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The University of Missouri-Rolla identified materials that permit the safe, reliable and economical operation of combined cycle gasifiers by the pulp and paper industry. The primary emphasis of this project was to resolve the material problems encountered during the operation of low-pressure high-temperature (LPHT) and low-pressure low-temperature (LPLT) gasifiers while simultaneously understanding the materials barriers to the successful demonstration of high-pressure high-temperature (HPHT) black liquor gasifiers. This study attempted to define the chemical, thermal and physical conditions in current and proposed gasifier designs and then modify existing materials and develop new materials to successfully meet the formidable material challenges. Resolving the material challenges of black liquor gasification combined cycle technology will provide energy, environmental, and economic benefits that include higher thermal efficiencies, up to three times greater electrical output per unit of fuel, and lower emissions. In the near term, adoption of this technology will allow the pulp and paper industry greater capital effectiveness and flexibility, as gasifiers are added to increase mill capacity. In the long term, combined-cycle gasification will lessen the industry's environmental impact while increasing its potential for energy production, allowing the production of all the mill's heat and power needs along with surplus electricity being returned to the grid. An added benefit will be the potential elimination of the possibility of smelt-water explosions, which constitute an important safety concern wherever conventional Tomlinson recovery boilers are operated. Developing cost-effective materials with improved performance in gasifier environments may be the best answer to the material challenges presented by black liquor gasification. Refractory materials were selected or developed that reacted with the gasifier environment to form protective surfaces in-situ; and were functionally-graded to give the best combination of thermal, mechanical and physical properties and chemical stability; and are relatively inexpensive, reliable repair materials. Material development was divided into 2 tasks: Task 1 was development and property determinations of improved and existing refractory systems for black liquor containment. Refractory systems of interest include magnesium aluminate and barium aluminate for binder materials, both dry and hydratable, and materials with high alumina contents, 85-95 wt%, aluminum oxide, 5.0-15.0 wt%, and BaO, SrO, CaO, ZrO2 and SiC. Task 2 was finite element analysis of heat flow and thermal stress/strain in the refractory lining and steel shell of existing and proposed vessel designs. Stress and strain due to thermal and chemical expansion has been observed to be detrimental to the lifespan of existing black liquor gasifiers. The thermal and chemical strain as well as corrosion rates must be accounted for in order to predict the lifetime of the gasifier containment materials. |
