Fuel Processing Technology最新文献_第6页

Influence of chain length and saturation on carboxylic acid pyrolysis mechanisms 链长和饱和度对羧酸热解机理的影响

IF 7.7 2区工程技术 Q1 CHEMISTRY, APPLIED

Fuel Processing Technology

Pub Date : 2025-09-16 DOI: 10.1016/j.fuproc.2025.108336

Bernardo A. Souto, Justice Asomaning, David C. Bressler

This study investigates radical-driven deoxygenation mechanisms during the non-catalytic pyrolysis of saturated and unsaturated carboxylic acids. Pyrolysis experiments were conducted at 410 °C, between 0.5 and 2 h, using carboxylic acids of varying carbon chain lengths (C6 to C18) and saturation levels, along with ketones. Feedstock conversion and deoxygenation products were quantified using GC–MS/FID for liquids and GC-TCD/FID for gases. Results demonstrated that carboxylic acid chain length significantly influences pyrolysis behavior, with significant differences in deoxygenation pathway linked to acid chain length and saturation level. Decarboxylation was the predominant pathway for short-chain carboxylic acids, whereas long-chain acids showed increased tendency towards decarbonylation. Short-chain saturated carboxylic acids favoured ketonic decarboxylation during the initial stages of pyrolysis, resulting in notable amounts of ketones and carbon dioxide. Subsequent decarbonylation of these ketones contributed to further deoxygenation, generating hydrocarbons and shorter-chain ketones via radical-driven mechanisms. In contrast unsaturated carboxylic acids underwent extensive cracking, which suppressed ketonic decarboxylation and led to reduced overall hydrocarbon yields. Additionally, mixed carboxylic acid feedstocks showed decreased conversion efficiencies, primarily due to limited intermolecular interactions necessary for effective ketonic decarboxylation. This work explores radical-driven, non-catalytic pyrolysis of fatty acids, providing a detailed mechanistic understanding of how chain length and saturation influence reaction pathway. The findings highlight key determinants of product selectivity and deoxygenation efficiency, providing valuable insights for optimizing feedstock compositions in pyrolysis-based sustainable biofuel production.

本研究探讨了饱和和不饱和羧酸非催化热解过程中自由基驱动的脱氧机制。热解实验在410°C， 0.5 ~ 2 h之间进行，使用不同碳链长度（C6 ~ C18）和饱和度的羧酸以及酮类。用GC-MS /FID和GC-TCD/FID分别对液体和气体的原料转化和脱氧产物进行定量。结果表明，羧酸链长度对热解行为有显著影响，羧酸链长度和饱和水平对脱氧途径有显著影响。短链羧酸的主要途径是脱羧，而长链羧酸的脱羧倾向增加。短链饱和羧酸在热解初期有利于酮脱羧，产生大量的酮和二氧化碳。随后这些酮类的脱碳作用促进了进一步脱氧，通过自由基驱动机制生成碳氢化合物和短链酮类。相反，不饱和羧酸发生了广泛的裂解，这抑制了酮脱羧，导致总烃收率降低。此外，混合羧酸原料的转化效率下降，主要是由于有效酮脱羧所必需的分子间相互作用有限。这项工作探索了自由基驱动的脂肪酸非催化热解，提供了链长和饱和度如何影响反应途径的详细机制理解。这些发现突出了产品选择性和脱氧效率的关键决定因素，为优化基于热解的可持续生物燃料生产中的原料组成提供了有价值的见解。

{"title":"Influence of chain length and saturation on carboxylic acid pyrolysis mechanisms","authors":"Bernardo A. Souto, Justice Asomaning, David C. Bressler","doi":"10.1016/j.fuproc.2025.108336","DOIUrl":"10.1016/j.fuproc.2025.108336","url":null,"abstract":"<div><div>This study investigates radical-driven deoxygenation mechanisms during the non-catalytic pyrolysis of saturated and unsaturated carboxylic acids. Pyrolysis experiments were conducted at 410 °C, between 0.5 and 2 h, using carboxylic acids of varying carbon chain lengths (C6 to C18) and saturation levels, along with ketones. Feedstock conversion and deoxygenation products were quantified using GC–MS/FID for liquids and GC-TCD/FID for gases. Results demonstrated that carboxylic acid chain length significantly influences pyrolysis behavior, with significant differences in deoxygenation pathway linked to acid chain length and saturation level. Decarboxylation was the predominant pathway for short-chain carboxylic acids, whereas long-chain acids showed increased tendency towards decarbonylation. Short-chain saturated carboxylic acids favoured ketonic decarboxylation during the initial stages of pyrolysis, resulting in notable amounts of ketones and carbon dioxide. Subsequent decarbonylation of these ketones contributed to further deoxygenation, generating hydrocarbons and shorter-chain ketones via radical-driven mechanisms. In contrast unsaturated carboxylic acids underwent extensive cracking, which suppressed ketonic decarboxylation and led to reduced overall hydrocarbon yields. Additionally, mixed carboxylic acid feedstocks showed decreased conversion efficiencies, primarily due to limited intermolecular interactions necessary for effective ketonic decarboxylation. This work explores radical-driven, non-catalytic pyrolysis of fatty acids, providing a detailed mechanistic understanding of how chain length and saturation influence reaction pathway. The findings highlight key determinants of product selectivity and deoxygenation efficiency, providing valuable insights for optimizing feedstock compositions in pyrolysis-based sustainable biofuel production.</div></div>","PeriodicalId":326,"journal":{"name":"Fuel Processing Technology","volume":"278 ","pages":"Article 108336"},"PeriodicalIF":7.7,"publicationDate":"2025-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145106191","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Production of CO2-free hydrogen via catalytic methane decomposition over Ce-promoted Ni/Al2O3 catalysts ce促进的Ni/Al2O3催化剂催化甲烷分解制无co2氢

IF 7.7 2区工程技术 Q1 CHEMISTRY, APPLIED

Fuel Processing Technology

Pub Date : 2025-09-16 DOI: 10.1016/j.fuproc.2025.108338

Byung Sun Yoon , Ki Cheol Kim , Min-Jae Kim , Jae-Rang Youn , Mincheol Kim , Taesung Jung , Sang Goo Jeon , Woohyun Kim , Chang Hyun Ko

Catalytic methane decomposition (CMD) is a promising reaction for CO₂-free hydrogen production, as it generates no CO₂ emissions and produces solid carbon byproducts. However, catalyst deactivation due to carbon accumulation necessitates the development of catalysts with high activity, stability, and high capacity for carbon products. In this study, Ce-promoted Ni/Al₂O₃ catalysts were synthesized with varying Ce loadings to investigate the role of Ce in enhancing catalyst performance. The addition of Ce was found to weaken the interaction between Ni and Al₂O₃, thereby increasing the surface concentration of metallic Ni⁰ and improving catalytic activity. Nevertheless, excessive Ce loading resulted in performance deterioration, primarily due to a significant reduction in mesoporous volume. This loss of physical space limited the growth of carbon products and hindered catalyst effectiveness. The results highlight the need to balance the promotional effects of Ce with the preservation of pore structure to optimize catalyst design for CMD.

催化甲烷分解（CMD）是一种很有前途的无二氧化碳制氢反应，因为它不产生二氧化碳排放，只产生固体碳副产品。然而，由于碳积累导致催化剂失活，需要开发具有高活性、稳定性和高碳产物容量的催化剂。在本研究中，合成了不同Ce负载的Ce促进Ni/Al2O3催化剂，以研究Ce在提高催化剂性能方面的作用。Ce的加入减弱了Ni和Al2O3之间的相互作用，从而提高了金属Ni0的表面浓度，提高了催化活性。然而，过量的Ce载荷导致性能下降，主要是由于介孔体积的显著减少。这种物理空间的损失限制了碳产物的生长，阻碍了催化剂的有效性。研究结果表明，需要平衡Ce的促进作用和保持孔隙结构，以优化CMD催化剂的设计。

{"title":"Production of CO2-free hydrogen via catalytic methane decomposition over Ce-promoted Ni/Al2O3 catalysts","authors":"Byung Sun Yoon , Ki Cheol Kim , Min-Jae Kim , Jae-Rang Youn , Mincheol Kim , Taesung Jung , Sang Goo Jeon , Woohyun Kim , Chang Hyun Ko","doi":"10.1016/j.fuproc.2025.108338","DOIUrl":"10.1016/j.fuproc.2025.108338","url":null,"abstract":"<div><div>Catalytic methane decomposition (CMD) is a promising reaction for CO<sub>2</sub>-free hydrogen production, as it generates no CO<sub>2</sub> emissions and produces solid carbon byproducts. However, catalyst deactivation due to carbon accumulation necessitates the development of catalysts with high activity, stability, and high capacity for carbon products. In this study, Ce-promoted Ni/Al<sub>2</sub>O<sub>3</sub> catalysts were synthesized with varying Ce loadings to investigate the role of Ce in enhancing catalyst performance. The addition of Ce was found to weaken the interaction between Ni and Al<sub>2</sub>O<sub>3</sub>, thereby increasing the surface concentration of metallic Ni<sup>0</sup> and improving catalytic activity. Nevertheless, excessive Ce loading resulted in performance deterioration, primarily due to a significant reduction in mesoporous volume. This loss of physical space limited the growth of carbon products and hindered catalyst effectiveness. The results highlight the need to balance the promotional effects of Ce with the preservation of pore structure to optimize catalyst design for CMD.</div></div>","PeriodicalId":326,"journal":{"name":"Fuel Processing Technology","volume":"278 ","pages":"Article 108338"},"PeriodicalIF":7.7,"publicationDate":"2025-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145096570","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Hydrothermal hydrodenitrogenation and hydrodesulfurization over nickel-based catalysts in sub/supercritical water 亚/超临界水中镍基催化剂的水热加氢脱氮和加氢脱硫

IF 7.7 2区工程技术 Q1 CHEMISTRY, APPLIED

Fuel Processing Technology

Pub Date : 2025-09-16 DOI: 10.1016/j.fuproc.2025.108332

Jie Zhang , Hulin Li , Hao Chen , Hong Zhang , Chuang Yang , Haobo Li

As an inherent by-product of the petroleum industry, oily sludge has substantial potential as energy resource due to its high oil content and calorific value. The hydrodenitrogenation/hydrodesulfurization of nitrogen/sulfur compounds quinoline and thiophene in oily sludge at sub/supercritical hydrothermal conditions was studied, along with its catalytic properties and reaction mechanism. The effects of nickel-based catalysts, hydrogen sources, and reaction conditions on hydrodenitrogenation (HDN) of quinoline were examined. A reaction kinetic model for quinoline in supercritical water was developed. An experimental investigation on hydrodesulfurization (HDS) of sulfur-containing thiophene was conducted, and the catalytic properties of nickel-based catalysts for simultaneous HDN and HDS of quinoline and thiophene were evaluated. Within 400–440 °C, ethanol was superior to formic acid as hydrogen source. Ni-Co/γ-Al₂O₃ had the most effective catalytic impact on denitrogenation of quinoline. The conversion efficiency of 5 wt% quinoline reached 94.67 %, while denitrogenation efficiency was 57.08 % at 24 MPa, 440 °C, and 60 min. The hydrogenation and ring-opening steps had significant effects on the overall denitrogenation process. The hydrodesulfurization catalysis from Ni-Mo/γ-Al₂O₃ was the most prominent for thiophene. At 24 MPa, 440 °C, and 60 min, the desulfurization efficiency of thiophene reached 57.34 %. Desulfurization of thiophene mainly followed the hydrogenation route, with thiophene rings being saturated before desulfurization occurred.

含油污泥作为石油工业的固有副产品，因其含油量高、热值高，具有巨大的能源潜力。研究了亚/超临界水热条件下含氮/含硫化合物喹啉和噻吩在含油污泥中的加氢脱氮/加氢脱硫及其催化性能和反应机理。考察了镍基催化剂、氢源和反应条件对喹啉加氢脱氮反应的影响。建立了喹啉在超临界水中的反应动力学模型。对含硫噻吩的加氢脱硫（HDS）进行了实验研究，并评价了镍基催化剂对喹啉和噻吩同时加氢脱硫和加氢脱硫的催化性能。在400 ~ 440℃范围内，乙醇作为氢源优于甲酸。Ni-Co/γ-Al2O3对喹啉脱氮的催化效果最好。在24 MPa、440℃、60 min条件下，5 wt%喹啉的转化率为94.67%，脱氮效率为57.08%。加氢和开环步骤对整个脱氮过程有显著影响。Ni-Mo/γ-Al2O3对噻吩的加氢脱硫催化作用最为显著。在24 MPa、440℃、60 min条件下，噻吩的脱硫效率可达57.34%。噻吩的脱硫主要采用加氢途径，脱硫前噻吩环被饱和。

{"title":"Hydrothermal hydrodenitrogenation and hydrodesulfurization over nickel-based catalysts in sub/supercritical water","authors":"Jie Zhang , Hulin Li , Hao Chen , Hong Zhang , Chuang Yang , Haobo Li","doi":"10.1016/j.fuproc.2025.108332","DOIUrl":"10.1016/j.fuproc.2025.108332","url":null,"abstract":"<div><div>As an inherent by-product of the petroleum industry, oily sludge has substantial potential as energy resource due to its high oil content and calorific value. The hydrodenitrogenation/hydrodesulfurization of nitrogen/sulfur compounds quinoline and thiophene in oily sludge at sub/supercritical hydrothermal conditions was studied, along with its catalytic properties and reaction mechanism. The effects of nickel-based catalysts, hydrogen sources, and reaction conditions on hydrodenitrogenation (HDN) of quinoline were examined. A reaction kinetic model for quinoline in supercritical water was developed. An experimental investigation on hydrodesulfurization (HDS) of sulfur-containing thiophene was conducted, and the catalytic properties of nickel-based catalysts for simultaneous HDN and HDS of quinoline and thiophene were evaluated. Within 400–440 °C, ethanol was superior to formic acid as hydrogen source. Ni-Co/γ-Al<sub>2</sub>O<sub>3</sub> had the most effective catalytic impact on denitrogenation of quinoline. The conversion efficiency of 5 wt% quinoline reached 94.67 %, while denitrogenation efficiency was 57.08 % at 24 MPa, 440 °C, and 60 min. The hydrogenation and ring-opening steps had significant effects on the overall denitrogenation process. The hydrodesulfurization catalysis from Ni-Mo/γ-Al<sub>2</sub>O<sub>3</sub> was the most prominent for thiophene. At 24 MPa, 440 °C, and 60 min, the desulfurization efficiency of thiophene reached 57.34 %. Desulfurization of thiophene mainly followed the hydrogenation route, with thiophene rings being saturated before desulfurization occurred.</div></div>","PeriodicalId":326,"journal":{"name":"Fuel Processing Technology","volume":"278 ","pages":"Article 108332"},"PeriodicalIF":7.7,"publicationDate":"2025-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145106198","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Pore structure evolution of semi-coke under steam atmosphere in the context of deep underground coal gasification 煤深埋地下气化条件下蒸汽气氛下半焦孔隙结构演化

IF 7.7 2区工程技术 Q1 CHEMISTRY, APPLIED

Fuel Processing Technology

Pub Date : 2025-09-12 DOI: 10.1016/j.fuproc.2025.108329

Yueming Liu, Shuqin Liu, Zihe Liu, Xuan Li, Jiahong Cao, Chuan Qi, Weibin Wang

Underground coal gasification (UCG) is one of the important ways for in-situ clean conversion of deep coal resources. Affected by groundwater influx, steam gasification becomes the dominant reaction for syngas production in the UCG process. This paper investigates the pressurized gas production characteristics of semi-coke under steam atmosphere range from atmospheric to 3 MPa. The gasified residual coke is characterized by N₂ adsorption-desorption, SEM, AFM, and Raman spectroscopy to analyze the evolution of pore structure and functional groups of semi-coke with changes in pressure and carbon conversion rate. The results show that the action of steam leads to the development of abundant microporous structures below 1 nm on the semi-coke surface. Under 3 MPa, the specific surface area of micropores increases from 17.64 m²/g to 435.46 m²/g, which is 4 times that under CO₂ atmosphere. Micropores serve as the main site for the initial reaction of steam gasification. Evolution of semi-coke structure based on functional groups is the result of competition between pressure-dominated chain scission and H radical-dominated polycondensation. The research results provide a theoretical basis for strengthening the hydrogen production process of deep underground coal gasification affected by groundwater.

煤炭地下气化是深部煤炭资源就地清洁转化的重要途径之一。受地下水涌入的影响，蒸汽气化成为UCG工艺合成气生产的主导反应。研究了半焦在常压~ 3mpa蒸汽气氛下的加压产气特性。采用氮气吸附-解吸、SEM、AFM、拉曼光谱等方法对气化后的残焦进行表征，分析半焦孔隙结构和官能团随压力和碳转化率变化的演变。结果表明：在水蒸气的作用下，半焦表面在1 nm以下形成了丰富的微孔结构；在3 MPa下，微孔比表面积由17.64 m2/g增加到435.46 m2/g，是CO₂气氛下的4倍。微孔是蒸汽气化初始反应的主要场所。基于官能团的半焦结构的演化是压力主导的链裂解和H自由基主导的缩聚竞争的结果。研究结果为地下水影响下深部煤气化制氢过程的强化提供了理论依据。

{"title":"Pore structure evolution of semi-coke under steam atmosphere in the context of deep underground coal gasification","authors":"Yueming Liu, Shuqin Liu, Zihe Liu, Xuan Li, Jiahong Cao, Chuan Qi, Weibin Wang","doi":"10.1016/j.fuproc.2025.108329","DOIUrl":"10.1016/j.fuproc.2025.108329","url":null,"abstract":"<div><div>Underground coal gasification (UCG) is one of the important ways for in-situ clean conversion of deep coal resources. Affected by groundwater influx, steam gasification becomes the dominant reaction for syngas production in the UCG process. This paper investigates the pressurized gas production characteristics of semi-coke under steam atmosphere range from atmospheric to 3 MPa. The gasified residual coke is characterized by N<sub>2</sub> adsorption-desorption, SEM, AFM, and Raman spectroscopy to analyze the evolution of pore structure and functional groups of semi-coke with changes in pressure and carbon conversion rate. The results show that the action of steam leads to the development of abundant microporous structures below 1 nm on the semi-coke surface. Under 3 MPa, the specific surface area of micropores increases from 17.64 m<sup>2</sup>/g to 435.46 m<sup>2</sup>/g, which is 4 times that under CO₂ atmosphere. Micropores serve as the main site for the initial reaction of steam gasification. Evolution of semi-coke structure based on functional groups is the result of competition between pressure-dominated chain scission and H radical-dominated polycondensation. The research results provide a theoretical basis for strengthening the hydrogen production process of deep underground coal gasification affected by groundwater.</div></div>","PeriodicalId":326,"journal":{"name":"Fuel Processing Technology","volume":"278 ","pages":"Article 108329"},"PeriodicalIF":7.7,"publicationDate":"2025-09-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145044873","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Thermal evolution and hydrocarbon generation of organic matter in shales via sequential high-pressure hydrous pyrolysis: Implications for in-situ conversion of unconventional resource 页岩有机质序贯高压水热解热演化与生烃：对非常规资源就地转化的启示

IF 7.7 2区工程技术 Q1 CHEMISTRY, APPLIED

Fuel Processing Technology

Pub Date : 2025-09-11 DOI: 10.1016/j.fuproc.2025.108327

Fengtian Bai , Clement N. Uguna , Will Meredith , Colin E. Snape , Christopher H. Vane , Chenggong Sun

Understanding kerogen transformation under geological conditions is critical for optimizing the in-situ conversion (ISC) process of organic-rich unconventional resources. Sequential high-pressure hydrous pyrolysis was employed to investigate the geological thermal evolution and hydrocarbon generation mechanisms of organic matter in immature Huadian (Type II₁ kerogen) and Fushun (Type I kerogen) shales. Experiments progressed through four thermal stages, that is Stage 1 (350 °C, 6 h), Stage 2 (350 °C, 24 h), Stage 3 (380 °C, 24 h), and Stage 4 (420 °C, 24 h), with comprehensive analysis of hydrocarbon products by gas-chromatography mass-spectrometry and solid residues by vitrinite reflectance (Ro) and Rock-Eval pyrolysis. The results revealed that the hydrocarbon-generation potential of these two shales declined sharply with a Ro of 0.78–1.23 %, correlating with peak oil generation. Type I kerogen (Fushun) exhibited higher reactivity, generating twice the cumulative oil yield (normalized by TOC) compared to Type II₁ (Huadian) and transitioning earlier to oil dominance. Biomarker evolution (OEP decline, sterane/hopane isomerization) in expelled oil and declining gas dryness index (C₁/ΣC₁–C₅) correlated strongly with the maturity of organic matter, enabling non-destructive ISC monitoring. Compared to typical temperatures used in ex-situ retorting (520 °C), the kerogen conversion was completed at lower temperatures of 350–420 °C in this study, validating prolonged heating as a viable low-energy ISC strategy. However, high-pressure conditions in geological formations may impede hydrocarbon expulsion efficiency, leading to the retention of viscous bitumen and thus necessitating engineered solutions for effective oil recovery. This research enriches the understanding of high-pressure pyrolysis mechanisms of immature/low-maturity unconventional resources and establishes a geochemical framework for optimizing ISC in recovering the oil from these source rocks, ultimately contributing to advancing sustainable exploitation of unconventional resources.

了解地质条件下的干酪根转化是优化富有机质非常规资源原位转化过程的关键。采用序次高压水热解方法，研究了华甸（ⅱ1型）和抚顺（ⅰ型）未成熟页岩有机质的地质热演化和生烃机制。实验通过了1阶段（350°C, 6 h）、2阶段（350°C, 24 h）、3阶段（380°C, 24 h）和4阶段（420°C, 24 h）四个热阶段，通过气相色谱-质谱法对烃类产物进行了综合分析，通过镜质体反射率（Ro）和岩石热解对固体残留物进行了综合分析。结果表明，这两种页岩的生烃潜力急剧下降，Ro值为0.78 ~ 1.23%，与生油峰值有关。ⅰ型干酪根（抚顺）表现出较高的反应性，其累积产油量（按TOC归一化）是ⅱ型干酪根（华甸）的2倍，且较ⅰ型干酪根（华甸）更早过渡到以油为主。排油中生物标志物的演化（OEP下降、甾烷/藿烷异构化）和天然气干燥指数（C1/ ΣC1-C5）的下降与有机质成熟度密切相关，从而实现非破坏性ISC监测。与非原位重整中使用的典型温度（520℃）相比，本研究中干酪根转化在350-420℃的较低温度下完成，验证了长时间加热是一种可行的低能耗ISC策略。然而，地质地层中的高压条件可能会阻碍排烃效率，导致粘性沥青的滞留，因此需要有效采油的工程解决方案。本研究丰富了对未成熟/低成熟非常规资源高压热解机理的认识，并建立了烃源岩中油气ISC优化的地球化学框架，最终为非常规资源的可持续开发做出贡献。

