Membrane for hydrogen purification stack and related developments

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1 Membrane for hydrogen purification stack and related developments Pr. Thierry BROUSSE Laboratoire de Génie des Matériaux et Procédés Associés, LGMPA- EA2664, Polytech-Nantes, Université de Nantes, rue Christian Pauc -BP 50609, Nantes, Cedex 3, France.

Location France - Region : Pays de la Loire (Loire Atlantique) Industrial area : ship building, aircraft industry, polymers for car industry Industrial

2 Location France - Region : Pays de la Loire (Loire Atlantique) Industrial area : ship building, aircraft industry, polymers for car industry Industrial centers of excellence : EMC2 (ensembles métalliques et composites complexes), véhicule haut de gamme, Scientific centers of excellence : materials science, energy,

3 Hydrogen in Région Pays de la Loire

Région Pays de la Loire : Mission H 2 Technical, economical and sociological developments of hydrogen based economy in the area Gathering industrial, technological and scientific forces

4 Région Pays de la Loire : Mission H 2 Technical, economical and sociological developments of hydrogen based economy in the area Gathering industrial, technological and scientific forces in the field of hydrogen Specificity : apply H 2 technology to ocean, seaside, rivers and canals Main projects : prototypes such as fishing ships and/or crossing riverboats (partner Semitan)

membranes, electrolysers (LGMPA) Fuel cell materials : SOFC (IMN, LGMPA) Fuel cell

5 Région Pays de la Loire : Different research labs working on H 2 Production : bioreactors for H 2 production (Seaweed, GEPEA), biomass (EMN), Purification : membranes, electrolysers (LGMPA) Fuel cell materials : SOFC (IMN, LGMPA) Fuel cell devices : water management (LTN) and also formation of students in these fields (Masters, PhD)

Group 11 leading French engineering schools :. Polytech Nantes 2000. Polytech Marseille 2001. Polytech Lille 2002. Polytech Orléans 2002. Polytech Tours 2002.

7 Group 11 leading French engineering schools :. Polytech Nantes Polytech Marseille Polytech Lille Polytech Orléans Polytech Tours Polytech Grenoble Polytech Montpellier Polytech Clermont-Ferrand (CUST) Polytech Nice-Sophia Polytech Paris-Université Pierre et Marie Curie Polytech Savoie 2006

8 Polyjoule project Students, professors and researchers from multidisciplinary areas (Lycée La Joliverie and Polytech Nantes) Build a vehicle equipped with a fuel cell able to ride the longest distance with the lowest energy amount Participation to the SHELL ECO MARATHON

9 SHELL ECO MARATHON (Nogaro( racing circuit) 1 st in 2007 with 2797 km using only the equivalent in H 2 of 1L of gazoline (fuel cell category) 2 nd in 2008 with 2830 km (fuel cell category)

10 LGMPA Laboratoire Génie G des Matériaux et Procédés s Associés (Polytech Nantes) (Materials engineering and related processes)

11 Why materials engineering at Polytech Nantes? Support to the school of engineering At the frontier between fundamental research / applied research / technological transfer

12 Mechanical properties Processes Thermal Engineering Materials Énergy Optical properties Geology Chemistry Biology

produced from existing energy sources (coal, oil, renewale energies, nuclear power

13 Hydrogen : energy vector An energy which can be carried and used a in a different place than where it is produced Energy vectors do not exist as natural energy but must be produced from existing energy sources (coal, oil, renewale energies, nuclear power plants, etc.)

14 But some requirements must be fulfilled Produce Électrolyseur GenHy 5m 3 /h Store

15 Carry Most important hydrogen pipeline network in northern Europe Source : Air Liquide Distribute

16 before using it

17 Different ways of producing on-site hydrogen, among which : Direct electrolysis of water Purified hydrogen from reforming reactors

Metallic hydrides / H 2 tank H 2 Stationary remote site (e.g.

