Total Petrochemicals Elastomers licensing history Origin 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, 1988. 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 . . Total Petrochemicals. CHEMICALS ANTWERPEN PETROCHEMICALS FINA 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. . . Total Petrochemicals. CHEMICALS ANTWERPEN PETROCHEMICALS FINA Elastomers NV – Process Basics Proprietary and confidentialinformation of

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

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

Raw Materials 1, 3 Butadiene: - Either 100% (extracted) butadiene or a selectively hydrogenated C 4 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 2005. –Typical composition (average January 1999 -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 (Methyl. Ethyl. Ceton, acetaldehyde): 97 ppm (partly removed by destillation) . . Total Petrochemicals. CHEMICALS ANTWERPEN PETROCHEMICALS FINA Elastomers NV – Process Basics Proprietary and confidentialinformation of

Raw Materials Styrene – purity > 99. 8 %wt – TBC: 10 - 15 ppm – max. H 2 O 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. . . Total Petrochemicals. CHEMICALS ANTWERPEN PETROCHEMICALS FINA Elastomers NV – Process Basics Proprietary and confidentialinformation of

Purification of butadiene by destillation ( for hydrotreated C 4 ) Boilers (C 3=, . . ) H 20 to sewer V= 800 m³ dry butadiene: (typical 1999 -2000) - 49 %wt 1. 3 Bd - 0. 1 ppm 1, 2 Bd - 0. 5 ppm Vi. Ac - 0. 7 ppm Et. Ac - <2 ppm propadieen - 7 ppm carbonyls (as acetaldehyde) V= 320 m³ Boilers (1, 2 Bd, C 8. . ) V= 800 m³ Dry butadiene to reactors wet butadiene. Boilers (1, 2 Bd, C 8. . ) . Total Petrochemicals. CHEMICALS ANTWERPEN PETROCHEMICALS FINA Elastomers NV – Process Basics Proprietary and confidentialinformation of

Purification of butadiene by mole sieves/alumina (for Extracted butadiene, >99% conc ) Boilers (C 3=, . . ) H 20 to sewer V= 800 m³ V= 320 m³ Alumina / Mole Sieves beds (TBC and oxygenates removal) V= 800 m³ Dry butadiene to reactors Dry butadiene : 60% weight 1, 3 C 4= ( diluted with isobutane ) . Expected impurity levels : < 0. 5 ppm . Total Petrochemicals. CHEMICALS ANTWERPEN PETROCHEMICALS FINA Elastomers NV – Process Basics Proprietary and confidentialinformation of

Purification of styrene Removed impurities : - H 2 O - TBC V= 800 m³ V= 45 m³ Activated alumina dryers dry styrene ( typically 5°C ) wet styrene to reactors . . Total Petrochemicals. CHEMICALS ANTWERPEN PETROCHEMICALS FINA Elastomers NV – Process Basics Proprietary and confidentialinformation of

Purification of solvents by destillation C 4’s/Isobutane is recycled Removed impurities : H 2 O to sewer H 2 O, 1, 3 buta dimer, V= 900 m³ Aox traces V= 800 m³ Styrene monomer wet solvent dry solvent V= 900 m³ V= 800 m³ To reactors boilers . . Total Petrochemicals. CHEMICALS ANTWERPEN PETROCHEMICALS FINA Elastomers NV – Process Basics Proprietary and confidentialinformation of

Reactorsection Capa (T/d) Yes 120 -170 min (HSE) ~130 T/d • line B: 3*35 m³ No ~85 min(SBS) 75~125 T/d • line C: 2*45 m³ Reactor ( 35 -45 m³ ) External Reactor Flashtanks Cycle time • line A: 3*35 m³ monomer butadiene styrene solvent initiator others 3 reactorlines: Yes 65 ~ 90 min(SBR/SBS) 120~165 T/d reactor overhead to C 4/C 6 splitters V= 75 m³ p= 2 barg blendtank off-gas recovery V= 45 m³ p= 80 mbarg 3 blendtanklines: flashtanks • line A: 3*300 m³ blendtank Antioxydant . . Total Petrochemicals. CHEMICALS ANTWERPEN PETROCHEMICALS FINA Elastomers NV – Process • line B: 3*300 m³ strippers / desolventiser • line C: 3*400 m³ Basics Proprietary and confidentialinformation of

