Journal of Analytical and Applied Pyrolysis最新文献

Co-pyrolysis of discarded disposable tableware and bamboo chopsticks: The effect of synergistic interactions on kinetic parameters and products 废弃一次性餐具和竹筷共热解：协同作用对动力学参数和产物的影响

IF 6.2 2区化学 Q1 CHEMISTRY, ANALYTICAL

Journal of Analytical and Applied Pyrolysis

Pub Date : 2026-05-01 Epub Date: 2026-01-22 DOI: 10.1016/j.jaap.2026.107640

Jinbao Zhang , Yangyifan Zhang , Huaqing Li , Ya Liu, Fengfu Yin

This study systematically investigates the co-pyrolysis behavior of a ternary system composed of polypropylene (PP), polystyrene (PS), and disposable bamboo chopsticks (DC), focusing on its pyrolysis characteristics, kinetic synergistic effects, and product distribution mechanisms. The reaction process was analyzed using thermogravimetric analysis (TGA), tubular furnace experiments, and GC-MS combined with various kinetic methods. The results indicate that co-pyrolysis exhibits a significant synergistic effect, with an apparent activation energy of 108.98 kJ/mol, markedly lower than the theoretical value of 217.31 kJ/mol. The kinetic mechanism follows a random nucleation and growth model (A_1/2). The pyrolysis oil yield reaches 67.33 %, exceeding the theoretical value of 64.78 %. Product analysis indicates that co-pyrolysis effectively promotes deoxygenation reactions and the formation of aromatic hydrocarbons. The relative contents of naphthalene derivatives, such as 1,2,3,4-tetrahydro-2-phenyl-naphthalene, and phenyl-alkene compounds are significantly increased, with the total aromatic hydrocarbon content rising by 26.54 %, while the content of oxygenated compounds is markedly reduced. Mechanistic analysis indicates that the synergistic deoxygenation primarily results from hydrogen transfer reactions and Diels–Alder pathways, effectively enhancing the quality of pyrolysis oil. This study provides a robust theoretical basis and a feasible process route for the co-pyrolysis of multi-component waste to produce high-value chemicals.

本研究系统研究了聚丙烯（PP）、聚苯乙烯（PS）和一次性竹筷（DC）三元体系的共热解行为，重点研究了其热解特征、动力学协同效应和产物分布机制。采用热重分析（TGA）、管式炉实验、气相色谱-质谱联用多种动力学方法对反应过程进行了分析。结果表明，共热解表现出明显的协同效应，表观活化能为108.98 kJ/mol，明显低于理论值217.31 kJ/mol。动力学机制遵循随机成核和生长模型（A1/2）。热解产油率达到67.33 %，超过理论值64.78 %。产物分析表明，共热解有效地促进了脱氧反应和芳烃的生成。萘衍生物（1,2,3,4-四氢-2-苯基萘）和苯烯烃化合物的相对含量显著增加，总芳烃含量上升26.54 %，含氧化合物含量明显降低。机理分析表明，协同脱氧主要由氢转移反应和Diels-Alder途径产生，有效地提高了热解油的质量。本研究为多组分废弃物共热解生产高价值化学品提供了坚实的理论基础和可行的工艺路线。

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引用次数: 0

Hydrogenation liquefaction behavior and catalytic mechanism of Naomaohu coal-derived asphaltenes over different catalysts 不同催化剂对直毛湖煤系沥青质的加氢液化行为及催化机理的影响

IF 6.2 2区化学 Q1 CHEMISTRY, ANALYTICAL

Journal of Analytical and Applied Pyrolysis

Pub Date : 2026-05-01 Epub Date: 2026-01-23 DOI: 10.1016/j.jaap.2026.107641

Ying Zhu , Mei Zhong , Yang Liu , Zhenghua Dai , Lijun Jin , Yalkunjan Tursun , Shikun Li

