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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

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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.

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Production of Elastomers (General overview)

storage of monomers Purification of monomers

Steam destillation

Finishing (Anderson, French, Welding Engineers)

packaging

Bulk homogenisation( optional)

Reactor & blending section

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Plot Plan

Solvent storage

Butadiene storage

Reaction area

Styrene&Chem. storage

Finishing

& Finishing Control Room

Warehouse

Solvent/Monomer Purification

Blendtanks

BoilersStrippers

Homogenisation silosElastomers Logistic Center

Fuel storage

Main Control Room

50 m

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Raw Materials1,3 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 C4 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 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)

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Raw MaterialsStyrene

– purity > 99.8 %wt

– TBC: 10 - 15 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.

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Purification of butadiene by destillation ( for hydrotreated C4 )

Boilers (C3=,..)H20 to sewer

Boilers (1,2 Bd, C8..)

wet butadiene

dry butadiene:(typical 1999-2000)- 49 %wt 1.3 Bd- 0.1 ppm 1,2 Bd- 0.5 ppm ViAc- 0.7 ppm EtAc- <2 ppm propadieen- 7 ppm carbonyls (as acetaldehyde)

Dry butadiene to reactors

V= 800 m³

Boilers (1,2 Bd, C8..)

V= 800 m³

V= 320 m³

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Purification of butadiene by mole sieves/alumina (for Extracted butadiene, >99% conc )

V= 800 m³

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 (C3=,..)H20 to sewer

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Purification of styrene

to reactors

wet styrene

dry styrene ( typically 5°C )

V= 800 m³V= 45 m³

Activated alumina dryers

Removed impurities :

- H2O

- TBC

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Purification of solvents by destillationC4’s/Isobutane is recycledH2O to sewer

boilers

wet solvent dry solvent

To reactors

V= 800 m³ V= 900 m³

V= 800 m³V= 900 m³

Removed impurities :H2O,

1,3buta dimer,

Aox traces

Styrene monomer

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Reactorsection

monomerbutadiene styrene solvent initiator others

reactor overheadto C4/C6 splitters

blendtank off-gas recovery

strippers /desolventiser

Reactor ( 35-45m³ ) flashtanks

blendtank

V= 75m³p= 2 barg

V= 45m³p= 80 mbarg

Antioxydant

3 reactorlines: External Reactor Capa (T/d)Flashtanks Cycle time

•line A: 3*35 m³ 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 Yes 65 ~ 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

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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.

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“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

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Treatment of flashed-off gases from reactors

Condensed flashed gases (C4+C6)

C4

Dry solvent

C6

C4 storage

Reactors( avoid underpressure)

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Blending of reactors

AOX, additivesReactor discharge

Blendtank « being filled »

Blendtank « being

homogenised/ analysed »

Blendtank « stripping »

Preconcentration/Stripping

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Strippers – solvent removal (steam destillation)

solution of blendtanks

condensor

oil

HP steam

1st stripper

2nd stripper

Solvent decanter

via crumbtankto finishing

Dispersing additive Dispersing agent

vapours

recycle water(of finishing)

wet solventtanks

filter

V= 45 m³T° ~ 90°C

V= 45 m³T° ~ 110°C

Stripper

•Polymer feed : 4 ~5 t/h

•Polymer solution concentration : 18 ~25%

H20

Solvent

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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.

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Drying equipment from Anderson

Crumb handling

Crumbtank3 ~ 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

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Drying equipment from French

Crumb handling

Johnson Screen+ vibrating shaker screen

Dewaterer

hotbox

Spiral elevator

recycle water to strippers

skimmer tank

recycletank

Crumbtank3 ~ 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

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PackagingPackaging 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 ~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

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Homogenisation and packaging outsourcing

Homogenise at AFE(operational since 03/1998)

Package at ELC(operational since 05/2000)

Usingconveyor belts

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Crumb blending silos : specificsFinaprene 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)

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Crumb silos :test results.

Outlet size according to the storage timeF411x

0

0,5

1

1,5

2

2,5

3

3,5

4

4,5

5

0 20 40 60 80 100 120 140 160 180 200

storage time [h]

critic

al ou

tlet d

iameter

[m]

Outlet size according to the storage timeF502

0

0,5

1

1,5

2

2,5

3

3,5

4

4,5

5

0 20 40 60 80 100 120 140 160 180 200

storage time [h]

critic

al ou

tlet d

iameter

[m]

Finaprene grades (SBS - crumbs) : very high « critical diameters »

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Silo discharge device

This technology is used for extremely bad flow characteristics

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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)

(Anderson)

Homogenisation

Homogenisation

Internal Packaging

External Packaging

(French)

30 kT/y

30 kT/y

40 kT/y

100 kT/y