Science and Technology Seminars in Tokyo March 27

Science and Technology Seminars in Tokyo March 27 th 2001

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

Perovskite materials - ABO 3 Ionic or mixed conductivity tailored by Oxygen non-stoichiometry giving ABO 3 -d 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 LPG Ethers Alcohols Syngas Fertilzer Acetyls Methanol Formaldehyde Diesel Gasoline MTBE Ammonia Hydrogen Chemicals Requirements No NOx emission Low CO 2 emission Science and Technology Seminars in Tokyo March 27 th 2001 Fuels

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

Dense oxygen permeable membranes - Mixed conductors O product 2 Chemical potential driven Pressure driven High pressure air Reaction Product Infinite O 2 selectivity High temperature operation (approximately 800°C) Air 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 CH 4 + ½ O 2 CH 4 + H 2 O CO + 2 H 2 CO + 3 H 2 Syngas Oxygen-Depleted Air Oxidizing Atmosphere Reducing atmosphere Air Natural Gas Stream Reforming Catalyst Membrane Science and Technology Seminars in Tokyo March 27 th 2001 Oxygen Reduction Catalyst

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

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

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 2 mm 1 mm 0. 67 mm 0. 5 mm 0. 4 mm 2 I /(sccm/cm min) 02 6 High oxygen flux Chemical stability Chemical compatibility Catalytic compatibility and activity Cost 5 x = 0. 67 x = 0. 33 x = 0 4 3 2 Sr. Fe Co O 3 -d 1 -x x T = 1000 °C 1 0 0. 5 1 1. 5 2 - -1 (1/L)/(m ) Science and Technology Seminars in Tokyo March 27 th 2001 2. 5

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

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

Membrane processing Powder synthesis Tube forming Sintering Sealing 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. Ba. Ce. O 3 Phosphates, e. g. La. PO 4 Science and Technology Seminars in Tokyo March 27 th 2001

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

Science and Technology Seminars in Tokyo March 27 th 2001