Chemical Engineering Science最新文献_第2页

An innovative dual-phase platform for biohydrogen production: Chlorella-based nutrient removal and E. aerogenes fermentation with PEMFC power generation evaluation 一种创新的双相生物制氢平台：基于小球藻的营养物去除和产气大肠杆菌发酵与PEMFC发电的评估

IF 4.3 2区工程技术 Q2 ENGINEERING, CHEMICAL

Chemical Engineering Science

Pub Date : 2026-05-15 Epub Date: 2026-02-03 DOI: 10.1016/j.ces.2026.123491

Ashwin Jacob , Abed Alaswad , B. Ashok , V. Praveen , L. Jino

This study pioneers the utilization of bakery wastewater (BW) as a cost-effective and sustainable growth medium for Chlorella pyrenoidosa, integrating bioremediation and renewable energy generation through biohydrogen production. Furthermore, the quality of the produced hydrogen is analysed in a proton exchange membrane fuel cell (PEMFC) stack in its raw and purified form. By adopting a dual-phase cultivation approach with native bacteria and C. pyrenoidosa, the process achieved complete BW treatment without dilution or sterilization, delivering nutrient removal efficiencies of 79% for chemical oxygen demand (COD), 94% for nitrogen (TNi), and 80.4% for phosphorus (TPo). Remarkably, the biomass demonstrated a high carbohydrate content (49%) with a productivity rate of 305.8 mg/L/d, underscoring its potential for biohydrogen generation. Subsequent dark fermentation using E. aerogenes and a probe-based pH stabilization protocol at a vol. of 363 mL of hydrogen, achieving a production rate of 59.72 mL/L/h and a yield of 1.5 mol/mol reducing sugars, outperforming established benchmarks. The hydrogen generated was utilized in a PEMFC to assess performance and durability using raw BW-derived hydrogen (BW H₂) and purified BW-derived hydrogen (PBW H₂). After 200 cycles, the PEMFC exhibited a performance reduction of 1.3 A/cm² with PBW H₂, while significant degradation was observed with BW H₂ (1.15 A/cm² to 0.3 A/cm²), primarily due to impurities impacting the membrane and electrode’s active area. This study’s novelty lies in developing an innovative dual-phase cultivation strategy, integrating indigenous wastewater bacteria to enhance nutrient removal and biomass production, offering a novel approach for treating bakery wastewater.

本研究将烘焙废水（BW）作为小球藻（Chlorella pyrenoidosa）具有成本效益和可持续性的生长培养基，通过生物制氢将生物修复和可再生能源生产结合起来。此外，在质子交换膜燃料电池（PEMFC）堆中以其原始和纯化形式分析了所产生的氢的质量。该工艺采用原生细菌和pyrenoidosa双相培养方法，无需稀释或灭菌即可完全处理生物体重，化学需氧量（COD）去除率为79%，氮（TNi）去除率为94%，磷（TPo）去除率为80.4%。值得注意的是，生物质碳水化合物含量高（49%），生产率为305.8 mg/L/d，强调了其生物制氢的潜力。随后，在363 mL氢气体积下，利用产气大肠杆菌和基于探针的pH稳定方案进行暗发酵，产率为59.72 mL/L/h，还原糖产量为1.5 mol/mol，优于既定基准。产生的氢气被用于PEMFC中，使用原BW衍生氢（BW H2）和纯化BW衍生氢（PBW H2）来评估性能和耐久性。经过200次循环后，使用PBW H2的PEMFC性能下降了1.3 a /cm2，而使用BW H2的PEMFC性能明显下降（1.15 a /cm2至0.3 a /cm2），这主要是由于杂质影响了膜和电极的活性区域。本研究的新颖之处在于开发了一种创新的双相培养策略，整合本地废水细菌来提高养分去除和生物质生产，为处理烘焙废水提供了一种新的途径。