To elucidate the conversion mechanism of Naomaohu coal-derived asphaltenes (NMH-ASP) in the high-temperature stage during the two-stage liquefaction (TSL) process, various catalysts, including Fe₂O₃, α-FeOOH, iron stearate (FeSA) and NiMo/γ-Al₂O₃, were presulfurized at low-temperature to reveal the effect of their active phase on liquefaction performance and products selectivity. The results showed that NMH-ASP conversion and oil yield dropped in the following order at 430 °C for 60 min: NiMo/γ-Al₂O₃ (85.32 wt%; 71.20 wt%) > FeSA (70.97 wt%; 63.71 wt%) > α-FeOOH (68.79 wt%; 61.50 wt%) > Fe₂O₃ (63.46 wt%; 54.76 wt%). The NiMoS phase from NiMo/γ-Al₂O₃ sulfurization exhibited superior H₂ activation ability, facilitating aromatic-ring hydrogenation and the cleavage of C_al–O and C_ar–O bonds, resulting in deep deoxygenation. Consequently, the liquefied oil showed the highest cycloalkane content (10.39 %) and the lowest oxygen-containing compounds (1.89 %), along with higher CO₂ content (1.50 wt%) in the gas. The Fe_1-xS phase of FeSA showed smaller, more uniform crystallite sizes, promoting the cleavage of aliphatic side chains and C_al–C_al bonds, leading to increased formation of chain alkanes (20.82 %) and C₁–C₄ gases (2.34 wt%). α-FeOOH-derived Fe_1-xS enhanced solvent hydrogen transfer to free radical fragments and promoted C_al–C_ar dealkylation, resulting in a higher benzene series content (29.62 %). However, the Fe_1-xS phase of Fe₂O₃ exhibited lower efficiency in C_ar–O bond cleavage, leading to the accumulation of phenols (8.21 %) and a higher content of the naphthalene series (43.49 %) due to insufficient aromatic-ring hydrogenation. This work provides theoretical guidance for catalyst design and process optimization in TSL.

为了阐明直毛湖煤系沥青质（NMH-ASP）在两段液化（TSL）过程中高温阶段的转化机理，采用Fe2O3、α-FeOOH、硬脂酸铁（FeSA）和NiMo/γ-Al2O3等催化剂进行了低温预硫化，揭示了其活性相对液化性能和产物选择性的影响。结果表明,按照以下顺序NMH-ASP转换和石油产量下降在430°C 60分钟:尼莫地平/γ氧化铝(85.32 wt %; 71.20 wt %)祝辞 FeSA(70.97 wt %; 63.71 wt %)祝辞 α-FeOOH(68.79 wt %; 61.50 wt %)祝辞 Fe2O3(63.46 wt %; 54.76 wt %)。由NiMo/γ-Al2O3硫化生成的NiMoS相表现出优异的H2活化能力，有利于芳香环加氢和Cal-O和Car-O键的裂解，从而产生深度脱氧。因此，液化油中环烷烃含量最高（10.39 %），含氧化合物含量最低（1.89 %），二氧化碳含量较高（1.50 wt%）。FeSA的Fe1-xS相晶粒尺寸更小、更均匀，促进了脂肪侧链和Cal-Cal键的断裂，增加了链烷烃（20.82 %）和C1-C4气体（2.34 wt%）的生成。α- feooh衍生的Fe1-xS增强了溶剂氢向自由基片段的转移，促进了Cal-Car脱烷基反应，提高了苯系物的含量（29.62 %）。然而，Fe2O3的Fe1-xS相对Car-O键的裂解效率较低，由于芳香环加氢不足，导致苯酚的积累（8.21 %）和萘系的含量较高（43.49 %）。该工作为TSL催化剂的设计和工艺优化提供了理论指导。

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引用次数: 0

Probing co-pyrolysis of rice straw with sulfur-donor thiourea: Insights into product evolution, reaction kinetics, thermodynamics, and compensation effects 水稻秸秆与硫供体硫脲共热解的探讨：对产物演化、反应动力学、热力学和补偿效应的见解

IF 6.2 2区化学 Q1 CHEMISTRY, ANALYTICAL

Journal of Analytical and Applied Pyrolysis

Pub Date : 2026-05-01 Epub Date: 2026-01-29 DOI: 10.1016/j.jaap.2026.107647

Zhitong Yao , Taoqi Yang , Baoyi Lin , Weihong Wu , Yang Chen , Nebojša Manić , Ljiljana Medic Pejic , Akash Kumar , Wei Qi

