pp technology

8/3/2019 PP Technology

1/29

PP TechnologyPP Technology

20102010ElEladad: Csernyik Istv: Csernyik Istvnn


2/29

22

ContentContent Introducing PPIntroducing PP

ApplicationApplication

HistoryHistory

ZieglerZiegler--Natta polymerizationNatta polymerization

Catalyst developmentCatalyst development

PP processesPP processes

Process controlProcess control

Process safetyProcess safety Key equipmentKey equipment

Investment costInvestment cost

Cost of productionCost of production


3/29

33

Introducing PPIntroducing PP

PPolyolyPP ropyleneropylene stereoregularstereoregular, crystalline polymer, crystalline polymer

HomopolymersHomopolymers

Random copolymers with 0,5Random copolymers with 0,5--4% ethylene content4% ethylene content Impact (block,Impact (block, heterophasicheterophasic) copolymers with 5) copolymers with 5--20 % ethylene20 % ethylene

contentcontent

TerpolymersTerpolymers -- with secondwith second comonomercomonomer

CharacteristicsCharacteristics

Melt indexMelt index 0,30,3-->100 min (230 C/2,16 kg)>100 min (230 C/2,16 kg)

Melting pointMelting point 142142 165165 CC

PolydispersityPolydispersity (TVK grades)(TVK grades) 3,53,5 55 reactor productsreactor products

22 33 controlled rheology (CR) productscontrolled rheology (CR) products

Broad range of mechanical propertiesBroad range of mechanical properties


4/29

44

ApplicationApplication

Film

16%

Fiber

18%

Injection

moulding

52%

Others

3%Tapes

2%

Sheet

5%Pipe

2%

Blow

moulding

2%


5/29

55

Application by PropertiesApplication by Properties

0,1 1 10 100 1000 10000

HOMO

RANDOM

HECO

MI, g/10 min/230 C

PIPE

SHEETINJECTION

MOULDING

FIBERFIBERmelt blown

FILM


6/2966

HistoryHistory

Discovered byDiscovered by GiulioGiulio Natta in 1954Natta in 1954

First industrial process developed byFirst industrial process developed by MontecatiniMontecatini in 1957in 1957

Catalyst is the driver for process and productCatalyst is the driver for process and productdevelopmentdevelopment

LicencesLicences available for 400available for 400 kt/ykt/y capacity single linescapacity single lines

Global consumptionGlobal consumption inin 2009:2009: 4444 millionmillion tt TVK PP plantsTVK PP plants

19781978 6060 kt/ykt/y Hercules slurry process, shut down in 1993Hercules slurry process, shut down in 1993

19821982 5050 kt/ykt/y Sumitomo bulk process, shut down in 2002Sumitomo bulk process, shut down in 2002

19891989 6060 kt/ykt/y SpheripolSpheripol process, debottlenecked to 100process, debottlenecked to 100 kt/ykt/y

19991999 140140 kt/ykt/y SpheripolSpheripol process, debottlenecked to 182process, debottlenecked to 182 kt/ykt/y


7/29

77

ZieglerZiegler--Natta PolymerizationNatta Polymerization 11

1. Base support MgCl2

2. TitanationInternal 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


8/29

88

ZieglerZiegler--Natta PolymerizationNatta Polymerization 22


9/29

99

Catalyst DevelopmentCatalyst DevelopmentGenerationGeneration

(year)(year)

CatalystCatalyst

compositioncompositionProductivityProductivity

(kg PP/ g cat)(kg PP/ g cat)

X.I.X.I.

(% )(% )

RemarksRemarks

1st1st

(1954)(1954)

--TiClTiCl

3*3*

0,33AlCl0,33AlCl

33

+ AlEt+ AlEt

22

ClCl

22--44 9090--9494 No morphological control,No morphological control,

deashing and atactic removaldeashing and atactic removal

necessarynecessary

2nd2nd

(1970)(1970)

--TiClTiCl

33 + AlEt+ AlEt

22

ClCl 1010--1515 9494--9797 Granular catalyst, deashingGranular 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 stereocontrol3rd3rd

(1971)(1971)

MgClMgCl

22

/TiCl/TiCl

44

/Benzoate/Benzoate

+ AlR+ AlR

33

/Benzoate/Benzoate

1515--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/Silane

4040--7070 9595--9999 Spherical catalyst with controlledSpherical catalyst with controlled

porosity, mediumporosity, medium--highhighstereocontrol, 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 verySame 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+ AlR33/Silane/Silane4040--7070 9595--9999 Same as 4th generation butSame as 4th generation but

broad MWDbroad MWD


10/29

1010

PP ProcessesPP Processes

First PP process: slurry phase technologyFirst PP process: slurry phase technologyin stirred tank reactors; numerous processin stirred tank reactors; numerous process

stepssteps necessarynecessary Deashing to remove catalyst residuesDeashing to remove catalyst residues

Atactic PP removalAtactic PP removal

UpUp--toto--date processesdate processes:: few process stepsfew process stepsonlyonly Bulk or gas phase polymerizationBulk or gas phase polymerization

Catalyst residuesCatalyst residues andand atactic PP removal notatactic PP removal notnecessarynecessary


