Hydroxide Formation and Carbon Species Distributions During High-Temperature Kraft Black Liquor Gasification
Dance, Michael Raymond, Jr.
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This work focuses on high-temperature kraft black liquor gasification in the presence of H2O and CO2 in a laboratory-scale Laminar Entrained-Flow Reactor (LEFR). The effects of gasification conditions on hydroxide formation, carbon gasification rate, carbonate carbon and fixed carbon levels, alkali metal and sulfur species retention, and char yield were studied at atmospheric pressure and at 900-1000oC, and at residence times of 0.5-1.5 s. The results suggest that carbon gasification rates may be enhanced in the presence of H2O and CO2, with fixed carbon conversions of up to 95% at the earliest residence times at 1000oC. CO2 and H2O gasifying agents cause a significant increase in carbonate formation, with 22% of the initial carbon input forming carbonate as compared to 16% with one gasifying agent. Carbonate levels increase to a maximum level and then decrease at 900oC, but at 1000oC, carbonate decomposition processes are more dominant and cause lower levels of carbonate even at early residence times. The results show that alkali metal retention is high until vaporization occurs after 1.4 s at 900oC and at early residence times at 1000oC. Moreover, the results indicate that sulfur retention is an exothermic process, as sulfur capture increases with temperature. At 900oC, no hydroxide is produced until after 1.4 s, but at 1000oC, hydroxide appears to form readily even at the earliest residence times studied. The char product yields a maximum mole percent of 18-19% hydroxide, starting at intermediate residence times at 1000oC. Generally, hydroxide is not produced until fixed carbon conversions approach 95%. The results can be explained in terms of the interactions of phenolate and carboxylate catalytic moieties in the char product. The hydroxide formation results suggest that it may be possible to develop a gasification-causticization process that does not require external chemicals and would make the energy-efficient and environmentally friendly black liquor gasification technology an economic reality.