PP TechnologyPP Technology

20102010ElElőőadadóó: Csernyik Istv: Csernyik Istváánn

22

ContentContentIntroducing PPIntroducing PPApplicationApplicationHistoryHistoryZieglerZiegler--Natta polymerizationNatta polymerizationCatalyst developmentCatalyst developmentPP processesPP processesProcess controlProcess controlProcess safetyProcess safetyKey equipmentKey equipmentInvestment costInvestment costCost of productionCost of production

33

Introducing PPIntroducing PP

PPolyolyPPropyleneropylene –– stereoregularstereoregular, crystalline polymer, crystalline polymerHomopolymersHomopolymersRandom copolymers with 0,5Random copolymers with 0,5--4% ethylene content4% ethylene contentImpact (block, Impact (block, heterophasicheterophasic) copolymers with 5) copolymers with 5--20 % ethylene 20 % ethylene contentcontentTerpolymersTerpolymers -- with second with second comonomercomonomer

CharacteristicsCharacteristicsMelt indexMelt index 0,30,3-->100 min (230 C/2,16 kg)>100 min (230 C/2,16 kg)Melting point Melting point 142 142 –– 165165 CCPolydispersityPolydispersity (TVK grades)(TVK grades)

3,5 3,5 –– 55 reactor productsreactor products2 2 –– 33 controlled rheology (CR) productscontrolled rheology (CR) products

Broad range of mechanical propertiesBroad range of mechanical properties

44

ApplicationApplication

Film16%

Fiber18%

Injection moulding

52%

Others3%

Tapes2%

Sheet5%Pipe

2%

Blow moulding

2%

55

Application by PropertiesApplication by Properties

0,1 1 10 100 1000 10000

HOMO

RANDOM

HECO

MI, g/10 min/230 C

PIPE

SHEET INJECTION MOULDING

FIBER FIBERmelt blown

FILM

66

HistoryHistory

Discovered by Discovered by GiulioGiulio Natta in 1954Natta in 1954First industrial process developed by First industrial process developed by MontecatiniMontecatini in 1957in 1957Catalyst is the driver for process and product Catalyst is the driver for process and product developmentdevelopmentLicencesLicences available for 400 available for 400 kt/ykt/y capacity single linescapacity single linesGlobal consumption Global consumption inin 2009: 2009: 4444 million million ttTVK PP plantsTVK PP plants

1978 1978 60 60 kt/ykt/y Hercules slurry process, shut down in 1993Hercules slurry process, shut down in 19931982 1982 50 50 kt/ykt/y Sumitomo bulk process, shut down in 2002Sumitomo bulk process, shut down in 20021989 1989 60 60 kt/ykt/y SpheripolSpheripol process, debottlenecked to 100 process, debottlenecked to 100 kt/ykt/y1999 1999 140 140 kt/ykt/y SpheripolSpheripol process, debottlenecked to 182 process, debottlenecked to 182 kt/ykt/y

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ZieglerZiegler--Natta PolymerizationNatta Polymerization 11

1. Base support MgCl2

2. Titanation Internal donorTiCl4

3. ZN catalyst

Ziegler - Natta catalyst preparation

(e.g. phtalate)

1. ZN catalyst

2. Activation Al-alkyl External donor(e.g. silane)

3. PolymerizationPropylene

4. PP product

Propylene polymerization

88

ZieglerZiegler--Natta PolymerizationNatta Polymerization 22

99

Catalyst DevelopmentCatalyst DevelopmentGenerationGeneration

(year)(year)Catalyst Catalyst

compositioncompositionProductivityProductivity

(kg PP/g cat)(kg PP/g cat)X.I.X.I.(%)(%)

RemarksRemarks

1st1st(1954)(1954)

δδ--TiClTiCl

3*3*

0,33AlCl0,33AlCl

33

+ AlEt+ AlEt

22

ClCl22--44 9090--9494 No morphological control, No morphological control,

deashing and atactic removal deashing and atactic removal necessarynecessary

2nd2nd(1970)(1970)

