Pub Date : 2026-01-05DOI: 10.1016/j.jaap.2026.107597
Mazlum Cengiz , İsmail Kayri , Hüseyin Aydın
This study provides a critical review of low-density polyethylene waste plastic oil as an alternative fuel for compression ignition engines. First, the feedstocks, pyrolysis and co-pyrolysis production routes, and the resulting physicochemical fuel properties are presented. Subsequently, the effects of neat low-density polyethylene waste plastic oil and its blends with diesel, additives, biofuels, and gaseous fuels on diesel engine combustion, performance, and emissions are systematically evaluated. A blend containing 20 vol% low-density polyethylene waste plastic oil in diesel fuel represented a viable configuration, while additives, exhaust gas recirculation, and advanced combustion strategies were essential for emission control. The available literature on LDPE-WPO and its blends with alcohols and additives remains limited. Furthermore, aging and storage stability, deposit formation, corrosion, and injector fouling have not been thoroughly investigated. Moreover, significant research gaps remain in fuel property standardization, large-scale production, long-term engine durability, advanced engine concepts, and life-cycle and techno-economic assessments.
{"title":"A holistic review on physicochemical properties and engine applications of low-density polyethylene pyrolysis oil","authors":"Mazlum Cengiz , İsmail Kayri , Hüseyin Aydın","doi":"10.1016/j.jaap.2026.107597","DOIUrl":"10.1016/j.jaap.2026.107597","url":null,"abstract":"<div><div>This study provides a critical review of low-density polyethylene waste plastic oil as an alternative fuel for compression ignition engines. First, the feedstocks, pyrolysis and co-pyrolysis production routes, and the resulting physicochemical fuel properties are presented. Subsequently, the effects of neat low-density polyethylene waste plastic oil and its blends with diesel, additives, biofuels, and gaseous fuels on diesel engine combustion, performance, and emissions are systematically evaluated. A blend containing 20 vol% low-density polyethylene waste plastic oil in diesel fuel represented a viable configuration, while additives, exhaust gas recirculation, and advanced combustion strategies were essential for emission control. The available literature on LDPE-WPO and its blends with alcohols and additives remains limited. Furthermore, aging and storage stability, deposit formation, corrosion, and injector fouling have not been thoroughly investigated. Moreover, significant research gaps remain in fuel property standardization, large-scale production, long-term engine durability, advanced engine concepts, and life-cycle and techno-economic assessments.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"194 ","pages":"Article 107597"},"PeriodicalIF":6.2,"publicationDate":"2026-01-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145920675","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-05DOI: 10.1016/j.jaap.2026.107600
Shanjian Liu , Guanshuai Zhang , Jiyan Ma , Qingqing Qian , Chengxizi Zhang , Bin Zhou
The production of high-value-added nitrogenous chemicals through pyrolysis technology is a new approach to realize the utilization of waste poultry feathers. In this research, aiming at the problem of low yield of nitrogenous chemicals obtained by conventional pyrolysis, it is proposed to use four catalysts, namely MCM-41, ZSM-5, ZIF-67 and γ-Al2O3, for the directional regulation of products during the pyrolysis process. The influence of catalyst types and addition ratios on the distribution of bio-oil components were investigated. The results indicated that MCM-41 and ZIF-67 significantly boosted the generation of nitrogen-containing compounds, especially nitriles and pyrroles. When using MCM-41, the nitrogenous compounds content grew from 66.3 % to a maximum of 81.8 %. Pyrroles increased from 7.7 % to 26.9 %, and that of nitriles rose from 9.9 % to 29.8 %. ZSM-5 and γ-Al2O3 had no significant effect on the generation of nitrogen-containing compounds. Finally, combined with the research findings, the influence mechanism of different types of catalysts on the migration and transformation of nitrogen in feather was analyzed. The results of this research provide a guide for the preparation of highly selective nitrogenous chemicals using feathers as raw materials.
