PROCESS ECONOMICS PROGRAM SRI INTERNATIONAL Menlo Park, California Abstract 94025 Process Economics POLVINYL Program Report No. 13E CHLORIDE (October 1991) This supplementary report reviews recent technical developments in the manufacture of polyvinyl chloride (PVC) resins by the suspension, bulk, emulsion, microsuspension, and solution processes; the prevention of polymer encrustation on the surfaces inside the reactor: and the removal of the residual monomers from the reaction products. The report also evaluates the process economics of various grades of PVC resin by the suspension, bulk, emulsion, and microsuspension processes. We consider production by the suspension process of the following grades: general purpose, high bulk density, skinless, low molecular weight, ultra-high molecular weight, high volume resistivity, and radiation resistant. We evaluate new liquid phase bulk process technology which employs a spherical polymerizer in place of the vertical polymerizer. In the production of dispersion resins, we include the batch, continuous, and seeded batch emulsion processes, as well as the batch and seeded batch microsuspension processes. PEP 89 SHW
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For detailed marketing data and information, the reader is referred to one of the SRI programs specializing in marketing research. The CHEMCAL ECONOMlCS HANDBOOK Program covers most major chemicals and chemical products produced in the United States and the WORLD PE7ROCHEMlCALS Program covers major hydrocarbons and their derivatives on a worldwide basis. In addition, the SRI D/RECTORY OF CHEMCAL PRODUCERS services provide detailed lists of chemical producers by company, product, and plant for the United States, Western Europe, Canada, and East Asia. ii
1 INTRODUCTION..................................................... l-l 2 SUMMARY... 2-l GENERAL ASPECTS... 2-l TECHNICAL ASPECTS... 2-2 Suspension Polymerization Process... 2-2 Bulk Polymerization Process... 2-3 Emulsion and Microsuspension Polymerization Processes... 2-5 Solution Polymerization Process... 2-5 PROCESS ECONOMICS... 2-6 Suspension Polymerization Process... 2-6 Bulk Polymerization Process... 2-6 Emulsion and Microsuspension Polymerization Processes... 2-6 Discussion of Economics... 2-8 3 INDUSTRY STATUS... 3-l CAPACITY, SUPPLY, AND DEMAND... 3-l CONSUMPTION PATTERN... 3-2 TECHNOLOGICAL DEVELOPMENTS... 3-2 SAFETY, HEALTH, AND ENVIRONMENTAL CONCERNS... 3-2 4 ENCRUSTATION PREVENTION AND MONOMER REMOVAL... 4-1 ENCRUSTATION PREVENTION... 4-l Surface Coatings... 4-l Suppressing Additives... 4-3 Other Encrustation Prevention... 4-4 MONOMER REMOVAL... 4-4 5 POLWINYL CHLORIDE BY SUSPENSION PROCESS... 5-l PROCESS REVIEW... 5-l High Bulk Density PVC... 5-4 Skinless Surface PVC... 5-4 Low Molecular Weight PVC... 5-6 Ultra-High Molecular Weight PVC... 5-6 High Volume Resistivity PVC... 5-6... - III -
CONTENTS (Continued) 5 POLWINYL CHLORIDE BY SUSPENSION PROCESS (Concluded) PVC For Medical Uses... 5-6 PROCESS DESCRIPTION... 5-7 Raw Material Storage and Makeup... 5-7 Polymerization and Monomer Stripping... 5-10 Monomer Recovery and Purification... 5-10 Product Drying and Finishing... 5-l 1 Bulk Handling... 5-11 Hydraulic Wash... 5-11 Other Cases of General Purpose Grade PVC... 5-l 1 PROCESS DISCUSSION... 5-17 COST ESTIMATES... 5-17 Economics of Basic Case... 5-17 Comparison of Economics... 5-l 0 SPECIALTY GRADES... 5-27 Case 4: High Bulk Density... 5-27 Case 5: Skinless... 5-27 Case 6: Low Molecular Weight... 5-27 Case 7: Ultra-High Molecular Weight... 5-29 Case 8: High Volume Resistivity... 5-29 Case 9: Radiation Resistant... 5-29 6 POLYVINYL CHLORIDE BY BULK PROCESS... 6-l PROCESS REVIEW... 6-l PROCESS DESCRIPTION... 6-3 Polymerization... 6-3 Monomer Recovery... 6-6 Product Finishing... 6-6 Bulk Handling... 6-6 Hydraulic Wash... 6-6 Other Cases... 6-6 PROCESS DISCUSSION... 6-12 - iv -
