PROCESS ECONOMICS PROGRAM

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1 Abstract - Process Economics Program Report No. 36B PROCESS ECONOMICS PROGRAM SRI INTERNATIONAL Menlo Park, California LOW DENSITY POLYETHYLENB (August 1980) Low density polyethylene continues to be the largest volume commodity plastic. Before 1977 it was made almost exclusively by free radical polymerization at extremely high pressures, typically 1000 to 3500 atmospheres. In 1977 however, Union Carbide announced a new low pressure route to LDPE having substantially lower investment and energy costs* Since this announcement, a great many companies have been active in developing similar low pressure routes, some with success. Three processes have currently reached full commercialization, namely, the gas phase process of Union Carbide and the solution processes of Dow and Du Pant. The resins produced by these low pressure processes have a linear molecular structure similar to that of HDPE (hence the name linear LDPE) but with some relatively short chain branching. Branching is achieved by copolymerizing ethylene with an alpha olefin such as butene-1, hexene-1, or octene-1. The combination of a linear backbone structure and branching results in resins with outstanding physical properties. These resins will compete effectively with conventional LDPE in many applications and will probably also find some new applications. This report gives detailed evaluations of the Union Carbide fluid bed process, the low pressure solution processes of Dow and Du Pont, and the Mitsui Toatsu process, which produces polymer as a slurry in an inert diluent. The economics of these processes are compared with updated economics for the high pressure tubular and autoclave reactor processes, and with the Stamicarbon solution process (for HDPE), for which LDPE capability is claimed. PEP'78 JC

2 PROCESS ECONOMICS PROGRAM SRI INTERNATIONAL Menlo Park, California Expires: July 1, 1981 PRICE SCHEDULE FOR REPORTS PHASES I THROUGH XI (PEP'75) (Offered Only to Clients of PEP'79 and PEP'80) Any report in above phases -- US$lOO PEP COST INDEX UPDATES: Extra copies of the PEP COST INDEX volume (and subsequent PEP COST INDEX UPDATES during active membership) are offered to current clients for a one-time charge of US$lOO.

3 - I% 0 on LOW DENSITY POLYETHYLENE Report No. 36B SUPPLEMENT B by JEFFREY C. F. CHEN ROBERT L. MAGOVERN KENNETH B. SINCLAIR a A private report by the August 1980 PROCESS ECONOMICS PROGRAM Menlo Park, California 94025

4 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 WORLD 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, product, and plant for the United States and Western Europe. ii

5 CONTENTS INTRODUCTION...., SUMMARY PROCESS COMPARISON AND ANALYSIS INDUSTRY STATUS CHEMISTRY... Reaction Mechanism for High Pressure Polymerization. Linear REVIEW OF PROCESSES Asahi Chemical Industry Chisso Corporation Farberwerke Hoechst Mitsui Petrochemical Industtiies Nippon Oil Nissan Petrochemical Industries Phillips Petroleum LINEAR LOW DENSITY POLYETHYLENE BY A MEDIUM PRESSURE SOLUTION PROCESS, DU PONT TECHNOLOGY... Du Pont Patents.... Process Description.... Process Discussion... Catalyst... Comonomer... Polymerization... Polymer Purification... Solvent Removing Unit.... Cost Estimates... Capital Costs.... Production Costs LINEAR LOW DENSITY POLYETHYLENE BY A LOW PRESSURE SOLUTION PROCESS... Process Description.... Process Discussion... Catalyst... Polymerization... Comonomer iii

6 CONTENTS 8 LINEAR LOW DENSITY POLYETHYLENE BY A LOW PRESSURE SOLUTION PROCESS (Continued) Solvent Recovery Finishing Cost Estimates Capital Costs Production Costs LINEAR LOW DENSITY POLYETHYLENE BY A GAS PHASE PROCESS, UNION CARBIDE TECHNOLOGY Union Carbide Patents Process Description Process Discussion Catalyst Reactor Comonomer Cost Estimates... 0 Capital Costs Production Costs LINEAR LOW DENSITY POLYETHYLENE BY A SLURRY PROCESS, MITSUI TOATSU TECHNOLOGY Mitsui Toatsu Patents Process Description Process Discussion Catalyst 'Reaction Flashing Diluent Purification Cost Estimates Capital Costs Production Costs LOW DENSITY POLYETHYLENE BY HIGH PRESSURE PROCESSES Changes in PEP Report 36A Design Cases Process Discussion Reactors Recycle Cooling Compression Cost Estimates Capital Costs Production Costs iv

7 CONTENTS APPENDIXA DESIGN AND COST BASES CITED REFERENCES PATENT REFERENCES BY COMPANY V

8 ILLUSTRATIONS Linear LDPE by a Low Pressure SdUtiOn Effect of Comonomer Cost and Content on Net Production Cost s. \ Effect of Change in Fixed Investment On Product Value Process, polymerization to Linear Polyethylene..... Effect of Branching on Density Linear Effect of Comonomer Content on Density Linear WIPE by a-medium Pressure Solution PrOCeSs, Flow Sheet Linear LDPE by a Medium Pressure Solution Process,, Effect of Comonomer Content on Copolymer Density Linear LDPE by a Medium Pressure Solution Process,, Effect of Solvent Content in Polymer Pellets On Stripping Time Linear LDPE by a Medium Pressure Solution Process,, Schematic Drawing of a Cylindrical Stripping Column for Removal of Solvent from Pellets Linear LDPE by a Medium Pressure Solution Process,, Effect of Operating Level and Plant Capacity on Production Cost , F1owSheet Effect of Operating Level and Plant Capacity on Production Cost UCC Technology, Pelletized Product Flow Sheet ,.....,. UCC Technology, Pelletized Product Effect of Operating Level and Plant Capacity on Production Cost Vii

