Handbook of Green Chemistry, Volume 6: Ionic Liquids

Handbook of Green Chemistry, Volume 6: Ionic Liquids......Page 1
Contents......Page 2
Part I - Green Synthesis......Page 3
1.1 The Status Quo of Green Ionic Liquid Syntheses......Page 5
1.2 Ionic Liquid Preparations Evaluated for Greenness......Page 6
1.3 Which Principles of Green Chemistry are Relevant to Ionic Liquid Preparations?......Page 8
Atom Economy......Page 9
1.6 Conductive Heating Preparation of 1-Alkyl-3-methylimidazolium Halide Salts......Page 10
1.7 Purification of 1-Alkyl-3-methylimidazolium Halide Salts......Page 14
SWOT Analysis: Conductively Heated Preparation of 1-Alkyl-3-Methylimidazolium Halide Salts and Their Subsequent Purification......Page 16
1.8 Ionic Liquid Syntheses Promoted by Microwave Irradiation......Page 17
SWOT Analysis: Microwave-promoted Syntheses of Ionic Liquids......Page 20
1.9 Syntheses of Ionic Liquids Promoted by Ultrasonic Irradiation......Page 22
SWOT Analysis: Ultrasound-promoted Syntheses of Ionic Liquids......Page 24
1.10 Simultaneous Use of Microwave and Ultrasonic Irradiation to Prepare Ionic Liquids......Page 25
SWOT Analysis: Simultaneous Use of Microwave and Ultrasonic Irradiation to Prepare Ionic Liquids......Page 26
1.11 Preparation of Ionic Liquids Using Microreactors......Page 27
SWOT Analysis: Preparation of Ionic Liquids Using Microreactors......Page 29
Purification of Hydrophobic Versus Hydrophilic Ionic Liquids......Page 30
SWOT Analyses: Purification of Hydrophobic and Hydrophilic Ionic Liquids......Page 31
SWOT Analysis: Decolorization of Ionic Liquids......Page 33
Acknowledgments......Page 36
References......Page 37
Part II - Green Synthesis Using Ionic Liquids......Page 41
2.1 General Aspects......Page 43
The Extremely Low Vapor Pressure of Ionic Liquids......Page 45
Stability of Ionic Liquids in Organic Reactions......Page 46
Liquid–Liquid Biphasic Organic Reactions......Page 48
Tunable Solubility Properties......Page 49
Product Isolation from Organic Reactions with Ionic Liquids......Page 51
Reactive or Catalytic Ionic Liquids in Organic Synthesis......Page 53
Introduction and Technical Background......Page 56
Ionic Liquids in Friedel–Crafts Reaction - the Unique Selling Point......Page 57
Liquid–Liquid Biphasic Catalysis......Page 58
Supported Ionic Liquid Phase (SILP) Friedel–Crafts Catalysis......Page 59
3.1 Solubility and Immobilization of Transition Metal Complexes in Ionic Liquids......Page 67
3.2 Ionic Liquid–Catalyst Interaction......Page 69
In Situ Carbene Complex Formation......Page 70
3.3 Distillative Product Isolation from Ionic Catalyst Solutions......Page 72
3.4 New Opportunities for Biphasic Catalysis......Page 74
3.5 Green Aspects of Nanoparticle and Nanocluster Catalysis in Ionic Liquids......Page 77
3.6 Green Aspects of Heterogeneous Catalysis in Ionic Liquids......Page 79
Feedstock Solubility......Page 81
Catalyst Solubility and Immobilization......Page 82
Halogen-containing Ionic Liquids Versus Halogen-free Ionic Liquids in Hydroformylation......Page 83
Hydroformylation in scCO2–Ionic Liquid Multiphasic Systems......Page 84
Reducing the Amount of Ionic liquid Necessary – the Supported Ionic Liquid Phase (SILP)\rCatalyst Technology in Hydroformylation......Page 85
References......Page 87
4.1 Introduction......Page 95
Direct Uses of HMF......Page 97
Derivatives of HMF......Page 98
Summary: Application of HMF and Its Derivatives......Page 100
General Aspects of HMF Manufacture......Page 101
Methods of Manufacture of HMF from Fructose......Page 102
Methods of Manufacture of HMF from Sugars Other Than Fructose......Page 106
4.4 HMF Manufacture in Ionic Liquids – Results of Detailed Studies in the Jena\rLaboratories......Page 107
Concentration and Time......Page 108
Effect of Water......Page 110
Effect of Purity......Page 111
Effect of the Choice of Ionic Liquid......Page 113
Other Saccharides......Page 114
Continuous Processing of HMF......Page 116
4.5 Conclusion......Page 119
References......Page 120
5.1 General Aspects......Page 125
5.2 Dissolution of Cellulose in Ionic Liquids......Page 129
5.3 Rheological Behavior of Cellulose Solutions in Ionic Liquids......Page 131
5.5 Cellulosic Fibers......Page 133
5.7 Fractionation of Biomass with Ionic Liquids......Page 136
References......Page 137
