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Membranes: a new separation technology for the purification of hydrogen and industrial solvents
J.F. Vente
Presented at the Lecture Dinner Meeting at AIChE“, Zoetermeer, 13 April 2010
ECN-L--10-009 April 2010
Membrane solutions for energy efficient separations www.ecn.nl
Membranes: a new separation technology for the purification of hydrogen and industrial solvents
Jaap Vente
Membrane solutions for energy efficient separations www.ecn.nl
ECN’s main features
•
ECN develops and implements high-level knowledge and technology
for the transition to sustainable energy management.
•
Annual turnover of 70 M€
(>25% from private contract research)
•
10-15 international patents / year (revenues: 1.5 M€/yr)
•
Approx. 600 reports and publications each year
•
(Inter)national co-operation with companies, universities and research institutes
Membrane solutions for energy efficient separations www.ecn.nl
Trias Energetica: to a sustainable energy system
2.
Maximise the use of renewable energy sources
1.
Reduce demand (energy saving)
3.
Use fossil fuels in the cleanest possible way
Energy demand
Membrane solutions for energy efficient separations www.ecn.nl
Renew
ables
Ene
rgy
effic
ienc
y
Clean and efficient (fossil) fuels
Supply issuesDemand reduction
Trias Energetica
Solar
Wind
Biomass
H2
, Fuel CellsCO2
-capture
Buildings
Smart grids
Industry
System innovations
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ECN role in technology development
Fundamental research
Lab-scale (1 kg/h)
Pilot-scale (100 kg/h)
Demonstration
Commercial
effort / €
total effortcooperation
ECN
Membrane solutions for energy efficient separations www.ecn.nl
ECN Energy Efficiency in Industry
Upgrading industrial waste heatIndustrial Heat Technology Thermo-acoustic heat pump
(13 fte)
Chemical heat pump
Combined unit operationsProces Intensification HEX reactors
(9 fte)
Membrane reactors
Molecular separationsMolecular Separation Technology Materials, processes
(12 fte)
Systems development
Membrane solutions for energy efficient separations www.ecn.nl
Molecular Separation technology
SeparationSeparationraw materials
REACTOR
and..and..
and..and..
and..and..
clean air
contaminants
products
by products
recycle
clean water
ScheidingScheiding
SeparationSeparation
SeparationSeparation
SeparationSeparationSeparationSeparationraw materials
REACTOR
and..and..
and..and..
and..and..
clean air
contaminants
products
by products
recycle
clean water
ScheidingScheiding
SeparationSeparation
SeparationSeparationSeparationSeparation
SeparationSeparation
Motivation•
474 PJ/year Energy use in NL (petro)chemical (NL≈2400 PJ/year)
•
Separation processes 190 PJ/year•
Exergetic efficiency 10%
Membrane solutions for energy efficient separations www.ecn.nl
Membrane separation
Feed
Permeate 9-
20 mm
30 -
100 cm
Membrane solutions for energy efficient separations www.ecn.nl
Separation principle
Dissolution and diffusionDense materials• Amorphous polymers; • Crystalline metals and oxides
Size and affinityPorous materials• Amorphous sol-gel based inorganic materials• Crystalline zeolites and related
Membrane solutions for energy efficient separations www.ecn.nl13
Membrane utilisationWater treatment
•
Purification of drinking water•
Treatment of sewage water
Gas separations•
Hydrogen recovery
•
Natural gas production•
Hydrogen production
•
Air separationMedical applications
•
Kidney dialysesOthers
•
Purification of organic solvents•
Volatile organic component recovery
Membrane solutions for energy efficient separations www.ecn.nl
Porous Membranessa
lt/m
etal
ions
Pore sizeµm
Microfiltration
10-2
10-1
1
101
10-4
10-3
bact
eria
viru
s colo
ïdal
par
ticle
s
prot
ein
gase
s
Ultrafiltration
PervaporationGas separation
Nanofiltration Activities ECN-MST
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Top view of intermediate layers(1) Course alumina
support: packing of 20 micron particles
1
(2) 600A layer: Regular packing of submicron particles
2
(3) γ
Al2
O3
layer; Dense packing of nano-particles
3
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Tubular microporous membranes
4 nm pores
120 nm pores
Pores < 1nmZrO2
/TiO2
1000 nm
Membrane solutions for energy efficient separations www.ecn.nl17
