상세정보

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 and 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 emphasizes 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.

New feature

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 emphasizes 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.

정보제공 :

Thermodynamic Models for Industrial Applications: From Classical and Advanced Mixing Rules to Association Theories -- Contents -- Preface -- About the Authors -- Acknowledgments -- List of Abbreviations -- List of Symbols -- Part A: Introduction -- 1 Thermodynamics for Process and Product Design -- Appendix -- References -- 2 Intermolecular Forces and Thermodynamic Models -- 2.1 General -- 2.1.1 Microscopic (London) approach -- 2.1.2 Macroscopic (Lifshitz) approach -- 2.2 Coulombic and van der Waals forces -- 2.3 Quasi-chemical forces with emphasis on hydrogen bonding -- 2.3.1 Hydrogen bonding and the hydrophobic effect -- 2.3.2 Hydrogen bonding and phase behavior -- 2.4 Some applications of intermolecular forces in model development -- 2.4.1 Improved terms in equations of state -- 2.4.2 Combining rules in equations of state -- 2.4.3 Beyond the Lennard-Jones Potential -- 2.4.4 Mixing rules -- 2.5 Concluding remarks -- References -- Part B: The Classical Models -- 3 Cubic Equations of State: The Classical Mixing Rules -- 3.1 General -- 3.2 On parameter estimation -- 3.2.1 Pure compounds -- 3.2.2 Mixtures -- 3.3 Analysis of the advantages and shortcomings of cubic EoS -- 3.3.1 Advantages of cubic EoS -- 3.3.2 Shortcomings and limitations of cubic EoS -- 3.4 Some recent developments with cubic EoS -- 3.4.1 Use of liquid densities in the EoS parameter estimation -- 3.4.2 Activity coefficients for evaluating mixing and combining rules -- 3.4.3 Mixing and combining rules – beyond the vdW1f and classical combining rules -- 3.5 Concluding remarks -- Appendix -- References -- 4 Activity Coefficient Models, Part 1: Random-Mixing Models -- 4.1 Introduction to the random-mixing models -- 4.2 Experimental activity coefficients -- 4.2.1 VLE -- 4.2.2 SLE (assuming pure solid phase) -- 4.2.3 Trends of the activity coefficients -- 4.3 The Margules equations -- 4.4 From the van der Waals and van Laar equation to the regular solution theory -- 4.4.1 From the van der Waals EoS to the van Laar model -- 4.4.2 From the van Laar model to the Regular Solution Theory (RST) -- 4.5 Applications of the Regular Solution Theory -- 4.5.1 General -- 4.5.2 Low-pressure VLE -- 4.5.3 Solid-liquid equilibria (SLE) -- 4.5.4 Gas-liquid equilibrium (GLE) -- 4.5.5 Polymers -- 4.6 SLE with emphasis on wax formation -- 4.7 Asphaltene precipitation -- 4.8 Concluding remarks about the random-mixing-based models -- Appendix -- References -- 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 -- 5.2.1 NRTL -- 5.2.2 UNIQUAC -- 5.2.3 On UNIQUAC’s energy parameters -- 5.2.4 On the Wilson equation parameters -- 5.3 The theoretical limitations -- 5.3.1 Necessity for three models -- 5.4 Range of applicability of the LC models -- 5.5 On the theoretical significance of the interaction parameters -- 5.5.1 Parameter values for families of compounds -- 5.5.2 One-parameter LC models -- 5.
.5.3 Comparison of LC model parameters to quantum chemistry and other theoretically determined values -- 5.6 LC models: some unifying concepts -- 5.6.1 Wilson and UNIQUAC -- 5.6.2 The interaction parameters of the LC models -- 5.6.3 Successes and limitations of the LC models -- 5.7 The group contribution principle and UNIFAC -- 5.7.1 Why there are so many UNIFAC variants -- 5.7.2 UNIFAC applications -- 5.8 Local-composition–free-volume models for polymers -- 5.8.1 Introduction -- 5.8.2 FV non-random-mixing models -- 5.9 Conclusions: is UNIQUAC the best local composition model available today? -- Appendix -- References -- 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 EoS for polymers -- 6.8.1 High-pressure polymer thermodynamics -- 6.8.2 A simple first approach: application of the vdW EoS to polymers -- 6.8.3 Cubic EoS for polymers -- 6.8.4 How to estimate EoS parameters for polymers -- 6.9 Conclusions: achievements and limitations of the EoS/GE models -- 6.10 Recommended models – so far -- Appendix -- References -- Part C: Advanced Models and Their Applications -- 7 Association Theories and Models: The Role of Spectroscopy -- 7.1 Introduction -- 7.2 Three different association theories -- 7.3 The chemical and perturbation theories -- 7.3.1 Introductory thoughts: the separability of terms in chemical-based EoS -- 7.3.2 Beyond oligomers and beyond pure compounds -- 7.3.3 Extension to mixtures -- 7.3.4 Perturbation theories -- 7.4 Spectroscopy and association theories -- 7.4.1 A key property -- 7.4.2 Similarity between association theories -- 7.4.3 Use of the similarities between the various association theories -- 7.4.4 Spectroscopic data and validation of theories -- 7.5 Concluding remarks -- Appendix -- References -- 8 The Statistical Associating Fluid Theory (SAFT) -- 8.1 The SAFT EoS: a brief look at the history and major developments -- 8.2 The SAFT equations -- 8.2.1 The chain and association terms -- 8.2.2 The dispersion terms -- 8.3 Parameterization of SAFT -- 8.3.1 Pure compounds -- 8.3.2 Mixtures -- 8.4 Applications of SAFT to non-polar molecules -- 8.5 GC SAFT approaches -- 8.5.1 French method60,61 -- 8.5.2 DTU method66 -- 8.5.3 Other methods -- 8.6 Concluding remarks -- Appendix -- References -- 9 The Cubic-Plus-Association Equation of State -- 9.1 Introduction -- 9.1.1 The importance of associating (hydrogen bonding) mixtures -- 9.1.2 Why specifically develop the CPA EoS? -- 9.2 The CPA EoS -- 9.2.1 General -- 9.2.2 Mixing and combining rules -- 9.3 Parameter estimation: pure compounds -- 9.3.1 Testing of pure compound parameters -- 9.4 The firs.
t applications -- 9.4.1 VLE, LLE and SLE for alcohol–hydrocarbons -- 9.4.2 Water–hydrocarbon phase equilibria -- 9.4.3 Water–methanol and alcohol–alcohol phase equilibria -- 9.4.4 Water–methanol–hydrocarbons VLLE: prediction of methanol partition coefficient -- 9.5 Conclusions -- Appendix -- References -- 10 Applications of CPA to the Oil and Gas Industry -- 10.1 General -- 10.2 Glycol–water–hydrocarbon phase equilibria -- 10.2.1 Glycol–hydrocarbons -- 10.2.2 Glycol–water and multicomponent mixtures -- 10.3 Gas hydrates -- 10.3.1 General -- 10.3.2 Thermodynamic framework -- 10.3.3 Calculation of hydrate equilibria -- 10.3.4 Discussion -- 10.4 Gas phase water content calculations -- 10.5 Mixtures with acid gases (CO2 and H2S) -- 10.6 Reservoir fluids -- 10.6.1 Heptanes plus characterization -- 10.6.2 Applications of CPA to 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 -- 11.3.1 The case of a strongly solvating mixture: acetone–chloroform -- 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 -- Appendix -- References -- 12 Extension of CPA and SAFT to New Systems: Worked Examples and Guidelines -- 12.1 Introduction -- 12.2 The case of sulfolane: CPA application -- 12.2.1 Introduction -- 12.2.2 Sulfolane: is it an ‘inert’ (non-self-associating) compound? -- 12.2.3 Sulfolane as a self-associating compound -- 12.3 Application of sPC–SAFT to sulfolane-related systems -- 12.4 Applicability of association theories and cubic EoS with advanced mixing rules (EoS/GE models) 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 -- 13.3.1 General -- 13.3.2 Discussion -- 13.3.3 Study of alcohols with generalized associating parameters -- 13.4 Glycols -- 13.5 Organic acids -- 13.6 Polar non-associating compounds -- 13.6.1 Theories for extension of SAFT to polar fluids -- 13.6.2 Application of the tPC–PSAFT EoS to complex polar fluid mixtures -- 13.6.3 Discussion: comparisons between various polar SAFT EoS -- 13.6.4 The importance of solvation (induced association) -- 13.7 Flow assurance (asphaltenes and gas hydrate inhibitors) -- 13.8 Concluding remarks -- References -- 14 Application of SAFT to Polymers -- 14.1 Overview -- 14.2 Estimation of polymer parameters for SAFT-type EoS -- 14.2.1 Estimation of polymer parameters for EoS: general -- 14.2.2 The Kouskoumvekaki et al. method -- 14.2.3 Polar and associating polymers -- 14.2.4 Parameters for co-polymers -- 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 .