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Science and Technology Seminars in Tokyo March 27th 2001
Science and Technology Seminars in Tokyo March 27th 2001
Mari-Ann Einarsrud
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
High PO 2
Mixed conductor
Conducts oxide ions/protons
and electrons
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-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 27th 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 27th 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 27th 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 CO2 emission
Science and Technology Seminars in Tokyo March 27th 2001
Fuels
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 detection
of CO, CO2, H2, NOx, etc
Solid oxide fuel cells
Current research activity low
Pilot plant at Kolsnes (SiemensWestinghouse, Norske Shell A/S, FMC
Kongsberg, NTNU and SINTEF)
Science and Technology Seminars in Tokyo March 27th 2001
Oxide ceramic membrane technology
Air
O2 +
4e-

2O2-
2O2-  O2 + 4e-
Oxygen
Dense membranes
O2 permeable (oxide ion
conductors)
H2 permeable (proton conductors)
Electically driven
Mixed conductor type
Microporous oxide membranes
High pressure Air
O2 + 4e-  2O2-
2O2-  O2 + 4e-
Low pressure Oxygen
Science and Technology Seminars in Tokyo March 27th 2001
Dense oxygen permeable membranes
- Mixed conductors
O2 product
Chemical potential driven
Pressure driven
High pressure air
Reaction Product
Infinite O2 selectivity
High temperature operation
(approximately 800°C)
Air
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
CH4 + ½ O2
 CO + 2H2
CH4 + H2O
 CO + 3H2
Syngas
Co-generation of electric
power and steam by using
non-permeate
Oxygen-Depleted Air
Oxidizing
Atmosphere
Reducing
atmosphere
Air
Natural Gas Stream
Reforming Catalyst
Membrane
Science and Technology Seminars in Tokyo March 27th 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 27th 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
CH4
Science and Technology Seminars in Tokyo March 27th 2001
CO2
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
2mm
1mm
0.67mm 0.5mm 0.4mm
I 02 /(sccm/cm 2 min)
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
SrFe1-x Co x O 3-d
T = 1000 °C
1
0
0.5
1
1.5
2
(1/L)/(m- -1)
Science and Technology Seminars in Tokyo March 27th 2001
2.5
Processing/design requirements
Air ~ 800 °C
Thin dense layer on
porous substrate
Gas tight sealing
High strength and
reliability
Chemical
expansion/stresses
Pure O2 product
Science and Technology Seminars in Tokyo March 27th 2001
Chemical expansion/stresses
Expansion produces stresses in O2 pressure
gradient
Air
Air
 Air
Tension
Science and Technology Seminars in Tokyo March 27th 2001
pO low
2
Compression
Membrane processing
Powder synthesis
Tube forming
Sintering
Sealing
Science and Technology Seminars in Tokyo March 27th 2001
High Temperature
Solid 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
CH 4
CD + H2 + CO2 + H2O
O2 + N2
N2
Partial oxidation
Syngas
Hydrogen separation
membranes
Natural gas to Syngas
Hydrogen extraction
Integrated design
Status (Argonne):
5 mln/min/cm2
Materials: Perovskites
CD + H2 + CO2 + H2O
H2
Dehydrogenated
syngas
Hydrogen extraction
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
Science and Technology Seminars in Tokyo March 27th 2001
Science and Technology Seminars in Tokyo March 27th 2001