Dr. Sameer Vijay (Borealis, Finland) - CAPEC
Dr. Sameer Vijay (Borealis, Finland) - CAPEC
Dr. Sameer Vijay (Borealis, Finland) - CAPEC
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Achieving higher purity<br />
in polyolefins<br />
Why & how of it<br />
<strong>Sameer</strong> <strong>Vijay</strong><br />
sameer.vijay@borealisgroup.com<br />
Process Research, PO R&D, Porvoo<br />
© 2009 <strong>Borealis</strong> AG<br />
1<br />
2009.06.04<br />
<strong>CAPEC</strong> Annual Meet 2009<br />
/SAV<br />
<strong>Borealis</strong> Group – at a glance<br />
• Leading provider of innovative, value creating plastics<br />
• Over 40 years of PO experience (Nordic/Scandinavian roots)<br />
• Unique Borstar® technology to develop tailored polyolefin solutions<br />
• Operating in over 20 countries employing about 5400 persons<br />
• Owners & JV<br />
© 2009 <strong>Borealis</strong> AG<br />
2<br />
2009.06.04<br />
<strong>CAPEC</strong> Annual Meet 2009<br />
/SAV
Providing solutions in Polyolefins<br />
Infrastructure<br />
Automotive<br />
Advanced Packaging<br />
© 2009 <strong>Borealis</strong> AG<br />
3<br />
2009.06.04<br />
<strong>CAPEC</strong> Annual Meet 2009<br />
/SAV<br />
…and in Base Chemicals<br />
phenol phenol and & acetone<br />
feedstocks and olefins<br />
melamine<br />
plant nutrients<br />
© 2009 <strong>Borealis</strong> AG<br />
4<br />
2009.06.04<br />
<strong>CAPEC</strong> Annual Meet 2009<br />
/SAV
Global polyolefin producers 2008<br />
Nameplate capacity 2008, ktpa<br />
World 0 5,000 10,000 15,000 Europe 0 2,000 4,000 6,000<br />
LyondellBasell<br />
ExxonMobil<br />
Dow<br />
SINOPEC<br />
SABIC<br />
Ineos<br />
Total<br />
<strong>Borealis</strong><br />
*<br />
Formosa Grp<br />
CNPC<br />
LyondellBasell<br />
Ineos<br />
Dow<br />
SABIC<br />
Total<br />
Polimeri Europa<br />
ExxonMobil<br />
Repsol<br />
TVK<br />
© 2009 <strong>Borealis</strong> AG<br />
5<br />
* Incl. Borouge<br />
Source: <strong>Borealis</strong>/CMAI<br />
2009.06.04<br />
<strong>CAPEC</strong> Annual Meet 2009<br />
/SAV<br />
Commitment to Innovation secures<br />
future growth – long term solutions<br />
‘Commodity’ ypath<br />
Feedstock Olefins Polyolefins Converters End users Consumers<br />
Reduce<br />
Recycle<br />
Recover<br />
‘Value Creation’ path<br />
Feedstock Olefins Polyolefins Converters End users Consumers<br />
Reduce<br />
Recycle<br />
Recover<br />
© 2009 <strong>Borealis</strong> AG<br />
6<br />
2009.06.04<br />
<strong>CAPEC</strong> Annual Meet 2009<br />
/SAV
Consistent effort on safety all the time!<br />
TRI frequency 1996 - 2008, own vs. contractors<br />
18<br />
16<br />
14<br />
12<br />
10<br />
8<br />
6<br />
4<br />
2<br />
0<br />
16,3<br />
14,8<br />
10,1<br />
9,5<br />
8,3<br />
6.9<br />
4,0<br />
3,8<br />
2,4<br />
17 1,7<br />
TRI frequency<br />
TRI own<br />
TRI contactors<br />
1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007 2008<br />
1.7<br />
17 1,7<br />
1,6<br />
© 2009 <strong>Borealis</strong> AG<br />
7<br />
2009.06.04<br />
<strong>CAPEC</strong> Annual Meet 2009<br />
/SAV<br />
Develop & encourage attitude towards safety!<br />
© 2009 <strong>Borealis</strong> AG<br />
8<br />
2009.06.04<br />
<strong>CAPEC</strong> Annual Meet 2009<br />
/SAV
Unwanted substances –<br />
Chemical species in PO product leading to -<br />
