PROCESS ECONOMICS PROGRAM

SRI INTERNATIONAL Menlo Park, California 94025 Abstract

Process Economics Program Report No. 13D

POLYVINYL CHLORIDE

(May 1982)

This supplementary report reviews recent developments in the tech- nology of vinyl chloride polymerization for manufacturing homopolymers, copolymers, and graft polymers. Also reviewed are vinyl chloride remov- al from the polymer at various stages of the polymerization process, and the prevention of polymer encrustation inside the polymerizer.

We revised the designs of three major processes, i.e., suspension, liquid-phase bulk, and emulsion polymerization, to incorporate some of the recent developments. Notable revisions are as follows: the reac- tor walls and the inserted devices are coated with a suppressant material to minimize polymer encrustation, and a self-contained batch transfer system is used to prevent VCM from escaping to the atmosphere. Consequently, a high pressure water wash system replaces the solvent cleaning facilities, and the vent gas scrubbing system is no longer needed. These features are also considered in the design of the micro- suspension process, a subject PEP has not covered before.

We have evaluated the economics of all the above processes for mak- ing homopolymer, and the bulk and suspension processes for making VC-VA copolymer and VC graft polymer. Finally, various additives that are essential for PVC compounding are selectively reviewed.

PEP '80 YRC Report No. 130

POLYVINYL CHLORIDE

SUPPLEMENT D

by YU-REN CHIN

May 1982

A private report by the PROCESS ECONOMICS PROGRAM

Menlo Park, California 94025 For detailed marketing data and information, the reader is referred to one of the SRI programs specializing in marketing research. The CHEMICAL ECONOMICS HANDBOOK Program covers most major chemicals and chemical products produced in the United States and the WORLU PETROCHEMICALS Program covers major hydrocarbons and their derivatives on a worldwide basis. In addition, the SRI DIRECTORY OF CHEMICAL PRODUCERS services provide detailed lists of chemical producers by company, prod- uct, and plant for the United States and Western Europe.

ii CONTENTS

1 INTRODUCTION ...... 1

2 SUMMARY ...... 3 General Aspects ...... 3 Technical Aspects ...... 5 Suspension Polymerization Process ...... 5 Bulk Polymerization Process ...... 8 Emulsion Polymerization Process ...... 9 Microsuspension Polymerization Process ...... 9 Process for Copolymers and Graft Polymers ...... 10 Economics and Process Comparison ...... 10 Suspension Polymerization Processes ...... 10 Bulk Polymerization Processes ...... 13 Emulsion Polymerization Processes ...... 13 Microsuspension Polymerization Processes ...... 13 Comparison between the Bulk and the Suspension Processes . . 14 Comparison between the Emulsion and the Microsuspension Processes...... 14

3 INDUSTRY STATUS ...... 15

4 ENCRUSTATION PREVENTION AND MONOMER REMOVAL ...... 33 Encrustation Prevention ...... 33 Surface Coating ...... 34 Encrustation Suppressing Additives ...... 35 Vinyl Chloride Stripping ...... 36 Polymerization Batch Transfer ...... 38

5 POLYVINYL CHLORIDE BY SUSPENSION PROCESS ...... 43 Review of Patents ...... 43 Process Description ...... 47 Raw Material Storage and Makeup ...... 49 Polymerization and Monomer Stripping ...... 49 Monomer Recovery and Purification ...... 50 Product Dewatering and Drying ...... 51 Bulk Handling ...... 51 Hydraulic Wash ...... 52 Process Discussion ...... 58 Cost Estimates ...... 58 Capital Investment ...... 58 Production Costs ...... 58 Economics of Other Cases ...... 59

iii CONTENTS

6 POLYVINYL CHLORIDE BY BULK PROCESS ...... 69 Review of Patents ...... 69 Process Description ...... 72 Polymerization ...... 72 Monomer Recovery ...... 74 Product Finishing ...... 74 Bulk Handling ...... 75 Hydraulic Wash ...... 75 Process Discussion ...... 81 Cost Estimates ...... 81 Capital Investment ...... 81 Production Costs ...... 81 Economics of Other Cases ...... 82

