IF 7.5 1区工程技术 Q2 ENERGY & FUELS

Fuel

Pub Date : 2025-12-10 DOI: 10.1016/j.fuel.2025.137936

Siphumelele Majodina , Jaco Olivier , Zenixole Tshentu , Adeniyi S. Ogunlaja

Hydrodesulfurization (HDS) is a key method for eliminating sulfur compounds from fuels, helping to meet strict environmental rules and lower sulfur dioxide emissions. Herein, Fe_xMo_1.0-TA 0.8 (x = 0, 0.5, 1.0, and 1.5) where TA (TiO₂/γ-Al₂O₃) were synthesized via the incipient impregnation method and utilised as catalyst for their application in HDS process was investigated. The corresponding Fe_xMo_1.0-TA 0.8 (x = 0, 0.5, 1.0, and 1.5) were prepared via the incipient impregnation method. Ultradispersed iron-molybdenum-based catalysts were prepared on a high-surface-area TA (TiO₂/γ-Al₂O₃), followed by sulfidation in CS₂ flow at 300 °C. STEM-EDS, and HRTEM microscopy attest that single atoms and few-atom clusters are predominant on the surface of the materials, while H₂-TPR, XPS, XRD, NH₃-TPD confirmed catalyst sulfidation, Fe-Mo interaction which influences specific dibenzothiophene HDS activity. The Fe_xMo_1.0-TA 0.8 (x = 0, 0.5, 1.0 and 1.5) catalyst yielded dibenzothiophene HDS activity of 66 %, 84 %, 91 % and 90 %, respectively. Fe_1.0Mo_1.0-TA 0.8 activity is due to the formation of more active MoS₂ phases with Mo⁴⁺ species, which is coupled with favourable structural properties. These findings provide new insights of HDS catalysts structure–activity relationships influenced by the presence of Ti³⁺ and Fe which weakens Mo-S/Fe-Mo-S bonds facilitating the formation of more sulfur vacancies (CUS), which is a critical step in the hydrodesulfurization of dibenzothiophene.

加氢脱硫（HDS）是消除燃料中含硫化合物的关键方法，有助于满足严格的环境法规并降低二氧化硫排放。本文以fexmo1.0 - ta0.8 （x = 0、0.5、1.0和1.5）为原料，通过初浸法制备了TA (TiO2/γ-Al2O3)，并将其作为催化剂应用于HDS工艺。采用初浸法制备相应的fexmo1.0 - ta0.8 （x = 0、0.5、1.0、1.5）。在高表面积的TA （TiO2/γ-Al2O3）上制备了超分散铁钼基催化剂，然后在300℃的CS2流中硫化。STEM-EDS和HRTEM显微镜证实材料表面以单原子和少原子簇为主，而H2-TPR、XPS、XRD、NH3-TPD证实催化剂硫化作用、Fe-Mo相互作用影响了二苯并噻吩的HDS活性。fexmo1.0 - ta0.8 （x = 0,0.5, 1.0和1.5）催化剂的二苯并噻吩HDS活性分别为66%，84%，91%和90%。fe1.0 mo1.0 - ta0.8的活性是由于与Mo4+形成了更活跃的MoS2相，这与良好的结构性能相结合。这些发现为HDS催化剂的结构-活性关系提供了新的见解，Ti3+和Fe的存在削弱了Mo-S/Fe-Mo-S键，促进了更多硫空位（CUS）的形成，这是二苯并噻吩加氢脱硫的关键步骤。

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引用次数: 0

Advanced catalytic materials for CO2 Methanation: Challenges and prospects 先进的CO2甲烷化催化材料：挑战与展望

