Journal of The Energy Institute最新文献_第10页

Beyond the peak temperature: An experimental evaluation of conventional vs. effective thermodynamic models for biomass pyrolysis 超越峰值温度：生物质热解的传统与有效热力学模型的实验评估

IF 6.2 2区工程技术 Q2 ENERGY & FUELS

Journal of The Energy Institute

Pub Date : 2025-10-13 DOI: 10.1016/j.joei.2025.102333

Hammed Adeniyi Salami, Javier Eliel Morales-Mendoza, Jorge Luis Domínguez-Arvizu, Felipe Angel Gaxiola-Cebreros, Blanca Cristina Hernández-Majalca, José Luis Bueno-Escobedo, Iyiade Gbolahan Alalade, Gabriela Edith Valenzuela-Castro, Lucero Pérez-Hernández, Alejandro López-Ortiz, Virginia Hidolina Collins-Martínez

Accurate interpretation of thermogravimetric data depends on the thermodynamic model used, yet experimental comparisons of standard methods are limited. This study critically evaluates the conventional (CA) and effective thermodynamic (ETA) approaches for analyzing the pyrolysis of Sotol bagasse (SB), an extractive-rich agro-industrial residue. Both models confirmed that SB pyrolysis is feasible and endothermic; however, they produced substantial differences in entropy (ΔS) and Gibbs free energy (ΔG) due to their theoretical foundations. The CA relies on a single peak temperature (Tp), which fails to represent the multi-stage nature of pyrolysis. In contrast, the ETA uses conversion-dependent temperatures (Tα), capturing reaction progression and biomass heterogeneity more accurately. Comparisons with other biomasses showed that CA consistently underestimates ΔS and overestimates ΔG below Tp, with the trend reversing above Tp, whereas ETA provided consistent and mechanistically meaningful trends. Although both models yielded similar enthalpy (ΔH), the ETA revealed a thermodynamic shift toward increased exothermicity and reduced spontaneity at higher conversions (α > 0.35), likely due to SB's high extractive content (≈23 %) and secondary charring reactions—information missed by CA. Overall, model selection strongly influences thermodynamic interpretation, and the ETA is validated as the superior approach for designing and optimizing pyrolysis of complex, extractive-rich, and non-extractive feedstocks.

热重数据的准确解释取决于所使用的热力学模型，然而标准方法的实验比较是有限的。本研究对传统的（CA）和有效的热力学（ETA）方法进行了批判性评价，以分析甘蔗渣（SB）的热解过程。两种模型均证实SB热解是可行的、吸热的；但是，由于理论基础的不同，它们在熵（ΔS）和吉布斯自由能（ΔG）上产生了很大的差异。CA依赖于单峰温度（Tp），不能代表热解的多阶段性质。相比之下，ETA使用与转化相关的温度（Tα），更准确地捕获反应过程和生物量异质性。与其他生物量的比较表明，CA在Tp以下持续低估ΔS和高估ΔG，在Tp以上趋势逆转，而ETA提供了一致且有机械意义的趋势。尽管两种模型的焓值相似（ΔH），但ETA揭示了在高转化率下放热性增加和自发性降低的热力学转变（α > 0.35），这可能是由于SB的高萃取物含量（≈23%）和二次炭化反应——CA遗漏的信息。总体而言，模型选择强烈影响热力学解释，ETA被证明是设计和优化复杂、富含萃取物的热解的最佳方法。非采掘原料。

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引用次数: 0

Physicochemical properties and carbon dioxide gasification reactivity analysis of lignin and lignite co-pyrolysis char 木质素与褐煤共热解炭的理化性质及二氧化碳气化反应性分析

IF 6.2 2区工程技术 Q2 ENERGY & FUELS

Journal of The Energy Institute

Pub Date : 2025-10-13 DOI: 10.1016/j.joei.2025.102337

Chunfu Yun , Kai Kong , Yanpeng Ban , Huacong Zhou , Jianxiu Hao , Na Li , Keduan Zhi , Yunfei Wang , Quansheng Liu