{"title":"Catalytic pyrolysis of endogenous nitrogen in feather protein enhances the generation of nitriles and pyrroles in pyrolysis oil: N element migration mechanism","authors":"Shanjian Liu , Guanshuai Zhang , Jiyan Ma , Qingqing Qian , Chengxizi Zhang , Bin Zhou","doi":"10.1016/j.jaap.2026.107600","DOIUrl":"10.1016/j.jaap.2026.107600","url":null,"abstract":"<div><div>The production of high-value-added nitrogenous chemicals through pyrolysis technology is a new approach to realize the utilization of waste poultry feathers. In this research, aiming at the problem of low yield of nitrogenous chemicals obtained by conventional pyrolysis, it is proposed to use four catalysts, namely MCM-41, ZSM-5, ZIF-67 and γ-Al<sub>2</sub>O<sub>3</sub>, for the directional regulation of products during the pyrolysis process. The influence of catalyst types and addition ratios on the distribution of bio-oil components were investigated. The results indicated that MCM-41 and ZIF-67 significantly boosted the generation of nitrogen-containing compounds, especially nitriles and pyrroles. When using MCM-41, the nitrogenous compounds content grew from 66.3 % to a maximum of 81.8 %. Pyrroles increased from 7.7 % to 26.9 %, and that of nitriles rose from 9.9 % to 29.8 %. ZSM-5 and γ-Al<sub>2</sub>O<sub>3</sub> had no significant effect on the generation of nitrogen-containing compounds. Finally, combined with the research findings, the influence mechanism of different types of catalysts on the migration and transformation of nitrogen in feather was analyzed. The results of this research provide a guide for the preparation of highly selective nitrogenous chemicals using feathers as raw materials.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"194 ","pages":"Article 107600"},"PeriodicalIF":6.2,"publicationDate":"2026-01-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145920674","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
To address the increasing scarcity of high-quality coking coal resources and the theoretical need to improve coke quality through optimized coal blending, Hongsheng coking coal (HSCC) and Kunpeng fat coal (KPFC) were selected as primary coals, with Huangling gas coal (HLGC) and Yonghesheng lean coal (YHSLC) as blending coals. By comprehensively utilizing X-ray photoelectron spectroscopy (XPS), solid-state 13C nuclear magnetic resonance (13C NMR), high-resolution transmission electron microscopy (HRTEM), a 10 kg laboratory-scale simulated coke oven, and coke thermal reactivity analysis, the relationship between carbon structures and coke properties in different coal blending systems during the coking process from 600 to 1000°C was systematically investigated. The results showed that coal blending characteristics significantly affect the uniformity of temperature and pressure distribution within the coke oven. An excessively high proportion of gas coal impedes heat transfer toward the center, while an increased proportion of lean coal aggravates temperature non-uniformity due to reduced plasticity. The thermal properties of coke can be directionally regulated by blending. A high proportion of aromatic bridgehead carbon (Xb) and a low degree of aromatic ring substitution (δ) are conducive to increasing coke strength after reaction (CSR). Additionally, a high lattice fringe tortuosity is associated with a high coke reactivity index (CRI). The 9HS1YHS and 8HS2YHS exhibit excellent thermal properties, while 7KP3HL demonstrates a synergistic effect. This multi-scale analysis provides a theoretical basis for optimizing blending ratios and coke quality.
{"title":"Insight into the relationship between carbon structure and coke performance during coal blending coking","authors":"Hanwen Zhu , Peng Yu , Xinni Zhao , Lu Tian , Hua Li , Xingxing Chen , Jinxiao Dou , Jianglong Yu","doi":"10.1016/j.jaap.2026.107598","DOIUrl":"10.1016/j.jaap.2026.107598","url":null,"abstract":"<div><div>To address the increasing scarcity of high-quality coking coal resources and the theoretical need to improve coke quality through optimized coal blending, Hongsheng coking coal (HSCC) and Kunpeng fat coal (KPFC) were selected as primary coals, with Huangling gas coal (HLGC) and Yonghesheng lean coal (YHSLC) as blending coals. By comprehensively utilizing X-ray photoelectron spectroscopy (XPS), solid-state <sup>13</sup>C nuclear magnetic resonance (<sup>13</sup>C NMR), high-resolution transmission electron microscopy (HRTEM), a 10 kg laboratory-scale simulated coke oven, and coke thermal reactivity analysis, the relationship between carbon structures and coke properties in different coal blending systems during the coking process from 600 to 1000°C was systematically investigated. The results showed that coal blending characteristics significantly affect the uniformity of temperature and pressure distribution within the coke oven. An excessively high proportion of gas coal impedes heat transfer toward the center, while an increased proportion of lean coal aggravates temperature non-uniformity due to reduced plasticity. The thermal properties of coke can be directionally regulated by blending. A high proportion of aromatic bridgehead carbon (<em>X</em><sub>b</sub>) and a low degree of aromatic ring substitution (<em>δ</em>) are conducive to increasing coke strength after reaction (CSR). Additionally, a high lattice fringe tortuosity is associated with a high coke reactivity index (CRI). The 9HS1YHS and 8HS2YHS exhibit excellent thermal properties, while 7KP3HL demonstrates a synergistic effect. This multi-scale analysis provides a theoretical basis for optimizing blending ratios and coke quality.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"194 ","pages":"Article 107598"},"PeriodicalIF":6.2,"publicationDate":"2026-01-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145920677","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-05DOI: 10.1016/j.jaap.2026.107596