IF 7.5 1区工程技术 Q2 ENERGY & FUELS

Fuel

Pub Date : 2025-12-09 DOI: 10.1016/j.fuel.2025.137952

Zhiwei Ye , Fan Huang , Luyao Wu , Shuangqian Wang , Lijun Zhang

Carbon dioxide (CO₂) is widely recognized as a primary greenhouse gas and a significant contributor to climate change. A promising mitigation strategy involves the chemical conversion of CO₂ into substitute natural gas (SNG) via reaction with renewable hydrogen, a process commonly known as CO₂ methanation. This review examines recent advancements and industrial application prospects of CO₂ methanation technology. The discussion commences with an analysis of the reaction mechanism and thermodynamics of CO₂ methanation, alongside an overview of recent developments in catalyst research. Building on this foundation, the review elaborates on the current status of industrial applications of CO₂ methanation technology, particularly in power-to-gas (P2G) sectors. However, CO₂ methanation technology currently faces challenges, including limitations in catalyst stability, the complexity of optimizing reaction conditions, and the need for by-product control. Looking ahead, the field is moving toward innovative concepts such as inverse catalysts that exploit interfacial synergy, 3D-printed autocatalytic reactors that integrate catalyst design with process intensification, and mechanochemical synthesis as a green, solvent-free preparation route. These emerging directions, alongside continued efforts in catalyst performance enhancement, process design optimization, and system integration, are expected to accelerate the sustainable industrial implementation of CO₂ methanation. Furthermore, the expansion of CO₂ methanation into hydrogen energy, energy storage, and environmental protection underscores its significant commercial and societal potential.

二氧化碳（CO2）被广泛认为是主要的温室气体，也是导致气候变化的重要因素。一种很有前景的缓解策略是通过与可再生氢的反应将二氧化碳化学转化为替代天然气（SNG），这一过程通常被称为二氧化碳甲烷化。本文综述了二氧化碳甲烷化技术的最新进展和工业应用前景。讨论首先分析了CO2甲烷化的反应机理和热力学，同时概述了催化剂研究的最新进展。在此基础上，综述详细阐述了二氧化碳甲烷化技术的工业应用现状，特别是在电力制气（P2G）领域。然而，二氧化碳甲烷化技术目前面临着诸多挑战，包括催化剂稳定性的限制、优化反应条件的复杂性以及对副产物控制的需求。展望未来，该领域正朝着创新概念发展，如利用界面协同作用的逆催化剂、将催化剂设计与工艺强化相结合的3d打印自催化反应器，以及作为绿色、无溶剂制备路线的机械化学合成。这些新兴方向，加上催化剂性能提升、工艺设计优化和系统集成方面的持续努力，有望加速二氧化碳甲烷化的可持续工业实施。此外，二氧化碳甲烷化在氢能、储能和环境保护方面的扩展凸显了其巨大的商业和社会潜力。

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引用次数: 0

Optimization of gas heater Efficiency: Impact of nozzle design and combustion modifications 燃气加热器效率的优化：喷嘴设计和燃烧修改的影响

IF 7.5 1区工程技术 Q2 ENERGY & FUELS

Fuel

Pub Date : 2025-12-09 DOI: 10.1016/j.fuel.2025.137968

Saeed Zeinali Heris , Vahid Zanjani , Seyed Borhan Mousavi

Improving the thermal efficiency and emissions performance of domestic gas heaters is essential for reducing residential energy consumption and mitigating urban air pollution. This study presents a structured, experimentally validated framework for optimizing a conventional gas heater through fifteen sequential combustion and heat recovery modifications. Unlike prior studies that focus on isolated design changes, our approach applies a stepwise, system-level strategy that integrates combustion geometry and flue pathway enhancements to improve energy efficiency and pollutant control simultaneously. Key interventions included nozzle diameter reduction (from 270 to 220), installation and perforation of a heat-retaining plate, and the addition of diagonal flow barriers and internal flue grooves to extend the exhaust path and enhance turbulence. Each modification was evaluated for its impact on thermal efficiency and CO emissions. While structural enhancements initially caused CO levels to spike up to 1460 ppm, subsequent tuning—including the use of a 220 optimized nozzle (2.2 mm diameter) paired with a matched burner—successfully stabilized combustion. The final configuration achieved a thermal efficiency of 77.78 %, up from a baseline of 68.6 %, demonstrating a 13.3 % absolute efficiency improvement and a 99 % reduction in CO emissions (1460 to 14 ppm). These results confirm that coordinated, low-cost geometric modifications can overcome performance trade-offs typically seen with single-parameter changes. The proposed framework offers a scalable and practical solution for retrofitting legacy heating systems to comply with modern energy efficiency and air quality standards.