Understanding the synergistic interactions between biomass and sulfur-containing additives during co-pyrolysis is crucial for controlling sulfur transformation pathways and tailoring sulfur-doped carbonaceous materials. In the present study, the pyrolysis conversion of rice straw, thiourea, and their blend were probed using thermogravimetric analysis coupled with evolved gas analysis (TG–FTIR–MS and TG–GC/MS), isoconversional kinetics, master-plots method, and thermodynamic evaluation. The thiourea addition could alter the decomposition behavior, shifting the decomposition peaks from 335 to 348°C for rice straw and 255–266°C for thiourea to 206–241°C and 331–347°C for the blend, indicating intermolecular interactions during co-pyrolysis. Product evolution analysis revealed a transition from oxygenated volatiles (e.g., acetic acid and furan derivatives) to sulfur-containing species such as methanethiol and carbonyl sulfide, demonstrating modified reaction pathways induced by thiourea. Thermokinetics analysis showed that the average E_a of the blend (200 kJ mol⁻¹) exceeded those of individual rice straw (157 kJ mol⁻¹) and thiourea (103 kJ mol⁻¹), reflecting kinetic restructuring and the formation of thermally stabilized intermediates. Master-plots analysis identified a three-dimensional phase-boundary (R3) mechanism as dominant at conversions below 0.65, with deviations at higher conversions due to multi-step reactions. Linear correlations between apparent activation energy and pre-exponential factor indicated the occurrence of kinetic compensation effect, while thermodynamic study revealed the enthalpy–entropy compensation, with compensation temperatures matching experimental conditions. The positive values for enthalpy change (140–201 kJ mol⁻¹) and Gibbs free energy change (141–109 kJ mol⁻¹) indicating the non-spontaneous nature of these conversions. These results provided integrated kinetic, thermodynamic, and mechanistic insights into sulfur–biomass interactions during co-pyrolysis and offered guidance for controlling sulfur transformation in biomass-derived carbonaceous materials.

了解共热解过程中生物质与含硫添加剂之间的协同作用对于控制硫转化途径和定制掺硫碳质材料至关重要。本研究采用热重-逸出气体分析（TG-FTIR-MS和TG-GC /MS）、等转化动力学、主图法和热力学评价方法对稻草、硫脲及其共混物的热解转化进行了研究。添加硫脲可以改变秸秆的分解行为，将秸秆的分解峰从335℃移至348℃，将硫脲的分解峰从255 ~ 266℃移至206 ~ 241℃和331 ~ 347℃，表明共热解过程中的分子间相互作用。产物演化分析揭示了从含氧挥发物（如乙酸和呋喃衍生物）到含硫物质（如甲硫醇和羰基硫化物）的转变，证明了硫脲诱导的改性反应途径。热动力学分析表明，混合物的平均Ea（200 kJ mol⁻¹）超过了单个稻草（157 kJ mol⁻¹）和硫脲（103 kJ mol⁻¹），反映了动力学重组和热稳定中间体的形成。主图分析发现，在0.65以下的转化过程中，三维相界（R3）机制占主导地位，而在更高的转化过程中，由于多步反应而出现偏差。表观活化能与指前因子呈线性相关，表明存在动力学补偿效应，而热力学研究表明存在焓熵补偿效应，补偿温度与实验条件相符。焓变的正数（140-201 kJ mol⁻¹）和吉布斯自由能的正数（141-109 kJ mol⁻¹）表明了这些转化的非自发性质。这些结果为共热解过程中硫-生物质相互作用的动力学、热力学和机理提供了综合见解，并为控制生物质衍生碳质材料中的硫转化提供了指导。

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引用次数: 0

The structure-dependent regulation of CaO on NOx precursors during the pyrolysis of distinct amino acids 不同氨基酸热解过程中CaO对NOx前体的结构依赖性调控

IF 6.2 2区化学 Q1 CHEMISTRY, ANALYTICAL

Journal of Analytical and Applied Pyrolysis

Pub Date : 2026-05-01 Epub Date: 2026-01-14 DOI: 10.1016/j.jaap.2026.107615

Jiangtao Meng , Haobo Chang , Lei Ren , Jingkuan Li , Jing Wang

Pyrolysis conversion of sewage sludge faces a technical bottleneck of NOx pollution caused by high ash content and rich protein components. Among them, the influence of CaO on nitrogen transformation during amino acid pyrolysis is significant, yet the underlying principles and mechanisms governing its effect across amino acid with different structures remain poorly understood. To address this issue, this study focused on four representative amino acids: leucine (Leu), aspartic acid (Asp), phenylalanine (Phe), and histidine (His). It systematically investigated the migration behavior of nitrogen during their pyrolysis, which was driven by the synergistic effects of temperature and CaO. The results demonstrated that CaO reconstructed the directional migration pathways of nitrogen into char, tar, and gas. This reconstruction is achieved through four key actions: complexation, alkaline deamination, hydrolysis, and CO₂ mineralization. This reconstruction exhibits a decisive structural dependency: In polar amino acids (Asp, His), CaO strongly complexes with carboxyl/imidazole groups at low temperatures (255 ℃ and 350 ℃). This interaction traps nitrogen intermediates and diverts them toward stable structures in char, such as nitrile-N and CaCxNy. Consequently, the formation of gas-phase NOx precursors is suppressed. In contrast, for non-polar amino acids (Leu, Phe), CaO’s alkaline effect dominates, enhancing early deamination to release NH₃ and promoting nitrogen migration via the isocyanic acid pathway, which increases nitrogen allocation to the gas phase. This study has revealed the pathway reconstruction mechanism and structural response patterns of nitrogen migration during pyrolysis under CaO influence. It further proposed design strategies for the directional regulation of nitrogen, thereby providing fundamental support and a mechanistic guide for achieving low-NOx pyrolysis and the conversion of N-rich biomass into the zero-carbon fuel, NH₃.