• Taste and odour active components<br />
• <strong>Dr</strong>inking water applications – pipes, caps & closures<br />
• Food contact packaging<br />
• Emissions (VOCs & Fogging compounds)<br />
• Automotive (especially car interiors)<br />
• Migration compounds (NIAS)<br />
• Medical & food packaging<br />
• Residues resulting in application defects<br />
• Films, Fibres, Cable insulation<br />
Oligomers / Low MW compounds (C 3 –C 24 )<br />
© 2009 <strong>Borealis</strong> AG<br />
9<br />
2009.06.04<br />
<strong>CAPEC</strong> Annual Meet 2009<br />
/SAV<br />
Expectations (and fears)<br />
DTU research results* created fears about health effects from plastic pipes<br />
© 2009 <strong>Borealis</strong> AG<br />
10<br />
2009.06.04<br />
<strong>CAPEC</strong> Annual Meet 2009<br />
/SAV<br />
*Brocca,D., Arvin,E. & Mosbæk,H. (2002) Water Research, 36, 3675-3680
Challenge –<br />
• Increasing demands on the PO industry to deliver safer and<br />
healthier products:<br />
• Food contact / <strong>Dr</strong>inking water / Medical<br />
• Strong demand for reduced odour and emissions for<br />
automotive interiors<br />
• Converters & customer concerns (Odour, die deposits &<br />
fumes)<br />
• Increased Analytical Capabilities allow better detection<br />
• Carve out new markets before others<br />
A <strong>Borealis</strong>’ “common” challenge!<br />
© 2009 <strong>Borealis</strong> AG<br />
11<br />
2009.06.04<br />
<strong>CAPEC</strong> Annual Meet 2009<br />
/SAV<br />
2-fold approach<br />
• Mitigate<br />
• Develop new technology concepts<br />
• Rapid implementation<br />
• Prevent<br />
• Identification of compounds - analytics<br />
• Formation mechanism - root cause<br />
Prevention could reduce process changes and costs involved<br />
with mitigation<br />
© 2009 <strong>Borealis</strong> AG<br />
12<br />
2009.06.04<br />
<strong>CAPEC</strong> Annual Meet 2009<br />
/SAV
Do you smell what I smell<br />
Taste & Odour<br />
• T&O panel (VDA270) – an internal panel grades<br />
on a 1-to-5 scale (vs. Reference), olfactometry<br />
VOC & Fog Emission<br />
• Static (VDA277) & Dynamic Headspace on GC or<br />
GCMS(VDA278)<br />
Develop test methods with lower detection capabilities<br />
© 2009 <strong>Borealis</strong> AG<br />
13<br />
2009.06.04<br />
<strong>CAPEC</strong> Annual Meet 2009<br />
/SAV<br />
Schematic - PO particle-form. process<br />
Purification Reactor(s) Separation/ Degassing Extrusion<br />
Recovery<br />
Feedstock Powder Pellets<br />
Wet End<br />
<strong>Dr</strong>y End<br />
© 2009 <strong>Borealis</strong> AG<br />
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<strong>CAPEC</strong> Annual Meet 2009<br />
/SAV
Where might they show up<br />
Wet End<br />
<strong>Dr</strong>y End<br />
Purification Reactor(s) Separation/ Degassing Extrusion<br />
Recovery<br />
Feedstock Powder Pellets<br />
(Co-) Monomer / Feed Wet-end <strong>Dr</strong>y-end Compounding<br />
T&O precursors, NIAS<br />
Emission, Fogging,<br />
T&O precursors<br />
Emission,<br />
T&O, NIAS<br />
Emission<br />
Odour, NIAS<br />
© 2009 <strong>Borealis</strong> AG<br />
15<br />
2009.06.04<br />
<strong>CAPEC</strong> Annual Meet 2009<br />
/SAV<br />
Feedstock Purification<br />
• Typical feedstock impurities – CO, CO 2 ,<br />
H 2 O, Sulfur compounds (~ ppm)<br />
