Return to DOE Report Table of Contents

Hydrogenation of Carbon Monoxide to Alkenes. A Critical Review of Theoretical Considerations and Processes - 1986

R. Snel

Council for Scientific and Industrial Research

In this pdf format, this document has 124 pages and is 6.07MB.

Table of Contents

1

 Introduction

4
2 Limitations on the selective production of olefins from Syngas 6
2.1 Economic constraints 6
2.2 Thermodynamic constraints 8
2.3 Kinetic constraints 12
2.3.1 Reaction kinetics 12
2.3.2 Polymerization kinetics 15
2.4 Contraints caused by methanation and carbon deposition 20
3 Chemisorption of the components of Syngas 25
3.1 Bonding interactions in syngas chemisorption 25
3.1.1 Chemisorption of hydrogen and carbon monoxide on transition metal surfaces 26
3.1.2 Influence of additives 32
3.1.3 Co-adsorption of hydrogen and carbon monoxide 36
3.2 The role of the electronic interaction principle and geometric principle in the chemisorption behavior of syngas 37
3.2.1 Catalyst basicity 37
3.2.2 Electron withdrawl ligand effect 41
3.2.3 Catalyst dispersion 41
3.2.4 Support interactions 45
4 Factors Affecting the Olefin Selectivity 48
4.1 Catalyst basicity effect 52
4.2 Catalyst dispersion effect 57
4.2.1 Zeolite ion exchange 59
4.2.2 Degradation of metal carbonyl clusters 59
4.2.3 Degradation of metal complexes 68
4.2.4 Formation of metal whiskers 69
4.2.5 Dispersion by solvated metal atoms 70
4.2.6 Dispersion by alloys 70
4.2.7 Support-induced dispersion 73
4.3 Electron withdrawl ligand effect 73
4.4 Support interactions 74
4.4.1 Support basically effect 74
4.4.2 Support dispersion effect 76
4.4.3 Schwab effect 78
4.4.4 Strong metal support interaction (SMSI) effects 79
4.4.5 Effect of matrix support effects 86
4.4.6 Geometric support effects 86
4.5 Demetallization of transition metals 87
4.6 Geometric effects 88
4.7 Promoters claimed to increase olefin selectivity in iron catalysts 88
5 Processes for the production of lower olefins 92
5.1 Fischer-Tropsch-based processes 92
5.1.1 The Synthol process 92
5.1.2 Liquid-phase synthesis 92
5.1.3 Modified Fischer-Tropsch processes for olefin production 94
5.2 Catalytic conversion of methanol 98
5.3 Indirect ethene production through ethanol 99
5.3.1 Through homologation and subsequent dehydration 99
5.3.2 Through direct ethanol production from syngas and subsequent dehydration 100
5.4 Indirect alkene production through mixed alcohols 100
6 Concluding Remarks 100
7 References 102