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引用次数: 0

On the H-atom abstractions from small fatty acid methyl esters by nitric oxide: An ab initio theoretical kinetic study 一氧化氮对小脂肪酸甲酯中h原子的萃取：从头算理论动力学研究

IF 4.3 2区工程技术 Q2 ENGINEERING, CHEMICAL

Chemical Engineering Science

Pub Date : 2026-05-15 Epub Date: 2026-02-04 DOI: 10.1016/j.ces.2026.123528

Ruirui Kong , Zhiheng Zhu , Ning La , Fashe Li , Hua Wang , Yaozong Duan

Small fatty acid methyl esters were selected as simplified surrogate fuels for biodiesel, and high-level quantum chemical calculations were conducted to study the H-abstraction reactions with nitric oxide (NO). The effects of carbon chain length and C=C bond were systematically investigated. The geometry optimization, frequency analysis and 1-dimensional hindered scan of stationary points were performed at the M06-2X/6–311++G(d,p) level of theory, and the single point energies were calculated using CCSD(T)/cc-pVXZ (X = D, T) and MP2/cc-pVYZ (Y = D, T and Q), which were extrapolated to the complete basis set. Rate coefficients were computed in the temperature range of 298 ∼ 2000 K using conventional transition state theory (TST). For the saturated fatty acid methyl esters, the barrier heights follow the order of primary carbon > secondary carbon > tertiary carbon, and the rate coefficients generally increase as the carbon chain length increases. For the unsaturated fatty acid methyl esters, H-abstraction reaction from the allylic carbon site shows the lowest barrier heights. Compared to the saturated counterparts, the barrier heights for abstracting from α_p carbon sites are almost comparable (MPa) or much smaller (n-MB), and the rate coefficients from α_p carbon site of M2B are consistently higher than those of n-MB. This is deduced the presence of the C=C bond significantly affects the barrier height of the H-abstraction reactions, and thereby influences the relative reactivity of carbon sites. This study helps to gain a deeper understanding of the interaction mechanism between fatty acid methyl esters and NO, and provides theoretical guidance for combustion kinetics models related to fatty acid methyl esters.

选择小脂肪酸甲酯作为生物柴油的简化替代燃料，并进行高阶量子化学计算，研究其与一氧化氮的抽氢反应。系统地考察了碳链长度和C=C键的影响。在M06-2X/ 6-311 ++G（d,p）理论水平上进行了平稳点的几何优化、频率分析和一维阻碍扫描，并利用CCSD(T)/cc- pvvxz （X = d， T）和MP2/cc-pVYZ （Y = d， T和Q）计算了单点能量，并将其外推到完整基集。利用传统的过渡态理论（TST）计算了298 ~ 2000 K温度范围内的速率系数。饱和脂肪酸甲酯的势垒高度依次为伯碳 >； 仲碳 >； 叔碳，速率系数一般随碳链长度的增加而增大。对于不饱和脂肪酸甲酯，烯丙基碳位吸氢反应的势垒高度最低。与饱和产物相比，M2B的αp位萃取势垒高度几乎相当（MPa）或更小（MB）， αp位萃取速率系数始终高于MB。由此推断，C=C双键的存在显著影响吸氢反应的势垒高度，从而影响碳位的相对反应活性。本研究有助于更深入地了解脂肪酸甲酯与一氧化氮的相互作用机理，并为脂肪酸甲酯相关燃烧动力学模型的建立提供理论指导。

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引用次数: 0

Role of non-newtonian rheology on gas-liquid mass transfer and bubble dynamics in T-junction microchannels 非牛顿流变性对t结微通道气液传质和气泡动力学的影响

IF 4.3 2区工程技术 Q2 ENGINEERING, CHEMICAL

Chemical Engineering Science

Pub Date : 2026-05-15 Epub Date: 2026-02-06 DOI: 10.1016/j.ces.2026.123525

Xingrui Zhou, Lian Duan, Jingru Sun, