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SPE Polyolefins Conference 2005 Low Density and Linear Low Density Polyethylene Presentation

Presented by J. Bayley

NOVA Chemicals Corporation

Note: The content of this presentation is intended for basic learning, the content may not describe or encompass all aspects of materials and processes

Overview of Presentation Topics

• Feedstock for the Manufacture of Polyethylene

• Polyethylene Basics

Unit 1 - LDPE

• Manufacturing Processes

• Properties

• Applications

• Future for LDPE

Unit 2 - LLDPE

• Molecular Information

• Comonomer Information

• Properties

• Catalyst vs Properties

• Manufacturing Processes

• Applications

• Future of LLDPE

Natural Gas to Ethane to Ethylene….

Ethane Supply System

Gas Field

Gas Plant

Ethane Supply System Gas Field Gas Plant Pipeline Reprocessing Plant Petrochemical Industry Ethane Residue Natural
Pipeline
Pipeline

Reprocessing

Plant

Petrochemical

Industry

Ethane
Ethane
Residue Natural Gas
Residue
Natural Gas

Energy Markets

Natural Gas Components

C

C

C

C

C

H

H

CO 2

1

2

3

4

5 +

2

2

0

S

Methane Ethane Propane Butane Pentane plus Water Sulphur Carbon dioxide

Pipeline System Post Gas Plant 90 – 100% 3 – 10%

Export Post Straddle Plant > 98% < 2%

   

< 1%

0

 

0

0

2%

< 2%

Nitrogen / Propane / Butane

Butane / Pentanes

Gas Plant - Separate Components

Methane / Ethane / Carbon Dioxide

- Separate Components Methane / Ethane / Carbon Dioxide Ethane / Propane Water Methane E t

Ethane / Propane

Water

Methane / Ethane / Carbon Dioxide Ethane / Propane Water Methane E t h a n

Methane

Ethane

Butane

Propane

Pentanes

Water

Carbon Dioxide

Nitrogen

n e Butane Propane Pentanes Water Carbon Dioxide Nitrogen Pentanes Natural Gas Pipeline Liquids Pipeline Natural

Pentanes Natural Gas Pipeline

Carbon Dioxide Nitrogen Pentanes Natural Gas Pipeline Liquids Pipeline Natural Gas Field Contains many components

Liquids Pipeline

Natural Gas Field

Contains many components in varying proportions

Reinjected underground

© 2005 NOVA Chemicals Corporation

De- propa nizer

Demetha nizer

De-b utan izer

De-e than izer

Pipeline Straddle Plant Extraction and Fractionation

Methane Ethane & C0 2 Propane Butane Pentane Plus Water Natural Gas to Fuel Markets
Methane
Ethane
& C0 2
Propane
Butane
Pentane Plus
Water
Natural Gas to Fuel Markets
Deh ydr ator
Confidential
© 2005 NOVA Chemicals Corporation
Natural Gas
Turbo-expander

Ethylene Manufacturing from Ethane

 

H

H

H

 

C

 

H

H

H

Ethane (C 2 H 6 )

  C   H H H Ethane (C 2 H 6 ) 800° C then fractionate

800° C then fractionate -160° C

H

H

 

C

C

C C H

H

H

H

2

1 6 0 ° C H H   C C H H H 2 Co-products Ethylene

Co-products

Ethylene (C 2 H 4 ) hydrogen

• In simple terms Ethane is converted into Ethylene (thermal decomposition) at high temperature in a steam furnace or cracker

• Refrigeration is used to separate the various components, co-products, etc.

