Achievements of the SuperGen DoSH 2 Project John TS Irvine Birmingham 18/10/11

xxxxation Title To Go Here Hydrogen Production

xxxxation Title To Go Here Current Hydrogen Production

xxxxation Title To Go Here Energy Devolution

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

WP1 H 2 from carbonaceous sources Ian Metcalfe Combined reaction and separation using:  Membranes  Periodic reactor operation

chemical looping membrane operation redox cycling H2OH2O H2H2 CO 2 CO ABO 3 ABO 3 -  periodic reduction/oxidation steps continuous process Advantages of both processes: feed gases do not mix high purity H 2 possible no down stream separation required CH 4 H2OH2O H 2 O ⇆ O + H 2 H2H2 Syngas O 2- gas feeds and products separated in timegas feeds and products separated in space hollow fibre membrane Perovskite oxygen carriers for hydrogen production from two processes x-section CH 4 + H 2 O CO + 3H 2 CO + H 2 O CO 2 + H 2 water-gas-shiftsteam reforming of methane

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. membrane operation chemical looping CH 4 + H 2 O CO + 3H 2 CO + H 2 O CO 2 + H 2 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. background levels of CO and CO o C 900 o C

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. Low Temperature Plasma-Catalysis for Hydrogen Production from Methane

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

Warwick (Martin Wills) 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. Staff key: PDRA David Morris: DJM PhD Tarn Johnson: TCJ

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). Two patent applications submitted (15/09/11)and now entering PCT phase. The above TB-PIM combines: High molecular mass (M w >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 m 2 g -1 ) Particularly selective for H 2 in mixture of H 2 /N 2 or H 2 /CH 4 (Note: data lie above Robeson upper bound in plots of permeability vs selectivity) For example:

xxxxation Title To Go Here Hydrogen from Biomass and Waste From Ethanol SUPERGEN DOSH 2 : Delivery of Sustainable Hydrogen

xxxxation Title To Go Here Membranes and Separation Ceramic Metal SUPERGEN DOSH 2 : Delivery of Sustainable Hydrogen

WP 2 H 2 from electrons John Irvine

Current-voltage (I-V) (2-electrode) 47% H 2 O / 53% N 2 | 900 °C | Conditioning: V, 2-5 min | Start potential: V | End potential: V | Scan rate: 10 mV s -1 B-site doping acted to significantly lower the steam electrolysis onset potential CompositionOnset potential (V) La 0.4 Sr 0.4 TiO La 0.4 Sr 0.4 Ni 0.06 Ti 0.94 O La 0.4 Sr 0.4 Fe 0.06 Ti 0.94 O La 0.4 Sr 0.4 TiO 3 La 0.4 Sr 0.4 Ni 0.06 Ti 0.94 O 2.94 La 0.4 Sr 0.4 Fe 0.06 Ti 0.94 O 2.97

Current-voltage (I-V) (2-electrode) 47% H 2 O / 53% N 2 | 900 °C | Conditioning: V, 2-5 min | Start potential: V | End potential: V | Scan rate: 10 mV s -1 B-site doping acted to significantly lower the steam electrolysis onset potential CompositionOnset potential (V) La 0.4 Sr 0.4 TiO La 0.4 Sr 0.4 Ni 0.06 Ti 0.94 O La 0.4 Sr 0.4 Fe 0.06 Ti 0.94 O La 0.4 Sr 0.4 TiO 3 La 0.4 Sr 0.4 Ni 0.06 Ti 0.94 O 2.94 La 0.4 Sr 0.4 Fe 0.06 Ti 0.94 O 2.97

xxxxation Title To Go Here V V V Polarization for CO 2 electrolysis at 900 o C Polarization resistance (Ω cm 2 ) CO 2 /CO ratio Ni/YS Z LSCM/ GDC LSCM/ GDC-1% Ni GDC impregnated LSCM 0.5Pd-GDC co- impregnated LSCM 90/ / /

xxxxation Title To Go Here Electrolysis Liquifaction SUPERGEN DOSH 2 : Delivery of Sustainable Hydrogen

xxxxation Title To Go Here SUPERGEN DOSH 2 : Delivery of Sustainable Hydrogen Ammonia Production Sociotechnical aspects

WP 3 Sociotechnical economics Malcolm Eames

ICEPT Techno-economic analysis Overview of research outputs to date Demand analysis of H 2 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 H 2 fuel cell urban buses”, In preparation London case study – H 2 from waste – “Assessing the role of H 2 from waste in developing sustainable H 2 infrastructures: a London case study” In preparation H 2 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 – “H 2 from biomass: spatially explicit modelling can improve infrastructure decision-making” Submitted to Int J Hydrogen Energy

xxxxation Title To Go Here 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 CO 2 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 CO 2 Capture Converting hydrocarbons to H 2 and CO 2 or rather than sequestering CO 2, hydrogen can be utilised to capture CO 2 to produce chemical feedstocks, fertilisers or liquid fuels.

xxxxation Title To Go Here SUPERGEN DOSH 2 : Delivery of Sustainable Hydrogen