Table of Contents
Chapter 1: Introduction
1 1 Identify the right physics in process simulation
1 2 What is a thermodynamic method?
1 2 1 The physical model
1 2 2 The algorithm
1 2 3 The data: properties or parameters?
1 2 4 Conclusions
1 3 Criteria for problem analysis
1 3 1 What property is given/requested?
1 3 2 What are the mixture components?
1 3 3 Where are the process conditions located with respect to the phase envelope?
1 4 Conclusions
Reference List
Chapter 2: From Fundamentals to Properties
2 1 Properties, states and phases
2 1 1 Properties
2 1 1 1 Volume
2 1 1 2 Pressure
2 1 1 3 Temperature
2 1 1 4 Entropy
2 1 1 5 Energies
2 1 2 Thermodynamic state
2 1 3 Gibbs’ phase rule, or how to read a phase diagram
2 1 3 1 Pure component application
2 1 3 2 Binary systems
2 1 3 3 Three phases Txy or Pxy diagrams
2 1 3 4 Ternary mixtures
2 1 3 5 Multicomponent system
2 1 4 Duhem’s phase rule (theorem)
2 2 Property computation
2 2 1 Some fundamental relationships
2 2 1 1 System properties
2 2 1 2 Phase properties
2 2 1 3 Mixture
2 2 1 4 Property of a pure component in a phase
2 2 2 Calculation of single phase “thermodynamic” properties
2 2 2 1 Residual approach (equations of state)
2 2 2 2 The excess approach (activity coefficients)
2 2 3 Phase equilibrium
2 2 3 1 Some basic principles for phase calculations
2 2 3 2 Practical applications of phase equilibrium
2 2 4 Chemical equilibrium
2 2 4 1 Basic principles for chemical equilibrium calculations
2 2 4 2 Model requirements for chemical equilibrium
Reference List
Chapter 3: From Components to Models
3 1 Pure Components: properties and parameters
3 1 1 Pure component properties and parameters
3 1 1 1 Physical properties as model parameters
3 1 1 2 Temperature dependent physical properties
3 1 2 Types of component
3 1 2 1 Database components
3 1 2 2 Non-database components (group contribution)
3 1 2 3 Petroleum fluid components
3 1 3 Screening methods for pure component property data
3 1 3 1 Internal check
3 1 3 2 External check
3 2 Mixtures: properties and parameters
3 2 1 Vapour-liquid equilibrium data
3 2 1 1 TPx (isobaric or isothermal)
3 2 1 2 Gas solubility
3 2 1 3 TPxy (isobaric or isothermal)
3 2 2 Liquid-liquid equilibrium data
3 3 Data fitting
3 3 1 General guidelines
3 3 1 1 Choosing the model
3 3 1 2 The parameters to be adjusted
3 3 1 3 The data
3 3 1 4 The objective function
3 3 1 5 The weighting factor
3 3 1 6 The initial values
3 3 1 7 Optimisation algorithm
3 3 1 8 The resulting uncertainties on the parameters
3 3 2 Detailed examples
3 3 2 1 Vapour pressure fit 3 3 2 2 VLE fit
3 3 3 Conclusion
3 4 Models for the mixture properties
3 4 1 Prediction of some phase diagrams using the infinite dilution activity coefficients 160
3 4 1 1 Positive and negative deviations from ideality
3 4 1 2 Azeotropy
3 4 1 3 Liquid-liquid equilibria
3 4 1 4 Conclusion
3 4 2 Activity models, or how the molecular structure affects the non-ideal behaviour 171
3 4 2 1 Enthalpic vs entropic contributions
3 4 2 2 Enthalpic deviation from ideality
3 4 2 3 Entropic deviation from ideality (athermal solutions)
3 4 2 4 Mixed enthalpic and entropic deviation from ideality
3 4 2 5 Electrolyte models
3 4 2 6 Conclusion on activity coefficient models
3 4 3 Equations of State, EoS (all fluid phases)
3 4 3 1 Introduction on the use of equations of state
3 4 3 2 Molecular basis for Equations of State
3 4 3 3 Virial equations of state
3 4 3 4 The cubic equations of state
3 4 3 5 The SAFT family equations of state
3 4 3 6 The lattice fluid equations of state
3 4 3 7 Conclusions for equations of state
3 4 4 Phase-specific models
3 4 4 1 Pure solid phases
3 4 4 2 Hydrates
3 4 4 3 Properties at infinite dilution
3 4 4 4 Gases in hydrocarbons: Grayson and Streed
3 5 What are the key components concentration range?
3 5 1 Phase appearance or phase envelope calculations
3 5 1 1 Vapour-Liquid Equilibrium (VLE) calculations
3 5 1 2 Liquid-Liquid Equilibrium (LLE) calculations
3 5 1 3 Liquid-Solid Equilibrium (LSE) calculations
3 5 2 Distribution coefficients calculation
3 5 2 1 Simple distillation
3 5 2 2 Azeotropic distillation
3 5 2 3 Impurities
Reference List
Chapter 4: From Phases to Method (Models) Selection
4 1 Single phase properties
4 1 1 PVT plot
4 1 2 Enthalpy and entropy plots
4 1 3 Derived properties
4 1 3 1 Heat capacities
4 1 3 2 Joule Thomson coefficient
4 1 3 3 Speed of sound
4 1 4 Model recommendations
4 1 4 1 Use of the one-fluid approximation
4 1 4 2 Use of mixing rules and excess properties
4 2 Phase equilibrium behaviour of industrially significant mixtures 264
4 2 1 Phase equilibrium classification
4 2 1 1 Fluid phases equilibrium
4 2 1 2 Fluid-solid equilibrium
4 2 2 Phase equilibrium in organic (hydrocarbon) mixtures
4 2 2 1 Vapour-liquid equilibrium in organic mixtures
4 2 2 2 Liquid-liquid in organic mixtures
4 2 2 3 Fluid-solid equilibrium in organic mixtures
4 2 2 4 Asphaltene precipitation
4 2 3 Phase equilibrium in presence of H2 or other supercritical gases
4 2 4 Phase equilibrium in presence of an aqueous phase
4 2 4 1 Fluid phase equilibrium
4 2 4 2 Solubilities
4 2 4 3 Fluid-Solid phase equilibrium (ice and hydrates)
4 2 5 Phase equilibrium in presence of CO2/H2S
4 2 5 1 CO2 and H2S with hydrocarbons at high pressures
4 2 5 2 CO2 and H2S solubilities in liquid hydrocarbons
4 2 5 3 Phase equilibria of industrial solvents with CO2 and H2S 310
4 2 6 Phase equilibrium in the presence of molecules containing heteroatoms (e g oxygenated)
4 2 6 1 Polar interactions
4 2 6 2 Hydrogen bonds: auto-association
4 2 6 3 Effect of cross-association
4 2 7 Other systems of industrial interest
4 2 7 1 Polymers
4 2 7 2 Ionic liquids
4 3 Conclusions: how to choose a model
4 3 1 The right questions
4 3 1 1 What is the property of interest?
4 3 1 2 What is the fluid composition?
4 3 1 3 What are pressure and temperature conditions of the process? 326
4 3 2 Decision Tree
Reference List
Reference List
Chapter 5 - Case Studies
5 1 Problem Solving Procedure
5 1 1 Evaluation of the most appropriate model(s)
5 1 1 1 Properties required
5 1 1 2 Fluid composition
5 1 1 3 Representative phases