Homogeneous Catalysis with Renewables (eBook)

Prof. Behr: Leader of the Chair of Technical Chemistry at TU Dortmund. Publications: - U. Onken, A. Behr, Chemische Prozesskunde, Lehrbuch der Technischen Chemie Band 3, Georg Thieme Verlag Stuttgart/New York, 1996 - M. Baerns, A. Behr, A. Brehm, J. Gmehling, H. Hofmann, U. Onken, A. Renken, Technische Chemie, Wiley-VCH, Weinheim, 1. Ed. 2006 - A. Behr, Angewandte homogene Katalyse, Wiley-VCH, Weinheim, 2008 - A. Behr, D. W. Agar, J. Jörissen, Einführung in die Technische Chemie, Spektrum Akademischer Verlag, Heidelberg, 2010 - A. Behr, P. Neubert, Applied Homogeneous Catalysis, Wiley-VCH, Weinheim, 2012 - M. Baerns, A. Behr, A. Brehm, J. Gmehling, O. Hinrichsen, U. Onken, R. Palkovits, A. Renken, Technische Chemie, Wiley-VCH, Weinheim, 2. Ed. 2013 - A. Behr, Einführung in die Chemie nachwachsender Rohstoffe, Spektrum Akademi-scher Verlag, Heidelberg, (in preparation) Dr. Vorholt: Ass. Prof. on the Chair of Technical Chemistry at TU Dortmund. Publications: - Contribution "Hydroformylation and Related Reactions of Renewable Resources" (A. Behr and A. J. Vorholt) in: Topics in Organometallic Chemistry, Eds.: M. A. R. Meier. B. M. Weckhuysen, P. C. A. Bruijnincx, Springer / Heidelberg, Vol. 39 (2012), 103-128 - Contribution “Oleochemistry” (A. Behr, A. J. Vorholt), in: Applied Homogeneous Catalysis with Organometallic Compounds, Eds.: B. Cornils, W. A. Herrmann, M. Beller, R. Paciello, Wiley-VCH, Weinheim, 2013 (in print)

Contents 6
1 Introduction 10
1.1 Advantages of Homogeneous Catalysis in Derivatisation of Renewables 10
1.2 Introduction into the Chemistry of Renewables 12
1.3 Introduction into the Main Groups of Renewables 14
1.3.1 Oleochemicals 14
1.3.2 Terpenes 16
1.3.3 Carbohydrates 19
1.3.4 Lignin 22
1.3.5 Peptides 23
1.3.6 Carbon Dioxide 24
References 26
General literature 26
Oleochemicals 26
Terpenes 27
Carbohydrates 27
Lignin 28
Peptides 28
Carbon dioxide 28
2 Hydrogenation of Renewables 29
2.1 Introduction 29
2.2 Hydrogenations of Carbon Dioxide 30
2.2.1 Interconversion of CO2/Formic Acid as Hydrogen Storage 35
2.2.2 Methanol 36
2.3 Lignin 38
2.4 Sugars 42
2.5 Fats 43
2.6 Conclusions 45
References 45
3 Hydroformylation of Renewables 49
3.1 Introduction 49
3.1.1 Mechanisms 49
3.1.2 Side Reactions 51
3.1.3 Catalyst Development in Industrial Hydroformylation Processes 53
3.2 Oleocompounds in Hydroformylation 54
3.2.1 Catalyst Development 54
3.2.2 Catalyst Recycling 57
3.2.3 Applications 61
3.3 Terpenes and Naturally Occurring Allylbenzenes 63
3.3.1 Catalyst Development 63
3.3.2 Catalyst Recycling 68
3.4 Conclusions 70
References 70
4 Amination of Renewables 73
4.1 Introduction 73
4.2 Carbohydrates 76
4.2.1 5-Hydroxymethylfurfural (HMF) 77
4.2.2 Levulinic Acid 77
4.2.3 Oils and Fats—Fatty Acid Esters 80
4.2.4 Terpenes 83
4.2.5 Myrcene 83
4.2.6 Citronellal 84
4.3 Conclusion 86
References 86
5 Telomerisation of Renewables 88
5.1 Introduction 88
5.2 Telomerisation Using Renewable Dienes 90
5.3 Telomerisation Using Renewable Nucleophiles 91
5.3.1 Lignin-Derived Phenols 91
5.3.2 Renewable Polyols 92
5.3.2.1 Glycerol 93
5.3.2.2 Sugars and Sugar-Derived Polyols 94
5.3.3 Telomerisation with CO2 95
5.4 Conclusion 96
References 96
6 Oxidation of Renewables 99
6.1 Introduction 99
6.2 Fatty Acids and Fatty Acid Derivatives 101
6.3 Terpenes and Terpene Alcohols 106
6.4 Lignin and Phenylpropanoids 108
6.5 Conclusions 109
References 110
7 Tandem Reactions with Renewables 113
7.1 Introduction 113
7.2 Tandem Reactions with Metathesis 116
7.2.1 Cross-Metathesis 116
7.2.2 Intramolecular Ring-Closing Metathesis 118
7.3 Tandem Reactions with Hydroformylations 118
7.3.1 Hydroformylation/Hydrogenation 119
7.3.2 Hydroformylation and C–O Bond Formation 120
7.3.2.1 Intermolecular Hydroformylation/Acetalisation 120
7.3.2.2 Intramolecular Hydroformylation/Lactolisation 122
7.3.3 Hydroformylation and C–C Bond Formation 124
7.3.3.1 Hydroformylation/Cyclisation 124
7.3.3.2 Hydroformylation/Alkylation 124
7.3.3.3 Hydroformylation/Aldol Condensation 125
7.3.3.4 Hydroformylation/Acyloin reaction 126
7.3.3.5 Hydroformylation/Arylation 126
7.3.4 Hydroaminomethylation for C–N Bond Formation 127
7.3.5 Alternative Syngas Resources for Hydroformylation 132
7.3.5.1 Reverse Water-Gas Shift Reaction (RWGS) 132
7.3.5.2 Formic Acid Decomposition 134
7.3.5.3 Polyol Degradation 136
7.4 Defunctionalisation—Overcoming Over-Functionalisation 137
7.4.1 Decarbonylative Dehydration 137
7.4.2 Glycerol Degradation 141
7.5 Isomerising Tandem Catalyses 142
7.5.1 Isomerising Metathesis 143
7.5.2 Isomerising Hydroformylation 145
7.5.3 Isomerising Hydroboration 147
7.5.4 Isomerising Trialkylsilylation 149
7.5.5 Isomerising Lactonisation 149
7.5.6 Isomerising Michael-Reactions 150
7.5.7 Isomerising Decarboxylation 151
7.5.8 Isomerising Transfer Hydrogenation 152
7.5.9 Isomerising Alkoxycarbonylations 152
References 156
8 Continuously Operated Telomerisations with Renewables in Miniplants 161
8.1 Telomerisation of Butadiene with Carbon Dioxide 162
8.2 Telomerisation of Butadiene with Glycerol 165
8.3 Telomerisation of Butadiene with Sucrose 166
References 167
9 Continuously Operated Cooligomerisation of Fatty Compounds with Ethylene 169
9.1 Introduction 169
9.1.1 Cooligomerisation of Fatty Compounds with Ethylene 170
9.2 Batch Investigations 170
9.2.1 Conjugation and Cooligomerisation in Laboratory Scale 170
9.2.2 Catalyst Recycling 172
9.2.3 Catalyst Leaching 173
9.2.4 Application of Ligands 173
9.3 Miniplant Investigations 175
9.3.1 Miniplant Concept for Continuous Operation 175
9.3.2 Miniplant Equipment 176
9.3.2.1 Vessels 176
9.3.3 Miniplant Operation in Continuous Manner 178
9.3.4 Hydrogenation 179
9.3.5 Optimised Miniplant Concept 179
References 182
10 Hydroamination and Telomerisation of ?-Myrcene 183
10.1 Introduction 183
10.2 Laboratory Experiments 185
10.2.1 Control of Reaction Pathways 185
10.2.2 Catalyst Recycling 187
10.3 Miniplant Investigations 188
10.3.1 Choice of Reactor 188
10.3.2 The Taylor-Couette Reactor 188
10.3.3 Design Aspects and Construction 190
10.3.4 Batch Experiments 191
10.3.5 Miniplant Concept 192
10.3.6 Continuous Experiments 193
10.4 Conclusion and Outlook 194
References 195
11 Continuously Operated Hydroformylation 196
11.1 Introduction 196
11.2 Batch Investigations: Catalyst Screening and Catalyst Recycling 197
11.3 Miniplant Process 200
11.3.1 Hydroformylation of Renewables in a Continuous Process 205
11.4 Conclusions 207
References 208
12 Future Developments in Homogenous Catalysis with Renewables 209
Index 211