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An Economic Case Study of Process Modiacation For AN ECONOMIC CASE STUDY OF PROCESS MODIACATION FOR THE ALLYL CHLbRJDE PROCESS By DICK U. V AN DER HELM Bachelor of Science in Chemical Engineenng Oklahoma State University Stillwater, Oklahoma 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, 1m OKLAHOMA STATE UNIVERSITY AN ECONOMlC CASE STUDY OF PROCESS MODIFICATION FOR THE ALLYL CHLORIDE PROCESS . Thesis Approved: II ACKNOWLEDGMENTS 1 would like to extend my sincere gratitude to my major advisor Dr. Karen A. High for her guidance, patience, encouragement, and friendship. I am also grateful to my committee members Dr. Jan Wagner and Dr. Arland H. Johannes (AJ.) for their insightful suggestions and advice. In addition, I would like to express my thanks to the University Center for Water Research which provided funding for this research. I would also like to express appreciation to several students for their help. Shyam and Manesh greatly accelerated my project by passing on the knowledge they gained in their research. Thanks to Mauricio, who always had an answer for my questions as we both traveled the bumpy road of research. The aforementioned people's friendship made this project more enjoyable and provided the motivation during those less than successful times. However, the most motivational force behind this document is Sarah. [have learned a great deal from her strong belief in herself and her talents. Without her love, support, and ready smile. 1 would be lost. III TABLE OF CONTENTS Chapter Page I. INTRODUCTION ............... ... : ...................................... ....... .. ...... 1 II. BACKGROUND .................................... " .. ............ .............. ........ 7 Environmental Background .. .. .......................................... ............... 7 Process Motivation ............................................... .................... ... 11 ASPEN PLUS ™ Modeling ............................................................. J3 Economic Analysis ............................................................ .......... 13 Optimization ... " ......................................................................... 14 Regulatory Risk Analysis ............................................................... 15 Hazard Identification ........................................................... 17 Qualitative Exposure Assessment ....................................... ..... 17 Toxicity Assessment. ........................................................... 17 Risk Level Determination ............................................... ....... 18 Maximum Concentration Evaluation ..... ................. .................... 18 Quantitative Exposure Assessment .................. ......................... 18 III. PROCESS DESCRIPTION .............................................................. 20 Process Chern istry ........ ............................................................... 20 Production Process ........................... ........................................... 21 Synthesis............................................ ............................. 21 Purification ..... ............................................. " ........... ....... 23 Recycle ................................. .................... ...................... 24 IV. GENERAL MEfHOOOLOOY ....................................... ................ .... 25 Process Model. ........................................................................... 25 Determination of Source Reduction Variables and Ranges ... ...................... 26 Econorn.ic Optimization .................... .............................................. 27 V. PROCESS MODEL ........................................................................ 29 Process Characterization ................................................................ 29 Sensiti vity Analysis ...................................................................... 33 Reactor Feed Temperature ........... , ................................... ..... 33 Reactor Feed Ratio ......................... ......... ................... ....... 33 Reactor Pressure ........................................ ........................ 33 Residence Time .................. ................... ..... ..... .. ............... 33 Process Modeling Tool. .................................................... ............. 33 V 1. SOURCE REDUCTION VARIABLES ................................................. 35 SRV s from Literature .................................................................... 35 IV Chapter Page SRVs' Ranges ............................................................................ 36 Vll. OPTIMIZATION AND ECONOMICS.................................................. 37 F.conomic Data ........................................................................... 37 Economic Optimization ...................... ............................................ 39 Reactor Pressure ................................................................ 41 Reactor Feed Ratio ...................................................... ........ 41 Reactor Temperature............................................................ 41 Sensitivity of Waste Costs .............................................................. 42 Regulatory Risk Analysis . .............................................................. 45 Hazard Identi'fication ........................................................... 46 Qualitative Exposure Assessment ............................................. 46 Toxici ty Assessment. ............ ............................................... 46 Risk Level Determination ...................................................... 46 Maximum Concentration Evaluation .......................................... 47 Quantitative Exposure Assessment .......................................... .47 VIII. CONCLUSIONS AND RECOMMENDATIONS .................................... 49 BIBUOORAPHY ..... ... ........................................................................ 52 APPENDI CES .................................................................................... 54 APPENDIX A--ASPEN PLUSTM INPUT ALES .......................... 55 APPENDIX B--ASPEN PLUSTM OUTPUT ALES ..... '" ............... 77 v LIST OF TABLES Table Page I. Company-Wide Pollution Prevention Programs ........................................ 9 2. Unit Operations and Their ASPEN PLUS ™ Models .................................. 30 3. Product F10wrates at Constant Feed Ratio, Reactor Temperature, and Reactor Pressure .................................................................................... 32 4. Source Reduction Variables and Ranges ................................................ 35 5. Utility Costs ................................................................................ 38 6. Chemical Prices .............................................................. ... ........... 38 7. Waste Treatment Costs .................................................................... 39 8. Economic Optimization Results ..................................... , .................... 40 9. Reactor Temperatures .......... ............................................................ 42 10. Toxicity Data ................................................................................ 47 V1 LIST OF FIGURES Figure Page I . Waste Minimization Techniques .......................................................... IO 2. PFD for Allyl Chloride Process .......................................................... 22 3. ASPEN PLUS ™ Flow Diagram of the Allyl Chloride Process .................. " .. 31 4. Preliminary Profit versus Increased Waste Costs ...................................... 43 5. Optimal Reactant Aowrate versus Increased Waste Costs ............................ 43 6. Waste Production Rate versus Increased Waste Costs ................................ 44 7. Feed Ratio versus Increased Waste Costs ............................................... 44 8. Propylene Feed and Reactor Temperatures versus Increased Waste Costs ........ .45 9. PFD of the Allyl Chloride Process with Stream and Block Labels ................... 56 vii NOMENCLATURE Abbreviations 12DCP 1,2-dichloropropane l3DCP 1,3-dichloropropene CAAA Clean Air Act Amendments Cl2 Chlorine COMP ASPEN PLUS ™ module for compressors CPI Chemical Processing Industry CSTR Continuous Stirred Tank Reactor DIPPR Design Institute of Physical Property Research DSTWU ASPEN PLUSTM module for shortcut distillation EPA Environmental Protection Agency HCI Hydrogen chloride HEATER ASPEN PLUSTM module for simple heaters HON Hazardous Organic NESHAPS MACT Maximum Achievable Control Technology MGal 1000 gallons MMBTU I mil1ion STUs NESHAPS National Emissions Standards for Hazardous Air Pollutants ORD EPA's Office of Research and Development PFR Plug Flow Reactor PPA Poll ution Prevention Act RADFRAC ASPEN PLUSTM module for rigorous distillation viii RCSTR ASPEN PLUS ™ module for CSTR RPLUG ASPEN PLUS ™ module for PFR SEP ASPEN PLUSTMmodule for separation of components SRV Source Reduction Variable VOCs Volatile Organic Compounds WRO Waste Reduction Option Equation Nomenclature AT A veraging time, days-year BW Body weight, kg C Concentration at exposure point, mglm3 CDI Chronic daily intake, mg/kg-day ED Exposure duration, years EF Exposure frequency, days HI Hazard Index RID Reference dose, mg/kg-day ix CHAPTER I INTRODUCfION Society's increasing environmental awareness
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