Hui Zhang , Yujie Zhang , Jiaofei Wang , Yonghui Bai , Xudong Song , Weiguang Su , Peng Lv , Guangsuo Yu
Catalytic pyrolysis is a promising method for converting biomass into high-value bio-oil, but the high water (15 %-35 %) and oxygen content in bio-oil limits its application. A dual-catalyst system of CaO and Ni/Char has shown effectiveness, but improving their interaction to reduce water formation and enhance bio-oil quality requires further research. This study investigated the effect of carrier type and Ni loading on bio-oil composition and water yield during the pyrolysis of corn straw in Py-GC/MS and a fixed-bed reactor. Results revealed that AC, compared to other supports like bio-char, showed weaker activity and selectivity in cracking bio-oil components. When a Ca-Ni binary catalyst was introduced, the water yield decreased by 9 % compared to Ni/AC, dropping from 31 % in non-catalytic pyrolysis of CS to 21 %. Interestingly, the amount of CaO in the binary system was only half of that in pure CaO catalysts, yet it achieved similar results in reducing water yield. The low-temperature water vapor adsorption of CaO and the catalytic role of Ni/AC synergistically promoted water conversion and bio-oil formation. Additionally, the improvement of Ni/AC on phenol formation combined with the inhibition of CaO on phenol decomposition increased phenolic content by 49 % from 40 % in non-catalytic pyrolysis. Higher Ni loading reduced oil yield but selectively retained phenols through the suppression of phenols cracking. The study also explored the different effects of high-activity and low-activity Ni-CaO systems.
{"title":"Enhancing bio-oil quality: The synergistic effects of a CaO and Ni/AC dual-catalyst system on catalytic pyrolysis of corn straw","authors":"Hui Zhang , Yujie Zhang , Jiaofei Wang , Yonghui Bai , Xudong Song , Weiguang Su , Peng Lv , Guangsuo Yu","doi":"10.1016/j.jaap.2026.107596","DOIUrl":"10.1016/j.jaap.2026.107596","url":null,"abstract":"<div><div>Catalytic pyrolysis is a promising method for converting biomass into high-value bio-oil, but the high water (15 %-35 %) and oxygen content in bio-oil limits its application. A dual-catalyst system of CaO and Ni/Char has shown effectiveness, but improving their interaction to reduce water formation and enhance bio-oil quality requires further research. This study investigated the effect of carrier type and Ni loading on bio-oil composition and water yield during the pyrolysis of corn straw in Py-GC/MS and a fixed-bed reactor. Results revealed that AC, compared to other supports like bio-char, showed weaker activity and selectivity in cracking bio-oil components. When a Ca-Ni binary catalyst was introduced, the water yield decreased by 9 % compared to Ni/AC, dropping from 31 % in non-catalytic pyrolysis of CS to 21 %. Interestingly, the amount of CaO in the binary system was only half of that in pure CaO catalysts, yet it achieved similar results in reducing water yield. The low-temperature water vapor adsorption of CaO and the catalytic role of Ni/AC synergistically promoted water conversion and bio-oil formation. Additionally, the improvement of Ni/AC on phenol formation combined with the inhibition of CaO on phenol decomposition increased phenolic content by 49 % from 40 % in non-catalytic pyrolysis. Higher Ni loading reduced oil yield but selectively retained phenols through the suppression of phenols cracking. The study also explored the different effects of high-activity and low-activity Ni-CaO systems.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"194 ","pages":"Article 107596"},"PeriodicalIF":6.2,"publicationDate":"2026-01-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145920673","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-03DOI: 10.1016/j.jaap.2026.107595
Lujie Wang , Yunfei Wang , Quansheng Liu , Jianxiu Hao , Na Li , Keduan Zhi , Huacong Zhou , Yanpeng Ban
The utilization of carbide slag (CS) as a calcium-based catalyst in coal gasification and pyrolysis presents significant economic and environmental benefits, enabling efficient conversion of low-rank coals such as lignite while facilitating the valorization of industrial waste. However, the impacts of different CS addition strategies on the thermal conversion behavior of lignite remain poorly understood. The present study addresses this issue by introducing CS as a catalyst in lignite by means of four different treatment methods, including physical mixing, mechanical activation, impregnation, and hydrothermal treatment. The treated samples were subjected to detailed physicochemical characterization, and the main syngas constituents during gasification and the dominant molecular species in pyrolysis tar were systematically analyzed. The results reveal that mechanical activation, impregnation, and hydrothermal treatment exerted pronounced influences on syngas composition, reducing the temperature corresponding to the maximum decomposition rate by 199 °C, 227 °C, and 229 °C, respectively, compared with the untreated lignite. The treatment method also affected the ratio of liquid product yields to gas product yields, where physical mixing and mechanical activation increased this ratio, while impregnation and hydrothermal treatment significantly decreased this ratio. Regarding liquid pyrolysis products, mechanical activation, impregnation, and hydrothermal treatment enhanced the formation of hydrocarbon compounds while reducing the abundance of alcohols, phenols, and ethers. This work provides valuable theoretical insights and practical guidance for optimizing calcium-based catalytic coal conversion, thereby advancing the development of clean and efficient coal utilization technologies.
