hydrogen production advances and perspectives...hydrogen production advances and perspectives ian s....
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Hydrogen production advances and perspectives
Ian S. MetcalfeProfessor of Chemical Engineering
School of Chemical Engineering and Advanced Materials
Newcastle University
31 January 2019
Fossil fuels important in any transition to a low-carbon fuel economy
In this WP we were not working on electrolysis or biological routes to hydrogen
But we must be able to do things better. Smaller, faster, cheaper and of course CCS
Scope
Most commonly steam reforming of e.g. naptha, natural gas or gasification of coal
Use methane (natural gas) as an example feedstock
Natural gas reforming, shift and CCS in integrated processes
Hydrogen production is not the difficult bit – separation and CCS
Scope
Here we select natural gas, methane, for illustrative purposes (reactions are high temperature because of stability of methane molecule)
CH4 + H2O = CO + 3H2 ΔHR0 = ~+210 kJ/mol
CH4 + 2H2O = CO2 + 4H2 ΔHR0 = ~+170 kJ/mol
CH4 + 0.5 O2 = CO + 2H2 ΔHR0 = ~-35 kJ/mol
CH4 + CO2 = 2CO + 2H2 ΔHR0 = ~+250 kJ/mol
CH4 = C + 2H2 ΔHR0 = ~+75 kJ/mol
CH4 + 2O2 = CO2 + 2H2O ΔHR0 = ~-890 kJ/mol
CH4 = 1.5H2 + 1/6 C6H6 ΔHR0 = ~+15 kJ/mol
Also
H2O + CO = CO2 + H2 ΔHR0 = -41 kJ/mol
Key reactions of methane
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
Uses
Hot air balloons
LightFuel
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 catalyst200oC, Cu catalyst
H2 + CO2PSA H2
CO2Energy intensive, very expensive, PSA separation.Cost increases with required purity.
2
Introduction | Steam-Iron Process | Thermodynamics | Materials | Results | Future Work
Hydrogen production
Low mole fraction CO2 in nitrogen
etc.
Steam methane reforming is endothermic so operation at lower temperature is attractive because of energy integration advantages
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) – needs air separation
WGS is equilibrium limited at high temperature. So clever ways to overcome equilibrium limitation and perform reaction and separation – membrane processes or dynamic processes
Reaction engineering challenges
Catalysts – low temperature reforming
J. Callison, N.D. Subramanian, S.M. Rogers, A. Chutia, D. Gianolio, C.R.A. Catlow, P.P. Wells, N. Dimitratos,
Directed aqueous-phase reforming of glycerol through tailored platinum nanoparticles, Applied Catalysis B: Environmental, Volume 238, 2018, 618-628
How can you get around equilibrium?
Reaction and separation
CO + H2O = CO2 + H2
Water-gas shift reaction thermodynamics
Hydrogen permeable membrane-based WGS
H2 OCO CO2
Hydrogen permeable e.g. Pd membranes
Breaks WGS equilibrium and allows higher temperature reaction
Al-Mufachi, N.A. & Rees, N.V. & Steinberger-Wilkens, R., 2015.
"Hydrogen selective membranes: A review of palladium-based dense metal
membranes," Renewable and Sustainable Energy Reviews, Elsevier,
vol. 47(C), pages 540-551.
Hydrogen permeable membrane-based WGS
40 Nm3 /h membrane reformer with product hydrogen purity of over 99.99%
Tokyo Gas et al, WHEC 16 / 13-16 June2006 – Lyon France
In situ hydrogen separation allows temperature reduction to 500 to 550°C in the membrane reformer
Dynamic processes for reaction and separation
Dynamic processes for separation
F.R. García-García, M. León, S. Ordóñez, K. Li
Studies on water–gas-shift enhanced by adsorption and membrane permeation
Catalysis Today, Volume 236, Part A, 2014, 57–63
Dynamic processes for reaction and separation
CO + H2O = CO2 + H2
Dynamic processes for reaction and separation
Sorption enhanced reactor.
F.R. García-García, M. León, S. Ordóñez, K. Li
Studies on water–gas-shift enhanced by adsorption and membrane permeation
Catalysis Today, Volume 236, Part A, 2014, 57–63
Traditional fixed-bed reactor.
Introduction | Steam-Iron Process | Thermodynamics | Materials | Results | Future Work
Process invented in 1907
Cyclic Process
Steam-Iron Process
Fe
Fe3O4
CO, H2
CO2, H2O
H2O
H2
STEAM-IRON
CYCLEA. Murugan, A. Thursfield and I. S.
Metcalfe, Energy Environ. Sci. 4(11) (2011) 4639-4649.
Concept
Water-gas shift reaction: CO + H2O ⇌ CO2 + H2
Oxidising agent: H2O
Product: H2
Product: CO2
Reducing agent: CO
Gradual OXIDATION of bed
Gradual REDUCTION of bed
Newcastle University, Patent WO 2017006121 A1
Hydrogen production
CL replaces:
Integral reactor set-up
Integral reactor set-up
Integral reactor set-up
Packed bed reactor operating at 800°C• 2.2 g LSFM6437 + 0.4 g yttria (80 to 160 μm). Feed duration 3
minutes.
Bed length 10 cm
Quartz plug
Summary – technical challenges for intensified hydrogen production
Role for intensified natural gas reforming, shift, separation and CCS in any energy transition
Lower temperature reforming is attractive because of energy integration advantages
Partial oxidation – needs integrated air separation
WGS and reforming with reaction and separation
Dynamic processes and membranes
Single CL reactor for reforming and shift
Oxidising agent: 3H2O
Product: 3H2
Product: 2H2O,CO2
Reducing agent: CH4
Gradual OXIDATION of bed
Gradual REDUCTION of bed
Oxidising agent: air
Product: oxygen depleted air
Gradual OXIDATION of bed
Reforming and shift combined:CH4 + 3H2O + 0.5 O2 ⇌ CO2 + 2H2O + 3H2
BEIS Hydrogen Supply Programme
£20M BEIS HYDROGEN SUPPLY PROGRAMME Phase 1 – Feasibility (£5m)Phase 2 – Pilot demonstration (£15m)
The programme will take a portfolio approach to funding and aims to fund a range of different solutions which could include:
Fossil fuel reformation with carbon captureOffshore productionElectrolysisBiohydrogenImport opportunitiesStorage of hydrogen
Future
Plenty of scope for continued innovation in hydrogen production
Dr W. Hu, Dr E. I. Papaioannou, Dr D. Neagu, Dr K. Kousi, C. de Leeuwe, S. Ungut, L. Bekris, Dr Brian Ray, Dr Alan Thursfield, Dr Arul Murugan, Dr Danai
Poulidi, Dr Cristina Dueso, Dr Claire Thompson, Professor John Evans (Durham), Dr Francisco Garcia
Garcia (Edinburgh), Dr Catherine Dejoie (ESRF, Grenoble)
EPSRC for funding under the SUPERGEN programme
Professor Paul Shearing, UCL
https://research.ncl.ac.uk/iontransport/
Acknowledgements
END