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OOxygen Transport MembranesBIGCO2 AchievementBIGCO2 Achievements
Paul Inge Dahl, Marie-Laure Fontaine, Florian Ahouanto, Christelle Denonville, Thijs Peters, Yngve Larring, Ove Paulsen,
Partow P. Henriksen, Rune Bredesen
SINTEF Ch i tSINTEF Materials and Chemistry
Trondheim CCS Conference, June 15, 2011
Outline
• IntroductionIntroductiono Air separation with OTMo Applications and integration concepts
• BIGCO2 Task A achievementso Membrane fabricationo Membrane fabricationo Sealing technologyo Membrane testingo Material development
• Summary• Summary
Air separationOxygen transport membranes (OTM)Oxygen transport membranes (OTM)
Dense layerPressurized air
(perovskite related)
Macroporous mechanicallyMacroporous mechanically strong support
(same composition)
Feed side:
Driving force Pressure vessel / housing
N22O2– 4e–
Feed side:High p(O2)
2
O2Permeate side:L w 2)o p(O2)
Applications and integration concepts• Oxygen production, i.e. for oxy-fuel
processes
O2-
O2(g), 1 atm O2(g) Air (30 atm)
O2-
O2(g), 1 atm O2(g) Air (30 atm)
N2(g)O2(g), 1 atm N2(g)O2(g), 1 atm
• Syn-gas production• Catalytic membrane reactor
O2-
CH4+H2O=CO(g)+H2(g) O2(g) Air
O2-
CH4+H2O=CO(g)+H2(g) O2(g) Air
N2(g)CO2(g)+H2O(g) N2(g)CO2(g)+H2O(g)
BIGCO2 Task AHi h t bHigh temperature membranes
• Overall objectives (2007-2011)Overall objectives (2007-2011)o Establish and develop fabrication and sealing
technology for ceramic high tem me ntechnology for ceramic high temperature membraneso Use the technology for fabrication of membrane
modules for oxygen and/o hydrogen separationmodules for oxygen and/or hydrogen separation
• Main activitieso Membrane fabrication o Sealing technologyo Sealing technologyo Testing and characterization
• Including material developmentIncluding material development
BIGCO2 Task A – Achievements • Fabrication of asymmetric tubular membranes
N O
22ln
16
2ln
2 Oil
ionelO p
LFRTJ
IIOp
I
L
O2Air
N2+O2
• Tubular membranes
162ln ionelLF I
Op2Air
• Tubular membraneso Extrusion of porous support
f thi d b l
Extruded tubular support
o Coating of thin densemembrane layer
D bDense membranelayer coated ontoporous support
BIGCO2 Task A – Achievements
Mixer
• Paste formulation and ceramic extrusion (La2NiO4)Mixer
As extruded tubular supports
m
m 100
cmPiston extruder
90 c
m 1
Tubular supports with close ends
BIGCO2 Task A – Achievements • Slurry preparation and coating of dense
membrane layers (La2NiO4) Coated supportsmembrane layers (La2NiO4)Stability of various dispersions investigated
Coated supports
Uncoated areas
SEM micrographs (cross-section) of selected asymmetric membranesSEM micrographs (cross-section) of selected asymmetric membranes
BIGCO2 Task A – Achievements • Sealing development – air braze
o Thermo-chemicall com atible with membrane materialy po Matching thermal expansion behaviour of braze, membrane/
housing material (HT alloy)Alloy 2,5
e
Alloycap
ane
1,5
2,0
2,5
(%)
Support Haynes 242Seal Ag-Cu braze CoolMembrane La2NiO4Sandvik Sanergy
embr
ane
allo
y
Bra
ze
Mem
bra
atin
g
0,5
1,0
Ther
mal
exp
.
