Polyethylene, Low Density, Supp. B.

, August 1980

PROCESS
ECONOMICS
PROGRAM
SRI INTERNATIONAL
Abstract - Menlo Park, California
64025
Process Economics Program Report No. 36B

LOW DENSITY POLYETHYLENB

(August 1980)

Low density polyethylene continues to be the largest volume commod-

ity plastic. Before 1977 it was made almost exclusively by free radi-
cal polymerization at extremely high pressures, typically 1000 to 3500
atmospheres. In 1977 however, Union Carbide announced a new low pres-
sure 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 applica-
tions.

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 up-
dated 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
 Polyethylene, Low Density, Supp. B., August 1980

PROCESS
ECONOMICS
a PROGRAM
SRI INTERNATIONAL
Menlo Park, California
94025

Expires: July 1, 1981

PRICE SCHEDULE FOR REPORTS PHASES I THROUGH XI (PEP'75)

(Offered Only to Clients of PEP'79 and PEP'80)

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 Polyethylene, Low Density, Supp. B., August 1980

- Report No. 36B

I%
0
0
on LOW DENSITY POLYETHYLENE

SUPPLEMENT B

by JEFFREY C. F. CHEN

ROBERT L. MAGOVERN
KENNETH B. SINCLAIR

0
a
August 1980

@a
A private report by the

PROCESS ECONOMICS PROGRAM

Menlo Park, California 94025

 Polyethylene, Low Density, Supp. B., August 1980

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, prod-
uct, and plant for the United States and Western Europe.

ii
 Polyethylene, Low Density, Supp. B., August 1980

CONTENTS

INTRODUCTION . . . . , . . . . . . . . . . . . . . . . . . . . 1

SUMMARY....................... . . . . . 3

PROCESS COMPARISON AND ANALYSIS. . . . . . . . . . . . . . . . 11

INDUSTRY STATUS. . . . . . . . . . . . . . . . . . . . . . . . 21

CHEMISTRY...................... . . . . . 35
Reaction Mechanism for High Pressure Polymerization. . . . . . 35
Linear Low Density Polyethylene. . . . . . . . . . . . . . . . 37

REVIEW OF PROCESSES. ................ . . . . . 41

Asahi Chemical Industry. .............. . . . . . 45
Chisso Corporation ................. . . . . . 45
Farberwerke Hoechst. ................ . . . . . 46
Mitsui Petrochemical Industtiies........... . . . . . 46
Nippon Oil ..................... . . . . . 46
Nissan Petrochemical Industries. .......... . . . . . 47
Phillips Petroleum ................. . . . . . 47

LINEAR LOW DENSITY POLYETHYLENE BY A MEDIUM PRESSURE

SOLUTION PROCESS, DU PONT TECHNOLOGY ........ . . . . . 55
Du Pont Patents. .................. . . . . . 55
Process Description. ................ . . . . . 60
Process Discussion ................. . . . . . 70
Catalyst ..................... . . . . . 70
Comonomer...................... . . . . . 71
Polymerization .................. . . . . . 71
Polymer Purification ............... . . . . . 74
Solvent Removing Unit. .............. . . . . . 74
Cost Estimates ................... . . . . . 78
Capital Costs. .................. . . . . . 78
Production Costs ................. . . . . . 78

LINEAR LOW DENSITY POLYETHYLENE BY A LOW PRESSURE

SOLUTION PROCESS .................. . . . . . 85
Process Description. ................ . . . . . 88
Process Discussion ................. . . . . . 96
Catalyst ..................... . . . . . 96
Polymerization .................. . . . . . 96
Comonomer..................... . . . . . 98

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 Polyethylene, Low Density, Supp. B., August 1980

CONTENTS

8 LINEAR LOW DENSITY POLYETHYLENE BY A LOW PRESSURE

SOLUTION PROCESS (Continued)
Solvent Recovery ...................... 98
Finishing ......................... 99
Cost Estimates ........................ 99
Capital Costs. ....................... 99
Production Costs ...................... 100