提高家用燃气加热器的热效率和排放性能对于降低住宅能耗和缓解城市空气污染至关重要。本研究提出了一个结构化的、经过实验验证的框架，通过15个顺序的燃烧和热回收修改来优化传统的燃气加热器。与之前的研究不同，我们的方法侧重于孤立的设计变化，采用逐步的系统级策略，将燃烧几何形状和烟道增强相结合，同时提高能源效率和污染物控制。关键的干预措施包括减少喷嘴直径（从270到220），安装和穿孔保温板，增加对角流屏障和内部烟道凹槽，以延长排气路径并增强湍流。评估了每种改性对热效率和CO排放的影响。虽然最初的结构改进导致CO水平飙升至1460 ppm，但随后的调整（包括使用220优化喷嘴（直径2.2 mm）和匹配的燃烧器）成功地稳定了燃烧。最终的配置实现了77.78%的热效率，高于68.6%的基线，表明绝对效率提高了13.3%，CO排放量减少了99%（1460至14ppm）。这些结果证实，协调、低成本的几何修改可以克服单参数更改通常出现的性能权衡。拟议的框架为改造传统供暖系统提供了一个可扩展和实用的解决方案，以符合现代能源效率和空气质量标准。

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引用次数: 0

Statistical optimization of biochar production via high-temperature carbonization through Taguchi and principal component analysis approaches 利用田口法和主成分分析法对高温炭化生产生物炭的统计优化

IF 7.5 1区工程技术 Q2 ENERGY & FUELS

Fuel

Pub Date : 2025-12-09 DOI: 10.1016/j.fuel.2025.137846

Jamin Jamir Escalante , Wei-Hsin Chen , Chien-Yuan Su , Po-Han Li , Kun-Yi Andrew Lin , Kanit Manatura

Biochar, a carbon-rich material derived from biomass through pyrolytic carbonization, is gaining prominence for its roles in energy production, carbon sequestration, and environmental remediation. This study investigates biochar production from various biomass wastes through high-temperature carbonization optimized via the Taguchi method, multi-step ANOVA, and composite desirability function coupled with principal component analysis (CDF-PCA). Experiments assessed the influence of carbonization temperature (300–750 °C), holding time (30–75 min), and biomass type (spent coffee grounds, cow manure, bamboo, food digestate) on solid yield and energy yield. The findings demonstrate that biomass type and temperature significantly determine biochar performance, with holding time exerting minor effects. Optimal conditions were identified as 300 °C and 45 min using food digestate, achieving a solid yield of 68.73 % and an energy yield of 42.69 %. Notably, bamboo delivered superior energy yield potential, while spent coffee grounds provided the highest calorific values (up to 25.27 MJ∙kg⁻¹). The study’s novelty lies in integrating Taguchi experimental design with multi-objective optimization using CDF-PCA, offering a robust framework to enhance multiple biochar properties simultaneously. These insights contribute to advancing sustainable waste valorization by enabling tailored biochar production for energy recovery and environmental applications.

生物炭是一种富含碳的材料，通过热解碳化从生物质中提取，因其在能源生产、碳固存和环境修复方面的作用而日益突出。本研究通过田口法、多步方差分析和复合期望函数结合主成分分析（CDF-PCA）对多种生物质废弃物高温碳化生产生物炭进行了优化。实验评估了炭化温度（300-750℃）、保温时间（30-75 min）和生物质类型（废咖啡渣、牛粪、竹子、食物消化液）对固体产量和能量产量的影响。结果表明，生物质类型和温度对生物炭性能有显著影响，保温时间影响较小。最佳条件为300℃、45 min，固体产率为68.73%，能量产率为42.69%。值得注意的是，竹子提供了优越的能量产出潜力，而废咖啡渣提供了最高的热值（高达25.27 MJ∙kg−1）。该研究的新颖之处在于将田口实验设计与CDF-PCA多目标优化相结合，为同时提高多种生物炭性能提供了一个稳健的框架。这些见解有助于通过为能源回收和环境应用量身定制生物炭生产来推进可持续废物增值。

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引用次数: 0

Co-pyrolysis of waste tires and used oil: RSM optimization and prediction of fuel properties 废轮胎与废油共热解：RSM优化及燃料性能预测

