Jim Keiser, Cam Hubbard, Ian Wright and Bob Swindeman Oak Ridge National Laboratory

1. Materials Evaluation For PulseEnhanced™ Steam Reforming GasifiersAndPerformance Of Materials InBlack Liquor And Biomass Gasifiers Jim Keiser, Cam Hubbard, Ian Wright and Bob Swindeman Oak Ridge National Laboratory with participation by GTI, IPST, LBNL and UMR

2. A “Request For Proposals” was released last fall for work that would support the demonstration technologies that have been selected by the U.S. Department of Energy • Georgia-Pacific, Big Island, Virginia – in cooperation with MTCI and StoneChem demonstrate the suitability of the reformer/gasifier to black liquor generated at this mill • Boise Corporation, DeRidder, Louisiana – in cooperation with the Gas Technology Institute put in place an advanced biomass gasification-based power generation system • Gaylord Container Corporation (recently purchased by Temple-Inland) – in cooperation with MTCI/StoneChem construct two demonstration facilities. One for recovery of liquor from a non-wood, semi-kraft process at mill in Spotswood, New Jersey. The second is a full-scale facility at the softwood kraft mill in Orange, Texas, which replaces the facility planned for the Pine Bluff, Arkansas, mill.

3. The RFP Encouraged The Proposers To Address Areas That Were Considered “Immediate Needs” • Fuels chemistry • Carbon management, tars, residual carbon, sulfur management • Containment • Metals, refractories, vessel design, understanding reactions • Mill integration • Causticizing load control, autocausticizing, sulfur recovery • Process control and optimization • Pulse heater design and control, liquor introduction control • Assurance and education • Long duration testing, independent verification, education A total of eight proposals were selected for funding

4. Georgia-Pacific Steam Reformer/Gasifier The Steam Reformer/Gasifier System Used In Two Of The Demonstration Projects Operates Below Smelt Melting Point • Pulse heated tubes are heat source for bed • Sodium carbonate is bed material • Bed is fluidized with steam • Operating temperature is kept below “sticky point” of smelt

5. The Project “Materials Evaluation For PulseEnhanced™ Steam Reforming Gasifiers” Will Result In A System For Realistic Materials Studies • MTCI/ThermoChem will undertake the design and construction to upgrade their Process Development Unit in Baltimore to make it more suitable for studies of process chemistry and materials performance. ORNL will provide materials support during the system upgrade. • ORNL will take the lead in the subsequent characterization and supply of samples before exposure, and will be responsible for the examination and characterization of samples after exposure. MTCI/ThermoChem will conduct the PDU exposure studies.

6. Task 1 – System Upgrading • The current system contains 3 electrically heated tubes that are positioned vertically in the bed • The facility will be significantly modified to provide a test facility with the following features • 12 tubes can be installed • Tubes will be horizontally mounted • Will be heated internally by PulseHeater • Tubes will incorporate internal shield tubes • Refractory lining will be incorporated • A new reformer vessel and a new first stage cyclone will be required

7. Task 2 – Materials Testing • Test materials will be selected and thoroughly characterized • Four tube each of three different materials will be tested • Test intervals will be 400 hr, 800 hr and 2000 hr • Replacement tubes installed after the first two intervals will result in samples with exposure times of 400, 800, 1200, 1600 and 2000 hr • Post-exposure characterization will be conducted • As possible, refractories will also be tested • Operating data will be collected during the test exposures • Following the 2000 hr study, new tubes will be installed and will be removed for examination at suitable intervals

8. Summary • The Process Development Unit at MTCI’s Baltimore facility will be extensively modified • The upgraded facility will permit exposure of horizontally-positioned, PulseHeated tubes in a fluidized bed • A carefully controlled 2000 hour test series will be conducted with tubes of three selected materials • Tubes exposed during subsequent periods will be characterized as they become available