污泥热解转化面临着高灰分和丰富蛋白质组分造成NOx污染的技术瓶颈。其中，CaO对氨基酸热解过程中氮转化的影响是显著的，但其对不同结构氨基酸影响的基本原理和机制尚不清楚。为了解决这一问题，本研究重点研究了四种具有代表性的氨基酸：亮氨酸（Leu）、天冬氨酸（Asp）、苯丙氨酸（Phe）和组氨酸（His）。系统研究了温度和CaO协同作用下氮在热解过程中的迁移行为。结果表明，CaO重建了氮向焦炭、焦油和气体的定向迁移路径。这种重建是通过四个关键作用实现的：络合、碱性脱氨、水解和二氧化碳矿化。这种重构表现出决定性的结构依赖性：在极性氨基酸（Asp, His）中，CaO在低温（255℃和350℃）下与羧基/咪唑基强配合。这种相互作用捕获了氮中间体，并将它们转移到碳中的稳定结构中，如腈- n和CaCxNy。因此，气相NOx前体的形成被抑制。相反，对于非极性氨基酸（亮氨酸、苯丙氨酸），CaO的碱性作用占主导地位，增强了早期脱胺作用释放NH3，促进了氮通过异氰酸途径迁移，增加了氮分配到气相。本研究揭示了CaO影响下热解过程中氮迁移的路径重构机制和结构响应模式。进一步提出氮定向调控的设计策略，为实现低nox热解和富n生物质转化为零碳燃料NH3提供基础支持和机制指导。

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引用次数: 0

Carboxylated UiO-66 metal-organic framework-supported nickel catalyst for hydrogenation of furfural to tetrahydrofurfuryl alcohol under mild conditions 羧化UiO-66金属-有机骨架负载镍催化剂在温和条件下糠醛加氢制四氢糠醇

IF 6.2 2区化学 Q1 CHEMISTRY, ANALYTICAL

Journal of Analytical and Applied Pyrolysis

Pub Date : 2026-05-01 Epub Date: 2026-01-14 DOI: 10.1016/j.jaap.2026.107616

Shuailong Dong , Bo Cai , Xinyi Luo , Mengyao Chen , Hui Pan

Selective hydrogenation is an important pathway to convert biomass-derived compounds to value-added chemicals. In this study, carboxylated metal-organic frameworks UiO-66-(COOH)₂ were prepared and used as a support to fabricate Ni-loaded catalyst by a simple impregnation method. The as-prepared catalyst 8Ni/UiO-66-(COOH)₂ could achieve a complete conversion of furfural (FAL) with a high selective yield of tetrahydrofurfuryl alcohol (THFOL) over 97 % under mild conditions (120 °C, 2 MPa H₂, 3 h). The XPS, Py-FTIR characterization showed that the introduction of a carboxyl group not only increased the acidic site of the catalyst, but also boosted the interaction between UiO-66 and metal Ni to form electron-rich Ni⁰ species. The catalyst poisoning test confirmed the critical role of the acid site in the hydrogenation of FAL. It is believed that the synergistic effect of metallic Ni and the carboxylated UiO-66 support contributed to the excellent catalytic activity of 8Ni/UiO-66-(COOH)₂. Moreover, the specific chemical adsorption of FAL on catalyst 8Ni/UiO-66-(COOH)₂ promoted the highly selective hydrogenation of FAL to THFOL. Based on the characterization and experiment results, a possible reaction pathway of the hydrogenation of FAL to THFOL over catalyst 8Ni/UiO-66-(COOH)₂ is proposed.

