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<p>Effective utilization of agricultural and woody residues is a cornerstone of Thailand’s Bio-Circular-Green economic model and global carbon-neutrality strategies. This study presents a comparative kinetic and thermodynamic analysis of low- and high-holocellulose biomass feedstocks decomposed under intermediate heating rates (100–150&#xa0;°C/min) relevant to fast pyrolysis. The discrete distributed activation energy model captures the complex, overlapping nature of the reactions while achieving high predictive accuracy. Kinetic results indicated that biomass complexity is significantly influenced by inorganic content; rice straw, with the highest ash fraction (14.7 wt%), required the most complex reactions (<InlineEquation ID="IEq1"> <EquationSource Format="TEX">\(\:n\)</EquationSource> </InlineEquation> = 35), suggesting an in-situ catalytic effect of indigenous minerals. The “overlapping reaction zone” hypothesis validated how intermediate heating rates induce a temporal kinetic overlap in which hemicellulose, cellulose, and lignin decompose simultaneously throughout the uniform, thermally thin particles, rather than strictly sequential thermal events. Thermodynamic analysis confirmed the endothermic (<InlineEquation ID="IEq2"> <EquationSource Format="TEX">\(\:{\varDelta\:H}_{i}\)</EquationSource> </InlineEquation> = 10–280&#xa0;kJ/mol) and non-spontaneous (<InlineEquation ID="IEq3"> <EquationSource Format="TEX">\(\:{\varDelta\:G}_{i}\)</EquationSource> </InlineEquation> = 170–220&#xa0;kJ/mol) nature of the process. The stability of Gibbs free energy (<InlineEquation ID="IEq4"> <EquationSource Format="TEX">\(\:{\sigma\:}_{\varDelta\:G}\)</EquationSource> </InlineEquation> = 10–25&#xa0;kJ/mol) across diverse feedstocks suggests standardized reactor designs for fast pyrolysis could effectively process various residues with comparable thermal efficiency, yielding &gt; 20 wt% bio-oil and &gt; 25 wt% biochar. These results help optimize bio-energy conversion and carbon sequestration in Southeast Asia.</p>

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Kinetic and thermodynamic analysis of holocellulosic biomass pyrolysis at intermediate heating rates using discrete distributed activation energy model

  • 期刊论文

  • 发表日期：

    2026年7月8日

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  • Panuphong Mankeed,
  • Thossaporn Onsree,
  • Nattawut Khuenkaeo,
  • Nakorn Tippayawong

摘要

Effective utilization of agricultural and woody residues is a cornerstone of Thailand’s Bio-Circular-Green economic model and global carbon-neutrality strategies. This study presents a comparative kinetic and thermodynamic analysis of low- and high-holocellulose biomass feedstocks decomposed under intermediate heating rates (100–150 °C/min) relevant to fast pyrolysis. The discrete distributed activation energy model captures the complex, overlapping nature of the reactions while achieving high predictive accuracy. Kinetic results indicated that biomass complexity is significantly influenced by inorganic content; rice straw, with the highest ash fraction (14.7 wt%), required the most complex reactions ( \(\:n\) = 35), suggesting an in-situ catalytic effect of indigenous minerals. The “overlapping reaction zone” hypothesis validated how intermediate heating rates induce a temporal kinetic overlap in which hemicellulose, cellulose, and lignin decompose simultaneously throughout the uniform, thermally thin particles, rather than strictly sequential thermal events. Thermodynamic analysis confirmed the endothermic ( \(\:{\varDelta\:H}_{i}\) = 10–280 kJ/mol) and non-spontaneous ( \(\:{\varDelta\:G}_{i}\) = 170–220 kJ/mol) nature of the process. The stability of Gibbs free energy ( \(\:{\sigma\:}_{\varDelta\:G}\) = 10–25 kJ/mol) across diverse feedstocks suggests standardized reactor designs for fast pyrolysis could effectively process various residues with comparable thermal efficiency, yielding > 20 wt% bio-oil and > 25 wt% biochar. These results help optimize bio-energy conversion and carbon sequestration in Southeast Asia.