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Chemical equilibrium calculations were performed with the program F*A*C*T to evaluate process configurations and conditions for kraft black liquor autocausticization with metal oxides, Fe2Os, Al203 and TiO2. It was found that Fe203 is unsuitable, since reducing conditions lead to formation of Fe, Fe0 and FeS. Al203 is also unsuitable as autocausticizing agent because some of its hydrates are soluble in white liquor. However TiO2 can be used for autocausticization, because it or its causticizing products are stable under high temperature reducing conditions, and the insoluble hydrolysis product can be reused in the autocausticizing process. The equilibrium calculations showed that it is not feasible to recover black liquor with TiO2 in the recovery furnace. However a combustion-reduction or gasification-sulfur recovery process involving autocausticization of kraft black liquor with TiO2 is thermodynamically possible.
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Autocausticizing of Kraft Black Liquor: Process Implications Based on Chemical Equilibrium Calculati