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Process Analysis of Sulfolane Process

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Process Analysis of Sulfolane Process PROCESS ANALYSIS OF SULFOLANE PROCESS: DEVELOPMENT AND APPLICATION OF PROCESS RETROFIT METHODOLOGY By C. SHY AMKUMAR Bachelor of Engineering (Honors) Birla Institute of Technology and Science, Pilani, India 1992 Submitted to the Faculty of the Graduate College of the Oklahoma State University in partial fulfillment of the requirements for the Degree of MASTER OF SCIENCE December, 1994 PROCESS ANALYSIS OF SULFOLANE PROCESS: DEVELOPMENT AND APPLICATION OF PROCESS RETROFIT METHODOLOGY Thesis Approved: Thesis bJVisor ii ACKNOWLEDGMENTS I would like to express my appreciation to my advisor, Dr. Karen A. High, for her sincere, prompt, and persistent intellectual and financial support on the sulfolane project. I enjoyed working with her in an informal and efficient atmosphere. I am grateful to my thesis committee members, Dr. A J. Johannes and Dr. Jan Wagner, for their expert guidance and criticism. I would like to thank Dr. Corinna Czekaj, Department of Chemistry, OSU, for her help with the process chemistry. I would also like to thank Jim O'Connor, Dr. Howard Efner, Dr. Mark Lashier, and Earl Clark at Phillips Petroleum Company for their collaborative support. My interaction with them was extremely helpful to my professional development. I wish to acknowledge Manesh Jayagopal, with whom I had the opportunity to share stimulating graduate research. I am greatly indebted to my family for having supported me emotionally. They have always encouraged me in my pursuits and had faith in my capabilities. I would like to make a special dedication to my late father, Calambur Srinivasan, for whom I had a lot of respect and affection. Lastly, I would like to thank my roommates and friends at Stillwater for their company, friendship, and support. This work was made possible by a National Science Foundation grant, CTS- 92 1 6384. iii TABLE OF CONTENTS Chapter Pa� I. INTRODUCTION .............................................. .......... ....... ... ....... 1 II. BACKGROUND ................... ................... ..................................... S Process Description ................................................ ... .............. ..... S Motivational Background ................................................................ f Existing Methodologies For Process Retrofit............... ......................... f Process Analysis Through Modeling ...................................... .......... � n;ti � ......................................................... ... ......... Eco�o c alysis . S Opttmtzatto n ............................................................................... 1 III. PROCESS DESCRIPTION ............................................................... 1 Process Chemistry .................................. ..................................... 1 Production Process ... ............ ................................ ........................ 1 Synthesis ....................................................................... .. 1 IV. GENERALMETHODOLOGY .............. ....................... ...................... 1 Process Modeling . ....................................................................... 1 Economic Analysis ............... .......... ............. ............ .................... 2 Generation, Optimization, and Selection of Retrofit Alternatives ................... 2 V. PROCESS MODEL ................................ ................................ .... .... 2 Process Characterization ........................................................ ........ 2 Process Modeling Tool .......................... ....................... .......... ....... 2 Physical Property Estimation For 3-sulfolene ................... ..................... 2 Comparison with sulfolane properties ............................ ............ 2 Process Model Of The Sulfolane Process ............................................. 3 Reaction step - Reactor R 1 ............. ........................................ 3 Treatment step - Vessel R2................ ..................................... 3 Hydrogenation step (R3) ....................................................... 3 VI. ECONOMIC ANALYSIS . ........ ...... .............................................. 4 Review Of Approach For Economic Analysis.................... .................... 4 Base Case Economics of Sulfolane Process . ...................... ................... 4 Economic analysis . ...... ....... ............... ......... ..... .......... .................. 4 VII. PROCESS RETROFIT ALTERNATIVES . ............................................ 4 Sensitivity Analysis .... ....... ....... ... .... ................... ..... ............... 4 Forecasting Future Scenarios .... ............................ ..... .......... .......... 5 Generation, Selection, and, Optimization of Alternatives ............. .............. 5 Conservationand optimization of raw material usage in reactor R 1 ... .... 5 IV Chapter Improvement of sulfurdioxide removal from reaction mixture ............ 5 Change of hydrogenation solvent in treatment tank R2..................... 5 Overcoming Rate Limitation in the Hydrogenation Step .................... 6 VIII. CONCLUSIONS AND RECOMMENDATIONS ..................................... 7 BIBLIOGRAPHY ................................................................................. 8 APPENDICES ..................................................................................... 9 APPENDIX A--ASPEN PLUS INPUT FILES........... .................. 9 v LIST OF TABLES Table P; 1 . Comparison of Physical Properties of 3-Sulfolene and Sulfolane .................... : 2. Base Case Results .......................................................................... t. 3 Reaction mixture - Composition and Bubble Points .............................. ..... � 4 . Physical Properties of AlternativeSolvents ............................................. ( 5. Hydrogenation Mixture - Estimated Properties ......................................... ( 6. Data for External DiffusionRate Calculation.................................. .......... ( 7. Range of Input Variables for External DiffusionRate Calculation ............. ...... � Effect of Parameters on Overcoming External Diffusion Limitation.................. 8. � vi LIST OF FIGURES Figure Pag 1 . Schematic diagram of sulfolane process ........................................... ...... 1 2. Generalmethodology ...................................................................... 1 3. Schematic diagram of sulfolene production reactor R1 ................................ 3 4. Block diagram of ASPEN PLUS model of Rl ......................................... 3 5. Schematic diagram of treatment vessel R2............................................... 3: Block diagram of ASPEN PLUS models for ....................................... 3' 6. R2 7. Schematic diagram of the hydrogenation reactor R3 ................................... 4� 8. Butadiene feed time vs. sulfolene mole fraction in the top zone of R1 ............... 5' 9. Effect of temperature on sulfur dioxide removal ...... .... ............... ............... 5 � 10. Reaction profiles for five R3 batches ..................................................... 7'- Vll NOME NCLATURE Bubble surface area (interfacial area) Specific catalyst surface area Ca,s Concentration of gas at the external surface of catalyst Concentration of gas in the bulk liquid Concentration of gas at bubble interface Specific heat of the mixture Cp,mix Ideal gas heat capacity cop ds Averagebubble diameter dl Diameter of impeller Diameter of catalyst particle Diameter of reactor Diffusivity of hydrogen Heat of formation at 29 8 K k Specific reaction rate constant Mass-transfer coefficientfor bubbles Mass-transfercoefficient for catalyst particles L Total height of reaction mixture above entrance of gas bubbles m Massconcentration of catalyst N Molarflux rate N Speed of agitation n Reactionorder Peclet number viii N Sherwood number Sh P Power consumption for agitation P c Critical pressure psat Vapor pressure Q Volumetric flow rate of gas Overallrate of reaction RA r Specific reaction rate if entire catalyst is exposed to surface concentration A,s < absorbed gas ST Surface tension of mixture T Temperature Tc Critical temperature Superficial velocity of gas in reactor Ug Terminal velocity of catalyst particle Ut VL Volume of reaction mixture Catalyst effectiveness factor 11 Density of catalyst particle Pp Density of gas Pg Density of reactionmixture Pr Gas hold-up Eg Viscosity of reaction mixture f.Jf ix CHAPTE R I INTRODUCTION Process enhancement strategies have become critical to present day operation of chemical industries. Since the regulatory nature of operation has become very stringent, a industry must anticipate changes and be prepared to upgrade its process to remain profitable. Regulatory compliance pressures and environmental awareness have increased the economic and social incentives for making processes cleaner. Redesigning existing processes for waste reduction is thus becoming a top priority. Therefore, it has become essential to develop methodologies that include environmental criteriain economic comparisons of improvement alternatives. The objective of this work is to develop such a methodology and to apply it to the sulfolane process of Phillips Petroleum Company. The retrofit of existing processes is a challenging task. Retrofit actions typically include, in order of increasing investment, (1) optimization of operating conditions, (2) repiping, (3) equipment modification, and (4) new equipment
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