7 POLYVINYL CHLORIDE BY EMULSION AND MICROSUSPENSION PROCESSES ...... 89 Review of Patents ...... 90 Economics Evaluation of Emulsion Process ...... 91 Process Description ...... 91 Raw Material Storage and Makeup ...... 92 Polymerization and Monomer Stripping ...... 92 Monomer Recovery and Dispersion Blending ...... 93 Product Drying ...... 94 Bulk Handling ...... 94 Hyl;L-aulicWash ...... 94 Process Discussion ...... 101 Cost Estimates ...... 101 Capital Investment ...... 101 Production Costs ...... 101 Economics of Other Cases ...... 102 Economic Evaluation of Microsuspension Process ...... 110 Process Description ...... 110 Polymerization and Monomer Stripping ...... 110 Product Drying ...... 112 Cost Estimates ...... 116 Capital Investment ...... 116 Production Costs ...... 116 Economics of Case 2 ...... 116

8 POLYVINYL CHLORIDE BY SOLUTION PROCESS ...... 125

iV CONTENTS

9 VINYL CHLORIDE COPOLYMERS AND GRAFT POLYMERS ...... 127 Vinyl Chloride Copolymers ...... 127 Vinyl Chloride-Vinyl Acetate Copolymer ...... 128 Vinyl Chloride-(Meth)acrylateCopolymers ...... 129 Vinyl Chloride-AcrylonitrileCopolymer ...... 129 Vinyl Chloride-Vinylidone Chloride Copolymers ...... 130 Graft Copolymers ...... 130 Vinyl Chloride Graft Polymers ...... 131 Grafted Polyvinyl Chloride Polymers ...... 132 Economic Evaluation of Plants for Making Vinyl Chloride Copolymers and Graft Polymers ...... 132 VC-VA Copolymer by Bulk Process ...... 132 VC-VA Copolymer by Suspension Process ...... 134 VC Grafted onto EP Rubber by Bulk Process ...... 134 VC Grafted onto EPDM Rubber by Suspension Process ..... 135 Economics ...... 135

10 ADDITIVES FOR PVC COMPOUNDING ...... 137 0- Stabilizers ...... 137 MetalSoaps ...... 138 Lead Compounds ...... 140 Organotin Compounds ...... 141 Plasticizers ...... 143 Lubricants and Processing Aids ...... 144 Other Additives ...... 145

APPENDIX A DESIGN AND COST BASIS ...... 147

PATENT SUMMARY TABLES ...... 151

329 0 CITED REFERENCES ...... PATENT REFERENCES BY COMPANY ...... i ...... 357

V ILLUSTRATIONS

0 4.1 Self-Contained Polymerization Batch Transfer System ...... 40 5.1 Polyvinyl Chloride by Suspension Process FlowSheet ...... 367 5.2 Polyvinyl Chloride by Suspension Process Effect of Operating Level and Plant Capacity 0 on Production Cost ...... 65 5.3 Polyvinyl Chloride by Suspension Process Effect of Monomer Cost on the Product Value ...... 66 6.1 Polyvinyl Chloride by Liquid Phase Bulk Process FlowSheet ...... 373 6.2 Polyvinyl Chloride by Liquid Phase Bulk Process Effect of Operating Level and Plant Capacity on Production Cost ...... 87 7.1 Polyvinyl Chloride by Batch Emulsion Process FlowSheet ...... 377 , 7.2 Polyvinyl Chloride by Batch Emulsion Process 0 Effect of Operating Level and Plant Capacity on Production Cost ...... 108 7.3 Polyvinyl Chloride by Seeded Microsuspension Process Effect of Operating Level and Plant Capacity on Production Cost ...... 122

