aldo steinfeld
TRANSCRIPT
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Liquid Fuels
from
Water, CO2, and Solar Energy
Aldo Steinfeld
IMDEA Energy4.4.2011
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Sunlight + H2O + CO2 = Fuels
Syngas(H2 , CO)
Liquid Fuels• Diesel• Jet Fuel• Methanol
H2O, CO2
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20 MW-electric/ 100 MW-thermal 11 MW-electric / 55 MW-thermal(Sevilla, Spain)
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H°
G°
TS°
-50
0
50
100
150
200
250
300
1000 2000 3000 4000 5000
[kJ/
mol
]
Temperature [K]
H2OHOH2OHO2
00.10.2
0.30.40.50.60.70.80.9
1
2000 2500 3000 3500 4000
Temperature [K]
Equilibrium Mole Fractionp = 1 bar
2 2 2H O H + ½ O
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H2/COH2O/CO2
O2
2nd step: Oxidation
1st step: Solar Reduction
ConcentratedSolar Energy
recycle
2ox redMO MO O
2 2
2
red ox
red ox
MO H O MO HMO CO MO CO
redMO
oxMO
oxMOTo
Liquid Fuels
Solar Thermochemical Splitting of H2O and CO2
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H2/COH2O/CO2
O2
2nd step: Oxidation
1st step: Solar Reduction
ConcentratedSolar Energy
recycle
20 5 ZnO Zn . O
2 2
2
Zn H O ZnO HZn CO ZnO CO
Zn
oxMO
oxMOTo
Liquid Fuels
Solar Thermochemical Splitting of H2O and CO2
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Qrerad
ZnO@ 298 K
QuenchQquench
Zn + ½ O2@ 2000 K
C = 5000
I = 1 kW/m2
T = 2000KQsolarConcentrated
SolarRadiation
Zn½ O2
HydrolyserQhyd
H2 ZnO
IdealFuelCell
WF.C.
QF.C.
H2O
F.C.
solar
WQ
h.r. with%58
h.r. no%35
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H2/COH2O/CO2
O2
2nd step: Oxidation
1st step: Solar Reduction
ConcentratedSolar Energy
recycle
20 5 ZnO Zn . O
2 2
2
Zn H O ZnO HZn CO ZnO CO
Zn
oxMO
oxMOTo
Liquid Fuels
Solar Thermochemical Splitting of H2O and CO2
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ZnO/Zn Cycle
rotary joint
quartz window
cavity-receiver
water/gasinlets/outlets
Zn+½ O2
ZnO
ConcentratedSolar
Radiation
ZnO feeder
• Chem. Eng. J. 150, 502-508, 2009.• Materials 3, 4922-4938, 2010.
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• Treactor = 2000 K
• Qsolar = 10 kW
• Cpeak = 5880 suns
• mZnO = 11 g/min
• Zn yield = 50 – 95 %
ZnO/Zn Cycle
rotary joint
quartz window
cavity-receiver
water/gasinlets/outlets
Zn+½ O2
ZnO
ConcentratedSolar
Radiation
ZnO feeder
600
800
1000
1200
1400
Shutter [%]
1600
1800
2000
2200
2400
10
20
30
40
50
60
70
80
90
100
100 200 300 400 5000 7006000
600
800
1000
1200
1400
ZnO
-Tem
pera
ture
[K]
1600
1800
2000
2200
2400
10
20
30
40
50
60
Time [sec]
70
80
90
100
100 200 300 400 5000 7006000
TemperatuTemperature [K]ShutteShutter [%]
• Chem. Eng. J. 150, 502-508, 2009.• Materials 3, 4922-4938, 2010.
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9 feed cycles; 131g each
Solar Reactor Technology
ZnO dissociated (g)# feed-cycles Measured Calculated 3 68.5 ± 5.2 63.95 59.5 ± 6.8 54.07 148.4 ± 28.8 223.39 224.2 ± 49.5 197.1
ZnO dissociated (g)# feed-cycles Measured Calculated 3 68.5 ± 5.2 63.95 59.5 ± 6.8 54.07 148.4 ± 28.8 223.39 224.2 ± 49.5 197.1
ZnO dissociated (g)# feed-cycles Measured Calculated 3 68.5 ± 5.2 63.95 59.5 ± 6.8 54.07 148.4 ± 28.8 223.39 224.2 ± 49.5 197.1
• Heat transfer + kinetic model validated
100 kW
A
eff 0 r
ERT
p
chemistryheattransfer
Tc k T k e H Tt
• AIChE J. 55, 1497-1504, 2009. • Chem. Eng. J. 150, 502-508, 2009.• Int. J. Heat Mass Transfer 52, 2444-2452, 2009.
