Fuel Processing Technology最新文献_第10页

Optimization of advanced biogas production via the DiCOM bioprocess utilizing the biogas test plant BTP2: Insights from multifactorial analysis 利用沼气测试厂BTP2通过DiCOM生物工艺优化先进沼气生产：来自多因素分析的见解

IF 7.7 2区工程技术 Q1 CHEMISTRY, APPLIED

Fuel Processing Technology

Pub Date : 2025-11-15 Epub Date: 2025-09-30 DOI: 10.1016/j.fuproc.2025.108343

Mansuur Husein , Liang Cheng , Francis Kwaku Attiogbe , Abdallah Abdelfattah , Hany S. El-Mesery , Emmanuel Nkudede

This study introduces an innovative optimization of the DiCOM bioprocess, which integrates aerobic composting and anaerobic digestion, utilizing the Biogas Test Plant BTP2 configured as a continuous stirred-tank reactor (CSTR). The research seeks to enhance biogas production from sewage sludge by examining the effects of key operational parameters, including temperature, pH, inoculum-to-substrate ratio, and stirrer speed. This investigation is pioneering in its use of a DiCOM-CSTR configuration, distinguishing it from previous studies that focused on fixed-bed or sequential systems. This approach facilitates continuous operation and enhances process control. A multifactorial experimental design was employed, utilizing Box-Behnken Design (BBD) and Response Surface Methodology (RSM), along with Principal Component Analysis (PCA), to evaluate the combined impacts of critical parameters such as temperature, pH, inoculum-to-substrate ratio (ISR), and stirrer speed. Under optimized conditions, a thermophilic temperature of 65 °C, neutral pH (7.0–7.5), ISR of 0.63, and controlled stirring speed of 100 rpm contributed to achieving a methane yield of up to 64.2 % and hydrogen sulfide concentrations as low as 3.9 ppm. The results surpass previously reported values, confirming the effectiveness of the proposed configuration and methodological approach. The integrated PCA-RSM framework provided enhanced multivariate insight into parameter interactions and process dynamics. Future studies should deepen the understanding of microbial community dynamics, assess the long-term operational stability of the DiCOM process, and evaluate its adaptability across diverse organic waste streams. This study not only advances the design and optimization of DiCOM systems but also offers a scalable approach for sustainable energy recovery from organic waste.

本研究介绍了DiCOM生物工艺的创新优化，该工艺将好氧堆肥和厌氧消化结合起来，利用沼气试验装置BTP2配置为连续搅拌槽反应器（CSTR）。该研究旨在通过检查关键操作参数的影响，包括温度、pH值、接种物与底物比和搅拌速度，来提高污水污泥的沼气产量。这项研究在使用DiCOM-CSTR配置方面是开创性的，与之前专注于固定床或顺序系统的研究不同。这种方法有利于连续操作，并加强过程控制。采用Box-Behnken设计（BBD）和响应面分析法（RSM），结合主成分分析（PCA），对温度、pH、接种物与底物比（ISR）和搅拌速度等关键参数的综合影响进行了评价。在优化条件下，亲热温度为65°C，中性pH值（7.0-7.5），ISR为0.63，控制搅拌速度为100 rpm，甲烷收率高达64.2%，硫化氢浓度低至3.9 ppm。结果超过了先前报道的值，证实了所建议的配置和方法方法的有效性。集成的PCA-RSM框架为参数交互和过程动力学提供了增强的多变量洞察。未来的研究应深化对微生物群落动态的理解，评估DiCOM工艺的长期运行稳定性，并评估其在不同有机废物流中的适应性。这项研究不仅推进了DiCOM系统的设计和优化，而且为有机废物的可持续能源回收提供了一种可扩展的方法。

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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 : 2025-11-15 Epub 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。

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引用次数: 0

Profiling the trapped and deactivating species on HZSM-5 zeolite during 1-butene oligomerization HZSM-5沸石在1-丁烯低聚过程中捕获和失活物质的分析