M
HT
a B
Coa
0,00 200 400 600 800 1000 1200
T
Temperature (°C)
BIGCO2 Task A – Achievements • Sealing development – air braze
o Thermo-chemicall com atible with membrane materialy po Matching thermal expansion behaviour of braze, membrane/
housing material (HT alloy)Alloy
e
Alloycap
ane 6460 61
62 58
59
Braze
embr
ane
allo
y
Bra
ze
Mem
bra
atin
g
52-54
63
57 5655
Cu2Cr2O5
ft 4 k t hi h (900 960C)M
HT
a B
Coa
46-48
49-51
Alloy
Cr2O3
2 2 5
o Detected challenges after 4 weeks at high temperature (900-960C): Undesired interaction between braze and protective coating Thermal expansion mismatch between formed chromium oxide and
cupper-chromium oxide (formed from reacton with Cu in braze)
BIGCO2 Task A – Achievements • Sealing development – glass ceramicsBaO-La2O3-SiO2 glass (BLS)
1,00
1,20
1,40
1,60
ansion
(%) La2NiO4
BLS cryst.
Ba2La8Si6O26
0,20
0,40
0,60
0,80
Thermal expa
0,00
,
0 200 400 600 800 1000 1200 1400Temperature (°C)
Seal
Ba La Si O
BaSi2O5
Ba3Si5O13
Reaction zone
Membrane
Ba2La8Si6O26
Ba2La2Si4O13
MembraneLa2NiO4
BIGCO2 Task A – Achievements • Sealing development – glass ceramicsBaO-La2O3-SiO2 glass (BLS) Na2O-CaO-Al2O3-SiO2 glass (NCAS1)
1,00
1,20
1,40
1,60
ansion
(%) La2NiO4
BLS cryst.
Ba2La8Si6O261.5
2.0
2.5
p. (%
)
Haynes 242NCAS1 (cryst) CoolLa2NiO4Sandvik Sanergy
0,20
0,40
0,60
0,80
Thermal expa
0.5
1.0
Ther
mal
exp
0,00
,
0 200 400 600 800 1000 1200 1400Temperature (°C)
0.00 200 400 600 800 1000 1200
Temperature (°C)Compatible with membrane materialCracks on interface seal alloy housing
SealSealSeal
Cracks on interface seal – alloy housingCompatible with alternative housing
oMachinable glass ceramic
Ba La Si O
BaSi2O5
Ba3Si5O13
Reaction zone
MembraneMachinableglass ceramic
AlloyBa2La8Si6O26
Ba2La2Si4O13
Membrane glass ceramicLa2NiO4
BIGCO2 Task A – Achievements • Sealing development – glass ceramicsBaO-La2O3-SiO2 glass (BLS) Na2O-CaO-Al2O3-SiO2 glass (NCAS1)
1 5
2.0
2.5
p. (%
)
Haynes 242NCAS1 (cryst) CoolLa2NiO4Sandvik Sanergy
1,00
1,20
1,40
1,60
ansion
(%) La2NiO4
BLS cryst.
Ba2La8Si6O26 Complex material systems
0.5
1.0
Ther
mal
exp
0,20
0,40
0,60
0,80
Thermal expa systems
Many possiblereaction products
0.00 200 400 600 800 1000 1200
Temperature (°C)
0,00
,
0 200 400 600 800 1000 1200 1400Temperature (°C)
Compatible with membrane materialCracks on interface seal alloy housing
to consider
Ba La Si O
BaSi2O5
Ba3Si5O13
SealSealSealSealSealSealSealSeal
Cracks on interface seal – alloy housingCompatible with alternative housing
oMachinable glass ceramic
Reaction zoneReaction zoneBa2La8Si6O26
Ba2La2Si4O13
MembraneMembraneMachinableglass ceramicMachinableglass ceramicMachinableglass ceramic
AlloyAlloyAlloy
La2NiO4MembraneMembrane glass ceramicglass ceramicglass ceramic
BIGCO2 Task A – Achievements • Membrane testing
• Various single tube modules investigatedg gAir outSweep
gasTubular membranes tested in Probostat™ cells up to 8 bars and
e
Brazedalloy caps
eve
ssel
p80% O2 (32 bar air equivalent)
Air
flow
Mem
bran
e
pres
sure
Gold seals
Glass ceramic
seal
M
Ste
el
Dense
Air inOxygen+
Sweep gas
alumina base
Machinedalloy caps
Sweep gas
BIGCO2 Task A – Achievements • Membrane testing
• Dense tubular membrane (reference material La2NiO4) tested over ( 2 4)2500 hours at various conditionso Pressurized up to 8 bars and 80% O2 in feed (32 bars air equivalent)o gas flows and temperature ranging from 800 to 1000Co Varying gas flows and temperature ranging from 800 to 1000C
BIGCO2 Task A – Achievements • Membrane testing
