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.

Alkali metals inherent in black liquor (BL) have strong catalytic activity during gasification. A catalytic co-gasification process based on BL with pyrolysis oil (PO) has the potential to be a part of efficient and fuel-flexible biofuel production systems. The objective of the paper is to investigate how adding PO into BL alters fuel conversion under gasification conditions. First, the conversion times of single fuel droplet were observed in a flat flame burner under different conditions. Fuel conversion times of PO/BL mixtures were significantly lower than PO and comparable to BL. Initial droplet size (300–1500 μm) was the main variable affecting devolatilization, indicating control by external heat transfer. Char oxidation was affected by droplet size and the surrounding gas composition. Then, the intrinsic reactivity of char gasification was measured in an isothermal thermogravimetric analyser at T = 993–1133 K under the flow of CO2–N2 mixtures. All the BL-based samples (100% BL, 20% PO/80% BL, and 30% PO/70% BL on mass basis) showed very high char conversion. Conversion rate of char gasification for PO/BL mixtures was comparable to that of pure BL although the fraction of alkali metal in char decreased because of mixing. The reactivities of BL and BL/PO chars were higher than the literature values for solid biomass and coal chars by several orders of magnitude. The combined results suggest that fuel mixtures containing up to 30% of PO on mass basis may be feasible in existing BL gasification technology.

The efficiency and flexibility of the BL gasification process may improve by mixing BL with more energy-rich fuels such as pyrolysis oil (PO). To improve understanding of the fuel conversion process, blends of BL and PO were studied in an atmospheric drop tube furnace. Experiments were performed in varying atmosphere (5% and 0% CO₂, balanced by N₂), temperature (800–1400 °C), particle size (90–200 μm and 500–630 μm) and blending ratio (0%, 20% and 40% of PO in BL on weight basis). Additionally, pine wood was used as a reference fuel containing little alkali. The addition of PO to BL significantly increased the combined yield of CO and H₂ and that of CH₄. BL/based fuels showed much lower concentration of tar in syngas than pine wood. Remarkably, the addition of PO in BL further promoted tar reforming in presence of CO₂. Unconverted carbon in the gasification residue decreased with increasing fractions of PO. Small fuel particles showed complete conversion at 1000 °C but larger particles did not reach complete conversion even at T = 1400 °C.

The catalytic activity of alkali compounds in black liquor (BL) enables gasification at low temperatures with high carbon conversion and low tar and soot formation. The efficiency and flexibility of the BL gasification process may be improved by mixing BL with fuels with higher energy content such as pyrolysis oil (PO). The fate of alkali elements in blends of BL and PO was investigated, paying special attention to the amount of alkali remaining in the particles after experiments at high temperatures. Experiments were conducted in a drop tube furnace under different environments (5% and 0% vol. CO₂ balanced with N₂), varying temperature (800–1400 °C), particle size (90–200 µm, 500–630 µm) and blending ratio (0%, 20% and 40% of pyrolysis oil in black liquor). Thermodynamic analysis of the experimental cases was also performed.

The thermodynamic results qualitatively agreed with experimental measurements but in absolute values equilibrium under predicted alkali release. Alkali release to the gas phase was more severe under inert conditions than in the presence of CO₂, but also in 5% CO₂ most of the alkali was found in the gas phase at T = 1200 °C and above. However, the concentration of alkali in the gasification residue remained above 30% wt. and was insensitive to temperature variations and the amount of PO in the blend. Thermodynamic analysis and experimental mass balances indicated that elemental alkali strongly interacted with the reactor’s walls (Al₂O₃) by forming alkali aluminates. The experience indicated that adding PO into BL does not lead to alkali depletion during high temperature gasification.