112
5.3.4 Photocatalytic Hydrogenation of Carbon Dioxide to Methanol
in the Gas Phase
125
5.3.5 Kinetic Study of the Hydrogenation of Carbon Dioxide to Methanol
in the Gas Phase
127
5.3.6 Mechanistic Study of the Hydrogenation of Carbon Dioxide to Methanol
in the Gas Phase
131
5.4 Selective Hydrogenation of Carbon Dioxide to Methanol in the Liquid Phase:
Homogeneous Catalysis
133
5.4.1 Introduction
133
5.4.2 Transition Metal Catalysts
133
5.4.3 Metal-Free Homogeneous Catalysts
135
5.4.4 Photocatalytic Hydrogenation of Carbon Dioxide to Methanol
in the Liquid Phase
136
5.4.5 Mechanism Study
137
5.5 Selective Hydrogenation of Carbon Dioxide into Methanol: Examples
of Industrial Pilot Production
143
5.6 Conclusions
147
References
147
Abstract This chapter is dedicated to methanol synthesis from carbon dioxide and
hydrogen. Methanol, chemical formula CH 3 OH, is an important platform molecule
which can be transformed into a large number of other chemicals, i.e., formaldehyde,
acetic acid, dimethyl ether, methyl tert-butyl ether, and methyl methacrylate, as well as
complex hydrocarbon mixtures, e.g., gasoline and diesel. Up to date, methanol is produced at industrial scale by steam reforming of natural gas, leading to high environmental impacts. The selective hydrogenation of carbon dioxide into methanol can be a
good alternative since it is possible to capture carbon dioxide from industrial processes
and to produce hydrogen from renewable energies, e.g., solar energy and wind energy.
From a thermodynamic point of view, carbon dioxide hydrogenation is strongly
influenced by the total pressure, temperature, and feeding composition. The use of a
catalyst is also mandatory to control the kinetic and the selectivity into methanol.
Among solid catalysts studied, copper-based catalysts have been found to be the best
catalytic systems. Promoters like zinc oxide were usually used. Nickel-, palladium-,
and silver-based catalysts also showed good catalytic performance compared to copper-based catalysts. Soluble catalysts have been intensively studied for this hydrogeL. Chen
Materials Science and Chemical Engineering, Stony Brook University,
Stony Brook, NY, USA
e-mail: lyufei.chen@stonybrook.edu
S. Singh
Faculty of Chemical and Natural Resources Engineering, Universiti Malaysia Pahang,
Gambang, Kuantan, Pahang, Malaysia
D.-V. N. Vo
Center of Excellence for Green Energy and Environmental Nanomaterials (CE@GrEEN),
Nguyen Tat Thanh University, Ho Chi Minh City, Vietnam
Faculty of Chemical and Natural Resources Engineering, Universiti Malaysia Pahang,
Gambang, Kuantan, Pahang, Malaysia
D. P. Minh et al.
5.3.4 Photocatalytic Hydrogenation of Carbon Dioxide to Methanol
in the Gas Phase
125
5.3.5 Kinetic Study of the Hydrogenation of Carbon Dioxide to Methanol
in the Gas Phase
127
5.3.6 Mechanistic Study of the Hydrogenation of Carbon Dioxide to Methanol
in the Gas Phase
131
5.4 Selective Hydrogenation of Carbon Dioxide to Methanol in the Liquid Phase:
Homogeneous Catalysis
133
5.4.1 Introduction
133
5.4.2 Transition Metal Catalysts
133
5.4.3 Metal-Free Homogeneous Catalysts
135
5.4.4 Photocatalytic Hydrogenation of Carbon Dioxide to Methanol
in the Liquid Phase
136
5.4.5 Mechanism Study
137
5.5 Selective Hydrogenation of Carbon Dioxide into Methanol: Examples
of Industrial Pilot Production
143
5.6 Conclusions
147
References
147
Abstract This chapter is dedicated to methanol synthesis from carbon dioxide and
hydrogen. Methanol, chemical formula CH 3 OH, is an important platform molecule
which can be transformed into a large number of other chemicals, i.e., formaldehyde,
acetic acid, dimethyl ether, methyl tert-butyl ether, and methyl methacrylate, as well as
complex hydrocarbon mixtures, e.g., gasoline and diesel. Up to date, methanol is produced at industrial scale by steam reforming of natural gas, leading to high environmental impacts. The selective hydrogenation of carbon dioxide into methanol can be a
good alternative since it is possible to capture carbon dioxide from industrial processes
and to produce hydrogen from renewable energies, e.g., solar energy and wind energy.
From a thermodynamic point of view, carbon dioxide hydrogenation is strongly
influenced by the total pressure, temperature, and feeding composition. The use of a
catalyst is also mandatory to control the kinetic and the selectivity into methanol.
Among solid catalysts studied, copper-based catalysts have been found to be the best
catalytic systems. Promoters like zinc oxide were usually used. Nickel-, palladium-,
and silver-based catalysts also showed good catalytic performance compared to copper-based catalysts. Soluble catalysts have been intensively studied for this hydrogeL. Chen
Materials Science and Chemical Engineering, Stony Brook University,
Stony Brook, NY, USA
e-mail: lyufei.chen@stonybrook.edu
S. Singh
Faculty of Chemical and Natural Resources Engineering, Universiti Malaysia Pahang,
Gambang, Kuantan, Pahang, Malaysia
D.-V. N. Vo
Center of Excellence for Green Energy and Environmental Nanomaterials (CE@GrEEN),
Nguyen Tat Thanh University, Ho Chi Minh City, Vietnam
Faculty of Chemical and Natural Resources Engineering, Universiti Malaysia Pahang,
Gambang, Kuantan, Pahang, Malaysia
D. P. Minh et al.