δδ--TiClTiCl

3 3 + AlEt+ AlEt

22

ClCl 1010--1515 9494--9797 Granular catalyst, deashing Granular catalyst, deashing necessarynecessary

(1968)(1968) MgClMgCl

22

/TiCl/TiCl

44

+ AlR+ AlR

33 4040 First MgClFirst MgCl

22

based catalyst for PE, based catalyst for PE, very low stereocontrolvery low stereocontrol

3rd3rd(1971)(1971)

MgClMgCl

22

/TiCl/TiCl

44

/Benzoate /Benzoate + AlR+ AlR

33

/Benzoate/Benzoate1515--3030 9595--9797 First MgClFirst MgCl

22

based catalyst for PP, based catalyst for PP, low stereocontrol, low Hlow stereocontrol, low H

22

response, broad MWDresponse, broad MWD

4th4th(1980)(1980)

MgClMgCl

22

/TiCl/TiCl

44

/Phtalate /Phtalate + AlR+ AlR

33

/Silane/Silane4040--7070 9595--9999 Spherical catalyst with controlled Spherical catalyst with controlled

porosity, mediumporosity, medium--high high stereocontrol, medium Hstereocontrol, medium H

22

response, medium MWDresponse, medium MWD

5th5th(1988)(1988)

MgClMgCl

22

/TiCl/TiCl

44

/Diether/Diether+ AlR+ AlR

33

/Silane (opt.)/Silane (opt.)7070--130130 9595--9999 Same as 4th generation but very Same as 4th generation but very

high activity, narrow MWD, high activity, narrow MWD, excellent Hexcellent H

22

responseresponse

6th6th(1999)(1999)

MgClMgCl

22

/TiCl/TiCl

44

/Succinate /Succinate + AlR+ AlR

33

/Silane/Silane4040--7070 9595--9999 Same as 4th generation but Same as 4th generation but

broad MWDbroad MWD

1010

PP ProcessesPP ProcessesFirst PP process: slurry phase technology First PP process: slurry phase technology in stirred tank reactors; numerous process in stirred tank reactors; numerous process steps steps necessarynecessary

Deashing to remove catalyst residuesDeashing to remove catalyst residuesAtactic PP removalAtactic PP removal

UpUp--toto--date processesdate processes: : few process steps few process steps onlyonly

Bulk or gas phase polymerizationBulk or gas phase polymerizationCatalyst residuesCatalyst residues andand atactic PP removal not atactic PP removal not necessarynecessary

1111

Slurry TechnologySlurry Technology Early PP Process Early PP Process –– Not used todayNot used today

1212

Spheripol Spheripol ProcessProcess Loop ReactorsLoop Reactors

1313

Spheripol Spheripol ProcessProcess GP Reactor and Monomer RecoveryGP Reactor and Monomer Recovery

1414

Spheripol Spheripol ProcessProcess AAdditivation and Pelletizingdditivation and Pelletizing

1515

Spheripol Spheripol ProcessProcessTypical process parametersTypical process parameters

Process stepProcess step Temperature, CTemperature, C Pressure, barPressure, bar

Catalyst activationCatalyst activation 1010 4040

PrepolymerizationPrepolymerization 2020 3535

Polymerization Polymerization --

loop reactorloop reactor 7070 3434

High pressure separationHigh pressure separation 9090 1818

Polymerization Polymerization --

ggas phase as phase reactorreactor

7575--8080 1010--1414

SteamSteaminging 105105 0,20,2

DryDryinging 9090 0,10,1

1616

UnipolUnipol ProcessProcess PolymerizationPolymerization

65-70 C25 bar

1717

UnipolUnipol ProcessProcess Degassing and RecoveryDegassing and Recovery

1818

ChissoChisso ProcessProcess PackedPacked GasGas PhasePhase ReactorsReactors

1919

SpherizoneSpherizone ProcessProcess

2020

SpherizoneSpherizone ProcessProcess MultizoneMultizone Reactor PrincipleReactor Principle