Part III - Ionic Liquids in Green Engineering......Page 139
6.1 Introduction......Page 141
Metal Extraction......Page 143
Extraction of Aromatic Hydrocarbons......Page 147
Proteins......Page 153
Conventional Process......Page 155
Ionic Liquids in Extractive Distillation......Page 157
Conclusions......Page 159
Desulfurization with Ionic Liquids......Page 160
Oxidative Desulfurization......Page 164
6.4 Combination of Separations in the Liquid Phase with Membranes......Page 165
Conventional Processes......Page 166
CO2 Separation with Functionalized Ionic Liquids......Page 167
CO2 Separation with Ionic Liquid (Supported) Membranes......Page 168
Equipment......Page 170
Hydrodynamics......Page 171
Mass Transfer......Page 173
Introduction......Page 174
Application of COSMO-RS......Page 175
Conclusions......Page 176
Abbreviations and Symbols......Page 177
References......Page 178
7.1 Introduction......Page 193
7.2 Electrolyte Properties of Ionic Liquids......Page 195
7.3 Electrochemical Stability......Page 198
7.4 Dye-sensitized Solar Cells......Page 200
References......Page 202
8.1 Introduction......Page 205
Wear and Friction Behavior......Page 206
Thermal Stability......Page 212
Viscosity Index and Pour Point......Page 215
Electric Conductivity......Page 217
Ionic Greases......Page 218
8.3 Applications, Conclusion and Future Challenges......Page 219
References......Page 220
9.1 Introduction......Page 223
9.2 Absorption Chillers......Page 224
9.3 Requirements and Challenges......Page 225
Crystallization Behavior......Page 226
Thermal Stability......Page 227
9.4 State of the Art and Selected Results......Page 228
References......Page 230
Part IV - Ionic Liquids and the Environment......Page 235
10.1 Introduction......Page 237
The T-SAR Approach and the \"Test Kit\" Concept......Page 238
Strategy for the Design of Sustainable Ionic Liquids......Page 240
10.2 (Eco)toxicity of Ionic Liquids......Page 241
Influence of the Side Chain......Page 245
Influence of the Head Group......Page 256
Influence of the Anion......Page 257
Toxicity of Ionic Liquids as a Function of the Surrounding Medium......Page 259
Combination Effects......Page 261
(Quantitative) Structure–Activity Relationships and Modes of Toxic Action......Page 263
Conclusion......Page 265
Introduction......Page 267
Testing of Biodegradability......Page 268
Results from Biodegradation Experiments......Page 270
Biodegradability of Ionic Liquid Anions......Page 271
Biodegradability of Imidazolium Compounds......Page 285
Pyridinium and 4-(Dimethylamino)pyridinium Compounds......Page 286
Biodegradability of Other Head Groups......Page 287
Misleading Interpretation of Biodegradation Data......Page 288
Metabolic Pathways of Ionic Liquid Cations......Page 290
10.4 Conclusion......Page 292
Toxicity and (Eco)toxicity of Ionic Liquids......Page 293
The Goal Conflict in Designing Sustainable Ionic Liquids......Page 295
Final Remarks......Page 296
References......Page 297
11.2 The Methodological Approach......Page 301
Introduction......Page 302
What is Eco-efficiency Analysis?......Page 304
11.3 The Design of the Eco-efficiency Study of BASIL......Page 305
Energy Consumption......Page 306
Global Warming Potential (GWP)......Page 308
The Ecological Fingerprint......Page 309
Cost Calculation......Page 310
11.5 The Creation of the Eco-efficiency Portfolio......Page 311
11.6 Scenario Analysis......Page 313
11.7 Conclusion......Page 314
11.8 Outlook......Page 315
References......Page 316
12.1 Introduction......Page 317
Solvent Selection Tools......Page 319
LCA Methodology......Page 320
The ECO Method......Page 321
The Key Objectives......Page 322
The Evaluation and Optimization Procedure......Page 323
12.3 Assessment of Ionic Liquid Synthesis – Case Studies......Page 324
Synthesis of Ionic Liquids: Extract from the Optimization Procedure......Page 326
Validation of EF as an Indicator for Several Impact Categories of the\rLCA Methodology......Page 328
Comparison of the Life Cycle Environmental Impacts of the Manufacture of Ionic Liquids with Molecular Solvents......Page 329
Case Study: Diels–Alder Reaction......Page 331
Evaluation of the Energy Factor EF......Page 332
Evaluation of the Cost Factor CF......Page 334
Decision Support......Page 336
12.5 Conclusions......Page 337
References......Page 338