• The furnace and auxiliary components are designed to efficiently produce as much Ethylene as possible and as few co-products as possible

• Co-Products such as Hydrogen, CO2 etc. can be sold for other uses

Brief History of Polyethylene

• PE synthesis discovered accidentally in 1932 by Imperial Chemical Company (ICI) Scientists

• First High Pressure LDPE plant built in 1939

• In 1953, large advancements were made by Scientist Carl Ziegler, inventor of a new catalyst system. A scientist named Giulio Natta also shares credit for this catalyst development

• Known today as the Ziegler-Natta Catalyst (Z/N), this catalyst facilitated polymer synthesis at lower temperatures and pressures - High Density Polyethylene (HDPE) materials were introduced soon after

• In the late 1970’s LLDPE materials were introduced to the market

• Significant Catalyst advances since that time with the advent of single-site catalysts

Polyethylene is

• A polymer of ETHYLENE or a copolymer of ethylene and a comonomer

• ETHYLENE - a gas composed of two carbons and four

hydrogen molecules. Formula: C 2 H 4

for polyethylene forms the backbone of the compound:

The monomer unit

H 2 C=CH 2

© 2005 NOVA Chemicals Corporation

Some Basic Definitions

Monomer - A chemical compound that can undergo polymerization. The basic building block of a polymer

Comonomer - One of the constituents of a copolymer

Copolymer - A product of copolymerization

Copolymerization - Polymerization of two different monomers

Homopolymer - Manufactured with no comonomer, with ethylene only

Practical Illustration of Polyethylene Designations

Practical Illustration of Polyethylene Designations LDPE (0.917 to 0.935 g/cc) HDPE (0.955 to 0.970 g/cc) LLDPE

LDPE

(0.917 to 0.935 g/cc)

HDPE

(0.955 to 0.970 g/cc)

LLDPE

(0.905 to 0.955 g/cc)

Polyethylene Designations

Polyethylene is classified by density ranges, as defined by ASTM:

LDPE

Type I

0.910 - 0.925 g/cc

MDPE

Type II

0.926 - 0.940 g/cc

HDPE

Type III

0.941 - 0.960 g/cc (Copolymer)

HDPE

Type IV >0.961 g/cc (Homopolymer)

Unit 1

PE Introduction and LDPE Overview

LDPE

• Molecular Structure LDPE - Long Chain Branching (LCB) results in unique polymer properties

Structure LDPE - Long Chain Branching (LCB) results in unique polymer properties © 2005 NOVA Chemicals

LDPE Manufacturing Processes

Two main LDPE manufacturing processes in use:

High Pressure Tubular Reactors

High Pressure Autoclave Reactors

LDPE Tubular Reactors (Simplified)

• A tubular LDPE Reactor is a long heat exchanger

• Free Radical polymerization uses Peroxide initiators or Oxygen to promote polymerization reactions

• Ethylene is circulated through a compressor - the main pressurization of the feed stream is accomplished by a hyper compressor

• Initiators are introduced at various points along the length of the tube - Zone temperatures are accurately controlled

• No backmixing takes place in the tubular system, residence time is limited/short

• The exothermic heat of reaction is removed via water jackets on the outside walls of the tube

• Upon exiting the reactor the material passes through medium pressure and low pressure separators (separates Ethylene from PE), PE moves to the extruder

Resin Manufacturing

High Pressure Tubular

PREHEATER

Initiator TUBULAR REACTOR Coolers S E P Wax A Drum Knockout R Pots A T
Initiator
TUBULAR REACTOR
Coolers
S
E
P
Wax
A
Drum
Knockout
R
Pots
A
T
O
R
To Disposal
Primary Secondary Compressor Compressor Telogen
Primary
Secondary
Compressor
Compressor
Telogen
RAW PRODUCT SILO
RAW
PRODUCT
SILO
Compressor Compressor Telogen RAW PRODUCT SILO To Finishing HOPPER Gear Pump and Pelletizer © 2005 NOVA

To Finishing

HOPPER
HOPPER
Compressor Telogen RAW PRODUCT SILO To Finishing HOPPER Gear Pump and Pelletizer © 2005 NOVA Chemicals

Gear Pump and Pelletizer

LDPE Autoclave Reactors (Simplified)

• Free radical type of polymerization uses Peroxide initiators typically

• System utilizes a stirred cylindrical vessel

• Ethylene feed gas and Peroxide are introduced to a compressor and then pumped with Peroxide initiator into the stirred autoclave vessel

• Proprietary designs baffle or partition the reactor into discreet zones enabling control of molecular species and amount of LCB of polymer in these zones

