Review for the Direct Synthesis of Dimethyl Carbonate

This review summarizes the state-of-the-art for direct synthesis of dimethyl carbonate (DMC) from carbon dioxide and methanol. In addition, conventional and alternative processes are also discussed in order to understand the advantages and disadvantages of the direct synthesis of DMC. Furthermore, the major applications of DMC are described: solvent, fuels additive, and building block for organic synthesis. The major drawbacks of the direct synthesis of DMC are the low yield and reaction rate, mostly induced by the highly stable carbon dioxide molecules. The development of novel catalyst and strategies to enhance the DMC yield – such as dehydrating agents that remove the water from the reacting mixture – are pointed out as the key solution for this route. Therefore, the main catalysts (homogeneous and heterogeneous catalysts) used so far are presented, together with the respective operating conditions and catalyst performance. The use of different dehydrating agents to increase the DMC yield is also discussed.

[1]  K. Tomishige,et al.  Catalytic CO2 conversion to organic carbonates with alcohols in combination with dehydration system , 2014 .

[2]  Kenji Nakao,et al.  Direct Cyclic Carbonate Synthesis from CO2 and Diol over Carboxylation/Hydration Cascade Catalyst of CeO2 with 2-Cyanopyridine , 2014 .

[3]  Yanji Wang,et al.  Highly efficient catalyst PdCl2–CuCl2–KOAc/AC@Al2O3 for gas-phase oxidative carbonylation of methanol to dimethyl carbonate: Preparation and reaction mechanism , 2014 .

[4]  Yuhan Sun,et al.  Synthesis of dimethyl carbonate by urea alcoholysis over Zn/Al bi-functional catalysts , 2014 .

[5]  Yu Na Lim,et al.  Metal‐Free Synthesis of Cyclic and Acyclic Carbonates from CO2 and Alcohols , 2014 .

[6]  Z. Zuo,et al.  A theoretical investigation on the mechanism of dimethyl carbonate formation on Cu/AC catalyst , 2014 .

[7]  Ting Qiu,et al.  Novel Procedure for the Synthesis of Dimethyl Carbonate by Reactive Distillation , 2014 .

[8]  Yuan-xin Wu,et al.  Surface structure and reaction property of CuCl2-PdCl2 bimetallic catalyst in methanol oxycarbonylation: A DFT approach , 2014 .

[9]  Yuhan Sun,et al.  Dimethyl carbonate synthesis over ZnO–CaO bi-functional catalysts , 2014 .

[10]  Subodh Kumar,et al.  An easy base-assisted synthesis of unsymmetrical carbonates from alcohols with dimethyl carbonate , 2014, Monatshefte für Chemie - Chemical Monthly.

[11]  Kun Liu,et al.  High-yield synthesis of dimethyl carbonate from the direct alcoholysis of urea in supercritical methanol , 2014 .

[12]  Philip Lutze,et al.  Synthesis of dimethyl carbonate and propylene glycol by transesterification of propylene carbonate with methanol: Catalyst screening, chemical equilibrium and reaction kinetics , 2013 .

[13]  Li-Wang Su,et al.  Flow chart of methanol in China , 2013 .

[14]  Zhanyang Gao,et al.  Highly efficient enzymatic preparation for dimethyl carbonate catalyzed by lipase from Penicillium expansum immobilized on CMC–PVA film , 2013 .

[15]  Jingxiang Zhao,et al.  Electrochemical conversion of CO2 into dimethyl carbonate in a functionalized ionic liquid , 2013 .

[16]  Yuan-Zhao Ji,et al.  Catalytic methyl transfer from dimethylcarbonate to carboxylic acids. , 2013, The Journal of organic chemistry.

[17]  Jingxiang Zhao,et al.  A functionalized basic ionic liquid for synthesis of dimethyl carbonate from methanol and CO2 , 2013 .

[18]  A. Konnov,et al.  Laminar Burning Velocities of Dimethyl Carbonate with Air , 2013 .

