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PETROCHEMICALS. FINA CHEMICALS ANTWERPEN. Total Petrochemicals Elastomers NV – Process Basics Proprietary and confidentialinformation of Total Petrochemicals.

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Presentation on theme: "PETROCHEMICALS. FINA CHEMICALS ANTWERPEN. Total Petrochemicals Elastomers NV – Process Basics Proprietary and confidentialinformation of Total Petrochemicals."— Presentation transcript:

1 PETROCHEMICALS. FINA CHEMICALS ANTWERPEN. Total Petrochemicals Elastomers NV – Process Basics Proprietary and confidentialinformation of Total Petrochemicals Elastomers licensing history Origin of the technology : startup of the Antwerpen plant ( now Atofina Elastomers ) in 1968 under a Phillips Petroleum Cy license, 50 kt/a, SBR. Revamps in 1978, 1981, Now SBR,SBS, K-resin like polymers. Other Phillips licensees : Calatrava plant, Spain, 1966, 105 kt/a ( now Dynasol ) Negromex, Mexico, 1968, 55 kt/a ( now Dynasol ) JEC, Japan, 1969, 32 kt/a ANIC, Italy, 1972, 25 kt/a ( now Polimeri Europa ) Technology rights acquired by (then) Petrofina in 1986 from Phillips Petroleum Cy. Licensed by Total Petrochemicals Elastomers : Woronez, Russia, 1993, 30 kt/a SBS LG Chemicals, South Korea, 30 kt/a, 1995, SBS Maoming, the PRC, 50 kt/a, 1997, PBD(10)-SBR(30)-SBS(10) 2 plants closed down : Phillips Borger plant, 48 kt/a, transferred to TSRC, Taiwan PACL, 23 kt/a, Australia

2 PETROCHEMICALS. FINA CHEMICALS ANTWERPEN. Total Petrochemicals Elastomers NV – Process Basics Proprietary and confidentialinformation of Operating experience in Antwerpen Operating since 1968, there have been no serious injuries or fatalities at the plant ( 36 years of operations ) During the plant’s lifetime, large modifications have been implemented : –Shift product range from SBR to SBS, PBD and block copolymers ( 1970-ies ) –Shift towards SBS copolymers and some diblock copolymers ( 1990-ies-now ) –Implementation of process improvements ( external flashing of reactors, preconcentration, solution recycle ) –Plant automation using computer based controls instead of pneumatis between 1981 and 2004 ( still ongoing ) –Addition of a high styrenics polymer line in 1988, with a direct desolventising system. –Addition of homogenisation silo’s. –Actual plant capacity : 100 kt/a.

3 PETROCHEMICALS. FINA CHEMICALS ANTWERPEN. Total Petrochemicals Elastomers NV – Process Basics Proprietary and confidentialinformation of Production of Elastomers (General overview) storage of monomersPurification of monomers Steam destillation Finishing (Anderson, French, Welding Engineers) packaging Bulk homogenisation ( optional) Reactor & blending section

4 PETROCHEMICALS. FINA CHEMICALS ANTWERPEN. Total Petrochemicals Elastomers NV – Process Basics Proprietary and confidentialinformation of Plot Plan Solvent storage Butadiene storage Reaction area Styrene&Chem. storage Finishing & Finishing Control Room Warehouse Solvent/Monomer Purification Blendtanks Boilers Strippers Homogenisation silos Elastomers Logistic Center Fuel storage Main Control Room 50 m

5 PETROCHEMICALS. FINA CHEMICALS ANTWERPEN. Total Petrochemicals Elastomers NV – Process Basics Proprietary and confidentialinformation of Raw Materials 1,3 Butadiene: - Either 100% (extracted) butadiene or a selectively hydrogenated C4 cut from a cracker unit can be used. – Atofina’s Antwerpen Elastomers plant uses hydrogenated C 4 coming from upstream naphta crackers/hydrogenation units (Fina Antwerp Olefins) – Switch to extracted butadiene is being designed for implementation and startup early –Typical composition (average January1999-June 2000): 1,3 Bd: 45 %wt. Butenes: 47 %wt Butanes: 8 %wt 1,2 Bd:1320 ppm - removed by destillation Vinyl Ac.:< 0.2 ppm Ethyl Ac.: 10 ppm- removed by destillation Propadiene: 240 ppm- removed by destillation Carbonyls (MethylEthylCeton, aceton, acetaldehyde): 97 ppm (partly removed by destillation)

6 PETROCHEMICALS. FINA CHEMICALS ANTWERPEN. Total Petrochemicals Elastomers NV – Process Basics Proprietary and confidentialinformation of Raw Materials Styrene – purity > 99.8 %wt – TBC: ppm – max. H2O content: 150 ppm (typical: 50 ppm) Solvent(typical composition) – cyclohexane: 82 %wt. – n-hexane: 14 %wt. – Raffinate-1 or isobutane : 3%wt – Polar additives ( ppm range ) are used as kinetics accelerator.