IF 7.5 1区工程技术 Q2 ENERGY & FUELS

Fuel

Pub Date : 2025-12-09 DOI: 10.1016/j.fuel.2025.137874

Rinlada Sirisangsawang , Nawaporn Permsombut , Puttiporn Thiamsinsangwon , Orawan Rojviroon , Natacha Phetyim

End-of-life tires (ELTs) and waste lubricant oil are abundant hydrocarbon-rich wastes that can be upgraded into liquid fuels instead of being landfilled or openly burned. This study investigates the co-pyrolysis of waste tires and used lubricant oil in the presence of CaO-based catalysts and applies response surface methodology (RSM) with a central composite design to optimize the process. Three coded factors, final temperature (386.36 to 453.63 °C), used oil ratio (12.96 to 97.04 wt%), and CaO loading (6.59 to 23.41 wt%), were varied in 19 experiments. Quadratic models were developed for seven responses, namely oil yield, cetane index, specific gravity, density, viscosity, and sulfur and chlorine contents, with R² mostly above 0.90, indicating good predictive capability. The optimum conditions (437 °C, 79.29 wt% used oil, and 12.05 wt% CaO) produced 63.4 ± 0.28 wt% oil with a cetane index of 51.5 ± 0.71 and a kinematic viscosity of 3.97 ± 0.07 cSt, which are close to diesel fuel specifications. Replacing commercial CaO with calcined cockle shell CaO under the same conditions slightly improved viscosity (3.90 ± 0.11 cSt) and reduced sulfur and chlorine levels to 0.242 ± 0.06 wt% and 18.55 ± 1.03 ppm, respectively, demonstrating the feasibility of using waste-derived CaO as a catalyst. The final set of RSM models was also implemented in a web-based calculation tool to enable rapid estimation of fuel properties from operating conditions.

报废轮胎（elt）和废润滑油是富含碳氢化合物的废物，可以升级为液体燃料，而不是填埋或公开燃烧。研究了在cao基催化剂的作用下废轮胎和废润滑油的共热解，并采用响应面法（RSM）和中心复合设计对热解过程进行了优化。19个实验中，最终温度（386.36 ~ 453.63℃）、废油比（12.96 ~ 97.04 wt%）和CaO负荷（6.59 ~ 23.41 wt%）三个编码因子发生了变化。对产油率、十六烷指数、比重、密度、粘度、硫氯含量等7个指标建立了二次模型，R2大多在0.90以上，预测能力较好。在最佳条件下（437℃，79.29 wt%废油，12.05 wt% CaO），得到的油质量分数为63.4±0.28 wt%，十六烷指数为51.5±0.71，运动粘度为3.97±0.07 cSt，接近柴油指标。在相同条件下，用煅烧的蛤壳CaO代替商用CaO，粘度（3.90±0.11 cSt）略有提高，硫和氯含量分别降至0.242±0.06 wt%和18.55±1.03 ppm，证明了将废物来源的CaO用作催化剂的可行性。最后一组RSM模型也在基于网络的计算工具中实现，以便根据运行条件快速估计燃料特性。

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引用次数: 0

Simulation of phase equilibria properties of fuels and blends of fuels with oxygenated compounds 燃料和含氧化合物混合燃料相平衡特性的模拟

IF 7.5 1区工程技术 Q2 ENERGY & FUELS

Fuel

Pub Date : 2025-12-09 DOI: 10.1016/j.fuel.2025.137864

Mariana González Prieto , Aylen Merlo Raimondi , Francisco Adrián Sánchez , Selva Pereda

Non-ideality in fuel-biofuel blends arises from the presence of oxygenated compounds in a non-polar substrate, significantly impacs on phase behavior and, consequently, fuel storage and transport, and engine performance. Volatility properties, which are key indicators of fuel quality, are regulated by standards and evaluated through standardized tests. This work explores the phase equilibrium of fuel-oxygenate blends using a predictive thermodynamic model and propose novel calculation methods to simulate volatility tests, including Reid Vapor Pressure, vapor lock protection temperature, and the distillation curve. Additionally, water tolerance in oxygenate/gasoline blends is predicted using a robust liquid–liquid equilibrium approach. The Group Contribution with Association Equation of State (GCA-EOS) model accurately captures the phase behavior across a wide range of biofuels, including advanced candidates such as 2-methyltetrahydrofuran and ethyl levulinate. The proposed models showed good predictive accuracy, with average relative deviations of 1,4% in distillation temperatures and average absolute deviations of 1.1 kPa for Reid vapor pressure. In liquid–liquid equilibrium calculations, the average absolute error was 0.02 for oxygenate partition coefficients and 0.37 for water. The proposed methodology enhances understanding of oxygenate effects in blends and provides predictive tools for fuel blend design, aiming to reduce the exploratory experimental work.