IF 7.7 2区工程技术 Q1 CHEMISTRY, APPLIED

Fuel Processing Technology

Pub Date : 2025-11-01 Epub Date: 2025-07-31 DOI: 10.1016/j.fuproc.2025.108297

Sepideh Izaddoust , Idoia Hita , Timo Kekäläinen , José Valecillos , Janne Jänis , Pedro Castaño , Eva Epelde

The transformation of 1-butene into valuable fuels using HZSM-5 zeolite catalysts is significantly hindered by deactivation caused by deposited species and coke formation. This work delves into the entrapment, formation, and growth of these species during 1-butene oligomerization at 275–325 °C, 1.5–40 bar, and space-times of 2–6 g_cat h mol_C⁻¹. We have employed an extensive characterization of the used catalysts, integrating conventional techniques with high-resolution mass spectrometry (Fourier Transform Ion Cyclotron Resonance Mass Spectrometry, FT-ICR MS). This advanced technique provides a detailed molecular-level analysis of these species. Our findings reveal that higher pressures promote oligomerization, resulting in an increased accumulation of trapped oligomer species. Conversely, higher temperatures facilitate the cracking of these oligomers into lighter fractions or their further conversion into coke molecules through condensation reactions. This dual behavior underscores the complex interplay between temperature and pressure in influencing the deactivation pathways. By understanding the overall reaction mechanism and the formation and growth patterns of trapped and deactivating species, we can develop strategies to mitigate catalyst deactivation, ultimately leading to more efficient industrial applications.

利用HZSM-5沸石催化剂将1-丁烯转化为有价值的燃料，由于沉积物和焦炭的形成而导致失活。这项工作深入研究了在275-325°C， 1.5-40 bar和2-6 gcat h molC−1的空间时间下，这些物种在1-丁烯寡聚过程中的捕获，形成和生长。我们对所用催化剂进行了广泛的表征，将传统技术与高分辨率质谱法（傅里叶变换离子回旋共振质谱法，FT-ICR MS）相结合。这项先进的技术为这些物种提供了详细的分子水平分析。我们的研究结果表明，较高的压力促进了低聚，导致被困低聚物种类的积累增加。相反，较高的温度有利于这些低聚物裂解成较轻的馏分或通过缩合反应进一步转化为焦炭分子。这种双重行为强调了影响失活途径的温度和压力之间的复杂相互作用。通过了解整个反应机制以及捕获和失活物种的形成和生长模式，我们可以制定减轻催化剂失活的策略，最终实现更有效的工业应用。

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引用次数: 0

Nano-molecular response of bituminous coal to ScCO₂ at different stage: Experiments and ReaxFF-MD/DFT insights 不同阶段烟煤对ScCO 2的纳米分子响应：实验和ReaxFF-MD/DFT见解

IF 7.7 2区工程技术 Q1 CHEMISTRY, APPLIED

Fuel Processing Technology

Pub Date : 2025-11-01 Epub Date: 2025-08-18 DOI: 10.1016/j.fuproc.2025.108305

Kui Dong , Jianhua Xiang , Shaoqi Kong , Bingyi Jia , Zhiyu Niu

The interaction between supercritical CO₂ (ScCO₂) and coal alters the physicochemical properties of the coal in a staged manner. This study quantitatively investigates the nano-molecular structural response of bituminous to ScCO₂ exposure using a combination of experiments and ReaxFF-MD/DFT simulations. The results show that:In the swelling stage, the coal matrix expanded and early radical formation occurred, leading to a reduction in intramolecular pore volume from 0.0326 to 0.0318 cm³/g, while intermolecular pores increased from 0.0119 to 0.0145 cm³/g, Car-Car from 145 to 149, Cal-H from 103 to 92, weak van der Waals and hydrogen bonds were cleaved. In the dissolution stage, aliphatic chains degraded and oxygen-containing groups formed, intramolecular and intermolecular pores expanded to 0.0334 and 0.0165 cm³/g, respectively, increasing Car–Car bonds to 150, and Cal-H to 89, electron density recovered with the development of aromatic conjugation and polar groups In the rearrangement stage, radicals recombined into new aromatics, compressing intermolecular pores to 0.0160 cm³/g, while intramolecular pores increased to 0.0346 cm³/g, reducing Car–Car bonds to 142 and Cal-H to 84, electrostatic potential strengthened, indicating molecular stabilization.This work provides a novel, stage-specific, and quantitatively supported mechanism of bituminous evolution under ScCO₂ conditions, offering theoretical insight into molecular-scale optimization strategies for CO₂-ECBM.