Vii TABLES

2.1 Polyvinyl Chloride Processes Summary of Technical Aspects ...... 6 2.2 Vinyl Chloride Copolymers and Graft Polymers Summary of Technical Aspects ...... 7 Polyvinyl Chloride Processes Summary of Economics ...... 11 2.4 Vinyl Chloride Copolymers and Graft Polymers Summary of Economics ...... 12 3.1 World PVC Capacities by Principal Areas (Millions of Metric Tons/yr) ...... 15 3.2 Projected Polyvinyl Chloride Capacity Worldwide ...... 22 3.3 Free World Polyvinyl Chloride Consumption History and Forecast (Thousands of Metric Tons) . , ...... 30 3.4 Forecasted Excess Capacity over Demand in 1986 0 (Thousands of Metric Tons) ...... 31 4.1 Surface Coating for Encrustation Prevention Patent Summary...... 152 4.2 Scale Suppressing Additives for Encrustation Prevention Patent Summary...... 182 4.3 Vinyl Chloride Monomer Removal Patent Summary...... 196 5.1 Polyvinyl Chloride by Suspension Process Patent Summary...... 234 5.2 Polyvinyl Chloride by Suspension Process Design Bases and Assumption ...... 48 0 5.3 Polyvinyl Chloride by Suspension Process Major Equipment ...... 53 5.4 Polyvinyl Chloride by Suspension Process Stream Flows ...... 56 5.5 Polyvinyl Chloride by Suspension Process Capital Investment ...... 61 5.6 Polyvinyl Chloride by Suspension Process Production Costs ...... 62

ix TABLES

5.7 Polyvinyl Chloride by Suspension Process Economics of Other Cases ...... 67 6.1 Polyvinyl Chloride by Liquid Phase Eulk Process Patent Summary...... 276 6.2 Polyvinyl Chloride by Vapor Phase Bulk Process Patent summary...... 279 6.3 Polyvinyl Chloride by Liquid Phase Bulk Process Design Bases and Assumptions ...... 76 6.4 Polyvinyl Chloride by Liquid Phase Bulk Process Major Equipment ...... 77 6.5 Polyvinyl Chloride by Liquid Phase Bulk Process StreamFlows ...... 80 6.6 Polyvinyl Chloride by Liquid Phase Bulk Process Capital Investment ...... 83 6.7 Polyvinyl Chloride by Liquid Phase Bulk Process Production Costs ...... 84 6.8 Polyvinyl Chloride by Liquid Phase Bulk Process Economics of Other Cases ...... 88 7.1 Polyvinyl Chloride by Emulsion Process Patent Summary...... 281 7.2 Polyvinyl Chloride by Microsuspension Process Patent Summary..,...... 285 7.3 Polyvinyl Chloride by Batch Emulsion Process Design Bases and Assumptions ...... 95 7.4 Polyvinyl Chloride by Batch Emulsion Process MajorEquipment ...... 96 7.5 Polyvinyl Chloride by Batch Emulsion Process Stream Flows ...... 100 7.6 Polyvinyl Chloride by Batch Emulsion Process Capital Investment ...... 104 7.7 Polyvinyl Chloride by Batch Emulsion Process Production Costs ...... 105 7.8 Polyvinyl Chloride by Emulsion Process Economics of Other Cases ...... 109

X TABLES

. 0 7.9 Polyvinyl Chloride by Microsuspension Process Design Bases and Assumptions ...... 111 7.10 Polyvinyl Chloride by Seeded Microsuspension Process Major Equipment and Utilities Summary . . . . . , ...... 113 7.11 Polyvinyl Chloride by Seeded Microsuspension Process Capital Investment ...... 118 7.12 Polyvinyl Chloride by Seeded Microsuspension Process Production Costs ...... 119 7.13 Polyvinyl Chloride by Microsuspension Process Economic Comparison Between Case 1 and Case 2 ...... 123 8.1 Polyvinyl Chloride by Solution Process Patent Summary...... 290 9.1 Vinyl Chloride Copolymers and Terpolymers Patent Summary ...... 291 9.2 Vinyl Chloride Grafted Polymers Patent Summary...... 295 9.3 Grafted Polyvinyl Chloride Polymers Patent Summary...... 300 9.4 Vinyl Chloride Copolymers and Graft Polymers Design Bases and Assumptions ...... 133 9.5 Vinyl Chloride Copolymers and Graft Polymers Process Economics ...... 136 10.1 Polyvinyl Chloride Compositions Patent Summary...... 301 10.2 Thermal Stabilizers for PVC Compositions Patent Summary...... 306 0 10.3 Lubricants for PVC Compositions Patent Summary ...... 320 10.4 Processing Aids for PVC Compositions Patent Summary...... 322 10.5 Flame and Smoke Suppressants for PCD Compositions 0 Patentsummary...... 323 10.6 Cross-Linking Agents for PVC Compositions Patentsummary...... 327

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