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Phase Equilibrium Engineering - 1st Edition - ISBN: 9780444563644, 9780444594716

Phase Equilibrium Engineering, Volume 3

1st Edition

Authors: Esteban Brignole Selva Pereda
Hardcover ISBN: 9780444563644
eBook ISBN: 9780444594716
Imprint: Elsevier
Published Date: 23rd April 2013
Page Count: 346
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Table of Contents

Series Page



Chapter 1. Phase Equilibrium and Process Development

1.1 The World of Phase Equilibria in Chemical Processes

1.2 Thermodynamic Modeling in Process Development

1.3 Definition of Phase Equilibrium Engineering

1.4 Phase Scenarios in Separation, Materials, and Chemical Processes

1.5 The Phase Design and the Phase Engineering Tools


Chapter 2. Intermolecular Forces, Classes of Molecules, and Separation Processes

2.1 Intermolecular Forces

2.2 Classification of Molecules

2.3 Separation Process Technology and Classes of Mixtures


Chapter 3. Phase Equilibrium Diagrams

3.1 Gibbs Criteria for Phase Equilibrium: The Phase Rule

3.2 The Phase Regions of Pure Components

3.3 Classification of Binary Fluid-Phase Behavior Diagrams

3.4 Classification of Ternary Fluid-Phase Behavior Diagrams

3.5 Phase Diagrams for Multicomponent Systems


Chapter 4. Physical Properties and Thermodynamic Models

4.1 Thermodynamic Modeling and Simulation

4.2 Physical Properties of Pure Compounds

4.3 The Compressibility Factor of Gases

4.4 The Virial EOS

4.5 Corresponding State Correlations

4.6 Prediction of Phase Equilibria

4.7 Predictive Models

4.8 Semiempirical Models

4.9 Selection of Thermodynamic Models

4.10 Problems

Appendix 4A

Appendix 4B


Chapter 5. A General Approach to Phase Diagrams for Binary Systems

5.1 Introduction and Scope

5.2 A Case That Required Special Analysis and New Tools

5.3 Some Problems and Solutions Regarding the Automated Calculation of Phase Diagrams

5.4 Different Projections of ULPEDs

5.5 Restricted Phase Diagrams (Beyond the Typical Cases)

5.6 Remarks and Conclusions

5.7 Problems


Chapter 6. Phase Equilibrium Engineering Principles

6.1 Case Study: Biphenyl Recovery from the Bottoms of the Toluene Column

6.2 Case Study: Natural Gas Liquid Extraction from Natural Gas

6.3 Case Study: Supercritical Biodiesel Production Process

6.4 Principles of Phase Equilibrium Engineering


Chapter 7. Phase Equilibrium Engineering in Distillation

7.1 Distillation and Class of Phase Behavior

7.2 Fractional Distillation Principles

7.3 Thermodynamic Tuning of Fractional Distillation Columns

7.4 Thermodynamic Tuning of a Multicomponent Distillation Train

7.5 Case Study: Parameterization of the Ethylene Plant Recovery Section

7.6 Phase Equilibrium Engineering Guidelines for Thermodynamic Tuning of Fractional Distillation

7.7 Energy and Thermodynamic Sensitivity in Distillation

7.8 Summary

Appendix: Mathematical Modeling of Multistage Fractional Distillation


Chapter 8. Separation of Azeotropic Mixtures

8.1 Solvents or Entrainers as Separating Agents

8.2 Homogeneous Azeotropic Distillation

8.3 Heterogeneous Azeotropic Distillation

8.4 Selection of Solvents for Separation Processes

8.5 Synthesis of Solvents by CAMD

8.6 Solvent Design in Liquid–Liquid Extraction

8.7 Solvent Selection or Design in EXD

8.8 Case Study: Solvent and Process Design for the Recovery of the Aromatic Fraction of Reforming Naphtha

8.9 Summary

8.10 High-Pressure Azeotropic Distillation

Appendix 8A


Chapter 9. Green Processes and High-Pressure Solvents

9.1 SCF Solvents

9.2 Solvent Tuning in Type V Phase Behavior

9.3 Solvent Tuning in Type III Phase Behavior

9.4 Supercritical Solvent Mixtures

9.5 Particle Micronization with SCFs

9.6 Summary


Chapter 10. High-Pressure Fractionation and Extraction of Natural Oils

10.1 Supercritical Fractionation

10.2 Supercritical Fractionation Phase Design

10.3 Phase Equilibria of Natural Oils in SCFs

10.4 Case Studies of Fractionation of Natural Oils

10.5 Summary


Chapter 11. Phase Equilibrium Engineering Principles in Reactive Systems

11.1 Key Physicochemical Attributes of Supercritical Reactors

11.2 Solvent Selection: Phase Behavior of Reactive Mixture and Solvents

11.3 Phase Behavior of SCFs with Homologous Families of Organic Compounds

11.4 Case Study: Solvent Selection

11.5 Experimental Tools for Tracking Phase Behavior in Reactive Systems

11.6 Phase Condition Design: Boundaries of the Reactive System in Gibbs Diagrams

11.7 Phase Conditions Design: Boundaries of the Reactive System in PT Diagrams


Chapter 12. Phase Equilibrium Engineering in Conceptual Process Design

12.1 Introduction

12.2 Phase Equilibrium Engineering of the Transesterification Reaction

12.3 Supercritical Fluid Extraction and Dehydration of Alcohols from Water

12.4 Final Remarks




Traditionally, the teaching of phase equilibria emphasizes the relationships between the thermodynamic variables of each phase in equilibrium rather than its engineering applications. This book changes the focus from the use of thermodynamics relationships to compute phase equilibria to the design and control of the phase conditions that a process needs.

Phase Equilibrium Engineering presents a systematic study and application of phase equilibrium tools to the development of chemical processes. The thermodynamic modeling of mixtures for process development, synthesis, simulation, design and optimization is analyzed. The relation between the mixture molecular properties, the selection of the thermodynamic model and the process technology that could be applied are discussed. A classification of mixtures, separation process, thermodynamic models and technologies is presented to guide the engineer in the world of separation processes. The phase condition required for a given reacting system is studied at subcritical and supercritical conditions.

The four cardinal points of phase equilibrium engineering are: the chemical plant or process, the laboratory, the modeling of phase equilibria and the simulator. The harmonization of all these components to obtain a better design or operation is the ultimate goal of phase equilibrium engineering.

Key Features

  • Methodologies are discussed using relevant industrial examples
  • The molecular nature and composition of the process mixture is given a key role in process decisions
  • Phase equilibrium diagrams are used as a drawing board for process implementation


Chemical engineers, chemical industry R&D scientists and process engineering professionals, and graduate students in Applied Process Thermodynamics


No. of pages:
© Elsevier 2013
23rd April 2013
Hardcover ISBN:
eBook ISBN:

Ratings and Reviews

About the Authors

Esteban Brignole

Affiliations and Expertise

Universidad Nacional del Sur, Argentina

Selva Pereda

Affiliations and Expertise

Universidad Nacional del Sur, Argentina