• Backmixing does take place in the autoclave system

• Walls of the autoclave unit are thick to accommodate high pressure - Heat of reaction is removed by the introduction of fresh feed

• Upon exiting the reactor the material passes through medium pressure and low pressure separators (separates Ethylene from LDPE polymer)

• Polymer enters the pelletization process to be pelletized

Resin Manufacturing

High Pressure Autoclave

Voluntary Telogen VA Purge Monomer MA Monomer Primary Secondary Initiator REACTOR SEPARATOR Compressor
Voluntary
Telogen
VA
Purge
Monomer
MA
Monomer
Primary
Secondary
Initiator
REACTOR
SEPARATOR
Compressor
Compressor
Methane
< C3
to Flare
RAW
PRODUCT
HOPPER
Hourly
SILO
D
D
Hold-Up
C
E
E
Hoppers
2
M
P
E
R
S
T
O
P
H
P
L
A
A
I
N
N
T
I
I
T
Z
Z
Gear Pump and
Pelletizer
E
E
E
To Finishing
R
R
R
Ethane to
C2
Solvent/Monomer
Flare
Removal

Comparison of High Pressure Autoclave and Tubular LDPE Manufacturing Processes

Information

Autoclave

Tubular

Length

20 ft

Up to 1 mile

Internal Diameter

3 ft

1-3 inches ID

Rx Temperature Range (°F)

350-500

350-600

Pressure within Rx (PSI)

15000-30000

20000-50000

Initiator Types

Organic Peroxide

Organic Peroxide or Oxygen

Typical Polymer Conversion Ranges per pass

Approx. 22% (varies with product mix)

Approx. 35% (varies with product mix)

Back Mixing Capability

Yes

No

General Observation

More precise tailoring of MW, MWD and Long chain branching (LCB)

Less capable of molecular tailoring and less uniform long chain branching (LCB)

General Observation

Comb-like LCB structure

Root-like LCB structure

(Note: This table provides general information. Technology may exist that is not encompassed by or include in this table. The information is intended for basic learning purposes only.)

Properties of LDPE Materials

LDPE Materials

Softness

Softer and more pliable than other PE types

Permeability

Higher, due to long chain branching and lower % crystallinity

Clarity

Available in high clarity for film applications - Improves clarity of LLDPE when blended with LDPE in low amounts

Processing

Shear thins in extrusion - processes easily at lower amps and pressures relative to LLDPE or HDPE

Equipment Needs

Screw/Die designed for LDPE required if extruding 100% LDPE

Melt Strength

Much higher than LLDPE due to presence of long chain side branched molecules - (Important for film blowing, foam etc.)

Other Pros

Less prone to melt fracture than LLDPE or HDPE

Suitability as a Blend Resin

Good, commonly used, can be detrimental to physical properties- LDPE is generally blended to improve ease of extrusion, increase melt strength or improve clarity of the end product

Shrink Properties

Possesses desirable biaxial shrink properties for shrink film

Limitations

Absolute physical properties lowest in class - extensional limitations or drawdown limitations exist - LLDPE and HDPE can be drawn much thinner in blown or cast film processes

LDPE Applications

• LDPE is still an important PE type

• The unique attributes of LDPE due to LCB provide desirable properties for some specific product applications

• LDPE is used at 100% in some applications such as conventional Shrink Film, Extrusion Coating, Wire and Cable Jacketing, LDPE Foam etc.

• LDPE is used as a property modifier in film and sheeting applications and is often blended with LLDPE (to improve clarity, processability, output rates, etc.)

2002 APC-LDPE Volume by End Use Process (based on Amercian Plastics Council 2002 Data)

Blow Molding

1%

Sheet (greater than 12

mil)

1% 6%
1%
6%

Injection Molding

Other Extruded Products

9%

Extrusion Coating

16%

Other (Resellers, Compounders)

23%

Film (less than 12 mil)

44%

LDPE Common Applications

Film Applications - Garment Films, Industrial Liner, Lamination films, Coextruded Food Packaging, Bakery Films, Film Blends (with LLDPE) for food packaging, Shrink Overwrap, Kitchen Cling Film, etc.