10 kW
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Solar radiative input 100 kW 10 kW
Cavity diameter 580 160 mm Cavity length 750 230 mm Outlet diameter 110 15 mm Al2O3-tile thickness 10 7 mm Outer shell diameter 1080 200 mm Aperture diameter 190 60 mm Window diameter 485 160 mm Solar concentration ratio 3500 3500 suns
Solar Reactor Technology100 kW
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H2/COH2O/CO2
O2
2nd step: Oxidation
1st step: Solar Reduction
ConcentratedSolar Energy
recycle
20 5 ZnO Zn . O
2 2
2
Zn H O ZnO HZn CO ZnO CO
Zn
oxMO
oxMOTo
Liquid Fuels
Solar Thermochemical Splitting of H2O and CO2
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nanoparticleformation
in-situ hydrolysis
Zn
ZnOH2O H2
Zn(g)
H2O(g)mixing
H2
ZnO
Aerosol reactor concept
H2O
Ar
steamgenerator
Ar
gas analysis
filter
Balance
evaporationzone
Zn Zn(g)
T = 1263 K
reaction zone
H2O + Zn ZnO + H2
T = 573-1263K
ExperimentalSet-up
Distance along reactor axis [cm]
0 20 40 60 80 100400
600
800
1000
1200
Zncrucible
evaporation
H2O/Arinjection
reaction zone
Tem
pera
ture
[K]
Quench rate: up to 106 K/s
Tsat
• Chem. Eng. Sc. 64, 1095-1101, 2009.• Chem. Eng. Sc. 65, 1855-1864, 2010.
2nd step: Syngas Production
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Reaction time (min)0 10 20 30 40 50 60 70
0
1
2
3
4
5
6
7
8
9TR = 973 K
Zn evaporation
= Zn-conversion = 90%
10-4
mol
/min H2 production
nanoparticleformation
in-situ hydrolysis
Zn
ZnOH2O H2
Zn(g)
H2O(g)mixing
H2
ZnO
Aerosol reactor concept
H2O
Ar
steamgenerator
Ar
gas analysis
filter
Balance
evaporationzone
Zn Zn(g)
T = 1263 K
reaction zone
H2O + Zn ZnO + H2
T = 573-1263K
ExperimentalSet-up
• Chem. Eng. Sc. 64, 1095-1101, 2009.• Chem. Eng. Sc. 65, 1855-1864, 2010.
2nd step: Syngas Production
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nanoparticleformation
in-situ hydrolysis
Zn
ZnOH2O H2
Zn(g)
H2O(g)mixing
H2
ZnO
Aerosol reactor concept
H2O
Ar
steamgenerator
Ar
gas analysis
filter
Balance
evaporationzone
Zn Zn(g)
T = 1263 K
reaction zone
H2O + Zn ZnO + H2
T = 573-1263K
ExperimentalSet-up
• Chem. Eng. Sc. 64, 1095-1101, 2009.• Chem. Eng. Sc. 65, 1855-1864, 2010.
2nd step: Syngas Production
TR = 823 K
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H2/COH2O/CO2
O2
2nd step: Oxidation
1st step: Solar Reduction
ConcentratedSolar Energy
recycle
2ox redMO MO O
2 2
2
red ox
red ox
MO H O MO HMO CO MO CO
redMO
oxMO
oxMOTo
Liquid Fuels
Solar Thermochemical Splitting of H2O and CO2
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H2O
N2
H2
N2 + O2
Nitrogen / Steam flow
Gas exhaust
Internal circulating fluidized bed (NiFe2O4/m-ZrO2)
Draft tube
Conical-shaped cap
Cyclone
CO2 (or steam) CO2 (or steam)
CO and CO2 (or H2 and H2O)
O2
Concentrated solar flux
Window
O2
Niigata U., JapanNiFe2O4
SNL, USACoFe2O4
U. of Colorado, USANiFe2O4
DLR, GermanyZnFe2O4
CNRS, FranceZnO, SnO2
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H2/COH2O/CO2
O2
2nd step: Oxidation
1st step: Solar Reduction
ConcentratedSolar Energy
recycle
2 2 22
CeO CeO O
2 2 2 2
2 2 2
CeO H O CeO HCeO CO CeO CO
redMO
oxMO
oxMOTo
Liquid Fuels
Solar Thermochemical Splitting of H2O and CO2
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Solar Reactor Technology
Science 330, 1797-1801, 2010.
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Solar Experimental Set-up
Science 330, 1797-1801, 2010.
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Solar Experimental Results
2solar-to-fuel
2
heating value of fuel produced 0.8% for CO -splitting0.7% for H O-splittingsolar energy input + energy for inert gas recycling
Science 330, 1797-1801, 2010.
