2nd Workshop

International Oxy-Combustion Research Network Hilton Garden Inn Windsor, CT, USA

25th and 26th January 2007

Hosted by:

Alstom Power Inc.

PRESENTATION - 12

Oxygen Production Technologies: Cryogenic and ITM

by: Kevin Fogash Air Products and Chemicals, USA

2nd Int'l Oxy-Combustion Workshop Page 1

Oxygen Production Technologies: Cryogenic and ITM

Phil Armstrong, Kevin FogashAir Products and Chemicals, Inc.Allentown, Pennsylvania

2nd IEAGHG International Oxy-Combustion Network WorkshopWindsor, CT, USA25-26 January 2007

2

Air Separation

Cryogenic air separation includes these major steps:

– Compressing air– Air impurity removal (Pretreatment)– Cooling/liquefying air– Distillation

Scale up of advanced oxygen production technology – ITM Oxygen

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The ASU Process

Heat

Air

Heat

Oxygen

Main and BoostAir Compression

Air Cooling andPretreatment Storage

CryogenicSeparation

4

Main & Boost Air CompressionInlet air flow determines machine selection

Air Flow

Axial-Radial

In-lineCentrifugal

Integral GearCentrifugal

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5

Brazed aluminum plate fin exchangers

Cools air streams against product streams to recover refrigeration

Ambient to cryogenic temperatures

Cryogenic Heat Exchange

Liquid Oxygen“Condensed” Boost AirNitrogenMain Air

Gaseous Oxygen

Boost AirNitrogenMain Air

Main Heat Exchanger

6

Separation by Distillation

LOX Pump

Air

Subcooler

LiquidOxygen

Nitrogen

LowPressureColumn

Reboiler-Condenser

“Cold Box”

HighPressureColumn

Pure Nitrogen (Boils at -190oC / -310oF)

Pure Oxygen (Boils at -177oC / -286oF)

Pure Nitrogen (Boils at -175oC / -283oF)

Enriched Air (Boils at -168oC / -270oF)

Gaseous Oxygen(Oxygen Compressor

Option)

to main heatexchange

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ManufacturingManufacture/erection approach is project specific

Shop manufactureddistillation columns

Shop manufacturedcold boxes

Field erectedcolumn can

8

Conceptual ITM Oxygen vessel scaled to match cryogenic oxygen plant output

ITM Oxygen Enables a Step-change Reduction in the Cost of Oxygen

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Ion Transport Membranes (ITM): High-flux, High-purity Oxygen

O2- electrons

compressed air

oxygen

P’

P’’O2

O2

O2- ½O2 + 2e-

½O2 + 2e- O2-

• Mixed-conducting ceramic membranes (non-porous)

• Typically operate at 800-900 °C

• Crystalline structure incorporatesoxygen ion vacancies

• Oxygen ions diffuse through vacancies

• 100% selective for O2

• ln1''2

'2

2 ⎟⎟⎠

⎞⎜⎜⎝

⎛∝

O

O

PP

LFluxO

L

10

Single-stage air separation leads to compact designs

Low pressure drop on the high-pressure sideHigh-temperature process has better synergy with power generation systemsExtraordinary flux enables large tonnage production economics

Ceramic Membranes: Revolutionary Technology for Tonnage Oxygen Supply

Compressed Compressed AirAir

OxygenOxygenProductProduct

0.5 TPD module(commercial-scale)

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ITM Oxygen integrates well with power generation cycles

AIROXYGEN

FUEL

HEATEXCHANGE

IONTRANSPORTMEMBRANE

HRSG

STEAM

OXYGENBLOWER

ELECTRICPOWER

OXYGEN

‘AIR’

ITM Oxygen separator integrated with a gas turbine-based power cycle

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ITM Oxygen is Simpler and Requires Less Power

ITM Oxygen With Power Integration

ITM O2 Has Much Simpler Flow Sheet and >35% Less CapitalITM O2 Has 35-60% Less Compression Energy Associated with Oxygen Separation

