Catalysis used in DMC production 1) Direct synthesis of dimethyl carbonate (DMC) using Cu-Ni/VSO as catalyst (X.L. Wu Y.Z.

Meng, M. Xiao, Y.X. Lu) (2006) --- Cu-Ni/VSO (V2O5-SiO2) catalyst is used Preparation of VSO: V2O5+ HCl (35wt%) at 363KVOCl3 VOCl3+SiO2 24h at 363K, the medium was neutralized with NH4OH. VSO is then filtered, dried at 393Kfor 12h and calcined at 723K in air for 5h. VSO is poured into the solution of Cu-Ni ammonia for 48h, dried at 393K in the air and calcined at 7223K in air for 5h. ---Optimum conditions for the reaction is found as 413K at 0.6MPa pressure. 2) Critical temperatures and pressures of reacting mixture in synthesis of dimethyl carbonate with methanol and carbon dioxide (Xing Cui Guo. Zhang Feng Qin, Guo Fu Wang, Jian Guo Wang) (2008) ----Supercritical conditions should be estimated for the whole mixture depending on the composition of the inlet composition, not for only CO2. High pressures increase the solubility of CO2 in the liquid mixture which can enhance the rate of DMC formation. Conditions of 453K and 30MPa may be useful. 3) Direct synthesis of dimethyl carbonate from carbon dioxide and methanol using supported copper (Ni, V, O) catalyst with photo-assistance (X.J. Wang, M. Xiao, S.J. Wang, Y.X. Lu, Y.Z. Menga ) (2007) --- V2O5+ HCl (35wt%) at 363KVOCl3 VOCl3+SiO2 (aged at room temperature for 24h) the reaction is carried out for 24h at 363K, and ammonia is added to neutralize the system, the mixture is filtered, dried at 383K for 6hand calcined at 723K in air. (V2O5 dispersed on SiO2) The mixture is then impregnated into the solution of Ni ammonia and aged. (Calcination temperature 723K). Cu impregnation is performed also. ---Photocatalytic synthesis of DMC, UV radiation enhanced DMC yield. ---Optimum 120-140C under 1atm with the assistance of UV light radiation.

4) Effect of acidbase properties of H3PW12O40/CexTi1xO2 catalysts on the direct synthesis of dimethyl carbonate from methanol and carbon dioxide: A TPD study of H3PW12O40/CexTi1xO2 catalysts (Kyung Won La, Ji Chul Jung, Heesoo Kim, SungHyeon Baeck, In Kyu Song) (2007) ---H3PW12O40 (WPA)/ CexTi1-xO2 ( 0<x<1) catalysts are prepared by sol-gel method. ---Ce(NO3)3.6H2O (Ce) and Ti(OCH(CH3)2)4 (Ti) are mixed in ethanol solution. NH4OH is added and dried. Calcined at 300C for 4h for CexTi1-xO2 ---- WPA is added to ethanol solution of Ce(NO3)3.6H2O (Ce) and Ti(OCH(CH3)2)4 (Ti) and NH4OH are mixed with the solution. The mixture is stirred, filtered. The precipitate is dried and calcined at 300C. xopt=0.1 ---Both acid and base sites are important for DMC formation. Lewis Acid sites CexTi1-xO2, Brnsted acid sites WPA. Metahnol is activated to methyl species on the acid sites which is the rate determining step. Base sites: Activation of methanol to methoxy species and methoxy carbonate anions takes place in basic sites. 5) Effect of the Brnsted acidity on the behavior of CO2 methanol reaction (L.A. Allaoui, A. Aouissi) (2006) --- H3PMo12O40 and Cu1.5PMo12O40 are used. Preparation of Cu1.5PMo12O40 is made by neutralizing 3 protons of H3PMo12O40 by Ba(OH)2.8H2O and adding CuSO4.6H2O (BaSO4 is taken out as precipitate). ---Side products; DME and formaldehyde (FA) are also seen. The selectivity towards DME is always greater than that of DMC in presence of H3PMo12O40. On the other hand for the Cu1.5PMo12O40, selectivity towards FA dominates. ---Brnsted acid sites are important to activate methanol but results as formation of other side products (DME or FA) 6) Direct synthesis of dimethyl carbonate on H3PO4 modified V2O5 (X.L. Wu, M. Xiao, Y.Z. Meng, Y.X. Lub.) (2005) --- V2O5 is calcined at 723K and impregnated by 85% H3PO4 solution. The solution is dried at 393K (3h) and calcined at 673K. ---P/V ration is an important factor in DMC formation (0.2 is optimum)

7) Synthesis of Dimethyl Carbonate from CH3OH and CO2 with Ce1-xZrxO2 Catalysts (B. Han, N. K. Park, J. H. Jun, W. C. Chang, B. G. Lee, B. S. Ahn, S. O. Ryu and T. J. Lee) (2004) --- Ce(NO3)3.6H2O (Ce) and ZrO(NO3)2.2H2O (Zr) are used in preparation of Ce1-xZrxO2 (Calcination temperature 600C) ---Increasing Zr content in the catalyst increased the mobility of oxygen which provides more basic sites (x=0.8, has the highest reactivity) ---PCO265atm at a temperature of 150C ---Reaction rate is found to be as R = k [ CO 2 ] [ MeOH ]
1 0.5

with the reaction mechanism.