7 PETROCHEMICALS. FINA CHEMICALS ANTWERPEN. Total Petrochemicals Elastomers NV – Process Basics Proprietary and confidentialinformation of Purification of butadiene by destillation ( for hydrotreated C4 ) Boilers (C 3 =,..) H20 to sewer Boilers (1,2 Bd, C 8..) wet butadiene dry butadiene: (typical ) - 49 %wt 1.3 Bd ppm 1,2 Bd ppm ViAc ppm EtAc - <2 ppm propadieen - 7 ppm carbonyls (as acetaldehyde) Dry butadiene to reactors V= 800 m³ Boilers (1,2 Bd, C 8..) V= 800 m³ V= 320 m³

8 PETROCHEMICALS. FINA CHEMICALS ANTWERPEN. Total Petrochemicals Elastomers NV – Process Basics Proprietary and confidentialinformation of Purification of butadiene by mole sieves/alumina (for Extracted butadiene, >99% conc ) V= 800 m³ Alumina / Mole Sieves beds (TBC and oxygenates removal) V= 320 m³ Dry butadiene to reactors Dry butadiene : 60% weight 1,3 C4= ( diluted with isobutane ) Expected impurity levels : < 0.5 ppm Boilers (C 3 =,..) H20 to sewer

9 PETROCHEMICALS. FINA CHEMICALS ANTWERPEN. Total Petrochemicals Elastomers NV – Process Basics Proprietary and confidentialinformation of Purification of styrene to reactors wet styrene dry styrene ( typically 5°C ) V= 800 m³ V= 45 m³ Activated alumina dryers Removed impurities : - H2O - TBC

10 PETROCHEMICALS. FINA CHEMICALS ANTWERPEN. Total Petrochemicals Elastomers NV – Process Basics Proprietary and confidentialinformation of Purification of solvents by destillation C4’s/Isobutane is recycled H2O to sewer boilers wet solventdry solvent To reactors V= 800 m³ V= 900 m³ V= 800 m³ V= 900 m³ Removed impurities : H2O, 1,3buta dimer, Aox traces Styrene monomer

11 PETROCHEMICALS. FINA CHEMICALS ANTWERPEN. Total Petrochemicals Elastomers NV – Process Basics Proprietary and confidentialinformation of Reactorsection monomer butadiene styrene solvent initiator others reactor overhead to C 4 /C 6 splitters blendtank off-gas recovery strippers / desolventiser Reactor ( 35-45m³ ) flashtanks blendtank V= 75m³ p= 2 barg V= 45m³ p= 80 mbarg Antioxydant 3 reactorlines: External Reactor Capa (T/d) Flashtanks Cycle time line A: 3*35 m³Yes min (HSE) ~130 T/d line B: 3*35 m³No ~85 min(SBS)75~125 T/d line C:2*45 m³Yes65 ~ 90 min(SBR/SBS)120~165 T/d 3 blendtanklines: line A: 3*300 m³ line B: 3*300 m³ line C: 3*400 m³

12 PETROCHEMICALS. FINA CHEMICALS ANTWERPEN. Total Petrochemicals Elastomers NV – Process Basics Proprietary and confidentialinformation of Reaction Control & Optimisation – Atofina technology “Solution recycle” technique ( energy saving ) Fully automated operations (computer control, PCS7 by Siemens) Very flexible product switch : recipe ( and sequence ) changes done in 5 minutes – no reprogramming needed. External flashing system for capacity increase through cycle time reduction.

13 PETROCHEMICALS. FINA CHEMICALS ANTWERPEN. Total Petrochemicals Elastomers NV – Process Basics Proprietary and confidentialinformation of “Solution recycle” technique reactor “Solution recycle” ( rubber solution) = Replace part of the solvent by rubber solution from reactors higher polymer concentration energy savings (stripping steam!) limited by final solution viscosity Blending tanks Aox, additives

14 PETROCHEMICALS. FINA CHEMICALS ANTWERPEN. Total Petrochemicals Elastomers NV – Process Basics Proprietary and confidentialinformation of Treatment of flashed-off gases from reactors Condensed flashed gases (C4+C6) C4 Dry solvent C6 C4 storage Reactors ( avoid underpressure)

15 PETROCHEMICALS. FINA CHEMICALS ANTWERPEN. Total Petrochemicals Elastomers NV – Process Basics Proprietary and confidentialinformation of Blending of reactors AOX, additives Reactor discharge Blendtank « being filled » Blendtank « being homogenised/ analysed » Blendtank « stripping » Preconcentration/Stripping