Cryogenic Air Separation

Main Air Compressor

Front-End Cleanup

Main Heat Exchanger

High Pressure

Column

Low Pressure Column

Main Reboiler

N2

O2

Waste

OXYGENOXYGEN

FUELFUEL

HeatExchange

HRSGSTEAMSTEAM

OxygenBlower

ELECTRICELECTRICPOWERPOWER

Oxygen‘Air’

AIRAIR

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ITM Oxygen has Excellent Economic Performance in Many Applications

n/a20+%n/a12,500 GTL

68%48%5008030Oxyfuel†*

69%27%2601500 Enrichment*

36%35%3002400Decarbonized Fuel†

37%35%458 3200 IGCC

Power for Oxygen

Capital for Oxygen

Power (MW)

Oxygen (sTPD) Application

Savings(% of Cryo ASU)Product

†enables carbon capture*uses existing gas turbine offerings

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ITM Oxygen Program

Goal: Reduce Cost of Oxygen by One-ThirdDOE/Air Products R&D started 1999 (11 year, $148 million)

– Phase 1: Technical Feasibility (0.1 TPD O2)– Phase 2: Prototype (1-5 TPD O2)– Phase 3: Pre-commercial Development (25+ TPD)

• Planning 150 TPDDevelopment Team

SOFCoSOFCo EFS EFS (McDermott)(McDermott)

GE Energy

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5 TPD SEP Skid Design – Isometric

Heater

RecycleCompressor

ControlRoom

MembraneVessel

Heat Exchangers

VacuumPumps

0.5 TPD O2

16

The SEP was started up in Oct. ’05, commissioned in April ‘06

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Initial SEP work highly successful

Several trials with 0.5-TPD modules since MayDemonstrated >99% oxygen purity from commercial-scale module and sealOxygen flux consistently has met or exceeded expectations, and has been steadyCurrently running modules through start-up/shutdown cycles to test reliability

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ITM O2, Possible DOE Proposal

0

2

4

6

8

10

2000 2005 2010 2015 2020

Year Onstream

Cap

acity

(T/D

)

5

150

2000

Phase 2

Phase 3

FutureGen

500

Future Work: Phase 3 Development Plan meets DOE FutureGen Schedule and Market Timing

5000

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Conclusions

Cryogenic air separation proven and available at scaleMajor Phase 2 ITM Oxygen development objectives have been met

– Built and tested commercial-scale ITM Oxygen modules successfully

Air Products and the U.S. DOE are planning an expanded Phase 3 to enable ITM Oxygen to produce large-tonnage quantities of oxygen in the FutureGen plant

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A significant portion of this report was prepared by Air Products and Chemicals, Inc. pursuant to a Cooperative Agreement partially funded by the United States Department of Energy, and neither Air Products and Chemicals, Inc. nor any of its contractors or subcontractors nor the United States Department of Energy, nor any person acting on behalf of either:

1. Makes any warranty or representation, express or implied, with respect to the accuracy, completeness, or usefulness of the information contained in this report, or that the use of any information, apparatus, method, or process disclosed in this report may not infringe privately owned rights; or

2. Assumes any liabilities with respect to the use of, or for damages resulting from the use of, any information, apparatus, method, or process disclosed in this report. Reference herein to any specific commercial products, process, or service by trade name, trademark, manufacturer, or otherwise, does not necessarily constitute or imply its endorsement, recommendation, or favoring by the United States Department of Energy. The views and opinions of authors expressed herein do not necessarily state or reflect those of the United States Department of Energy.

This paper was written with support of the U.S. Department of Energy under Contract No. DE-FC26-98FT40343. The Government reserves for itself and others acting on its behalf a royalty-free, nonexclusive, irrevocable, worldwide license for Governmental purposes to publish, distribute, translate, duplicate, exhibit and perform this copyrighted paper.

Disclaimer

Acknowledgment: DOE/NETL

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