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  • Praxair Business Confidential

    Praxair’s Oxygen Transport

    Membrane Technology for Syngas

    and Power Applications

    Juan Li

    DOE/NETL Carbon Capture Meeting

    Pittsburgh, PA ● June 26, 2015

    OTM

  • Praxair OTM Technology NT43088 22

    Project Overview – OTM for Industrial Applications

     OTM for Industrial Applications (ARRA)

    5 year (2010-2015)

    $55MM, 63% DOE share

    ─ Project Objectives

    • Develop robust, cost effective membranes

    • Develop multi-tube OTM modules

    • Demonstrate conversion of NG to syngas with OTM modules

    • TEA of NG-fired oxycombustion power cycle with CCS

  • Praxair OTM Technology NT43088 33

    Project Overview – OTM-Enhanced Gasification

     OTM-Enhanced Coal Syngas for

    Carbon Capture Power Systems and

    Fuel Synthesis Applications

    $10MM, 50% DOE share

    2 year, Oct. 1 2014 - Sept. 30 2016

    ─ Project Objectives

    • TEA of OTM-enhanced IG-NGCC process w/CO2 capture

    • Develop OTM with integrated catalyst

    • Develop OTM supporting layer and ceramic seal for high pressure application

    • Develop OTM modules and demonstrate in small-pilot scale test with simulated coal syngas

    Dryer

    CO2

    Water

    CO2 Compressors

    Purif.

    Impurities

    CPU

    O 2

    O2 -Depleted Air

    Air

    Air Heater

    OTM

    CONVERTER

    BFW

    Air

    Steam Cycle

    SELEXOL

    AGR

    HRSG

    F-CLASS GT

    WGS

    SG COOLING

    Steam

    H2

    CO2

    N2

    NG HDS

    Steam

    H2

    To H2 product or

    Fischer-Tropsch

    Synthesis (Synfuels)

    Cryo

    ASU Slag

    Air

    N2

    Hg

    Removal

    DeS

    Sulfur

    Coal

    Slurry Char

    O2

    CB&I Gasifier

    (E-Gas)

  • Praxair OTM Technology NT43088 4

    Praxair OTM – How it works:

    Combustion-driven air separation at high pressure without ASU and air compression

    Dual phase

    dense layer

    Cross SectionHigh

    Pressure

    Fuel

    Porous support Active layers

    Electrons

    Pure

    Oxygen

    Low

    Pressure

    Air

    950-1000oC

    Oxy-

    combustion

    Product

  • Praxair OTM Technology NT43088 5

    Praxair OTM Syngas Technology

    Combined reforming in a single integrated efficient package

    Primary Steam

    Methane Reformer Air Separation

    Unit

    Secondary AutoThermal

    Reformer

    Multi-Process

    Combined

    Reforming

    Solid state

    combined

    reforming with

    OTM

    O2

    Heat OTM

    (with catalyst)

    Low

    Pressure

    Air

    Steam + NGSyngas

    Partially

    Reformed

    Syngas

    Reformer

    Reforming

    Catalyst

  • Praxair OTM Technology NT43088 66

    OTM-Enhanced IG-NGCC Concept (NG+Coal)

    Integration of OTM Syngas into Coal + NG Power Cycle w/ CCS

    Low

    Pressure

    Air

    O2-

    Heat

    OTM

    + Catalyst

    Depleted

    Air

    Natural Gas

    + Steam Coal

    Syngas

    Reformer

    Upgraded

    SyngasFlex-fuel Power with CO2, H2, and or FT Liquids co-products

  • Praxair OTM Technology NT43088 77

    Gasifier Integration Vision

    Synergies in GTCC + Fossil Fuel to Liquids

  • Praxair OTM Technology NT43088 8

    An ARRA Success Story…

    Breakthrough innovations on all fronts

    O2- O2-

    Depleted

    Air

    Steam

    + NG

    Syngas

    OTM

    Reforming

    Catalyst

    O2

    Heat OTM

    (with catalyst)

    Low

    Pressure

    Air

    Steam + NGSyngas

    Partially

    Reformed

    Syngas Reformer

    Reforming

    Catalyst

    Early OTM

    • 2X increase in O2 flux • 4X increase in creep life • 10X reduction in degradation

    Membrane

    System

    • Optimal H2/CO ratio • Higher NG conversion • Lower CO2 footprint

    • Low pressure shell • Scalable architecture • Modular construction

    Process

    • Demonstrated complete syngas island

    • Robust operability and control

  • Praxair OTM Technology NT43088 99

    Test Systems Developed in ARRA Project

    Successful integration of membranes into systems

    Successful multi-module syngas

    production

    • Operating with 6 panel modules (216

    OTM tubes)