选择性加氢是将生物质衍生化合物转化为增值化学品的重要途径。本研究制备了羧基化金属-有机骨架UiO-66-(COOH)2，并采用简单浸渍法制备了负载ni催化剂。制备的8Ni/ uuo -66-(COOH)2催化剂在温和条件下（120℃，2 MPa H2, 3 h）可实现糠醛（FAL）的完全转化，四氢糠醇（THFOL）的选择性收率超过97 %。XPS和Py-FTIR表征表明，羧基的引入不仅增加了催化剂的酸性位点，而且促进了UiO-66与金属Ni之间的相互作用，形成富电子的Ni0物质。催化剂中毒试验证实了酸区在FAL加氢过程中的关键作用。认为金属Ni与羧化UiO-66载体的协同作用是8Ni/UiO-66-(COOH)2具有优异催化活性的原因。此外，FAL在8Ni/UiO-66-(COOH)2催化剂上的特异性化学吸附促进了FAL高度选择性加氢成THFOL。根据表征和实验结果，提出了在8Ni/UiO-66-(COOH)2催化剂上催化FAL加氢制THFOL的可能反应途径。

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引用次数: 0

Advances in multiphysics modelling and scale-up pathways for microwave-assisted pyrolysis in bioenergy applications 微波热解在生物能源应用中的多物理场建模和放大途径研究进展

IF 6.2 2区化学 Q1 CHEMISTRY, ANALYTICAL

Journal of Analytical and Applied Pyrolysis

Pub Date : 2026-05-01 Epub Date: 2026-01-13 DOI: 10.1016/j.jaap.2026.107613

Arian Shabruhi Mishamandani , Faisal Asfand , Muhammad Usman Saeed Akhtar , Sulaiman O. Fadlallah , M. Imran Khan , John M. Allport , Grant M. Campbell , Jose Maria Sanchez-Hervas

Achieving a sustainable energy future requires efficient renewable conversion pathways, with biomass emerging as a promising alternative. Microwave-assisted pyrolysis (MAP) has attracted growing interest due to its high energy efficiency and product yields, yet its complex interplay of electromagnetic, thermal, and chemical processes demands advanced modelling for reliable design and optimisation. Despite the use of diverse software tools to study MAP, systematic evaluations of their capabilities remain scarce. This review critically assesses major modelling platforms used in MAP research, including process simulators (e.g., Aspen Plus, Aspen HYSYS), Computational fluid dynamics (CFD)-based solvers (e.g., COMSOL Multiphysics, ANSYS CFX, OpenFOAM), and statistical or machine learning environments (e.g., MATLAB, Design Expert). Their applications are compared in terms of feedstock dependence, operating conditions, and modelling features. Process simulators are particularly effective for flowsheet analysis and techno-economic studies, while CFD tools capture transport phenomena and reactor-scale behaviour with high resolution. Data-driven platforms complement these approaches by enabling optimisation and predictive analytics. Given the complexity of MAP, a modular modelling strategy is recommended, treating stages such as drying, heating, and pyrolysis independently with tailored methods. By consolidating existing knowledge and identifying gaps, this review provides a practical guide for researchers and engineers to select and integrate the most suitable numerical approaches for advancing MAP system development.

实现可持续能源的未来需要有效的可再生能源转换途径，而生物质正成为一种有希望的替代方案。微波辅助热解（MAP）因其高能效和产品产量而吸引了越来越多的兴趣，但其复杂的电磁、热和化学过程的相互作用需要先进的建模来进行可靠的设计和优化。尽管使用了多种软件工具来研究MAP，但对其能力的系统评估仍然很少。本文批判性地评估了MAP研究中使用的主要建模平台，包括过程模拟器（例如，Aspen Plus, Aspen HYSYS），基于计算流体动力学（CFD）的求解器（例如，COMSOL Multiphysics, ANSYS CFX, OpenFOAM）以及统计或机器学习环境（例如，MATLAB, Design Expert）。它们的应用在原料依赖性、操作条件和建模特征方面进行了比较。过程模拟器在流程图分析和技术经济研究中特别有效，而CFD工具则以高分辨率捕获传输现象和反应器规模行为。数据驱动平台通过实现优化和预测分析来补充这些方法。考虑到MAP的复杂性，建议采用模块化建模策略，以量身定制的方法独立处理干燥、加热和热解等阶段。通过巩固现有知识和识别差距，本文综述为研究人员和工程师选择和整合最合适的数值方法以推进MAP系统开发提供了实用指南。