超临界CO₂（ScCO₂）与煤的相互作用使煤的物理化学性质发生阶段性改变。本研究采用实验和ReaxFF-MD/DFT模拟相结合的方法，定量研究了沥青对ScCO 2暴露的纳米分子结构响应。结果表明：在膨胀阶段，煤基体膨胀并发生早期自由基形成，导致分子内孔体积由0.0326减小至0.0318 cm3/g，分子间孔由0.0119增大至0.0145 cm3/g， Car-Car由145增大至149，Cal-H由103增大至92，弱范德华键和氢键断裂；在溶解阶段，脂肪链降解，含氧基团形成，分子内孔和分子间孔分别扩大到0.0334和0.0165 cm3/g， Car-Car键增加到150个，Cal-H键增加到89个，电子密度随着芳香偶联和极性基团的发展而恢复。重排阶段，自由基重新结合形成新的芳烃，分子间孔压缩到0.0160 cm3/g，分子内孔增加到0.0346 cm3/g。Car-Car键减少到142，Cal-H键减少到84，静电电位增强，表明分子稳定。这项工作提供了一种新的、特定阶段的、定量支持的ScCO 2条件下沥青演化机制，为CO 2 -ECBM的分子尺度优化策略提供了理论见解。

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引用次数: 0

Multi-hollow dielectric barrier discharge plasma: An energy-efficient strategy towards mild ammonia synthesis 多空心介质阻挡放电等离子体：温和氨合成的节能策略

IF 7.7 2区工程技术 Q1 CHEMISTRY, APPLIED

Fuel Processing Technology

Pub Date : 2025-11-01 Epub Date: 2025-07-29 DOI: 10.1016/j.fuproc.2025.108292

Shanzhi Liu , Jiabao Lv , Zhikai Lang , Xingqi Li , Jianhua Yan , Xiaodong Li , Yaqi Peng , Yunchao Li , Dingkun Yuan , Jian Wu , Angjian Wu

Renewable-driven non-thermal plasma (NTP) technology provides a potentially sustainable alternative for ammonia (NH₃) production. Nonetheless, energy efficiency remains a critical bottleneck in NTP reactors. Herein, we propose a multi-hollow dielectric barrier discharge (MDBD) plasma reactor to realize nitrogen hydrogenation towards ambient NH₃ synthesis, with the physicochemical characteristics systematically explored for the first time. Transient discharge dynamics were captured by electrical characterization, meanwhile the active intermediate species and the low-temperature properties of MDBD were unveiled by optical spectrum diagnosis. Effects of feed gas, flow rate and specific energy input (SEI) on reaction activity were investigated in terms of energy efficiency (EE) and energy consumption (EC). Notably, remarkable reaction efficacy was realized under low driving powers. For a fully-developed 'steady' discharge, an EE of 1.32 g/kWh and an EC of 46.44 MJ/mol could be attained at 3.20 W. Under a pulse-like fluctuating 'flicker' mode at merely 1.15 W, the EE and EC were improved to 1.78 g/kWh and 34.35 MJ/mol, respectively, further highlighting the energy-effectiveness of MDBD. This work provides a novel approach for energy-efficient, environmental-friendly and distributed NH₃ production.

可再生驱动的非热等离子体（NTP）技术为氨（NH3）的生产提供了一种潜在的可持续替代方案。尽管如此，能源效率仍然是NTP反应堆的关键瓶颈。本文提出了一种多空心介质阻挡放电（MDBD）等离子体反应器，用于实现氮加氢合成环境NH3，并首次系统地探索了其物理化学特性。通过电学表征捕获了MDBD的瞬态放电动态，同时通过光谱诊断揭示了MDBD的活性中间物质和低温特性。从能量效率（EE）和能量消耗（EC）两方面考察了原料气、流量和比能量输入（SEI）对反应活性的影响。值得注意的是，在低驱动功率下，反应效果显著。对于完全发展的“稳定”放电，在3.20 W时可以达到1.32 g/kWh的EE和46.44 MJ/mol的EC。在1.15 W的脉冲波动“闪烁”模式下，EE和EC分别提高到1.78 g/kWh和34.35 MJ/mol，进一步突出了MDBD的能效。这项工作为高效、环保和分布式的NH3生产提供了一种新的途径。