Co-gasification of biomass with coal enables more efficient utilization of carbon resources and reduces greenhouse gas emissions. In this study, the isothermal CO₂ gasification behavior of lignin/Manglai lignite co-pyrolysis char was investigated at 900–1100 °C using a thermogravimetric analyzer and a fixed-bed reactor. The structural characteristics of co-pyrolysis char were analyzed by N₂ adsorption-desorption, scanning electron microscopy, Raman spectroscopy, X-ray diffraction, Fourier transform infrared spectroscopy, and X-ray fluorescence spectroscopy. The results show that the degree of graphitization of co-pyrolysis char is higher than that of lignin and lignite char. Additionally, the morphology of the internal minerals in the char changes during the gasification process, resulting in a significant reduction in gasification reactivity. The gasification reactivity of lignin/Manglai lignite (LLC) co-pyrolysis char is lower than that of single lignin char, and its maximum CO formation rate and gas accumulation are the lowest at 1100 °C pyrolysis temperature. These findings highlight the influence of pyrolysis temperature on char structure and gasification performance, and provide valuable insights for optimizing the co-gasification process and improving CO₂ utilization efficiency. This study provides new insights into the gasification behavior of lignin–lignite mixtures and offers practical implications for sustainable energy utilization.

生物质与煤共气化可以更有效地利用碳资源，减少温室气体排放。本研究采用热重分析仪和固定床反应器，研究了木质素/芒莱褐煤共热解焦在900 ~ 1100℃的等温CO2气化行为。采用N2吸附-解吸、扫描电镜、拉曼光谱、x射线衍射、傅里叶变换红外光谱和x射线荧光光谱分析共热解炭的结构特征。结果表明，共热解炭的石墨化程度高于木质素和褐煤炭。此外，在气化过程中，炭中内部矿物的形态发生变化，导致气化反应性显著降低。木质素/芒莱褐煤（LLC）共热解炭的气化反应活性低于单一木质素炭，在1100℃热解温度下，其最大CO生成速率和气体富集量最低。这些发现突出了热解温度对炭结构和气化性能的影响，为优化共气化工艺和提高CO2利用效率提供了有价值的见解。该研究为木质素-褐煤混合物的气化行为提供了新的见解，并为可持续能源利用提供了实际意义。

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引用次数: 0

Experimental and chemical kinetic analysis of laminar burning velocity of ammonia/dimethyl ether/air mixture at elevated temperature and pressure using a reduced-updated skeletal reaction model 基于简化骨架反应模型的高温高压下氨/二甲醚/空气混合物层流燃烧速度实验及化学动力学分析

IF 6.2 2区工程技术 Q2 ENERGY & FUELS

Journal of The Energy Institute

Pub Date : 2025-10-13 DOI: 10.1016/j.joei.2025.102334

Anand Shankar Singh , Shawnam , V. Mahendra Reddy , Sudarshan Kumar

Recently, ammonia has garnered significant interest from several organizations as a potential environmentally friendly fuel, primarily due to its superior volumetric energy density and convenient storage, handling, and transportation characteristics. However, the practical application of ammonia still needs to be significantly improved due to its lower laminar burning velocity, narrow flammability limit, and higher NOx production. Ignition enhancer fuels like methane, hydrogen, and Dimethyl ether (DME) can be added to ammonia as ignition enhancers to curb its slower reaction kinetics and improve its flame propagation characteristics. In the present work, the heated diverging channel technique is used for the experimental measurement of laminar burning velocity for NH₃/DME/air premixed flames for premixed temperatures and pressures of 300–700 K and 1–5 atm. Furthermore, a reduced– updated (RU) skeletal reaction model is proposed based on the available literature. The proposed RU model, along with available reaction models, are validated for the above-stated experimental measurement conditions. Also, chemical kinetic analysis is performed considering the RU model to understand the laminar burning velocity reaction kinetics using the sensitivity, flame structure, and rate of production analysis.

最近，氨作为一种潜在的环保燃料引起了一些组织的极大兴趣，主要是因为它具有优越的体积能量密度和方便的储存、处理和运输特性。但氨的层流燃烧速度较低，可燃性极限较窄，NOx产生量较高，在实际应用中仍需显著提高。可以将甲烷、氢和二甲醚（DME）等助燃燃料添加到氨中作为助燃剂，以抑制其较慢的反应动力学并改善其火焰传播特性。本文采用热发散通道技术对NH3/二甲醚/空气预混火焰在300-700 K、1-5 atm预混温度和压力下的层流燃烧速度进行了实验测量。此外，在现有文献的基础上，提出了一个简化更新（RU）骨架反应模型。提出的RU模型以及可用的反应模型在上述实验测量条件下进行了验证。同时，采用RU模型进行化学动力学分析，利用灵敏度、火焰结构和产率分析来了解层流燃烧速度反应动力学。

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引用次数: 0

Optimizing crystallinity of La2O2CO3 to boost reverse water-gas shift reaction performance over Co-based supported catalysts 优化La2O2CO3结晶度，提高co基负载型催化剂的水气倒转反应性能

IF 6.2 2区工程技术 Q2 ENERGY & FUELS

Journal of The Energy Institute

Pub Date : 2025-10-09 DOI: 10.1016/j.joei.2025.102331

Xiao-Yu Zhang , Wen-Lin Li , Zhi-Hao Ma , Sheng Li , Wei-Wei Yan , Li Li , Xing-Shun Cong , Xian-Yong Wei , Zhi-Xin Li

Reverse water-gas shift (RWGS) reaction has become an important strategy to couple application of carbon resources and hydrogen energy. However, Co-based supported catalysts in RWGS reaction consistently experience deactivation under high-temperature operation, predominantly caused by carbon deposition and metal sintering, which present major barriers to the commercial deployment. Here, crystallinity for La₂O₂CO₃ supports were modulated to govern the metal-support interaction and CO₂ adsorption performance on Co-based supported catalysts, thereby optimizing RWGS reaction performance. Despite of poorly crystallized La₂O₂CO₃-1 fostered a stronger interaction with Co species, which detrimentally compromised CO₂ adsorption capacity and inherent anti-coking functionality of La₂O₂CO₃ themselves. In contrast, employing well-crystallized La₂O₂CO₃-2 as the support yielded the Co/La₂O₂CO₃-2 catalyst, exhibiting superior CO₂ adsorption, exceptional resistance to carbon deposition, outstanding activity, high CO selectivity, and remarkable stability—maintaining consistent CO₂ conversion and selectivity for over 100 h at 600 °C. This crystallinity-driven strategy effectively balances the Co-La₂O₂CO₃ interaction, presenting a novel way to boost RWGS reaction performance over Co-based supported catalysts.

逆水气转换（RWGS）反应已成为碳资源与氢能耦合应用的重要策略。然而，在RWGS反应中，co基负载型催化剂在高温操作下经常失活，主要是由碳沉积和金属烧结引起的，这是商业应用的主要障碍。本文通过调节La2O2CO3载体的结晶度来控制金属-载体相互作用和co基负载催化剂对CO2的吸附性能，从而优化RWGS反应性能。尽管La2O2CO3-1结晶较差，但其与Co的相互作用较强，不利于La2O2CO3本身的CO2吸附能力和抗结焦功能。相比之下，采用结晶良好的La2O2CO3-2作为载体制备的Co/La2O2CO3-2催化剂具有优异的CO2吸附性能、优异的抗碳沉积性能、优异的活性、高Co选择性和卓越的稳定性——在600℃下保持100小时以上的CO2转化和选择性。这种结晶驱动策略有效地平衡了Co-La2O2CO3相互作用，为提高co基负载催化剂上RWGS反应性能提供了一种新方法。

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引用次数: 0

Particulate number emissions and particle micro-characteristics from natural gas engines: the role of lubricating oils 天然气发动机的颗粒数排放和颗粒微观特征：润滑油的作用

IF 6.2 2区工程技术 Q2 ENERGY & FUELS

Journal of The Energy Institute

Pub Date : 2025-10-09 DOI: 10.1016/j.joei.2025.102332

Yi Wang , Lina Zhang , Kongzhao Xing , Haozhong Huang , Tiejian Lin , Hui Wang , Xiaoyu Guo

Reducing particulate number (PN) emissions from lubricating oils (L-oil) in natural gas engines is key to meeting the next-stage emission regulations. However, insufficient understanding remains of how the L-oils combustion affects the physicochemical properties of particles in natural gas engines. This study investigated the effects of L-oil composition and viscosity on the emission characteristics of natural gas engines through experiments. TEM-EDX was employed to analyze differences in microstructure and chemical composition between particles generated by different L-oils. The results indicated that, at 1700 r/min and 10 % load, emission performance deteriorated significantly with L-Soil30 (mineral base oil and high-sulfur additives), with PN emissions reaching 2.79 ∗ 10⁷ N/cc. By contrast, the PN emissions of L-oil30 (synthetic base oil) with a similar viscosity grade were only 9.23 % of those of L-Soil30. As L-oil viscosity increased, the emissions of CO, HC and PN all decreased, while the proportion of accumulation mode particles increased. According to TEM-EDX results, a regular spherical ZnO particle was present in soot particles of L-Soil30, which adsorbed carbon particles to form cluster-like particle aggregates. However, the particle morphology of L-oil30 was chain-like. The L-oil50 particles were irregular in morphology, appeared as flocculent aggregates, and had a larger primary particle diameter. Additionally, EDX spectrum showed that as L-oil viscosity increased, the C content in particles increased while O content decreased. Meanwhile, particles from synthetic oils had a higher Si content. This study can provide guidance for reducing PN emissions from natural gas engines.

减少天然气发动机润滑油（L-oil）的颗粒数（PN）排放是满足下一阶段排放法规的关键。然而，对于l -油燃烧如何影响天然气发动机中颗粒的物理化学性质，人们的认识仍然不够充分。本研究通过实验研究了l -油成分和粘度对天然气发动机排放特性的影响。采用TEM-EDX分析了不同l -油生成的颗粒之间微观结构和化学成分的差异。结果表明，在1700 r/min和10%负荷下，L-Soil30（矿物基础油和高硫添加剂）的排放性能显著恶化，PN排放量达到2.79∗107 N/cc。相比之下，相似粘度等级的L-oil30（合成基础油）的PN排放量仅为L-Soil30的9.23%。随着l -油粘度的增加，CO、HC和PN的排放量均降低，堆积型颗粒的比例增加。TEM-EDX结果表明，L-Soil30的烟尘颗粒中存在规则的球形ZnO颗粒，其吸附碳颗粒形成团簇状颗粒聚集体。而l -oil - 30的颗粒形貌呈链状。l -oil - 50颗粒形态不规则，呈絮状聚集体，初生颗粒直径较大。此外，EDX谱显示，随着l -油粘度的增加，颗粒中C含量增加，O含量降低。同时，合成油颗粒的Si含量较高。该研究可为减少天然气发动机PN排放提供指导。

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引用次数: 0

Investigation of the effect of hydrogen addition on the combustion and emissions performance of high compression ratio liquid methane gas (LMG) Engine 加氢对高压缩比液态甲烷（LMG）发动机燃烧和排放性能影响的研究

IF 6.2 2区工程技术 Q2 ENERGY & FUELS

Journal of The Energy Institute

Pub Date : 2025-10-04 DOI: 10.1016/j.joei.2025.102319

Kaimin Liu , Penghong Liao , Xiaopeng Feng , Jintao Zhou , Zhi Jiang , Hui Peng , Jiaji Jiang

To investigate the effect of hydrogen addition on the combustion and emission performance of a high-compression-ratio liquid methane gas (LMG) engine under continuously varying loads, this study considered an inline 6-cylinder 4-valve single-point injection spark ignition liquefied natural gas (LNG) engine as an object to comprehensively discuss the combustion process, engine performance, and emissions characteristics under different loads and speeds at different hydrogen energy share (HES) by means of coupled experiments and simulations. The results show, with an increase in hydrogen concentration, the brake-specific fuel consumption (BSFC) of the LMG engine showed a decreasing trend, the peak cylinder pressureincreased significantly, the maximum pressure rise rate also increased significantly, and the location of 50 % mass fraction burned (MFB) was advanced significantly. In terms of emissions, with the gradual increase in the hydrogen energy ratio, the NO_X emissions show an increasing trend and HC emissions showed a decreasing trend. With the increase in HES the location of peak combustion temperature (LPCT) advanced approximately 43.08 %. However, although the addition of hydrogen significantly increased the combustion rate of the LMG, the knocking became more intense as a result, and the tendency increased sharply when the HES increased from 12 % to 20 %.

为研究连续变载荷下加氢对高压缩比液态甲烷（LMG）发动机燃烧与排放性能的影响，本研究以直列6缸4气门单点喷射火花点火液化天然气（LNG）发动机为研究对象，对燃烧过程、发动机性能、通过耦合实验和模拟，研究了不同负荷和速度下不同氢能量份额（HES）下的排放特性。结果表明：随着氢气浓度的增加，LMG发动机的制动比油耗（BSFC）呈下降趋势，汽缸峰值压力显著升高，最大压力上升速率也显著提高，50%质量分数燃烧（MFB）位置显著提前；在排放方面，随着氢能比的逐渐提高，NOX排放量呈增加趋势，HC排放量呈下降趋势。随着HES的增加，燃烧温度峰值位置（LPCT）提高了约43.08%。然而，氢气的加入虽然显著提高了轻燃发动机的燃烧速率，但却使爆震变得更加强烈，并且当氢气含量从12%增加到20%时，这种趋势急剧增加。

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引用次数: 0

In-depth insight into cyclic methyl-siloxanes in waste tires pyrolysis oil (WTPO), high silicon content gasoline, and high silicon content diesel 深入了解废轮胎热解油（WTPO）、高硅汽油、高硅柴油中的环甲基硅氧烷

IF 6.2 2区工程技术 Q2 ENERGY & FUELS

Journal of The Energy Institute

Pub Date : 2025-10-03 DOI: 10.1016/j.joei.2025.102323

Runtian Xia , Mingxing Liu , Naixin Wang , Ke Wang , Junqiang Li , Yanxuan Fan , Zhaolin Fu , Jie Zhao , Qundan Zhang , Wei Wang , Yanbo Hou , Zhiping Tao

Waste tire pyrolysis oil (WTPO) serves as a valuable feedstock for sustainable fuels and high-value-added chemicals. However, the silicon content and siloxane content of WTPO have not been observed in detail, and the similarity of siloxane morphology between WTPO and commercial gasoline and diesel has not been discussed in depth. To address this gap, our research group collected 24 WTPO samples from China, along with 3 commercial gasoline samples and 4 commercial diesel samples exhibiting abnormal silicon content, between 2023 and 2025. The silicon content and siloxane content of the samples were determined by inductively coupled plasma optical emission spectrometer (ICP-OES) and gas chromatography-quadrupole mass spectrometry (GC-MS), respectively. The results indicate that the silicon content ranges of WTPO are <1 ppm to 3674 ppm. Analysis of siloxane morphology revealed that cyclic permethylsiloxanes (Dn, where n denotes the number of Si atoms) are widely present in WTPO. In the detected WTPO samples, the maximum contents of D4, D3, and D5 reach 2251 ppm, 923 ppm, and 475 ppm, respectively. Furthermore, the type and content distribution of cyclic methyl-siloxanes in high silicon content WTPO, high silicon content gasoline, and high silicon content diesel samples demonstrate a strong similarity. This study emphasizes that the potential threats posed by silicon-containing molecules in WTPO to the environment, organisms, and industrial equipment should be evaluated in advance of large-scale commercialization.

废轮胎热解油（WTPO）是可持续燃料和高附加值化学品的重要原料。然而，对WTPO的硅含量和硅氧烷含量没有进行详细的观察，也没有对WTPO与商品汽油和柴油之间硅氧烷形态的相似性进行深入的讨论。为了解决这一空白，我们的研究小组在2023年至2025年间从中国收集了24个WTPO样品，以及3个硅含量异常的商业汽油样品和4个商业柴油样品。采用电感耦合等离子体发射光谱仪（ICP-OES）和气相色谱-四极杆质谱联用仪（GC-MS）测定样品中的硅含量和硅氧烷含量。结果表明，WTPO的硅含量范围为1 ~ 3674 ppm。硅氧烷的形态分析表明，环过甲基硅氧烷（Dn，其中n表示Si原子数）广泛存在于WTPO中。在检测到的WTPO样品中，D4、D3和D5的最高含量分别达到2251 ppm、923 ppm和475 ppm。此外，环甲基硅氧烷在高硅WTPO、高硅汽油和高硅柴油样品中的类型和含量分布具有很强的相似性。本研究强调，在大规模商业化之前，应评估WTPO中含硅分子对环境、生物和工业设备的潜在威胁。

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引用次数: 0

Interpretable machine learning models for forecasting elemental composition of solid biomass fuels from proximate analyses in energy processes 从能源过程的近似分析中预测固体生物质燃料元素组成的可解释机器学习模型

IF 6.2 2区工程技术 Q2 ENERGY & FUELS

Journal of The Energy Institute

Pub Date : 2025-10-03 DOI: 10.1016/j.joei.2025.102322

Paulino José García–Nieto , Esperanza García–Gonzalo , José Pablo Paredes–Sánchez , Luis Alfonso Menéndez–García