[19]  Chang-jiang Guo,et al.  Synthesis of dimethyl carbonate over starch-based Carbon-supported Cu nanoparticles catalysts , 2013 .

[20]  Yoshinao Nakagawa,et al.  Ceria-catalyzed conversion of carbon dioxide into dimethyl carbonate with 2-cyanopyridine. , 2013, ChemSusChem.

[21]  D. Wu,et al.  Synthesis of Phenylethenyl Methyl Carbonate by Methoxycarbonylation of Phenylacetaldehyde with Dimethyl Carbonate , 2013 .

[22]  李玲玲,et al.  H-ZSM-5催化甲苯与碳酸二甲酯和甲醇甲基化的反应机理 , 2013 .

[23]  E. Molins,et al.  Boosted CO2 reaction with methanol to yield dimethyl carbonate over Mg-Al hydrotalcite-silica lyogels. , 2013, Chemical communications.

[24]  Hong Wang,et al.  Electrosynthesis of Dimethyl Carbonate from Methanol and Carbon Monoxide under Mild Conditions , 2013 .

[25]  Ying-jie Zhou,et al.  Effects of Mo promoters on the Cu–Fe bimetal catalysts for the DMC formation from CO2 and methanol , 2013 .

[26]  A. Rodrigues,et al.  Kinetic study for the direct synthesis of dimethyl carbonate from methanol and CO2 over CeO2 at high pressure conditions , 2013 .

[27]  Songping D. Huang,et al.  A novel synthetic approach for preparing dimethyl carbonate from dimethoxymethane and O2 over Cu-MCM-48 , 2013 .

[28]  B. Cheng,et al.  Study on the reaction between bisphenol A and dimethyl carbonate over organotin oxide , 2013 .

[29]  M. Xiao,et al.  Direct Synthesis of Dimethyl Carbonate from CO2 and CH3OH Using 0.4 nm Molecular Sieve Supported Cu-Ni Bimetal Catalyst , 2012 .

[30]  Ung Gi Hong,et al.  Synthesis of dimethyl carbonate from urea and methanol over ZnO(X)–CeO2(1 − X) catalysts prepared by a sol–gel method , 2012 .

[31]  P. Claus,et al.  CO2‐Folgechemie: Direktsynthese von Dimethylcarbonat durch Carboxylierung von Methanol an Cer‐basierten Mischoxiden , 2011 .

[32]  G. Rodeheaver,et al.  Isocyanate-functional adhesives for biomedical applications. Biocompatibility and feasibility study for vascular closure applications. , 2011, Journal of biomedical materials research. Part B, Applied biomaterials.

[33]  Yuhan Sun,et al.  Recent progress in phosgene-free methods for synthesis of dimethyl carbonate , 2011 .

[34]  D. Murzin,et al.  Kinetics of dimethyl carbonate synthesis from methanol and carbon dioxide over ZrO2–MgO catalyst in the presence of butylene oxide as additive , 2011 .

[35]  D. Murzin,et al.  The Effect of Alkoxide Ionic Liquids on the Synthesis of Dimethyl Carbonate from CO2 and Methanol over ZrO2–MgO , 2011 .

[36]  I. Song,et al.  Direct synthesis of dimethyl carbonate from methanol and carbon dioxide over H3PW12O40/CeXZr1−XO2 catalysts: Effect of acidity of the catalysts , 2011 .

[37]  Yoshinao Nakagawa,et al.  Tandem Carboxylation‐Hydration Reaction System from Methanol, CO2 and Benzonitrile to Dimethyl Carbonate and Benzamide Catalyzed by CeO2 , 2011 .

[38]  I. Song,et al.  Direct Synthesis of Dimethyl Carbonate from Methanol and Carbon Dioxide over Ga2O3/Ce0.6Zr0.4O2 Catalysts: Effect of Acidity and Basicity of the Catalysts , 2011 .

