Mari-Ann Einarsrud

3. Mari-Ann Einarsrud

4. Mari-Ann Einarsrud Professor, Department of Chemistry, Norwegian University of Science and Technology, Trondheim, Norway

5. Mari-Ann Einarsrud Functional oxide materials for energy applications

6. High PO 2 Low PO 2 Functional oxide materials • Ionic conductor • Conducts oxide ions or protons • Mixed conductor • Conducts oxide ions/protons and electrons

7. Perovskite materials - ABO3 • Ionic or mixed conductivity tailored by • Oxygen non-stoichiometry giving ABO3-d • Chemical substitution • Materials based on La and alkaline earth on A-site and transition metal (Co and Fe) on B-site

8. Norwegian experience in the field • University of Oslo • Defect chemistry, structure and transport properties, superconductors, magnetic oxides, solid oxide fuel cells • Norwegian University of Science and Technology • Solid oxide fuel cells, electrochemical conversion of natural gas, superconductors • SINTEF and Norwegian industry • Solid oxide fuel cells (Norcell and Mjølner projects > $ 15 mill)

9. Norwegian challenges • Vast resources of natural gas • Remote to main users • Norwegian oil companies have access to gas fields in West Africa and the Middle East • Energy demanding and/or oxygen consuming industry • Chemical, refining, metallurgy, pulp and paper

10. Gas to liquid technology - GTL • Bringing natural gas to marked LPG Ethers Alcohols Syngas Fertilzer Acetyls Diesel Methanol Formal-dehyde Gasoline MTBE Fuels Ammonia Hydrogen Chemicals • Requirements • No NOx emission • Low CO2 emission

11. Energy applications • Oxide ceramic membrane technology • Production of liquid energy carriers and chemicals • Oxygen generation • Low emission CO2 power generation • H2 technology • CO2 separation • Sensors for detectionof CO, CO2, H2, NOx, etc • Solid oxide fuel cells • Current research activity low • Pilot plant at Kolsnes (Siemens-Westinghouse, Norske Shell A/S, FMC Kongsberg, NTNU and SINTEF)

12. Oxide ceramic membrane technology Air • Dense membranes • O2 permeable (oxide ion conductors) • H2 permeable (proton conductors) • Electically driven • Mixed conductor type • Microporous oxide membranes O2 + 4e- 2O2- 2O2- O2 + 4e- Oxygen High pressure Air O2 + 4e- 2O2- 2O2- O2 + 4e- Low pressure Oxygen

13. O product 2 Dense oxygen permeable membranes- Mixed conductors • Chemical potential driven • Pressure driven • Infinite O2 selectivity • High temperature operation (approximately 800°C) High pressure air Reaction Product Air

14. Applications of dense oxygen permeable membranes • Production of synthesis gas (CO and H2) from natural gas - intermediate to GTL • Combined technology: partial oxidation of natural gas and steam reforming • Co-generation of electric power and steam by using non-permeate CH4 + ½ O2  CO + 2H2 CH4 + H2O  CO + 3H2 Syngas Oxygen-Depleted Air Oxidizing Atmosphere Reducing atmosphere Air Natural Gas Stream OxygenReductionCatalyst Reforming Catalyst Membrane

15. Impact of membrane technology on GTL Conventional Process Reformer Oxygen Plant Fisher-Tropsch Reactor Separation /Upgrading Liquid Products Air Nat. Gas / Steam 30 % 15 % 30% 25 % CAPITAL INVESTMENT Ceramic Membrane Process Fisher-Tropsch Reactor Syngas Reactor Separation /Upgrading Air Liquid Products Nat. Gas / Steam

16. CH CO 4 2 Impact of membrane technology on environment • Low green house gas emissions • No NOx emission Liquid Fuels Natural Gas Synthesis Gas Greenhouse Gas Emissions Conventional Syngas Ceramic Membrane Syngas Net Process Yield

17. Applications of dense oxygen permeable membranes • Generation of oxygen gas • Energy efficient process industry, combustion processes (no NOx + less CO2) • Special applications: fish farms, medical applications, welding, etc. • Environmental clean-up technologies • Generation of N2 gas • Co-generation of electric power and steam

18. 2 I /(sccm/cm min) 02 SrFe Co O T = 1000 °C 1-x x 3-d (1/L)/(m ) - -1 Material requirements 2mm 0.67mm 0.4mm 1mm 0.5mm • High oxygen flux • Chemical stability • Chemical compatibility • Catalytic compatibilityand activity • Cost 6 5 x = 0.67 x = 0.33 x = 0 4 3 2 1 0 0.5 1 1.5 2 2.5

19. Pure O product 2 Processing/design requirements Air ~ 800 °C • Thin dense layer on porous substrate • Gas tight sealing • High strength and reliability • Chemical expansion/stresses

20. pO low 2 Chemical expansion/stresses • Expansion produces stresses in O2 pressure gradient  Air Air Air Tension Compression

21. Membrane processing • Powder synthesis • Tube forming • Sintering • Sealing

22. High TemperatureSolid State Proton Conductors • Applications • Fuel cells • Dehydrogenation pumps • Steam electrolyzers • Sensors (H2O, H2) • Intermediate temperature challenge • Materials • Perovskites, e.g. BaCeO3 • Phosphates, e.g. LaPO4

23. CH 4 N H O + N 2 2 2 2 CD + H + CO + H O CD + H + CO + H O 2 2 2 2 2 2 Mixed proton - electron conductors • Hydrogen separation membranes • Natural gas to Syngas • Hydrogen extraction • Integrated design • Status (Argonne): • 5 mln/min/cm2 • Materials: Perovskites Partial oxidation Syngas Dehydrogenated syngas Hydrogen extraction

24. Microporous membranes • Sol-gel prepared thin microporous membranes with carefully controlled thickness and pore size • Separation of H2 from syn gas • CO2 separation and adsorption

25. Summary Functional oxide materials are crucial in the development of new environmental friendly technologies for energy production and utilization Dense oxygen or hydrogen permeable membranes Solid oxide fuel cells Sensors Microporous membranes