Materials Development For High-Temperature, High-Pressure Black Liquor Gasifiers Jim Keiser Oak Ridge National Laboratory Oak Ridge, Tennessee With Contributions From PSL, Paprican, IPST and Simulent, Inc

G Euro  Proposal prepared for April 15 th Request For Proposals  Reportedly one of several chosen for further consideration  No official confirmation of selection for funding

G Euro Objectives Of The Proposed Project “Materials Development For High-Temperature, High-Pressure Black Liquor Gasification”  Provide the pulp and paper industry with extensive information on the behavior of materials for HTHP black liquor gasifiers to support wise selection of materials  Provide information that can be used in engineering designs, optimization of operating conditions and prediction of lifetimes of materials  Develop models to predict the flow and distribution of various chemical species in the gasifier  Develop models to predict the stresses and interactions between structural components of both atmospheric- and high-pressure gasifiers

G Euro Experimental Approach - Tasks  Design and construct a HTHP testing facility at ORNL  Expose candidate materials at ORNL, Piteå and other suitable facilities  Characterize exposed samples for phase changes and changes in thermophysical and mechanical properties  Develop models to predict 1) compositions and flow patterns of the various chemical species contacting the gasifier vessel and 2) thermochemical stability of refractories  Develop finite element models to predict the stresses between metallic and refractory components  Conduct corrosion studies to identify materials compatible with the green liquor produced in the gasifier  Recommend containment materials for the gasifier

G Euro Task 1 – Construct Test Facility  Laboratory-scale pressurized test facility  Expose metallic and refractory materials  Simulate temperatures, pressures and chemical species of HTHP black liquor gasifier  Vary exposure time and cycling of atmosphere and temperature to obtain kinetics information  Especially interested in effect of elevated pressure on reaction rates, system energetics, reaction mechanisms and reaction products  Test system will also be available to other researchers possible to obtain information about chemical species under HTHP conditions

G Euro Task 2 & 3 – Expose And Characterize Samples  Commercial and experimental materials will be exposed in the ORNL test system  Materials will be offered to operators of other gasifiers, including Piteå, for exposure  All materials will be thoroughly characterized before exposure  Exposed samples will be evaluated to determine effects of exposure on phases present as well as thermophysical and mechanical properties  Results will be used as input for modeling studies

G Euro Tasks 4 & 5 – Develop Mathematical Models  Establish subcontract with Simulent Inc. for spray and atomization modeling  Conduct thermochemical modeling to predict composition of materials that will be resistant to gasifier environment  Establish subcontract with Process Simulations Limited for extension of their gasifier model to predict chemical species present and temperature distribution  Conduct finite element modeling to predict stresses that may be developed as a result of interactions between gasifier components

G Euro Task 6 – Conduct Green Liquor Corrosion Studies  Green liquor is a highly caustic solution that can be very corrosive to materials  The green liquor produced in the HTHP gasifier is expected to be at a higher temperature and higher concentration than green liquor in a recovery boiler  The Pulp and Paper Research Institute of Canada (Paprican) has carried out project on selection of materials for containment of green liquor from black liquor recovery boilers  A subcontract will be established with Paprican to take the lead on this task

G Euro Task 7 – Recommend Materials Based on results from characterization of samples exposed in high-temperature, high-pressure gasifier material recommendations will be offered