Membrane fabrication
suspension
coat
speed
“dry”
wet evaporation
septum
coat vessel
Coat Vessel
coatspeed
meniscus
Membrane solutions for energy efficient separations www.ecn.nl19
What is pervaporationPervaporation is a membrane based separation technique
= permeation + evaporation= selective evaporation of liquids via a membrane= much more energy efficient than distillation
Feed Permeate
Membrane
Evaporation
Pervaporation
Membrane solutions for energy efficient separations www.ecn.nl20
Commercial available PV membranesPolymers
•
Sulzer: PVA•
Vaperma: polyimide
Ceramics•
Mitsui, Mitsubishi: Zeolite A
•
Pervatech: Silica
Membrane solutions for energy efficient separations www.ecn.nl21
SiftekTM Membrane by VapermaHydrophilic polyimide hollow fiber concept
Vapour permeation from the bore side
100m2
membrane area per module
Water-Rich Permeate
Dry Ethanol
Ethanol- Water
Vapour Mixture
Source
Membrane solutions for energy efficient separations www.ecn.nl22
20m3/day Demonstration unitBio-ethanol dehydrationDistillation and membrane
Source
Membrane solutions for energy efficient separations www.ecn.nl23
Developments in Zeolite A membranes (1)Manufacturing companiesMitsui Engineering and ShipbuildingHyflux in collaboration with BP and DalianHitachiInocermic together with GFTMitsubishi Chemical Company formerly BNRI
Crystalline microporous material3D –
architecture.
Source
Membrane solutions for energy efficient separations www.ecn.nl24
Developments in Zeolite A membranes (3)
Source
1997
2000
2007
2008
Pervaporation 75ºC
Vapour Permeation 150ºC
Membrane solutions for energy efficient separations www.ecn.nl25
Present challengesHigher application temperaturesHigher acid resistanceHigher stability in aggressive solventsLarger application window w.r.t. water contentEffective methanol removalResistance against condensation
Amorphous inorganic microporous networks
•
SiO2
•
Methylated SiO2
•
Ti/ZrO2
•
HybSi®: SiO2
with organic bridges
Membrane solutions for energy efficient separations www.ecn.nl26
Large scale production
Coat robot Drying Carousel Welding robot
Furnace Module
Membrane solutions for energy efficient separations www.ecn.nl
HybSi® membranes from bridged precursorsStrategy:
replace Si—O—Si bonds by Si—C—C—Si bonds
Collaboration with Universities of Twente and Amsterdam (Ashima Sah, Andre ten Elshof, Hessel Castricum, Marjo Mittelmeijer), started in 2003
SiSiEtO
OEt
OEtOEt
OEtOEt
HNO3, H2O
SiO
SiSi
OSi
O
OOH
OSi
Si
Si
Si
OH
OHOH
OHSi
SiSi
SiHO OH
HO OH
HOOH
Membrane solutions for energy efficient separations www.ecn.nl
Precursor selection for improved performance
Precursors:Recipe 1: BTESE + MTESRecipe 2: BTESERecipe 3: BTESM
MTES BTESE BTESM
Hybrid layer
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100
98
96
94
92
90
88W
ater
cont
ent i
n th
e pe
rmea
te (%
)6004002000
Time on stream (d)
25
20
15
10
5
0
Wat
er fl
ux (k
g/m
2 h)
6004002000Time on stream (d)
Performance HybSi® membranes, 150oC
Life time state-of-the-art Me-SiO2
Feed: 5 wt.% water in n-BuOH
J. Membr. Sci. 2008, 324, 111
Life time >650 days
Recipe 1
Recipe 2
Membrane solutions for energy efficient separations www.ecn.nl
Application testing - alcoholsFeed = 5 wt.% water in alcohol
T = 55 70 85 95 °C
100
80
60
40
20
0
Wat
er c
onte
nt p
erm
eate
(wt.%
)
Recipe 3 Recipe 2 Recipe 1
MeOH EtOH PrOH BuOH
ChemSusChem 2008, 2, 158
Membrane solutions for energy efficient separations www.ecn.nl
Acid stability
Feed : 5 wt.% water in n-BuOH0.005 –
0.5 wt.% HNO3Recipe 2
3.0
2.5
2.0
1.5
1.0
0.5
Wat
er fl
ux (k
g/m
2 h)
50403020100Time on stream (d)
100
90
80
70W
ater
con
tent
per
mea
te (w
t.%)
0.005 0.05 0.5 wt% HNO3
Feed : 5 wt.% water in EtOH0.1 wt% HAcRecipe 3
2.6
2.4
2.2
2.0
1.8
1.6
1.4
1.2
1.0W
ater
flux
(kg/
m2 h)
5040302010Time on stream (d)
100
95
90
85
80
75
70
Wat
er c
onte
nt p
erm
eate
(wt.%
)
0.1 wt% HAc
Acid stability very promising
Membrane solutions for energy efficient separations www.ecn.nl
Origins of stability of hybrid silica-
More stable bonds
-
Higher crack propagation energy
-
Lower surface diffusion coefficient
-
Lower solubility
Vente Membranes bij Rhodia.pptx
Membrane solutions for energy efficient separations www.ecn.nl
How to use HybSi®?
