Total Petrochemicals Elastomers licensing history

1
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

2
Operating experience in Antwerpen

• Operating since 1968, there have been no serious
  injuries or fatalities at the plant ( 36 years
  of operations )
• During the plants 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 silos.
• Actual plant capacity 100 kt/a.

3
Production of Elastomers (General overview)

Reactor blending section
storage of monomers
Purification of monomers
Bulk homogenisation ( optional)
Steam destillation
packaging
Finishing (Anderson, French, Welding Engineers)
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Plot Plan
Elastomers Logistic Center
Homogenisation silos
Warehouse
StyreneChem. storage
Solvent storage
Finishing Finishing Control Room
Fuel storage
Butadiene storage
Solvent/Monomer Purification
Main Control Room
Boilers
Reaction area
Strippers
Blendtanks
50 m
5
Raw Materials

• 1,3 Butadiene
• - Either 100 (extracted) butadiene or a
  selectively hydrogenated C4 cut from a
• cracker unit can be used.
• Atofinas 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. lt 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
Raw Materials

• Styrene
• purity gt 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 3wt
• Polar additives ( ppm range ) are used as
  kinetics accelerator.

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Purification of butadiene by destillation ( for
hydrotreated C4 )
dry butadiene (typical 1999-2000) - 49 wt 1.3
Bd - 0.1 ppm 1,2 Bd - 0.5 ppm ViAc - 0.7 ppm
EtAc - lt2 ppm propadieen - 7 ppm carbonyls (as
acetaldehyde)
Boilers (C3,..) H20 to sewer

V 800 m³
V 320 m³
Boilers (1,2 Bd, C8..)
V 800 m³
Dry butadiene to reactors
wet butadiene
Boilers (1,2 Bd, C8..)
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Purification of butadiene by mole sieves/alumina
(for Extracted butadiene, gt99 conc )
Boilers (C3,..) H20 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 C4 ( diluted with
isobutane )
Expected impurity levels lt 0.5 ppm
9
Purification of styrene

• Removed impurities
• H2O
• TBC

V 45 m³
V 800 m³
Activated alumina dryers
dry styrene ( typically 5C )
wet styrene
10
Purification of solvents by destillation
C4s/Isobutane is recycled H2O to sewer
Removed impurities

H2O, 1,3buta dimer, Aox traces Styrene monomer
V 900 m³
V 800 m³
wet solvent
dry solvent
V 900 m³
V 800 m³
boilers
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Reactorsection

• 3 reactorlines External Reactor Capa
  (T/d)
• Flashtanks Cycle time
• line A 335 m³ Yes 120-170 min (HSE) 130 T/d
• line B 335 m³ No 85 min(SBS) 75125 T/d
• line C245 m³ Yes 65 90 min(SBR/SBS) 120165
  T/d

reactor overhead to C4/C6 splitters

monomer butadiene styrene solvent
initiator others
V 75m³ p 2 barg
V 45m³ p 80 mbarg
Reactor ( 35-45m³ )

• 3 blendtanklines
• line A 3300 m³
• line B 3300 m³
• line C 3400 m³

flashtanks
blendtank
strippers / desolventiser
Antioxydant
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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.

13
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)
14
Treatment of flashed-off gases from reactors
C4
C4 storage
Condensed flashed gases (C4C6)
Reactors( avoid underpressure)
Dry solvent
C6
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Blending of reactors
Blendtank  being homogenised/ analysed 
Blendtank  stripping 
Blendtank  being filled 
AOX, additives
Reactor discharge
Preconcentration/Stripping
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Strippers solvent removal (steam destillation)

• Stripper
• Polymer feed 4 5 t/h
• Polymer solution concentration 18 25

condensor
filter

vapours
1st stripper
Solvent decanter
V 45 m³ T 90C
V 45 m³ T 110C
Solvent
solution of blendtanks
HP steam
wet solventtanks
H20
via crumbtank to finishing
oil
recycle water (of finishing)
2nd stripper
Dispersing additive
Dispersing agent
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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
Crumbtank 3 8 crumb conc.
Water content 92 97

Johnson Screen vibrating shaker screen
Water content 50
Spiral elevator
topexpeller
Water content lt 0.8
Water content 8 (normally), upper limit20
skimmer tank
Middle expeller
Water content 2 (normally), upper limit 15
expander
recycletank

• Top Middle expeller
• 90 kW

Crumb handling
hotbox

• Expander
• 400 kW
• Turbulator T 155C 175C

recycle water to strippers
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Drying equipment from French
Crumbtank 3 8 crumb conc.
Water content 92 97

Johnson Screen vibrating shaker screen
Water content 50
Spiral elevator
Dewaterer
Water content lt 0.8
Water content 2 normally, upper limit 15
Dryer

• Dewaterer
• 375 kW

recycletank
skimmer tank
Crumb handling
hotbox

• Dryer
• 840 kW
• Dieplate T 145C 175C

recycle water to strippers
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Packaging

• 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 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
Homogenisation and packaging outsourcing
Homogenise at AFE (operational since 03/1998)
Package at ELC (operational since 05/2000)
Using conveyor belts
22
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)

23
Crumb silos test results.
Finaprene grades (SBS - crumbs) very high
 critical diameters 

24
Silo discharge device

• This technology is used for extremely bad flow
  characteristics

25
Current process at Atofinas Antwerp elastomers
plant
Internal Packaging
30 kT/y
Reactorline A
Blendtankline A
Stripperline A
Fin.line C
30 kT/y
(French)
External Packaging
Reactorline B
Blendtankline B
Stripperline B
Homogenisation
40 kT/y
Homogenisation
Reactorline C
Blendtankline C
Desolventiser
100 kT/y