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LDPE Technology

Előadó: Csernyik István

2010

Content
What is LDPE Application History Process theory Autoclave process Tubular process Process steps Process control Process safety Key equipment Investment cost Cost of production
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What is LDPE Low Density PolyEthylene Typical properties Density 0.16 kg) Melting point 120 C Polydispersity 5.935 Melt index 0.3->20 g/10 min (190 C/2.915-0.5 – 6 (TVK tubular grades) 3 .

Application Other 14% Extrusion coating 10% Injection moulding 7% Blow moulding 4% Film 65% 4 .

1 0.935 5 .92 0. kg/dm 3 0.915 0. g/10 min/190 C EXTRUSION COATING EXTRUSION COATING INJECTION MOULDING 1 FILM EXTRUSION BLOW MOULDING 0.93 0.Application by Properties 100 10 MI.925 Density.

History LDPE was discovered by ICI in 1933 → autoclave process in 1938 BASF developed the first tubular process during WW II High variation of autoclave and tubular processes by different licensors Nowadays licences available up to 400 kt/y plant capacity Global consumption in 2009: 18 million t TVK LDPE plants 1970 .ICI autoclave process 24 kt/y – debottlenecked to 50 kt/y 1991 .BASF tubular process 60 kt/y 6 .

Process Theory 1 Free radical reaction Initiation I → R· + R· Initiators: typically organic peroxides Propagation Termination Combination Rx· + Ry·→ Px+y R· + CH2CH2 → RCH2CH2· R(CH2CH2)n-1CH2CH2· + CH2CH2 → R(CH2CH2)nCH2CH2· Disproportioning Rx· + Ry·→ Px + Py 7 .

Process Theory 2 Other reactions Chain transfer – important to control molecular weight by monomer Rx· + CH2CH2→Px + R1· by modifier Rx· + M→Px + M· Cracking – results in shorter chains Rx·→Py + Rx-y· 8 .

Process Theory 3 Branching – LDPE characterised by high degree of short and long chain branching Short chain branching – responsible for density Intramolecular chain transfer and copolymerisation result in short chain branches C C H C C C Long chain branching Intermolecular chain transfers give long chain branches C C C C C H C C C C C C C C 9 .

Autoclave Process Autoclave reactor Primary compressor Secondary compressor 1400 bar 170 C Ethylene 250 bar Initiators (Peroxides) 240 C Wax separator 280 C HP separator Oil separator 280 bar 250 C LP separator 0.LDPE .5 bar 250 C Degassing Extruder Bagging Bulk loading 10 .

Autoclave Reactor Total 725 l Autoclave reactor MK 10 L = 4750 mm d = 18” ethylene Top Zone Thermocouple 1 (1st T control) Thermocouple 2 Thermocouple 3 Thermocouple 4 (2nd T control) Thermocouple 5 Thermocouple 6 2nd Zone Thermocouple 7 (control 2nd zone T) peroxides 3rd Zone Thermocouple 8 Thermocouple 9 (control 3rd zone T) 4th Zone Thermocouple 10 (control 4th zone T) 11 .

Tubular Process LP Recycle HP Recycle Initiator (Oxygen) Primary Compressor Secondary Compressor Preheater 2400-2900 bar Reaction Zone I HP Separator 250 bar Purge Fresh Ethylene Modifier Precooler 180-310 C 280 bar 250 C LP Separator Reaction Zone II 0.5 bar 250 C Degassing Bagging Bulk loading Extruder 12 .LDPE .

Autoclave vs. Tubular Process Autoclave Conversion up to 21% adiabatic. EVA up to 10% vinyl acetate Reactor capacity up to 400 kt/y 13 . reaction heat removed by reactant only 1300-2000 bar operating pressure Higher capacity of hyper compressor Organic peroxide initiators only Specialty polymer capability – EVA copolymers over 40% vinyl acetate Lower reactor capacity – 150 kt/y Tubular Conversion up to 36% reaction heat partly removed by coolant 2500-3200 bar operating pressure Lower capacity of hyper but higher load Cheaper oxygen initiator possible Film grades with higher clarity.

Process Steps 1 Compression Increase make up ethylene pressure to reaction pressure Recycle unreacted ethylene Inject modifier and comonomer Injection of initiators Control temperatures for required product properties One phase reaction – two phase only at lower pressure and temperature Short residence time – some minutes 14 Reaction .

oils) Cool down recycle ethylene 15 .Process Steps 2 HP separator Separate melt LDPE and unreacted ethylene LP separator Remove unreacted ethylene Feed tank for extruder HP recycle Remove low molecular weight polymer (wax) Cool down recycle ethylene LP recycle Remove low molecular weight polymer (wax.

Process Steps 3 Extrusion Homogenization Additive dosing Pelletizing Degassing Remove residual ethylene (generally less than 1000 ppm) from LDPE – to avoid explosive gas mixtures 16 .

Process Control Melt index (Molecular weight) P↑ MI↓ (Mw↑) T↑ MI↑ (Mw↓) [Modifier]↑ MI↑ (Mw↓) P↑ T↑ D↑ D↓ Density Pressure range: 1300-3000 bar Temperature range: 160-310 C 17 .

Process Safety Risk of decomposition Decomposition: ethylene or polyethylene decomps to C and H2 High temperature. contaminations favour decomposition Reactor and HP separator in confined area – generally behind concrete wall Interlock system to avoid decomposition and protect equipment Special metal gaskets at high pressures Gas detectors Fire fighting system 18 . high pressure.

250 bar discharge Secondary compressor (Hyper) Two stages 250 bar suction.1 bar suction.Key Equipment Compressors Primary compressor (Booster+Primary) 5 stages 0. 3000 bar discharge Extruder Hot melt extruder for homogenization 19 .

Hyper Compressor Arrangement 20 .

Hyper Compressor Cylinder 21 .

Extruder Arrangement 22 .

Single-screw Extruder 23 .

1 213.5 534. USD/t Autoclave Autoclave Tubular 135 kt 3x135 kt 400 kt million USD 91.1 60.6 142.6 1581 1320 934 24 .5 125.7 231.3 118.4 61.6 130.Investment cost Basis: USGC 2008Q1 Process Plant size ISBL OSBL Other project cost Total investment Specific investment.2 160.4 373.

Cost of Production Basis: USGC 2008Q1 Autoclave Autoclave Tubular 135 kt 3x135 kt 400 kt USD/t Ethylene 1354 1354 1347 Catalysts&chemicals 8 8 5 Additives 14 14 14 1376 1366 Total raw materials 1376 Power Other utilities Steam credit Total utilities Direct cash cost Allocated cash cost Total fixed costs Total cash cost 51 9 60 34 37 71 1507 51 9 60 22 27 49 1485 58 7 -34 31 14 18 32 1429 100% 95% 90% Total fixed costs Total utilities 85% Total raw materials 80% 135 kt Autoclave 3x135 kt Autoclave 400 kt Tubular 25 .

Appendix: Metal Gasket 26 .

Appendix: Hyper compressor cylinder 27 .

Appendix: Blown Film Extrusion 28 .

Appendix: Extrusion Coating 29 .