PP Technology
2010
Elad: Csernyik Istvn
Content
Introducing PP Application History Ziegler-Natta polymerization Catalyst development PP processes Process control Process safety Key equipment Investment cost Cost of production
2
Introducing PP
PolyPropylene stereoregular, crystalline polymer
Homopolymers Random copolymers with 0,5-4% ethylene content Impact (block, heterophasic) copolymers with 5-20 % ethylene content Terpolymers - with second comonomer
Characteristics
Melt index 0,3->100 min (230 C/2,16 kg) Melting point 142 165 C Polydispersity (TVK grades)
3,5 5 23 reactor products controlled rheology (CR) products
Broad range of mechanical properties
3
Application
Sheet Pipe 5% 2% Tapes Others 3% 2% Film 16%
Fiber 18% Blow m oulding 2%
Injection m oulding 52%
Application by Properties
HECO SHEET INJECTION MOULDING
RANDOM F IL M
HOMO
FIBER
PIPE
FIBER
melt blown
0,1
10 100 MI, g/10 min/230 C
1000
10000
History
Discovered by Giulio Natta in 1954 First industrial process developed by Montecatini in 1957 Catalyst is the driver for process and product development Licences available for 400 kt/y capacity single lines Global consumption in 2009: 44 million t TVK PP plants
1978 1982 1989 1999 60 kt/y Hercules slurry process, shut down in 1993 50 kt/y Sumitomo bulk process, shut down in 2002 60 kt/y Spheripol process, debottlenecked to 100 kt/y 140 kt/y Spheripol process, debottlenecked to 182 kt/y
Ziegler-Natta Polymerization 1
Ziegler - Natta catalyst preparation
Propylene polymerization
1. Base support MgCl2
1. ZN catalyst
2. Activation
2. Titanation TiCl4 Internal donor
(e.g. phtalate)
Al-alkyl
External donor
(e.g. silane)
3. Polymerization
Propylene
3. ZN catalyst
4. PP product
Ziegler-Natta Polymerization 2
Catalyst Development
Generation (year)
1st (1954) 2nd (1970) (1968) 3rd (1971) 4th (1980)
Catalyst composition
-TiCl3*0,33AlCl3 + AlEt2Cl -TiCl3 + AlEt2Cl MgCl2/TiCl4 + AlR3 MgCl2/TiCl4/Benzoate + AlR3/Benzoate MgCl2/TiCl4/Phtalate + AlR3/Silane
Productivity (kg PP/g cat)
2- 4
X.I. (%)
90-94
Remarks
No morphological control, deashing and atactic removal necessary Granular catalyst, deashing necessary First MgCl2 based catalyst for PE, very low stereocontrol First MgCl2 based catalyst for PP, low stereocontrol, low H2 response, broad MWD Spherical catalyst with controlled porosity, medium-high stereocontrol, medium H2 response, medium MWD Same as 4th generation but very high activity, narrow MWD, excellent H2 response Same as 4th generation but 9 broad MWD
10-15
94-97 40
15-30
95-97
40-70
95-99
5th (1988) 6th (1999)
MgCl2/TiCl4/Diether + AlR3/Silane (opt.) MgCl2/TiCl4/Succinate + AlR3/Silane
70-130
95-99
40-70
95-99
PP Processes
First PP process: slurry phase technology in stirred tank reactors; numerous process steps necessary
Deashing to remove catalyst residues Atactic PP removal
Up-to-date processes: few process steps only
Bulk or gas phase polymerization Catalyst residues and atactic PP removal not necessary
10
Slurry Technology
Early PP Process Not used today
11
Loop Reactors
Spheripol Process
12
GP Reactor and Monomer Recovery
Spheripol Process
13
Additivation and Pelletizing
Spheripol Process
14
Spheripol Process
Typical process parameters
Process step Catalyst activation Prepolymerization Polymerization - loop reactor High pressure separation Polymerization - gas phase reactor Steaming Drying Temperature, C 10 20 70 90 75-80 105 90 Pressure, bar 40 35 34 18 10-14 0,2 0,1
15
Polymerization
Unipol Process
65-70 C 25 bar
16
Degassing and Recovery
Unipol Process
17
Chisso Process
Packed Gas Phase Reactors
18
Spherizone Process
19
Spherizone Process
Multizone Reactor Principle
20
Spherizone Process
Broad MWD 35
Extended Product Properties
Pressure pipe classification PP-R 125
Maximum stiffness Homopolymer 2550 MPa flexural modulus
Random Minimum brittle -3 C transition temperature 2,3 Narrow MWD
Impact-Stiffness balance HECO: 5 KJ/m2 Izod 1650 MPa flexural modulus
Spherizone Spheripol Gas phase
21
Process control
Melt index Isotactic index (stereoregularity) MWD H2 concentration in reactors external donor (alkyl/donor ratio) different H2 concentration in reactors, catalyst ethylene feed+C2/C3 ratio in GP reactor
22
Ethylene content
Process Safety
Risk of high volume liquid hydrocarbon Interlock system
Emergency kill to prevent reaction runaway Action valves automatically operated by predefined process parameters to separate/blow-down equipment
Closed blow-down system
Pressure safety valves, blow-down valves release to closed system, connected to Flare to burn blown hydrocarbon
Double mechanical seal on pumps in liquid propylene service Gas detectors Fire fighting system
23
Key Equipment
Reactors
Loop with axial circulating pump Gas phase
Gas circulating blower/compressor Extrusion line
24
Gas Circulating Blower
25
Basis: USGC 2008Q1; 400 kt
Investment cost
Technology Product ISBL OSBL Other project cost Total investment Specific investment, USD/t
Bulk Gas phase Bulk+Gas phase Gas phase Multizone PP Homo PP Homo PP Heco PP Heco PP Heco million USD 117 100,6 133,9 125 133,9 108,7 101,3 113,3 107,5 113 119,8 113,4 125,9 122,2 125,6 345,5 315,3 373,1 354,7 372,5
864
788
933
887
931
26
Cost of Production
Basis: USGC 2008Q1; 400 kt
Bulk Gas phase Bulk+Gas phase Gas phase Multizone PP Homo PP Homo PP Heco PP Heco PP Heco USD/t Propylene 1351 1352 1243 1249 1243 Ethylene 107 107 107 Catalysts&Chemicals 13 14 16 20 16 Additives 10 10 13 13 13 1379 1389 1379 Total raw materials 1374 1376 Power Steam Other utilities Total utilities Variable cost Direct cash cost Allocated cash cost Total fixed cost Total cash cost 19 9 5 33 1407 14 16 30 1437 17 4 6 27 1403 12 15 27 1430 21 9 6 36 1415 14 18 32 1447 21 4 5 30 1419 14 17 31 1450 23 4 6 33 1412 14 18 32 1444 Technology Product
100% 95% 90% 85% 80% PP Homo PP Homo PP Heco Bulk PP Heco PP Heco
Total fixed cost Total utilities Total raw materials
Gas phase Bulk+Gas Gas phase Multizone phase
27
Appendix: BOPP Film Production
Stenter Process
28
Appendix: Injection Moulding
29