2121

SpherizoneSpherizone ProcessProcess Extended Product PropertiesExtended Product Properties

Spherizone

Spheripol

Gas phase

Broad MWD35

2,3Narrow MWD

Maximum stiffnessHomopolymer2550 MPa flexural modulus

RandomMinimum brittle-3 C transitiontemperature

Pressure pipeclassificationPP-R 125

Impact-Stiffness balanceHECO: 5 KJ/m2 Izod1650 MPa flexural modulus

2222

Process controlProcess controlMelt indexMelt index HH

22

concentration in reactorsconcentration in reactors

Isotactic index Isotactic index (stereoregularity)(stereoregularity)

external donorexternal donor

((alkyl/donor alkyl/donor ratio)ratio)

MWDMWD different Hdifferent H

2 2 concentration in concentration in reactors, catalystreactors, catalyst

Ethylene contentEthylene content ethylene feed+Cethylene feed+C

22

/C/C

3 3 ratio in GP ratio in GP reactorreactor

2323

Process SafetyProcess SafetyRisk of high volume liquid hydrocarbonRisk of high volume liquid hydrocarbonInterlock systemInterlock system

Emergency kill to prevent reaction runawayEmergency kill to prevent reaction runawayAction valves automatically operated by predefined process Action valves automatically operated by predefined process parameters to separate/blowparameters to separate/blow--down equipmentdown equipment

Closed blowClosed blow--down systemdown systemPressure safety valves, blowPressure safety valves, blow--down valves release to closed down valves release to closed system, connected tosystem, connected toFlare to burn blown hydrocarbonFlare to burn blown hydrocarbon

Double mechanical seal on pumps in liquid propylene Double mechanical seal on pumps in liquid propylene serviceserviceGas detectorsGas detectorsFire fighting systemFire fighting system

2424

Key EquipmentKey Equipment

ReactorsReactorsLoopLoop with axial circulating pumpwith axial circulating pumpGas phaseGas phase

Gas circulating blower/compressorGas circulating blower/compressorExtrusion lineExtrusion line

2525

Gas Circulating BlowerGas Circulating Blower

2626

Investment costInvestment cost Basis: USGC 2008Q1; 400 Basis: USGC 2008Q1; 400 ktkt

Technology Bulk Gas phase Bulk+Gas phase Gas phase MultizoneProduct PP Homo PP Homo PP Heco PP Heco PP Heco

ISBL 117 100,6 133,9 125 133,9OSBL 108,7 101,3 113,3 107,5 113Other project cost 119,8 113,4 125,9 122,2 125,6Total investment 345,5 315,3 373,1 354,7 372,5

Specific investment, USD/t 864 788 933 887 931

million USD

2727

Cost of ProductionCost of Production Basis: USGC 2008Q1; 400 Basis: USGC 2008Q1; 400 ktkt

Technology Bulk Gas phase Bulk+Gas phase Gas phase MultizoneProduct PP Homo PP Homo PP Heco PP Heco PP Heco

Propylene 1351 1352 1243 1249 1243Ethylene 107 107 107Catalysts&Chemicals 13 14 16 20 16Additives 10 10 13 13 13Total raw materials 1374 1376 1379 1389 1379

Power 19 17 21 21 23Steam 9 4 9 4 4Other utilities 5 6 6 5 6Total utilities 33 27 36 30 33

Variable cost 1407 1403 1415 1419 1412

Direct cash cost 14 12 14 14 14Allocated cash cost 16 15 18 17 18Total fixed cost 30 27 32 31 32

Total cash cost 1437 1430 1447 1450 1444

USD/t

80%

85%

90%

95%

100%

PP Homo PP Homo PP Heco PP Heco PP Heco

Bulk Gas phase Bulk+Gasphase

Gas phase Multizone

Total f ixed cost

Total utilities

Total raw materials

2828

Appendix: Appendix: BOPP Film ProductionBOPP Film Production

Stenter Process

2929

Appendix: Appendix: Injection MouldingInjection Moulding