Extrusion Coating Applications - Paper Board Coating, Package Coating, Coating of other substrates (Examples foil coating, drink box coating, etc.)

Injection Molding - Lids, Caps and Closures

Other Examples - Wire and Cable applications, PE Foam, Pipe and Conduit, Non-abrasive films, Blow Molded squeeze bottles, etc.

The Future of LDPE

• Conventional LDPE has existed for many years and was predicted to be replaced by LLDPE

• LDPE future capacity growth is likely to be less than for LLDPE, though demand continues to be strong for LDPE

• LDPE is valued as performance modifier for extrusion processing or to obtain desired physical properties such as clarity

• Manufacturers can be expected to push the boundaries of their processes and exploit existing technology, but significant advances in resin morphology are not widely expected to occur in this class of materials

Unit 2

Introduction to LLDPE

LLDPE - General Information

• Linear Low Density Polyethylene (LLDPE) is made by the copolymerization of ethylene and a comonomer

- (Example: Ethylene and Octene copolymerized - can be described as an Ethylene-Octene Copolymer)

• LLDPE is composed of long linear molecules, the main polymer chain is composed of long strings of repeating Ethylene units - Short side chains (from comonomer) link onto the main polymer chains

• LLDPE typically has no long chain branching (LCB)

• LLDPE materials are typically copolymers but terpolymers and quatropolymers have also been made

• LLDPE typically has a narrow distribution of main chain molecule lengths (LDPE and HDPE tend to be broader)

LLDPE - Molecular Diagram

• LLDPE consists of long linear molecules with short side chain branches (SCB)

• SCB length is a function of comonomer type employed

side chain branches (SCB) • SCB length is a function of comonomer type employed © 2005
side chain branches (SCB) • SCB length is a function of comonomer type employed © 2005

Polyethylene Comonomers - Commonly Used

• Butene - A four carbon long molecule Formula: C 4 H 8

H 2 C=CH-CH 2 -CH 3

• Hexene - A six carbon long molecule Formula: C 6 H 12

H 2 C=CH-CH 2 -CH 2 -CH 2 -CH

3

• Octene - An eight carbon long molecule Formula: C 8 H 16

H 2 C=CH-CH 2 -CH 2 -CH 2 -CH

2 -CH 2 -CH 3

Comonomer Type - Product Properties

• Short side chain branching type influences product toughness - (Example: Butene, Hexene, Octene)

• Short side chains, like those made with butene comonomer are less effective at disrupting chain folding

• Longer side chains, like those formed with hexene and octene are longer and result in superior physical properties

• Z/N catalysts tend to have more difficulty than single-site catalysts in placing comonomer on the longer chain (higher molecular weight) portion of the polymer thus more comonomer ends up on the shorter chains

• Comonomer addition levels are used to control resin density

- (Example: Increased comomomer content increases short chain branch content and results in reduced resin density)

Effect of Comonomer Type on Physical Properties

Melt Index

1.0

1.0

1.0

Density

0.919

0.918

0.920

Comonomer Type

butene

hexene

octene

Dart Impact (grams/mil)

100

200

335

Low Friction Puncture (J/mm)

34

50

56

Elmendorf Tear Strength MD (grams/mil

100

300

400

Elmendorf Tear Strength TD (grams/mil)

300

650

710

Tensile Strength MD (psi)

4800

5300

6800

Tensile Strength TD (psi)

3700

4500

6400

Properties of LLDPE Materials

LLDPE Materials

Softness

Softer relative to HDPE but not as soft and pliable as LDPE

Permeability

Higher % crystallinity relative to LDPE-Barrier Properties dependant on part thickness and resin density to a large degree

Clarity

Clarity not as good as for LDPE in most cases- LDPE can be blended to improve clarity

Processing

Stiff in shear during extrusion- Narrow molecular weight distribution, processes at higher amps and head pressures relative to LDPE

Equipment Needs

Screw/Die designed for LLDPE required if extruding-Extruders, Screws, Dies and Air Rings need to be designed for LLDPE