9 LINEAR LOW DENSITY POLYETHYLENE BY A GAS PHASE PROCESS,

UNION CARBIDE TECHNOLOGY ................... 107
Union Carbide Patents. .................... 108
Process Description ..................... 111
Process Discussion ...................... 118
Catalyst..........................11 8
Reactor ........................... 118
Comonomer. ........................ .120
Cost Estimates........................ 0
Capital Costs. ....................... 120
Production Costs ...................... 121

10 LINEAR LOW DENSITY POLYETHYLENE BY A SLURRY PROCESS,

MITSUI TOATSU TECHNOLOGY ................... 133
Mitsui Toatsu Patents. .................... 133
Process Description. ..................... 134
Process Discussion ...................... 143
Catalyst..........................14 3
'Reaction .......................... 143
Flashing..........................14 4
Diluent Purification .................... 145
Cost Estimates ........................ 146
Capital Costs. ....................... 146
Production Costs ...................... 146

11 LOW DENSITY POLYETHYLENE BY HIGH PRESSURE PROCESSES. ..... 153

Changes in PEP Report 36A Design Cases ............ 153
Process Discussion ...................... 163
Reactors..........................16 3
Recycle Cooling. ...................... 165
Compression.........................16 5
Cost Estimates ........................ 167
Capital Costs. ....................... 167
Production Costs ...................... 167

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 Polyethylene, Low Density, Supp. B., August 1980

CONTENTS

APPENDIXA DESIGN AND COST BASES ................ 179

CITED REFERENCES. ........................ 185

PATENT REFERENCES BY COMPANY ................... 191

V
 Polyethylene, Low Density, Supp. B., August 1980

ILLUSTRATIONS

3.1 Linear LDPE by a Low Pressure SdUtiOn Process,

Effect of Comonomer Cost and Content on Net
Production Cost . . . . . . . . . . . l s . l l l l
. . . . 13

3.2 Low Density Polyethylene \

Effect of Change in Fixed Investment On
Product Value . . . . . . . . . . . . . l . l l l
. . . . 18

polymerization to Linear Polyethylene . . . . . . . . . . 38

5.1 l

6.1 Low Density Polyethylene

Effect of Branching on Density. . . . . . . l l . . . . . . 44

6.2 Linear Low Density Polyethylene

Effect of Comonomer Content on Density. . . . . . . . . . . 52

7.1 Linear WIPE by a-Medium Pressure Solution PrOCeSs,

Du Pont Technology Flow Sheet . . . . . . . . . . . . . .
l
193

7.2 Linear LDPE by a Medium Pressure Solution Process,

Du Pont Technology,
Effect of Comonomer Content on Copolymer Density. . . . . . 72
7.3 Linear LDPE by a Medium Pressure Solution Process,
Du Pont Technology,
l- Effect of Solvent Content in Polymer Pellets
On Stripping Time. . . . . . . . . . . . . . . . . . . . . 76
7.4 Linear LDPE by a Medium Pressure Solution Process,
Du Pont Technology,
Schematic Drawing of a Cylindrical Stripping Column
for Removal of Solvent from Pellets . . . . . . . . . . . . 77
7.5 Linear LDPE by a Medium Pressure Solution Process,
Du Pont Technology,
Effect of Operating Level and Plant Capacity on
Production Cost . . . . . . . . . . , . . . . . . . . . . . 84
8.1 Linear LDPE by a Low Pressure Solution Process

a- 8.2
F1owSheet.....................
Linear LDPE by a Low Pressure Solution Process
Effect of Operating Level and Plant Capacity
. . . . 197

on Production Cost. . . . . . . . . . . . . . . . . . . . . 106

9.1 Linear LDPE by a Gas Phase Process,

a 9.2
UCC Technology, Pelletized Product
Flow Sheet. . . . . . . . . . . . . . . . . , . . . . . , .
Linear LDPE by a Gas Phase Process,
199