Azeotrope separation, Debottlenecking, Capacity increase
Membrane solutions for energy efficient separations www.ecn.nl
Where to use HybSi®
Permeating species
Retained species Azeotrope (wt% retained species)
Water Acetonitrile 83.7
Water Ethanol 95.5
Water n-Propanol 71.7
Water t-Butanol 88.3
Water Methyl acetate 95.0
Water Methyl ethylketone 89.0
Water Tetrahydrofuran 95.0
Methanol Toluene 31.0
Methanol Methyl acetate 81.3
Methanol Tetrahydrofuran 69.0
Azeotropes
Membrane solutions for energy efficient separations www.ecn.nl
Hydrogen for ammonia production
Desulphurisation Membrane Reactor
Natural gas Steam
N2
Syngas(H2 + N2)
CO2 + H2OH2 H2 H2
Desulphurisation Membrane Reactor
Natural gas Steam
N2
Syngas(H2 + N2)
CO2 + H2OH2 H2 H2H2H2 H2H2 H2H2
New scheme including membrane reactor
ConventionalDesulphurisation
Reformer1
Reformer2 HT Shift LT Shift
CO2 removalMethanation
Natural gas
Steam Air
Syngas(H2 + N2)
CO2
Fuel gas
800 oC 980 oC480 oC 350 oC 200 oC
50 oC275 oC
H2OH2O
140 bar 30 bar
43 bar
Desulphurisation
Reformer1
Reformer2 HT Shift LT Shift
CO2 removalMethanation
Natural gas
Steam Air
Syngas(H2 + N2)
CO2
Fuel gas
800 oC 980 oC480 oC 350 oC 200 oC
50 oC275 oC
H2OH2O
140 bar 30 bar
43 bar
Membrane solutions for energy efficient separations www.ecn.nl
Membrane reactor: Concept
Steam reforming: CH4 + H2O 3 H2 + CO (ΔH = 206 kJ/mol)
Water-gas shift: CO + H2O H2 + CO2 (ΔH = - 41 kJ/mol)
CH4 + 2 H2O 4 H2 + CO2
Steam reforming: CH4 + H2O 3 H2 + CO (ΔH = 206 kJ/mol)
Water-gas shift: CO + H2O H2 + CO2 (ΔH = - 41 kJ/mol)
CH4 + 2 H2O 4 H2 + CO2CH4 + 2 H2O 4 H2 + CO2
Membrane solutions for energy efficient separations www.ecn.nl
1,0E-10
1,0E-09
1,0E-08
1,0E-07
1,0E-06
1,0E-05
1,0E-04
0 2 4 6 8
time [days]
Perm
eanc
e [m
ol/m
2 sPa]
0
5
10
15
20
25
30
35
CH
4 co
nver
sion
incr
ease
Stable H2 permeance
No membrane
No membraneStable CH4 permeance
1,0E-10
1,0E-09
1,0E-08
1,0E-07
1,0E-06
1,0E-05
1,0E-04
0 2 4 6 8
time [days]
Perm
eanc
e [m
ol/m
2 sPa]
0
5
10
15
20
25
30
35
CH
4 co
nver
sion
incr
ease
Stable H2 permeance
No membrane
No membraneStable CH4 permeance
Depending on conditions CH4
conversion may increase with >30%
H2
/CH4
sel > 1000
Shift in equilibrium, membrane reactor testing
Membrane solutions for energy efficient separations www.ecn.nl
H2 transport in dense Pd alloy membranes
1.
