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
Elastomers
NV – Process
PETROCHEMICALS
FINA CHEMICALS
ANTWERPEN
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
Elastomers
NV – Process
PETROCHEMICALS
FINA CHEMICALS
ANTWERPEN
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
Elastomers
NV – Process
PETROCHEMICALS
FINA CHEMICALS
ANTWERPEN
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
Elastomers
NV – Process
PETROCHEMICALS
FINA CHEMICALS
ANTWERPEN
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 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)
.
.
Total Petrochemicals
Elastomers
NV – Process
PETROCHEMICALS
FINA CHEMICALS
ANTWERPEN
Basics Proprietary and confidentialinformation of
Raw Materials
Styrene
– 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.
.
.
Total Petrochemicals
Elastomers
NV – Process
PETROCHEMICALS
FINA CHEMICALS
ANTWERPEN
Basics Proprietary and confidentialinformation of
Purification of butadiene by
destillation ( for hydrotreated C4 )
Boilers (C3=,..)
H20 to sewer
V= 800 m³
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)
V= 320 m³
Boilers (1,2 Bd, C8..)
V= 800 m³
Dry butadiene
to reactors
wet butadiene
.
Boilers (1,2 Bd, C8..)
.
Total Petrochemicals
Elastomers
NV – Process
PETROCHEMICALS
FINA CHEMICALS
ANTWERPEN
Basics Proprietary and confidentialinformation of
Purification of butadiene by mole sieves/alumina
(for Extracted butadiene, >99% 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 : < 0.5 ppm
.
Total Petrochemicals
Elastomers
NV – Process
PETROCHEMICALS
FINA CHEMICALS
ANTWERPEN
Basics Proprietary and confidentialinformation of
Purification of styrene
Removed impurities :
- H2O
- TBC
V= 45 m³
V= 800 m³
Activated alumina dryers
dry styrene ( typically 5°C )
wet styrene
to reactors
.
.
Total Petrochemicals
Elastomers
NV – Process
PETROCHEMICALS
FINA CHEMICALS
ANTWERPEN
Basics Proprietary and confidentialinformation of
Purification of solvents by destillation
C4’s/Isobutane is recycled
Removed impurities :
H2O to sewer
H2O,
1,3buta 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
Elastomers
NV – Process
PETROCHEMICALS
FINA CHEMICALS
ANTWERPEN
Basics Proprietary and confidentialinformation of
Reactorsection
monomer
butadiene
styrene
solvent
initiator
others
3 reactorlines:
External
Reactor
Flashtanks Cycle time
Capa (T/d)
•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
reactor overhead
to C4/C6 splitters
V= 75m³
p= 2 barg
blendtank off-gas
recovery
V= 45m³
p= 80 mbarg
Reactor
( 35-45m³ )
3 blendtanklines:
flashtanks
•line A: 3*300 m³
•line B: 3*300 m³
blendtank
Antioxydant
.
.
Total Petrochemicals
Elastomers
NV – Process
PETROCHEMICALS
FINA CHEMICALS
ANTWERPEN
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, 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.
.
.
Total Petrochemicals
Elastomers
NV – Process
PETROCHEMICALS
FINA CHEMICALS
ANTWERPEN
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
Elastomers
NV – Process
PETROCHEMICALS
FINA CHEMICALS
ANTWERPEN
Basics Proprietary and confidentialinformation of
Treatment of flashed-off gases from reactors
C4
C4 storage
Condensed flashed gases (C4+C6)
Reactors
( avoid underpressure)
Dry solvent
C6
.
.
Total Petrochemicals
Elastomers
NV – Process
PETROCHEMICALS
FINA CHEMICALS
ANTWERPEN
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
Elastomers
NV – Process
PETROCHEMICALS
FINA CHEMICALS
ANTWERPEN
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
1st stripper
Solvent decanter
V= 45 m³
T° ~ 90°C
V= 45 m³
T° ~ 110°C
solution of
blendtanks
Solvent
HP steam
wet solventtanks
H20
via crumbtank
to finishing
oil
recycle water
(of finishing)
2nd stripper
Dispersing additive
.
.
Total Petrochemicals
Elastomers
NV – Process
PETROCHEMICALS
FINA CHEMICALS
ANTWERPEN
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
Elastomers
NV – Process
PETROCHEMICALS
FINA CHEMICALS
ANTWERPEN
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
limit20 %
skimmer tank
Water content: < 0.8%
Middle expeller
Water content: ~ 2% (normally),
upper limit 15 %
expander
recycletank
Top & Middle expeller
•90 kW
hotbox
Expander
Crumb
handling
•400 kW
•Turbulator T°: 155°C ~175°C
recycle water
to strippers
.
.
Total Petrochemicals
Elastomers
NV – Process
PETROCHEMICALS
FINA CHEMICALS
ANTWERPEN
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 kW
recycletank
skimmer tank
hotbox
Dryer
•840 kW
recycle water
to strippers
.
Crumb
handling
•Dieplate T°: 145°C ~175°C
.
Total Petrochemicals
Elastomers
NV – Process
PETROCHEMICALS
FINA CHEMICALS
ANTWERPEN
Basics Proprietary and confidentialinformation of
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
.
.
Total Petrochemicals
Elastomers
NV – Process
PETROCHEMICALS
FINA CHEMICALS
ANTWERPEN
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
Elastomers
NV – Process
PETROCHEMICALS
FINA CHEMICALS
ANTWERPEN
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
Elastomers
NV – Process
PETROCHEMICALS
FINA CHEMICALS
ANTWERPEN
Basics Proprietary and confidentialinformation of
Crumb silos :test results.
Finaprene grades (SBS - crumbs) : very high « critical diameters »
Outlet size according to the storage time
F502
5
5
4,5
4,5
critical outlet diameter
[m]
critical outlet diameter
[m]
Outlet size according to the storage time
F411x
4
3,5
3
2,5
2
4
3,5
3
2,5
2
1,5
1,5
1
1
0,5
0,5
0
0
0
20
40
60
80
100
120
140
160
180
storage time [h]
.
200
0
20
40
60
80
100
120
140
160
storage time [h]
.
Total Petrochemicals
Elastomers
NV – Process
PETROCHEMICALS
FINA CHEMICALS
ANTWERPEN
Basics Proprietary and confidentialinformation of
180
200
Silo discharge device
This technology is used for extremely bad flow characteristics
.
.
Total Petrochemicals
Elastomers
NV – Process
PETROCHEMICALS
FINA CHEMICALS
ANTWERPEN
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 kT/y
Bales
Stripperline A
Fin.line C
30 kT/y
(French)
External Packaging
Reactorline B
Blendtankline B
Stripperline B
Homogenisation
Bags
Big Bags
Bulk
40 kT/y
Reactorline C
Blendtankline C
.
Desolventiser
.
Total Petrochemicals
Elastomers
NV – Process
PETROCHEMICALS
FINA CHEMICALS
ANTWERPEN
Homogenisation
Basics Proprietary and confidentialinformation of
100 kT/y