16 PETROCHEMICALS. FINA CHEMICALS ANTWERPEN. Total Petrochemicals Elastomers NV – Process Basics Proprietary and confidentialinformation of Strippers – solvent removal (steam destillation) solution of blendtanks condensor oil HP steam 1st stripper 2nd stripper Solvent decanter via crumbtank to finishing Dispersing additiveDispersing agent vapours recycle water (of finishing) wet solventtanks filter V= 45 m³ T° ~ 90°C V= 45 m³ T° ~ 110°C Stripper Polymer feed : 4 ~5 t/h Polymer solution concentration : 18 ~25% H20 Solvent

17 PETROCHEMICALS. FINA CHEMICALS ANTWERPEN. Total Petrochemicals Elastomers NV – Process Basics Proprietary and confidentialinformation of Finishing : rubber drying equipment Different technologies available, each offering specific advantages Drying equipment design not a Total Petrochemicals activity Main rubber drying equipment vendors : Anderson, French and Welding Engineers. Own ( Antwerpen ) experience : Anderson and French equipment, Welding Engineers through LG licensee.

18 PETROCHEMICALS. FINA CHEMICALS ANTWERPEN. Total Petrochemicals Elastomers NV – Process Basics Proprietary and confidentialinformation of Drying equipment from Anderson Crumb handling Crumbtank 3 ~ 8 % crumb conc. Johnson Screen + vibrating shaker screen topexpeller Middle expeller expander hotbox Spiral elevator recycle water to strippers skimmer tank recycletank Water content: 92 ~ 97 % Water content: ~ 50 % Water content: ~ 8% (normally), upper limit20 % Water content: ~ 2% (normally), upper limit 15 % Water content: < 0.8% Top & Middle expeller 90 kW Expander 400 kW Turbulator T°: 155°C ~175°C

19 PETROCHEMICALS. FINA CHEMICALS ANTWERPEN. Total Petrochemicals Elastomers NV – Process Basics Proprietary and confidentialinformation of Drying equipment from French Crumb handling Johnson Screen + vibrating shaker screen Dewaterer hotbox Spiral elevator recycle water to strippers skimmer tank recycletank Crumbtank 3 ~ 8 % crumb conc. Dryer Water content: 92 ~ 97 % Water content: ~ 2% normally, upper limit 15% Water content: ~ 50 % Water content: < 0.8% Dewaterer 375 kW Dryer 840 kW Dieplate T°: 145°C ~175°C

20 PETROCHEMICALS. FINA CHEMICALS ANTWERPEN. Total Petrochemicals Elastomers NV – Process Basics Proprietary and confidentialinformation of Packaging Packaging without homogenisation Bales - blocks of compressed rubber, film wrapped, packed in boxes Crumb/pellets: boxes, bags ( kg ) on pallets, big-bags ( up to 750 kg ) Packaging with homogenisation ( developed by Atofina ) Can only be done on Crumb/pellets Advantages : –homogenised lots of ~100T ( 1 day production on a line ), less administration –daytime packaging possible ( reduction in personnel cost ) –Packaging equipment failure does not necessitate drying line stop –packaging types : same as crumbs/pellets above, plus bulk containers

21 PETROCHEMICALS. FINA CHEMICALS ANTWERPEN. Total Petrochemicals Elastomers NV – Process Basics Proprietary and confidentialinformation of Homogenisation and packaging outsourcing Homogenise at AFE (operational since 03/1998) Package at ELC (operational since 05/2000) Using conveyor belts

22 PETROCHEMICALS. FINA CHEMICALS ANTWERPEN. Total Petrochemicals Elastomers NV – Process Basics Proprietary and confidentialinformation of Crumb blending silos : specifics Finaprene crumbs are fluffy and sticky : low bulk density ( ) bad flow properties ( sticking ) vibrating discharge devices do not work properly (dampening of vibrations by rubber) Efficient Blending needs “shearing” flow, not funnel flow avoid segregation (granulometry, fines, …) Influence of storage time (up to 132 h) Tests performed at external testing facilities Special silo technologies needed : »overcome bridging problems during emptying »ensure shearing flow (for blending)

23 PETROCHEMICALS. FINA CHEMICALS ANTWERPEN. Total Petrochemicals Elastomers NV – Process Basics Proprietary and confidentialinformation of Crumb silos :test results. Finaprene grades (SBS - crumbs) : very high « critical diameters »

24 PETROCHEMICALS. FINA CHEMICALS ANTWERPEN. Total Petrochemicals Elastomers NV – Process Basics Proprietary and confidentialinformation of Silo discharge device This technology is used for extremely bad flow characteristics

25 PETROCHEMICALS. FINA CHEMICALS ANTWERPEN. Total Petrochemicals Elastomers NV – Process Basics Proprietary and confidentialinformation of Current process at Atofina’s Antwerp elastomers plant Bags Big Bags Bulk Bags Big Bags Bales Reactorline A Reactorline B Reactorline C Blendtankline A Blendtankline B Blendtankline C Stripperline A Stripperline B Desolventiser Fin.line C Fin.line A Fin.line B (Anderson) Homogenisation Internal Packaging External Packaging (French) 30 kT/y 40 kT/y 100 kT/y


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