui, HY
Wang, T [1 ]
Wang, FJ
Gu, CR
Wang, PL
Dai, YY
机构
[1] Tsing Hua Univ, Dept Chem Engn, Beijing 100084, Peoples R China
[2] Shanghai Petrochem Co Ltd, SINOPEC, Shanghai 200540, Peoples R China
关键词
D O I
10.1021/ie021014b
中图分类号
TQ [化学工业];
学科分类号
0817 ;
摘要
The synthesis of dimethyl carbonate (DMC) from ethylene oxide (EO), methanol, and carbon dioxide was investigated. In the proposed one-pot synthesis of DMC, the reaction of EO with CO2 was coupled simultaneously with the reaction of ethylene carbonate with methanol under reaction conditions at which carbon dioxide was in supercritical state. The catalysts were experimentally screened at temperatures from 80 to 140 degreesC and pressures from 5.0 to 15.0 MPa. The mixture of KI and K2CO3 showed the highest catalytic activity for the one-pot DMC synthesis. The preferential weight ratio of KI to K2CO3 in the mixed catalyst ranges from 1:3 to 5:3. The effects of the reaction conditions, such as catalyst concentration, temperature, pressure, reaction time, and reactant compositions, were experimentally studied. High temperature favors the formation of the desired products, DMC and ethylene carbonate. The effect of pressure on the DMC yield is not significant. A high EO content in the feed is beneficial to increasing the selectivity of the desired products. Using the mixture of KI and K2CO3 (weight ratio of KI/K2CO3 = 1:1) as the catalyst with a molar ratio of catalyst to EO of 0.05, the DMC selectivity can reach above 73.0% at 100.0% EO conversion with less than 4.0% selectivity of the byproduct 2-methoxyethanol at the appropriate reaction conditions.
引用
收藏
页码:3865 / 3870
页数:6
相关论文
共 28 条
[1]  
ABRAMS E, 1979, K OTHMER ENCY CHEM T
[2]  
Aresta M, 1997, CHEMTECH, V27, P32
[3]   Synthesis of dimethyl carbonate and glycols from carbon dioxide, epoxides, and methanol using heterogeneous basic metal oxide catalysts with high activity and selectivity [J].
Bhanage, BM ;
Fujita, S ;
Ikushima, Y ;
Arai, M .
APPLIED CATALYSIS A-GENERAL, 2001, 219 (1-2) :259-266
[4]  
Buysch H.-J, 1980, Patent No. [US 4181676, 4181676]
[5]   Reaction of dialkyltin methoxide with carbon dioxide relevant to the mechanism of catalytic carbonate synthesis [J].
Choi, JC ;
Sakakura, T ;
Sako, T .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1999, 121 (15) :3793-3794
[6]   Direct synthesis of dimethyl carbonate from carbon dioxide and methanol catalyzed by base [J].
Fang, SN ;
Fujimoto, K .
APPLIED CATALYSIS A-GENERAL, 1996, 142 (01) :L1-L3
[7]   Synthesis of dimethyl carbonate by vapor phase oxidative carbonylation of methanol over Cu-based catalysts [J].
Han, MS ;
Lee, BG ;
Suh, I ;
Kim, HS ;
Ahn, BS ;
Hong, SI .
JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL, 2001, 170 (1-2) :225-234
[8]  
Huang CH, 1998, J INF SCI ENG, V14, P1
[9]   Promoting effect of phosphoric acid on zirconia catalysts in selective synthesis of dimethyl carbonate from methanol and carbon dioxide [J].
Ikeda, Y ;
Sakaihori, T ;
Tomishige, K ;
Fujimoto, K .
CATALYSIS LETTERS, 2000, 66 (1-2) :59-62
[10]  
JESSUP PJ, Patent No. 4600408