Report No. 19-A LINEAR POLYETHYLENE AND POLYPROPYLENE Supplement A by ROBERT Consultant L. MAGOVERN October 1969 A private report by the PROCESS ECONOMICS PROGRAM STANFORD RESEARCH INSTITUTE I MENLO PARK, CALIFORNIA
CONTENTS INTRODUCTION... SUMMARY... INDUSTRY STATUS... CHEMISTRY OF PROPYLENE AND ETRYLRNE POLYMERIZATION... General...... Isotactic Catalyst... Mechanism Studies... Kinetics... Polyethylene... Zieglier Catalysts... Metal Oxide and Solid Catalysts... POLYOLEFIN PROPERTIES AND APPLICATIONS... Linear Polyethylene by the Ziegler Process... Linear Polyethylene by Metal Oxide Catalysts... Ethylene Polymers... High Molecular Weight Ethylene Polymers...... REVIEW OF POLYPROPYLENE PROCESSES... Avisun Corporation... Dow Chemical Company... Eastman Kodak Company... Esso Research and Engineering Company... Hercules Incorporated... Montecatini-Edison Sp A.... Phillips Petroleum Company... Rexall Drug and Chemical Company... Shell Oil Company... Others... PRODUCTION OF POLYPROPYLENE... Process Discription... Process Discussion... Cost Estimates... Capital Costs... Production Costs... 1 3 13 31 31 34 35 38 41 41 41 42 45 45 45 47 48 50 55 58 60 61 66 67 69 71 73 74 83 85 87 99 107 107 108 V
CONTENTS 8 PRODUCTION OF LINEAR POLYETHYLENE... 113 Review of Processes... 113 Phillips Particle Form Process... 113 Solvay and Cie. (Belgium)... 114 Particle Form Process Description... 117 Process Discussion... 127 Cost Estimates... 135 Capital Costs... 135 Production Costs... 135 Comparison with Other Processes... 142 9 PRODUCTION OF POLYPROPYLENE FIBERS... 155 Industry Status... 155 Review of Processes... 158 Dyeing... 158 Fiber Formation by Melt-Spinning... 160 Fiber Formation by Fibrillation and Film Slitting... 161 Fiber Processing... 162 Production of Continuous Filament Yarn... 164 Process Discussion... 167 Capital Cost... 168 Production Costs... 168 APPENDIX A DESIGN AND COST BASIS... 175 APPENDIX B PHYSICAL DATA... 181 APPENDIX C RAW MATERIAL SPECIFICATIONS... 183 APPENDIX D PROPERTIES OF POLYETHYLENE... 185 APPENDIX E PROPERTIES OF POLYPROPYLENE... 189 CITED REFERENCES... 195 PATENT REFERENCES BY COMPANY... 241 vi
ILLUSTRATIONS 4.1 6.1 6.2 6.3 7.1 7.2 7.3 8.1 8.2 8.3 8.4 9.1 9.2 The Titanium Layer in Y-TiCl,, Showing Cleavage totis Units....................... 36 Process--Rexall Patent........,., 75 Process--Shell Patent,....,..,... 78 Polymer Solids Drying and Recovery--Shell Patent..... 79 Production................. 91 Plant Stream Balance......,..... 103 on Production Cost..,,................ 111 Linear Polyethylene--Particle Form............ 119 Linear Polyethylene--Particle Form on Production Cost...........,.,...... 141 Linear Polyethylene by a Ziegler Catalyst on Production Cost.................... 151 Linear Polyethylene by a Metal Oxide Catalyst on Production Cost..,....,,.,.,....... 152 Production of Continuous Filament Yarn.,. 165 Production of Continuous Filament Yarn Effect of Yarn Denier on Fixed Capital Requirement and Production Cost,.................,. 173 vii
TABLES 3.1 3.2 3.3 3.4 3.5 3.6 5.1 5.2 5.3 5.4 6.1 6.2 6.3 6.4 6.5 7.1 7.2 7.3 7.4 7.5 Polyethylene Production and Sales... Linear Polyethylene Uses... Estimated World Consumption of Polyethylene... Estimated World Polyethylene Production Capacity... Linear Polyethylene Plant Capacities... Plant Capacities... Melt Index-Dependent Properties of Phillips Ethylene Homopolymers... Physical Properties of Polyolefins Made by the Phillips Process... Melt Flow-Intrinsic Viscosity-Molecular Weight Relationships for Typical Commercial... Relationship of Structural Parameters to Physical Properties of... Avisun Catalyst Systems Eastman Catalyst Systems Montecatini Catalyst Systems Phillips Catalyst Systems Shell Catalyst Systems Comparison of Process Steps... Major Process Equipment and Utilities Summary... Stream Flows... Total Capital Investment... Production Costs... 13 15 16 17 19 25 46 49 51 52 59 62 70 72 76 86 91 97 105 109
TABLES 8.1 Olefin Polymerization by Solvay and Cie Patent Summary,.,......,.,.,........ 115 8.2 Linear Polyethylene--Particle Form Major Process Equipment and Utilities Summary....... 119 8.3 Linear Polyethylene--Particle Form Stream Flows....................... 125 8.4 Phillips Loop-Type Heactor Descriptions...,...... 129 8.5 Linear Polyethylene--Particle Form Total Capital Investment................. 137 8.6 Linear Polyethylene--Particle Form Production Costs...,................. 139 8.7 8.8 8.9 8.10 8.11 9.1 9.2 9.3 9.4 9.5 9.6 9.7 Linear Polyethylene Comparison of Processes,.....,..,..... Linear Polyethylene by a Ziegler Catalyst Total Capital Investment.............. Linear Polyethylene by a Ziegler Catalyst Production Costs.................. Linear Polyethylene by a Metal Oxide Catalyst Total Capital Investment.............. Linear Polyethylene by a Metal Oxide Catalyst Production Costs.................. Fiber Consumption in the United States Companies Producing Multifilaments and Staple.,... Production of Slit Film Fabric..,. Production of Continuous Filament Yarn Major Process Equipment and Utilities Summary.... Production of Continuous Filament Yarn Total Capital Investment,............. Continuous Filament Yarn-165 Denier Production Costs.....,............ Continuous Filament Yarn-840 Denier Production Costs...,................. 142... 143... 145... 147... 149... 156... 157... 163... 165... 169... 170... 171 X
TABLES D.l Properties of Polyethylene................ 185 D.2 Effect of Basic Molecular Properties on Physical Properties of Polyethylene................ 187 E.l Properties of... 189 E.2 Physical Properties of Copolymers... 191 E.3 Chemical Resistance of........... 192 xi