• Dense tubular membrane (reference material La2NiO4) tested over ( 2 4)2500 hours at various conditionso Pressurized up to 8 bars and 80% O2 in feed (32 bars air equivalent)o gas flows and temperature ranging from 800 to 1000C
0,025
8 bars/900C
o Varying gas flows and temperature ranging from 800 to 1000C
o Data currently being processed for modelling purposes
Measurements at 2-8 bars, constant sweep flow
0,015
0,02
O2
flu
x
/4 bars/900C2 bars/900C1 bars/900C
for modelling purposes Ambipolar conductivity Flux model as function of T, pO2
and membrane thickness
0,01
Rel
ativ
e O and membrane thickness
Preliminary model indicates flux goal of 10 mL/(cm2min) is achievable
0
0,005
15 25 35 45 55 65 75 85
R achievable
Oxygen % in Feed side
BIGCO2 Task A – Achievements • Material development
• Im roved stabilit in reducin atmos here b B-site substitution with p y g p yiron (La2Ni1-xFexO4, x < 0.3) and no CO2 absorption (from HPTGA)
• Improved transport properties by A-site deficiency (La2-xNiO4, x<0.5)
BIGCO2 Task A – Achievements • Material development
• Im roved stabilit in reducin atmos here b B-site substitution with p y g p yiron (La2Ni1-xFexO4, x < 0.3) and no CO2 absorption (from HPTGA)
• Improved transport properties by A-site deficiency (La2-xNiO4, x<0.5)
0,025
0,030La-deficientFe-substitutedLa2NiO4 reference
o Improved O2 flux of La2-xNiO4compared to reference material (La2NiO4)
900C
Air/Ar gradient1000C 800C
0,015
0,020
m-1
min
-1
( 2 4) Doubled at 900C
o Decreased activation energy: From measurements in
0,010
0,015
P / m
l cm From measurements in
Air/Ar gradient La2NiO4: 86 kJ/mol La2-xNi2O4: 45 kJ/mol
0,000
0,005
0,75 0,80 0,85 0,90 0,95
2-x 2 4
1000T-1 / K-1
BIGCO2 Task A – Achievements • Material development
• Im roved stabilit in reducin atmos here b B-site substitution with p y g p yiron (La2Ni1-xFexO4, x < 0.3) and no CO2 absorption (from HPTGA)
• Improved transport properties by A-site deficiency (La2-xNiO4, x<0.5)
0,040
0,045
0,050La-deficientFe-subsitutedLa2NiO4 reference
o Improved O2 flux of La2-xNiO4 compared to reference material (La2NiO4)
O2/Ar gradient1000C 900C 800C
0,025
0,030
0,035
m-1
min
-1
( 2 4) Doubled at 900C
o Decreased activation energy: From measurements in
0,015
0,020
0,025
P / m
l cm From measurements in
Air/Ar gradient La2NiO4: 86 kJ/mol La2-xNi2O4: 45 kJ/mol
0,000
0,005
0,010
0,75 0,80 0,85 0,90 0,95
2-x 2 4
o La2Ni1-xFexO4: Flux comparable to reference material at high pO2
1000T-1 / K-1material at high pO2
Summaryy• BIG!!! BIGCO2 achievements on OTM
o Membrane fabricationo Membrane fabrication• Long porous tubular supports (up to 1 m)• Asymmetric membranes with thin dense layers (10-20 µm)
o Material development• Increased stability with Fe-substitution• Increased transport properties by La-deficiency
o Membrane testing• Long term tests (2500+ hours) of tubular membranes• Pressurized tests u to 8 bars 32 bars air ressure e uivalentp ( p q )• Modeling using experimental results in progress
o Sealing with brazing or glass ceramics in progress
• OTM: high potential for various applications when integrated in high temperature syste -fuel Pox )integrated in high temperature systems (oxy-fuel, Pox,…)
AcknowledgementgFunding through the BIGCO2 project, performed under the strategicNorwegian research program Climit.
Thanks to the Research Council of Norway (178004/I30 and 176059/I30)and Gassnova (182070) for their support.
And supporting industrial partners:
Thank you for your kind attention!y y