OTM - An Advanced Oxygen Technology for IGCC · Performance Composite OTM Ultra low leak rates achieved in a single firing step 0 100 200 300 400 500 600 700 800 900 0 2040 6080 Differential

www.praxair.com

Ravi Prasad, Jack Chen, Bart van Hassel, John Sirman, James White, Eric Shreiber, Joe Corpus, Joshua HarnantoRavi Prasad, Jack Chen, Bart van Hassel, John Sirman, James White, Eric Shreiber, Joe Corpus, Joshua Harnanto

San Francisco, Oct 30, 2002San Francisco, Oct 30, 2002

Gasification Technologies 2002Gasification Technologies 2002

OTM - An Advanced Oxygen Technology for IGCC

Gasification 2002RP 10-30--02

Copyright 2002 Praxair Technology, Inc. All rights reserved.

Use of Oxygen in IGCC

Oxygen is the preferred oxidantReduced costs for gasifier, heat recovery, acid gas removalEnhanced potential for CO2 sequestrationBut added cost for ASU

O2 supply options:Cryogenic: Most mature & commercialPSA: Small-medium sizesPolymeric Membranes: Small, low purityOTM: Emerging breakthrough technology



Why OTM?

High operating temperature enables efficient integration with IGCC

0

20

40

60

80

100

-200 25 40 700-1000

Process Temperature (C)

Ox

yge

n P

uri

ty (

%)

Cryo OTM

PolyMem

PSA



OTM = Oxygen Transport Membrane

•Oxides of Metals

•Oxygen Ion & Electron

Transport

•Produces Pure O2

•High T Operation

(500-1000°C)

•Pressure Driven Oxygen

Separation

Mixed Conductor Transport Mechanism

--Charge Transfer

Recombination

Charge Transfer Dissociation

-- Adsorption

O2Bulk

Diffussion

Desorption

BulkDiffussion

--IonMigration

Electron Migratione- OTM

Low Pressure Oxygen

High Pressure Air



Praxair’s Integrated OTM Approach

IntegratedTechnology

Program

MaterialsSynthesis

PowderProduction

Thin FilmDevelopment

Element Fabrication

ProcessEngineering

SystemsEngineering

Over 25 Development Partners



OTM Integration in IGCCBasis for Assessment

Illinois #6 coal as feedstock

Westinghouse 501G gas turbineAnchor point for all calculations : ~272 MW power output from GT

Shell technology used for gasification

O2 production:Advanced Cryo: Advanced cryo tailored for IGCCOTM integrated with GTOTM+SOFC Integrated with GTOTM with steam integration



IGCC with OTM and SOFC

Air

O2

Coal

Steam CycleFlue Gas

Gasification &Clean-up

Clean Syngas

Gas Turbine

Steam &Water

Exchange

OTM

SupplementalCompressor

Steam

Sulfur

N2Air

ExtractedAir

SOFC

BFW

BFW



OTM integration with IGCC produces significant benefits to environment and consumer

OTM integration with IGCC produces significant benefits to environment and consumer

Cost and Efficiency of Power Generation via IGCC

40

42

44

46

48

50

52

54

Effic

ienc

y (%

HH

V)

Cryo OTMOTM

+SOFC

40

42

44

46

48

50

52

Cos

t of E

lect

rici

ty

(mils

/kW

h)

Cryo OTMOTM+S

OFC

SOFC @$800/kW

SOFC @$400/kW



Project Plan

Joint DOE/Praxair program objective:Commercialize OTM membranes for IGCC Applications

Phase1: 1999 - 2002Material developmentComposite OTM developmentProof of concept in multi-element pilot reactor

Phase2: 2002 - 2004Manufacturing of full size elementsDevelopment of specialized componentsEngineering validation in larger pilot reactor

Phase3: 2004 - 2007Pre-commercial demonstration



OTM Materials Options

Fluorite, AO2

Brownmillerite A2B2O5

Perovskites, ABO3

Pyrochlores, A2B2O7

O=

e -

Dual Phase



Evolution of Advanced OTM Materials

•Simultaneous improvement of flux & strength is a significant accomplishment

0

20

40

6080

100

120

O2

Flu

x

(% H

urd

le R

ate

)