11/29

1111

Slurry TechnologySlurry Technology

Early PP ProcessEarly PP Process Not used todayNot used today


12/29

1212

SpheripolSpheripol ProcessProcess

Loop ReactorsLoop Reactors


13/29

1313


GP Reactor and Monomer RecoveryGP Reactor and Monomer Recovery


14/29

1414


AAdditivation and Pelletizingdditivation and Pelletizing


15/29

1515


Typical process parametersTypical process parameters

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

Catalyst activationCatalyst activation 1010 4040

PrepolymerizationPrepolymerization 2020 3535

PolymerizationPolymerization --

loop reactorloop reactor 7070 3434

High pressure separationHigh pressure separation 9090 1818

PolymerizationPolymerization -- ggas phaseas phasereactorreactor 7575--8080 1010--1414SteamSteaminging 105105 0,20,2

DryDryinging 9090 0,10,1


16/29

1616

UnipolUnipol ProcessProcess

PolymerizationPolymerization

65-70 C25 bar


17/29

1717

UnipolUnipol ProcessProcess

Degassing and RecoveryDegassing and Recovery


18/29

1818

ChissoChisso ProcessProcess

PackedPacked GasGas PhasePhase ReactorsReactors


19/29

1919

SpherizoneSpherizone ProcessProcess


20/29

2020


MultizoneMultizone Reactor PrincipleReactor Principle


21/29

2121


Extended Product PropertiesExtended Product Properties

Spherizone

Spheripol

Gas phase

Broad MWD

35

2,3

Narrow MWD

Maximum stiffness

Homopolymer

2550 MPa flexural modulus

Random

Minimum brittle

-3 C transition

temperature

Pressure pipe

classification

PP-R 125

Impact-Stiffness balance

HECO: 5 KJ/m2 Izod

1650 MPa flexural modulus


22/29

2222

Process controlProcess control

Melt indexMelt index HH 22 concentration in reactorsconcentration in reactors

Isotactic indexIsotactic index

(stereoregularity)(stereoregularity) external donorexternal donor ((alkyl/donoralkyl/donorratio)ratio)

MWDMWD different Hdifferent H 22 concentration inconcentration inreactors, catalystreactors, catalystEthylene contentEthylene content ethylene feed+Cethylene feed+C 22 /C

/C 33 ratio in GPratio in GPreactorreactor


23/29

2323

Process SafetyProcess Safety

Risk of high volume liquid hydrocarbonRisk of high volume liquid hydrocarbon

Interlock systemInterlock system

Emergency kill to prevent reaction runawayEmergency kill to prevent reaction runaway Action valves automatically operated by predefined processAction valves automatically operated by predefined process

parameters to separate/blowparameters to separate/blow--down equipmentdown equipment

Closed blowClosed blow--down systemdown system Pressure safety valves, blowPressure safety valves, blow--down valves release to closeddown valves release to closed

system, connected tosystem, connected to

Flare to burn blown hydrocarbonFlare to burn blown hydrocarbon

Double mechanical seal on pumps in liquid propyleneDouble mechanical seal on pumps in liquid propyleneserviceservice

Gas detectorsGas detectors

Fire fighting systemFire fighting system


24/29

2424

Key EquipmentKey Equipment

ReactorsReactors LoopLoop with axial circulating pumpwith axial circulating pump

Gas phaseGas phase

Gas circulating blower/compressorGas circulating blower/compressor

Extrusion lineExtrusion line


25/29

2525

Gas Circulating BlowerGas Circulating Blower


26/29

2626

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

Technology Bulk Gas phase Bulk+Gas phase Gas phase Multizone

Product PP Homo PP Homo PP Heco PP Heco PP Heco

ISBL 117 100,6 133,9 125 133,9

OSBL 108,7 101,3 113,3 107,5 113Other project cost 119,8 113,4 125,9 122,2 125,6

Total investment 345,5 315,3 373,1 354,7 372,5

Specific investment,

USD/t 864 788 933 887 931

million USD


27/29

2727

Cost of ProductionCost of Production

Basis: USGC 2008Q1; 400Basis: USGC 2008Q1; 400 ktktTechnology Bulk Gas phase Bulk+Gas phase Gas phase Multizone

Product PP Homo PP Homo PP Heco PP Heco PP Heco

Propylene 1351 1352 1243 1249 1243

Ethylene 107 107 107

Catalysts&Chemicals 13 14 16 20 16

Additives 10 10 13 13 13

Total raw materials 1374 1376 1379 1389 1379

Power 19 17 21 21 23

Steam 9 4 9 4 4

Other utilities 5 6 6 5 6

Total utilities 33 27 36 30 33

Variable cost 1407 1403 1415 1419 1412

Direct cash cost 14 12 14 14 14

Allocated cash cost 16 15 18 17 18

Total 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+Gas

phase

Gas phase Multizone

Total fixed costTotal utilities

Total raw materials


28/29

2828

Appendix:Appendix: BOPP Film ProductionBOPP Film ProductionStenter Process


29/29

2929

Appendix:Appendix: Injection MouldingInjection Moulding

pp technology

Documents