Pyrolysis is an important technology to convert lignocellulosic biomass to a renewable liquid energy carrier known as pyrolysis oil or bio-oil. Herein we report the pyrolysis of pigeon pea wood, a widely available biomass in the Philippines, in a semi-continuous reactor at gram scale. The effects of process conditions such as temperature (400–600 °C), nitrogen flow rate (7–15 mL min⁻¹) and particle size of the biomass feed (0.5–1.3 mm) on the product yields were determined. A Box-Behnken three-level, three-factor fractional factorial design was carried out to establish process-product yield relations. Of particular interest is the liquid product (bio-oil), of which the yield was shown to depend on all independent variables in a complex manner. The optimal conditions for highest bio-oil yield (54 wt.% on dry feed intake) were a temperature of 466 °C, a nitrogen flow rate of 14 mL min⁻¹ and a particle size of 1.3 mm. Validation of the optimized conditions proved that the average (n = 3) experimental bio-oil yield (52 wt.%) is in good agreement with the predicted value from the model. The properties of product oils were determined using various analytical techniques including gas chromatography-mass spectrometry (GC–MS), gel-permeation chromatography (GPC), nuclear magnetic resonance spectroscopy (¹³C- and HSQC-NMR) and elemental and proximate analyses. The bio-oils were shown to have low ash content (0.2%), high heating value (29 MJ kg⁻¹) and contain high value-added phenolics compounds (41%, GC peak area) as well as low molecular weight aldehydes and carboxylic acids. GPC analysis indicated the presence of a considerable amount of higher molecular weight compounds. NMR measurements showed that a large proportion of bio-oil contains aliphatic carbons (~60%), likely formed from the decomposition of (hemi)cellulose components, which are abundantly present in the starting pigeon pea wood. Subsequent preliminary scale-up pyrolysis experiments in a fluidized bed reactor (~100 g_feed h⁻¹, 475 °C and N₂ flow rate of 1.5 L min⁻¹) gave a non-optimized bio-oil yield of 44 wt.%. Further fractionation and/or processing are required to upgrade these bio-oils to biofuels and biobased chemicals.

Pili nutshell (PS), an abundant agro-industrial byproduct in the Bicol Region, Philippines, demonstrates substantial potential as a solid biofuel and bioenergy feedstock. Proximate and ultimate analyses revealed high volatile matter (72.00 ± 0.20 wt%), low ash content (4.33 ± 0.76 wt%), and a higher heating value of 20.60 MJ/kg, indicating strong suitability as a solid fuel for thermochemical conversion and biofuel production. Thermogravimetric analysis (TGA) was conducted from 30 °C to 900 °C at heating rates of 10, 15, and 20 °C/min under nitrogen to examine its thermal decomposition behavior. The process followed three stages: initial moisture loss, active devolatilization, and lignin-rich char formation. The resulting kinetic and thermodynamic parameters are directly relevant for designing fast pyrolysis processes aimed at liquid biofuel production and optimizing downstream fuel utilization of the derived bio-oil and char. Kinetic analysis using the Coats–Redfern method identified third-order reaction (CR03) and diffusion-controlled (DM6) models as best-fitting, with activation energies ranging from 64.03–96.21 kJ/mol (CR03) and 66.98–104.72 kJ/mol (DM6). Corresponding thermodynamic parameters—ΔH (58.67–90.95 kJ/mol), ΔG (201.51–231.46 kJ/mol), and ΔS (−174.57 to −255.08 kJ/mol·K)—indicated an endothermic, non-spontaneous, entropy-reducing reaction pathway. Model-free methods confirmed a highly reactive zone at α = 0.3–0.6, with consistent E_a values (~130–190 kJ/mol). These findings affirm the viability of PS for fast pyrolysis, offering data-driven insights for optimizing advanced fuel and bioenergy systems in line with circular economy objectives.