8) Study on application of membrane reactor in direct synthesis DMC from CO2 and CH3OH over CuKF/MgSiO catalyst (Chuan-Feng Li, Shun-He Zhong) (2003) ---Cu-KF/MgSiO catalyst is prepared. Mg4(OH)2CO3+HClO4 Mg(ClO4)2. Natrium was added to alcohol and turned into silica gel. The products are mixed and precipitate is filtered. Cu(NO3)2.3H2O (Cu) is used as Cu precursor. Calcination temperature 400C for 6h. ---P=1MPa., membrane catalytic reactors (hydrophilic properties where water is diffusing through) are found to be more effective than conversional catalytic reactors. 9) Catalytic and direct synthesis of dimethyl carbonate starting fromcarbon dioxide using CeO2-ZrO2 solid solution heterogeneous catalyst: effect of H2O removal from the reaction system (Keiichi Tomishige, Kimio Kunimori) (2002) --- CeO2-ZrO2 are used in different ratios for preparation of catalyst (calcinations temperature 1273K) ---P=6MPa, T=383K. DMP is added to remove water Different behaviours are observed at different DMP flow rates. Ce/(Ce+Zr)= 0.2-0.33is found to be optimum. 10) Novel reaction route for dimethyl carbonate synthesis from CO2 and methanol (Tiansheng Zhao , Yizhuo Han, Yuhan Sun) (2000) ---Metal acetates are used as precursor of catalysts (Na, Mn, Co, Ni, Cu, Zn, Hg). Ni is found to be the best of all. ---The reactions are performed near supercritical region; P=9.3MPa, T=305K

---Reaction mechanism is involved. 11) Supercritical Synthesis of Dimethyl Carbonate from CO 2 and Methanol (Tiansheng Zhao, Yizhuo Han, and Yuhan Sun) (2000) ---Ni acetates are used as the precursor of the catalyst. ---Supercritical conditions are used.(T=285K, optimum pressure 9.3MPa) 12) Selective and high yield synthesis of dimethyl carbonate directly from carbon dioxide and methanol (Jun-Chul Choi, Liang-Nian He, Hiroyuki Yasuda and Toshiyasu Sakakura) (2002) ---Bu2Sn(OMe)2 is used as the catalyst. ---The experimental consists of a reaction vessel (autoclave reactor) and molecular sieve 3A is used to dehydrate the system. Without the use of molecular sieve 3A, the DMC yield is zero order wrt catalyst amount. ---Supercritical conditions are used (T=180C, P=300atm) 13) Synthesis of dimethyl carbonate in supercritical carbon dioxide (D. BallivetTkatchenko, R. A. Ligabue, L. Plasseraud) (2006) ---Derivatives of n-butylmethoxytin are used in the reactions. n-Bu3SnOCH3 and n-Bu2Sn(OCH3)2 are synthesized from n-Bu3SnCl and n-Bu3SnCl2. [n-Bu2SnOCH3]2O is obtained from a mixture from n-Bu2SnO and n-Bu2Sn(OCH3)2 ---Supercritical conditions are used. Temperature at 423K and pressure between 9MPa to 20MPa, further increase in the pressure did not enhance the result of the reaction. ---Reaching supercritical conditions for the system suppresses the effects of mass transfer resistances. Under these conditions CO2 behaves like a reactant and solvent. Single phase is achieved with supercritical conditions. 14) Synthesis of dimethyl carbonate from methanol and carbon dioxide in the presence of polyoxometalates under mild conditions (Chunjie Jiang, Yihang Guo, Chungang Wang, Changwen Hua,, YueWu, Enbo Wang) (2003) ----WPA/ZrO2 composites with different WPA loaded catalysts are used. ZrOCl2.8H2O in EtOH is stirred at 343K and cooled to room temperature and pH of the solution is adjusted to 7 by using NH4OH, the solution is than added to WPA.12H2O (in

EtOH). Then water is added until gelling. After gelation the solids are filtered/dried and calcined at 573K for 4h. ---Acid sites are directly related to the reaction mechanism. Reaction conditions P=1MPa at T=343K-423K 15) Synthesis of dimethyl carbonate from methanol and carbon dioxide using potassium methoxide as catalyst under mild conditions (Qinghai Cai, Chao Jin, Bin Lu, Hejin Tangbo, Yongkui Shan) (2005) ---CH3OK is used as the catalyst in presence of CH3I which is used as a promoter in the reaction. ---K+CH3OH CH3OK (violent reaction) ---The reactions are performed under mild conditions (T=80C, P=7.3MPa). Two maxima occurred in yield vs. pressure graph; between 1.5-2MPa and 7-7.5MPa indicating that no higher pressures are needed. ---Reaction mechanism is proposed with determined reaction rate parameters (preexponential factor and activation energy). 1st order reaction wrt to CO2 concentration. 16) Catalytic Properties and Structure of Zirconia Catalysts for Direct Synthesis of Dimethyl Carbonate from Methanol and Carbon Dioxide (Keiichi Tomishige, Yoshiki Ikeda, Tomohiro Sakaihori, and Kaoru Fujimoto) (2000) ---Zr catalysts are obtained by calcining ZrO2. xH2O at different temperatures between T=388Kand 1073K (3h, in air) and used in the reaction. ---Reactions are performed in autoclave reactors at a pressure of 5MPa between 413K to 463K. ---DMC formation has a maxima at a calcinations temperature of 673K. ---Reaction mechanism is involved. Rate determining step is the activation of MeOH on the acid sites, which brings the need to acidic properties of the catalysts.