Alkaline pulping catalyzed ordered conversion of bark in supercritical water

The hydrophilicity of lignocellulosic biomass hinders the application of a high concentration slurry for supercritical water gasification, thereby reducing the gasification efficiency and energy self-sufficiency. A pretreatment method of alkaline pulping with KOH and NaOH was proposed to achieve the high feed concentration for continuous reactor and macromolecular simplification for barrier reduction of conversion. In this study, bark as an example of lignocellulosic biomass, whose 30 wt% and 40 wt% slurries with favorable rheology and stability, was prepared by alkaline pulping successfully. The minimum alkali consumption of NaOH and KOH pulping for 30 wt% and 40 wt% were 11%–14%, 16%–20%, and 16%–21%, 23%–28%, respectively. The most economical conditions were 180 °C and 24% KOH addition. All slurries prepared by NaOH and KOH at 180 and 200 °C could satisfy the industrial standard of coal-water slurry, and only 3–5 times higher than water viscosity. The bark macromolecules were restructured due to the hydrolysis of cellulose and lignin by breaking down the hydrogen bond and ether bond with trivial hydrocarbon matrix loss. The scattered crystal growth facilitated the uniform premixing of bark and water. Meanwhile, a surface particle charges potential increase leading to a heightened repulsive force by alkaline pulping furtherly enhanced the premixing effect. Additionally, metal ions could be deposited onto the bark surface during alkaline pulping. The chemical modification leading by alkaline pulping achieved the premixing of feedstock and water to form bark slurry. The conversion barrier was decreased to fulfill the ordered conversion, and 95.66% gasification efficiency for 40 wt% bark slurry was displayed at 600 °C with a preheated water of 6. Phenolic compounds and hydrocarbons were the most dominant components in liquid products. Polycyclic aromatic hydrocarbons in liquid products were detected at 620 °C with a preheated water of 4. The functional groups of organic matter in the slurry were significantly converted into the gas phase, and lattice oxygen was produced in the solid product. The alkali recovery was 65% at the optimal gasification condition, and achieved the maximum of 80% at 580 °C. The successful completion of this research affirms the dominance of the pulping-alkali recovery-gasification method for expanding the application of SCWG of lignocellulosic biomass in large engineering projects.