113
nation. Ru complexes appeared as the best homogeneous catalyst. Other metal-free
homogeneous catalysts, e.g., N-heterocyclic carbenes, have been found to be active
and selective in this reaction. Efforts have been made on the mechanistic study of the
reaction in both the gas and liquid phases. Large industrial production has started
in several countries showing the interest and the feasibility of the process.
Keywords Carbon dioxide · Methanol · Hydrogenation · Heterogeneous
catalysis · Photocatalysis · Homogeneous catalysis · Selectivity · Kinetic study ·
Mechanism study · Pilot production
Abbreviations
Me
methyl group or CH 3 −
MEFCO2
methanol fuel from CO 2
mV
millivolts
phen
phenanthroline
PNN ligands phosphorus–nitrogen–nitrogen pincer ligands
ptpbα
pyrido[2,3:5,6]pyrazino[2,3-f][1,10]phenanthroline
ptpbβ
pyrido[3,4,5,6]pyrazino[2,3-f][1,10]phenanthroline
Ru(acac) 3
ruthenium(III) acetylacetonate
SPIRE
Sustainable Process Industry through Resource and Energy
Efficiency
TMM
trimethylenemethane
Triphos
1,1,1-tris(diphenylphosphinomethyl)ethane
μM
micromole per litre or 10
−6
mole per litre
5.1 Introduction
Methanol, chemical formula CH 3 OH, is among the most important chemicals
thanks to its versatility. As summarized in Fig. 5.1, methanol can be used for producing a large number of chemicals like formaldehyde, acetic acid, dimethyl ether,
methyl tert-butyl ether, and methyl methacrylate, as well as complex hydrocarbons
mixtures, e.g., gasoline and diesel. These are used in various sectors of building,
electronics, painting, insulation, pharmaceutic, packaging, and automotive, among
others (Dalena et al. 2018; Leonzio 2018). The world production of methanol
reached around 38 and 95 millions of tons in 2006 and 2016 (Methanol Institute
2019), respectively, demonstrating its highly increasing production rate and the
interest in studying this molecule.
To date, coal and natural gas are the two main feedstocks for methanol production at the large industrial scale (Dalena et al. 2018; Methanol Institute 2019). Coal
5 Selective Hydrogenation of Carbon Dioxide into Methanol
nation. Ru complexes appeared as the best homogeneous catalyst. Other metal-free
homogeneous catalysts, e.g., N-heterocyclic carbenes, have been found to be active
and selective in this reaction. Efforts have been made on the mechanistic study of the
reaction in both the gas and liquid phases. Large industrial production has started
in several countries showing the interest and the feasibility of the process.
Keywords Carbon dioxide · Methanol · Hydrogenation · Heterogeneous
catalysis · Photocatalysis · Homogeneous catalysis · Selectivity · Kinetic study ·
Mechanism study · Pilot production
Abbreviations
Me
methyl group or CH 3 −
MEFCO2
methanol fuel from CO 2
mV
millivolts
phen
phenanthroline
PNN ligands phosphorus–nitrogen–nitrogen pincer ligands
ptpbα
pyrido[2,3:5,6]pyrazino[2,3-f][1,10]phenanthroline
ptpbβ
pyrido[3,4,5,6]pyrazino[2,3-f][1,10]phenanthroline
Ru(acac) 3
ruthenium(III) acetylacetonate
SPIRE
Sustainable Process Industry through Resource and Energy
Efficiency
TMM
trimethylenemethane
Triphos
1,1,1-tris(diphenylphosphinomethyl)ethane
μM
micromole per litre or 10
−6
mole per litre
5.1 Introduction
Methanol, chemical formula CH 3 OH, is among the most important chemicals
thanks to its versatility. As summarized in Fig. 5.1, methanol can be used for producing a large number of chemicals like formaldehyde, acetic acid, dimethyl ether,
methyl tert-butyl ether, and methyl methacrylate, as well as complex hydrocarbons
mixtures, e.g., gasoline and diesel. These are used in various sectors of building,
electronics, painting, insulation, pharmaceutic, packaging, and automotive, among
others (Dalena et al. 2018; Leonzio 2018). The world production of methanol
reached around 38 and 95 millions of tons in 2006 and 2016 (Methanol Institute
2019), respectively, demonstrating its highly increasing production rate and the
interest in studying this molecule.
To date, coal and natural gas are the two main feedstocks for methanol production at the large industrial scale (Dalena et al. 2018; Methanol Institute 2019). Coal
5 Selective Hydrogenation of Carbon Dioxide into Methanol