{"title":"Synergistic regulation of lignite thermal conversion and product evolution by carbide slag addition strategies","authors":"Lujie Wang , Yunfei Wang , Quansheng Liu , Jianxiu Hao , Na Li , Keduan Zhi , Huacong Zhou , Yanpeng Ban","doi":"10.1016/j.jaap.2026.107595","DOIUrl":"10.1016/j.jaap.2026.107595","url":null,"abstract":"<div><div>The utilization of carbide slag (CS) as a calcium-based catalyst in coal gasification and pyrolysis presents significant economic and environmental benefits, enabling efficient conversion of low-rank coals such as lignite while facilitating the valorization of industrial waste. However, the impacts of different CS addition strategies on the thermal conversion behavior of lignite remain poorly understood. The present study addresses this issue by introducing CS as a catalyst in lignite by means of four different treatment methods, including physical mixing, mechanical activation, impregnation, and hydrothermal treatment. The treated samples were subjected to detailed physicochemical characterization, and the main syngas constituents during gasification and the dominant molecular species in pyrolysis tar were systematically analyzed. The results reveal that mechanical activation, impregnation, and hydrothermal treatment exerted pronounced influences on syngas composition, reducing the temperature corresponding to the maximum decomposition rate by 199 °C, 227 °C, and 229 °C, respectively, compared with the untreated lignite. The treatment method also affected the ratio of liquid product yields to gas product yields, where physical mixing and mechanical activation increased this ratio, while impregnation and hydrothermal treatment significantly decreased this ratio. Regarding liquid pyrolysis products, mechanical activation, impregnation, and hydrothermal treatment enhanced the formation of hydrocarbon compounds while reducing the abundance of alcohols, phenols, and ethers. This work provides valuable theoretical insights and practical guidance for optimizing calcium-based catalytic coal conversion, thereby advancing the development of clean and efficient coal utilization technologies.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"194 ","pages":"Article 107595"},"PeriodicalIF":6.2,"publicationDate":"2026-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145921190","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-02DOI: 10.1016/j.jaap.2026.107594
Jiamei Yu , Bolinfeng Li , Chen Zhao , Xuerui Ma , Yufeng Wu
Pyrolysis shows great potential for recycling retired photovoltaic module laminates, as it can decompose organic components (e.g., EVA and backsheets) and efficiently recover metals and glass. To address the challenges posed by the coexistence of EVA, PET and PVF in retired photovoltaic laminates, this work comprehensively analyzes the thermo-chemical interactions between organic components and their synergetic effects in co-pyrolysis processes through both experimental and theoretical techniques. Unexpectedly, the co-pyrolysis of binary EVA/PET and EVA/PVF mixtures exhibits a promoting effect, evidenced by the lower activation energy and higher comprehensive pyrolysis index compared with individual pyrolysis. Furthermore, EVA/PET co-pyrolysis increases the CO2 ratio by 8 %, and EVA/PVF co-pyrolysis enhances the HF production by approximately 26 %. In contrast, the co-existence of PET and PVF shows inhibitory effects. For the co-pyrolysis of ternary mixtures, as the concentration of EVA increases from 1:3, 1:2, 1:1, to 2:1, the activation energy increases subsequently from 222.25 kJ/mol, 233.90 kJ/mol, 236.27 kJ/mol, to 255.69 kJ/mol, indicating that an increased concentration of EVA is unfavorable to the co-pyrolysis. Moreover, the decomposition pathways of EVA, PET, and PVF pyrolysis are identified by DFT calculations. The bond dissociation sequence is consistent with the molecular dynamics simulations. This work not only enhances the understanding of the synergetic effects of multi-organic components in the co-pyrolysis process, but also aids in the development of more effective pyrolysis processes for recycling PV module by regulating the composition of organic polymers.
