Louisiana State University LSU Digital Commons LSU Historical Dissertations and Theses Graduate School 1964 High Vacuum Distillation. David Bernard Greenberg Louisiana State University and Agricultural & Mechanical College Follow this and additional works at: https://digitalcommons.lsu.edu/gradschool_disstheses Recommended Citation Greenberg, David Bernard, "High Vacuum Distillation." (1964). LSU Historical Dissertations and Theses. 978. https://digitalcommons.lsu.edu/gradschool_disstheses/978 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]. This dissertation'has been 65—3377 microfilmed exactly as received GREENBERG, David Bernard, 1928- HIGH VACUUM DISTILLATION.' Louisiana State University, Ph.D., 1964 Engineering, chemical University Microfilms, Inc., Ann Arbor, Michigan HIGH VACUUM DISTILLATION A Dissertation Submitted to the Graduate Faculty of the Louisiana State University snd Agricultural and Mechanical College in partial fulfillment of the requirements for the degree of Doctor of Philosophy i n The Department of Chemical Engineering by' David Bernard Greenberg B.S., Carnegie Institute of Technology, 1952 M.S., The Johns Hopkins University, 1959 August, l$6k ACKNOWLEDGMENT The author is deeply indebted to Dr. Bernard Pressburg whose guidance, assistance, and direction were major factors in bringing this research to fruition. Sincere appreciation is also extended to Dr. Jesse Coates who took time from his busy schedule to offer council and advice on many of the theoretical aspects encountered during the course of this work. The author also wishes to acknowledge gratefully the aid received from the Ethyl Corporation for lending the modified CMS-5 molecular s till with-which the experimental work was carried out. Sincere thanks are especially extended to Mr. Hoyt Cragg, of the Ethyl Corpora­ tion, who gave much technical assistance in setting up and operating the still. Appreciation is also tendered to Charles Pfizer and Company, Pittsburgh Chemical Company, Allied Chemical and Dye Corporation, and Union Carbide and Chemical Company for supplying samples and physical property data which were used in this study. TABLE OF CONTENTS PAGE ABSTRACT.................................... ................................................ vi i CHAPTER I INTRODUCTION ...................................................................................................... 1 II THEORY . .................................................................................. 6 1. Theoretical Rate of Vaporization .......................... 6 2. Significance of the Evaporation Coefficient .................. 10 III EXPERIMENTAL WORK ............................ .1 7 1. The Centrifugal Molecular Still .............................................. 17 2. Modification of the Original S till ..........................................24 3. Calibration Procedures and Physical Measurements . 25 4. Test Materials...............................................................................29 5. Sample. Preparation and Experimental. Procedure .... 32 IV INTERPRETATION OF RESEARCH ..................................35 1. The Mathematical Model ................................................................35 2* Method of Solution of the Mathematical Model .... 45 3. Experimental R e s u lts ............................................. 47 V DISCUSSION OF RESULTS ..... ........................................................ 53 1. General . ................................................. 53 2. Analysis of the Phthalate and Sebacate R uns ......................58 3. Analysis of the Glycerol Runs ......................................................62 CHAPTER PAGE VI CONCLUSIONS AND RECOMMENDATIONS........................................................67 SELECTED BIBLIOGRAPHY........................ ....................................................................70 APPENDIX A NOMENCLATURE .................................................................... 73 B SKETCH OF COORDINATE SYSTEM . ' .............................................................75 C COMPUTER ANALYSIS OF EXPERIMENTAL RUNS ......... 76 D NORMALIZED GRAPHS FOR SELECTED RUNS...............................................98 AUTOBIOGRAPHY.......................... 104 i v I LIST OF TABLES TABLE PAGE I Experimental and Estimated Evaporation Coefficients .... 12 II Centrifugal Still - Characteristics and Operating F eatures ..................................................................................................................23 III Mid-Rotor Flow and Thermal C onditions ................' ............................59 IV Constant Temperature Runs - Glycerol ............................................ 6 l V Run No. k - G lycerol ......................................................................................77 VI Run No. 6 - Glycerol............................................................................. j8 VII Run No. 9 “ G lycerol ......................................................................................79 VIII Run No. 11 - G lycerol ................................. 80 IX Ri|n No. 13 “ G lycerol ............................................................................. 81 X Run No. Ik - Glycerol......................................................................................82 XI Run No. 15 - Glycerol .....................................................................83 XII Run No. 16 - G lycerol ......................................................................................8k XIII Run No. 18 - G lycerol ...................................................................................8 5 XIV Run No. 19 “ G lycerol ............................ .8 6 XV Run No. 20 - G lycerol ................................................... 87 XVI Run No. 21 - Glycerol ................................................................................. 88 XVII Run No. 23 “ G lycerol ......................................................................................89 XVIII Run No. 25 “ Glycerol . ................................................ 90 XIX Run No. 33 " Dibutyl P h th a la te ................................................................... 91 XX Run No. 38 - Dibutyl P h th a la te ................................................................... 92 v TABLE PAGE XXI Run No. kj - Dibutyl P h th alate .................................................................93 XXII Run No. 51 " Dibutyl P h th alate ............................ XXIII Run. No. 59 - Dibutyl P h th alate .................................................................95 XXIV Run No. 77 - Di (2-Ethylhexyl) Phthalate ...........................................96 XXV Run No. 97 ■ Di (2-Ethylhexyl) S ebacate ..............................................97 LIST OF FIGURES FIGURE PAGE 1 Centrifugal Still - Front View ........................................................ 18 2 Bell Jar and Receiver .............................................................................. 19 3 Centrifugal Still - Rear View ..............................................................20 k Diffusion Pump System ...............................................................................21 5 Bell Jar and Calibrated Receiver ..........................................................22 6 Feed Pump C alibration ..................................................................................30 7 Flow Pattern on Rotor - 50 C entipoises ...........................................37 8 Flow Pattern on Rotor - 30 Centipoises • • . ..................................38 9 Flow Pattern on Rotor - 20 C entipoises ..................................... 39 10 Flow Pattern on Rotor - 10 C en tip o ises ...........................................^0 11 Experimental Rates - Glycerol • .......................................................^8 12 Experimental R ates- Dibutyl Phthalate • • ............................. ^ 13 Experimental Rates - Dibutyl Sebacate ........................................... '50 11+ Experimental Rates - Di (2-Ethylhexyl) Phthalate .... 51 15 Experimental Rates - Di (2-Ethylhexyl) Sebacate • • • • • 52 16 Run No. k - Glycerol.....................................................................................98 17 Run No. 9 ■ G lycerol ................................................................. 99 18 Run No. Ik - Glycerol ................................. 100 19 Run No. 38 - Dibutyl P h th a la te ............................................................101 20 Run No. 59 " Di butyl S ebacate ...............................................................102 21 Run No. 97 " Di (2-Ethylhexyl) Sebacate ..........................................103 v i i ABSTRACT Present knowledge in the field of molecular distillation has ♦ not reached the point where it can be applied to designing commercial s tills without extensive bench and pilot scale development. Analysis of the literature indicates that additional experimental data and improved methods of applying the fundamental laws of transport phenomena to this problem are needed. This research was conducted, therefore, for the purpose of contributing to the experimental and theoretical knowledge in the field. The centrifugal s ti l l design was chosen for experimental study