Abstract Process Economics Program Report 128C POLYPROPYLENE UPDATE (November 2001)

Transcription

1 Abstract Process Economics Program Report 128C POLYPROPYLENE UPDATE (November 2001) This report continues our evaluation of polypropylene processes. Isotactic polypropylene produced with metallocene catalyst represents less than 0.5% of the total global polypropylene capacity. The vast majority of polypropylene is produced with Ziegler-Natta catalyst. However, growth rate for metallocene polypropylene (mpp) is expected to be good, approximately 8% annual from ExxonMobil Chemical and Basell are the leading producers of mpp. ExxonMobil Chemical produces the resin in the Sumitomo stirred reactor bulk process and Basell produces it in the Novolen vertical stirred-bed process. With ExxonMobil and Basell recent mpp research and development agreement, it should soon be introduced into the Spheripol process. In this report, we compare the operating economics for Ziegler-Natta and metallocene catalysts for the production of polypropylene impact copolymer. The three leading process technologies are chosen for the analysis. They are the Spheripol, Unipol, and Novolen processes. The Spheripol process uses two bulk slurry loop reactors in series with a fluidized bed gas-phase reactor. The Unipol process uses two fluidized bed gas-phase reactors in series. Lastly, the Novolen process uses two vertical stirred-bed gas-phase reactors in series. We have selected a design capacity of 441-million lb/yr (200,000 t/yr). Both metallocene catalyst and Ziegler-Natta catalyst are evaluated. In addition, a speculative second-generation metallocene catalyst is evaluated. For the Unipol and Novolen processes, SHAC and PTK Ziegler-Natta catalysts are used, respectively. For the Spheripol process, Basell fifthgeneration Ziegler-Natta system is used. The first-generation metallocene catalyst system, a silica supported metallocene catalyst with methyl aluminoxane (MAO) co-catalyst that was developed jointly by Exxon and Hoechst, is used for the case studies. The speculative secondgeneration metallocene catalyst is a silica supported metallocene catalyst with a non-coordinating anion, e.g., tri(n-butyl)ammonium tetrakis(pentafluorophenyl)boron and tris(pentafluorophenyl)borane, as a co-catalyst. We conclude that the operating economics for a first-generation metallocene catalyst is cent/lb higher than for the Ziegler-Natta systems. A speculative second-generation metallocene catalyst can reduce the margin to cent/lb but these systems are known to be difficult to commercialize because of their sensitivity to poisons. Although Basell fifth generation Ziegler-Natta catalyst has a much higher catalyst activity, nearly four times, than either SHAC or PTK catalysts, the operating economics are slightly higher for the Spheripol process. PEP 99 SLB

2 CONTENTS GLOSSARY... xi 1 INTRODUCTION SUMMARY INDUSTRY STATUS TECHNICAL ASPECT Comparison of Economics Comparison of Process Economics INDUSTRY STATUS INTRODUCTION Basell BP ExxonMobil Chemical Dow PLANT CAPACITY PROJECTED SUPPLY AND DEMAND POLYPROPYLENE END-USES PRICES METALLOCENE POLYPROPYLENE (MPP) INDUSTRIAL STATUS Projected Supply and Demand Commercial Basell ExxonMobil Chemical Atofina (TotalFinaElf) /Mitsui Chemical/Grand Polymer Developmental Japan Polychem Chisso iii

3 CONTENTS Dow Chemical Novolen Technology Holdings POLYPROPYLENE CATALYST TECHNOLOGY INTRODUCTION SINGLE-SITE CATALYST ADVANCED ZIEGLER-NATTA CATALYST COMPARISON OF METALLOCENE AND ADVANCED ZIEGLER-NATTA CATALYST SYSTEMS Product Properties Cost POLYPROPYLENE BY THE UNIPOL TM PROCESS USING FLUIDIZED BED REACTORS INTRODUCTION CATALYST REVIEW PROCESS DESCRIPTION Section Section COST ESTIMATES POLYPROPYLENE BY THE NOVOLEN TM PROCESS USING VERTICAL STIRRED-BED REACTORS INTRODUCTION CATALYST REVIEW PROCESS DESCRIPTION Section COST ESTIMATES POLYPROPYLENE BY THE SPHERIPOL TM PROCESS USING A BULK SLURRY LOOP REACTOR AND A GAS-PHASE REACTOR iv

4 CONTENTS INTRODUCTION CATALYST REVIEW PROCESS DESCRIPTION Section COST ESTIMATES APPENDIX A: PATENT SUMMARY TABLES... A-1 APPENDIX B: DESIGN AND COST BASES... B-1 APPENDIX C: CITED REFERENCES... C-1 APPENDIX D: PATENT REFERENCES BY COMPANY... D-1 APPENDIX E: PROCESS FLOW DIAGRAM... E-1 v

5 ILLUSTRATIONS 2.1 Process Technologies For Polypropylene Production, PP Capacity Growth by Processes Price History For Polypropylene and Propylene, 1976-mid Dimethylsilanediylbis(2-Methyl-4Phenylindenyl)Zirconium Dichloride Effect of Mao on Supported Productivity Effect of Productivity on Cost Effect of Al/Zr Ratio on Cost Effect of Metallocene Cost on Cost Comparison of Melting Point of mpp and ZN PP Comparison of MFR Response to Hydrogen For mpp and ZN PP Polypropylene ICP by A Fluidized Bed Process (Unipol TM Technology)... E Polypropylene ICP by A Vertical Stirred Bed Process (Novolen TM Technology).. E Polypropylene ICP by The Spheripol TM Process With A Ziegler-Natta... E Polypropylene ICP by The Spheripol TM Process With A Metallocene... E-11 vi