{"title":"Experimental and computational exploration of co-pyrolysis characteristics and kinetics of hybrid organic components of retired photovoltaic laminates","authors":"Jiamei Yu , Bolinfeng Li , Chen Zhao , Xuerui Ma , Yufeng Wu","doi":"10.1016/j.jaap.2026.107594","DOIUrl":"10.1016/j.jaap.2026.107594","url":null,"abstract":"<div><div>Pyrolysis shows great potential for recycling retired photovoltaic module laminates, as it can decompose organic components (e.g., EVA and backsheets) and efficiently recover metals and glass. To address the challenges posed by the coexistence of EVA, PET and PVF in retired photovoltaic laminates, this work comprehensively analyzes the thermo-chemical interactions between organic components and their synergetic effects in co-pyrolysis processes through both experimental and theoretical techniques. Unexpectedly, the co-pyrolysis of binary EVA/PET and EVA/PVF mixtures exhibits a promoting effect, evidenced by the lower activation energy and higher comprehensive pyrolysis index compared with individual pyrolysis. Furthermore, EVA/PET co-pyrolysis increases the CO<sub>2</sub> ratio by 8 %, and EVA/PVF co-pyrolysis enhances the HF production by approximately 26 %. In contrast, the co-existence of PET and PVF shows inhibitory effects. For the co-pyrolysis of ternary mixtures, as the concentration of EVA increases from 1:3, 1:2, 1:1, to 2:1, the activation energy increases subsequently from 222.25 kJ/mol, 233.90 kJ/mol, 236.27 kJ/mol, to 255.69 kJ/mol, indicating that an increased concentration of EVA is unfavorable to the co-pyrolysis. Moreover, the decomposition pathways of EVA, PET, and PVF pyrolysis are identified by DFT calculations. The bond dissociation sequence is consistent with the molecular dynamics simulations. This work not only enhances the understanding of the synergetic effects of multi-organic components in the co-pyrolysis process, but also aids in the development of more effective pyrolysis processes for recycling PV module by regulating the composition of organic polymers.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"194 ","pages":"Article 107594"},"PeriodicalIF":6.2,"publicationDate":"2026-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145920738","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Methane decomposition is increasingly recognized as pivotal technology for simultaneous production of H2 and carbon nanomaterials, yet its industrial implementation is severely constrained by high operating temperatures and rapid deactivation to thermal catalytic systems. By integrating in-situ optical emission spectroscopy with multi-scale characterization, it is demonstrated that plasma serves a four-fold function in the Fe-based catalytic system: (1) excitation of CH4 into a controllable radical pool, (2) enhancement of radical adsorption energy on Fe surfaces through plasma-induced electronic polarization, (3) implementation of a hydrogen-mediated "pathway pruning" mechanism wherein H* abstracts H from CHx* species, preventing gas-phase polymerization while simultaneously accelerating surface-catalyzed carbon assembly, and (4) in-situ etching of amorphous carbon and promotion of surface hydrogen-assisted dehydrogenation on M-H sites. These coupled mechanisms synergistically suppress electrode carbon deposition, enabling sustained discharge stability and maintaining the plasma discharge in high-efficiency tip-discharge regime. Consequently, at 700 °C, the plasma-catalytic system achieves methane conversion of 42.67 % (compared to 25 % in pure plasma at 700 °C, and 19.25 % in pure thermal catalytic at 750 °C), hydrogen selectivity of 57.88 %, carbon yield of 105 mg·gcat−1·h−1, and uniform CNTs with enhanced graphitization. This work provides a quantitative mechanistic blueprint for designing next-generation plasma-catalytic systems that overcome the limitations of conventional thermal processes.