{"title":"Thermal evolution and hydrocarbon generation of organic matter in shales via sequential high-pressure hydrous pyrolysis: Implications for in-situ conversion of unconventional resource","authors":"Fengtian Bai , Clement N. Uguna , Will Meredith , Colin E. Snape , Christopher H. Vane , Chenggong Sun","doi":"10.1016/j.fuproc.2025.108327","DOIUrl":"10.1016/j.fuproc.2025.108327","url":null,"abstract":"<div><div>Understanding kerogen transformation under geological conditions is critical for optimizing the in-situ conversion (ISC) process of organic-rich unconventional resources. Sequential high-pressure hydrous pyrolysis was employed to investigate the geological thermal evolution and hydrocarbon generation mechanisms of organic matter in immature Huadian (Type II<sub>1</sub> kerogen) and Fushun (Type I kerogen) shales. Experiments progressed through four thermal stages, that is Stage 1 (350 °C, 6 h), Stage 2 (350 °C, 24 h), Stage 3 (380 °C, 24 h), and Stage 4 (420 °C, 24 h), with comprehensive analysis of hydrocarbon products by gas-chromatography mass-spectrometry and solid residues by vitrinite reflectance (Ro) and Rock-Eval pyrolysis. The results revealed that the hydrocarbon-generation potential of these two shales declined sharply with a Ro of 0.78–1.23 %, correlating with peak oil generation. Type I kerogen (Fushun) exhibited higher reactivity, generating twice the cumulative oil yield (normalized by TOC) compared to Type II<sub>1</sub> (Huadian) and transitioning earlier to oil dominance. Biomarker evolution (OEP decline, sterane/hopane isomerization) in expelled oil and declining gas dryness index (C<sub>1</sub>/ΣC<sub>1</sub>–C<sub>5</sub>) correlated strongly with the maturity of organic matter, enabling non-destructive ISC monitoring. Compared to typical temperatures used in ex-situ retorting (520 °C), the kerogen conversion was completed at lower temperatures of 350–420 °C in this study, validating prolonged heating as a viable low-energy ISC strategy. However, high-pressure conditions in geological formations may impede hydrocarbon expulsion efficiency, leading to the retention of viscous bitumen and thus necessitating engineered solutions for effective oil recovery. This research enriches the understanding of high-pressure pyrolysis mechanisms of immature/low-maturity unconventional resources and establishes a geochemical framework for optimizing ISC in recovering the oil from these source rocks, ultimately contributing to advancing sustainable exploitation of unconventional resources.</div></div>","PeriodicalId":326,"journal":{"name":"Fuel Processing Technology","volume":"278 ","pages":"Article 108327"},"PeriodicalIF":7.7,"publicationDate":"2025-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145044874","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

3D-printed NiZr0.1/SiOC monolithic catalysts with synergistic Zr doping for enhanced low-temperature CO2 methanation: dual-pathway mechanism and structural stability 增效Zr掺杂的3d打印NiZr0.1/SiOC整体催化剂增强低温CO2甲烷化：双途径机理和结构稳定性

IF 7.7 2区工程技术 Q1 CHEMISTRY, APPLIED

Fuel Processing Technology

Pub Date : 2025-09-08 DOI: 10.1016/j.fuproc.2025.108328

Honglei Mi , Yifan Zhang , Faliang Luo

Monolithic NiZr_0.1/SiOC catalysts with tailored architectures were fabricated via direct ink writing (DIW) 3D printing for CO₂ methanation. Zr doping markedly enhanced low-temperature activity (<300 °C) by improving Ni dispersion, strengthening metal-support interactions, and suppressing particle agglomeration. Structural characterization revealed that Zr doping optimized pore accessibility and active-site exposure, while in situ studies confirmed a dual-pathway reaction mechanism involving formate and CO intermediates. The 30 % NiZr_0.1/SiOC catalyst exhibited exceptional performance, achieving 95.09 % CO₂ conversion at 320 °C and 91.56 % at 290 °C with 100 % CH₄ selectivity. Long-term stability tests (335 h) demonstrated robust anti-coking and anti-sintering properties, attributed to Zr-induced stabilization of Ni nanoparticles. This work highlights the synergy between additive manufacturing and dopant engineering for designing high-performance catalysts for CO₂ methanation.

采用直接墨水写入（DIW） 3D打印技术制备了具有定制结构的单片NiZr0.1/SiOC催化剂，用于二氧化碳甲烷化。Zr掺杂通过改善Ni分散、加强金属支撑相互作用和抑制颗粒团聚，显著提高了低温活性（<300°C）。结构表征表明，Zr掺杂优化了孔隙可达性和活性位点暴露，而原位研究证实了涉及甲酸酯和CO中间体的双途径反应机制。30% NiZr0.1/SiOC催化剂表现出优异的性能，在320°C和290°C下，CO2转化率分别达到95.09%和91.56%，CH4选择性为100%。长期稳定性测试（335小时）显示出强大的抗焦化和抗烧结性能，这归功于锆诱导的Ni纳米颗粒的稳定。这项工作强调了增材制造和掺杂工程之间的协同作用，以设计高性能的二氧化碳甲烷化催化剂。