Melt Strength

Much lower than LDPE due to NO long chain side branched molecules, only short chain branching generally

Suitability as a Blend Resin

Can be blended into LDPE where desired- Eg: Can be blended into shrink film to modify shrinkage properties

Shrink Properties

Long linear molecules tend to orient highly in the machine direction- shrinkage as a result is more imbalanced relative to LDPE

Strengths of LLDPE

High physical properties possible depending on comonomer used, catalyst used and molecular architecture- Very good elongational ability, can be drawn down thinner as a film than LDPE, higher strength than LDPE permits downgaging

Limitations of LLDPE

Prone to surface melt fracture in blown film and sheet extrusion-Process Conditions and Process aid additives are used to off-set this problem

© 2005 NOVA Chemicals Corporation

Catalyst Information

• Metal based catalysts facilitate the reactions required to polymerize and convert Ethylene to PE

• Z/N catalyst is in common use today though modifications and improvements have been made

• Next generation catalysts known as single-site catalysts and Metallocene catalysts also exist and are used in the production of mLLDPE, sLLDPE and HDPE

*Note: Metallocene catalysts fall into the single-site catalyst family

Catalyst Influence on LLDPE Properties

• A conventional Z/N catalyst has a variety of active reaction sites producing varied polymer molecules

• The result is a heterogeneous distribution of molecules having:

– broader distribution of molecular weight (molecular lengths)

– varied comonomer incorporation levels across the molecular weight distribution (MWD)

Catalyst Influence on LLDPE Properties

• New advanced Z/N catalysts improve comonomer placement - comonomer is more uniformly distributed, less bias for the low molecular weight (MW) range

• Improved comonomer placement results in improved physical properties

• MWD of LLDPE is often narrow to maximize finished physical properties

• Narrowing the MWD can make the polymer challenging to process (less shear thinning) therefore MWD is an important consideration in resin design

Properties for Products Manufactured using Advanced Ziegler-Natta Catalyst

Dart Impact *

using Advanced Ziegler-Natta Catalyst Dart Impact * Hexene Gas Phase Z/N Hexene Gas Phase Advanced Z/N

Hexene Gas Phase Z/N

Hexene Gas Phase Advanced Z/N

Octene Solution Z/N

Octene Solution Advanced Z/N

*These are typical values – advances in technology have significant improvements to product properties.

Properties for Products Manufactured using Advanced Ziegler-Natta Catalyst

MD Elmendorf Tear Stength *

Advanced Ziegler-Natta Catalyst MD Elmendorf Tear Stength * Hexene Gas Phase Z/N Hexene Gas Phase Advanced

Hexene Gas Phase Z/N

Hexene Gas Phase Advanced Z/N

Octene Solution Z/N

Octene Solution Advanced Z/N

*These are typical values – advances in technology have significant improvements to product properties.

Properties for Products Manufactured using Advanced Ziegler-Natta Catalyst

Melt Index

1.0

1.0

0.8

0.6

Density

0.918

0.920

0.916

0.916

Comonomer Type

Hexene

Octene

Super hexene

Octene

Process

Gas Phase

Solution

GasPhase

Solution

Catalyst Type

Z/N

Z/N

Advanced Z/N

Advanced Z/N

Dart Impact (grams/mil)

200

335

500

620

Elmendorf Tear Strength MD (grams/mil)

300

400

400

450

Elmendorf Tear Strength TD (grams/mil)

650

710

600

750

Tensile Strength MD (psi)

5300

6800

6100

7400

Single-Site Catalyst (SSC) Information

• Every catalyst reaction site is the same, thus the molecules produced are more uniform

• Every polymer molecule contains the same amount of comonomer (can result in improved properties)

• Reduction in low molecular weight polymer component historically resulted in extrusion challenges largely addressed now by resin design and extrusion equipment improvements

• Metallocene catalysts are a subset of the broader single-site family

• Single-site catalyzed materials tend to have reduced low molecular weight grease levels

Molecular Weight Distribution by GPC Z/N versus SSC 1.6 SSC polymer MI=1.9 PD=2.3 1.4 Z/N
Molecular Weight Distribution by GPC
Z/N versus SSC
1.6
SSC polymer MI=1.9 PD=2.3
1.4
Z/N polymer MI=5.0 PD=5.8
1.2
1
0.8
0.6
0.4
0.2
0
2
2.5
3
3.5
4
4.5
5
5.5
6
6.5
7
Log(mw)
dW/dLog(mw).

