Green Solvents, Volume 6

Series Editor:Paul T. Anastas joined Yale University as Professor and iserves as the Director of the Center for Green Chemistry and Green Engineering at Yale. From 2004-2006, Paul Anastas has been the Director of the Green Chemistry Institute in Washington, D.C. Until June of 2004 he served as Assistant Director for Environment at e White House Office of Science and Technology Policy where his responsibilities included a wide range of environmental science issues including furthering international public-private cooperation in areas of Science for Sustainability such as Green Chemistry. In 1991, he established the industry-government-university partnership Green Chemistry Program, which was expanded to include basic research, and the Presidential Green Chemistry Challenge Awards. He has published and edited several books in the field of Green Chemistry and is one of the inventors the 12 principles of Green Chemistry. Volume Editors:PD Dr. Annegret Stark and Prof. Peter WasserscheidAnnegret Stark studied pharmaceutical chemistry at the University of Applied Sciences in Isny, Germany. She conducted her diploma thesis in 1997 in the labs of R.D. Singer at St. Mary's University in Halifax, Nova Scotia, who inspired her to take up a researcher's career in the field of ionic liquids. After finishing her PhD in K.R. Seddon's research group at the Queen's University of Belfast, Northern Ireland, in 2001, she moved on to South Africa for a SASOL-sponsored postdoc in the group of H.G. Raubenheimer at Stellenbosch University (2001-2003).Since 2011, she heads her own research group at the Institute for Technical Chemistry in Leipzig, Germany. Her research focus lies, on the one hand, on the elucidation of structure-induced interactions between ionic liquids and solutes, and the resulting effects on the reactivity of these. On the other hand, she is interested in the application of microreaction technology, e.g. in the conversion of highly reactive intermediates. Both, ionic liquids and microreaction technology, are exploited as tools with the goal to provide sustainable chemical and engineering concepts. Peter Wasserscheid studied chemistry at the RWTH Aachen. After receiving his diploma in 1995 he joined the group of Prof. W. Keim at the Institute of Technical and Macromolecular Chemistry at the RWTH Aachen for his PhD thesis. In 1998 he moved to BP Chemicals in Sunbury/GB for an industrial postdoc for six months. He returned to the Institute of Technical and Macromolecular Chemistry at the RWTH Aachen where he completed his habilitation entitled "Ionic Liquids - a new Solvent Concept for Catalysis". In the meantime, he became co-founder of Solvent Innovation GmbH, Cologne, one of the leading companies in ionic liquid production and application (since December 2007 a 100% affiliate of Merck KGaA, Darmstadt). In 2003 he moved to Erlangen as successor Prof. Emig and since then is heading the Institute of Reaction Engineering. In 2005 he also became head of the department "Chemical and Bioengineering" of the University Erlangen-Nuremberg. P. Wasserscheid has received several awards including the Max-Buchner-award of DECHEMA (2001), the Innovation Award of the German Economy (2003, category "start-up") together with Solvent Innovations GmbH and the Leibniz Award of the German Science Foundation (2006). His key research interests are the reaction engineering aspects of multiphase catalytic processes with a particular focus on ionic liquid reaction media. The Wasserscheid group belongs to the top research teams in the development and application of ionic liquids in general, and in developing the ionic liquid technology for catalytic applications in special. For various reaction types the group has successfully demonstrated greatly enhanced performance of ionic liquid based catalyst systems vs. conventional systems.Peter Wasserscheid has a scientific track record of more than 130 publications in peer-reviewed scientific journals plus many papers in the form of proceedings. Moreover, he is a co-inventor of more than 40 patents, most of them in the field of ionic liquids.SET III - Green Processes:

• lonic Liquids and Green Chemistry – an Extended Preface XIIIAbout the Editors XXIList of Contributors XXIIIPart I Green Synthesis 11 The Green Synthesis of Ionic Liquids 3Maggel Deetlefs and Kenneth R. Seddon1.1 The Status Quo of Green Ionic Liquid Syntheses 31.2 Ionic Liquid Preparations Evaluated for Greenness 41.3 Which Principles of Green Chemistry are Relevant to Ionic Liquid Preparations? 61.4 Atom Economy and the E-factor 71.4.1 Atom Economy 71.4.2 The E-factor 81.5 Strengths, Weaknesses, Opportunities, Threats (SWOT) Analyses 81.6 Conductive Heating Preparation of 1-Alkyl-3-methylimidazolium Halide Salts 81.7 Purification of 1-Alkyl-3-methylimidazolium Halide Salts 121.7.1 SWOT Analysis: Conductively Heated Preparation of 1-Alkyl-3- Methylimidazolium Halide Salts and Their Subsequent Purification 141.8 Ionic Liquid Syntheses Promoted by Microwave Irradiation 151.8.1 Microwave-assisted Versus Traditional Ionic Liquid Preparations 181.8.2 SWOT Analysis: Microwave-promoted Syntheses of Ionic Liquids 181.9 Syntheses of Ionic Liquids Promoted by Ultrasonic Irradiation 201.9.1 SWOT Analysis: Ultrasound-promoted Syntheses of Ionic Liquids 221.10 Simultaneous Use of Microwave and Ultrasonic Irradiation to Prepare Ionic Liquids 231.10.1 SWOTAnalysis: Simultaneous Use of Microwave and Ultrasonic Irradiation to Prepare Ionic Liquids 241.11 Preparation of Ionic Liquids Using Microreactors 251.11.1 SWOT Analysis: Preparation of Ionic Liquids Using Microreactors 271.12 Purification of Ionic Liquids with Non-halide Anions 281.12.1 Purification of Hydrophobic Versus Hydrophilic Ionic Liquids 281.12.2 SWOT Analyses: Purification of Hydrophobic and Hydrophilic Ionic Liquids 291.13 Decolorization of Ionic Liquids 311.13.1 SWOT Analysis: Decolorization of Ionic Liquids 311.14 Conclusion 34References 36Part II Green Synthesis Using Ionic Liquids 392 Green Organic Synthesis in Ionic Liquids 41Peter Wasserscheid and JoniJoni2.1 General Aspects 412.1.1 The Extremely Low Vapor Pressure of Ionic Liquids 432.1.2 Stability of Ionic Liquids in Organic Reactions 442.1.3 Liquid-Liquid Biphasic Organic Reactions 462.1.3.1 Tunable Solubility Properties 472.1.3.2 Product Isolation from Organic Reactions with Ionic Liquids 492.1.4 Reactive or Catalytic Ionic Liquids in Organic Synthesis 512.2 Friedel-Crafts Alkylation 542.2.1 Introduction and Technical Background 542.2.2 Ionic Liquids in Friedel-Crafts Reaction – the Unique Selling Point 552.2.3 Liquid-Liquid Biphasic Catalysis 562.2.4 Supported Ionic Liquid Phase (SILP) Friedel-Crafts Catalysis 57References 593 Transition Metal Catalysis in Ionic Liquids 65Peter Wasserscheid3.1 Solubility and Immobilization of Transition Metal Complexes in Ionic Liquids 653.2 Ionic Liquid-Catalyst Interaction 673.2.1 Activation of Transition Metal Complexes by Lewis Acidic Ionic Liquids 683.2.2 In Situ Carbene Complex Formation 683.3 Distillative Product Isolation from Ionic Catalyst Solutions 703.4 New Opportunities for Biphasic Catalysis 723.5 Green Aspects of Nanoparticle and Nanocluster Catalysis in Ionic Liquids 753.6 Green Aspects of Heterogeneous Catalysis in Ionic Liquids 773.7 Green Chemistry Aspects of Hydroformylation Catalysis in Ionic Liquids 793.7.1 Feedstock Solubility 793.7.2 Catalyst Solubility and Immobilization 803.7.3 Use of Phosphite Ligands in Ionic Liquids 813.7.4 Halogen-containing Ionic Liquids Versus