Science and Technology Seminars in Tokyo March 27th 2001

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

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

Science and Technology Seminars in Tokyo March 27th 2001