Synthesis and thermo-oxidative kinetic analysis of cellulose microfibers from palm leaves using ammonia fiber expansion

Global urbanization is driving high volumes of agricultural and food waste, creating an urgent need for sustainable and effective technologies to convert biomass into valuable products. This study explores the conversion of palm waste into cellulose microfibers (CMF) using Ammonia Fiber Expansion (AFEX) followed by acid hydrolysis, with a focus on structural characterization, thermal stability, and reaction kinetics compared to raw material. The resulting CMF exhibited elongated, uniform fibers with smooth surfaces, with lengths of 0.1-3.0 mm, and diameters of 5-20 μm. X-ray analysis revealed a significant increase in the carbon/oxygen ratio, from 1.8 ± 0.2 in raw palm leaves to 2.7 ± 0.3 in CMF, indicating enhanced carbon content due to dehydration and reduction of carbonyl groups. FTIR spectra confirmed effective removal of lignin and hemicellulose after treatment, further supporting this chemical transformation. Thermal analysis demonstrated that CMF possesses higher heat content than raw leaves, suggesting its potential for energy-related applications. TGA showed that CMF decomposes at slightly higher temperatures, indicating improved thermal stability. Isoconversional kinetic analysis using the Vyazovkin Nonlinear (NLN) and Kissinger-Akahira-Sunose (KAS) methods revealed variable effective activation energies (E_α), consistent with a complex degradation mechanism. Overall, CMF displayed lower E_α values than raw biomass, especially at early and mid-reaction stages. Kinetic modeling at 50% conversion showed a markedly higher pre-exponential factor (A_α) for raw leaves (2.8 × 10¹³ s⁻¹) compared to CMF (7.4 × 10⁹ s⁻¹), reflecting structural alterations from treatment. Both raw and CMF samples exhibited negative activation entropy (ΔS^≠) values of - 237.7 and - 240.3 J mol⁻¹ K⁻¹, respectively, suggesting greater molecular order in activated complexes. The enthalpy of activation (ΔH^≠) was 149.7 ± 3.9 kJ mol⁻¹ for raw leaves versus 120.4 ± 3.9 kJ mol⁻¹ for CMF, Gibbs free energy of activation (ΔG^≠) was slightly higher for raw leaves (297.0 ± 3.9 kJ mol⁻¹) compared to CMF (269.4 ± 3.9 kJ mol⁻¹), primarily due to differences in ΔH^≠. These kinetic parameters are crucial for any future implementation of palm leaves conversion into CMF at the industrial scale.