CO2-splitting H2O-splitting
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Solar Experimental Results
Simultaneous splitting of CO2 & H2O• H2O/CO2 = 7 → H2/CO = 1.91
• Fuel/O2 = 2
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Solar Experimental Results
0
0.1
0.2
0.3
0.4
0.5
0.6
0 50 100 150 200 250 300 350 400 450
Rate [m
L min
‐1g‐
1 ]
700
900
1100
1300
1500
1700
1900
0 50 100 150 200 250 300 350 400 450
Temperature [K]
Time [min]
2.14 ml O2
g-1 CeO2
1.73 ml O2
g-1 CeO2
1.46 ml O2
g-1 CeO2
1.69 ml O2
g-1 CeO2
1.56 ml O2
g-1 CeO2
1.48 ml O2
g-1 CeO2
1.34 ml O2
g-1 CeO2
1.28 ml O2
g-1 CeO2
1.23 ml O2
g-1 CeO2
1.23 ml O2
g-1 CeO2
2.65 ml H2 g-1
1.22 ml CO g-1
H2/CO ratio: 2.17
2.45 ml H2 g-1
1.06 ml CO g-1
H2/CO ratio: 2.31
2.43 ml H2 g-1
1.03 ml CO g-1
H2/CO ratio: 2.36
2.29 ml H2 g-1
0.99 ml CO g-1
H2/CO ratio: 2.32
2.00 ml H2 g-1
2.00 ml CO g-1
H2/CO ratio: 2.01
2.17 ml H2 g-1
0.90 ml CO g-1
H2/CO ratio: 2.43
2.10 ml H2 g-1
0.91 ml CO g-1
H2/CO ratio: 2.28
2.19 ml H2 g-1
0.83 ml CO g-1
H2/CO ratio: 2.63
1.76 ml H2 g-1
0.76 ml CO g-1
H2/CO ratio: 2.31
1.92 ml H2 g-1
0.74 ml CO g-1
H2/CO ratio: 2.59
Simultaneous splitting of CO2 & H2O
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30 m
m
35 mm 43 mm
30 m
m
35 mm 43 mm
30 m
m
35 mm 43 mm
Reticulate Porous Ceramic
RPC
• ASME Journal of Heat Transfer 132, 023305 1-9, 2010.
• average pore diameter = 2.54 mm• total porosity = 92%• specific surface = 11 mm-1
I
s
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Radiative properties of RPC
0
10 22
-
I sexp - s
I
. cm
MC ray tracing
Change of attenuation augmentation augmentation
radiation by by byintensity absorption+scattering internal emission incoming scattering
i
4s
b i0
dII I I d
ds 4
I
s
• ASME Journal of Heat Transfer 132, 023305 1-9, 2010.
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2D D
2
0 1D
Re
p u F uK
pd c cu
-7 2
1
1.353 10 444.02
K mF m
• Navier-Stokes by DNS• 0.2<Re<200• 0.1<Pr<10
Fluid transport properties across RPC
• Int. J. Heat and Fluid Flow 29, 315–326, 2008
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Heat transfer transport across RPC
• Navier-Stokes by DNS• 0.2<Re<200• 0.1<Pr<10
• J. Heat Transfer 130, 032602, 2008.• J. Heat Transfer, 132, 023305 1-9, 2010
''sf
sflm
dz z
z
sf
q Ah
T A
0.56 0.47Nu 1.56 0.6Re Pr
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CO2 Capture from Air
CaO + CO2 CaCO3calcination/carbonation
CO2-depleted air / CO2
atmospheric air
2
2
CO ,released
CO ,captured
n99%
n
Chem. Eng. J. 146, 244–248, 2009.
T=390 °C / 850°C
input 390 ppm
0 1000 2000 3000 4000 5000 60000
2000
4000
6000
8000
10000
12000
Time [sec]
CO
2[p
pm]
100
200
300
400
500
600
700
800
900
Temperature [°C
]
Cal
cina
tion
Cal
cina
tion
Cal
cina
tion
Cal
cina
tion
Cal
cina
tion
Car
bona
tion
Car
bona
tion
Car
bona
tion
Car
bona
tion
Car
bona
tion
850°C
390°C
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• Diamine-functionalized silica gel• CO2 adsorption from air at 25 °C and 1 bar• Pure CO2 desorption at 74-90 °C and 10-150 mbar
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Solar Energy
atmosphericair
adsorption
ConcentratedSolar EnergyConcentratedSolar Energy
oxidation
reduction
H2O
CO2-depletedair
liquid fuelsfor transportation
catalytic conversion
desorptionsyngasCO2
H2OCO2
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Jan WurzbacherChris GebaldRoman BaderGiw ZanganehClemens SuterMen WirzAnastasia StamatiouEmilie ZermattenJonathan ScheffePhilipp FurlerGilles MaagMichael KruesiIllias HischierWilly VillasmilPhilipp HaueterMatt RoesleTom CooperPeter LoutzenhiserDominic HerrmannEnrico GuglielminiNic Piatkowski
Tina DaumChristian Wieckert
Ivo AlxneitDaniel Mayer
Alwin FreiYvonne BauerleChristian Hutter
Peter SchallerTony Meier
Marc ChambonDaniel Wuillemin