燃料-生物燃料混合物的非理想性源于非极性基质中含氧化合物的存在，这对相行为产生了重大影响，从而影响了燃料的储存和运输以及发动机性能。挥发性是燃油质量的关键指标，有标准规定，并通过标准化测试进行评估。本研究使用预测热力学模型探索了燃料-氧混合物的相平衡，并提出了新的计算方法来模拟挥发性测试，包括Reid蒸气压、汽锁保护温度和蒸馏曲线。此外，使用稳健的液-液平衡方法预测了氧合物/汽油混合物的耐水性。基于状态关联方程（GCA-EOS）的群体贡献模型准确地捕捉了各种生物燃料的相行为，包括先进的候选生物燃料，如2-甲基四氢呋喃和乙酰丙酸乙酯。该模型具有较好的预测精度，对蒸馏温度的平均相对偏差为1.4%，对Reid蒸气压的平均绝对偏差为1.1 kPa。在液液平衡计算中，氧分配系数的平均绝对误差为0.02，水分配系数的平均绝对误差为0.37。所提出的方法增强了对混合燃料中含氧效应的理解，并为燃料混合设计提供了预测工具，旨在减少探索性实验工作。

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引用次数: 0

Carrier effects in FeCl3-impregnated adsorbents for Hg0 capture: structure-chemistry-transport relationships fecl3浸渍吸附剂中Hg0捕获的载流子效应：结构-化学-传输关系

IF 7.5 1区工程技术 Q2 ENERGY & FUELS

Fuel

Pub Date : 2025-12-09 DOI: 10.1016/j.fuel.2025.137967

Fei Ye , Xiang Shao , Qingyu Ge , Junfeng Zhao , Qiang Zhou , Jun Zhang , Yifan Xu

Capturing Hg⁰ under flue gas conditions remains challenging due to low reactivity and high volatility. Active species (FeCl₃) impregnation promotes oxidation, but the property is largely affected by the carrier architecture and surface chemistry that determine active-site dispersion and transport. In this work, we prepare FeCl₃-impregnated sorbents (0.4 wt%) on MCM-41, ZSM-5, activated carbon (AC), and fly ash (FA). Structure, surface chemistry, and transport are related to Hg⁰ removal. XRD, SEM and N₂-sorption show framework retention on silica hosts, hierarchical porosity on AC, and surface overlayers on FA. XPS further confirms Fe³⁺ with substantial surface FeCl₃ on all samples, while oxygen speciation differs (O_β-rich on AC vs O_α-dominated on silica/ash). Correspondingly, Hg-TPD resolves weak (physisorbed/Cl-ligated) and strong (Hg-O-Fe) states whose fractions track fixed-bed performance (60–180 °C; N₂/O₂/SO₂). Consequently, Fe-AC achieves the highest and most sustained removal, Fe-MCM-41 follows, and Fe-ZSM-5/Fe-FA break through early due to pore-mouth or shell-limited access. Overall, the results highlight three carrier design principles for Hg⁰ capture with FeCl₃: maintain continuous or hierarchical transport pathways after loading, stabilize dispersed Fe³⁺-O-Cl domains with adequate surface chloride and adsorbed oxygen, and avoid surface overlayers that confine reaction to an outer shell.