{"title":"Plasma-catalytic methane decomposition: Radical-mediated pathways and controlled CNTs growth over plasma-modified Fe catalyst","authors":"Shizhang Wang, Shaozeng Sun, Dongdong Feng, Jipeng Chen, Guanwei Wang, Qi Shang, Yijun Zhao, Yu Zhang","doi":"10.1016/j.jaap.2025.107591","DOIUrl":"10.1016/j.jaap.2025.107591","url":null,"abstract":"<div><div>Methane decomposition is increasingly recognized as pivotal technology for simultaneous production of H<sub>2</sub> and carbon nanomaterials, yet its industrial implementation is severely constrained by high operating temperatures and rapid deactivation to thermal catalytic systems. By integrating in-situ optical emission spectroscopy with multi-scale characterization, it is demonstrated that plasma serves a four-fold function in the Fe-based catalytic system: (1) excitation of CH<sub>4</sub> into a controllable radical pool, (2) enhancement of radical adsorption energy on Fe surfaces through plasma-induced electronic polarization, (3) implementation of a hydrogen-mediated \"pathway pruning\" mechanism wherein H* abstracts H from CH<sub>x</sub>* species, preventing gas-phase polymerization while simultaneously accelerating surface-catalyzed carbon assembly, and (4) in-situ etching of amorphous carbon and promotion of surface hydrogen-assisted dehydrogenation on M-H sites. These coupled mechanisms synergistically suppress electrode carbon deposition, enabling sustained discharge stability and maintaining the plasma discharge in high-efficiency tip-discharge regime. Consequently, at 700 °C, the plasma-catalytic system achieves methane conversion of 42.67 % (compared to 25 % in pure plasma at 700 °C, and 19.25 % in pure thermal catalytic at 750 °C), hydrogen selectivity of 57.88 %, carbon yield of 105 mg·g<sub>cat</sub><sup>−1</sup>·h<sup>−1</sup>, and uniform CNTs with enhanced graphitization. This work provides a quantitative mechanistic blueprint for designing next-generation plasma-catalytic systems that overcome the limitations of conventional thermal processes.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"194 ","pages":"Article 107591"},"PeriodicalIF":6.2,"publicationDate":"2025-12-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145920680","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-31DOI: 10.1016/j.jaap.2025.107592
Na Liu , Tianyu Lu , Yajing He , Qingfa Zhang , Mingfeng Wang , Weiwei Liu , Zhong Ma , Shihong Zhang , Haiping Yang , Bin Li
Oxidative torrefaction of large paulownia wood particle (12 ×12 ×12 mm) was conducted in a fixed-bed reactor, and the effects of oxygen concentration (0–21 vol%) and torrefaction temperature (200–290 °C) on the torrefaction process and product properties were investigated. The results showed that oxygen concentration was a dominant factor regulating the torrefaction process: as oxygen concentration increased from 0 to 21 vol% at 260 °C, the torrefied wood yield decreased from 80.32 wt% to 55.54 wt%, while the yields of torrefied gas and liquid increased significantly. Torrefied gas was dominated by CO2 and CO, with low oxygen concentrations (≤10 vol%) favoring CO formation and high concentrations (≥15 vol%) promoting CO2 generation. The synergy of higher temperature and oxygen further enhanced biomass thermal decomposition. A 5–15 vol% oxygen concentration was identified as optimal, yielding torrefied wood with elevated carbon content (up to 66.95 wt%), higher heating value (up to 26.91 MJ/kg), reduced H/C (0.73) and O/C (0.32) ratios, and enhanced aromaticity. Excessive oxygen (21 vol%) caused over-oxidation particularly at higher temperatures, resulting in a low energy yield of 55.59 %. This study clarifies the regulatory mechanisms of oxidative torrefaction for large biomass particle and provides critical data for its industrialization, suggesting that flue gas can be used as a cost-effective atmosphere and that matching temperature, residence time, and oxygen concentration is key to avoiding over-oxidation.
