Introduction to Supercritical Fluids

Richard Lee Smith, Jr. received his Ph.D in Chemical Engineering at the Georgia Institute of Technology, USA, in 1985. He is Professor in the Graduate School of Environmental Studies at Tohoku University, Japan since 2002. He is Senior Editor of The Journal of Supercritical Fluids and has authored more than 350 scientific papers related to properties, reactions, separations, and material processing with supercritical fluids.Hiroshi Inomata received his Doctor of Engineering from Tohoku University in 1986. He is former Director of the Research Center of Supercritical Fluid Technology and Professor at Tohoku University, Japan. He is the author of more than 250 scientific papers related to thermodynamics, phase equilibria and molecular simulation of supercritical fluids.Cor J. Peters holds affiliate Distinguished Professorships in Chemical Engineering at both Colorado School of Mines and the University of Maryland, USA. Prior to his current positions, he was chairman of the Chemical Engineering Department at the Petroleum Institute in Abu Dhabi, currently Khalifa University of Science and Technology. Simultaneously to this position, he was the Director of the Gas Research Center. In academic education, he has taught a variety of courses, e.g.: Thermodynamics, Advanced Thermodynamics, Applied Thermodynamics, Natural Gas Processing, Statistical Thermodynamics, Phase Equilibria and Physical Chemistry. His research expertise covers fields like complex phase equilibria, with main applications on natural gas and gas-condensates. Furthermore, ionic liquids, deep eutectic solvents, hydrogen storage, gas hydrates, supercritical fluid technology, desalination and CO2-sequestration belong to his scientific interest. Dr Peters is a Fellow of the American Institute of Chemical Engineers and of the International Union of Pure and Applied Chemistry.

• Part I – for Multi-disciplinary instruction1. Supercritical Fluids: Fundamentals of State Changes, Processes, and Systems1.1 State Changes, Processes and Systems 1.2 Organization of the text 1.3 Basic vocabulary 1.4 Some notes on pressure 1.5 Chapter Summary 1.6 References and Additional Reading 1.7 End of Chapter Problems 2. Material-Energy-Entropy Balances of Supercritical Fluid Processes 2.1 Introduction 2.2 Analysis of devices and processes 2.3 Practical process I: Transcritical CO2 hot water heating system 2.4 Practical process II: Flavor extraction with supercritical CO2 2.5 Practical process III: Fine particle formation with supercritical H2O 2.6 Chapter Summary 2.7 References and Additional Reading 2.8 End of Chapter Problems 2.9 End of Chapter Projects 2.10 Report format 3. Chemical Information for Supercritical Fluids with AI-assisted Approaches3.1 Introduction 3.2 Search engines and AI tools 3.3 Reliable sources of chemical information 3.4 Chemical property databases: reference substances 3.5 Chemical property databases: non-reference substances 3.6 Chemical literature databases 3.7 Bibliometrics 3.8 Chapter Summary 3.9 References and Additional Reading 3.10 End of Chapter Problems 4. Commercial Applications of Supercritical Fluid Technology-Past and Present4.1 Historical background 4.2 Characteristic features common to all supercritical fluids 4.3 Extraction with supercritical CO2 4.4 Commercial food products 4.5 Methods for improving yield and modifying selectivity 4.6 Dietary supplements 4.7 Green chemistry with supercritical CO2 4.8 Polymer synthesis 4.9 Separations 4.10 Characteristic features of supercritical water 4.11 Commercial chemical and waste recycling processes 4.12 Commercial hydrothermal and supercritical oxidation processes 4.13 Particle formation 4.14 Coating and Film Deposition 4.15 Polymer Processing 4.16 Food