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Applying the Principle of Corresponding States To APPLYING THE PRINCIPLE OF CORRESPONDING STATES TO MULTI-COMPONENT HYDROCARBON MIXTURES (JET FUELS) Thesis Submitted to The School of Engineering of the UNIVERSITY OF DAYTON In Partial Fulfillment of the Requirements for The Degree of Master of Science in Chemical Engineering By Matthew David Evanhoe UNIVERSITY OF DAYTON Dayton, Ohio December, 2015 Approval Page APPLYING THE PRINCIPLE OF CORRESPONDING STATES TO MULTI- COMPONENT HYDROCARBON MIXTURES (JET FUELS) Name: Evanhoe, Matthew David APPROVED BY: _________________________________ _________________________________ Zachary J. West, Ph.D. Donald K. Phelps, Ph.D. Advisory Committee Chairman Senior Research Chemist Research Engineer, UDRI Air Force Research Laboratory ______________________________ Kevin J. Myers, D.Sc., P.E. Committee Member Graduate Academic Advisor, Professor, Chemical Engineering Department ______________________________ _____________________________ John G. Weber, Ph.D. Eddy M. Rojas, Ph.D., M.A., P.E. Associate Dean Dean School of Engineering School of Engineering ii Approval Page ABSTRACT APPLYING THE PRINCIPLE OF CORRESPONDING STATES TO MULTI- COMPONENT HYDROCARBON MIXTURES (JET FUELS) Name: Evanhoe, Matthew University of Dayton Advisor: Dr. Zachary West Aviation turbine fuel is required to meet stringent product specifications due the critical importance it plays inside of the turbines during the fuel’s use. The specification tests for military and commercial grades of jet fuel include over twenty individual analyses, which are costly in both time and money. In addition, these specifications were designed for petroleum derived fuels and are not always applicable to new finished fuels from alternative sources. For these reasons, it is desirable to develop tools to assess a broad range of jet fuel properties based on the underlying chemical composition. This work outlines a methodology to predict two fuel properties, i.e., density and viscosity, using a theoretical model called generalized corresponding states (GCSP), a subset of the corresponding states principal (CSP). The work analyzes different methods to calculate the critical properties of the mixtures’ components. The components are of vital importance to GCSP. It also investigates reference fluids of the system, which is another important factor in modelling with GCSP. Results for the separate physical parameters, using an initial set of over 50 jet fuels, indicates model predictions fall within an average iii Approval Page error range that spans from 0.01% to 7.29%, and is strongly dependent on the critical properties and reference fluids used. Additional improvements to current models and methods are proposed. iv Approval Page ACKNOWLEDGMENTS First and foremost, I would like to acknowledge and thank my primary advisor, Dr. Zachary West, for all the time and effort he invested into helping me succeed with my education. His input, while I didn’t always like it, was invaluable and the product would have been far inferior without his help. Second, I would like to thank the other committee members, Dr. Donald Phelps and Dr. Kevin Myers, for the time they spent reviewing the work. Also, the members of my workplace who were instrumental in the GCxGC work as well as providing insightful information, Rich Striebich, Linda Shafer, and Milissa Greisenbrock. Finally, I would like to thank AFRL for sponsoring the work. This material is based on research sponsored by the Air Force Research Laboratory under agreement number FA8650-10-2-2934. The U.S. Government is authorized to reproduce and distribute reprints for Governmental purposes notwithstanding any copyright notation thereon. The views and conclusions contained herein are those of the authors and should not be interpreted as necessarily representing the official policies or endorsements, either expressed or implied, of the Air Force Research Laboratory or the U.S. Government. v Approval Page TABLE OF CONTENTS ABSTRACT ....................................................................................................................... iii ACKNOWLEDGMENTS ...................................................................................................v LIST OF FIGURES .............................................................................................................x LIST OF TABLES ........................................................................................................... xiii LIST OF SYMBOLS AND ABBREVIATIONS ............................................................ xiv CHAPTER 1 – INTRODUCTION ......................................................................................1 CHAPTER 2 – BACKGROUND ........................................................................................3 2.1 Fuels Characterization ................................................................................................3 2.1.1 Detailed Hydrocarbon Type via GCxGC ........................................................... 4 2.2 Corresponding States Principle and Related Topics ..................................................5 2.2.1 Generalized Corresponding States Principle ...................................................... 6 2.2.2 Reference Fluids, Critical Properties, and Mixing Rules ................................... 7 2.3 Objective ..................................................................................................................13 CHAPTER 3 – METHODS ...............................................................................................14 vi Approval Page 3.1 GCSP Method ..........................................................................................................14 3.1.1 Density .............................................................................................................. 15 3.1.2 Viscosity ........................................................................................................... 17 3.1.3 Error Measurement ........................................................................................... 17 CHAPTER 4 – RESULTS AND DISCUSSIONS.............................................................19 4.1 Density .....................................................................................................................19 4.1.1 Pseudo-Groups.................................................................................................. 19 4.1.2 Examining Reference Fluids ............................................................................ 30 4.1.3 Three-Parameter GCSP .................................................................................... 35 4.2 Viscosity ...................................................................................................................37 CHAPTER 5 – CONCLUSIONS AND FUTURE WORK ...............................................42 REFERENCES ..................................................................................................................44 APPENDIX A – Compounds Database ........................................................................... A.1 Appendix A.1 DIPPR 801 database compounds .......................................................... A.1 A.1.1 Alkyl-Benzenes (Aromatics) ......................................................................... A.1 A.1.2 Cyclo-aromatics ............................................................................................. A.3 A.1.3 Di-aromatics .................................................................................................. A.3 A.1.4 Di-cycloparaffins ........................................................................................... A.4 A.1.5 Iso-paraffins ................................................................................................... A.5 A.1.6 Monocyclo-paraffins...................................................................................... A.6 vii Approval Page A.1.7 n-paraffins ...................................................................................................... A.8 A.1.8 Tricyclo-paraffins .......................................................................................... A.8 Appendix A.2 Reference Fluid Property Correlations ................................................. A.9 A.2.1 Density Reference Fluids ............................................................................... A.9 A.2.2 Viscosity Reference Fluids .......................................................................... A.10 APPENDIX B – Pseudo-Groups/Reference Fluids ......................................................... B.1 Appendix B.1 – Pseudo-Groups ................................................................................... B.1 B.1.1 Numerical Regression ..................................................................................... B.1 B.1.2 Riazi Estimation .............................................................................................. B.4 B.1.3 Hybrid Method ................................................................................................ B.6 Appendix B.2 – Reference Fluid Results ..................................................................... B.9 B.2.1 DENSITY ....................................................................................................... B.9 B.2.2 VISCOSITY .................................................................................................. B.12 APPENDIX C – Tables of Fuel Properties ...................................................................... C.1
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