Selective and high yield synthesis of dimethyl carbonate directly from carbon dioxide and methanol

Supercritical carbon dioxide is efficiently converted to dimethyl carbonate (DMC) via the reaction with methanol in the presence of a catalytic amount of dialkyltin oxide or its derivatives. The removal of water is the key to accomplishing the high conversion by shifting the equilibrium to dimethyl carbonate. Dehydration is successfully carried out by circulating the reaction mixture through a dehydrating tube packed with molecular sieve 3A. Under the effective dehydration conditions, the DMC yield is almost linearly dependent on the reaction time, catalyst amount, methanol concentration, and CO2 pressure.

[1]  N. Isaacs,et al.  High pressure routes to dimethyl carbonate from supercritical carbon dioxide , 1999 .

[2]  Takeshi Sako,et al.  Synthesis of dimethyl carbonate from carbon dioxide: catalysis and mechanism , 2000 .

[3]  T. Sakakura,et al.  Metal-Catalyzed Dimethyl Carbonate Synthesis from Carbon Dioxide and Acetals , 1999 .

[4]  P. Jessop,et al.  Homogeneous catalysis in supercritical fluids. , 1999, Science.

[5]  Walter Leitner,et al.  Carbon Dioxide as a Raw Material: The Synthesis of Formic Acid and Its Derivatives from CO2 , 1995 .

[6]  †. Danielle Ballivet-Tkatchenko,et al.  Reactivity of Carbon Dioxide with n-Butyl(phenoxy)-, (alkoxy)-, and (oxo)stannanes: Insight into Dimethyl Carbonate Synthesis , 2000 .

[7]  T. Sakakura,et al.  Reaction of Dialkyltin Methoxide with Carbon Dioxide Relevant to the Mechanism of Catalytic Carbonate Synthesis , 1999 .

[8]  J. Kizlink,et al.  Preparation of Dimethyl Carbonate from Methanol and Carbon Dioxide in the Presence of Organotin Compounds , 1994 .

[9]  K. Tomishige,et al.  Catalytic properties and structure of zirconia catalysts for direct synthesis of dimethyl carbonate from methanol and carbon dioxide , 2000 .

[10]  T. Sakakura,et al.  C-H bond activation in dense carbon dioxide: rhodium-catalyzed methane carbonylation and alkane dehydrogenation. , 2001, The Journal of organic chemistry.

[11]  Yoshiki Ikeda,et al.  A novel method of direct synthesis of dimethyl carbonate from methanol and carbon dioxide catalyzed by zirconia , 1999 .

[12]  Juraj Kizlink,et al.  Preparation of Dimethyl Carbonate from Methanol and Carbon Dioxide in the Presence of Sn(IV) and Ti(IV) Alkoxides and Metal Acetates , 1995 .

[13]  Ryoji Noyori,et al.  Homogeneous Hydrogenation of Carbon Dioxide , 1995 .

[14]  P. Tundo.  Selective monomethylation reactions of methylene-active compounds with dimethylcarbonate. An example of clean synthesis , 2000 .

[15]  M. Okano,et al.  Selective Conversion of Carbon Dioxide to Dimethyl Carbonate by Molecular Catalysis. , 1998, The Journal of organic chemistry.

[16]  I. Horváth,et al.  NMR under high gas pressure , 1991 .

[17]  J. Kizlink.  Synthesis of Dimethyl Carbonate from Carbon Dioxide and Methanol in the Presence of Organotin Compounds , 1993 .

[18]  K. Tomishige,et al.  Promoting effect of phosphoric acid on zirconia catalysts in selective synthesis of dimethyl carbonate from methanol and carbon dioxide , 2000 .

[19]  T. Sakakura,et al.  Hydrosilation of polyfluoroolefin in dense carbon dioxide , 2001 .