{"title":"Oxidative torrefaction of large biomass particle in a fixed-bed reactor","authors":"Na Liu , Tianyu Lu , Yajing He , Qingfa Zhang , Mingfeng Wang , Weiwei Liu , Zhong Ma , Shihong Zhang , Haiping Yang , Bin Li","doi":"10.1016/j.jaap.2025.107592","DOIUrl":"10.1016/j.jaap.2025.107592","url":null,"abstract":"<div><div>Oxidative torrefaction of large paulownia wood particle (12 ×12 ×12 mm) was conducted in a fixed-bed reactor, and the effects of oxygen concentration (0–21 vol%) and torrefaction temperature (200–290 °C) on the torrefaction process and product properties were investigated. The results showed that oxygen concentration was a dominant factor regulating the torrefaction process: as oxygen concentration increased from 0 to 21 vol% at 260 °C, the torrefied wood yield decreased from 80.32 wt% to 55.54 wt%, while the yields of torrefied gas and liquid increased significantly. Torrefied gas was dominated by CO<sub>2</sub> and CO, with low oxygen concentrations (≤10 vol%) favoring CO formation and high concentrations (≥15 vol%) promoting CO<sub>2</sub> generation. The synergy of higher temperature and oxygen further enhanced biomass thermal decomposition. A 5–15 vol% oxygen concentration was identified as optimal, yielding torrefied wood with elevated carbon content (up to 66.95 wt%), higher heating value (up to 26.91 MJ/kg), reduced H/C (0.73) and O/C (0.32) ratios, and enhanced aromaticity. Excessive oxygen (21 vol%) caused over-oxidation particularly at higher temperatures, resulting in a low energy yield of 55.59 %. This study clarifies the regulatory mechanisms of oxidative torrefaction for large biomass particle and provides critical data for its industrialization, suggesting that flue gas can be used as a cost-effective atmosphere and that matching temperature, residence time, and oxygen concentration is key to avoiding over-oxidation.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"194 ","pages":"Article 107592"},"PeriodicalIF":6.2,"publicationDate":"2025-12-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145920672","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-31DOI: 10.1016/j.jaap.2025.107590
Yifei Yang , Xiaopeng Bai , Guanghui Wang , Daochun Xu , Wenbin Li , Chen Cai
Ball milling (BM) was a commonly used pretreatment method for pyrolysis. However, the lack of standardized BM intensity parameters made quantitative comparisons between BM pretreatment regulated pyrolysis studies difficult, which limited the practical application of BM pretreatment research findings in industrial production. In this study, the intensity of BM pretreatment was quantitatively evaluated by combining high-speed imaging measurements with discrete element method (DEM) analysis, where the kinetic energy dose was introduced as a measurement parameter. The pyrolysis reaction process and product distribution of Pennisetum giganteum (PG) samples were analyzed in combination with the targeted action sites of mechanical energy during the pretreatment process, and the regulatory mechanism of mechanical energy on the pyrolysis process and outcomes of lignocellulose was investigated. The kinetic energy dose-benefit calculation formula was utilized to analyze the benefits of consuming a unit amount of mechanical energy on the pyrolysis at different kinetic energy dose levels. The results showed that during the BM process, changes in certain physicochemical properties (Crystallinity, C-O and C-C bond content, and aromatic groups) occurred only after the kinetic energy dose reached a threshold. For most properties, unit kinetic energy dose benefits decreased with increasing kinetic energy dose. Under the pretreatment conditions specified in this study, a kinetic energy dose (D) of 200–400 kJ/g maximizes the benefit for pyrolysis oil production from PG, thereby providing a quantitative framework for optimizing BM pretreatment.
{"title":"Targeted regulation mechanism of pyrolysis reaction via ball milling pretreatment based on kinetic energy dose benefit analysis","authors":"Yifei Yang , Xiaopeng Bai , Guanghui Wang , Daochun Xu , Wenbin Li , Chen Cai","doi":"10.1016/j.jaap.2025.107590","DOIUrl":"10.1016/j.jaap.2025.107590","url":null,"abstract":"<div><div>Ball milling (BM) was a commonly used pretreatment method for pyrolysis. However, the lack of standardized BM intensity parameters made quantitative comparisons between BM pretreatment regulated pyrolysis studies difficult, which limited the practical application of BM pretreatment research findings in industrial production. In this study, the intensity of BM pretreatment was quantitatively evaluated by combining high-speed imaging measurements with discrete element method (DEM) analysis, where the kinetic energy dose was introduced as a measurement parameter. The pyrolysis reaction process and product distribution of <em>Pennisetum