Halogen-free Ionic Liquids in Hydroformylation 813.7.5 Hydroformylation in scCO2-Ionic Liquid Multiphasic Systems 823.7.6 Reducing the Amount of Ionic liquid Necessary – the Supported Ionic Liquid Phase (SILP) Catalyst Technology in Hydroformylation 833.8 Conclusion 85References 854 Ionic Liquids in the Manufacture of 5-Hydroxymethylfurfural from Saccharides. An Example of the Conversion of Renewable Resources to Platform Chemicals 93Annegret Stark and Bernd Ondruschka4.1 Introduction 934.1.1 Areas of Application for HMF and its Derivatives 954.1.1.1 Direct Uses of HMF 954.1.1.2 Derivatives of HMF 964.1.2 Summary: Application of HMF and Its Derivatives 984.2 HMF Manufacture 994.2.1 General Aspects of HMF Manufacture 994.2.2 Methods of Manufacture of HMF from Fructose 1004.2.3 Methods of Manufacture of HMF from Sugars Other Than Fructose 1044.2.4 Deficits in HMF Manufacture 1054.3 Goals of Study 1054.4 HMF Manufacture in Ionic Liquids – Results of Detailed Studies in the Jena Laboratories 1054.4.1 Temperature 1064.4.2 Concentration and Time 1064.4.3 Effect of Water 1084.4.4 Effect of Purity 1094.4.5 Effect of the Choice of Ionic Liquid 1114.4.6 Other Saccharides 1124.4.7 Continuous Processing of HMF 1144.5 Conclusion 117References 1185 Cellulose Dissolution and Processing with Ionic Liquids 123Uwe Vagt5.1 General Aspects 1235.2 Dissolution of Cellulose in Ionic Liquids 1275.3 Rheological Behavior of Cellulose Solutions in Ionic Liquids 1295.4 Regeneration of the Cellulose and Recycling of the Ionic Liquid 1315.5 Cellulosic Fibers 1315.6 Cellulose Derivatives 1345.7 Fractionation of Biomass with Ionic Liquids 1345.8 Conclusion and Outlook 135References 135Part III Ionic Liquids in Green Engineering 1376 Green Separation Processes with Ionic Liquids 139Wytze (G. W.) Meindersma, Ferdy (S. A. F.) Onink, and Andre B. de Haan6.1 Introduction 1396.2 Liquid Separations 1416.2.1 Extraction 1416.2.1.1 Metal Extraction 1416.2.1.2 Extraction of Aromatic Hydrocarbons 1456.2.1.3 Proteins 1516.2.2 Extractive Distillation 1536.2.2.1 Conventional Process 1536.2.2.2 Ionic Liquids in Extractive Distillation 1556.2.2.3 Conclusions 1576.3 Environmental Separations 1586.3.1 Desulfurization and Denitrogenation of Fuels 1586.3.1.1 Conventional Desulfurization 1586.3.1.2 Desulfurization with Ionic Liquids 1586.3.1.3 Oxidative Desulfurization 1626.3.1.4 Conclusions 1636.4 Combination of Separations in the Liquid Phase with Membranes 1636.4.1 Conclusions 1646.5 Gas Separations 1646.5.1 Conventional Processes 1646.5.2 CO2 Separation with Standard Ionic Liquids 1656.5.3 CO2 Separation with Functionalized Ionic Liquids 1656.5.4 CO2 Separation with Ionic Liquid (Supported) Membranes 1666.5.5 Olefin-Paraffin Separations with Ionic Liquids 1686.5.6 Conclusions 1686.6 Engineering Aspects 1686.6.1 Equipment 1686.6.2 Hydrodynamics 1696.6.3 Mass Transfer 1716.6.4 Conclusions 1726.7 Design of a Separation Process 1726.7.1 Introduction 1726.7.2 Application of COSMO-RS 1736.7.3 Conclusions 1746.8 Conclusions 175References 1767 Applications of Ionic Liquids in Electrolyte Systems 191William R. Pitner, Peer Kirsch, Kentaro Kawata, and Hiromi Shinohara7.1 Introduction 1917.2 Electrolyte Properties of Ionic Liquids 1937.3 Electrochemical Stability 1967.4 Dye-sensitized Solar Cells 198References 2008 Ionic Liquids as Lubricants 203Marc Uerdingen8.1 Introduction 2038.2 Why Are Ionic Liquids Good Lubricants? 