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1972 Catalytic Reforming of Methylcyclopentane. Douglas Maurice Selman Louisiana State University and Agricultural & Mechanical College
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Recommended Citation Selman, Douglas Maurice, "Catalytic Reforming of Methylcyclopentane." (1972). LSU Historical Dissertations and Theses. 2242. https://digitalcommons.lsu.edu/gradschool_disstheses/2242
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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
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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
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3. Axial Temperature Profile ...... 86
4. Catalytic Effects of Reactor Walls ...... 88
B. Catalyst "Llneout" Behavior ......