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引用次数: 0

Catalytic conversion of eucalyptus pre-hydrolysis liquor-derived xylo-oligosaccharides to furfural using dual-acidic functionalized covalent organic frameworks 双酸功能化共价有机框架催化桉木预水解液衍生低聚木糖转化为糠醛

IF 7.7 2区工程技术 Q1 CHEMISTRY, APPLIED

Fuel Processing Technology

Pub Date : 2025-11-01 Epub Date: 2025-08-28 DOI: 10.1016/j.fuproc.2025.108317

Peng Gan, Kai Zhang, Jingli Yang, Baobin Wang, Guihua Yang, Chengcheng Qiao, Lei Zhang, Jiachuan Chen

The application of biorefinery technologies to convert xylo-oligosaccharide (XOS) from pulping process into biofuels or high-value chemicals holds significant potential for extending the value chain of the pulp and paper industry, while simultaneously promoting sustainability. In this study, a series of dual-acid functionalized covalent organic frameworks (COFs) were synthesized to catalyze the one-step liquid-phase conversion of XOS into furfural. The results indicated that TAPT-DHPA exhibited exceptional catalytic activity, achieving a furfural yield of 78.6 % at 180 °C for 3 h with 0.16 wt% catalyst. Furthermore, TAPT-DHPA demonstrated excellent stability, maintaining a furfural yield above 77 % after six reuse cycles. Bader charge analysis via VASP software revealed the presence of both Brønsted and Lewis acid active sites in TAPT-DHPA, arising from the ionization of hydrogen in phenolic hydroxyl groups and the strong electron-withdrawing nature of the triazine ring, respectively. These characteristics are key factors in TAPT-DHPA's superior catalytic performance. Density functional theory calculations confirmed that the most favorable pathway for furfural production involves a cyclic anhydride intermediate, with the rate-limiting step being the initial dehydration of D-xylose triggered by proton attack on the 2-OH group. The addition of TAPT-DHPA reduced the activation energy of this rate-limiting step by 54.43 %.

应用生物炼制技术将低聚木糖（XOS）从制浆过程转化为生物燃料或高价值化学品，对于扩大纸浆和造纸工业的价值链具有巨大潜力，同时促进可持续性。本研究合成了一系列双酸功能化共价有机框架（COFs），催化XOS一步液相转化为糠醛。结果表明，TAPT-DHPA具有良好的催化活性，在0.16 wt%的催化剂作用下，180°C反应3 h，糠醛收率为78.6%。此外，TAPT-DHPA表现出优异的稳定性，在重复使用6次后，糠醛收率保持在77%以上。通过VASP软件进行的Bader电荷分析显示，在tpt - dhpa中存在Brønsted和Lewis酸活性位点，它们分别是由酚羟基上氢的电离和三嗪环的强吸电子性质引起的。这些特性是tpt - dhpa具有优异催化性能的关键因素。密度泛函数理论计算证实，最有利的糠醛生产途径涉及环酸酐中间体，限速步骤是质子攻击2-OH基团引发d -木糖的初始脱水。TAPT-DHPA的加入使这一限速步骤的活化能降低了54.43%。

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引用次数: 0

Effect of transition metal on the physical and hydrogen storage properties of the dynamically stable novel ARhH3 (A = Mg, Ca, and Sr) hydrides for solid-state hydrogen storage application: A DFT and AIMD study 过渡金属对动态稳定新型ARhH3 （A = Mg, Ca, Sr）氢化物物理和储氢性能的影响：DFT和AIMD研究