Bulk diffusion2.
Adsorption of hydrogen molecules
3.
Dissociation into atoms4.
Absorption of atoms
5.
Diffusion of atoms6.
Recombination
7.
Desorption
CO2
H2OH2
H2 H2
H2
H
HH
H1
2
3 54 6
7
Pd alloy membrane
High pressure Low pressure
CO2
H2OH2
H2 H2
H2
H
HH
H1
2
3 54 6
7
Pd alloy membrane
High pressure Low pressure
Membrane solutions for energy efficient separations www.ecn.nl
ManufacturingTwo distinct approaches
Electroless plating
Dalian Institute of Chemical Physics
Worcester Polytechnic Institute
Energy research Centre of the Netherlands
Magnetron sputtering
Southwest Research Institute
SINTEF
Membrane solutions for energy efficient separations www.ecn.nl
Electroless plating route
(3) Sequential reduction and deposition of metal ions.
(4) Alloying step by heat treatment
(1) Support pore size reduction
(2) Seeding of support
Membranes of up to 90 cm
Membrane solutions for energy efficient separations www.ecn.nl
Long term behaviour
Steam reforming reactor tests, CH4
20% / N2
20% / H2
O 60%Feed flow 2 –
10 Nl/min; Pfeed = 25 –
42 bar;
T = 530 –
590ºC;
ECN –
membrane made by electroless plating
20
30
40
50
60
70
80
90
100
0 10 20 30 40 50
Duration [days]
Con
vers
ion
CH
4 [%
]
0,00
0,02
0,04
0,06
0,08
0,10
0,12
0,14
Flux
[mol
/m2s
]
MR expThermoH2 fluxCH4 flux
Membrane solutions for energy efficient separations www.ecn.nl
Towards implementation: drivers and challenges
Large-scalehydrogen
production
On-site H2production
H2 recovery &purification
Research market
Precombustiondecarbon.
Dehydro-genation
Carbon deposition
Lifetime T > 600 oC
reproduciblemembrane
Technological challenges
System integration
Membrane cost
Membrane flux
Lifetime T > 500 oC
Membrane cost
Market size
Market drivers
Efficiency
Lower investment
Lower investment & process integration
Efficiency& investment
Manufacturing capabilityLifetime at T > 400 oC
Membrane solutions for energy efficient separations www.ecn.nl
Technology transfer to the market (1)
Production procedure up to 90 cm tubes
High quality membranes:
-high selectivity (1000-7000)
-H2
permeance 32-48 Nm3/m2hbar0.5
at 450°C
Thin layer defect free membrane
on tubular ceramic support
Membrane solutions for energy efficient separations www.ecn.nl
Technology transfer to the market (2)
Prototype hydrogen separation modules
Small scale:Single tube~40 cm2
Hydrogen flow: 0.15 -
1 Nm3/hUp to 70 bars
Partners:CRL Energy (New Zealand)University of the Basque Country (Spain)
Membrane solutions for energy efficient separations www.ecn.nl
Technology transfer to the market (3)
Prototype hydrogen separation modules
To full length multi tubular (1/8
to 1/2
m2)Up to 6 Nm3/hrUp to 25 bar
Partners:Technip KTI (Italy)N-GHY (France)
Membrane solutions for energy efficient separations www.ecn.nl
Next steps, separation modules•
On site H2
production–
600 kWth, = 350 kWe
–
12 m2
membrane
•
Partnering for:–
Further scaling up
–
Commercialisation–
Marketing
Membrane solutions for energy efficient separations www.ecn.nl
www.hysep.comwww.hybsi.com
Membrane solutions for energy efficient separations www.ecn.nl
www.hysep.com www.hybsi.com [email protected]
www.ecn.nl/memtech