{"title":"3D-printed NiZr0.1/SiOC monolithic catalysts with synergistic Zr doping for enhanced low-temperature CO2 methanation: dual-pathway mechanism and structural stability","authors":"Honglei Mi , Yifan Zhang , Faliang Luo","doi":"10.1016/j.fuproc.2025.108328","DOIUrl":"10.1016/j.fuproc.2025.108328","url":null,"abstract":"<div><div>Monolithic Ni<img>Zr<sub>0.1</sub>/SiOC catalysts with tailored architectures were fabricated via direct ink writing (DIW) 3D printing for CO<sub>2</sub> methanation. Zr doping markedly enhanced low-temperature activity (<300 °C) by improving Ni dispersion, strengthening metal-support interactions, and suppressing particle agglomeration. Structural characterization revealed that Zr doping optimized pore accessibility and active-site exposure, while in situ studies confirmed a dual-pathway reaction mechanism involving formate and CO intermediates. The 30 % Ni<img>Zr<sub>0.1</sub>/SiOC catalyst exhibited exceptional performance, achieving 95.09 % CO<sub>2</sub> conversion at 320 °C and 91.56 % at 290 °C with 100 % CH<sub>4</sub> selectivity. Long-term stability tests (335 h) demonstrated robust anti-coking and anti-sintering properties, attributed to Zr-induced stabilization of Ni nanoparticles. This work highlights the synergy between additive manufacturing and dopant engineering for designing high-performance catalysts for CO<sub>2</sub> methanation.</div></div>","PeriodicalId":326,"journal":{"name":"Fuel Processing Technology","volume":"278 ","pages":"Article 108328"},"PeriodicalIF":7.7,"publicationDate":"2025-09-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145009891","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Support effect in Ni-based catalysts for methane steam reforming: Role of MxOy-Al2O3 (M = Ni, Mg, Co) supports for enhanced catalyst stability 甲烷蒸汽重整Ni基催化剂的支撑效应：MxOy-Al2O3 （M = Ni, Mg, Co）支撑对提高催化剂稳定性的作用

IF 7.7 2区工程技术 Q1 CHEMISTRY, APPLIED

Fuel Processing Technology

Pub Date : 2025-09-08 DOI: 10.1016/j.fuproc.2025.108325

Yi Lin , Zaixing Wang , Lina Tang , Shi Jiang , Yu Guo , Xiaoqin Liu

Ni-based catalysts supported on composite metal oxides (NiO-Al₂O₃, MgO-Al₂O₃, Co₃O₄-Al₂O₃) were synthesized via coprecipitation followed by Ni impregnation to investigate the influence of support composition on catalyst stability in methane steam reforming. Accelerated deactivation protocols (methane decomposition, high-temperature sintering, hydrothermal oxidation) revealed hydrothermal oxidation as the primary cause of irreversible deactivation. The 10Ni/NiAl catalyst (10 wt% Ni/10 wt% NiO-Al₂O₃) showed remarkable regenerability after 923 K hydrothermal treatment, fully restoring its activity. This was attributed to coexisting reduced Ni species and readily reducible NiO, facilitating rapid reactivation. Other catalysts formed thermally stable NiAl₂O₄, leading to permanent deactivation. Methane cracking at 973 K had negligible effect, and 10Ni/NiAl catalyst exhibited the lowest carbon deposition (17.02 %). Under extreme hydrogen purged at 1223 K, only the 10Ni/CoAl catalyst exhibited a minor activity decline. The superior stability of 10Ni/NiAl was attributed to an in situ-formed NiAl composite metal oxides during 973 K calcination, which effectively anchored Ni particles, suppressed sintering, and prevented extensive oxidation.

采用共沉淀法和Ni浸渍法制备了复合金属氧化物（NiO-Al2O3、MgO-Al2O3、Co3O4-Al2O3）负载Ni基催化剂，研究了负载组分对甲烷蒸汽重整催化剂稳定性的影响。加速失活方案（甲烷分解、高温烧结、水热氧化）表明水热氧化是不可逆失活的主要原因。10Ni/NiAl催化剂（10wt % Ni/ 10wt % NiO-Al2O3）经923 K水热处理后表现出明显的再生能力，完全恢复了活性。这是由于还原镍和容易还原的NiO共存，促进了快速的再活化。其他催化剂形成热稳定的NiAl2O4，导致永久失活。在973 K时，甲烷裂解的影响可以忽略不计，10Ni/NiAl催化剂的碳沉积最低（17.02%）。在1223 K的极端吹氢条件下，只有10Ni/CoAl催化剂的活性略有下降。10Ni/NiAl优异的稳定性归功于在973 K煅烧过程中原位形成的NiAl复合金属氧化物，它有效地锚定了Ni颗粒，抑制了烧结，防止了广泛的氧化。

{"title":"Support effect in Ni-based catalysts for methane steam reforming: Role of MxOy-Al2O3 (M = Ni, Mg, Co) supports for enhanced catalyst stability","authors":"Yi Lin , Zaixing Wang , Lina Tang , Shi Jiang , Yu Guo , Xiaoqin Liu","doi":"10.1016/j.fuproc.2025.108325","DOIUrl":"10.1016/j.fuproc.2025.108325","url":null,"abstract":"<div><div>Ni-based catalysts supported on composite metal oxides (NiO-Al<sub>2</sub>O<sub>3</sub>, MgO-Al<sub>2</sub>O<sub>3</sub>, Co<sub>3</sub>O<sub>4</sub>-Al<sub>2</sub>O<sub>3</sub>) were synthesized via coprecipitation followed by Ni impregnation to investigate the influence of support composition on catalyst stability in methane steam reforming. Accelerated deactivation protocols (methane decomposition, high-temperature sintering, hydrothermal oxidation) revealed hydrothermal oxidation as the primary cause of irreversible deactivation. The 10Ni/NiAl catalyst (10 wt% Ni/10 wt% NiO-Al<sub>2</sub>O<sub>3</sub>) showed remarkable regenerability after 923 K hydrothermal treatment, fully restoring its activity. This was attributed to coexisting reduced Ni species and readily reducible NiO, facilitating rapid reactivation. Other catalysts formed thermally stable NiAl<sub>2</sub>O<sub>4</sub>, leading to permanent deactivation. Methane cracking at 973 K had negligible effect, and 10Ni/NiAl catalyst exhibited the lowest carbon deposition (17.02 %). Under extreme hydrogen purged at 1223 K, only the 10Ni/CoAl catalyst exhibited a minor activity decline. The superior stability of 10Ni/NiAl was attributed to an in situ-formed NiAl composite metal oxides during 973 K calcination, which effectively anchored Ni particles, suppressed sintering, and prevented extensive oxidation.</div></div>","PeriodicalId":326,"journal":{"name":"Fuel Processing Technology","volume":"278 ","pages":"Article 108325"},"PeriodicalIF":7.7,"publicationDate":"2025-09-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145020277","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Reaction characteristics of La/Co doped Mg-Fe-Al-O spinel oxygen carriers for chemical looping steam methane reforming La/Co掺杂Mg-Fe-Al-O尖晶石氧载体化学环蒸汽甲烷重整反应特性

