science and technology seminars in tokyo march 27 th 2001
TRANSCRIPT
Science and Technology Seminars in Tokyo March 27th 2001
Mari-Ann Einarsrud
Professor, Department of Chemistry, Norwegian University of Science and Technology, Trondheim, Norway
Science and Technology Seminars in Tokyo March 27th 2001
Mari-Ann Einarsrud
Functional oxide materials for energy applications
Science and Technology Seminars in Tokyo March 27th 2001
Functional oxide materials
Ionic conductor Conducts oxide ions or protons
Mixed conductorConducts oxide ions/protons and electrons
High PO2
Low PO 2
Science and Technology Seminars in Tokyo March 27th 2001
Perovskite materials - ABO3
Ionic or mixed conductivity tailored by
Oxygen non-stoichiometry giving ABO3-
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 27th 2001
Norwegian experience in the field
University of OsloDefect chemistry, structure and transport properties, superconductors, magnetic oxides, solid oxide fuel cells
Norwegian University of Science and TechnologySolid oxide fuel cells, electrochemical conversion of natural gas, superconductors
SINTEF and Norwegian industrySolid oxide fuel cells (Norcell and Mjølner projects > $ 15 mill)
Science and Technology Seminars in Tokyo March 27th 2001
Norwegian challenges
Vast resources of natural gasRemote 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 27th 2001
Gas to liquid technology - GTL
Bringing natural gas to marked
RequirementsNo NOx emission
Low CO2 emission
EthersLPG
Alcohols
GasolineDiesel
Syngas
Fuels
Fertilzer
Methanol
MTBE
HydrogenAmmonia
Formal-dehyde
Acetyls
Chemicals
Science and Technology Seminars in Tokyo March 27th 2001
Energy applications
Oxide ceramic membrane technologyProduction 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 cellsCurrent 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 27th 2001
Oxide ceramic membrane technology
Dense membranesO2 permeable (oxide ion conductors)
H2 permeable (proton conductors)Electically driven
Mixed conductor type
Microporous oxide membranesHigh pressure Air
Low pressure Oxygen
Oxygen
Air
O2 + 4e- 2O2-
2O2- O2 + 4e-
O2 + 4e- 2O2-
2O2- O2 + 4e-
Science and Technology Seminars in Tokyo March 27th 2001
Dense oxygen permeable membranes- Mixed conductors
Chemical potential driven
Pressure driven
Infinite O2 selectivity
High temperature operation (approximately 800°C)
High pressure air
Air
O product2
Reaction Product
Science and Technology Seminars in Tokyo March 27th 2001
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
Syngas
Reducingatmosphere
Oxygen-Depleted Air
Air
OxygenReductionCatalyst
OxidizingAtmosphere
Natural Gas Stream
Reforming Catalyst
Membrane
CH4 + ½ O2 CO + 2H2
CH4 + H2O CO + 3H2
Science and Technology Seminars in Tokyo March 27th 2001
Impact of membrane technology on GTL
OxygenPlant
Reformer Fisher-TropschReactor
Separation /Upgrading
Syngas Reactor Fisher-TropschReactor
Separation /Upgrading
Conventional Process
Air Nat. Gas / Steam Liquid Products
15 %25 %30 %30%
Ceramic Membrane Process
Air
Nat. Gas / Steam Liquid Products
CAPITAL INVESTMENT
Science and Technology Seminars in Tokyo March 27th 2001
Impact of membrane technology on environment
Low green house gas emissions
No NOx emission
CH4 CO2
Conventional Syngas
Ceramic Membrane Syngas
Greenhouse Gas Emissions
NaturalGas
SynthesisGas
LiquidFuels
Net
Pro
ces
s Y
ield
Science and Technology Seminars in Tokyo March 27th 2001
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
Science and Technology Seminars in Tokyo March 27th 2001
Material requirements
High oxygen flux
Chemical stability
Chemical compatibility
Catalytic compatibilityand activity
Cost
x = 0.67x = 0.33x = 0
SrFe Co OT = 1000 °C
1-x x 3-d
0 0.5 1.5 2.51 2
1
2
3
4
5
62mm 0.67mm 0.4mm1mm 0.5mm
I /(
sccm
/cm
min
)0
22
(1/L)/(m )- -1
Science and Technology Seminars in Tokyo March 27th 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 product2
Science and Technology Seminars in Tokyo March 27th 2001
Chemical expansion/stresses
Expansion produces stresses in O2 pressure gradient
Air Air Air pO low2
Tension Compression
Science and Technology Seminars in Tokyo March 27th 2001
Powder synthesis
Tube forming
Sintering
Sealing
Membrane processing
Science and Technology Seminars in Tokyo March 27th 2001
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
Science and Technology Seminars in Tokyo March 27th 2001
Mixed proton - electron conductors
Hydrogen separation membranes
Natural gas to Syngas
Hydrogen extraction
Integrated design
Status (Argonne): 5 mln/min/cm2
Materials: Perovskites
CH 4
CD + H + CO + H O2 2 2
O + N2 2
N2
Partial oxidationSyngas
Dehydrogenatedsyngas
Hydrogen extraction
CD + H + CO + H O2 2 2H2
Science and Technology Seminars in Tokyo March 27th 2001
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
Science and Technology Seminars in Tokyo March 27th 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