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引用次数: 0

In-situ mechanistic elucidation of 1-hexadecene pyrolysis as a polyethylene model compound 1-十六烯作为聚乙烯模型化合物热解的原位机理分析

IF 6.2 2区化学 Q1 CHEMISTRY, ANALYTICAL

Journal of Analytical and Applied Pyrolysis

Pub Date : 2026-05-01 Epub Date: 2026-01-09 DOI: 10.1016/j.jaap.2026.107606

Yinzhi Wang , Yunqing Zhou , Zhenzhen Wu , Hualiang Li , Chuanqi Shi , Siyi Bao , Jianhua Yan , Hao Zhang

The pyrolysis mechanism of polyethylene (PE) remains elusive owing to its inherent complexity and the difficulty in identifying reactive intermediates. In this work, 1-hexadecene was employed as a model compound and pyrolyzed in a custom low-pressure flow tube reactor. The pyrolysis intermediates and products were detected via in-situ electron ionization molecular beam mass spectrometry (EI-MBMS) across 300–980 °C. A total of up to 59 species were identified, including primary pyrolysis intermediates (PPIs), primary pyrolysis products (PPPs), secondary reaction intermediates (SRIs), and secondary reaction products (SRPs), with 16 key species quantified. Three distinct pyrolysis stages were revealed: at the initial stage (320–680°C), 1-hexadecene underwent limited decomposition, dominated by β-scission near the double bond, producing mainly unsaturated hydrocarbons, while hydrogen transfer reactions exhibited pronounced olefin selectivity. At the stage with increasing temperature (680–880°C), the radical concentration increased sharply, promoting extensive β-scission and the onset of secondary reactions. Aromatic precursors such as cyclopentadiene emerged, accompanied by intensified dehydrogenation. At the final stage (880–980°C), the reactant was nearly depleted, and olefins underwent deep cracking. Both Diels–Alder reactions and the chain reaction hydrocarbon aggregation (CHRCR) mechanism jointly drove aromatization, with the propargyl radical (C₃H₃) serving as a key intermediate for the first aromatic ring formation. This study systematically elucidates the pyrolysis pathway of 1-hexadecene from radical initiation to aromatic and small-molecule formation, highlighting the temperature-dependent transition from primary bond scission to extensive dehydrogenation and aromatization. The findings offer fundamental insights for accurate modeling and optimization of polyethylene pyrolysis in chemical recycling.

聚乙烯（PE）的热解机理由于其固有的复杂性和难以识别的反应中间体而一直不为人所知。在这项工作中，以1-十六烯为模型化合物，在定制的低压流管反应器中进行热解。通过原位电子电离分子束质谱（EI-MBMS）在300-980°C范围内检测热解中间体和产物。共鉴定出59种，包括一次热解中间体（PPIs）、一次热解产物（PPPs）、二次反应中间体（SRIs）和二次反应产物（SRPs），其中16种被量化。结果表明：在初始阶段（320 ~ 680℃），1-十六烯进行有限分解，以双键附近的β-裂解为主，主要生成不饱和烃，而氢转移反应具有明显的烯烃选择性。在温度升高阶段（680 ~ 880℃），自由基浓度急剧升高，促进了β的广泛断裂和二次反应的发生。芳香族前体如环戊二烯出现，并伴有脱氢反应加剧。在最后阶段（880 ~ 980℃），反应物几乎耗尽，烯烃发生深度裂化。Diels-Alder反应和链式烃聚集（CHRCR）机制共同驱动芳构化，丙炔自由基（C3H3）是形成第一个芳环的关键中间体。本研究系统地阐明了1-十六烯从自由基起始到芳香和小分子形成的热解途径，强调了从初级键断裂到广泛脱氢和芳构化的温度依赖转变。研究结果为化学循环中聚乙烯热解的精确建模和优化提供了基础见解。

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引用次数: 0

In situ assessment of lignin pyrolysis reactions and their interactions with polysaccharides in Japanese cedar wood cell walls by TG-MS and Py-GC/MS 利用TG-MS和Py-GC/MS原位评价杉木细胞壁中木质素热解反应及其与多糖的相互作用