IF 7.7 2区工程技术 Q1 CHEMISTRY, APPLIED

Fuel Processing Technology

Pub Date : 2025-09-05 DOI: 10.1016/j.fuproc.2025.108322

Shiyi Chen , Fangjun Wang , Jun Du , Shubo Chen , Wenguo Xiang

Chemical looping steam methane reforming (CLSMR) is an efficient and promising method to co-produce syngas and hydrogen. In this work, the La/Co doped Mg-Fe-Al-O spinel was synthesized via co-precipitation method as oxygen carrier in CLSMR. The introduction of La ions enhances the dispersion of the iron oxide on the particle surface and retards the growth of the oxygen carrier grain size, and the incorporation Co ions creates oxygen vacancies, which facilitates the lattice oxygen migration. The results reveal the optimal ratios of La: Co is 5:5 in the doping. In the reduction, the La5Co5 sample generates the syngas with a H₂/CO molar ratio of ∼2, a CH₄ conversion rate of 85.1 %, and a syngas yield of 3.75 mmol/g_oc. In the oxidation, H₂ is produced with a yield of 1.25 mmol/g_oc and a concentration > 95 vol%. In SEM and XRD characterization analysis, the La5Co5 oxygen carrier after multiple reaction cycles exhibits minimal sintering, with stable phases and slight changes in grain size. The LaCo synergistic effect can also enhance the methane partial oxidation. The deep-reduced oxygen carrier owns sufficient oxygen vacancies as active sites for steam splitting to produce high concentration hydrogen.

化学循环蒸汽甲烷重整（CLSMR）是一种高效、有前途的合成气和氢气联产方法。本文采用共沉淀法在CLSMR中合成了La/Co掺杂的Mg-Fe-Al-O尖晶石作为氧载体。La离子的引入增强了氧化铁在颗粒表面的分散，延缓了载氧颗粒尺寸的增长，Co离子的加入产生了氧空位，促进了晶格氧的迁移。结果表明，La: Co的最佳配比为5:5。在还原过程中，La5Co5样品生成的合成气H2/CO摩尔比为~ 2，CH4转化率为85.1%，合成气产率为3.75 mmol/goc。在氧化过程中，H2的产率为1.25 mmol/goc，浓度为95 vol%。SEM和XRD表征分析表明，经过多次反应循环后的La5Co5氧载体烧结最小，物相稳定，晶粒尺寸变化不大。LaCo的协同作用也能促进甲烷的部分氧化。深度还原氧载体具有足够的氧空位作为裂解蒸汽生成高浓度氢的活性位点。

{"title":"Reaction characteristics of La/Co doped Mg-Fe-Al-O spinel oxygen carriers for chemical looping steam methane reforming","authors":"Shiyi Chen , Fangjun Wang , Jun Du , Shubo Chen , Wenguo Xiang","doi":"10.1016/j.fuproc.2025.108322","DOIUrl":"10.1016/j.fuproc.2025.108322","url":null,"abstract":"<div><div>Chemical looping steam methane reforming (CLSMR) is an efficient and promising method to co-produce syngas and hydrogen. In this work, the La/Co doped Mg-Fe-Al-O spinel was synthesized via co-precipitation method as oxygen carrier in CLSMR. The introduction of La ions enhances the dispersion of the iron oxide on the particle surface and retards the growth of the oxygen carrier grain size, and the incorporation Co ions creates oxygen vacancies, which facilitates the lattice oxygen migration. The results reveal the optimal ratios of La: Co is 5:5 in the doping. In the reduction, the La5Co5 sample generates the syngas with a H<sub>2</sub>/CO molar ratio of ∼2, a CH<sub>4</sub> conversion rate of 85.1 %, and a syngas yield of 3.75 mmol/g<sub>oc</sub>. In the oxidation, H<sub>2</sub> is produced with a yield of 1.25 mmol/g<sub>oc</sub> and a concentration > 95 vol%. In SEM and XRD characterization analysis, the La5Co5 oxygen carrier after multiple reaction cycles exhibits minimal sintering, with stable phases and slight changes in grain size. The La<img>Co synergistic effect can also enhance the methane partial oxidation. The deep-reduced oxygen carrier owns sufficient oxygen vacancies as active sites for steam splitting to produce high concentration hydrogen.</div></div>","PeriodicalId":326,"journal":{"name":"Fuel Processing Technology","volume":"278 ","pages":"Article 108322"},"PeriodicalIF":7.7,"publicationDate":"2025-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144997659","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

A comprehensive review of the catalytic transformation for biomass derivatives into high-value fuels and chemicals over bimetallic Ni-Re catalysts 综述了双金属Ni-Re催化剂催化生物质衍生物转化为高价值燃料和化学品的研究进展

IF 7.7 2区工程技术 Q1 CHEMISTRY, APPLIED

Fuel Processing Technology

Pub Date : 2025-09-04 DOI: 10.1016/j.fuproc.2025.108326

Pratikkumar Lakhani, Atthapon Srifa

Ni-Re bimetallic catalysts provide an excellent synergy of hydrogenation activity from Ni and oxophilic acidity from ReO_X, allowing for effective conversion of biomass-derived molecules into fuels and chemicals. This review highlights recent developments in Ni-Re catalyst synthesis, structure-performance relationships, and applications in key transformations such as furfural, 5-hydroxymethylfurfural, and levulinic acid upgrading, and hydrodeoxygenation of fatty acid esters. The discussion highlights bifunctional mechanisms, hydrogen spillover, and metal-support interactions in controlling selectivity. Catalyst deactivation challenges and regeneration strategies are also addressed. Finally, future research directions are suggested with emphasis on atomic-scale catalyst design, integration of green hydrogen, and industrial use in sustainable biorefineries.