IF 7.7 2区工程技术 Q1 CHEMISTRY, APPLIED

Fuel Processing Technology

Pub Date : 2025-11-01 Epub Date: 2025-08-22 DOI: 10.1016/j.fuproc.2025.108312

Md. Rabbi Talukder , Md Rasidul Islam

A thorough examination of the physical and hydrogen storage properties of novel ARhH₃ (A = Mg, Ca, and Sr) hydrides employs first-principles Density Functional Theory. The mechanical, dynamic, thermodynamic, and phase stability of ARhH₃ hydrides were validated by assessing the Born stability criteria, phonon spectra, formation energies, and tolerance factors, respectively. Both the PBE and HSE06 functionals revealed that each of the entitled perovskites exhibits metallic character (E_g = 0 eV), showcasing remarkable conductivity that boosts charge transfer and facilitates the efficient (de)hydrogenation kinetics. Optical functions exhibited great potency in both the visible and UV spectra. The Cauchy pressure, Pugh's, and Poisson's ratios revealed the ductile nature of ARhH₃ perovskites. Furthermore, these perovskites exhibit excellent mechanical properties, including Young's modulus of 43.51–127.76 GPa, machinability index of 2.13–11.76, melting temperature of 1483.98–1684.06 K, sound velocity of 1945.51–3452.84 ms⁻¹, and notable anisotropic behavior. The thermal stability of these hydrides was confirmed by the thermodynamic evaluations and AIMD simulations. MgRhH₃, CaRhH_3, and SrRhH₃ demonstrated substantial gravimetric hydrogen storage capacities of 2.34, 2.07, and 1.56 wt%, as well as volumetric storage capacities of 117.65, 103.14, and 93.36 gH₂/L, respectively. Interestingly, the hydrogen desorption temperatures for MgRhH₃, CaRhH_3, and SrRhH₃ are recorded at 481 K, 531 K, and 493 K, respectively, enabling them to be highly suitable for practical solid-state hydrogen storage applications.

采用第一性原理密度泛函理论对新型ARhH3 （A = Mg， Ca和Sr）氢化物的物理和储氢性能进行了全面的研究。通过计算Born稳定性标准、声子谱、形成能和容差系数，分别验证了ARhH3氢化物的力学稳定性、动力学稳定性、热力学稳定性和相稳定性。PBE和HSE06官能团都表明，每一种钙钛矿都具有金属性质（Eg = 0 eV），表现出显著的导电性，促进电荷转移，促进有效的（脱）氢化动力学。光学函数在可见光谱和紫外光谱中都表现出很强的效力。柯西压力、皮尤和泊松比值揭示了ARhH3钙钛矿的延展性。此外，这些钙钛矿具有优异的力学性能，杨氏模量为43.51 ~ 127.76 GPa，可切削性指数为2.13 ~ 11.76，熔化温度为1483.98 ~ 1684.06 K，声速为1945.51 ~ 3452.84 ms−1，各向异性行为显著。热力学评价和AIMD模拟证实了这些氢化物的热稳定性。MgRhH3、CaRhH3和SrRhH3的重量储氢容量分别为2.34%、2.07和1.56 wt%，体积储氢容量分别为117.65、103.14和93.36 gH2/L。有趣的是，MgRhH3、CaRhH3和SrRhH3的氢解吸温度分别为481 K、531 K和493 K，这使得它们非常适合实际的固态储氢应用。

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引用次数: 0

Hierarchical Mo/HTNU-9 boosts methane aromatization with mitigated carbon deposition 分层Mo/HTNU-9促进甲烷芳构化，减轻碳沉积

IF 7.7 2区工程技术 Q1 CHEMISTRY, APPLIED

Fuel Processing Technology

Pub Date : 2025-11-01 Epub Date: 2025-09-02 DOI: 10.1016/j.fuproc.2025.108323

Jing Hu, Xiaodong Chen, Chunxue Yang, Jingjing Tian, Xin Kang, Xiaohui Wang, Jinglin Liu