IF 6.2 2区化学 Q1 CHEMISTRY, ANALYTICAL

Journal of Analytical and Applied Pyrolysis

Pub Date : 2026-05-01 Epub Date: 2026-01-20 DOI: 10.1016/j.jaap.2026.107638

Daijiro Taira, Takashi Nomura, Eiji Minami, Haruo Kawamoto

Understanding the thermal degradation of lignin and polysaccharides in wood cell walls is essential for optimizing biomass pyrolysis. In this study, Japanese cedar (Cryptomeria japonica) was analyzed using thermogravimetric-mass spectrometry (TG-MS). Coupled with pyrolysis-gas chromatography-mass spectrometry (Py-GC/MS), TG-MS enabled semi-quantitative analysis of key volatile products evolved during thermal degradation, each corresponding to distinct m/z values. Comparison between intact wood and isolated milled wood lignin (MWL) revealed the influence of cell wall supramolecular structures on lignin pyrolysis. The water (m/z 18) evolution profiles from both materials exhibited six distinct peaks, indicating stepwise lignin decomposition across six temperature ranges up to 1000 °C. β-Ether cleavage predominantly yielded coniferyl aldehyde rather than coniferyl alcohol at early stages, suggesting a polymer effect that promotes in situ C_γ oxidation—an observation rarely observed in model compound studies. The formation temperatures of pyrolysis products followed the order: β-ether bond cleavage < side-chain saturation < methoxy group demethylation. In intact wood, secondary reactions such as side-chain saturation and demethylation occurred at significantly lower temperatures than in MWL. Since the pyrolysis product profiles of MWL remained largely unaffected by the addition of sugars, the enhanced reactivity in wood is attributed to the influence of the cell wall ultrastructure. This study is the first to provide detailed in situ insights into the thermal degradation behavior of lignin and polysaccharides within wood cell walls, offering valuable contributions to the field of wood pyrolysis.

了解木质素和多糖在木材细胞壁中的热降解对优化生物质热解至关重要。本研究采用热重质谱法（TG-MS）对杉木（Cryptomeria japonica）进行了分析。结合热解-气相色谱-质谱（Py-GC/MS）， TG-MS可以对热降解过程中产生的关键挥发性产物进行半定量分析，每个挥发性产物对应不同的m/z值。通过对完整木材和分离木质素（MWL）的比较，揭示了细胞壁超分子结构对木质素热解的影响。两种材料的水（m/z 18）演化谱显示出6个不同的峰，表明木质素在高达1000℃的6个温度范围内逐步分解。β-醚裂解在早期阶段主要产生针叶醛而不是针叶醇，这表明聚合物效应促进了原位Cγ氧化——这在模型化合物研究中很少观察到。热解产物的形成温度顺序为：β-醚键裂解<； 侧链饱和<； 甲氧基去甲基化。在完整木材中，侧链饱和和去甲基化等二次反应在明显低于MWL的温度下发生。由于MWL的热解产物谱在很大程度上不受添加糖的影响，因此木材中的反应性增强归因于细胞壁超微结构的影响。该研究首次对木质素和多糖在木材细胞壁内的热降解行为提供了详细的原位洞察，为木材热解领域提供了有价值的贡献。

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引用次数: 0

Mechanism study on the influence of moisture on the distribution of typical gases during non-caking coal pyrolysis based on ReaxFF 基于ReaxFF的无结块煤热解过程中水分对典型气体分布影响机理研究

IF 6.2 2区化学 Q1 CHEMISTRY, ANALYTICAL

Journal of Analytical and Applied Pyrolysis

Pub Date : 2026-05-01 Epub Date: 2026-01-29 DOI: 10.1016/j.jaap.2026.107635

Jie Cui, Zengchao Feng

To reveal the regulatory mechanism of moisture on the distribution of typical gases during non-caking coal pyrolysis, a single-molecule model of non-caking coal was constructed and optimized based on characterization test results, with the molecular formula C₁₇₉H₁₄₂N₂O₄₉. Four pyrolysis systems (ZR, ZQ-5 %H₂O, ZQ-15 %H₂O, and ZQ-25 %H₂O) were designed, and ReaxFF MD simulations were performed on the pyrolysis process under different final temperature conditions using a three-stage simulation strategy. The results indicate that the total mass fraction of pyrolysis gases gradually increases with the rise of moisture content. Temperature is the core regulatory factor for the generation of typical gases, while the effect of moisture is temperature-dependent. Below 3000 K, moisture inhibits CO₂ formation and promotes CH₄/C₂H₄/H₂ generation; above 3000 K, it exerts a promoting effect on all gases. Moisture significantly regulates the time sequence of gas generation and exerts differential impacts on the formation pathways of various gases: the yields of C₂H₄ and H₂ increase with increasing moisture content, CO₂ is less affected, and CH₄ shows a dual response of "generation-consumption". This study provides theoretical support for optimizing the non-caking coal pyrolysis process and directionally regulating gas products, and offers important reference value for the clean conversion of low-rank coal.