2048.2.1 Wear and Friction Behavior 2048.2.2 Pressure Behavior 2108.2.3 Thermal Stability 2108.2.4 Viscosity Index and Pour Point 2138.2.5 Corrosion 2158.2.6 Electric Conductivity 2158.2.7 Ionic Greases 2168.3 Applications, Conclusion and Future Challenges 217References 2189 New Working Pairs for Absorption Chillers 221Matthias Seiler and Peter Schwab9.1 Introduction 2219.2 Absorption Chillers 2229.3 Requirements and Challenges 2239.3.1 Thermodynamics, Heat and Mass Transfer 2249.3.2 Crystallization Behavior 2249.3.3 Corrosion Behavior 2259.3.4 Viscosity 2259.3.5 Thermal Stability 2259.4 State of the Art and Selected Results 2269.5 Abbreviations 228References 228Part IV Ionic Liquids and the Environment 23310 Design of Inherently Safer Ionic Liquids: Toxicology and Biodegradation 235Marianne Matzke, Jürgen Arning, Johannes Ranke, Bernd Jastorf, and Stefan Stolte10.1 Introduction 23510.1.1 The T-SAR Approach and the “Test Kit” Concept 23610.1.2 Strategy for the Design of Sustainable Ionic Liquids 23810.2 (Eco)toxicity of Ionic Liquids 23910.2.1 Influence of the Side Chain 24310.2.2 Influence of the Head Group 25410.2.3 Influence of the Anion 25510.2.4 Toxicity of Ionic Liquids as a Function of the Surrounding Medium 25710.2.5 Combination Effects 25910.2.6 (Quantitative) Structure-Activity Relationships and Modes of Toxic Action 26110.2.7 Conclusion 26310.3 Biodegradability of Ionic Liquids 26510.3.1 Introduction 26510.3.2 Testing of Biodegradability 26610.3.3 Results from Biodegradation Experiments 26810.3.3.1 Biodegradability of Ionic Liquid Anions 26910.3.3.2 Biodegradability of Imidazolium Compounds 28310.3.3.3 Pyridinium and 4-(Dimethylamino)pyridinium Compounds 28410.3.3.4 Biodegradability of Other Head Groups 28510.3.4 Misleading Interpretation of Biodegradation Data 28610.3.5 Metabolic Pathways of Ionic Liquid Cations 28810.3.6 Abiotic Degradation 29010.3.7 Outlook 29010.4 Conclusion 29010.4.1 Toxicity and (Eco)toxicity of Ionic Liquids 29110.4.2 Biodegradability of Ionic Liquids 29310.4.3 The Goal Conflict in Designing Sustainable Ionic Liquids 29310.4.4 Final Remarks 294References 29511 Eco-efficiency Analysis of an Industrially Implemented Ionic Liquidbased Process – the BASF BASIL Process 299Peter Saling, Matthias Maase, and Uwe Vagt11.1 The Eco-efficiency Analysis Tool 29911.1.1 General Aspects 29911.2 The Methodological Approach 29911.2.1 Introduction 30011.2.2 What is Eco-efficiency Analysis? 30211.2.3 Preparation of a Specific Life-cycle Analysis for All Investigated Products and Processes 30311.3 The Design of the Eco-efficiency Study of BASIL 30311.4 Selected Single Results 30411.4.1 Energy Consumption 30411.4.2 Global Warming Potential (GWP) 30611.4.3 Water Emissions 30711.4.4 The Ecological Fingerprint 30711.4.5 Cost Calculation 30811.5 The Creation of the Eco-efficiency Portfolio 30911.6 Scenario Analysis 31111.7 Conclusion 31211.8 Outlook 313References 31412 Perspectives of lonic Liquids as Environmentally Benign Substitutes for Molecular Solvents 315Denise Ott, Dana Kralisch, and Annegret Stark12.1 Introduction 31512.2 Evaluation and Optimization of R&D Processes: Developing a Methodology 31712.2.1 Solvent Selection Tools 31712.2.2 LCA Methodology 31812.2.3 The ECO Method 31912.2.3.1 The Key Objectives 32012.2.3.2 The Evaluation and Optimization Procedure 32112.3 Assessment of Ionic Liquid Synthesis – Case Studies 32212.3.1 Synthesis of Ionic Liquids: Extract from the Optimization Procedure 32412.3.2 Validation of EF as an Indicator for Several Impact Categories of the LCA Methodology 32612.3.3 Comparison of the Life Cycle Environmental Impacts of the Manufacture of Ionic Liquids with Molecular Solvents 32712.4 Assessment of the Application of Ionic Liquids in Contrast to Molecular Solvents 32912.4.1 Case Study: Diels-Alder Reaction 32912.4.1.1 Evaluation of the Solvent Performance 33012.4.1.2 Evaluation of the Energy Factor EF 33012.4.1.3 Evaluation of the Environmental and Human Health Factor EHF – Examples 33212.4.1.4 Evaluation of the Cost Factor CF 33212.4.1.5 Alternative Ionic Liquid Choices 33412.4.1.6 Decision Support 33412.5 Conclusions 335References 336lndex 341