chemical production of hydrogen with in- situ separation · 2015. 9. 21. · a. murugan, a....
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Chemical production of hydrogen with in-
situ separation
Ian S. Metcalfe
Professor of Chemical Engineering
Newcastle University
21 May 2013
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Introduction
Uses of hydrogen
How is hydrogen made
Process intensification
Gas solid reactions, simultaneous reaction and separation
and ‘breaking’ equilibrium
Membranes
Chemical looping
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Ammonia production
Fuel upgrading (HDS, HDN and
hydrocracking)
Hydrogenation of fats in the food industry
Hydrogen as a fuel is not a significant use
If you produce and sell hydrogen it will not
be used as a fuel
Uses of hydrogen
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Uses
Hot air balloons
Light Fuel
Agriculture
Hydrogenation
Fuel cell
Conventional Method (steam methane reforming)
CH4 + H2O 3 H2 + CO
CO + H2O H2 + CO2
Steam reforming
700 – 1100oC, Ni catalyst
Water gas shift
350oC, Fe catalyst 200oC, Cu catalyst
H2 + CO2 PSA H2
CO2 Energy intensive, very expensive, PSA separation. Cost increases with required purity.
2
Introduction | Steam-Iron Process | Thermodynamics | Materials | Results | Future Work
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Hydrogen production
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5× (CH4 + 2H2O = CO2 + 4H2) ΔHR0 = ~+850 kJ/mol
CH4 + 2O2 = CO2 + 2H2O ΔHR0 = ~-890 kJ/mol
6CH4 + 2O2 + 8H2O = 6CO2 + 20H2 Autothermal
Not far off
CH4 + 0.5O2 + H2O = CO2 + 3H2
Energy balance
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Improved selectivity of reforming (avoid carbon deposition
and loss of catalyst activity). Modifying Ni catalysts.
Partial oxidation instead of reforming – remove need for
heat transfer (capital cost of plant depends on heat transfer
load and reformers are heat transfer limited NOT kinetically
limited). Involves air separation.
New processes involving reaction and separation –
dynamic or membrane processes.
Processes to ‘break’ equilibrium for WGS (also allows
higher temperatures to be used). LT WGS catalysts are not
suitable for distributed processes due to slow kinetics.
Catalytic reaction engineering challenges
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Produce hydrogen from dissociation of water
H2 O
Use of a reduced solid surface for the dissociation
of water and production of hydrogen:
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Produce hydrogen from dissociation of water
CO
O
CO2
Use of a reduced solid surface for the dissociation
of water and production of hydrogen:
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Produce hydrogen from dissociation of water
H2 O
CO CO2
Use of a reduced solid surface for the dissociation
of water and production of hydrogen:
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Water-gas shift reaction thermodynamics
CO + H2O = CO2 + H2
ΔHR0 (25C) = -41 kJ/mol
ΔGR0 (810C) = 0 kJ/mol
OHCO
HCO
PP
PPK
RT
GK
2
22
0
ln
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Virtual
oxygen
chemical
potential
Equilibrium
Batch operation
Time
2
2
H
OH
P
P
2CO
CO
P
P
CO + H2O = CO2 + H2
H2O
CO CO2, CO
H2, H2O
WGS thermodynamics – batch operation
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Membrane-based WGS
Virtual
oxygen
chemical
potential
Equilibrium
Co-current operation
Length
2
2
H
OH
P
P
2CO
CO
P
P
CO + H2O = CO2 + H2
H2O
CO CO2, CO
H2, H2O
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Membrane-based WGS
Virtual
oxygen
chemical
potential
Counter-current operation
Length
2
2
H
OH
P
P
2CO
CO
P
P
CO + H2O = CO2 + H2
H2, H2O
CO CO2, CO
H2O
No equilibrium limitation
Smaller driving forces for
permeation
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Chemical looping WGS
CO + H2O = CO2 + H2
CO2 CO
H2O H2
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Materials
ceramic of choice : perovskite (mineral CaTiO3)
general formula ABO3 (A+2B+4O3 or A+3B+3O3)
Ca2+ / large cation e.g., La, Sr
lattice O2- anion
Ti4+ / small cation e.g., Co, Fe
lattice O2- anion vacancy
A
B
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H2O H2
membrane
CH4
CO 2H2
O2-
2h+
O
Hydrogen production from SMR
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Microtubular membranes
LSCF (La0.6 Sr0.4 Co0.2 Fe0.8 O3-δ)
Supplied by Kang Li of Imperial College
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Membrane-based steam reforming – LSCF 900°C
CH4 (5%) – 20ml(STP)min-1
H2O (7.2%) – 20ml(STP)min-1 H2O ⇆ O + H2 H2
O2- CO,H2
T = 900°C
0 100 200 3000.0
0.2
0.4
0.6
0.8
1.0
Mo
le fra
ctio
n / %
Time / hours
H2
CH4
CH4 off
R.V. Franca, A. Thursfield and I. S.
