hybsi® membranes from materials research to …life time state of the art methylated silica life...
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HybSi® membranes from materials research to energy savings
Rob Kreiter
Gepresenteerd als colloquium voor de groep Inorganic Materials Science, Universiteit Twente, 28 mei 2010
ECN-L--10-047 June 2010
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www.ecn.nl
HybSi® membranes from materials research to energy savings
Rob Kreiter
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•2 •30-6-2010
Why energy research?
• Security of supply• Limited supply of (fossil) fuels• Climate change and environmental impact• Creating new business (New Green Deal)
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•3 •30-6-2010
Climate targets 2020
EU NetherlandsGreenhouse gasesemission reduction
20% (30%1) 30%2
Energy efficiency improvement
20% 2% per year
Biofuels 10% binding minimum 10%Renewables 20% 20% (incl. bio fuel)
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•4 •30-6-2010
ECN: Mission
Mission: ECN develops and brings to market high-quality knowledge and technology for a sustainable energy system
Universities IndustryProduct
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•5 •30-6-2010
ECN: Research history
Start as Reactor Centre of the Netherlands (RCN) (1955)Start Wind Energy and Coal programmes (1975)RCN renamed in ECN (1978)Start Fuel Cell programme (1985)Start Solar Energy programme (1990)Start Environmental Research programme (1990)Start Biomass projects in the Coal programme (1994)Start Energy in the Built Environment programme (1997)Merger nuclear research ECN/KEMA in NRG (1998)Start Energy Efficiency in the Industry programme (1998)Start Intelligent Electricity Grids programme (2000)
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•6 •30-6-2010•6 •30-6-2010
Research at ECN: Savings, Renewables, Clean Fossil
Solar Energy Wind Energy
Policy Studies
H2 & Clean Fossil Fuels
Efficiency & Infrastructure
Biomass
Engineering & Services
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•7 •30-6-2010
Policy Studies
Policy research and consultancy:• International energy & climate policy• National energy & emission strategy• Energy in transport & built environment• Energy production, grids & markets• Energy innovation & society
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Solar Energy
• Crystalline silicon photovoltaics- Materials & characterisation- Device architecture & integration- Process development & application
• Thin-film photovoltaics- Thin-film silicon photovoltaics- Organic photovoltaics
• PV module technology
8 30-6-2010
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•9 •30-6-2010
Wind Energy
• Aero-elasticity (a.o. wind turbine control)• Design calculations (software)• Condition surveillance and measurement techniques• Wind farm aerodynamics• Maintenance and management wind turbines (O&M Tool)
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•10 •30-6-2010
Biomass, Coal & Environmental Research:
• Biomass and coal gasification• Syngas and Substitute Natural Gas• Biofuels and chemicals• Emission reduction technology• Environmental research
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•11 •30-6-2010
Efficiency & Infrastructure
Energy in the Built Environment• Building energetics• Thermal systems & heat pumps• Interaction & adaptation
Intelligent Energy Grids• Intelligent supply & demand
management• Grid coupling & quality• Electricity storage
Energy Efficiency in Industry• Industrial Heat Technology• Molecular Separation Technology• Process Intensification
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•12 •30-6-2010
Hydrogen & Clean Fossil Fuels
Hydrogen• Transition & infrastructure• Production & storage• Fuel cells (PEMFC)
Clean Fossils• CCS-technology
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•13 •30-6-2010
Engineering & Services: Research infrastructure
• Design and construction of high-quality components and installations
• Material analysis• Software development
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Incentive for membrane research at ECN• 40% of energy use in (petro)chemical for separations• Dutch separation processes use 190 PJ/year (= 6*109 m3 natural gas)• Low exergetic efficiency, so large energy saving potential
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Scheiding
Separation
Separation
Separation
Waste heat
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Industrial membrane applications (PV/VP, GS)
Pervaporation (PV)/ Vapour permeation (VP):• Dewatering of organics• Organic/organic separations• Savings potential for NL: 10 PJ/y
Gas separation (GS)• H2 from steam reforming/water-gas shift• Savings potential for NL: 25 PJ/y
Mem
bran
e
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Tubular (microporous) membranes
4 nm pores
120 nm pores
Membrane layer 1 μm
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Membrane preparation
Ceramic tube
Sol/solution
membrane film
Septum
Sol/solution
Coating speed
Meniscus
Tubes: 30 – 100 cm
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Mountains and (microporous) membranes
Membrane stability is challenged by:• (Hydro)thermal conditions• Aggressive solvents• Acids
Microporous sol-gel membranes• Are thermodynamic mountain tops• Are highly reactive or soluble• Densify / change phase
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Our approaches towards stability
Initial developments:
• Sol-gel SiO2 and Me-SiO2
More recent:
• Ceramic-supported polyimide membranes
• Microporous titania and zirconia membranes
Latest development:
• Organic - inorganic hybrid silica
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Improving hydrothermal stability of silicaMixed oxides (Zr, Co, Ni, Nb, Fe, Al)
Tsuru, J.Membr.Sci. 2006, 271, 86; da Costa, Sep.Pur.Technol. 2009, 66, 299Boffa, ten Elshof, J.Membr.Sci. 2008, 319, 256
Si
Si O
O OO
OO Si
O
Si
Si
SiO
Si
Si
Si
Si
Si
Si
Si
OO
OHOO
O
OH
OO
OO
O
O
OSi
Si O
O OO
OO Si
O
Si
Si
SiO
Si
Si
Si
Si
Si
Si
Si
Si
CH3O
CH3
OH3CCH3
OO
OH
H3C
O
H3C
CH3
O
CH3
OO
O
O
O
Lower water sorption
Carbon doped Silica Da Costa Adv.Funct.Mat. 2006, 16, 1215
Methylated silicaDe Vos, Verweij, J.Membr.Sci. 1999, 158, 277
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SiO2 and MeSi pervaporation results (95ºC)
• 5 wt.% H2O in BuOH, 10 mbar
• Addition of MTES gives better performance with time
• Constant performance for >18 months!
