Virginia Commonwealth University VCU Scholars Compass Theses and Dissertations Graduate School 2015 MEASUREMENTS AND MODELING OF HYDROCARBON MIXTURE FLUID PROPERTIES UNDER EXTREME TEMPERATURE AND PRESSURE CONDITIONS Babatunde A. Bamgbade Virginia Commonwealth University Follow this and additional works at: https://scholarscompass.vcu.edu/etd Part of the Complex Fluids Commons, Petroleum Engineering Commons, and the Thermodynamics Commons © The Author Downloaded from https://scholarscompass.vcu.edu/etd/3967 This Dissertation is brought to you for free and open access by the Graduate School at VCU Scholars Compass. It has been accepted for inclusion in Theses and Dissertations by an authorized administrator of VCU Scholars Compass. For more information, please contact [email protected]. Measurements and Modeling of Hydrocarbon Mixture Fluid Properties under Extreme Temperature and Pressure Conditions A dissertation submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy at Virginia Commonwealth University. by Babatunde A Bamgbade Doctor of Philosophy Virginia Commonwealth University, 2015 Directors: Dr. Frank B. Gupton Professor, Department of Chemical and Life Science Engineering And Dr. Mark A. McHugh Emeritus Professor, Department of Chemical and Life Science Engineering Virginia Commonwealth University Richmond, Virginia August, 2015 Acknowledgment All glory be to God the Alpha and Omega for seeing me through this journey. I express my profound gratitude to my advisor, Professor Mark A. McHugh for supporting, encouraging, guiding, and where necessary showing me tough love throughout this research over the years. His devotion and passion to science, his great personality, and also a remarkable sense of humor causes me to marvel at the man behind the name and makes me feel that I have the best advisor ever. He also shows an express belief in me even when I doubt myself. I appreciate my PhD committee members, Professor Frank Gupton, Professor Stephen Fong, Professor Vamsi Yadavalli, Professor, James McLeskey, Professor Worth Longest, and Dr. Isaac Gamwo for their time and efforts as well as valuable suggestions for my research. I acknowledge Dr. Deepak Tapriyal, Professor Robert Enick, Dr. Ward Burgess, Dr. Hseen Baled and Dr. Yue Wu for their continual support, valuable remarks, and helpful technical discussions. I also want to thank my colleagues in Dr. McHugh’s research group, Mr. Matthew Newkirk, Mr., Mr. Sean Dudek, Dr. Rajendar R. Mallepally, Dr. Kun Liu, and Mr. Michael Marin for their helpful discussions and exchange of ideas. I thank all my friends and colleagues who have contributed to this journey in one way or another I especially thank my family for their continual support, prayers, and advice. I would like to take this time to remember my dad, who sadly passed on during this academic journey. RIP Dad! I acknowledge National Energy Technology Laboratory for providing the financial support for this project. Finally, I want to express my deep gratitude to my darling wife for her support and putting with my late night experiments and studies. All those times are remembered and well-appreciated. I wish every one of them good health and happiness. ii © Babatunde A. Bamgbade 2015 All Rights Reserved iii Table of Contents List of Tables ................................................................................................................................. vi List of Figures .............................................................................................................................. xiii List of Abbreviations .................................................................................................................. xix Abstract ...................................................................................................................................... xxii Chapter 1 Introduction .....................................................................................................................1 1.1 Importance of Hydrocarbon Fluid Properties at Extreme Conditions ....................................1 1.2 Correlations and Models for Representing Hydrocarbon Fluid Properties ............................3 1.2.1 Cubic-Based Equation of State (EoS) Models .....................................................................4 1.2.2 SAFT-Based EoS Models: Perturbed-Chain Statistical Associating Fluid Theory .............7 1.3 Objectives of This PhD Study...............................................................................................11 Chapter 2 High-Pressure Experimental Techniques ......................................................................12 2.1 Methods for Measuring High-Pressure Density ...................................................................12 2.2 Experimental Techniques ......................................................................................................19 2.2.1. Internal View Cell Volume Calibration and Density Measurements .........................19 2.2.2 Procedure for Phase Behavior Determination..............................................................23 2.3 Error Analysis .......................................................................................................................24 2.3.1 Uncertainty Associated with Reported Density Data ..................................................24 2.3.2. Uncertainty Associated with Reported Mixture Compositions ..................................25 Chapter 3 Experimental and Modeling Results: Pure Compounds ...............................................26 3.1 Experimental Results ............................................................................................................26 3.1.1 Propane ........................................................................................................................26 3.1.2 Squalane .......................................................................................................................29 3.1.3 Bis (2-ethylhexyl) Phthalate (DEHP)...........................................................................32 3.2 Correlations with the Modified Tait Equation ......................................................................35 3.3 EoS Modeling .......................................................................................................................38 3.3.1 Peng-Robinson (PR) and Volume-Translated (VT) PREoS ........................................39 3.3.2 Perturbed-Chain Statistical Associating Fluid Theory (PC-SAFT) EoS .....................44 3.4 Final Comments ....................................................................................................................53 Chapter 4 Experimental and Modeling Results: Propane Binary Mixtures ...................................54 4.1 Experimental Results ............................................................................................................54 iv 4.1.1 Propane-Decane (C3-C10) Mixture Density .................................................................54 4.1.2 Propane-Eicosane (C3-C20) Mixture Density ...............................................................60 4.1.3 Propane-Squalane (C3-C30) Mixture Density ...............................................................64 4.1.4 Propane-Eicosane (C3-C20) Mixture Phase Behavior ..................................................71 4.2 Correlations and Excess Volume Properties .........................................................................75 4.2.1 Modified Tait Equation ................................................................................................75 4.2.2 Mixture Molar Volumes and Excess Mixture Molar Volumes ...................................81 4.3. Equation of State Modeling .................................................................................................86 4.3.1 Peng-Robinson (PR) and Volume-Translated (VT) PREoS ........................................86 4.3.2 Perturbed-Chain Statistical Associating Fluid Theory (PC-SAFT) EoS .....................90 4.3.3 Comparison of Equation of State Model Predictions for Binary Mixture Density......98 4.3.4 Modeling Results for Propane-Eicosane (C3-C20) Phase Behavior ...........................108 4.3.5 Concept of Hybrid PC-SAFT EoS .............................................................................112 4.4 Final Comments ..................................................................................................................114 Chapter 5 Experimental and Modeling Results for Two Crude Oil Samples ..............................115 5.1 Introduction .........................................................................................................................115 5.2 Experimental Results and Correlations ...............................................................................116 5.2.1 Experimental Results: Density of Crude Oil Samples ...............................................116 5.2.2 Modified Tait Equation Fit to Experimental Data .....................................................121 5.3 PC-SAFT EoS Modeling Methods for Crude Oil ...............................................................122 5.3.1 Characterization Results ............................................................................................124 5.3.2 Asphaltene Precipitation and Solid Phase Extraction ................................................125 5.3.3 GC Analyses and Crude Oil Molecular Weight Determination