9 ILLUSTRATIONS 9.3 UCC Technology, Unpelletized Product Effect of Operating Level and Plant Capacity on Production Cost Linear LDPE by a Slurry Process, Mitsui Toatsu Technology PlowSheet Linear LDPE by a Slurry Process, Mitsui Toatsu Technology Effect of Operating Level and Plant Capacity on Production Cost LDPE by a High Pressure Process PlowSheet LDPE by a High Pressure Process FlowSheet ' LDPE by a High Pressure Process Effect of Operating Level and Plant Capacity on Production Cost LDPE by a High Pressure Process Effect of Operating Level and Plant Capacity on Production Cost Viii

10 TABLES Properties of LLDPE and Comentional LDPEinCaat Films Impact Strength and ESCR of LLDPE and Conventional LDPE Resins in Injection Melded Containers Sumaryof Economics Comparative Econcxi~ics of Processes, Process Cooaparison Plant Capacities as of End Production in the United States Major U.S. Producers and Market Shares Estimated U.S. Consumption of LDPE Resins, Estimated U.S. Consumption of Film Resin, U.S. List Prices... e Linear Effect of Branching on Density Linear References to Copolymers, Hoechst Patents Linear References to Copolymers, Mitsui Petrochemical Patents... Linear Effect of &monomer Content on Density, Mitsui Petrochemical Data....., Linear References to Copolymers, Phillips Petroleum Patents.... Linear LDPE, PatentSunmary ix

11 TABLES 7.2 Linear LDPE by a Medium Pressure Solution Process, Major Equipment i Linear LDPE by a Medium Pressure Solution Process, StreamFlows Linear LDPE by a Medium Pressure Solution Process, Utilities Smry, Linear LDPE by a Medium PresStIre SolUtioU Process Reactor Design Basis Linear LDPE by a Medium Pressure Solution Process, Capital Investment Linear LDPE by a Medium Pressure Solution Process, Capital Investment by Section Linear LDPE by a Medium Pressure Solution Process, Production Costs Linear LDPE by a Medium Pressure Solution Process, Direct Operating Costs by Section Summary of a Dow Chemical Patent on a High Efficiency Catalyst Major Equipment , ' StreamFlows Utilities Summary Reactor Design Basis Total Capital Investment Capital Investment by Section Production Costs x

12 Direct Operating Costs by Section ,. 105 Linear by a Gas Phase Process, Union Carbide Technology Major Equipment , UCC Technology, Pelletized Product StreamFlows UCC Technology, Unpellitized Product Utilities Summary.., Union Carbide Technology Reactor Design Basis UCC Technology, Pelletized Product Total Capital Investment UCC Technology, Pelletized Product Capital Investment by Section UCC Technology, Pelletized Product Production Costs UCC Technology, Pelletized Product Direct Operating Costs by Section UCC Technology, Unpelletized Product Total Capital Investment UCC Technology, Unpelletized Product Capital Investment by Section....., UCC Technology, Unpelletized Product Production Costs UCC Technology, Unpelletised Product Direct Operating Costs by Section Xi

13 TABLES 10.1 Linear LDPE, Mitsui Toatsu Technology PatentSummary Linear LDPE by a Slurry Process, Mitsui Toatsu Process Major Equipment......, , Linear LDPE by a Slurry Process, Mitsui Toatsu Process StreamFlows Linear LDPE by a Slurry Process, Mitsui Toatsu Process Utilities Summary Linear LDPE by a Slurry Process, Mitsui Toatsu Technology Reactor Design Basis Linear LDPE by a Slurry Process, Mitsui Toatsu Process Total Capital Investment Linear LDPE by a Slurry Process, Mitsui Toatsu Process Capital Investment by Section Linear LDPE by a Slurry Process, Mitsui Toatsu Process Production Costs Linear LDPE by a Slurry Process, Mitsui Toatsu Process Direct Operating Costs by Section.... e LDPE by a High Pressure Process Major Equipment D LDPE by a High Pressure Process Major Equipment LDPE by a High Pressure Process StreamFlows LDPE by a High Pressure Process StreamFlows xii.

14 TABLES 11.5 LDPE by a High Pressure Process Utilities Summary LDPE by a High Pressure Process Utilities Summary LDPE by High Pressure Processes Reactor Design Basis LDPE by a High Pressure Process Total Capital Investment LDPE by a Righ Pressure Process Capital Investment by Section LDPE by a High Pressure Process Production Costs LDPE by a High Pressure Process Direct Operating Costs by Section LDPE by a High Pressure Process Total Capital Investment IDPE by a High Pressure Process Capital Investment by Section LDPE by a High Pressure Process Production Costs LDPE by a High Pressure Process Direct Operating Costs by Section, Xiii

PROCESS ECONOMICS PROGRAM

PROCESS ECONOMICS PROGRAM SRI INTERNATIONAL Menlo Park, California 94025 Abstract Process Economics Program Report No. 19C HIGH DENSITY POLYETHYLENE High density polyethylene is manufactured by polymerizing