Carbon Dioxide Recovery and Utilization is a complete and informative resource on the carbon dioxide sources and market at the European Union level, with reference to the world situation. The book covers the following themes: - Sources of carbon dioxide and their purity, - Market of carbon dioxide and its uses, - Separation techniques of carbon dioxide from flue gases, - Analysis of the potential of each technique and application, - Basic science and technology of supercritical CO2, - Reactions in supercritical CO2 and its use as reactive solvent, - Utilization of CO2 in the synthesis of chemicals with low energy input, - Conversion of CO2 into fuels: existing techniques, - Dry reforming of methane, - Assessment of the use of carbon dioxide for the synthesis of methanol. This book is unique in providing integrated information and a perspective on innovative technologies for the use of carbon dioxide. The book is suitable for use as a textbook for courses in chemical engineering and chemistry. It is also of great interest as a general reference for those involved with technologies for avoiding carbon dioxide production and for economists. This is an invaluable reference for specialists on synthetic chemistry, gas separation, supercritical fluids, carbon dioxide marketing, renewable energy and sustainable development. In addition, it will be useful for those working in the chemical industry and for policy makers for carbon dioxide mitigation, innovative technologies, carbon recycling, and power generation.

Proceedings of the NATO Advanced Study Institute, Pugnochiuso, Italy, June 22-July 3, 1986

Carbon Dioxide Recovery and Utilization is a complete and informative resource on the carbon dioxide sources and market at the European Union level, with reference to the world situation. The book covers the following themes: - Sources of carbon dioxide and their purity, - Market of carbon dioxide and its uses, - Separation techniques of carbon dioxide from flue gases, - Analysis of the potential of each technique and application, - Basic science and technology of supercritical CO2, - Reactions in supercritical CO2 and its use as reactive solvent, - Utilization of CO2 in the synthesis of chemicals with low energy input, - Conversion of CO2 into fuels: existing techniques, - Dry reforming of methane, - Assessment of the use of carbon dioxide for the synthesis of methanol. This book is unique in providing integrated information and a perspective on innovative technologies for the use of carbon dioxide. The book is suitable for use as a textbook for courses in chemical engineering and chemistry. It is also of great interest as a general reference for those involved with technologies for avoiding carbon dioxide production and for economists. This is an invaluable reference for specialists on synthetic chemistry, gas separation, supercritical fluids, carbon dioxide marketing, renewable energy and sustainable development. In addition, it will be useful for those working in the chemical industry and for policy makers for carbon dioxide mitigation, innovative technologies, carbon recycling, and power generation.

The activation of carbon dioxide by transition metal complexes has been extensively studied. both experimentally and theoretically. 1 Central reactions in this chemistry are the insertion of C02 into M-X bonds. where X = H. C. 0. and N. (eq. 1-4). We are presently investigating the mechanistic aspects of these reaction processes and will herein deSCribe our current level of understanding. Comparisons of the pathway of the carbon-carbon bond fonning process in transition metal chemistry with the well known analogous chemistry involving organolithium reagents will be presented. Furthermore. the role of these reaction types in both homogeneous and heterogenous catalytic processes leading to useful chemicals will be elaborated. _OM> (1) lMt-H + ~ lMlopi _OM> (2) [Mt-R + C0. 2 [M]0. 2CR _OM> (3) [Mt-OR+ ~ [M]0. 2COR _OM> (4) [Mt-NR2 + C0. 2 [M]~CNR2 Insertion of C02 into the Metal-Hydride Bond. The reaction of anionic group 6 (Cr. Mo. W) transition metal hydrides with carbon dioxide to afford metalloformates occurs readlly at ambient temperature and 2 reduced pressures of carbon dioxide. This insertion process is referred to the normal pathway (Scheme 1). There are no documented cases of C02 insertion into the metal hydride bond to provide the alternative. metallocarboxylic acid. isomer (referred in Scheme 1 as abnormal). 3 Recent theoretical studies ascribe this preference to an unfavorable electrostatic interaction and poorer orbital overlap in the latter pro­ 4 cess. Nevertheless.

The activation of carbon dioxide by transition metal complexes has been extensively studied. both experimentally and theoretically. 1 Central reactions in this chemistry are the insertion of C02 into M-X bonds. where X = H. C. 0. and N. (eq. 1-4). We are presently investigating the mechanistic aspects of these reaction processes and will herein deSCribe our current level of understanding. Comparisons of the pathway of the carbon-carbon bond fonning process in transition metal chemistry with the well known analogous chemistry involving organolithium reagents will be presented. Furthermore. the role of these reaction types in both homogeneous and heterogenous catalytic processes leading to useful chemicals will be elaborated. _OM> (1) lMt-H + ~ lMlopi _OM> (2) [Mt-R + C0. 2 [M]0. 2CR _OM> (3) [Mt-OR+ ~ [M]0. 2COR _OM> (4) [Mt-NR2 + C0. 2 [M]~CNR2 Insertion of C02 into the Metal-Hydride Bond. The reaction of anionic group 6 (Cr. Mo. W) transition metal hydrides with carbon dioxide to afford metalloformates occurs readlly at ambient temperature and 2 reduced pressures of carbon dioxide. This insertion process is referred to the normal pathway (Scheme 1). There are no documented cases of C02 insertion into the metal hydride bond to provide the alternative. metallocarboxylic acid. isomer (referred in Scheme 1 as abnormal). 3 Recent theoretical studies ascribe this preference to an unfavorable electrostatic interaction and poorer orbital overlap in the latter pro­ 4 cess. Nevertheless.

