The high temperature interactions of alkali metal compounds with solids present in coal conversion processes are investigated. A temperature and concentration programmed reaction method is used to investigate the mechanism by which organically bound alkali is released from carbonaceous substrates. Vaporization of the alkali is preceded by reduction of oxygen-bearing groups during which CO is generated. A residual amount of alkali remains after complete reduction. This residual level is greater for potassium, indicating that potassium has stronger interactions with graphitic substrates than sodium. Other mineral substrates were exposed to high temperature alkali chloride vapors under both nitrogen and simulated flue gas atmospheres to investigate their potential application as sorbents for the removal of alkali from coal conversion flue gases. The compounds containing alumina and silica are found to readily adsorb alkali vapors and the minerals kaolinite, bauxite and emathlite are identified as promising alkali sorbents. The fundamentals of alkali adsorption on kaolinite, bauxite and emathlite are compared and analyzed both experimentally and through theoretical modeling. The experiments were performed in a microgravimetric reactor system; the sorbents were characterized before and after alkali adsorption using scanning Auger microscopy, X-ray diffraction analysis, mercury porosimetry and atomic emission spectrophotometry. The results show that the process is not a simple physical condensation, but a complex combination of several diffusion steps and reactions. There are some common features among these sorbents in their interactions with alkali vapors: In all cases the process is diffusion influenced, the rate of adsorption decreases with time and there is a final saturation limit. However, there are differences in reaction mechanisms leading to potentially different applications for each sorbent. Bauxite and kaolinite react with NaCl and water vapor to form nephelite and carnegieite and release HCl to the gas phase. However, emathlite reacts to form albite and HCl vapor. Albite has a melting point significantly lower than nephelite and carnegieite; therefore, emathlite is more suitable for lower temperature sorption systems downstream of the combustors/gasifiers, while kaolinite and bauxite are suitable as in-situ additives.

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