Hydrogen production advances and perspectives

Ian S. MetcalfeProfessor of Chemical Engineering

School of Chemical Engineering and Advanced Materials

Newcastle University

i.metcalfe@ncl.ac.uk

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