MariAnn Einarsrud

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Mari-Ann Einarsrud
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Mari-Ann Einarsrud

• Professor, Department of Chemistry, Norwegian
  University of Science and Technology, Trondheim,
  Norway

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Mari-Ann Einarsrud

• Functional oxide materials for energy applications

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Functional oxide materials

• Ionic conductor
• Conducts oxide ions or protons
• Mixed conductor
• Conducts oxide ions/protons and electrons

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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

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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 gt 15 mill)

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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

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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

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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)

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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
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Dense oxygen permeable membranes- Mixed
conductors

• Chemical potential driven
• Pressure driven
• Infinite O2 selectivity
• High temperature operation (approximately 800C)

High pressure air
Reaction Product
Air
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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
Reducing atmosphere
Oxidizing Atmosphere
Air
Natural Gas Stream
OxygenReductionCatalyst
Reforming Catalyst
Membrane
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Impact of membrane technology on GTL
Conventional Process
Reformer
Oxygen Plant
Fisher-Tropsch Reactor
Separation /Upgrading
Air
Nat. Gas / Steam
Liquid Products
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30
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CAPITAL INVESTMENT
Ceramic Membrane Process
Syngas Reactor
Fisher-Tropsch Reactor
Separation /Upgrading
Air
Nat. Gas / Steam
Liquid Products
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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
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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

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Material requirements
2mm
0.67mm
0.4mm
1mm
0.5mm
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• High oxygen flux
• Chemical stability
• Chemical compatibility
• Catalytic compatibilityand activity
• Cost

5
x 0.67 x 0.33 x 0
4
3
2
1
0
0.5
1.5
2.5
1
2
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Processing/design requirements
Air 800 C

• Thin dense layer on porous substrate
• Gas tight sealing
• High strength and reliability
• Chemical expansion/stresses

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Chemical expansion/stresses

• Expansion produces stresses in O2 pressure
  gradient

?
Air
Air
Air
Tension
Compression
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Membrane processing

• Powder synthesis
• Tube forming
• Sintering
• Sealing

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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

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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
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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

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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

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