CONTENTS (Continued) 6 POLYVINYL CHLORIDE BY BULK PROCESS (Concluded) COST ESTIMATES... 6-12 Economics of Basic Case... 6-12 Comparison of Economics... 6-13 7 POLWINYL CHLORIDE BY EMULSION AND MICROSUSPENSION PROCESSES... 7-l PROCESS REVIEW... 7-2 PROCESS DESCRIPTION... 7-4 Raw Material Storage and Makeup... 7-4 Polymerization and Monomer Stripping... 7-4 Monomer Recovery and Purification... 7-6 Product Drying and Finishing... 7-6 Bulk Handling... 7-6 Hydraulic Wash... 7-7 PROCESS DISCUSSION... 7-13 COST ESTIMATES... 7-13 OTHER CASES... 7-21 Case 2: A Batch Seeded Emulsion Process... 7-21 Case3:AContinuousEmulsionProcess... 7-21 Case 4: A Batch Microsuspension Process... 7-21 Case 5: A Batch Seeded Microsuspension Process... 7-22 8 POLYVINYL CHLORIDE BY SOLUTION PROCESS........................ 6-l APPENDIX A: PATENT SUMMARY TABLES...................a... A-l APPENDIX B: DESIGN AND COST BASES... B-l DESIGN CONDITIONS... B-3 COST BASES... B-3 Capital Investment... B-3 Production Costs... B-4 Effect of Operating Level on Production Costs... B-5 APPENDIX C: CITED REFERENCES........................................ C-l -v-
CONTENTS (Concluded)) APPENDIX D: PATENT REFERENCES BY COMPANY... D-l APPENDIX E: PROCESS FLOW DIAGRAMS... E-l - vi -
ILLUSTRATIONS 3.1 WORLD PVC CONSUMPTION BY USE AND TYPE... 3-15 5.1 POLYVINYL CHLORIDE BY SUSPENSION PROCESS... E-3 5.2 POLYVINYL CHLORIDE BY SUSPENSION PROCESS EFFECT OF OPERATING LEVEL AND PLANT CAPACITY ON PRODUCTION COST..............................#... 5-24 5.3 POLYVINYL CHLORIDE BY SUSPENSION PROCESS EFFECT OF VINYL CHLORIDE COST ON PRODUCT VALUE.,......... 5-25 6.1 POLYVINYL CHLORIDE BY LIQUID PHASE BULK PROCESS............ E-l 1 6.2 POLYVINYL CHLORIDE BY LIQUID PHASE BULK PROCESS EFFECT OF OPERATING LEVEL AND PLANT CAPACITY ON PRODUCTION COST........................................ 6-19 6.3 POLYVINYL CHLORIDE BY UQUID PHASE BULK PROCESS EFFECT OF VINYL CHLORIDE COST ON PRODUCT VALUE........... 6-20 7.1 POLYVINYL CHLORIDE BY BATCH EMULSION PROCESS............. E-15 7.2 POLYVINYL CHLORIDE BY BATCH EMULSION PROCESS EFFECT OF OPERATING LEVEL AND PLANT CAPACITY ON PRODUCTION COST........................*... 7-l 9 7.3 POLYVINYL CHLORIDE BY BATCH EMULSION PROCESS EFFECT OF VINYL CHLORIDE COST ON PRODUCT VALUE........... 7-20 - vii -.
TABLES 2.1 POLYVINYL CHLORIDE PROCESSES SUMMARY OF TECHNICAL ASPECTS...*... 2-4 2.2 POLYVINYL CHLORIDE PROCESSES SUMMARY OF ECONOMICS..................................... 2-7 3.1 HISTORICAL AND PROJECTED WORLD PVC CAPACITY, PRODUCTION, AND CONSUMPTION BY REGIONS....#... 3-5 3.2 POLYVINYL CHLORIDE PRODUCERS AND YEAR-END CAPACITIES WORLDWIDE................................................. 3-6 3.3 PVC CONSUMPTION BY CONVERSION PROCESS AND BY END USE IN THE UNITED STATES.......................*m...*...*. 3-16 3.4 STANDARDS FOR VCM EXPOSURE AND CONTENT IN FOOD-CONTACT PVC ARTICLES..,**..,...,... 3-17 4.1 ENCRUSTATION PREVENTION PATENT SUMMARY...,...a...,... A-5 4.2 VINYL CHLORIDE MONOMER REMOVAL PATENT SUMMARY..................................*... A-l 6 5.1 REACTOR DESIGN AND CONTROL FOR VINYL CHLORIDE POLYMERIZATION PATENT SUMMARY..........a...*...*... A-21 5.2 POLYVINYL CHLORIDE BY SUSPENSION PROCESS PATENT SUMMARY....a... A-26 5.3 POLYVINYL CHLORIDE BY SUSPENSION PROCESS LIST OF PATENTS FOR SPECIALTY GRADES.,................,.... 