Thermodynamic Models for Industrial Applications: From Classical and Advanced Mixing Rules to Association Theories

Using an applications perspective Thermodynamic Models for Industrial Applications provides a unified framework for the development of various thermodynamic models, ranging from the classical models to some of the most advanced ones. Among these are the Cubic Plus Association Equation of State (CPA EoS) and the Perturbed Chain Statistical Association Fluid Theory (PC-SAFT). These two advanced models are already in widespread use in industry and academia, especially within the oil & gas, chemical and polymer industries. Presenting both classical models such as the Cubic Equations of State and more advanced models such as the CPA, this book provides the critical starting point for choosing the most appropriate calculation method for accurate process simulations. Written by two of the developers of these models, Thermodynamic Models for Industrial Applications emphasises model selection and model development and includes a useful "which model for which application" guide. It also covers industrial requirements as well as discusses the challenges of thermodynamics in the 21st Century. More information is available online at www.wiley.com/go/kontogeorgis Acknowledgement About the Authors Preface Abbreviations and Symbols Introduction 1 Thermodynamics for Process and Product Design References Appendix 1 A Appendix 1B 2 Intermolecular Forces and Thermodynamic Models 2.1 General 2.2 Coulombic and van der Waals forces 2.3 Quasi-chemical forces with emphasis on hydrogen bonding 2.4 Some applications of intermolecular forces in model development 2.5 Concluding remarks References Part A: The Classical Models 3 Cubic Equations of state - The classical mixing rules 3.1 General 3.2 On the parameter estimation 3.3 Analysis of the advantages and shortcomings of cubic EoS 3.4 Some recent developments with cubic EoS 3.5 Concluding remarks References Appendix 3A Appendix 3B 4. Activity coefficient models. Part 1. Random-mixing based models 4.1 Introduction to the random-mixing models 4.2 Experimental activity coefficients 4.3 The Margules equation 4.4 From the van der Waals to van Laar and to the Regular Solution Theory 4.5 Applications of the Regular Solution Theory 4.6 Solid-Liquid Equilibria with emphasis on Wax formation 4.7 Asphaltene precipitation 4.8 Concluding Remarks about the random-based models - In two words References Appendix 4A Appendix 4B Appendix 4C 5. Activity Coefficient Models. Part 2. Local-composition models: From Wilson and NRTL to UNIQUAC and UNIFAC 5.1 General 5.2 Overview of the local composition models 5.3 The theoretical limitations 5.4 Range of applicability of the LC models 5.5 On the theoretical significance of the interaction parameters 5.6 Local-composition models - some unifying concepts 5.7 The group-contribution principle and UNIFAC 5.8 Local composition - Free Volume models for polymers 5.9 Conclusions. Is UNIQUAC the best local composition model available today? References Appendix 5A Appendix 5B Appendix 5C 6. The EoS/GE mixing rules for cubic equations of state 6.1 General 6.2 The infinite pressure limit (the Huron-Vidal mixing rule) 6.3 The zero-reference pressure limit (The Michelsen approach) 6.4 Successes and limitations of zero reference pressure models 6.5 The Wong-Sandler (WS) mixing rule 6.6 EoS/GE approaches suitable for asymmetric mixtures 6.7 Applications of the LCVM, MHV2, PSRK and WS mixing rules 6.8 Cubic Equations of State for polymers 6.9 Conclusions.Achievements and Limitations of the EoS/GE models 6.10 Recommended models - so far References Appendix 6A Part B: Advanced Models and their Applications 7. Association theories and models - and the role of spectroscopy 7.1 Introduction 7.2 Three different association theories 7.3 The Chemical and Perturbation Theories 7.4 Spectroscopy and Association theories 7.5 Concluding remarks References Appendix 7A Appendix 7B 8. The Statistical Associating Fluid Theory (SAFT) 8.1 The SAFT EoS - history and major developments, a fast look 8.2 The SAFT equations 8.3 Parameterization of SAFT 8.4 Applications of SAFT to non-polar molecules 8.5 Group-contribution (GC) SAFT approaches 8.6 Concluding remarks References Appendix 8A Appendix 8B 9. The Cubic-Plus-Association (CPA) equation of state 9.1 Introduction 9.2 The CPA Equation of State 9.3 Parameter estimation - Pure compounds 9.4 The first applications 9.5 Conclusions References Appendix 9A Appendix 9B Appendix 9C Appendix 9D 10. Applications of CPA to the oil and gas industry 10.1 General 10.2 Glycol - water - hydrocarbon phase equilibria 10.3 Gas hydrates 10.4 Gas phase water content calculations 10.5 Mixtures with acid gases CO2 and H2S 10.6 Reservoir fluids 10.7 Conclusions References 11. Applications of CPA to chemical industries 11.1 Introduction 11.2 Aqueous mixtures with heavy alcohols 11.3 Amines and Ketones 11.4 Mixtures with organic acids 11.5 Mixtures with ethers and esters 11.6 Multifunctional chemicals - glycolethers and alkanolamines 11.7 Complex aqueous mixtures 11.8 Concluding remarks References Appendix 11A 12. Extension of CPA and SAFT to new systems: Worked out examples and guidelines 12.1 Introduction 12.2 The case of sulfolane - CPA application 12.3 Application of sPC-SAFT to sulfolane related systems 12.4 Applicability of association theories and cubic EoS with advanced mixing rules (EoS/GEmodels) to polar chemicals 12.5 Phenols 12.6 Conclusions References 13. Applications of SAFT to polar and associating mixtures 13.1 Introduction 13.2 Water-hydrocarbons 13.3 Alcohols, amines and alkanolamines 13.4 Glycols 13.5 Organic Acids 13.6 Polar non-associating compounds 13.7 Flow assurance (asphaltenes and gas hydrate inhibitors) 13.8 Concluding Remarks References 14. Applications of SAFT to polymers 14.1 Overview 14.2 Estimation of parameters for polymers for SAFT-type equations of state 14.3 Low pressure phase equilibria (VLE and LLE) using simplified PC-SAFT 14.4 High pressure phase equilibria 14.5 Co-polymers 14.6 Concluding remarks References Appendix 14A Appendix 14B