giganteum</em> (PG) samples were analyzed in combination with the targeted action sites of mechanical energy during the pretreatment process, and the regulatory mechanism of mechanical energy on the pyrolysis process and outcomes of lignocellulose was investigated. The kinetic energy dose-benefit calculation formula was utilized to analyze the benefits of consuming a unit amount of mechanical energy on the pyrolysis at different kinetic energy dose levels. The results showed that during the BM process, changes in certain physicochemical properties (Crystallinity, C-O and C-C bond content, and aromatic groups) occurred only after the kinetic energy dose reached a threshold. For most properties, unit kinetic energy dose benefits decreased with increasing kinetic energy dose. Under the pretreatment conditions specified in this study, a kinetic energy dose (<em>D</em>) of 200–400 kJ/g maximizes the benefit for pyrolysis oil production from PG, thereby providing a quantitative framework for optimizing BM pretreatment.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"194 ","pages":"Article 107590"},"PeriodicalIF":6.2,"publicationDate":"2025-12-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145920735","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-31DOI: 10.1016/j.jaap.2025.107589
Zhuoyao Chen , Zhaosheng Yu , Xiaoqian Ma , Wenchang Yue , Wen Xiao , Xiaojing Wang
To address the issues of difficult pore structure regulation, high cost, and pollution in traditional porous carbon preparation, this study utilizes poplar wood and yeast as biomass raw materials to prepare porous carbon (PYPACs) via co-pyrolysis combined with the green activator KHCO3. Volatiles released during yeast pre-carbonization can "stretch" the carbon matrix to form initial pores, and the N and O heteroatoms contained in yeast can construct active sites, guiding KHCO3 etching to form a porous structure. The sample PW1Y1–400 exhibits the optimal comprehensive performance when the mass ratio of poplar wood to yeast is 1:1 and the pre-carbonization temperature is 400°C. PW1Y1–400 achieves a specific capacitance of 369.7 F/g at 0.5 A/g. The assembled symmetric supercapacitor (PW1Y1–400/SSC) delivers a specific capacitance of 288.35 F/g at 0.25 A/g. It maintains a capacity retention rate of 98.19 % and a Coulombic efficiency retention rate of 99.94 % after 10000 cycles. At a power density of 75 W/kg, it exhibits an energy density of 12.01 Wh/kg. This method realizes a fully green and pollution-free process, providing a new path for the green production of porous carbon.
针对传统多孔炭制备存在孔隙结构调节困难、成本高、污染等问题，本研究以杨木和酵母为生物质原料，结合绿色活化剂KHCO3共热解制备多孔炭（PYPACs）。酵母预碳化过程中释放的挥发物可以“拉伸”碳基体形成初始孔隙，酵母中含有的N和O杂原子可以构建活性位点，引导KHCO3蚀刻形成多孔结构。当杨木与酵母的质量比为1:1，预炭化温度为400℃时，样品PW1Y1-400的综合性能最佳。PW1Y1-400在0.5 a /g时的比电容为369.7 F/g。组装的对称超级电容器（PW1Y1-400 /SSC）在0.25 a /g时提供288.35 F/g的比电容。循环10000次后容量保留率为98.19 %，库仑效率保留率为99.94 %。在功率密度为75 W/kg时，其能量密度为12.01 Wh/kg。该方法实现了全绿色无公害工艺，为多孔碳的绿色生产提供了新的途径。
{"title":"Yeast-induced carbon matrix impaction for active site construction: Directed etching and green activation mechanism of poplar-based porous carbon","authors":"Zhuoyao Chen , Zhaosheng Yu , Xiaoqian Ma , Wenchang Yue , Wen Xiao , Xiaojing Wang","doi":"10.1016/j.jaap.2025.107589","DOIUrl":"10.1016/j.jaap.2025.107589","url":null,"abstract":"<div><div>To address the issues of difficult pore structure regulation, high cost, and pollution in traditional porous carbon preparation, this study utilizes poplar wood and yeast as biomass raw materials to prepare porous carbon (PYPACs) via co-pyrolysis combined with the green activator KHCO<sub>3</sub>. Volatiles released during yeast pre-carbonization can \"stretch\" the carbon matrix to form initial pores, and the N and O heteroatoms contained in yeast can construct active sites, guiding KHCO<sub>3</sub> etching to form a porous structure. The sample PW1Y1–400 exhibits the optimal comprehensive performance when the mass ratio of poplar wood to yeast is 1:1 and the pre-carbonization temperature is 400°C. PW1Y1–400 achieves a specific capacitance of 369.7 F/g at 0.5 A/g. The assembled symmetric supercapacitor (PW1Y1–400/SSC) delivers a specific capacitance of 288.35 F/g at 0.25 A/g. It maintains a capacity retention rate of 98.19 % and a Coulombic efficiency retention rate of 99.94 % after 10000 cycles. At a power density of 75 W/kg, it exhibits an energy density of 12.01 Wh/kg. This method realizes a fully green and pollution-free process, providing a new path for the green production of porous carbon.</div></div>","PeriodicalId":345,"journal":{"name":"Journal of Analytical and Applied Pyrolysis","volume":"194 ","pages":"Article 107589"},"PeriodicalIF":6.2,"publicationDate":"2025-12-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145920737","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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