[39]  K. Xie,et al.  Structural feature and catalytic performance of Cu―SiO2―TiO2 cogelled xerogel catalysts for oxidative carbonylation of methanol to dimethyl carbonate , 2011 .

[40]  A. Mohamed,et al.  Optimization of supercritical dimethyl carbonate (SCDMC) technology for the production of biodiesel and value-added glycerol carbonate , 2010 .

[41]  D. Luan,et al.  Direct synthesis of dimethyl carbonate over activated carbon supported Cu-based catalysts , 2010 .

[42]  D. Ballivet-Tkatchenko,et al.  Carbon dioxide conversion to dimethyl carbonate: The effect of silica as support for SnO2 and ZrO2 catalysts , 2010 .

[43]  D. Murzin,et al.  Synthesis of dimethyl carbonate from methanol and carbon dioxide : Circumventing thermodynamic limitations , 2010 .

[44]  Z. Al-Othman,et al.  Direct synthesis of dimethyl carbonate from methanol and carbon dioxide using heteropolyoxometalates: the effects of cation and addenda atoms , 2010 .

[45]  K. Tomishige,et al.  Catalytic synthesis of dialkyl carbonate from low pressure CO2 and alcohols combined with acetonitrile hydration catalyzed by CeO2 , 2010 .

[46]  Athanasios Tsolakis,et al.  A Comparison of Diesel and Biodiesel Emissions Using Dimethyl Carbonate as an Oxygenated Additive , 2010 .

[47]  Z. Al-Othman,et al.  Gas-Phase Synthesis of Dimethyl Carbonate from Methanol and Carbon Dioxide Over Co1.5pw12o40 Keggin-Type Heteropolyanion , 2010, International journal of molecular sciences.

[48]  A. Börner,et al.  Organic carbonates as solvents in synthesis and catalysis. , 2010, Chemical reviews.

[49]  N. Keller,et al.  Catalysts, mechanisms and industrial processes for the dimethylcarbonate synthesis , 2010 .

[50]  A. Kochel Solvothermal synthesis, characterization and properties of [ReCl5(py)]− complex with T (Néel) of 5.5 K , 2010 .

[51]  W. Fan,et al.  Organotin compounds immobilized on mesoporous silicas as heterogeneous catalysts for direct synthesis of dimethyl carbonate from methanol and carbon dioxide , 2010 .

[52]  G. Stoica,et al.  Na-dawsonite derived aluminates for DMC production by transesterification of ethylene carbonate , 2009 .

[53]  K. Tomishige,et al.  Low pressure CO(2) to dimethyl carbonate by the reaction with methanol promoted by acetonitrile hydration. , 2009, Chemical communications.

[54]  Juliana Garcia Moretz-Sohn Monteiro,et al.  Sustainability metrics for eco-technologies assessment, part I: preliminary screening , 2009 .

[55]  T. Sakakura,et al.  The synthesis of organic carbonates from carbon dioxide. , 2009, Chemical communications.

[56]  S. Saka,et al.  Dimethyl carbonate as potential reactant in non-catalytic biodiesel production by supercritical method. , 2009, Bioresource technology.

[57]  Juliana Garcia Moretz-Sohn Monteiro,et al.  Sustainability metrics for eco-technologies assessment, Part II. Life cycle analysis , 2009 .

[58]  Yongsheng Guo,et al.  Effects of dimethyl or diethyl carbonate as an additive on volatility and flash point of an aviation fuel. , 2009, Journal of hazardous materials.

[59]  B. Lu,et al.  Studies on synthesis of dimethyl carbonate from methanol and carbon dioxide , 2009 .

[60]  B. Bhanage,et al.  Synthesis of dimethyl carbonate via transesterification of ethylene carbonate with methanol using poly-4-vinyl pyridine as a novel base catalyst , 2008 .

[61]  T. Sakakura,et al.  Tin- or titanium-catalyzed dimethyl carbonate synthesis from carbon dioxide and methanol: Large promotion by a small amount of triflate salts , 2008 .