5-5 5.4 POLYVINYL CHLORIDE BY SUSPENSION PROCESS: GENERAL PURPOSE GRADE DESIGN BASES AND ASSUMPTIONS...........*...a... 5-6 5.5 POLYVINYL CHLORIDE BY SUSPENSION PROCESS: SPECIALTY GRADES DESIGN BASES AND ASSUMPTIONS............................. 5-9 5.6 POLYVINYL CHLORIDE BY SUSPENSION PROCESS STREAM FLOWS.....,...a... 5-12 5.7 POLYVINYL CHLORIDE BY SUSPENSION PROCESS MAJOR EQUIPMENT..........................*... 5-14 5.6 POLYVINYL CHLORIDE BY SUSPENSION PROCESS UTILITIES SUMMARY.......................................... 5-16 - ix -
TABLES (Continued) 5.9 POLYVINYL CHLORIDE BY SUSPENSION PROCESS TOTAL CAPITAL INVESTMENT................................... 5-19 5.10 POLYVINYL CHLORIDE BY SUSPENSION PROCESS CAPlTAL INVESTMENT BY SECTION.........,.................... 5-20 5.11 POLYVINYL CHLORIDE BY SUSPENSION PROCESS PRODUCTION COSTS......I... 5-22 5.12 POLWINYL CHLORIDE BY SUSPENSION PROCESS: GENERALWRPOSE GRADE COMPARISON OF PROCESS ECONOMICS................... a..... 5-26 5.13 POLYVINYL CHLORIDE BY SUSPENSION PROCESS: SPECIALTY GRADES COMPARISON OF PROCESS ECONOMICS......................... 5-26 6.1 POLYVINYL CHLORIDE BY LIQUID PHASE BULK PROCESS PATENT SUMMARY........................................... A-56 6.2 POLYVINYL CHLORIDE BY VAPOR PHASE BULK PROCESS PATENT SUMMARY........................................... A-61 6.3 POLYVINYL CHLORIDE BY LIQUID PHASE BULK PROCESS DESIGN BASES AND ASSUMPTIONS............................. 6-5 6.4 POLYVINYL CHLORIDE BY LIQUID PHASE BULK PROCESS STREAM FLOWS.............................................. 6-6 6.5 POLYVINYL CHLORIDE BY LIQUID PHASE BULK PROCESS MAJOR EQUIPMENT....................................I... 6-9 6.6 POLYVINYL CHLORIDE BY LIQUID PHASE BULK PROCESS UTIUTIES SUMMARY....,...,...m... 6-11 6.7 POLYVINYL CHLORIDE BY LIQUID PHASE BULK PROCESS TOTAL CAPITAL INVESTMENT................................... 6-14 6.6 POLYVINYL CHLORIDE BY LIQUID PHASE BULK PROCESS CAPlTAL INVESTMENT BY SECTION,..,... 6-15 6.9 POLYVINYL CHLORIDE BY LIQUID PHASE BULK PROCESS PRODUCTION COSTS.......................................... 6-17 6.10 POLYVINYL CHLORIDE BY LIQUID PHASE BULK PROCESS COMPARISON OF PROCESS ECONOMICS,.........,..,.,.....,... 6-21 7.1 POLYVINYL CHLORIDE BY EMULSION PROCESS PATENT SUMMARY........................................... A-63 -X-
TABLES (Continued) 7.2 7.3 7.4 7.5 7.6 7.7 7.6 7.9 POLYVINYL CHLORIDE BY MICROSUSPENSION PROCESS PATENT SUMMARY........................................... POLYVINYL CHLORIDE BY EMULSION AND MICROSUSPENSION PROCESSES DESIGN BASES AND ASSUMPTIONS.,...,... POLYVINYL CHLORIDE BY BATCH EMULSION PROCESS STREAM FLOWS.............................................. POLYVINYL CHLORIDE BY BATCH EMUILSION PROCESS MAJOR EQUIPMENT..........................*... POLYVINYL CHLORIDE BY BATCH EMULSION PROCESS UTILITIES SUMMARY.......................................... POLYVINYL CHLORIDE BY BATCH EMULSION PROCESS TOTAL CAPITAL INVESTMENT..,.,...,..,...,,... POLYVINYL CHLORIDE BY BATCH EMULSION PROCESS CAPITAL INVESTMENT BY SECTION.............................. POLYVINYL CHLORIDE BY BATCH EMULSION PROCESS PRODUCTION COSTS......................................... A-74 7-5 7-8 7-9 7-12 7-14 7-15 7-17 7.10 7.11 POLYVINYL CHLORIDE BY EMULSION AND MICROSUSPENSION PROCESSES MAJOR EQUIPMENT DIFFERENCES..,... 7-23 POLYVINYL CHLORIDE BY EMULSION AND MICROSUSPENSION PROCESSES COMPARISON OF PROCESS ECONOMICS......................... 7-24 6.1 POLYVINYL CHLORIDE BY SOLUTlON PROCESS PATENT SUMMARY....#... A-79 - xi -