Louisiana State University LSU Digital Commons LSU Historical Dissertations and Theses Graduate School 1992 Phase Equilibria of Supercritical Carbon Dioxide and Hydrocarbon Mixtures. Hyo-guk Lee Louisiana State University and Agricultural & Mechanical College Follow this and additional works at: https://digitalcommons.lsu.edu/gradschool_disstheses Recommended Citation Lee, Hyo-guk, "Phase Equilibria of Supercritical Carbon Dioxide and Hydrocarbon Mixtures." (1992). LSU Historical Dissertations and Theses. 5325. https://digitalcommons.lsu.edu/gradschool_disstheses/5325 This Dissertation is brought to you for free and open access by the Graduate School at LSU Digital Commons. It has been accepted for inclusion in LSU Historical Dissertations and Theses by an authorized administrator of LSU Digital Commons. For more information, please contact [email protected]. INFORMATION TO USERS This manuscript has been reproduced from the microfilm master. 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Photographs included in the original manuscript have been reproduced xerographically in this copy. Higher quality 6" x 9" black and white photographic prints are available for any photographs or illustrations appearing in this copy for an additional charge. Contact UMI directly to order. University Microfilms International A Bell & Howell Information Com pany 300 North Zeeb Road. Ann Arbor. Ml 48106-1346 USA 313/761-4700 800/521-0600 Order Number 9301073 Phase equilibria of supercritical carbon dioxide and hydrocarbon m ixtures Lee, Hyo-Guk, Ph.D. The Louisiana State University and Agricultural and Mechanical Col., 1992 UMI 300 N. Zeeb Rd. Ann Arbor, MI 48106 PHASE EQUILIBRIA OF SUPERCRITICAL CARBON DIOXIDE AND HYDROCARBON MIXTURES A Dissertation Submitted to the Graduate Faculty of the Louisiana State University and Agricultural and Mechanical College in partial fulfillment of the requirements for the degree of Doctor of Philosophy in The Department of Chemical Engineering by Hyo-Guk Lee B.S., Hanyang University, Seoul, Korea, 1975 M.S., Korea Advanced Institute of Science and Technology, 1981 May, 1992 ACKNOWLEDGEMENTS I wish to thank Dr. Frank R. Groves for his guidance and patience throughout this investigation. In particular, his help in analysis of the experimental results and thorough review of this work are greatly appreciated. Dr. Kerry M. Dooley. Dr. Arthur M. Sterling, Dr. Douglas P. Harrison of Chemical Engineering Department and Dr. Philip A. Schenewerk in Petroleum Engineering Department are appreciated for serving as members of the advisory committee. I express my gratitude to Dr. Zaki A. Bassiouni and Dr. Joanne M. Wolcott of Petroleum Engineering Department for financial support and for providing the exper­ imental apparatus. Coworkers in the C 02 group are also appreciated for their help in my experiments. Finally I must thank my brothers and sisters for their financial and mental support, my wife for her desperate patience, and my sister-in-law who has served me like my mother. TABLE OF CONTENTS p_a.se. ACKNOWLEDGEMENTS................................................................................................ ii ABSTRACT .......................................................................................................................... xii CHAPTER i INTRODUCTION ..................................................................................... 1 1.1 Motivation and Background .......................................................... 1 1.2 Research Objectives ........................................................................ 3 1.3 Literature Review ............................................................................ 4 CHAPTER 2 VAPOR-LIQUID EQUILIBRIA OF BINARY CO, AND HYDRO­ CARBON MIXTURES............................................................................. 8 2.1 Introduction ...................................................................................... 8 2.2 Calculation of VLE by Activity Coefficient Method ............... 10 2.2.1 Liquid Fugacity of Pure Supercritical C 0 2...................... 11 2.2.2 Pressure Correction for Activity Coefficient ................. 13 2.2.3 Liquid Molar Volume of Pure Component .................... 17 2.2.4 Other Parameters ................................................................ 19 2.3 Parameter Search ............................................................................. 19 2.4 Results and Analysis ....................................................................... 24 2.5 D iscussion ................................. 37 CHAPTER 3 PHASE EQUILIBRIA OF SUPERCRITICAL CO, AND HYDRO­ CARBON SOLID ...................................................................................... 39 3.1 Literature Review ............................................................................ 39 3.2 Theory' ............................................................................................. 41 3.2.1 EOS Method ....................................................................... 41 3.2.2 Activity coefficient Method .............................................. 42 3.3 Correlation using the E O S ............................................... 43 3.3.1 Sublimation Pressure and Molar Volume of S o lu te 43 3.3.2 Correlation using the SRK-EOS ...................................... 45 3.3.3 Correlation using the Modified PR-EOS ....................... 57 3.4 Correlation using the Activity Coefficient ................................. 60 3.5 D iscussion ......................................................................................... 62 CHAPTER 4 SOLID-LIQUID EQUILIBRIA OF HYROCARBON/HYDRO- CARBON MIXTURES............................................................................. 66 4.1 Introduction ...................................................................................... 66 4.2 Experimental ..................................................................................... 67 4.2.1 A pparatus............................................................................. 67 4.2.2 Materials .............................................................................. 69 4.2.3 Experimental Procedure ................................................... 69 4.2.4 Results ................................................................................. 71 4.3 T heory ................................................................................................ 75 4.3.1 Ideal Solubility ................................................................... 75 4.3.2 Temperature Dependency of the Activity Coefficient .. 78 4.3.3 Pressure Dependency of the Activity Coefficient ........ 80 4.3.4 Prediction of the Saturation Lines .................................. 81 4.4 Discussion ......................................................................................... 99 iii CHAPTER 5 EQUILIBRIA OF SUPERCRITICAL CO„ LIGHT HYDROCAR­ BON LIQUID AND HEAVY HYDROCARBON SOLID MIX­ TURES .............................................................................................................. 102 5.1 Introduction .......................................................................................... 102 5.2 Experimental ......................................................................................... 103 5.3 Results ................................................................................................... 104 5.4 Correlation ............................................................................. 121 5.4.1 Model equations ..................................................................... 121 5.4.2 Application to Systems Containing nC2„ .......................... 125 5.4.3 Application to C 02/nC„/Xylene/Phenanthrene System 130 5.5 Discussion ................................................................................ 141 CHAPTER 6 CONCLUSIONS AND RECOMMENDATIONS FOR FUTURE WORK .............................................................................................................. 143 6.1 Conclusions .......................................................................................... 143 6.2 Recommendations for Future Work .............................................. 146 NOMENCLATURE ................................................................................................................. 149 REFERENCES ...................................... 151 APPENDICES ........................................................................................................................... 159 A Partial Molar Volume by SRK-EOS ...............................................