Thermodynamics and Applications in Hydrocarbon Energy Production

549 Pages·2016·20.544 MB·English

by  Abbas Firoozabadi

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Dedicated to my wife Ghashang
and to my mother Azra
About the Author
Abbas Firoozabadi is the director of the Reservoir Engineering Research Institute
(RERI) and a professor at Yale University. He is the author of Thermodynamics of
Hydrocarbon Reservoirs and has published some 200 papers. More than 70 of the
papers have appeared in Society of Petroleum Engineers (SPE) journals. Firoozabadi
is a member of the National Academy of Engineering (USA).
Contents
Preface
Acknowledgments
Notation
1 Review of Basic Concepts in Bulk Phase Equilibrium Thermodynamics
1.1 Conditions for Equilibrium
1.1.1 Thermal Equilibrium
1.1.2 Mechanical Equilibrium
1.1.3 Chemical Equilibrium
1.2 Mathematical Properties of U and S
1.3 Gibbs-Duhem Equation
1.4 Other Fundamental Equations
1.5 Internal Energy Minimum Principle
1.5.1 Relation between Partial Derivatives of Implicit Functions
1.5.2 Reciprocity Relation
1.6 Chemical Potential of a Component in a Mixture
1.7 Partial Molar Quantities
1.8 Fugacity
1.9 Ideal and Nonideal Fluids
1.9.1 Ideal Gas
1.9.2 Ideal Solution
1.9.3 Nonideal Solution
1.10 Activity Coefficient
1.11 Relation between γ and GE
i
1.11.1 Pressure and Temperature Derivative of γ
i
1.12 Activity Coefficient Models
1.12.1 Margules Activity Coefficient Equations
1.12.2 Van Laar Activity Coefficient Equations
1.12.3 Scatchard-Hildebrand Regular-Solution Activity Coefficients
1.12.4 Flory-Huggins Polymer-Solution Activity Coefficients
1.13 Legendre Transformation
1.14 Jacobian Transformation
1.15 Maxwell’s Relations
1.16 Examples and Theory Extension
1.17 Problems
1.18 References
2 General Theory of Bulk Phase Equilibria
2.1 Equilibrium Condition under the Influence of Gravity
2.1.1 Conditions for Pronounced Compositional Variation
2.2 Equilibrium Condition for Curved Interfaces
2.2.1 Effect of Curvature on Saturation Pressure: Condensation and
Vaporization in Porous Media
2.3 Equilibrium Condition for Charged Systems
2.3.1 Electrostatic Energy of a Sphere with Uniform Charge
2.3.2 Criteria of Equilibrium for a Charged System
2.4 Examples and Theory Extension
2.5 Problems
2.6 References
3 Equation-of-State Representation of Fluid Phase Behavior and Properties
3.1 EOS Representation of Volumetric and Phase Behavior
3.1.1 Algebraic Form of Cubic Equations
3.1.2 Peng-Robinson Equation of State (PR-EOS)
3.1.3 Phase Behavior of Mixtures with Well-Defined Components
3.1.4 Reservoir Fluid Phase Behavior and Volumetric Properties
3.1.5 CO Dissolution in Petroleum Fluids and Property Changes
2
3.2 Associating Species
3.3 Cubic-Plus-Association Equation of State
3.3.1 CPA-EOS
3.3.2 Water-Containing Mixtures
3.3.3 Asphaltene Precipitation Modeling
3.4 Two-Phase Isothermal Compressibility
3.5 Two-Phase Isentropic Compressibility and Two-Phase Sonic Velocity
3.6 Single-Phase Sonic Velocity and Temperature Change due to Expansion
3.6.1 Heating and Cooling due to Expansion
3.7 Examples and Theory Extension
3.8 Problems
3.9 References
4 Stability and Criticality
4.1 Stability Analysis and Stability Limit
4.1.1 Stability Analysis for a Single-Component
4.1.2 Stability Analysis in a Two-Component System
4.1.3 Stability Analysis for Multicomponent Mixtures
4.2 Criticality Analysis
4.2.1 Single-Component Fluid
4.2.2 Two-Component Fluid
4.2.3 Multicomponent Fluid
4.3 Alternative Approach for Critical-Point Calculation
4.3.1 Single-Component Fluids
4.3.2 Two-Component Fluids
4.3.3 Three-Component Fluids
4.4 Examples and Theory Extension
4.5 Problems
4.6 References
5 Phase Equilibrium Computations
5.1 Gibbs Free Energy Surface Analysis
5.2 Tangent-Plane Distance (TPD) Analysis
5.3 Stability Testing
5.3.1 SSI Method
5.3.2 Newton Method
5.4 Two-Phase Split Computations
5.4.1 SSI Method
5.4.2 Newton Method
5.5 Three-Phase Split Calculations
5.5.1 SSI Method
5.5.2 Newton Method
5.6 Direct Minimization of Gibbs Free Energy in Multiphase Split Calculation
5.7 Phase-Split Calculations in Reduced Space
5.7.1 Zero Interaction Coefficients
5.7.2 Nonzero Interaction Coefficients
5.8 Critical-Point Calculation
5.8.1 Numerical Solution
5.8.2 One-D Search
5.8.3 Initial Guess
5.9 Examples and Theory Extension
5.10 Problems
5.11 References
6 Theory of Irreversibility and Diffusion in Multicomponent Mixtures
6.1 Irreversibility in a Closed System
6.1.1 Entropy Production Strength
6.2 Derivation of Diffusion Flux and Diffusion Coefficients in Multicomponent
Mixtures
6.2.1 Phenomenological Laws of Irreversible Thermodynamics
6.2.2 Diffusion Mass Flux
6.2.3 Thermal Convection
6.2.4 Natural Convection and Diffusion in Porous Media
6.2.5 Compositional Variation in Hydrocarbon Reservoirs
6.3 Prediction of Past Climate Changes from Irreversible Thermodynamics
6.3.1 Ice Core Data
6.3.2 Sampling
6.3.3 Ice Dating
6.3.4 Trapped Air Dating
6.3.5 Temperature Modeling
6.4 Examples and Theory Extension
6.5 Problems
6.6 Appendix
6.6.1 Scalars, Vectors, Tensors, and their Products
6.6.2 Multiplication of a Vector by a Scalar
6.6.3 Scalar Product or Dot Product (·) of Two Vectors
6.7 References
7 Interfacial Thermodynamics
7.1 Plane Interface
7.2 Curved Interface
7.3 Thermodynamic Functions
7.4 Effect of Curvature on Interfacial Tension
7.5 Work of Cluster Formation: Single-Component Systems
7.5.1 Spherical Clusters
7.5.2 Incompressible Clusters
7.5.3 Gas Clusters
7.6 Cap-Shaped Clusters
7.7 Derivation of the Young Equation
7.8 Driving Force (Δµ)
7.8.1 Condensation from Vapor at Constant T
7.8.2 Evaporation from Liquid at Constant T
7.9 Thermodynamic Functions and Gibbs Adsorption Equation without
Chemical Equilibrium
7.10 Helmholtz Free Energy of an Open System