18 Direct electrolysis of water : integrated systems (CETH) Renewable energy sources Transports (captive fleets) Pure H 2 and/or Hythane (H 2 /CH 4 mix) Wind H 2 fuel station H 2 Production H 2 storage Wind stator H 2 H 2 Photovoltaic Electrolyser GENHY Metallic hydrides / H 2 tank H 2 Stationary remote site (e.g. telecom towers) Power (electricity) or Combined Heat and Power (CHP) Technologies: Fuel cell ICE H 2 turbine H 2 Industrial hydrogen use Utilities (hydrogen used as electricity storage medium) Hythane (H 2 /CH 4 mix)

Electrolysers: developed by CETH since 2002 2002

partnership with Université d Orsay And Polytech

Nm 3 /h manual control prototype Proof of

atmospheric pressure Fully integrated 0,1 Nm 3

19 Electrolysers: developed by CETH since Development of MEA assembly through electroless and pulsed electrolysis, without precious metals, in partnership with Université d Orsay And Polytech Nantes Laboratory test of electrolysis First 0,1 Nm 3 /h manual control prototype Proof of concept at 36 bars Fully automated 0,5 Nm 3 /h atmospheric pressure Fully integrated 0,1 Nm 3 /h at 10 bars with H 2 purification Fully integrated 5 Nm 3 /h at 10 bars

20 Electrolysers A promising technology with still some performances to implement Challenges for coupling industrial/academic partners enhance the cycle life (avoid corrosion problems, play on materials engineering and architectures, etc.) improve electrolysis yields (decrease interface resistance, use of surface treatments, etc.)

21 Purified hydrogen from reforming reactors required metallic membranes Bio EtOH Reforming Stage H 2 CO X CO 2 X 700 C H 2 purification 600 C % Fuel cell C

22 Hydrogen purification stacks Pd membranes are currently used for hydrogen purification Molécule d hydrogène (1) Absorption (2) Dissociation Pd foils ( 20 µm) pinhole free (3) Diffusion Palladium Costs limitation for extended uses (4) Recombinai son (5) Dé sorption Gases mixture Pd alloy membrane Pure H 2 Porous Ni based substrate

23 Two strategies to reduce costs and improve efficiency Thin film membranes ( 5 µm) instead of foils ( 20 µm) Pd alloys such as PdAg and PdCu instead of pure Palladium Both strategies lead to palladium decrease in the membrane, so a direct impact on the total cost But in both cases, the membrane should be supported on a porous substrate Gases mixture Pd alloy membrane Pure H 2 Porous Ni based substrate

24 Architecture of the multi-layer layer filtration system 10 µm Need of materials engineering

25 Coupling a membrane and a PEM Fuel Cells ANR project (french national research agency) PANH program Serge Besse Eric Gernot Pierre Millet René Le Gall Arnaud Deschamps Awatef Hassini

Coupling a membrane and a PEMFC Purification membrane

coupling with synthetic gases Pile Hélion Raccordement

essais CETH Four de la Membrane CETH Eau générée par

26 Coupling a membrane and a PEMFC Purification membrane 60 g/h CETH PEM fuel cell 1 kw Hélion 200 hours coupling with synthetic gases Pile Hélion Raccordement : H 2 pur N 2 Evacuation humidité côté H 2 Banc d essais CETH Four de la Membrane CETH Eau générée par la pile Partie électrique et automatisation Acquisition de données

27 Purification membranes Efficient for coupling a reforming reactor and a device such as a PEMFC which does not tolerate impurities Progress can be made by tuning materials and architectures decrease the cost (use of alternative materials, monitor thin film architecture, etc.) improve performances (monitoring of gas flows, pressures, etc.)

28 Meeting the future Electrolysers and purification membrane stack bring pertinent answers to hydrogen production and purification Progresses can be made in different fields (economical, technological, etc.) Coupling in a European project Regions development policy, industrial products and R & D skills from academic partners help to meet nowadays requirements for hydrogen economy

29 Thank you for your attention Questions and comments? More informations : polyjoule.org polyjoule@univ-nantes.fr arnaud.deschamps@ceth.fr

Hydrogen & Renewable Energy

HELION HELION HYDROGEN POWER Hydrogen & Renewable Energy DERBI 2009 Conference, Perpignan, June 11th 2009 Jean-Christophe HOGUET HELION HELION Subsidiary of AREVA R, renewable energy Business Unit Wind