• Right kind of purifiers – becoming standard<br />
everywhere<br />
• Catch – Detection level / Detectors<br />
• Anything below detection level could still cause<br />
T&O impurities in final product<br />
© 2009 <strong>Borealis</strong> AG<br />
16<br />
2009.06.04<br />
<strong>CAPEC</strong> Annual Meet 2009<br />
/SAV
•<br />
Reaction driver<br />
• Different catalyst systems <br />
varying VOC / Fog components<br />
Low MW<br />
• MW distribution is governed by<br />
catalyst characteristics<br />
• H 2 / Co-monomer / donor (with ZN<br />
catalysts) response<br />
Oligomers C6-C21 (µg/g)<br />
• Narrower MWD possible with<br />
single-centre catalysts<br />
ZN Catalyst 1 ZN Catalyst 2 SS Catalyst<br />
© 2009 <strong>Borealis</strong> AG<br />
17<br />
2009.06.04<br />
<strong>CAPEC</strong> Annual Meet 2009<br />
/SAV<br />
Novel catalyst concept<br />
Catalyst preparation based on emulsion technology<br />
Emulsification<br />
Solidification<br />
Liquid/liquid<br />
two-phase system<br />
• Formation:<br />
• inert solvent<br />
• in-situ<br />
• Catalyst chemistry<br />
Emulsion<br />
• Particle Size<br />
• Size Distribution<br />
Suspension<br />
• Catalyst morphology<br />
• Compactness<br />
• Particle shape<br />
• Surface properties<br />
© 2009 <strong>Borealis</strong> AG<br />
18<br />
2009.06.04<br />
<strong>CAPEC</strong> Annual Meet 2009<br />
/SAV
Borstar® PE/PP Process<br />
• Combination of slurry (PE) or bulk (PP) loop<br />
reactor with gas-phase reactor/s (GPR)<br />
• Unique mix of properties possible by<br />
varying split between the reactors<br />
Processability Mechanical strength<br />
Slurry/Bulk<br />
Gas-phase<br />
Mw<br />
© 2009 <strong>Borealis</strong> AG<br />
19<br />
2009.06.04<br />
<strong>CAPEC</strong> Annual Meet 2009<br />
/SAV<br />
Powder treatment<br />
• Polymer bed purged with steam / Air / N 2 at<br />
low pressure<br />
• Stop further polymerization<br />
• AKA steaming, purging, stripping, degassing<br />
• Particle morphology & size affects<br />
desorption behaviour – C 6 desorbs faster<br />
than C 12 – effective for LMW(< C 9 )<br />
• Low pressure purging or increasing<br />
temperature in purging<br />
Steam<br />
N 2<br />
PURGE<br />
BIN<br />
TO<br />
RECOVERY<br />
UNIT<br />
TO PELLETIZING<br />
Residence time (avg.) has a big effect<br />
© 2009 <strong>Borealis</strong> AG<br />
20<br />
2009.06.04<br />
<strong>CAPEC</strong> Annual Meet 2009<br />
/SAV
Stripping polymer particle<br />
Thermodynamics dictates<br />
concentration of LMW within polymer<br />
– mass transfer in 3 steps multiple<br />
math models with estimated<br />
diffusivities<br />
Steam<br />
Polymer particle<br />
after GPR<br />
N 2<br />
C8 C10 C12<br />
C8 model C10 model C12 model<br />
Developing good prediction models –<br />
• Solubility of unwanted molecules (LMW) in<br />
polymer<br />
• Effect of residence time distribution &<br />
temperature<br />
VOC (ppm)<br />
0 20 40 60 80<br />
© 2009 <strong>Borealis</strong> AG<br />
21<br />
2009.06.04<br />
<strong>CAPEC</strong> Annual Meet 2009<br />
/SAV<br />
heating time (min)<br />
Inside extruder<br />
• High temperature, shear & presence of<br />
Oxy-compounds (purging, conveying,<br />
additives) T&O substances<br />
• Reducing oxygen content<br />
• Staged de-volatilization - different low<br />
pressure levels (30-50% reduction)<br />