9. The Project “Performance Of Materials In Black Liquor And Biomass Gasification” Will Address Materials Issues In The Gasification Demonstration Projects Task 1.0 Laboratory studies • Use laboratory test facilities to simulate the chemical, thermal and mechanical cycling environments of gasifiers and conduct exposure tests of metallic and refractory materials Task 2.0 Fluidized bed simulations • Modify an existing fluidized bed test system at LBNL and conduct tests of metallic and refractory materials in this system Task 3.0 Biomass air heater studies • Construct a module and expose tubular samples to an environment anticipated for the GTI biomass gasifier system air heater Task 4.0 Gasifier component analysis • Examine any metallic or refractory samples removed from pilot scale or demonstration scale gasifier facilities

10. For Task 1 Laboratory Studies Will Be Conducted • When possible, existing laboratory facilities will be used • As needed, new test systems will be constructed • Metallic and refractory materials will be tested • Test conditions will be selected to simulate the chemical, thermal and mechanical cycling environments in the demonstration systems

11. ORNL’s CS&T Group Is Well Equipped For Conducting Corrosion Studies In Aggressive Environments • High temperature exposure facilities – air, oxygen, water vapor, SO2, CO/CO2, He/vacuum with controlled additions • High-temperature, high-pressure mixed gas rigs • Microbalances – air, oxygen, water vapor, H2S • Thermal convection loops – molten salts, liquid metals • Molten salt/liquid metal handling equipment • Aqueous corrosion laboratory – polarization, electrokinetics, electrochemical noise, AC impedance, slow-strain-rate testing

12. Other Groups In The M&C Division Can Provide Other Experimental And Analytical Capabilities • Microstructural analysis – light microscopy, scanning electron microscopy, transmission electron microscopy, electron microprobe spectroscopy, microhardness, etc • Mechanical properties – tensile and compressive strength, creep strength, impact strength, flexure strength, • Thermophysical properties – x-ray phase identification, x-ray and neutron diffraction residual stress measurement, thermal conductivity, coefficient of thermal expansion, specific heat, etc. • The Materials Processing Group and the Materials Joining Group can provide information on material fabrication

13. Task 2 Is Intended To Study The Effects Of A Fluidized Bed On Steam Reformer/Gasifier Tubes And Refractories • Studies conducted in the U.S. on coal combustion fluidized beds showed it was very difficult experimentally to reproduce the degradation of bed tubes • The test facility developed by Lawrence Berkeley National Laboratory and the Electric Power Research Institute did the best job of reproducing the damage patterns seen in fluidized bed combustors • We will contract with LBNL to modify their system to conduct tests for this project • Internally heated bed tube • Sodium carbonate bed material • Fluidized with steam • Modify cover gas to include H2S • Evaluate refractory materials as vessel liner

14. For Task 2, The LBNL Fluidized Bed Test System Will Be Modified Then Utilized In This Project LBNL fluidized bed system with furnace door open and upper mechanism in raised position; tubular sample and sample holder are shown above

15. In Task 3, Materials Will Be Identified For The Air Heaters In The GTI-Boise Biomass Gasifier • The GTI biomass gasifier builds on existing technologies • Increases mill generated power by up to 28 MW • Supplements existing boiler and power generation system • Increases use of wood waste fuel • Tube materials are limiting issue for the two air heaters

16. Boise-GTI Biomass Gasification Based Power System

17. Task 4 Provides For Examination Of Gasifier Components • Our experience on other projects has shown that degraded materials are offered to us for examination • In some cases, no funding has been available for thorough examination of these components • This task will provide funds for examination of degraded components that we believe have some relevance to the demonstration projects

18. Summary • Laboratory studies will evaluate materials behavior in environments considered relevant to the demonstration projects • Degradation studies of refractories and metallic tubes will be conducted in a system modified to simulate the fluidized bed of a steam reformer/gasifier • High temperature corrosion studies will be conducted to identify metallic alloys suitable for use at 1400°F, 1600°F and 1800°F (760°C, 871°C and 982°C) in the gasifier and boiler environments • Degraded components of gasifiers or other relevant systems will be characterized when considered of value to the demonstration projects