Proceedings of the NATO Advanced Study Institute, Pugnochiuso, Italy, June 22-July 3, 1986

Carbon Dioxide Recovery and Utilization is a complete and informative resource on the carbon dioxide sources and market at the European Union level, with reference to the world situation. The book covers the following themes: - Sources of carbon dioxide and their purity, - Market of carbon dioxide and its uses, - Separation techniques of carbon dioxide from flue gases, - Analysis of the potential of each technique and application, - Basic science and technology of supercritical CO2, - Reactions in supercritical CO2 and its use as reactive solvent, - Utilization of CO2 in the synthesis of chemicals with low energy input, - Conversion of CO2 into fuels: existing techniques, - Dry reforming of methane, - Assessment of the use of carbon dioxide for the synthesis of methanol. This book is unique in providing integrated information and a perspective on innovative technologies for the use of carbon dioxide. The book is suitable for use as a textbook for courses in chemical engineering and chemistry. It is also of great interest as a general reference for those involved with technologies for avoiding carbon dioxide production and for economists. This is an invaluable reference for specialists on synthetic chemistry, gas separation, supercritical fluids, carbon dioxide marketing, renewable energy and sustainable development. In addition, it will be useful for those working in the chemical industry and for policy makers for carbon dioxide mitigation, innovative technologies, carbon recycling, and power generation.

Proceedings of the NATO Advanced Study Institute, Pugnochiuso, Italy, June 22-July 3, 1986

Carbon Dioxide Recovery and Utilization is a complete and informative resource on the carbon dioxide sources and market at the European Union level, with reference to the world situation. The book covers the following themes: - Sources of carbon dioxide and their purity, - Market of carbon dioxide and its uses, - Separation techniques of carbon dioxide from flue gases, - Analysis of the potential of each technique and application, - Basic science and technology of supercritical CO2, - Reactions in supercritical CO2 and its use as reactive solvent, - Utilization of CO2 in the synthesis of chemicals with low energy input, - Conversion of CO2 into fuels: existing techniques, - Dry reforming of methane, - Assessment of the use of carbon dioxide for the synthesis of methanol. This book is unique in providing integrated information and a perspective on innovative technologies for the use of carbon dioxide. The book is suitable for use as a textbook for courses in chemical engineering and chemistry. It is also of great interest as a general reference for those involved with technologies for avoiding carbon dioxide production and for economists. This is an invaluable reference for specialists on synthetic chemistry, gas separation, supercritical fluids, carbon dioxide marketing, renewable energy and sustainable development. In addition, it will be useful for those working in the chemical industry and for policy makers for carbon dioxide mitigation, innovative technologies, carbon recycling, and power generation.

The activation of carbon dioxide by transition metal complexes has been extensively studied. both experimentally and theoretically. 1 Central reactions in this chemistry are the insertion of C02 into M-X bonds. where X = H. C. 0. and N. (eq. 1-4). We are presently investigating the mechanistic aspects of these reaction processes and will herein deSCribe our current level of understanding. Comparisons of the pathway of the carbon-carbon bond fonning process in transition metal chemistry with the well known analogous chemistry involving organolithium reagents will be presented. Furthermore. the role of these reaction types in both homogeneous and heterogenous catalytic processes leading to useful chemicals will be elaborated. _OM> (1) lMt-H + ~ lMlopi _OM> (2) [Mt-R + C0. 2 [M]0. 2CR _OM> (3) [Mt-OR+ ~ [M]0. 2COR _OM> (4) [Mt-NR2 + C0. 2 [M]~CNR2 Insertion of C02 into the Metal-Hydride Bond. The reaction of anionic group 6 (Cr. Mo. W) transition metal hydrides with carbon dioxide to afford metalloformates occurs readlly at ambient temperature and 2 reduced pressures of carbon dioxide. This insertion process is referred to the normal pathway (Scheme 1). There are no documented cases of C02 insertion into the metal hydride bond to provide the alternative. metallocarboxylic acid. isomer (referred in Scheme 1 as abnormal). 3 Recent theoretical studies ascribe this preference to an unfavorable electrostatic interaction and poorer orbital overlap in the latter pro­ 4 cess. Nevertheless.

The activation of carbon dioxide by transition metal complexes has been extensively studied. both experimentally and theoretically. 1 Central reactions in this chemistry are the insertion of C02 into M-X bonds. where X = H. C. 0. and N. (eq. 1-4). We are presently investigating the mechanistic aspects of these reaction processes and will herein deSCribe our current level of understanding. Comparisons of the pathway of the carbon-carbon bond fonning process in transition metal chemistry with the well known analogous chemistry involving organolithium reagents will be presented. Furthermore. the role of these reaction types in both homogeneous and heterogenous catalytic processes leading to useful chemicals will be elaborated. _OM> (1) lMt-H + ~ lMlopi _OM> (2) [Mt-R + C0. 2 [M]0. 2CR _OM> (3) [Mt-OR+ ~ [M]0. 2COR _OM> (4) [Mt-NR2 + C0. 2 [M]~CNR2 Insertion of C02 into the Metal-Hydride Bond. The reaction of anionic group 6 (Cr. Mo. W) transition metal hydrides with carbon dioxide to afford metalloformates occurs readlly at ambient temperature and 2 reduced pressures of carbon dioxide. This insertion process is referred to the normal pathway (Scheme 1). There are no documented cases of C02 insertion into the metal hydride bond to provide the alternative. metallocarboxylic acid. isomer (referred in Scheme 1 as abnormal). 3 Recent theoretical studies ascribe this preference to an unfavorable electrostatic interaction and poorer orbital overlap in the latter pro­ 4 cess. Nevertheless.

Proceedings of the NATO Advanced Study Institute, Pugnochiuso, Italy, June 22-July 3, 1986