Catalytic Reforming of Methylcyclopentane. Douglas Maurice Selman Louisiana State University and Agricultural & Mechanical College
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Louisiana State University LSU Digital Commons LSU Historical Dissertations and Theses Graduate School 1972 Catalytic Reforming of Methylcyclopentane. Douglas Maurice Selman Louisiana State University and Agricultural & Mechanical College Follow this and additional works at: https://digitalcommons.lsu.edu/gradschool_disstheses Recommended Citation Selman, Douglas Maurice, "Catalytic Reforming of Methylcyclopentane." (1972). LSU Historical Dissertations and Theses. 2242. https://digitalcommons.lsu.edu/gradschool_disstheses/2242 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 dissertation was produced from a microfilm copy of the original document. 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Further reproduction prohibited without permission. I I 72-28,377 SELMAN, Douglas Maurice, 19M-2- CATALYTIC REFORMING OF METHYLCYCLOPENTANE. The Louisiana State University and Agricultural and Mechanical College, Ph.D., 1972 Engineering, chemical University Microfilms, A XEROX Company, Ann Arbor, Michigan © 1972 Douglas Maurice Selman ALL RIGHTS RESERVED ----.— ^ ^-r- n w K o m r i ; a o n n n r T t r m Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. CATALYTIC REFORMING OF METHYLCYCLOPENTANE 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 Douglas Maurice Selman B.S., The University of Texas, 1965 M.S., The University of Texas, 1967 May, 1972 Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. PLEASE NOTE: Some pages may have indistinct print. Filmed as received. University Microfilms, A Xerox Education Company Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. "In all thy ways acknowledge Him, and He shall direct thy paths." - Proverbs 3;6 ii Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. ACKNOWLEDGEMENTS This author wishes to first acknowledge Professor Alexis Voorhles, Jr. who provided the opportunity for this undertaking. Association with a man of his scientific reasoning and organizing ability has provided perhaps the greatest learning experience for this author. His example of dedication and diligence will always be remembered. The financial support from Esso Research and Engineering Company is gratefully acknowledged as well as analytical support from the Esso Research Laboratories in Baton Rouge. This author is indebted to Mamerto Luzarraga and Ken Clem who as project associates contributed to this work through numerous informal discussions. Mrs. Arlene C. Smith is acknowledged for her diligent efforts in typing this dissertation. Finally, special acknowledgement is given to my wife, Jo Karen, who cheerfully took over many of my duties at home and who provided encouragement and motivation at times when these were needed. ill Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. TABLE OF CONTENTS PAGE LIST OF TABLES ...................................................... LIST OF FIGURES ..................................................... ABSTRACT ............................................................. CHAPTER .............................................................. I. INTRODUCTION ............................................... 1 II. LITERATURE SURVEY ......................... 4 A. Introduction ......................... 4 B. Reforming Catalysts .................................. 8 1. Reforming Catalyst Development ................. 9 2. Dual-Function Reforming Catalysts ............. 11 a. Hydrogenation-Dehydrogenation Component ... 11 b. Acidic Component ............ 14 c. Relationship Between Acidic and Metal Sites 16 3. "Bimetallic" Dual- Function Catalysts ......... 18 C. Methylcyclopentane Reforming Reaction Mechanisms .. 19 1. Ring Isomerization-Dehydrogenation Reactions .. 20 2. Ring Opening Reactions .......................... 22 3. Composite Reaction Scheme ...................... 25 List of References - Chapter II ....................... 28 III. EXPERIMENTAL EQUIPMENT AND PROCEDURE ................... 33 iv Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. PAGE A. General ...................................... 33 B. Experimental Equipment ............................... 33 1. Feed System ................. 34 2. Product Recovery and Sampling................... 36 3. Reactor ................. ................... 37 4. Instrumentation.................................. 39 C. Analytical Equipment ................................. 40 D. Materials ............................................. 42 E. Experimental Procedure ............................... 43 1. Catalyst Activation ............................. 43 2. Catalyst "Lineout" .............................. 43 3. Procedure for Process Variable Study ........... 48 4. Yield Calculations From Experimental Data .... 50 IV. MATHEMATICAL MODELING TECHNIQUE ......................... 51 A. Introduction .................................... 51 B. Reaction Mechanisms In Heterogeneous Catalysis .... 52 C. Simplified Methylcyclopentane Reaction Mechanism .. 54 D. Derivation of Reaction Rate Equations ............. 54 E. Solution of the Differential Rate Equations ....... 66 F. Evaluation of the Reaction Rate Constants ......... 71 G. Correlation of Rate Constants ...................... 81 List of References - Chapter I V ......................... 82 V. EXPLORATORY EXPERIMENTAL D A T A ........................... 83 A. Reactor Considerations .......................... 83 1. Reactor Type ..................................... 83 2. Extent of Axial Dispersion ..................... 85 v Reproduced with permission of the copyright owner. Further reproduction prohibited without permission. PAGE 3. Axial Temperature Profile ........ .............. 86 4. Catalytic Effects of Reactor Walls ...... 88 B. Catalyst "Llneout" Behavior ......................... 88 C. Test for Mass Transfer Limitations ................. 97 1. External Mass Transfer .......................... 98 2. Pore Diffusion ............. 102 List of References - Chapter V .......................... 108 VI. EXPERIMENTAL EFFECT OF SPACE T I M E ........................ 109 A. Introduction ...................... 109 B. Effect of Space Time on Reaction Products ......... 110 C. Evaluation of Kinetic Model .......................... 122 D. Kinetic Model Predictions ...................... 133 List of References - Chapter VI ......................... 137 VII. EXPERIMENTAL EFFECT OF PRESSURE AND TEMPERATURE ........ 138 A. Introduction .......................................... 138 B. Pressure-Temperature Effect on Product Selectivity 142 C. Correlation of the Reaction Rate Constants ........ 170 List of References - Chapter VII ........ 194 VIII. CONCLUSIONS ................................................ 195 A. Reaction Mechanism for Catalytic Reforming of Methylcyclopentane ................................... 195 B. Kinetic Model for Methylcyclopentane Reforming .... 197 G. Comparison of Ft and Ft-Re Catalysts ............... 198 D. Practical Implications of Experimental Data ...... 199 IX. RECOMMENDATIONS ...........................................