由于低反应性和高挥发性，在烟气条件下捕获Hg0仍然具有挑战性。活性物质（FeCl3）浸渍促进氧化，但其性质在很大程度上受载流子结构和表面化学的影响，这些结构和表面化学决定了活性位点的分散和传输。在这项工作中，我们在MCM-41、ZSM-5、活性炭（AC）和粉煤灰（FA）上制备了fecl3浸渍吸附剂（0.4 wt%）。结构、表面化学和输运与Hg0的去除有关。XRD、SEM和n2吸附结果表明，二氧化硅基体上骨架保留，AC表面有分层孔隙，FA表面有表面复盖层。XPS进一步证实，所有样品表面都有大量的Fe3+，而氧的形态不同（AC上富含o β，而二氧化硅/灰分上以o α为主）。相应的，Hg-TPD可以分解弱态（物理吸附态/ cl -结合力态）和强态（Hg-O-Fe），其组分遵循固定床性能（60-180℃；N2/O2/SO2）。结果表明，Fe-AC的去除效果最高、持续时间最长，Fe-MCM-41次之，Fe-ZSM-5/Fe-FA由于孔口或壳限制进入，较早突破。总体而言，研究结果强调了用FeCl3捕获Hg0的三个载流子设计原则：在加载后保持连续或分层运输途径，用足够的表面氯化物和吸附氧稳定分散的Fe3+-O-Cl结构域，避免表面覆盖层将反应限制在外壳上。

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引用次数: 0

NiMoP/S-stabilized Ti3C2Tx on nickel foam as an efficient electrocatalyst for hydrogen evolution reaction in alkaline medium NiMoP/ s稳定的Ti3C2Tx在泡沫镍上作为碱性介质析氢反应的高效电催化剂

IF 7.5 1区工程技术 Q2 ENERGY & FUELS

Fuel

Pub Date : 2025-12-09 DOI: 10.1016/j.fuel.2025.137921

Deepak Singh, Mohammad Saquib, Amit C. Bhosale

Identifying electrocatalysts with high activity and cost-effectiveness is crucial for large-scale water electrolysis. This study develops a highly efficient HER electrocatalyst under alkaline conditions (1 M KOH) by depositing bi-metallic Ni-Mo phosphide onto sulfur-doped MXene (Ti₃C₂T_x) coated nickel foam using a single-step, low-cost, and sustainable hydrothermal method. The NiMoP/S-Ti₃C₂T_x@NF forms a dense, uniform layer and delivers excellent HER activity, requiring only 121 mV to reach at 10 mA cm⁻² and exhibits a low Tafel slope of 46 mV dec^-1. Sulfur doping of MXene plays a key role, reducing the overpotential by 87 mV compared to NiMoP/Ti₃C₂T_x@NF (208 mV). The catalyst demonstrates remarkable durability, with just a 31 mV increase in overpotential at 100 mA cm⁻² after 10,000 LSV cycles and continuous stable operation for 30 h at 121 mV. The catalyst also exhibited a high electrochemically active surface area, low charge transfer resistance (1.94 Ω), and a Faradaic efficiency of 98.2% at −100 mA cm⁻², confirming excellent charge-to-gas conversion and superior electrocatalytic performance.

寻找高效、经济的电催化剂是大规模水电解的关键。本研究采用单步、低成本、可持续的水热法，在碱性条件下（1 M KOH）将双金属Ni-Mo磷化物沉积在含硫MXene （Ti3C2Tx）包覆泡沫镍上，开发了一种高效的HER电催化剂。NiMoP/S-Ti3C2Tx@NF形成致密、均匀的层，具有优异的HER活性，仅需121 mV即可达到10 mA cm - 2， Tafel斜率低至46 mV / dec1。MXene的硫掺杂起到了关键作用，与NiMoP/Ti3C2Tx@NF （208 mV）相比，其过电位降低了87 mV。该催化剂表现出卓越的耐久性，在100 mA cm - 2下，经过10,000 LSV循环和121 mV连续稳定运行30小时后，过电位仅增加31 mV。该催化剂还具有较高的电化学活性表面积，较低的电荷转移电阻（1.94 Ω），在−100 mA cm−2下的法拉第效率为98.2%，证实了优异的电荷-气体转化和优越的电催化性能。

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引用次数: 0

Enhancing the prediction capability of a literature COx methanation kinetic model 提高文献COx甲烷化动力学模型的预测能力

IF 7.5 1区工程技术 Q2 ENERGY & FUELS

Fuel

Pub Date : 2025-12-09 DOI: 10.1016/j.fuel.2025.137834

Juan J. Ríos , Jorge Ancheyta , Angeles Mantilla , Andrey Elyshev , Andrey Zagoruiko