Methane dehydroaromatization (MDA) offers a promising route for converting methane into aromatics, yet rapid catalyst deactivation via coking remains a critical barrier. This study addresses this challenge through TPAOH-assisted hierarchical pore engineering of HTNU-9 zeolite. Controlled desilication (0.25 mol/L TPAOH, 24 h) generates micro-mesoporous Mo/HTNU-9-24 while retaining microporous integrity, achieving a 22 % increase in methane conversion (14.7 % vs. 11.4 % for pristine Mo/HTNU-9) at 700 °C. The hierarchical architecture enhances mass transfer and Mo dispersion via synergistic effects. Silanol-rich mesopore surfaces and mild alkalinity stabilize Mo species, selective removal of strong acid sites coupled with spatial confinement of mesopores mitigate coke accumulation. The optimized catalyst exhibits prolonged stability due to restricted Mo agglomeration and efficient carbon precursor diffusion. These findings establish a dual strategy (pore topology control and acid site modulation) to synchronize active center dynamics and coke resistance, advancing the rational design of hierarchical zeolites for industrial MDA applications.

甲烷脱氢芳化（MDA）为甲烷转化为芳烃提供了一条很有前途的途径，但通过焦化使催化剂快速失活仍然是一个关键障碍。本研究通过tpaoh辅助HTNU-9沸石的分层孔隙工程来解决这一挑战。控制脱硅（0.25 mol/L TPAOH, 24 h）生成微介孔Mo/HTNU-9-24，同时保持微孔完整性，在700℃下甲烷转化率提高22%（14.7%比原始Mo/HTNU-9的11.4%）。分层结构通过协同效应增强了传质和钼的分散。富硅醇的介孔表面和温和的碱度稳定了钼，选择性去除强酸位点加上介孔的空间限制减轻了焦炭的积累。优化后的催化剂表现出较长的稳定性，因为它限制了钼的团聚和有效的碳前驱体扩散。这些发现建立了一种双重策略（孔隙拓扑控制和酸位调制）来同步活性中心动力学和抗焦性，促进了分层沸石的合理设计，用于工业MDA应用。

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引用次数: 0

Leaching behavior of germanium from germanium-rich lignite: A further comprehension of its occurrence state 富锗褐煤中锗的浸出行为：对其赋存状态的进一步认识

IF 7.7 2区工程技术 Q1 CHEMISTRY, APPLIED

Fuel Processing Technology

Pub Date : 2025-11-01 Epub Date: 2025-07-30 DOI: 10.1016/j.fuproc.2025.108298

Zhiyuan Zhang , Yanyan Xu , Guixia Fan , Yingrui Jin , Daoguang Teng , Guosheng Li , Peng Li , Yijun Cao

Germanium, a critical metal used in many strategy fields, is widely acknowledged as organic affinity. Germanium is main occurred in the humus of lignite, but its exact occurrence state remains unclear. In this work, various methods were employed to leach germanium from lignite to reveal the germanium occurrence state. Germanium tends to accumulate in specific germanium-endowed structures, but most germanium is bound to and encapsulated in enwrapping structures such as humic acid. It could be extracted either by co-extraction with humic acid (e.g. ammonoxidation, alkaline leaching) or by dissociating the germanium-endowed structure (e.g. thionyl chloride leaching, acid demineralization, and hydrochloric acid leaching). In germanium-rich lignite, germanium was directly connected to oxygen and chelated by the phenolic hydroxyl in the ortho- in the form of a five-membered ring. Furthermore, germanium existed in the germanium-endowed structure in the form of a six-coordinated, deformed octahedron, externally encapsulated by interfering substances. Therefore, this study provides a theoretical basis for targeted extraction of germanium from germanium-rich lignite.

锗是一种广泛应用于许多战略领域的重要金属，具有有机亲和性。锗主要存在于褐煤腐殖质中，但其确切的赋存状态尚不清楚。本文采用多种方法对褐煤中锗进行浸出，揭示锗的赋存状态。锗倾向于在特定的赋锗结构中积累，但大多数锗与腐植酸等包裹结构结合并被包裹。它可以通过与腐植酸共萃取（如氨氧化、碱浸）或通过解离赋予锗的结构（如亚硫酰氯浸出、酸脱矿和盐酸浸出）来提取。在富锗褐煤中，锗与氧直接相连，并与邻位酚羟基以五元环的形式螯合。此外，锗以六配位的变形八面体形式存在于赋锗结构中，外部被干扰物质包裹。因此，本研究为富锗褐煤中定向提取锗提供了理论依据。

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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 : 2025-11-01 Epub 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。

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