为揭示水分对无结块煤热解过程中典型气体分布的调控机理，基于表征试验结果，构建了无结块煤单分子模型并进行优化，分子式为C₁₇₉H₁₄₂N₂O₄₉。设计了ZR、ZQ-5 %H₂O、ZQ-15 %H₂O和ZQ-25 %H₂O四个热解体系，采用三阶段模拟策略对不同终温条件下的热解过程进行了ReaxFF MD模拟。结果表明：随着含水率的增加，热解气体的总质量分数逐渐增大；温度是典型气体产生的核心调节因子，而湿度的影响则依赖于温度。在3000 K以下，水分抑制CO₂的形成，促进CH₄/C₂H₄/H₂的生成；在3000 K以上，对所有气体都有促进作用。水分显著调节气相生成的时间顺序，对各种气体的形成途径产生不同的影响：C₂H₄和H₂的产率随水分含量的增加而增加，CO₂的影响较小，而CH₄则表现出“生成-消耗”的双重响应。本研究为优化无结块煤热解工艺和定向调节气产物提供了理论支持，为低阶煤的清洁转化提供了重要参考价值。

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引用次数: 0

Enhanced waste-to-fuel gas conversion via co-pyrolysis of purified terephthalic acid sludge ash and phoenix tree’s leaves 利用纯化对苯二甲酸污泥灰和梧桐树叶共热解提高废物制气转化率

IF 6.2 2区化学 Q1 CHEMISTRY, ANALYTICAL

Journal of Analytical and Applied Pyrolysis

Pub Date : 2026-05-01 Epub Date: 2026-01-21 DOI: 10.1016/j.jaap.2026.107639

Zhou Yang , Hanchuan Liu , Yongjuan Zhao , Shiyi Ye , Yulong Liang , Hongyu Zhao , Xinxin Xing , Xiaoyuan Wang , Yinfeng Wang

Purified terephthalic acid (PTA) production generates substantial sludge, which is characterized by the high content of metal elements (such as Ca, Co and Mn) in the ash, classifying it as a hazardous organic waste. This study comprehensively investigated the synergistic pyrolysis of PTA sludge ash (PTASA) and phoenix tree’s leaves (PTL) for syngas production. Through systematic characterisation of the physicochemical properties of PTASA and PTL, combined with thermal degradation behavior analysis and pyrolysis experiments, the aim was to determine the optimal conditions for producing high-value gas. The results showed that when the mixing ratio of PS850 (PTASA calcinated at 850℃) reached 30 %, the values of total mass loss (TML) and comprehensive pyrolysis index (CPI) as well as the quality of syngas have reached the best level. In addition, compared with PTL mono-pyrolysis, adding PTASA could increase the total volatile products by 16.4 %, owing to the cooperative pyrolysis for CO, CC and C-O groups. Moreover, in-situ co-pyrolysis proved superior to ex-situ conditions for hydrogen-rich gas production. The PTASA calcined at 750°C(PS750) exhibited the most pronounced catalytic effect with stable microstructure and excellent metal mineral composition, and the total effective gas (CO + H₂ + CH₄) yields of 442.52 mL/g, which was 4 % higher than that of the co-pyrolysis process of PS850 and PTL. This study provides significant insights for expanding the high-value utilization of solid waste resources.

纯化对苯二甲酸（PTA）生产产生大量污泥，其特点是灰分中金属元素（如Ca、Co和Mn）含量高，属于危险有机废物。本研究对PTA污泥灰（PTASA）和凤凰叶（PTL）协同热解制合成气进行了全面研究。通过系统表征PTASA和PTL的理化性质，结合热降解行为分析和热解实验，确定高值气的最佳产气条件。结果表明，当PS850（850℃煅烧的PTASA）的掺量为30 %时，其总失重（TML）、综合热解指数（CPI）及合成气质量均达到最佳水平。此外，由于CO、CC和C-O基团的协同热解，与PTL单热解相比，PTASA的加入可使总挥发产物增加16.4 %。此外，原位共热解条件优于非原位共热解条件生产富氢气体。750℃煅烧的PTASA （PS750）具有稳定的微观结构和优良的金属矿物组成，催化效果最为显著，总有效气体（CO + H₂+ CH₄）产率为442.52 mL/g，比PS850和PTL共热解的产率提高了4. %。本研究为扩大固体废物资源的高价值利用提供了重要的见解。

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引用次数: 0