OTM1 OTM2 OTM3

Generation of Material

0

20

40

60

80

100

Rel

ativ

e S

tren

gth

OTM1 OTM2 OTM3

Generation of Material



Components of Praxair’s High Performance Composite OTM

Ultra low leak rates achieved in a single firing step

0100200300400500600700800900

0 20 40 60 80

Differential Pressure, PSI

Flow

Rat

e, C

C/S

ec Generation 2

Al2O3

Generation 1

Year 1 Year 2 Year 3

1.E-12

1.E-11

1.E-10

1.E-09

1.E-08

1.E-07

1.E-06

1.E-05

1.E-04

Lea

k R

ate

[cc/

sec]

Target Leak Rate

Low resistance Substrates Gas Tight Films



PSC: Commercial Technology for OTM Powder Production

Calcination

Y1Ba2Cu3O7

Each particle isan intimate mixture of Y2O3,CuO, BaCO3

Advanced Process

CalcinationY1Ba2Cu3Ox

BaCO3

CuO

Y2O3

CuO

Y2Ba1Cu1O5Ba2CO3

Y2O3

Conventional

Micro-scale stoichiometry controlWell suited for complex, multi-cation chemistriesHighly flexible - Over 400 mixed oxide compositions made



Element Fabrication

Praxair has access to fabrication technology fromAmocoBPStatoilWestinghouse

Praxair & its partners have fabricated and tested a wide range of element geometries

Plates, monoliths, tubes….

Final selection is based on many considerations



Assessment of ElementGeometry

Tubular Variants: Preferred configuration

Attribute Tubular Planar MonolithSealing Best Difficult Very Difficult

Manifolding Easier Difficult Very Difiicult

Strength Self Supporting Not self supporting Could be self supporting

FabricationExisting Technology

Multiple Options Most advanced for

large size

Existing technology for small size

Difficult for large size

Very Difficult for any size

Scaleup Easy Difficult Very Difficult

Mnf Yield on Functional Element

High Low for complex geometry Low

Area/Volume Ratio Medium High Very High

Thermal Management Easy Fair Difficult

Replacement Single tube Entire stack Entire Monolith



Praxair Technology for Large OTM Elements

Unique semi works manufacturing facility operational



Seal Technology Development at Praxair

75

80

85

90

95

100

Prod

uct O

2 Pu

rity

(%)

1997 1999 2001 2002

0%

20%

40%

60%

80%

100%

0 240 480 720 960 1200

Hours

Leak

(% ta

rget

max

imum

)

0

200

400

600

800

1000

Temperature (°C

)

Commercial Target Maximum

0%

20%

40%

60%

80%

100%

Cycle #

Leak

(% ta

rget

max

imum

)

0

100

200

300

400

500

600

700

800

900

1000

Temperature (°C

)

Commercial Target Maximum

1 5 10 2115



Multi-Element Pilot Reactor

• 0.2 TPD capacity•Pilot plant producing high purity O2 using composite tubes•Target Flux demonstrated•Life test in progress



Advances in OTM Technology at Praxair

120% of target flux achieved @ 150C lower temperature

6x flux improvement

Oxygen purity > 99.5%

Successful 1000+ hr life test @ 275psi & 900C

Thin Film MembraneStable flux performanceNo membrane degradation

10 thermal cycles (25-900C at 275 psi) achieved with no degradation0

102030405060708090

100110120

O2

Flux

(% o

f Tar

get)

19

99

20

00

20

01

20

02

He Purged

Un- Purged

1050C

1050C

950C

900C



Summary

Ceramic membranes offer potential for low cost oxygenLowest capital cost, power consumption, and oxygen cost2-7% gain in efficiency COE reduction of 8-15%

Project has made substantial progress120% of commercial flux achievedHigh pressure cyclable seals & gas tight membranes99.5%+ O2 purity reached at 275 psi ∆PMulti-element pilot system operational

Pilot and pre-commercial demonstrations are essential steps to commercialization

Documents

OTM - An Advanced Oxygen Technology for IGCC · Performance Composite OTM Ultra low leak rates achieved in a single firing step 0 100 200 300 400 500 600 700 800 900 0 2040 6080 Differential