Reaction Control & Optimisation – Atofina technology • “Solution recycle” technique ( energy saving ) • Fully automated operations (computer control, PCS 7 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. . . Total Petrochemicals. CHEMICALS ANTWERPEN PETROCHEMICALS FINA Elastomers NV – Process Basics Proprietary and confidentialinformation of

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

Treatment of flashed-off gases from reactors C 4 storage Condensed flashed gases (C 4+C 6) Reactors ( avoid underpressure) Dry solvent C 6 . . Total Petrochemicals. CHEMICALS ANTWERPEN PETROCHEMICALS FINA Elastomers NV – Process Basics Proprietary and confidentialinformation of

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

Strippers – solvent removal (steam destillation) filter Stripper condensor • Polymer feed : 4 ~5 t/h • Polymer solution concentration : 18 ~25% vapours 1 st stripper Solvent decanter V= 45 m³ T° ~ 90°C V= 45 m³ T° ~ 110°C solution of blendtanks Solvent HP steam wet solventtanks H 20 via crumbtank to finishing oil recycle water (of finishing) 2 nd stripper Dispersing additive . . Total Petrochemicals. CHEMICALS ANTWERPEN PETROCHEMICALS FINA Elastomers NV – Process Dispersing agent 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. . . Total Petrochemicals. CHEMICALS ANTWERPEN PETROCHEMICALS FINA Elastomers NV – Process Basics Proprietary and confidentialinformation of

Drying equipment from Anderson Crumbtank 3 ~ 8 % crumb conc. Water content: 92 ~ 97 % Johnson Screen + vibrating shaker screen Water content: ~ 50 % Spiral elevator topexpeller Water content: ~ 8% (normally), upper limit 20 % skimmer tank Water content: < 0. 8% Middle expeller Water content: ~ 2% (normally), upper limit 15 % expander recycletank Top & Middle expeller hotbox • 90 k. W Expander Crumb handling • 400 k. W • Turbulator T°: 155°C ~175°C recycle water to strippers . . Total Petrochemicals. CHEMICALS ANTWERPEN PETROCHEMICALS FINA Elastomers NV – Process Basics Proprietary and confidentialinformation of

Drying equipment from French Crumbtank 3 ~ 8 % crumb Water content: 92 ~ 97 % conc. Johnson Screen + vibrating shaker screen Water content: ~ 50 % Spiral elevator Dewaterer Water content: < 0. 8% Water content: ~ 2% normally, upper limit 15% Dryer Dewaterer • 375 k. W recycletank skimmer tank Dryer Crumb handling • 840 k. W recycle water to strippers . hotbox • Dieplate T°: 145°C ~175°C . Total Petrochemicals. CHEMICALS ANTWERPEN PETROCHEMICALS FINA Elastomers NV – Process Basics Proprietary and confidentialinformation of

Packaging without homogenisation • Bales - blocks of compressed rubber, film wrapped, packed in boxes • Crumb/pellets: boxes, bags ( 15 -25 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 ~100 T ( 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 . . Total Petrochemicals. CHEMICALS ANTWERPEN PETROCHEMICALS FINA Elastomers NV – Process Basics Proprietary and confidentialinformation of

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

Crumb blending silos : specifics Finaprene crumbs are fluffy and sticky : low bulk density (200 -300) 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). . Total Petrochemicals. CHEMICALS ANTWERPEN PETROCHEMICALS FINA Elastomers NV – Process Basics Proprietary and confidentialinformation of

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

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

Current process at Atofina’s Antwerp elastomers plant Internal Packaging Fin. line A (Anderson) Bags Big Bags Fin. line B (Anderson) Reactorline A Blendtankline A 30 k. T/y Bales Stripperline A Fin. line C 30 k. T/y (French) External Packaging Reactorline B Blendtankline B Stripperline B Homogenisation Bags Big Bags Bulk 40 k. T/y Reactorline C Blendtankline C . Desolventiser . Total Petrochemicals. CHEMICALS ANTWERPEN PETROCHEMICALS FINA Elastomers NV – Process Homogenisation Basics Proprietary and confidentialinformation of 100 k. T/y