Biomass is a renewable and sustainable source of green energy. A key factor in evaluating its energy potential is its elemental composition—primarily carbon (C), hydrogen (H), and oxygen (O). This information is vital for accurate material balance calculations, efficient design and operation of combustion systems, and determining oxidant requirements for combustion and gasification. It also enables prediction of gas composition from these processes. While ultimate analysis provides this elemental data (i.e., carbon (C), hydrogen (H), oxygen (O), nitrogen (N), and sulphur (S)), it is expensive and time-consuming. In contrast, proximate analysis is simpler, offering data on moisture content (MC), volatile matter (VM), ash content (Ash), and fixed carbon (FC). Predicting elemental composition from proximate analysis requires robust models. This study develops nonlinear predictive models using two machine learning (ML) techniques: multilayer perceptron (MLP) and a hybrid approach combining the Harmonic Search Optimization Algorithm (HSOA) with Multivariate Adaptive Regression Splines (MARS). Based on a dataset of 203 biomass samples, six ML models were built to estimate C, H, and O content. Results show these ML models outperform traditional linear models in accuracy and generalizability. Specifically, the optimal HS/MARS models achieved coefficients of determination of 0.8339, 0.8676, and 0.8714 for C, H, and O, respectively. The HS/MARS models also outperformed the MLP models, demonstrating their superior predictive capability.

生物质是一种可再生和可持续的绿色能源。评估其能量潜力的一个关键因素是其元素组成——主要是碳(C)、氢(H)和氧(O)。这些信息对于精确的物质平衡计算、燃烧系统的有效设计和操作以及确定燃烧和气化的氧化剂要求至关重要。它还可以预测这些过程中的气体成分。虽然最终分析提供了这些元素数据(即碳(C)、氢(H)、氧(O)、氮（N)和硫(S)），但它既昂贵又耗时。相比之下，近似分析更简单，提供有关水分含量（MC），挥发物（VM），灰分含量（ash）和固定碳（FC）的数据。从近似分析预测元素组成需要稳健的模型。本研究使用两种机器学习（ML）技术开发非线性预测模型：多层感知器（MLP）和将谐波搜索优化算法（HSOA）与多元自适应回归样条（MARS）相结合的混合方法。基于203个生物质样品的数据集，建立了6个ML模型来估计C、H和O的含量。结果表明，这些机器学习模型在准确性和泛化性方面优于传统的线性模型。其中，HS/MARS模型对碳、氢和氧的决定系数分别为0.8339、0.8676和0.8714。HS/MARS模型也优于MLP模型，证明了其优越的预测能力。

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引用次数: 0

Co-hydrothermal liquefaction of spirulina + corn straw: Reaction mechanism, pathways and kinetic studies 螺旋藻+玉米秸秆共水热液化：反应机理、途径及动力学研究

IF 6.2 2区工程技术 Q2 ENERGY & FUELS

Journal of The Energy Institute

Pub Date : 2025-10-02 DOI: 10.1016/j.joei.2025.102330

Yi Wang , Xinyi Li , Yuqi Wang , Donghai Xu , Lili Qian , Pavel A. Strizhak , Vadim A. Yakovlev , Le Wu , Lan Zheng , Xin Ding

In this work, a global kinetic pathway network and quantitative reaction kinetic model have been proposed and applied to accurately present the product changes and migratory behavior in co-hydrothermal liquefaction (co-HTL) of spirulina + corn straw. The reaction kinetic model involves the decomposition of feedstock to produce water-insoluble biocrude, as well as the mutual transformation processes between several different products. Moreover, the proposed model can accurately describe the temporal variation trends of different product yields. By analyzing reaction rate constant k_i and activation energy E_a, the rate-controlling steps for the non-catalytic and catalytic systems are determined as the pathway of water-insoluble biocrude to solids and that of aqueous-phase products converting to water-soluble biocrude, respectively. Finally, the optimal kinetic parameters obtained from model fitting outcomes were used to accurately predict the distribution and variation of different product yields over a wider range of temperature and time.