6 TABLES 2.1 Comparison of Ziegler-Natta and Metallocene Costs Comparison of Unipol TM and Novolen TM Gas-Phase Processes Comparison of Processes Comparison of Capital Investment with Ziegler-Natta System Comparison of Capital Investment with Mettallocene System Comparison of Economics with Ziegler-Natta System Comparison of Economics with A First-Generation Metallocene System Leading Global Producers Estimated End-2001 Leading Global Producers Polypropylene Producers and Their Plant Capacities Polypropylene Supply by Region, Polypropylene Demand by Region, World Polypropylene Consumption by End Use, Polypropylene End-Use Patterns by Major Regions in U.S. Prices of Polypropylene by Grade Progress in Ziegler-Natta Comparison of Films Generated from Ziegler-Natta and Metallocene PP Comparison of Ziegler-Natta and Metallocene Costs Polypropylene ICP by A Fluidized Bed Gas Phase Process (Unipol TM Technoloy) With Shac TM Ziegler-Natta System Design Bases and Assumptions Unipol Process For Polypropylene ICP with Shac TM Ziegler-Natta Stream Flows Unipol Process For Polypropylene ICP with Shac TM Ziegler-Natta Major Equipment Unipol Process For Polypropylene ICP with Shac TM Ziegler-Natta Utilities Summary Unipol Process For Polypropylene ICP with Shac TM Ziegler-Natta Total Capital Investment vii

7 TABLES 5.6 Unipol Process For Polypropylene ICP with Shac TM Ziegler-Natta Capital Investment by Section Unipol Process For Polypropylene ICP with Shac TM Ziegler-Natta Production Costs Polypropylene ICP by A Fluidized Bed Gas Phase Process (Unipol TM Technology) With A First Generation Metallocene System Design Bases And Assumptions Polyproylene ICP by A Fluidized Bed Gas Phase Process (Unipol TM Technology) With A Second Generation Metallocene System Design Bases and Assumptions Unipol Process For Polypropylene ICP with A First Generation Metallocene Production Cost Unipol Process For Polypropylene ICP with A Second Generation Mettalocene Production Cost Polypropylene ICP by A Vertical Stirred Bed Gas Phase Process (Novolen TM Technology) With PTK TM Ziegler-Natta System Design Bases and Assumptions Novolen Process For Polypropylene ICP with PTK TM Ziegler-Natta Steam Flows Novolen Process For Polypropylene ICP with PTK TM Ziegler-Natta Major Equipment Novolene Process For Polypropylene ICP with PTK TM Ziegler-Natta Utilities Summary Novolene Process For Polypropylene ICP with PTK TM Ziegler-Natta Total Capital Investment Novolene Process For Polypropylene ICP with PTK TM Ziegler-Natta Capital Investment by Section Novolene Process For Polypropylene ICP with PTK TM Ziegler-Natta Production Costs Polypropylene ICP by A Vertical Stirred Bed Gas Phase Process (Novolen TM Technology) With A First Generation Metallocene System Design Bases and Assumptions viii

8 TABLES 6.9 Polypropylene ICP by A Vertical Stirred Bed Gas Phase Process (Novolen TM Technology) With A Second Generation Metallocene Design Bases and Assumptions Novolen Process For Polypropylene ICP With A First Generation Metallocene Production Costs Novolen Process For Polypropylene ICP With A Second Generation Metallocene Production Costs Basell/Montell Internal Electron Donors Polypropylene ICP by A Bulk Slurry Loop and A Gas Phase Process (Sheripol TM Technology) With An Advanced Ziegler-Natta System Design Bases and Assumptions Spheripol TM Process For Polypropylene ICP With An Advanced Ziegler-Natta Stream Flows Spheripol TM Process For Polypropylene ICP With An Advanced Ziegler-Natta Major Equipment Spheripol TM Process For Polypropylene ICP With An Advanced Ziegler-Natta Utilities Summary Spheripol TM Process For Polypropylene ICP With An Advanced Ziegler-Natta Total Capital Investment Spheripol TM Process For Polypropylene ICP With An Advanced Ziegler-Natta Capital Investment by Section Spheripol TM Process For Polypropylene ICP With An Advanced Ziegler-Natta Production Costs Polypropylene ICP by A Bulk Slurry Loop and A Gas Phase Process (Spheripol TM Technology) With A First Generation Metallocene System Design Bases and Assumptions Spheripol TM Process For Polypropylene ICP With A First Generation Metallocene System Major Equipment ix

9 TABLES 7.11 Spheripol TM Process For Polypropylene ICP with A First Generation Metallocene System Total Capital Investment Spheripol TM Process For Polypropylene ICP with A First Generation Metallocene System Capital Investment by Section Spheripol TM Process For Polypropylene ICP with A First Generation Metallocene System Production Costs Polypropylene ICP by A Bulk Slurry Loop and A Gas Phase Process (Spheripol TM Technology) With A Second Generation Metallocene System Design Bases and Assumptions Spheripol TM Process For Polypropylene ICP With A Second Generation Metallocene System Production Costs A-1 Single-Site Patent Summary... A-3 A-2 Ziegler-Natta Patent Summary... A-15 A-3 Process Patent Summary... A-24 x