Ni- re双金属催化剂提供了来自Ni的氢化活性和来自ReOX的亲氧酸性的良好协同作用，允许有效地将生物质衍生分子转化为燃料和化学品。本文综述了Ni-Re催化剂的合成、结构-性能关系以及在糠醛、5-羟甲基糠醛、乙酰丙酸升级和脂肪酸酯加氢脱氧等关键转化中的应用。重点讨论了控制选择性的双功能机制、氢溢出和金属支持相互作用。还讨论了催化剂失活的挑战和再生策略。最后，提出了未来的研究方向，重点是原子级催化剂的设计、绿色氢的集成和可持续生物炼制的工业应用。

引用次数: 0

Molecular insights into the influence mechanism of carbon structure in iron coke after gasification on its combustion behavior and kinetics: Experiments, ReaxFF MD, and DFT 气化后铁焦碳结构对其燃烧行为和动力学影响机理的分子研究：实验，ReaxFF MD，和DFT

IF 7.7 2区工程技术 Q1 CHEMISTRY, APPLIED

Fuel Processing Technology

Pub Date : 2025-09-03 DOI: 10.1016/j.fuproc.2025.108324

Jie Wang , Wei Wang , Xuheng Chen , Bowen Chen , Runsheng Xu

Iron coke has attracted attention as a low-carbon ironmaking fuel due to its high reactivity and efficient resource utilization. However, the structural characteristics of iron coke after gasification and their effect mechanisms affecting subsequent combustion remain unclear. This study investigated the effects of gasification on the carbon structure of iron coke using XRD and Raman spectroscopy, and revealed the influence mechanism of carbon structure on combustion behavior and kinetics through combined thermogravimetric analysis, ReaxFF MD, and DFT calculations. The results demonstrate that the gasification reaction catalyzed by iron/iron oxides induces more defects in the carbon structure of iron coke. The higher the gasification degree of iron coke, the greater its following combustion reactivity. Increasing the heating rate in the non-isothermal combustion process can markedly enhance the combustion performance of iron coke. ReaxFF MD simulations reveal that oxygen radicals preferentially attack and react with vacancy defects in the carbon structure, which is the primary reason for the increased reactivity of defective structures. Due to the curling effect between carbon layers, the activation energy during combustion initially increases and then decreases with rising carbon conversion. DFT calculations indicate that vacancy defects in the carbon structure play a critical role in enhancing combustion behavior. On one hand, the increased defects provide more active sites, reducing the adsorption energy for O₂ molecules. On the other hand, the synergistic effect of van der Waals interactions and chemical bonds in defective carbon structures effectively reduces activation energy for the combustion reaction.

铁焦作为一种低碳炼铁燃料，因其高反应性和资源高效利用而备受关注。然而，气化后铁焦的结构特征及其对后续燃烧的影响机理尚不清楚。本研究利用XRD和拉曼光谱研究了气化对铁焦碳结构的影响，并结合热重分析、ReaxFF MD和DFT计算揭示了碳结构对燃烧行为和动力学的影响机理。结果表明，铁/铁氧化物催化的气化反应导致铁焦碳结构缺陷增多。气化程度越高的铁焦，其后续燃烧反应活性越大。在非等温燃烧过程中，提高加热速率可以显著提高焦炭的燃烧性能。ReaxFF MD模拟表明，氧自由基优先攻击碳结构中的空位缺陷并与之发生反应，这是缺陷结构反应活性增加的主要原因。由于碳层之间的卷曲效应，燃烧时的活化能随着碳转化率的升高先升高后降低。DFT计算表明，碳结构中的空位缺陷对提高燃烧性能起着至关重要的作用。一方面，增加的缺陷提供了更多的活性位点，降低了O2分子的吸附能。另一方面，缺陷碳结构中的范德华相互作用和化学键的协同作用有效地降低了燃烧反应的活化能。

{"title":"Molecular insights into the influence mechanism of carbon structure in iron coke after gasification on its combustion behavior and kinetics: Experiments, ReaxFF MD, and DFT","authors":"Jie Wang , Wei Wang , Xuheng Chen , Bowen Chen , Runsheng Xu","doi":"10.1016/j.fuproc.2025.108324","DOIUrl":"10.1016/j.fuproc.2025.108324","url":null,"abstract":"<div><div>Iron coke has attracted attention as a low-carbon ironmaking fuel due to its high reactivity and efficient resource utilization. However, the structural characteristics of iron coke after gasification and their effect mechanisms affecting subsequent combustion remain unclear. This study investigated the effects of gasification on the carbon structure of iron coke using XRD and Raman spectroscopy, and revealed the influence mechanism of carbon structure on combustion behavior and kinetics through combined thermogravimetric analysis, ReaxFF MD, and DFT calculations. The results demonstrate that the gasification reaction catalyzed by iron/iron oxides induces more defects in the carbon structure of iron coke. The higher the gasification degree of iron coke, the greater its following combustion reactivity. Increasing the heating rate in the non-isothermal combustion process can markedly enhance the combustion performance of iron coke. ReaxFF MD simulations reveal that oxygen radicals preferentially attack and react with vacancy defects in the carbon structure, which is the primary reason for the increased reactivity of defective structures. Due to the curling effect between carbon layers, the activation energy during combustion initially increases and then decreases with rising carbon conversion. DFT calculations indicate that vacancy defects in the carbon structure play a critical role in enhancing combustion behavior. On one hand, the increased defects provide more active sites, reducing the adsorption energy for O<sub>2</sub> molecules. On the other hand, the synergistic effect of van der Waals interactions and chemical bonds in defective carbon structures effectively reduces activation energy for the combustion reaction.</div></div>","PeriodicalId":326,"journal":{"name":"Fuel Processing Technology","volume":"277 ","pages":"Article 108324"},"PeriodicalIF":7.7,"publicationDate":"2025-09-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144931866","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0