A high load of inorganics in raw lignocellulosic biomass is known to inhibit the yield of bio-oil and alter the chemical reactions during fast pyrolysis of biomass. In this study, palm kernel shell (PKS), an agricultural residue from palm oil production, and two other woody biomass samples (mahogany (MAH) sawdust and iroko (IRO) sawdust) were pretreated with distilled water or an acidic solution (either acetic, formic, hydrochloric (HCl) or sulfuric acid (H₂SO₄)) before fast pyrolysis in order to investigate its effect on the primary products and pyrolysis reaction pathways. The raw and pretreated PKS, MAH and IRO were pyrolysed at 600 °C and 5 s with a micro-pyrolyser connected to a gas chromatograph–mass spectrometer/flame ionisation detector (GC-MS/FID). Of the leaching solutions, HCl was the most effective in removing inorganics from the biomass and enhancing the primary pyrolysis product formed compared to the organic acids (acetic and formic acid). The production of levoglucosan was greatly improved for all pretreated biomasses when compared to the original biomass but especially after HCl pretreatment. Additionally, the relative content of the saccharides was maximised after pretreatment with H₂SO_4, which was due to the increased production of levoglucosenone. The relative content of the saccharides increased by over 70%. This increase may have occurred due to a possible reaction catalysed by the remaining acid in the biomass. The production of furans, especially furfural, was increased for all pretreatments but most noticeable when H₂SO₄ was used. However, the relative content of acids and ketones was generally reduced for PKS, MAH and IRO across all leaching solutions. The relative content of the phenol-type compound decreased to a large extent during pyrolysis after acid pretreatment, which may be attributed to dehydration and demethoxylation reactions. This study shows that the production of valuable chemicals could be promoted by pretreatment with different acid solutions.

Co-pyrolysis is one possible method to handle different biomass leftovers. The success of the implementation depends on several factors, of which the quality of the produced bio-oil is of the highest importance, together with the throughput and constraints of the feedstock. In this study, the fast co-pyrolysis of palm kernel shell (PKS) and woody biomass was conducted in a micro-pyrolyser connected to a Gas Chromatograph–Mass Spectrometer/Flame Ionisation Detector (GC–MS/FID) at 600 °C and 5 s. Different blend ratios were studied to reveal interactions on the primary products formed from the co-pyrolysis, specifically PKS and two woody biomasses. A comparison of the experimental and predicted yields showed that the co-pyrolysis of the binary blends in equal proportions, PKS with mahogany (MAH) or iroko (IRO) sawdust, resulted in a decrease in the relative yield of the phenols by 19%, while HAA was promoted by 43% for the PKS:IRO-1:1 pyrolysis blend, and the saccharides were strongly inhibited for the PKS:MAH-1:1 pyrolysis blend. However, no difference was observed in the yields for the different groups of compounds when the two woody biomasses (MAH:IRO-1:1) were co-pyrolysed. In contrast to the binary blend, the pyrolysis of the ternary blends showed that the yield of the saccharides was promoted to a large extent, while the acids were inhibited for the PKS:MAH:IRO-1:1:1 pyrolysis blend. However, the relative yield of the saccharides was inhibited to a large extent for the PKS:MAH:IRO-1:2:2 pyrolysis blend, while no major difference was observed in the yields across the different groups of compounds when PKS and the woody biomass were blended in equal amounts and pyrolysed (PKS:MAH:IRO-2:1:1). This study showed evidence of a synergistic interaction when co-pyrolysing different biomasses. It also shows that it is possible to enhance the production of a valuable group of compounds with the right biomass composition and blend ratio.