Causticizing for Black Liquor Gasifiers

The cost-benefit outlook of black liquor gasification (BLG) could be greatly improved if the smelt causticization step could be achieved in situ during the gasification step. Or, at a minimum, the increase in causticizing load associated with BLG could be mitigated. A number of chemistries have been proven successful during black liquor combustion. In this project, three in situ causticizing processes (titanate, manganate, and borate) were evaluated under conditions suitable for high temperature entrained flow BLG, and low temperature steam reforming of black liquor. The evaluation included both thermodynamic modeling and lab experimentation. Titanate and manganate were tested for complete direct causticizing (to thus eliminate the lime cycle), and borates were evaluated for partial causticizing (to mitigate the load increase associated with BLG). Criteria included high carbonate conversion, corresponding hydroxide recovery upon hydrolysis, non process element (NPE) removal, and economics. Of the six cases (three chemistries at two BLG conditions), only two were found to be industrially viable: titanates for complete causticizing during high temperature BLG, and borates for partial causticizing during high temperature BLG. These two cases were evaluated for integration into a gasification-based recovery island. The Larsen [28] BLG cost-benefit study was used as a reference case for economic forecasting (i.e. a 1500 tpd pulp mill using BLG and upgrading the lime cycle). By comparison, using the titanate direct causticizing process yielded a net present value (NPV) of $25M over the NPV of BLG with conventional lime cycle. Using the existing lime cycle plus borate autocausticizing for extra capacity yielded a NPV of $16M