Gas-Expanded Liquids and Near-Critical Media Green Chemistry and Engineering ACS Symposium Series, Vol. 1006

Gas-expanded liquids and near-critical fluids are tunable solvent media for conducting chemical reactions, separations, and materials processing. In recent years, there has been an expanding body of fundamental and applied research in the use of these media, particularly for applications to sustainable processes based on the principles of green chemistry and engineering. This volume spans research and development activities ranging from theoretical and experimental investigations of the fundamental science underlying the field to developmental aspects of the technology for commercial applications. An introduction and overview of the field is included, as well as both new developments and reviews organized in the general topical areas of thermodynamics and transport properties (including both experimental and modeling studies), reactions, and materials processing. To the best of our knowledge, this is the first such compilation in this field with contributions from leading research groups.

Introduction and Overview. Chapitre 1. Gas-Expanded Liquids (GXLs): Fundamentals and Applications. Thermodynamics and Transport Properties: Experiment and Modeling. Chapitre 2. Phase Equilibrium, Structure and Transport Properties of Carbon Dioxide-Expanded Liquids: A Molecular Simulation Study. Chapitre 3. On the Molecular-Based Modeling of Dilute Ternary Systems in Compressible Media: Formal Results and Thermodynamic Pitfalls. Chapitre 4. Viewing the Cybotactic Structure of Gas-Expanded Liquids. Chapitre 5. Solvatochromism and Solvation Dynamics in CO2-Expanded Liquids. Chapitre 6. Phase Behavior and Equilibria of Ionic Liquids and Refrigerants: 1-Ethyl-3-Methyl-Imidazolium Bis(trifluoromethylsulfonyl)imide ([EMIm][Tf2N]) and R-134a. Reactions. Chapitre 7. In Situ Alkylcarbonic Acid Catalysts Formed in CO2-Expanded Alcohols. Chapitre 8. Catalytic Oxidation Reactions in Carbon Dioxide Expanded Liquids Using the Green Oxidants Oxygen and Hydrogen Peroxide. Chapitre 9. Hydrogenation of CO2-Expanded Liquid Terpenes: Phase Equilibrium-Controlled Kinetics. Chapitre 10. Hydroformylation in CO2-Expanded Media. Chapitre 11. Hydrogenation in Biphasic Ionic Liquid/Carbon Dioxide Systems. Chapitre 12. Sulfur Trioxide Containing Caprolactamium Hydrogen Sulfate: An Expanded Ionic Liquid for Large Scale Production of e-Caprolactam. Materials Processing. Chapitre 13. Emulsion-Templated Porous Materials using Concentrated Carbon Dioxide-in-Water Emulsions and Inexpensive Hydrocarbon Surfactants. Chapitre 14. Fluoropolymer Synthesis in Carbon Dioxide Expanded Liquids: A Practical Approach to Avoid the Use of PFOA. Chapitre 15. Green Methods for Processing and Utilizing Metal Complexes. Chapitre 16. Application of Gas eXpanded Liquids for Nanoparticle Processing: Experiment and Theory. Chapitre 17. Development of a Novel Precipitation Technique for the Production of Highly Respirable Powders: The Atomized Rapid Injection for Solvent Extraction (ARISE) Process.

Keith Hutchenson is a Research Fellow in DuPont Central Research and Development and is located at the DuPont Experimental Station in Wilmington, DE. His research interests include supercritical fluid technology, chemical process development, and reaction engineering, and he has worked on a number of process development projects in several DuPont business units during his 22-year career with DuPont. Aaron Scurto is an Assistant Professor and DuPont Young Professor in the Department of Chemical and Petroleum Engineering at the University of Kansas. His research interests include phase equilibrium thermodynamics, homogeneous catalysis, solvent effects on reactions and materials processing, particularly in supercritical fluids and ionic liquids. Bala Subramaniam is the Dan F. Servey Distinguished Professor of Chemical and Petroleum Engineering and the Director of the Center for Environmentally Beneficial Catalysis, a National Science Foundation Engineering Research Center, at the University of Kansas. He has held visiting Professorships at ETH in Zurich, Switzerland and the University of Nottingham, UK. His research interests are in catalytic reaction engineering, crystallization, and exploiting supercritical fluids and gas-expanded liquids for benign chemicals processing.