Pilot-scale entrained flow gasification experiments were carried out at the 3 MWth LTU Green Fuels black liquor gasification (BLG) plant, using ∼140 tons of Kraft black liquor (BL) with a dry solids content of ∼72.5%. Comprehensive mass and energy balances were performed to quantify process performance under varying pressure, load, and oxygen/fuel ratio. Carbon conversion efficiency of the BLG process was 98.3%–99.2% and did not vary systematically in response to process changes. The unconverted carbon is almost exclusively present as dissolved organic carbon in the green liquor (GL) stream. GL is an aqueous solution of sodium carbonate and sodium sulfide used to recover the inorganic pulping chemicals present in BL for reuse in the pulp mill. A small fraction of syngas CO is converted to formate ions dissolved in GL through reaction with hydroxide ions. Unconverted carbon present in GL solids is insignificant. Syngas produced is subsequently upgraded to methanol and dimethyl ether (DME) in an integrated fuel synthesis facility. Concentration of H2 in syngas is not significantly affected by operating point changes in the domain investigated, while CO and CO2 concentrations are. Syngas hydrocarbon concentration values are typically in the single-digit parts per million (ppm) with the exception of C6H6, which was present at 16–127 ppm. CH4 is present at 0.5%–1.2%, with lower concentrations at higher temperatures, and shows good correlation with C6H6. A quantity of 24%–27% of BL sulfur ended up in the syngas as 1.5%–1.7% H2S and 64–72 ppm COS. Cold gas efficiencies (CGEs) on a lower heating value (LHV) basis, when including syngas CH4, were 52%–55% and decreased at higher temperature. CGEs on an LHV basis, when considering only H2 and CO with a sulfur-free BL heating value relevant for catalytic syngas upgrading, were 58%–60% and showed the opposite temperature dependence. Good mass and energy balance closures show the figures presented to be reliable. The results obtained from this study demonstrate process stability at varying operating conditions and can be further used for techno-economic analysis and design purposes.
Tar and soot in product gas have been a major technical challenge toward the large-scale industrial installation of biomass gasification. This study aims at demonstrating that the formation of tar and soot can be reduced simultaneously using the catalytic activity of alkali metal species. Pine sawdust was impregnated with aqueous K2CO3 solution by wet impregnation methods prior to the gasification experiments. Raw and alkali-impregnated sawdust were gasified in a laminar drop-tube furnace at 900–1400 °C in a N2–CO2 mixture, because that creates conditions representative for an entrained-flow gasification process. At 900–1100 °C, char, soot and tar decreased with the temperature rise for both raw and alkali-impregnated sawdust. The change in tar and soot yields indicated that potassium inhibited the growth of polycyclic aromatic hydrocarbons and promoted the decomposition of light tar (with 1–2 aromatic rings). The results also indicated that the catalytic activity of potassium on tar decomposition exists in both solid and gas phases. Because alkali salts can be recovered from product gas as an aqueous solution, alkali-catalyzed gasification of woody biomass can be a promising process to produce clean product gas from the entrained-flow gasification process at a relatively low temperature.
This paper describes a pilot scale high pressure entrained flow gasification experiment with spent cooking liquor from a sodium sulfite based delignification process in the DP-1 black liquor gasifier in Pitea, Sweden. Approximately 92 tons of sulfite thick liquor were gasified during 100 h of operation without any operational problems despite the new feedstock. The syngas quality was found to be good for all operating points with the CH 4 content below 0.3% and H 2 /CO ratio between 1.03 and 1.15. The experiment shows that the process capacity is limited by green liquor quality parameters primarily dependent on the presence of small amounts of unconverted carbon. The pilot plant capacity was found to be somewhat lower than for Kraft black liquor on mass basis but higher when measured as thermal load, due to the higher heating value of sulfite thick liquor. Mass and energy balances were made difficult by the unavailability of measured green liquor and syngas flow rates, which lead to the necessity of using alternative approaches for the estimation of these flows. Using these estimates, overall mass and energy balances were closed to within 5% for all operating points except one, and the process cold gas efficiency was 60−68% on sulfurfree lower heating value basis. Carbon balances indicate that 95−97% of feedstock carbon leaves with the syngas, mainly as CO and CO 2 with the remainder being mostly green liquor carbonate. More than 95% of the feedstock sodium is found in green liquor, while 3−5% ends up in the gas condensate purge stream. The sulfur balance does not close as well as other elements but indicates that 70−73% of the feedstock sulfur ends up in the syngas as H 2 S and COS with the remainder being present in green liquor as dissolved sulfide salts.
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