Achievements of the SuperGen DoSH 2 Project

1. John TS Irvine Birmingham 18/10/11 Achievements of the SuperGen DoSH2 Project

2. Hydrogen Production

3. Current Hydrogen Production

4. Energy Devolution

5. 12 Universities £5M 71 man-years 6 PhD Students and 500 researcher months

6. WP1 H2 from carbonaceous sources Ian Metcalfe Combined reaction and separation using: • Membranes • Periodic reactor operation

7. Perovskite oxygen carriers for hydrogen production from two processes water-gas-shift steam reforming of methane CO + H2O CO2 + H2 CH4 + H2O CO + 3H2 chemical looping membrane operation periodic reduction/oxidation steps continuous process CO gas feeds and products separated in time gas feeds and products separated in space CO2 H2O ⇆ O+ H2 H2O H2 ABO3-d O2- CH4 Syngas redox cycling ABO3 hollow fibre membrane • Advantages of both processes: • feed gases do not mix • high purity H2 possible • no down stream separation required x-section H2 H2O

8. CO + H2O CO2 + H2 membrane operation CH4 + H2O chemical looping CO + 3H2 850oC 900oC background levels of CO and CO2 Example results: Products as a function of cycle number. Plotted are the products from the water-splitting phase. High purity hydrogen is produced. We have done over 170 cycles, the most reported to date. Example results: Products as a function of time. Plotted together are the products from the water-splitting side and the methane oxidation side. Syngas and hydrogen are produced; overall we have steam reforming. Continuous operation for over 400 hours is the longest reported to date for this process.

9. Low Temperature Plasma-Catalysis for Hydrogen Production from Methane Researchers in Manchester have developed a novel and promising technology – plasma-catalysis, for highly-efficient conversion of methane (in the form of biogas or landfill gas) into hydrogen and other value-added chemicals (carbon nanomaterials, oxygenates, etc). This process combines the advantages of fast and low temperature reaction from nonthermal plasma and high selectivity from catalysis. The physical and chemical interactions between the plasma and catalyst can generate a synergistic effect, which provides a unique way to separate the activation steps from the selective reactions at low temperatures. Plasma can also reduce and activate supported metal catalysts, enhancing metal dispersion on the catalyst surface and catalyst stability, which opens a new route for catalyst treatment at low temperatures.

10. Warwick (Martin Wills) Staff key: PDRA David Morris: DJM PhD Tarn Johnson: TCJ WP 1.1 (Formation of hydrogen from alcohols) – work by TCJ. (i) The application of iron-based cyclone catalysts to the synthesis of methanol, ethanol and isopropanol from large alcohols commonly found in biomass. Catalysts below: Used in oxidation of alcohols (below): and for alcohol formylation (right): Catalysts below: Used in asymmetric reduction of ketones: (ii) Encapsulation of catalysts in a PIM membrane, and is testing in hydrogen transfer; open to return to in future (Cardiff/Warwick collaboration). (iii) Synthesis of di-iron complexes for electrochemical hydrogen generation; subject of ongoing studies with Prof P. R. Unwin (Warwick).

11. Warwick (Martin Wills) Staff key: PDRA David Morris: DJM PhD Tarn Johnson: TCJ WP 1.1 (Formation of hydrogen from alcohols) – work by DJM. Formation of hydrogen from alcohols using light-promoted process on inorganic support. Hydrogen gas measurement by gas chromatography. Good progress has been made towards a synthetic catalysis system, as shown below: DJM has now left the HDel project to take up a position elsewhere; this work will be continued when a second PDRA is appointed at Warwick.

