Kinetics and thermodynamics of non-isothermal pyrolysis mechanisms in Cucumis sativus peels

IF 2.1 4区化学 Q4 CHEMISTRY, PHYSICAL

Reaction Kinetics, Mechanisms and Catalysis Pub Date : 2026-05-28 DOI:10.1007/s11144-026-03165-2

Qurat ul Ain Abid, Muhammad Azeem Arshad, Farah Kanwal, Khurram Shahzad Munawar

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Abstract

Cucumis sativus (cucumber) peels were comprehensively studied for thermochemical conversion potential using thermo-kinetic investigation with a focus on multi-step degradation behavior. Proximate and elemental analyses confirmed good pyrolysis characteristics such as high volatile matter (66.70%) and reasonable fixed carbon (24.54%) which made it suitable for bioenergy applications. The TGA showed that there are three regions of degradation: moisture removal, active devolatilization (129–315 °C) and slow degradation of lignin (residual char 23%). One of the novelty aspects of this work is the combination of the generalized linear integral method (GLIM) and Fraser-Suzuki peak deconvolution to resolve overlapping reactions to obtain reliable kinetic parameters. The deconvolution results gave three pseudo-components; hemicellulose (P-HC_l), cellulose (P-C_l) and lignin (P-L_g). Their activation energies were 135 ± 2, 154 ± 3 and 98 ± 2 kJ mol⁻¹. The activation energy for all conversions showed insignificant variations, conforming to single-step kinetics for the individual component. The process models determined by the advanced reaction model determination methodology suggest reaction order model for P-HC_l, nucleation-growth for P-C_l and a rather complex diffusion for P-L_g. The thermodynamic analysis showed that lignin degradation is probably the least spontaneous and with relatively ordered transition state. The overall combined GLIM–Fraser–Suzuki approach is more comprehensive in terms of biomass pyrolysis kinetics, gives better/reliable mechanistic understanding of the pyrolysis process, and may lead to a more dependable design and optimization of reactors in the waste-to-energy system.

Graphical Abstract

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黄瓜皮非等温热解机理的动力学和热力学研究

采用热动力学研究方法对黄瓜皮的热化学转化势进行了全面研究，重点研究了黄瓜皮的多步降解行为。近似分析和元素分析证实了其良好的热解特性，如高挥发物（66.70%）和合理的固定碳（24.54%），使其适合生物能源应用。TGA结果表明，木质素有三个降解区域：除湿、主动脱挥发（129 ~ 315℃）和缓慢降解（残余炭23%）。这项工作的一个新颖方面是将广义线性积分法（GLIM）和Fraser-Suzuki峰反褶积相结合来解决重叠反应以获得可靠的动力学参数。反褶积结果给出了三个伪分量；半纤维素（P-HCl）、纤维素（P-Cl）和木质素（P-Lg）。它们的活化能分别为135±2、154±3和98±2 kJ mol−1。所有转化的活化能变化不大，符合单个组分的单步动力学。采用先进的反应模型确定方法确定的过程模型表明，P-HCl为反应顺序模型，P-Cl为成核生长模型，P-Lg为相当复杂的扩散模型。热力学分析表明，木质素的降解可能是最不自发的，并且具有相对有序的过渡态。整体结合的gim - fraser - suzuki方法在生物质热解动力学方面更加全面，对热解过程的机理理解更好/更可靠，并可能导致更可靠的设计和优化反应器在废物转化为能源系统中。图形抽象

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来源期刊

Reaction Kinetics, Mechanisms and Catalysis CHEMISTRY, PHYSICAL-

CiteScore

3.30

自引率

5.60%

发文量

201

审稿时长

2.8 months

期刊介绍： Reaction Kinetics, Mechanisms and Catalysis is a medium for original contributions in the following fields: -kinetics of homogeneous reactions in gas, liquid and solid phase; -Homogeneous catalysis; -Heterogeneous catalysis; -Adsorption in heterogeneous catalysis; -Transport processes related to reaction kinetics and catalysis; -Preparation and study of catalysts; -Reactors and apparatus. Reaction Kinetics, Mechanisms and Catalysis was formerly published under the title Reaction Kinetics and Catalysis Letters.