Physical and Optical Properties for Materials Made Using Single-Site Catalyst

 

Supplier A

Supplier A

Supplier B

Supplier C

Z/N

Comonomer Type

octene

octene

hexene

hexene

octene

Melt Index (grams/10 minutes)

0.97

0.94

1.14

1.08

0.95

Density

0.9171

0.9172

0.9168

0.9193

0.9203

Melt Flow Ratio (I21/I2)

22.3

27.5

16

16.2

27.2

Amps

34

32

39

36.5

31.1

Volts

156

144

142

137

143

Pressure (psi)

2925

2640

3070

3120

2810

Specific Power (lbs/hr./amp)

1.19

1.26

1.04

1.09

1.29

Dart Impact (grams)

990

1050

1200

920

180

Frictionless Puncture (J/mm)

118

93

114

91

45

Elmendorf Tear MD (grams)

255

265

190

235

430

Elmendorf Tear TD (grams)

325

370

330

320

730

Haze (%)

2

2

3

7

15

45 Gloss (%)

88

87

87

57

40

Hexane Extractables (%)

0.3

0.4

0.4

0.5

1.1

Seal Initiation Temperature (C)

103

103

99

103

111

Resin Manufacturing Processes

• LLDPE Processes:

– Gas Phase

– Solvent Based / Solution

– Slurry Loop

• Most LLDPE is produced in single reactor systems, but some processes used to manufacture LLDPE do use multiple reactors

Gas Phase Process (Simplified)

• Feed gases such as Ethylene, Butene or Hexene, Hydrogen etc. are introduced to the fluidized bed in the base of the gas phase reactor

• Catalyst is introduced to the reactor

• The exothermic heat of reaction is controlled by the fresh feed gas circulation

• High Rx throughput rates and low conversion rates per pass are typically achieved - feed gases recycle through the reactor entering at the base and exiting at the top

• Granular PE product is produced in the reactor and intermittently discharged out of the reactor into a purge bin, hydrocarbons are removed, granular materials conveyed to pelletization followed by pellet conveying to finishing area

Example of Gas Phase Process (Simplified)

Compressor Comonomer Recovery Unit
Compressor
Comonomer
Recovery Unit
Reactor Product Discharge System Product Degassing and Drying Hexene Railcar
Reactor
Product
Discharge
System
Product
Degassing
and Drying
Hexene Railcar

Cooling Water

Exchanger

Catalyst Preparation Ethylene Dryer Degassing and Drying Butene Railcar
Catalyst
Preparation
Ethylene
Dryer
Degassing
and Drying
Butene Railcar

Nitrogen

Hydrogen

Isopentane

Co-Catalyst

Flare

Solution Polymerization Process (Simplified)

• All aspects of reaction take place in solution

• All raw ingredients including, Ethylene feed, Hydrogen, etc. are dissolved into a solvent resulting in a solution composed of the raw ingredients required

• Catalyst is introduced to the reactor/s

• Solution is introduced into one or more stirred autoclave reactors - temperature, residence time and mixing are controlled

• Polymer solution exits the reactor/s, solvent is flashed off in a separator and returns to distillation

• Polymer passes through a low pressure separator into an extruder

• A devolatization extuder is used in some cases to remove residual hydrocarbons while stripping vessels (post-extrusion) may also be used in some processes to accomplish this task

Low Pressure Solution Process (Simplified)