    • Representative commercial process

    elements

    • Multiple successful heating / cooling

    cycles

    • Capacity up to 190 Nm3/hr syngas

    Modules have shown excellent

    operational flexibility

    • 17 Modules tested (>370 OTM

    tubes)

    • More than 8,000 hrs of flux testing

    • >40 module thermal cycles

    • Ceramics robust to thermal and

    chemical cycling

    Single Tube Testing Module Testing System Testing

    Membranes can deliver

    requirements of the process

    • Flux and fuel conversion

    demonstrated

    • >42,000 hrs over 67 tubes

    • Focus on Gen 2 membrane

    characterization at high pressure

  • Praxair OTM Technology NT43088 1010

    Technology Development ─ Seal and Membrane

    High temp burst test

    Baseline Aging Test (BAT)

    Pressure integrity: > 4X safety factor

    Accelerated life and reliability testing of tubes &

    seals in progress

    Creep/reliability testOn-line laser creep test Normalized creep life

    0.0 1.0 2.0 3.0 4.0

    12 samples

    Gen.1 Gen.2

    C om

    m ercial target

    ~4X increase in OTM creep life

    Run time, hrs

    Thermal cycles

    Failures

    BAT # 01 16350 10 0

    BAT # 02 14400 7 0

    BAT # 03 13390 8 0

  • Praxair OTM Technology NT43088 11

    Integrated Combined Reformer Panel Array

    Combined reforming in a single pass

    ceramic membranes

    reformer

    OTMs

    Reformers

    NG + Steam

    to reformers

    Product

    Syngas

    Thermal integration

  • Praxair OTM Technology NT43088 12

    Reliable Operation of Development System

    Technology ready for larger scale demonstration

    • 6 panel arrays (216 OTM tubes)

    • Daily operation since October 2014

    • 7 full thermal cycles

    • >100 start-up / shut-down cycles

  • Praxair OTM Technology NT43088 13

    OTM Development System

    Panels have operated through multiple thermal,

    pressure, fuel cycles and shocks

    3 panels

    108 tubes

    deep thermal

    cycles

    process

    stream

    cycles

    Power failure

    System Upgrades

    6 panels

    216 tubes

    NG

    Flow

    OTM

    Temp

    Air

    Temp

  • Praxair OTM Technology NT43088 14

    Panel Array Scale-up

    Larger panels through longer ceramic units / more units

    Single Panel

    36 tubes Double Panel

    184 tubes

    (5x Increase)

    2 ft. 4 ft.

  • Praxair OTM Technology NT43088 1515

    O 2

    O2 -Depleted Air

    Air

    Air Heater

    OTM

    CONVERTER

    BFW TDA CO2

    Separation

    System

    WGS

    SG COOLING

    Steam

    H2

    CO2

    Vent

    NG

    O2

    CO2

    Syngas

    Generator

    NG HDS

    Steam

    H2

    Steam

    Syngas Product Flare

    Small-Pilot Scale Integration

    Slipstream:

    shift and separation

    PX Syngas Generators

    (simulate coal syngas) OTM Syngas Reactor TDA Shift/Separation Skid

  • Praxair OTM Technology NT43088 1616

    Summary and Plan

     Key Result

    ─ Step change in membrane materials and mfg. process

    ─ OTM and seals robust to pressure and thermal cycles

    ─ Demonstrated process to make syngas with ceramic membranes

    ─ Module design to achieve thermal integration and facilitate scale-up

    ─ Compelling economics for chemicals synthesis and power w/CCS applications

     Next Step

    ─ ARRA Project

    • TEA of OTM-based NG-fired power cycle

    ─ OTM-enhanced Gasification Project

    • Process simulation and TEA of OTM-enhanced IGCC process

    • Development of OTM with integrated catalyst for high pressure operation

    • Small-pilot scale test of OTM converter with TDA’s WGS/CO2 separation equipment

  • Praxair OTM Technology NT43088 17

    Acknowledgements

    This material is based upon work supported by the Department of Energy under Award Number DE-FE26-07NT43088 and DE-

    FE0023543. Neither the United States Government nor any agency thereof, nor any of their employees, makes any warranty, express or

    implied, or assumes any legal liability or responsibility for the accuracy, completeness, or usefulness of any information, apparatus,

    product, or process disclosed, or represents that its use would not infringe privately owne