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 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.

Author Notes

Georgios M. Kontogeorgis is Associate Professor in the Department of Chemical Engineering at the Technical University of Denmark in Lyngby (Denmark). He received his PhD in Chemical Engineering in the Institut for Kemiteknik at the Technical University of Denmark. He became a Research Associate at the Technical University of Athens (Greece) where he gained his MSc in Chemical Engineering. Professor Kontogeorgis has had a teaching appointment at the Department of Environmental Engineering, Xanthi (Greece) and at the Air Force Academy, Athens (Greece) and he was then co-founder and technical director of the research and software company IGVP Ltd. His awards include the Empirikion Foundation Award for Achievements in Chemistry, the Dana Lim Prize and he is listed in Who's Who in Finance and Industry, Who's Who in Science and Engineering, American Association for Advancement of Science. Professor Kontogeorgis is part of the Steering committee of ESAT (European Seminar of Applied Thermodynamics). His research focuses on four areas: energy, materials and nanotechnology, the environment and biotechnology.

Georgios K. Folas was educated at the Technical University of Athens (Greece) where he received an MSc in Chemical Engineering. His Master Thesis was deemed one of the top five MSc theses in chemical engineering for the year 2000 awarded by the Technical Chamber of Greece. He gained his PhD in Chemical Engineering at the Institut for Kemiteknik, Technical University of Denmark. Dr. Folas has been employed as an R&D plastics engineer, Chrostiki S.A and currently works as Senior Flow Assurance Engineer at Aker Kværner Engineering & Technology AS.

Acknowledgement

About the Authors

Preface

Abbreviations and Symbols

Introduction

1 Thermodynamics for Process and Product Design

References

Appendix 1

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/G E 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/G E 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 CO 2 and H 2 S

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/G E 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

13.4 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

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Summary

Summary

Author Notes

Table of Contents