HDPE Technology

Including MDPE and LLDPE

2011

Content

HDPE, MDPE and LLDPE linear polyethylenes Application History Catalysts HDPE processes Process control Process safety Key equipment Investment cost Cost of production
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The Linear Polyethylene Family

HDPE, MDPE, LLDPE: LLDPE: linear polyethylenes Classification by density determined by short chain branching through comonomer content

No of S CB

LLDP E

M D PE HD PE

0,91 5

0,926

0,940

0,970

Properties

Melt index 0,03 - >100 g/10 min (190 C/2,16 kg) Melting point 120120-140 C Polydispersity (TVK grades) grades)

Monomodal Bimodal

6-8 1010-20

Application

HDPE/MDPE

Other 4% Pipe 22%

Film 16% Fiber 2%

Injection moulding 20%

Blow moulding 36%

LLDPE
Extrusion coating 6% Injection moulding 5%

Other 12%

Film 77%

Application by Properties
100
Narrow MWD Medium MWD Broad MWD

10
min) ) MFR (g/10 min

LLDPE INJECTION MOULDING MDPE ROTOMOULDING LLDPE BLOWN & CAST FILM

HDPE INJECTION MOULDING

MDPE YARN FILAMENTS

HDPE BLOW MOULDING

0,1

LLDPE-MDPE-HDPE WIRE AND CABLE (Medium to broad MWD)

HDPE FILM PIPES

0,01 0,890

0,900

0,910

0,920

0,930

0,940

0,950

0,960

Density (g/cc)

0,970 5

History

HDPE discovered in 1951 by P. Hogan and R. Banks Mid 1950s: commercial HDPE production in slurry process (Hoechst) and solution process (Phillips Petroleum) 1961: slurry loop reactor technology by Phillips Petroleum 1968: first gas phase process by Union Carbide Mid 1970s: first LLDPE process by Union Carbide Various processes available up to 400 kt/y capacity Global consumption, 2009

TVK HDPE plants

HDPE/MDPE LLDPE

30 million t/y 19,2 19,2 mil million t/y

1986: Phillips slurry loop process 140 kt/y, debottlenecked to 190 190 kt/y 2004: Mitsui slurry, cascade reactor technology 200 kt/y

Catalysts

Chromium

Silica supported hexavalent Cr Activation at high temperature before use Cocatalyst not necessary Medium to broad molecular weight distribution MgCl2 supported TiCl4 Metal alkyl cocatalyst necessary Narrow molecular weight distribution Preferred for bimodal products in cascade reactor technology very broad MWD Still developing Cocatalyst necessary Very narrow molecular weight distribution Bimodal capability in single reactor technology

Ziegler(-Natta)

Metallocene (single site)

Processes and Products

Gas phase processes
HDPE/MDPE
Melt index limit

Solution processes Slurry processes

High quality film grades

Best for blow moulding and pipe grades

Loop slurry only with density limit

LLDPE
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Gas Phase Process

Polymerization

85-110 C 20-25 bar

Gas phase process

Gas Phase Process

Additivation and Pelletizing

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Gas Phase Processes Characteristics

Catalyst: chromium, Ziegler, (metallocene) Fluidized bed reactor

70-110 C 15-30 bar Long residence time

Swing technology: LLDPE HDPE capability Simple process design Low investment and operating cost Bimodal capability with two reactors
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Solution Process

150-250 C 30-100 bar

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Solution Processes
Characteristics

Catalyst: Ziegler, (metallocene) Polymerization takes place in solution

30-130 bar 150-300 C Short residence time

Broad product range: LLDPE HDPE Bimodal capability with cascade reactors Higher investment and operating cost
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ChevronPhillips Slurry Loop Process

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ChevronPhillips Slurry Loop Process Characteristics

Catalyst: chromium, Ziegler, (metallocene) Chromium catalyst activation

Reaction in loop reactor

Fluidized bed activator Heat treatment in air at 600600-870 C

Flash separation

8585-105 C; 42 bar 3-6 % ethylene concentration Isobutane diluent Heat removed by coolant in reactor jacket very good surface/volume ratio 10 bar; 80 C