Chem.Commun. 2004, 834-835
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MeSi pervaporation up to 165ºC
• 2.5 wt.% H2O in BuOH, 10 mbar• Failure within weeks• No clear relation with temperature
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HybSi® membranes from bridged silica precursorsStrategy: replace Si—O—Si bonds by Si—C—Si bonds
Collaboration with Universities of Twente and Amsterdam (Ashima Sah, Andre ten Elshof, Hessel Castricum), started in 2003
WO2007081212, 2006; Chem. Commun. 2008, 1103-1105
SiSiEtO
OEt
OEtOEt
OEtOEt
HNO3, H2O
SiO
SiSi
OSi
O
OOH
OSi
Si
Si
Si
OH
OHOH
OHSi
SiSi
SiHO OH
HO OH
HOOH
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Screening precursors for HybSi® membranes
Overview of precursors: D.A. Loy, K.J. Shea Chem.Rev. 2005, 1431
R
Tailored network
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High-throughput screening (HTS) of hybrid silica sols
Automated synthesis of sols was performed varying:• Precursor type• Temperature• H2O/OR• H+/OR
Total of ~160 individual sol preparations• 6.5 mL scale• 1 standard in each run• Analysis using DLS
Chemspeed ASW1000
Malvern Zetasizer Nano ZS
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HTS – Example results
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Precursors and PV performance
Precursors:• BTESE + MTES• BTESE • BTESM
MTES BTESE BTESM
Hybrid layer
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Performance hybrid membranes, 150oC
Feed = 5 wt.% water in n-BuOH
First membrane madeBTESE/MTES
Life time state of the art methylated silica
Life time >650 days
J. Mater. Chem. 2008, 18, 2150-2158
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Performance hybrid membranes, 150oC
Feed: 5 wt.% water in n-BuOH
J. Membr. Sci. 2008, 324, 111-118Life time state of the art methylated silica
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Performance hybrid membranes, 190°C
Feed : 5 wt.% water in n-BuOHRecipe 2
• Performance similar to 150°C
• On stream >1 month
• Selectivity stable
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Application testing - solvents
Feed = 5 wt.% water in solvent; BTESE/MTES
Temperature. = 55 70 85 95 70 55 70 120 °C
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Application testing - alcoholsFeed = 5 wt.% water in alcohol
T = 55 70 85 95 °C
ChemSusChem 2009, 2, 158-160
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Acid stability
Feed : 5 wt.% water in n-BuOH0.005 – 0.5 wt.% HNO3BTESE
Feed : 5 wt.% water in EtOH0.15 wt% HAcBTESM
J.Mater.Chem. 2008, 18, 1-10 ChemSusChem 2009, 2, 158-160
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Towards gas separation: hydrogen selectivity
BTESE
Similar findings by: M. Kanezashi, JACS 2009, 131, 2, 414
BTESM
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Scaling up
Check www.HybSi.com and www.HySep.comfor pilot test equipment
Pilot plant installation (PV/VP), 1000 litre liquidAmem= 1 m2 (24 tubes)Tmax = 150oCPmax = 10 bar
Single tube test module (GS)Amem= 40 cm2
Tmax = 650oCPmax = 50 bar
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Conclusions and perspective• Hybrid silica sols
o Preparation is simple and can be automatedo A wide range of precursors can be usedo Particle size and fractal dimension can be tuned
• HybSi® membraneso Have a high hydrothermal stabilityo Show excellent PV performance and potential in H2 separationo Are highly acid stableo Are readily scaled up and reproduced
• Current focuso Industrial demonstrationso Licensing HybSi® membrane productiono Expanding the scope to other industrial separations
•Figure 4.3•Figure 4.3•Figure 4.3
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HybSi® timeline2003 Start of organic-inorganic hybrid membranes, Twente University IMS
2005 First joint experiment Twente and ECN on tubular membrane2006 Second set of membranes coated on tubes
Patent applied on microporous hybrid silica membranes2007 Membrane of 2005 still running2008 First publication on hybrid silica membrane selected as ‘Hot Article’
3 more publications follow2009 Second patent applied on specific separations
Publication is selected for cover of ChemSusChemTrade name HybSi® is registered and www.hybsi.com is launched
2010 HybSi® licensing negotiations
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38 30-6-2010
Further information and acknowledgements
Chem. Commun., 2008, 1103-1105J. Mater. Chem., 2008, 18, 2150-2158J. Sol-Gel Sci. Technol., 2008, 48, 203-211J. Mem. Sci, 2008, 324, 111-118ChemSusChem, 2009, 2, 158-160J. Sol-Gel Sci. Technol., 2010, acceptedPatents: WO2007081212
WO2010008283ECNJ.F. Vente D.P. Shanahan M.D.A. Rietkerk H.M. van VeenG.G. Paradis
Twente University / University of AmsterdamA. Sah J.E. ten ElshofH.L. Castricum A.J.A. Winnubst
www.hybsi.com
www.ecn.nl/memtech