Processing 4.17 Chromatography 4.18 Gas-Expanded Liquids (GXLs) 4.19 List of companies involved with supercritical fluids 4.20 Chapter Summary 4.21 References and Additional Reading 4.22 End of Chapter Problems Part II – for Specialized discipline instruction5. Practical Thermodynamic Expressions for Supercritical Fluid Phase Equilibria5.1 Introduction to thermodynamics 5-15.2 Thermodynamic state functions 5-45.3 Material, energy, and entropy balances 5-115.4 Thermodynamic systems 5-155.5 Basic thermodynamic relationships 5-265.6 Fugacity 5-305.7 Phase stability 5-395.8 Selected thermodynamic phase equilibrium criteria 5-445.9 Practical expressions 5-475.11 Chapter Summary 5-595.12 References and Additional Reading 5-605.13 End of Chapter Projects 5-605.14 Report Format 5-626. Fluid Property Calculations with Equations of State using Excel VBA Functions6.1 Overview of equations of state (EoS) 6.2 Calculation of CO2 properties with Excel VBA functions 6.3 Calculation of H2O properties with Excel VBA functions 6.4 Mathematically simple equations of state 6.5 Cubic equations of state 6.6 Pure component fugacity from a cubic equation of state 6.7 Application of cubic EoS to mixtures 6.8 Modern cubic equation of state formulations 6.9 Relating EoS parameters to solution models 6.10 Molecular-based equations of state 6.11 Chapter Summary 6.12 References and Additional Reading 6.13 End of Chapter Problems6.14 Report Format 7. Phase Equilibria and Phase Behavior of Supercritical Fluid Systems 7.1 Overview 7.2 Solid-vapor equilibria (SVE) 7.3 Solid-Liquid-Vapor equilibria (SLVE) 7.4 Vapor-Liquid equilibria (VLE) 7.5 Numerical solution method for vapor-liquid equilibria 7.6 Critical points of mixtures 7.7 Numerical solution method for critical points of mixtures7.8 Three-dimensional visualization of phase equilibria 7.9 Phase behavior of binary mixtures 7.10 Phase behavior of ternary mixtures 7.11 Chapter Summary 7.12 References and Additional Reading 7.13 End of Chapter Problems 7.14 End of Chapter Projects 7.15 Report Format 8. Mass Transfer Models for Hydrothermal and Supercritical Fluid Systems8.1 Overview 8.2 Extraction curves of botanicals 8.3 Simple mathematical models for extraction curves 8.4 Logistic models 8.5 Combination models 8.6 Momentum-diffusion transport models 8.7 Dimensionless groups commonly used in mass transfer 8.8 Mechanistic mass transfer models 8.9 Recommendations for extraction models 8.10 Chapter Summary 8.11 References and Additional Reading 8.12 End of Chapter Problems 8.13 End of Chapter Projects 8.14 Report Format9. Heat Transfer in Transcritical Heat Exchangers and Cycle Analysis9.1 Overview 9.2 Heat exchangers 9.3 Modes of heat transfer 9.4 Thermophysical properties of fluids in the critical region 9.5 Dimensionless groups commonly used in heat transfer 9.6 Analysis of shell-and-tube heat exchangers 9.7 Estimation of heat exchanger area 9.8 Cycle analysis 9.9 Equations of change 9.10 Chapter Summary 9.11 References and Additional Reading 9.12 End of Chapter Problems 9.13 End of Chapter Projects 9.14 Report Format 10. Chemical Equilibrium and Reaction Kinetics in Supercritical Fluid Systems 10.1 Overview 10.2 Thermochemistry 10.3 Chemical equilibrium 10.4 Le Chatlier's principle 10.5 Calculation of chemical equilibrium 10.6 Chemical reactors 10.7 Reaction kinetics 10.8 Chapter Summary 10.9 References and Additional Reading 10.10 End of Chapter Problems 10.11 End of Chapter Projects 10.12 Report Format 11. User's Guide to Programs in Introduction to Supercritical Fluids11.1 Guide to Visual Basic for Applications (VBA) in Excel 11.2 Building User-Defined Functions, Subroutines and Macros in VBA 11.3 Guide to importing data into 3D Grapher 11.4 Guidance on Excel workbooks supplied with the text