UCC Technology, Pelletized Product

Effect of Operating Level and Plant Capacity
on Production Cost. . . . . . . . . . . . . . . . . . . . . 131

Vii
 Polyethylene, Low Density, Supp. B., August 1980

ILLUSTRATIONS

9.3 Linear LDPE by a Gas Phase Process,

UCC Technology, Unpelletized Product
Effect of Operating Level and Plant Capacity
on Production Cost. . . . . . . . . . . . . . . . . . . . . 132
10.1 Linear LDPE by a Slurry Process,
Mitsui Toatsu Technology
PlowSheet......................... 203
10.2 Linear LDPE by a Slurry Process,
Mitsui Toatsu Technology
Effect of Operating Level and Plant Capacity
on Production Cost. . . . . . . . . . . . . . . . . . . . . 152
11.1 LDPE by a High Pressure Process
Autoclave Reactor
PlowSheet......................... 205
11.2 LDPE by a High Pressure Process
Tubular Reactor
FlowSheet. . . . . . . . . . . . . . . . . . . . . . . . .' 209
11.3 LDPE by a High Pressure Process
Autoclave Reactor

a
Effect of Operating Level and Plant Capacity
on Production Cost. . . . . . . . . . . . . . . . . . . . . 177
11.4 LDPE by a High Pressure Process
Tubular Reactor
Effect of Operating Level and Plant Capacity
on Production Cost. . . . . . . . . . . . . . . . . . . . . 178

Viii
 Polyethylene, Low Density, Supp. B., August 1980

TABLES

2.1 Properties of LLDPE and Comentional

LDPEinCaat Films. . . . . . . . . . . . . . . . . . . . . 7
2.2 Impact Strength and ESCR of LLDPE and Conventional
LDPE Resins in Injection Melded Containers. . . . . . . . . 8
2.3 Low Density Polyethylene
Sumaryof Economics. . . . . . . . . . . . . . . . . . . . 9
3.1 Low Density Polyethylene
Comparative Econcxi~ics
of Processes, . . . . . . . . . . . . 12
3.2 Low Density Polyethylene
Process Cooaparison . . . . . . . . . . . . . . . . . . . . 14
4.1 Low Density Polyethylene
Plant Capacities as of End 1979 . . . . . . . . . . . . . . 22
4.2 Low Density Polyethylene
Production in the United States . . . . . . . . . . . . . . 29
4.3 Low Density Polyethylene
Major U.S. Producers and Market Shares. . . . . . . . . . . 30
- 4.4 Low Density Polyethylene
Estimated U.S. Consumption of LDPE Resins, 1979 . . . . . . 32
4.5 Low Density Polyethylene
Estimated U.S. Consumption of Film Resin, 1978. . . . . . . 32
4.6 Low Density Polyethylene
U.S. List Prices. . . e . . . . . . . . . . . . . . . . . . 33
6.1 Linear Low Density Polyethylene
Effect of Branching on Density. . . . . . . . . . . . . . . 43
6.2 Linear Low Density Polyethylene
References to Copolymers, Hoechst Patents . . . . . . . . . 49

l 6.3 Linear Low Density Polyethylene

References to Copolymers, Mitsui Petrochemical Patents. . . 50
6.4 Linear Low Density Polyethylene
Effect of &monomer Content on Density,
Mitsui Petrochemical Data . . . . . , . . . . . . . . . . . 51

a 6.5 Linear Low Density Polyethylene

References to Copolymers, Phillips Petroleum Patents. . . . 53
7.1 Linear LDPE, Du Pont Technology
PatentSunmary . . . . . . . . . . . . . . . . . . . . . . 59

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 Polyethylene, Low Density, Supp. B., August 1980