[62]  T. Sakakura,et al.  Reaction of dibutyltin oxide with methanol under CO2 pressure relevant to catalytic dimethyl carbonate synthesis , 2008 .

[63]  T. Sakakura,et al.  Synthesis of dimethyl carbonate from carbon dioxide catalyzed by titanium alkoxides with polyether-type ligands. , 2008, ChemSusChem.

[64]  S. Chankeshwara Dimethyl Carbonate (DMC): A Versatile and Environmentally Benign Building Block , 2008 .

[65]  M. Xiao,et al.  Direct synthesis of dimethyl carbonate from carbon dioxide and methanol using supported copper (Ni, V, O) catalyst with photo-assistance , 2007 .

[66]  M. Aresta,et al.  Utilisation of CO2 as a chemical feedstock: opportunities and challenges. , 2007, Dalton transactions.

[67]  Hiroyuki Yasuda,et al.  Transformation of carbon dioxide. , 2007, Chemical reviews.

[68]  S. Baeck,et al.  Effect of acid–base properties of H3PW12O40/CexTi1−xO2 catalysts on the direct synthesis of dimethyl carbonate from methanol and carbon dioxide: A TPD study of H3PW12O40/CexTi1−xO2 catalysts , 2007 .

[69]  M. Sankar,et al.  Transesterification of cyclic carbonates with methanol at ambient conditions over tungstate-based solid catalysts , 2006 .

[70]  M. Voinov,et al.  Improved Synthesis of 1‐Hydroxy‐2,2,5,5‐tetramethyl‐3‐imidazoline 3‐Oxide (HTIO) , 2006 .

[71]  Ho-mu Lin,et al.  Synthesis of dimethyl carbonate from urea and methanol catalyzed by the metallic compounds at atmospheric pressure , 2006 .

[72]  K. Kunimori,et al.  Direct synthesis of organic carbonates from the reaction of CO2 with methanol and ethanol over CeO2 catalysts , 2006 .

[73]  R. Keiski,et al.  Direct synthesis of dimethyl carbonate with supercritical carbon dioxide: Characterization of a key organotin oxide intermediate , 2006 .

[74]  Chunshan Song Global challenges and strategies for control, conversion and utilization of CO2 for sustainable development involving energy, catalysis, adsorption and chemical processing , 2006 .

[75]  M. Xiao,et al.  Direct synthesis of dimethyl carbonate (DMC) using Cu-Ni/VSO as catalyst , 2006 .

[76]  C. Westbrook,et al.  Chemical kinetic modeling study of the effects of oxygenated hydrocarbons on soot emissions from diesel engines. , 2006, The journal of physical chemistry. A.

[77]  Ho-mu Lin,et al.  Synthesis of dimethyl carbonate from urea and methanol using polyphosphoric acid as catalyst , 2005 .

[78]  M. Xiao,et al.  Direct synthesis of dimethyl carbonate on H3PO4 modified V2O5 , 2005 .

[79]  K. Kunimori,et al.  Novel Route to Propylene Carbonate: Selective Synthesis from Propylene Glycol and Carbon Dioxide , 2004 .

[80]  T. Root,et al.  Kinetic studies of carbonylation of methanol to dimethyl carbonate over Cu+X zeolite catalyst , 2003 .

[81]  M. Shirai,et al.  Concurrent Synthesis of Dimethyl Carbonate and Ethylene Glycol via Transesterification of Ethylene Carbonate and Methanol Using Smectite Catalysts Containing Mg and/or Ni , 2002 .

[82]  K. Kunimori,et al.  Catalytic and direct synthesis of dimethyl carbonate starting from carbon dioxide using CeO2-ZrO2 solid solution heterogeneous catalyst: effect of H2O removal from the reaction system , 2002 .

[83]  A. Bell,et al.  Effects of Catalyst Phase Structure on the Elementary Processes Involved in the Synthesis of Dimethyl Carbonate from Methanol and Carbon Dioxide over Zirconia , 2002 .