12. Amine-containing Polymers of Intrinsic Microporosity (PIMs) Mariolino Carta, Neil B. McKeown, Cardiff University (Chemistry). PIMs provide microporous materials due to the rigid and contorted structure of the polymer. We have found that Tröger’s base (TB) formation can be used as a polymerisation reaction starting from an aromatic diamine. This is a new way of making polymers (although the reaction was first reported in 1887). For example: • The above TB-PIM combines: • High molecular mass (Mw >100,000 g mol-1 by GPC) • Solubility in common solvents (e.g. chloroform, THF) and good film formation. • High apparent surface area (BET = 1000 m2 g-1) • Particularly selective for H2 in mixture of H2/N2 or H2/CH4 • (Note: data lie above Robeson upper bound in plots of permeability vs selectivity) Two patent applications submitted (15/09/11)and now entering PCT phase.

13. SUPERGEN DOSH2:Delivery of Sustainable Hydrogen Hydrogen from Biomass and Waste From Ethanol

14. SUPERGEN DOSH2:Delivery of Sustainable Hydrogen Membranes and Separation Ceramic Metal

15. WP 2 H2 from electrons John Irvine

16. Current-voltage (I-V) (2-electrode) 47% H2O / 53% N2 |900 °C |Conditioning: - 1.7 V, 2-5 min | Start potential: - 1.7 V | End potential: - 0.4 V | Scan rate: 10 mV s-1 La0.4Sr0.4TiO3 La0.4Sr0.4Ni0.06Ti0.94O2.94 La0.4Sr0.4Fe0.06Ti0.94O2.97 • B-site doping acted to significantly lower the steam electrolysis onset potential

17. Current-voltage (I-V) (2-electrode) 47% H2O / 53% N2 |900 °C |Conditioning: - 1.7 V, 2-5 min | Start potential: - 1.7 V | End potential: - 0.4 V | Scan rate: 10 mV s-1 La0.4Sr0.4TiO3 La0.4Sr0.4Ni0.06Ti0.94O2.94 La0.4Sr0.4Fe0.06Ti0.94O2.97 • B-site doping acted to significantly lower the steam electrolysis onset potential

18. Polarization for CO2 electrolysis at 900oC 0.706 V 0.849 V 0.169 V • 1 wt% Pd-GDC co-impregnated LSCM cathode

19. SUPERGEN DOSH2:Delivery of Sustainable Hydrogen Electrolysis Liquifaction

20. SUPERGEN DOSH2:Delivery of Sustainable Hydrogen Ammonia Production Sociotechnical aspects

21. WP 3 Sociotechnical economics Malcolm Eames

22. ICEPT Techno-economic analysisOverview of research outputs to date • Demand analysis of H2 as transport fuel • “Battery electric vehicles, hydrogen fuel cells and biofuels. Which will be the winner?” Energy Environ. Sci., 2011, 4 (10), 3754 – 3772 • “An analysis of the market for H2 fuel cell urban buses”, In preparation • London case study – H2 from waste • “Assessing the role of H2 from waste in developing sustainable H2 infrastructures: a London case study” In preparation • H2 for energy storage and UK-wide infrastructure • “The role of large scale storage in a GB low carbon energy future: issues and policy challenges” Energy Policy 39 (2011) 4807–4815 • “H2from biomass: spatially explicit modelling can improve infrastructure decision-making” Submitted to Int J Hydrogen Energy

23. Key Themes going forward Energy Storage to address intermittency • Hydrogen can extend use of renewable or even nuclear electricity through storage. Excess power could be utilised for transport or chemicals moving renewable electricity to equally important sectors for CO2 reduction, i.e. transport and chemicals. Hydrogen for transport • Hydrogen/fuel cell vehicles are a type of electric transport closely linked with batteries. They offer range extension, long distance vehicles and greater payload. This can offer decentralised, largely self-contained energy systems with enhanced security. Hydrogen in CO2 Capture • Converting hydrocarbons to H2 and CO2 or rather than sequestering CO2, hydrogen can be utilised to capture CO2 to produce chemical feedstocks, fertilisers or liquid fuels.

24. SUPERGEN DOSH2:Delivery of Sustainable Hydrogen