TABLES

7.2 Linear LDPE by a Medium Pressure Solution Process,

Du Pont Technology
Major Equipment. . . . . . . . . i . . . . . . . . . . . . 63
7.3 Linear LDPE by a Medium Pressure Solution Process,
Du Pont Technology
StreamFlows....................... 66
7.4 Linear LDPE by a Medium Pressure Solution Process,
Du Pont Technology
Utilities Smry, . . . . . . . . . . . . . . . . . . . . 69
7.5 Linear LDPE by a Medium PresStIre SolUtioU Process
Du Pont Technology
Reactor Design Basis . . . . . . . . . . . . . . . . . . . 73
7.6 Linear LDPE by a Medium Pressure Solution Process,
Du Pont Technology
Capital Investment . . . . . . . . . . . . . . . . . . . . 80
7.7 Linear LDPE by a Medium Pressure Solution Process,
Du Pont Technology
Capital Investment by Section. . . . . . . . . . . . . . . 81
7.8 Linear LDPE by a Medium Pressure Solution Process,
Du Pont Technology
Production Costs . . . . . . . . . . . . . . . . . . . . . 82
7.9 Linear LDPE by a Medium Pressure Solution Process,
Du Pont Technology
Direct Operating Costs by Section. . . . . . . . . . . . . 83
8.1 Summary of a Dow Chemical Patent on a High
Efficiency Catalyst. . . . . . . . . . . . . . . . . . . . 87
.8.2 Linear LDPE by a Low Pressure Solution Process
Major Equipment . . . . . . . . . . . . . . . . , . . . . 91
8.3 Linear LDPE by a Low Pressure Solution Process '
StreamFlows....................... 93
8.4 Linear LDPE by a Low Pressure Solution Process
Utilities Summary. . . . . -. . . . . . . . . . . . . . . . 95
8.5 Linear LDPE by a Low Pressure Solution Process
Reactor Design Basis . . . . . . . . . . . . . . . . . . . 97
8.6 Linear LDPE by a Low Pressure Solution Process
Total Capital Investment . . . . . . . . . . . . . . . . . 102
8.7 Linear LDPE by a Low Pressure Solution Process
Capital Investment by Section. . . . . . . . . . . . . . . 103
8.8 Linear LDPE by a Low Pressure Solution Process
Production Costs . . . . . . . . . . . . . . . . . . . . . 104

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 Polyethylene, Low Density, Supp. B., August 1980

8.9 Linear LDPE by a Low Pressure Solution Process

Direct Operating Costs by Section. . . . . . . . . . , . 105
9.1 Linear Low Density Polyethylene by a Gas
Phase Process, Union Carbide Technology
Major Equipment. . . . . . . . . . . . . . . . . . , . . 114
9.2 Linear LDPE by a Gas Phase Process,
UCC Technology, Pelletized Product
StreamFlows . . . . . . . . . . . . . . . . . . . . . 116

- 9.3 Linear LDPE by a Gas Phase Process,

UCC Technology, Unpellitized Product
Utilities Summary. . , . . . . . . . . . . . . . . . . . 117
9.4 Linear LDPE by a Gas Phase Process,
Union Carbide Technology
Reactor Design Basis . . . . . . . . . . . . . . . . . . 119
9.5 Linear LDPE by a Gas Phase Process,
UCC Technology, Pelletized Product
Total Capital Investment . . . . . . . . . . . . . . . . 123
9.6 Linear LDPE by a Gas Phase Process,
UCC Technology, Pelletized Product

l
Capital Investment by Section. . . . . . . . . . . . . . 124
9.7 Linear LDPE by a Gas Phase Process,
UCC Technology, Pelletized Product
Production Costs . . . . . . . . . . . . . . . . . . . . 125
9.8 Linear LDPE by a Gas Phase Process,
UCC Technology, Pelletized Product
Direct Operating Costs by Section. . . . . . . . . . . . . 126