Metcalfe, ‘La0.6Sr0.4Co0.2Fe0.8O3
microtubular membranes for hydrogen
production from water splitting’ J.
Membrane Sci. 389 (2012) 173– 181.
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Introduction | Steam-Iron Process | Thermodynamics | Materials | Results | Future Work
Process invented in 1907 Requires no separation step High Purity H2
Cyclic Process
Steam-Iron Process (using natural gas reducing feed)
Fe
Fe3O4
CO
CO2
H2O
H2
STEAM-
IRON
CYCLE
3
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Baur-Glaessner phase diagram
M. F. Bleeker, S. R. A. Kersten and H. J. Veringa, Catalysis Today, 2007, 127, 278-290.
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CO2
O2- 2h+
Chemical looping WGS
H2 O H2O
O2- 2h+
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CO2
O2- 2h+
O2- 2h+
CO
CO2
Chemical looping WGS
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La0.7Sr0.3FeO3-δ (LSF731) oxygen deficiency (δ) in relation to pH2O/pH2
850oC
A. Murugan, A. Thursfield and I. S.
Metcalfe, ‘A chemical looping process
for hydrogen production using iron-
containing perovskites’ Energy Environ.
Sci. 4(11) (2011) 4639-4649
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Fe60 behaviour
1st (solid line) and 150th (dashed line) isothermal chemical looping WGS cycles recorded at 850oC for 50 mg of (c) Fe60, reduction in carbon monoxide (d) Fe60, reoxidation in water. Arrows indicate oxidation state changes of iron in Fe60 according to thermodynamic studies.
Fixed bed microreactor
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LSF731 behaviour
1st (solid line) and 150th (dashed line) isothermal chemical looping WGS cycles recorded at 850oC for 50 mg of (a) LSF731, reduction in carbon monoxide (b) LSF731, reoxidation in water. Arrows indicate oxidation state changes of iron in Fe60 according to thermodynamic studies.
Fixed bed microreactor
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Cycling of LSF731 and iron oxide
Molar production (with error bars) during isothermal cycling at 850oC for 50 mg of (a) LSF731, reduction in carbon monoxide (b) LSF731, reoxidation in water, (c) and (d) are for iron oxide.
A. Murugan, A. Thursfield and I. S.
Metcalfe, ‘A chemical looping
process for hydrogen production
using iron-containing perovskites’
Energy Environ. Sci. 4(11) (2011)
4639-4649
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Uses of hydrogen
How is hydrogen made
Process intensification
Gas solid reactions, simultaneous reaction and separation
and ‘breaking’ equilibrium
Membranes
Chemical looping
Conclusion
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Dr Alan Thursfield, Dr Arul Murugan, Dr Danai Poulidi,
Dr Cristina Dueso, Dr Anne Huber, Dr Rafael Vilar
Franca, Ms Claire Thompson, Dr Walairat Suksamai,
Hang Qi
EPSRC for funding under the SUPERGEN
programme and PLATFORM grant, ERC Advanced
Grant
Professor Kang Li, Imperial College
http://research.ncl.ac.uk/appcat/
Acknowledgements
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References
Tan, X., Li, K., Thursfield, A., Metcalfe. I. S., ‘Oxyfuel combustion using a catalytic ceramic
membrane reactor’, Catalysis Today 131 (2008) 292–304.
R.V. Franca, A. Thursfield and I. S. Metcalfe, ‘La0.6Sr0.4Co0.2Fe0.8O3 microtubular membranes
for hydrogen production from water splitting’ J. Membrane Sci. 389 (2012) 173– 181.
A. M. Kierzkowska, C. D. Bohn, S. A. Scott, J. P. Cleeton, J. S. Dennis and C. R. Muller, Ind.
Eng. Chem. Res., 2010, 49, 5383–5391.
A. Murugan, A. Thursfield and I. S. Metcalfe, ‘A chemical looping process for hydrogen
production using iron-containing perovskites’ Energy Environ. Sci. 4(11) (2011) 4639-4649
Alan Thursfield, Arul Murugan, Rafael Franca and Ian S. Metcalfe, ‘'Chemical looping and
oxygen permeable ceramic membranes for hydrogen production – A review'’, Energy
Environ. Sci. 5(6) (2012) 7421-7459
http://research.ncl.ac.uk/appcat/
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