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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
77
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