Recycle Stream

Catalyst Catalyst 5 1 2
Catalyst
Catalyst
5
1
2

Pelletized

Product

Stream Catalyst Catalyst 5 1 2 Pelletized Product Vapors 4 3 Ethylene Hydrogen Comonomer 1. Stirred
Stream Catalyst Catalyst 5 1 2 Pelletized Product Vapors 4 3 Ethylene Hydrogen Comonomer 1. Stirred
Vapors 4
Vapors
4
Catalyst Catalyst 5 1 2 Pelletized Product Vapors 4 3 Ethylene Hydrogen Comonomer 1. Stirred Autoclave

3

Catalyst Catalyst 5 1 2 Pelletized Product Vapors 4 3 Ethylene Hydrogen Comonomer 1. Stirred Autoclave

Ethylene

Hydrogen

Comonomer

2 Pelletized Product Vapors 4 3 Ethylene Hydrogen Comonomer 1. Stirred Autoclave Reactors 2. Separator 3.
2 Pelletized Product Vapors 4 3 Ethylene Hydrogen Comonomer 1. Stirred Autoclave Reactors 2. Separator 3.

1. Stirred Autoclave Reactors

2. Separator

3. Separator

4. Pelletizer

5. Compressor

© 2005 NOVA Chemicals Corporation

Slurry Process Description (Simplified)

• Description is simplified but based on the Phillips Slurry loop design that can produce LLDPE, MDPE, HDPE, mLLDPE

• The reactor is a circulation loop, water jacketed to remove heat

• A hydocarbon carrier circulates the reactive ingredients around the loop reactor

• The reaction of Ethylene, Comonomer, Hydrogen, etc. results in polymer particles forming, suspended on the carrier

• Polymer settles out and is removed from the reactor into a flash vessel that separates granular polymer from residual hydrocarbon

• Polymer granules exit the flash vessel into a purge vessel where hydrocarbons are removed

• Additives are incorporated, granular material is extruded and pelletized

Low Pressure Slurry Process (Simplified)

Circulating

Pump Operating Conditions 200 - 250 o F 500 - 600 psi Ethylene Hydrogen Comonomer
Pump
Operating Conditions
200 - 250 o F
500 - 600 psi
Ethylene
Hydrogen
Comonomer
LOOP
REACTOR
Flash Tank
Catalyst
Vapors
DRYER
Granular
Polyethylene
RECYCLE STREAM

2002 APC-LLDPE Volume by End Use Process (based on Amercian Plastics Council 2002 Data)

Sheet (greater than 12 mil)

1%

Other Extruded Products

3%

Sheet (greater than 12 mil) 1 % Other Extruded Products 3% Pipe and Conduit 1% Injection

Pipe and Conduit

1%

Injection Molding

7%

Products 3% Pipe and Conduit 1% Injection Molding 7% Film (less than 12 mil) 65% All

Film (less than 12 mil)

65%

All Other Uses

23%

LLDPE by Market in N.A.

• 65% Film (12 mils or less)

• 7% Injection Molding

• The remainder is spread out over a variety of production processes such as:

– Pipe and Conduit

– Sheeting

– Blow Molding

– Compounding

Source:

APC Resin Statistics

Typical Applications

LLDPE

– Grocery sacks

– Garbage bags

– Stretch wrap film

– Agricultural film and tubing

– Milk pouches

– Wire and cable coatings

– Housewares

– Large outdoor toys

– Chemical storage tanks

– Landfill covers

Future Development/Outlook

• The PE Industry is continuously improving product performance by:

– New Catalyst developments
– New reactor configurations and manufacturing process improvements
– Technology Licensing - existing technologies licensed to operate on new technology platforms => could result in novel Polyethylene materials

=> could result in novel Polyethylene materials – Polyethylene is evolving Stay Tuned! © 2005 NOVA

– Polyethylene is evolving Stay Tuned!

References and Acknowledgements

• NOVA Chemicals Internal Literature

• Kirk Othmer Encyclopedia of Chemical Technology

• American Plastics Council

• Chem Systems (2003)

• Commodity Thermoplastics (JP Arlie)

• Judy Webb-Barrett (NOVA Chemicals)

• Lan Nguyen (NOVA Chemicals)

• Chris Foy (NOVA Chemicals)

Questions?