Degassing

85 C; 0,1 bar
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Phillips Process at TVK

Polymerization
Hexene-1 Purification Hexene-1 Comonomer Ethylene Purification Ethylene Compressor Ethylene

Flash Gas Compressor

Loop Reactor

Isobutane Distillation and Purification

C ataly st

Flash Tank

Flash Gas Filter

Circulating Pump Isobutane and Nitrogen Recovery Unit Dryer

Settling Legs and Product Take off Valves

Purge Column

Powder silo

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Phillips Process at TVK

Additivation and Pelletizing
Extruder hopper

Spin dryer Classifier

Additive blender

Dewatering screen

Main feeder

Rotary feeder

Premix feeder Pellet water tank CIM Air blower Extruder Pellet water pump

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Slurry Process

CSTR- Cascade Stirred Reactor

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Slurry Process CSRT

Reactor and Surroundings

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Slurry Process - CSTR

Process Characteristics

Catalyst: Ziegler, (metallocene) Low reaction pressure and temperature

6-8 bar, 7070-90 C Overhead condensators Slurry coolers Reactor jacket Different molecular weight polymer in 1st and 2nd reactor Comonomer built into high molecular weight polymer

Reaction heat removed by

Bimodal product capability

Diluent and polymer separation by centrifuge Diluent cleaning for low polymer removal
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Process Control

Melt index

Density [comonomer] D Molecular weight distribution

Ziegler catalyst [H2]/[Et] MI Chromium catalyst: T, [Et], [H2] T MI [Et] MI [H2] MI

Catalyst type Reactors operated at different parameters

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Process Safety

Risk of high volume liquid hydrocarbon Interlock system

Emergency kill to prevent reaction runaway except for CSRT Action valves automatically operated by predefined process parameters to separate/blowseparate/blow-down equipment Pressure safety valves, blowblow-down valves release to closed system, connected to Flare to burn blown hydrocarbon

Closed blow-down system

Double mechanical seal on pumps in liquefied gas service Gas detectors Fire fighting system
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Key Equipment

Reactors
Loop with axial circulating pump Gas phase

Decanter centrifuge in CSTR only Extrusion line

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Reactors

Loop reactors

Gas phase reactors

Long jacketed pipe straight vertical sections interconnected by elbows at top and bottom Built in axial pump to circulate slurry Good surface to volume ratio easy reaction heat removal

Vertical pressure vessel with increased top section to reduce polymer carry over Long residence time Reaction heat removed by external heat exchanger in recycle gas stream Difficult reaction control
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Loop Reactor Circulating Pump

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Decanter Centrifuge

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CMP Extrusion Line Arrangement

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CMP Elements

28

14

Mixing in CMP

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Investment Cost
Basis: WE 2010 Q1
Process Capacity Investment, million EUR ISBL OSBL Other project costs Total investment Specific investment cost, EUR/t LLDPE HDPE Gas phase Gas phase 325 300 98 49 53 200 615 94 47 50 191 637 HDPE Slurry 300 88 44 48 180 600
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Cost of Production
Basis: WE 2010 Q1
EUR/t
LLDPE HDPE HDPE Gas phase Gas phase Slurry 851,8 927,8 927,8 96,2 19,9 19,9 17,9 967,9 947,7 945,7 28,9 7 35,9 17,1 13,7 30,8 1034,6 26,9 8,4 35,3 15,8 14,7 30,5 1013,5 29 13,5 42,5 18,2 14,2 32,4 1020,6
Total raw materials Total utilities Total fixed costs

Ethylene Comonomer Catalysts&chemicals Total raw materials Power Other utilities Steam credit Total utilities Direct fix costs Allocated fix costs Total fixed costs Total cash costs

100% 90% 80% 70% 60% 50% 40% 325 kt Gas phase LLDPE 300 kt Gas phase HDPE 300 kt Slurry HDPE

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Appendix: Typical Mechanical Seal

Rotary Seal Packing
Product

Stationary Seal Packing

Spring

Rotary Seal Ring

Stationary Seal Ring

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Appendix: Blow Moulding

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Appendix: Pipe Extrusion

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