本文建立了螺旋藻+玉米秸秆共水热液化（co-HTL）过程的全球动力学通路网络和定量反应动力学模型，并应用该模型准确表征了螺旋藻+玉米秸秆共水热液化（co-HTL）过程中的产物变化和迁移行为。反应动力学模型包括原料分解生成不溶于水的生物原油，以及几种不同产物之间的相互转化过程。该模型能较准确地描述不同产品产量的时间变化趋势。通过对反应速率常数ki和活化能Ea的分析，确定了非催化体系和催化体系中水不溶性生物原油转化为固体和水相产物转化为水溶性生物原油的速率控制步骤。最后，利用模型拟合结果得到的最优动力学参数，准确预测了不同产物产率在较宽温度和时间范围内的分布和变化。

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引用次数: 0

Synthesis of Ni-Ce loaded on CaO-Ca9Al6O18/Ca12Al14O33 sorbent-catalyst bifunctional materials for enhancing hydrogen production from biomass gasification 负载Ni-Ce的CaO-Ca9Al6O18/Ca12Al14O33吸附-催化剂双功能材料的合成

IF 6.2 2区工程技术 Q2 ENERGY & FUELS

Journal of The Energy Institute

Pub Date : 2025-10-01 DOI: 10.1016/j.joei.2025.102328

Chengjun Wei, Xi Zeng, Xi Wang, Zheng Jian, Guangjing Hao, Chao Xiao, Dehong Gong

Ni–Ce/CaO–Ca₁₂Al₁₄O₃₃ (Ni–Ce/C₁₂A₇) and Ni–Ce/CaO–Ca₉Al₆O₁₈ (Ni–Ce/C₉A₃) catalysts were synthesized from different calcium–aluminum precursors and evaluated for H₂ production via catalytic reforming of pine sawdust. At a Ni/Ce molar ratio of 1.5, Ni–Ce/C₉A₃(AN–CF)—prepared using Al(NO₃)₃·9H₂O (AN) and Ca(CHO₂)₂ (CF)—exhibited the best performance, achieving a peak H₂ concentration of 90.97 vol% and an H₂ yield of 294.31 mL/g, compared with 85.51 vol% and 228.19 mL/g for Ni–Ce/C₁₂A₇(AN–CA). The superior performance was attributed to the uniform, mesh-like pore network of Ni–Ce/C₉A₃(AN–CF) and to the stability of its average pore diameter during catalytic process. In cyclic tests, Ni–Ce/C₉A₃(AN–CF) maintained stable performance for the first four cycles but underwent rapid deactivation from cycle 5 and was nearly deactivated by cycle 10. Ni–Ce/C₁₂A₇(AN–CA) exhibited a more gradual performance decline. The observed deactivation was primarily ascribed to the phase transformation of Ca₉Al₆O₁₈ to Ca₁₂Al₁₄O₃₃ under H₂O–CO₂ atmospheres, which caused pore collapse and sintering of Ni–Ce active species. Although Ca₉Al₆O₁₈ exhibited greater resistance to CaO-particle sintering than Ca₁₂Al₁₄O₃₃, its thermodynamic instability under reaction conditions limited long-term cyclic performance.

以不同的钙铝前驱体为原料合成了Ni-Ce / CaO-Ca12Al14O33 （Ni-Ce /C12A7）和Ni-Ce / CaO-Ca9Al6O18 （Ni-Ce /C9A3）催化剂，并对松木木屑催化重整制氢性能进行了评价。在Ni/Ce摩尔比为1.5时，用Al(NO3)3·9H2O （AN）和Ca(CHO2)2 （CF）制备的Ni - Ce/C9A3（AN - CF）表现最好，H2峰浓度为90.97 vol%， H2产率为294.31 mL/g，而Ni - Ce/C12A7（AN - Ca）的H2峰浓度为85.51 vol%， H2产率为228.19 mL/g。优异的性能归因于Ni-Ce /C9A3（AN-CF）均匀的网状孔隙网络及其在催化过程中平均孔径的稳定性。在循环试验中，Ni-Ce /C9A3（AN-CF）在前四个循环中保持稳定的性能，但从第5个循环开始迅速失活，到第10个循环时几乎失活。Ni-Ce /C12A7（AN-CA）的性能下降更为缓慢。失活的主要原因是在H2O-CO2气氛下，Ca9Al6O18向Ca12Al14O33相变，导致孔隙坍塌和Ni-Ce活性物质烧结。尽管Ca9Al6O18表现出比Ca12Al14O33更强的抗cao颗粒烧结性能，但其在反应条件下的热力学不稳定性限制了其长期循环性能。

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