[84]  Hiroyuki Yasuda,et al.  Selective and high yield synthesis of dimethyl carbonate directly from carbon dioxide and methanol , 2002 .

[85]  Pietro Tundo,et al.  The chemistry of dimethyl carbonate. , 2002, Accounts of chemical research.

[86]  J. Lemmon,et al.  Reaction of silicate minerals to form tetramethoxysilane. , 2002, Inorganic chemistry.

[87]  F. Rivetti,et al.  Developments in the production and application of dimethylcarbonate , 2001 .

[88]  Masahiko Arai,et al.  Synthesis of dimethyl carbonate and glycols from carbon dioxide, epoxides, and methanol using heterogeneous basic metal oxide catalysts with high activity and selectivity , 2001 .

[89]  M. Asadullah,et al.  Structure of the Active Sites on H3PO4/ZrO2 Catalysts for Dimethyl Carbonate Synthesis from Methanol and Carbon Dioxide , 2001 .

[90]  M. Asadullah,et al.  CeO2–ZrO2 Solid Solution Catalyst for Selective Synthesis of Dimethyl Carbonate from Methanol and Carbon Dioxide , 2001 .

[91]  M. Selva,et al.  Dimethylcarbonate for eco-friendly methylation reactions. , 2001, Chemosphere.

[92]  Heriberto Cabezas,et al.  The waste reduction (WAR) algorithm: environmental impacts, energy consumption, and engineering economics , 2000 .

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

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

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

[96]  Yuhan Sun,et al.  Novel reaction route for dimethyl carbonate synthesis from CO2 and methanol , 2000 .

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

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

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

[100]  Yoshio Ono,et al.  Catalysis in the Production and Reactions of Dimethyl Carbonate, an Environmentally Benign Building-Block , 1997 .

[101]  Christopher L. Marshall,et al.  Review of Dimethyl Carbonate (DMC) Manufacture and Its Characteristics as a Fuel Additive , 1997 .

[102]  Fredrik Bertilsson,et al.  CO2 utilization options, part II: Assessment of dimethyl carbonate production , 1996 .

[103]  K. Fujimoto,et al.  Direct synthesis of dimethyl carbonate from carbon dioxide and methanol catalyzed by base , 1996 .

[104]  J. Sundermeyer,et al.  Gas-phase oxycarbonylation of methanol for the synthesis of dimethyl carbonate using copper-based Supported Ionic Liquid Phase (SILP) catalysts , 2014 .

[105]  Zhong Li,et al.  Surface reactions of CuCl2 and HY zeolite during the preparation of CuY catalyst for the oxidative carbonylation of methanol , 2014 .

[106]  K. Tomishige,et al.  Direct conversion of CO2 with diols, aminoalcohols and diamines to cyclic carbonates, cyclic carbamates and cyclic ureas using heterogeneous catalysts , 2014 .

[107]  J. Bian,et al.  Graphene nanosheet as support of catalytically active metal particles in DMC synthesis , 2011 .

[108]  T. Meyer,et al.  Solar Fuels and Next Generation Photovoltaics: The UNC-CH Energy Frontier Research Center , 2011 .

[109]  V. V. Mahajani,et al.  Studies in transesterification of ethylene carbonate to dimethyl carbonate over Amberlyst A-21 catalyst , 2006 .

[110]  M. Arai,et al.  Synthesis of dimethyl carbonate and glycols from carbon dioxide, epoxides and methanol using heterogeneous Mg containing smectite catalysts: effect of reaction variables on activity and selectivity performance , 2003 .

[111]  Jae-Duck Kim,et al.  Synthesis of dimethyl carbonate from methanol and supercritical carbon dioxide , 2001 .

[112]  U. Romano,et al.  SYNTHESIS OF DIMETHYL CARBONATE FROM METHANOL, CARBON MONOXIDE, AND OXYGEN CATALYZED BY COPPER COMPOUNDS , 1981 .