• Vented, vacuum staged, multiple vents<br />
0<br />
• Carriers to enhance (by bubble growth) or<br />
control polymer temperature<br />
100<br />
90<br />
80<br />
70<br />
60<br />
50<br />
40<br />
30<br />
20<br />
10<br />
Total VOC<br />
Total T&O<br />
Components<br />
Loop GPR Powder Pellet<br />
PO-volatile equilibrium data is scarce<br />
© 2009 <strong>Borealis</strong> AG<br />
22<br />
2009.06.04<br />
<strong>CAPEC</strong> Annual Meet 2009<br />
/SAV
Post-pellet treatments<br />
• Pellet degassing to remove<br />
• VOCs, Fogging compounds (>C 9 )<br />
100<br />
• New T&O components formed in extruder 80<br />
• Pellet size is less of a factor – TD<br />
governs desorption<br />
• Steam or hot air blowers (longer RT)<br />
• Deodorizing silos, steamers, recirculation<br />
G<br />
Relative total VOC/FOG<br />
120<br />
60<br />
40<br />
20<br />
0<br />
Lab Tests with Pellets<br />
Reference<br />
VOC<br />
FOG<br />
Steaming,<br />
100°C, 6hrs<br />
Aeration,<br />
100°C, 6hrs<br />
Final cleaning step before pellets move to storage silos<br />
© 2009 <strong>Borealis</strong> AG<br />
23<br />
2009.06.04<br />
<strong>CAPEC</strong> Annual Meet 2009<br />
/SAV<br />
1 + 2 + 3 = 10<br />
• Effect of devolatilization is multiplicative,<br />
beginning with catalyst & additives<br />
• Control of VOC & T&O substances requires<br />
balancing act with product properties<br />
• Lead in creating value & market through<br />
innovative solutions – reliability & focus on<br />
improvement and quality<br />
© 2009 <strong>Borealis</strong> AG<br />
24<br />
2009.06.04<br />
<strong>CAPEC</strong> Annual Meet 2009<br />
/SAV
Continuing innovations<br />
• Mitigation tech. increase energy use &<br />
investment<br />
• Different plant configurations and wide<br />
VOC Reduction (up to 30%)<br />
product mix need different purification tech. BorPure TM ‘As bottled’ taste<br />
100<br />
80<br />
60<br />
40<br />
20<br />
0<br />
2006 2008<br />
• Several improvement projects in progress<br />
• New organoleptic products launched<br />
© 2009 <strong>Borealis</strong> AG<br />
25<br />
2009.06.04<br />
<strong>CAPEC</strong> Annual Meet 2009<br />
/SAV<br />
Concluding remarks<br />
Achieving purity is tough!<br />
<strong>Borealis</strong> continues its progress in –<br />
• Determining nature & sources of impurities<br />
• Establishing better analytical methods<br />
• Estimating desorption rates for high MW for<br />
math models (purge bin or pellet silos)<br />
• Implementing several of the technologies in<br />
its manufacturing plants<br />
Increased purity is a valued property for PO & <strong>Borealis</strong>’ customers<br />
© 2009 <strong>Borealis</strong> AG<br />
26<br />
2009.06.04<br />
<strong>CAPEC</strong> Annual Meet 2009<br />
/SAV
The information contained herein is to our knowledge accurate and reliable as of the date of publication. <strong>Borealis</strong> extends no warranties and makes no<br />
representations as to the accuracy or completeness of the information contained herein, and assumes no responsibility regarding the consequences of its<br />
use or for any printing errors.<br />
© 2009 <strong>Borealis</strong> AG<br />
27<br />
2009.06.04<br />
<strong>CAPEC</strong> Annual Meet 2009<br />
/SAV
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