9.9 Linear LDPE by a Gas Phase Process,

UCC Technology, Unpelletized Product
Total Capital Investment . . . . . . . . . . . . . . . . 127
9.10 Linear LDPE by a Gas Phase Process,
UCC Technology, Unpelletized Product
Capital Investment by Section. . . . . , . . . . . . . . 128
9.11 Linear LDPE by a Gas Phase Process,
UCC Technology, Unpelletized Product
Production Costs . . . . . . . . . . . . . . . . . . . . 129
9.12 Linear LDPE by a Gas Phase Process,
UCC Technology, Unpelletised Product
Direct Operating Costs by Section . . . . . . . . . . . 130

Xi
 Polyethylene, Low Density, Supp. B., August 1980

TABLES

10.1 Linear LDPE,

Mitsui Toatsu Technology
PatentSummary...................... 135

10.2 Linear LDPE by a Slurry Process,

Mitsui Toatsu Process
Major Equipment. . . . . . , . . . . . . . , . . . . . . . 138
10.3 Linear LDPE by a Slurry Process,
Mitsui Toatsu Process
StreamFlows....................... 140

10.4 Linear LDPE by a Slurry Process,

Mitsui Toatsu Process
Utilities Summary. . . . . . . . . . . . . . . . . . . . . 142

10.5 Linear LDPE by a Slurry Process,

Mitsui Toatsu Technology
Reactor Design Basis . . . . . . . . . . . . . . . . . . . 144

10.6 Linear LDPE by a Slurry Process,

Mitsui Toatsu Process
Total Capital Investment . . . . . . . . . . . . . . . . . 148

10.7 Linear LDPE by a Slurry Process,

Mitsui Toatsu Process
Capital Investment by Section. . . . . . . . . . . . . . . 149

10.8 Linear LDPE by a Slurry Process,

Mitsui Toatsu Process
Production Costs . . . . . . . . . . . . . . . . . . . . . 150

10.9 Linear LDPE by a Slurry Process,

Mitsui Toatsu Process
Direct Operating Costs by Section. . . . e . . . . . . . . 151

11.1 LDPE by a High Pressure Process

Autoclave Reactor
Major Equipment . . . . . . . . . . . . . . D . . . . . . 155

11.2 LDPE by a High Pressure Process

Tubular Reactor
Major Equipment . . . . . . . . . . . . . . . . . . . . . 157
11.3 LDPE by a High Pressure Process
Autoclave Reactor
StreamFlows....................... 159
11.4 LDPE by a High Pressure Process
Tubular Reactor
StreamFlows....................... 160

xii

.
 Polyethylene, Low Density, Supp. B., August 1980

TABLES

11.5 LDPE by a High Pressure Process

Autoclave Reactor
Utilities Summary. . . . . . . . . . . . . . . . . . . . . 161
-
11.6 LDPE by a High Pressure Process
Tubular Reactor
Utilities Summary. . . . . . . . . . . . . . . . . . . . . 162
11.7 LDPE by High Pressure Processes
l- 11.8
Reactor Design Basis . . . . . . . . . . . . . . . . . . .
LDPE by a High Pressure Process
164

Autoclave Reactor
Total Capital Investment . . . . . . . . . . . . . . . . . 169
11.9 LDPE by a Righ Pressure Process
Autoclave Reactor
Capital Investment by Section. . . . . . . . . . . . . . . 170
11.10 LDPE by a High Pressure Process
Autoclave Reactor
Production Costs . . . . . . . . . . . . . . . . . . . . . 171
11.11 LDPE by a High Pressure Process
Autoclave Reactor
Direct Operating Costs by Section. . . . . . . . . . . . . 172
11.12 LDPE by a High Pressure Process
Tubular Reactor
Total Capital Investment . . . . . . . . . . . . . . . . . 173
11.13 IDPE by a High Pressure Process
Tubular Reactor
Capital Investment by Section. . . . . . . . . . . . . . . 174
11.14 LDPE by a High Pressure Process
Tubular Reactor
Production Costs . . . . . . . . . . . . . . . . . . . . . 175
11.15 LDPE by a High Pressure Process
Tubular Reactor
Direct Operating Costs by Section, . . . . . . . . . . . . 176

Xiii