A kinetic model for CO_x methanation based on the reactions of methanation of CO and CO₂, and reverse water–gas shift is compared with a literature kinetic model that only considers the methanation of CO and reverse water–gas shift. The model is assessed under non-isothermal plug flow reactor conditions. To validate the predictive capability, temperature profiles, species molar fractions, and methane production were simulated and compared with experimental data. The proposed model includes mechanistic expressions accounting for competitive adsorption and product inhibition effects, which significantly improve its accuracy in capturing the system thermal and reactive behavior. Statistical validation through residual analysis and parity plot, along with regression metrics, confirms the superior performance of the proposed model. Notably, the inclusion of the CO₂ methanation pathway led to a 15% increase in CH₄ yield which adjusted better to the experimental data, emphasizing its importance in reactor modeling for CO_x hydrogenation. These results underscore the relevance of complete kinetic formulations in supporting process design, optimization, and scale-up in Power-to-Gas and synthetic natural gas production.

将基于CO和CO2甲烷化反应和水气反移反应的COx甲烷化动力学模型与文献中只考虑CO甲烷化反应和水气反移反应的动力学模型进行了比较。该模型在非等温塞流反应器条件下进行了评估。为了验证预测能力，模拟了温度分布、物种摩尔分数和甲烷产量，并与实验数据进行了比较。该模型包含考虑竞争吸附和产物抑制效应的机制表达式，显著提高了其捕获系统热行为和反应行为的准确性。通过残差分析和奇偶图以及回归指标进行统计验证，证实了所提出模型的优越性能。值得注意的是，CO2甲烷化途径的加入使CH4产率提高了15%，这与实验数据更吻合，强调了其在COx加氢反应器建模中的重要性。这些结果强调了完整的动力学公式在支持工艺设计、优化和扩大电制气和合成天然气生产中的重要性。

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引用次数: 0

Mechanistic study on the formation of decalin during hydrotreating of low-temperature coal tar 低温煤焦油加氢处理过程中十氢化萘生成机理研究

IF 7.5 1区工程技术 Q2 ENERGY & FUELS

Fuel

Pub Date : 2025-12-09 DOI: 10.1016/j.fuel.2025.137818

Chaowen Yu, Lihong Wei, Ximeng Hu, Tianhua Yang, Yanlong Li, Zuoxi Liu

Efficient conversion of aromatic compounds in low-temperature coal tar (LTCT) into cycloalkanes is a key step in producing high-density components of coal-based jet fuel. In this study, a combined ReaxFF molecular dynamics and density functional theory approach was employed to construct model systems based on representative LTCT components, with pure naphthalene and 1-naphthol serving as reference systems. The molecular-level hydrogenation network and key reaction mechanisms were systematically elucidated. The results reveal that variations in hydrogenation activity among LTCT components lead to competitive adsorption of H• radicals, resulting in significantly higher local H• concentrations around naphthalene and 1-naphthol compared with their pure systems, thereby increasing decalin yields at 650 K (20 % and 6.66 %, respectively). In addition, hydrogenation at secondary positions is primarily governed by kinetic control, while the influence of thermodynamic factors becomes more pronounced with increasing H• concentration. These findings deepen the understanding of LTCT hydrogenation mechanisms and provide theoretical insights for the design of highly selective hydrogenation catalysts.

低温煤焦油（LTCT）中芳香族化合物高效转化为环烷烃是生产煤基航空燃料高密度组分的关键步骤。本研究采用ReaxFF分子动力学和密度泛函理论相结合的方法，以纯萘和1-萘酚为参比体系，构建了具有代表性的LTCT组分的模型体系。系统地阐明了分子水平的加氢网络和关键反应机理。结果表明，LTCT组分之间的加氢活性变化导致H•自由基的竞争性吸附，导致萘和1-萘酚周围的局部H•浓度显著高于其纯体系，从而提高了650 K下的十氢化萘收率（分别为20%和6.66%）。此外，二级位置的氢化主要受动力学控制，而热力学因素的影响随着H•浓度的增加而更加明显。这些发现加深了对LTCT加氢机理的理解，并为高选择性加氢催化剂的设计提供了理论见解。

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