Kraft Black Liquor Gasification And Direct Causticization With Ti02 In A Fluidized Bed PDF Download

Gasification of black liquor (BLG) has distinct advantages over direct combustion in Tomlinson recovery boilers. In this project we seek to resolve causticizing issues in order to make pressurized BLG even more efficient and cost-effective. One advantage of BLG is that the inherent partial separation of sulfur and sodium during gasification lends itself to the use of proven high yield variants to conventional kraft pulping which require just such a separation. Processes such as polysulfide, split sulfidity, ASAQ, and MSSAQ can increase pulp yield from 1% to 10% over conventional kraft but require varying degrees of sulfur/sodium separation, which requires additional [and costly] processing in a conventional Tomlinson recovery process. However during gasification, the sulfur is partitioned between the gas and smelt phases, while the sodium all leaves in the smelt; thus creating the opportunity to produce sulfur-rich and sulfur-lean white liquors for specialty pulping processes. A second major incentive of BLG is the production of a combustible product gas, rich in H2 and CO. This product gas (a.k.a. "syngas") can be used in gas turbines for combined cycle power generation (which is twice as efficient as the steam cycle alone), or it can be used as a precursor to form liquid fuels, such as dimethyl ether or Fischer Tropsh diesel. There is drawback to BLG, which has the potential to become a third major incentive if this work is successful. The causticizing load is greater for gasification of black liquor than for combustion in a Tomlinson boiler. So implementing BLG in an existing mill would require costly increases to the causticizing capacity. In situ causticizing [within the gasifier] would handle the entire causticizing load and therefore eliminate the lime cycle entirely. Previous work by the author and others has shown that titanate direct causticizing (i.e. in situ) works quite well for high-temperature BLG (950°C), but was limited to pressures below about 5 bar. It is desirable however to operate BLG at 20-30 bar for efficiency reasons related to either firing the syngas in a turbine, or catalytically forming liquid fuels. This work focused on achieving high direct causticizing yields at 20 bars pressure. The titanate direct causticizing reactions are inhibited by CO2. Previous work has shown that the partial pressure of CO2 should be kept below about 0.5 bar in order for the process to work. This translates to a total reactor pressure limit of about 5 bar for airblown BLG, and only 2 bar for O2-blown BLG. In this work a process was developed in which the CO2 partial pressure could be manipulated to a level under 0.5 bar with the total system pressure at 10 bar during O2-blown BLG. This fell short of our 20 bar goal but still represents a substantial increase in the pressure limit. A material and energy balance was performed, as well as first-pass economics based on capital and utilities costs. Compared to a reference case of using BLG with a conventional lime cycle [Larson, 2003], the IRR and NVP were estimated for further replacing the lime kiln with direct causticizing. The economics are strongly dependent on the price of lime kiln fuel. At $6/mmBTU the lime cycle is the clear choice. At $8/mmBTU the NPV is $10M with IRR of 17%. At $12/mmBTU the NPV is $45M with IRR of 36%. To further increase the total allowable pressure, the CO2 could be further decreased by further decreasing the temperature. Testing should be done at 750C. Also a small pilot should be built.