Science and Technology Seminars in Tokyo March 27 th 2001

Mari-Ann Einarsrud

Science and Technology Seminars in Tokyo March 27 th 2001 Mari-Ann Einarsrud Professor, Department of Chemistry, Norwegian University of Science and Technology, Trondheim, Norway

Science and Technology Seminars in Tokyo March 27 th 2001 Mari-Ann Einarsrud Functional oxide materials for energy applications

Science and Technology Seminars in Tokyo March 27 th 2001 Functional oxide materials Ionic conductor Conducts oxide ions or protons Mixed conductor Conducts oxide ions/protons and electrons High PO 2 Low PO 2

Science and Technology Seminars in Tokyo March 27 th 2001 Perovskite materials - ABO 3 Ionic or mixed conductivity tailored by Oxygen non-stoichiometry giving ABO 3-  Chemical substitution Materials based on La and alkaline earth on A-site and transition metal (Co and Fe) on B-site

Science and Technology Seminars in Tokyo March 27 th 2001 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)

Science and Technology Seminars in Tokyo March 27 th 2001 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

Science and Technology Seminars in Tokyo March 27 th 2001 Gas to liquid technology - GTL Bringing natural gas to marked Requirements No NO x emission Low CO 2 emission Ethers LPG Alcohols Gasoline Diesel Syngas Fuels Fertilzer Methanol MTBE Hydrogen Ammonia Formal- dehyde Acetyls Chemicals

Science and Technology Seminars in Tokyo March 27 th 2001 Energy applications Oxide ceramic membrane technology Production of liquid energy carriers and chemicals Oxygen generation Low emission CO 2 power generation H 2 technology CO 2 separation Sensors for detection of CO, CO 2, H 2, 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)

Science and Technology Seminars in Tokyo March 27 th 2001 Oxide ceramic membrane technology Dense membranes O 2 permeable (oxide ion conductors) H 2 permeable (proton conductors) Electically driven Mixed conductor type Microporous oxide membranes High pressure Air Low pressure Oxygen Oxygen Air O 2 + 4e -  2O 2- 2O 2-  O 2 + 4e - O 2 + 4e -  2O 2- 2O 2-  O 2 + 4e -

Science and Technology Seminars in Tokyo March 27 th 2001 Dense oxygen permeable membranes - Mixed conductors Chemical potential driven Pressure driven Infinite O 2 selectivity High temperature operation (approximately 800°C) High pressure air Air O product 2 Reaction Product

Science and Technology Seminars in Tokyo March 27 th 2001 Applications of dense oxygen permeable membranes Production of synthesis gas (CO and H 2 ) 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 Syngas Reducing atmosphere Oxygen-Depleted Air Air Oxygen Reduction Catalyst Oxidizing Atmosphere Natural Gas Stream Reforming Catalyst Membrane CH 4 + ½ O 2  CO + 2H 2 CH 4 + H 2 O  CO + 3H 2

Science and Technology Seminars in Tokyo March 27 th 2001 Impact of membrane technology on GTL Oxygen Plant Reformer Fisher-Tropsch Reactor Separation / Upgrading Syngas Reactor Fisher-Tropsch Reactor Separation / Upgrading Conventional Process AirNat. Gas / Steam Liquid Products 15 % 25 % 30 % Ceramic Membrane Process Air Nat. Gas / Steam Liquid Products CAPITAL INVESTMENT

Science and Technology Seminars in Tokyo March 27 th 2001 Impact of membrane technology on environment Low green house gas emissions No NO x emission CH 4 CO 2 Conventional Syngas Ceramic Membrane Syngas Greenhouse Gas Emissions Natural Gas Synthesis Gas Liquid Fuels Net Process Yield

Science and Technology Seminars in Tokyo March 27 th 2001 Applications of dense oxygen permeable membranes Generation of oxygen gas Energy efficient process industry, combustion processes (no NOx + less CO 2 ) Special applications: fish farms, medical applications, welding, etc. Environmental clean-up technologies Generation of N 2 gas Co-generation of electric power and steam

Science and Technology Seminars in Tokyo March 27 th 2001 Material requirements High oxygen flux Chemical stability Chemical compatibility Catalytic compatibility and activity Cost x = 0.67 x = 0.33 x = 0 SrFe Co O T = 1000 °C 1-xx3-d mm0.67mm0.4mm 1mm0.5mm I /(sccm/cm min) 02 2 (1/L)/(m ) -

Science and Technology Seminars in Tokyo March 27 th 2001 Processing/design requirements Thin dense layer on porous substrate Gas tight sealing High strength and reliability Chemical expansion/stresses Air ~ 800 °C Pure O product 2

Science and Technology Seminars in Tokyo March 27 th 2001 Chemical expansion/stresses Expansion produces stresses in O 2 pressure gradient Air pO low 2 Tension Compression 

Science and Technology Seminars in Tokyo March 27 th 2001 Powder synthesis Tube forming Sintering Sealing Membrane processing

Science and Technology Seminars in Tokyo March 27 th 2001 High Temperature Solid State Proton Conductors Applications Fuel cells Dehydrogenation pumps Steam electrolyzers Sensors (H 2 O, H 2 ) Intermediate temperature challenge Materials Perovskites, e.g. BaCeO 3 Phosphates, e.g. LaPO 4

Science and Technology Seminars in Tokyo March 27 th 2001 Mixed proton - electron conductors Hydrogen separation membranes Natural gas to Syngas Hydrogen extraction Integrated design Status (Argonne): 5 ml n /min/cm 2 Materials: Perovskites CH 4 CD + H + CO + H O O + N 22 N 2 Partial oxidation Syngas Dehydrogenated syngas Hydrogen extraction CD + H + CO + H O H 2

Science and Technology Seminars in Tokyo March 27 th 2001 Microporous membranes Sol-gel prepared thin microporous membranes with carefully controlled thickness and pore size Separation of H 2 from syn gas CO 2 separation and adsorption

Science and Technology Seminars in Tokyo March 27 th 2001 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

Science and Technology Seminars in Tokyo March 27 th 2001