HybSi® membrane
technology: the market
within reach
J.F. Vente
May 2013
ECN-L--13-025
HybSi® membrane technology:
the market within reach
Jaap Vente
Programma Xs2HiTek Workshop, Microfluidics & Procestechnologie, 15 mei 2013, Plant One
www.ecn.nl
considering
revamped
No new bio-ethanol plant
will be build without HybSi®
membrane technology
(in ten years time)
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Membrane solutions for energy efficient separations
Principles of molecular separation
Based on differences
Thermodynamic properties
sorption behaviour, vapour pressure
Distillation
Molecular properties
Mol weight, molecular size, dipole moment etc.
Membranes
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Membrane solutions for energy efficient separations
A short history of distillation
2004
Modern industrial layout
1597
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Membrane solutions for energy efficient separations
Distillation characteristics
• Frequently used: workhorse of the separation industry
• Well studied and optimised
• Reliable (most of the time)
• Energy intensive & exergy killer
• Limitations close to and at azeotropes liquid & vapour have the
• Tweaks with pressure
• Entrainer  two additional columns
same composition
• Alternatives
• Mol sieve
• Membranes
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Membrane solutions for energy efficient separations
Distillation characteristics
• Frequently used: workhorse of the separation industry
• Well studied and optimised
• Reliable (most of the time)
• Energy intensive & exergy killer
• Limitations close to and at azeotropes liquid & vapour have the
• Tweaks with pressure
• Entrainer  two additional columns
same composition
• Alternatives
• Mol sieve
• Membranes
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Membrane solutions for energy efficient separations
Energy and costs savings
7
Application
Conventional
process
Energy
savings
Costs savings
Pay back
period
Bio-ethanol
Distillation + mol
sieve
30%
20% (3 €ct/l lower EtOH
production cost)
3 years
Acetone
Distillation
40%
25%
2 years
Esterification
reactions
Distillation (batch
process)
50%
30%
± 1 year
Methanol from
toluene
Extraction +
distillation
50%
30%
± 1 year
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Membrane solutions for energy efficient separations
What is so special about HybSi®?
Organic – inorganic hybrid silica
with exceptional stability cf. commercial competition
• Higher application temperatures
•
•
•
•
•
8
- 190°C
Higher resistance against acids and alkalines
- ~ 0 < pH < ~8
Higher stability in aggressive solvents
- NMP, MEK
Larger application window w.r.t. water content
- Measurement up 60% performed
Effective methanol removal
- Feasibility shown
Resistance against condensation
- All liquid feed no issue
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Membrane solutions for energy efficient separations
Zeolite
Polymeric
Preparation of a membrane
Coating step
Coating
speed
Sol
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Hybrid layer
Meniscus
Membrane solutions for energy efficient separations
Long term performance
• 150°C
• 3% H2O in BuOH
• Measurement stopped
100
7
98
6
96
5
94
4
92
2
Water flux (kg/m h)
8
3
90
Flux
Concentration
2
88
0
200
400
600
Time on stream (d)
800
1000
J. Mem. Sci. 2011, 380,124
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Membrane solutions for energy efficient separations
Waterconcentrate in the permeate (%)
after 1000 days
Acid stability
• 70°C
• 5% H2O in EtOH
• Water content in permeate:
>85%
2.2
0.1 mol% HAc
1 mol% HAc
10 mol% HAc
2
Water flux (kg/m h)
2.0
1.8
1.6
1.4
1.2
1.0
0
Kreiter, ChemSusChem, 2009, 2, 158
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10
20
30
Time on stream (d)
Membrane solutions for energy efficient separations
40
50
Acid stability
Water purity in permeate (%)
• 100°C
• 10% H2O in HAc
Water flux (A.U.)
1.0
0.5
0.0
0
100
200
300
100
95
90
0
100
Time (d)
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Membrane solutions for energy efficient separations
200
Time (d)
300
Moving out of the laboratory
In house long term testing ~40 cm2
To come to generic acceptance
On site system testing 1 m2
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Membrane solutions for energy efficient separations
Pilot testing
1m2 of membrane area
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Membrane solutions for energy efficient separations
Pilot testing at Plant One
Dehydrate ~ 7.5 m3 of organic solvents
from ~ 30% H2O to ~< 2% H2O
Large containers!
Chemical storage: secondary confinement
LARGE drip trays!
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Membrane solutions for energy efficient separations
Pilot testing
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Membrane solutions for energy efficient separations
Experiences and Results
• Successful scale up by a factor of >100
• Membrane stable under test conditions
• Initial performance satisfactory
Deposites
HybSi® layer
Alumina layer
• Long term testing  scaling
 demands CIP procedures
or pre-treatment
• Reserve sufficient time
(when working with flammable liquids)
• HAZOP sessions
• Modifications of the experimental set up
• Discussions with fire brigade
• Selection of test samples and procedures
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Membrane solutions for energy efficient separations
Industrial involvement
• Commitment from end users
•
- Tests & module sales
- Process analyses
- Letters of Intent to come to
actual utilisation
Interest from OEM
- Letters of interests
- Active participation
• Contract with manufacturers
- Licence granted to Pervatech
(NL) and CTI (FR)
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Membrane solutions for energy efficient separations
Acknowledgements
• Industrial collaborators
•
•
•
•
•
•
•
•
Sabic IP
Huntsman
Air Products
DSM
Sulzer Chemtech
Pervatech
CTI
Trion partners
• Knowledge network
• Universities of Twente,
Amsterdam, Bilbao,
Eindhoven
• Financial support
• STW
• AgentschapNL
• ISPT
Membrane development team
www.ecn.nl/memtech
Membrane solutions for energy efficient separations
Public available information
www.HybSi.com
Follow us on Twitter:@HybSi_membranes
Sign up: HybSi news letter
For more information
please contact me:
[email protected]
+31 – 224 56 4916
20
Scientific Papers
J. Mater.Chem A. doi: 10.1039/C3TA00120B
J. Mem. Sci., 2013, 428, 127
J. Mater. Chem., 2012, 22, 7258
J. Chem. Techn. & Biotechn., 2012, 87, 943
AIChE J., 2011, 58, 1862
J. Mem. Sci., 2011, 380, 124
Advan. Func. Mater., 2011, 21, 2319
J .Mem. Sci., 2011, 371, 179
J. Sol-Gel Sci Techn., 2011, 57, 245
ChemSusChem., 2009, 2, 158
J. Mem. Sci., 2008, 319, 126
J. Sol-Gel Sci Techn, 2008, 48, 203
J. Mater. Chem., 2008, 18, 2150
Chem. Commun., 2008, 1103
Membrane solutions for energy efficient separations
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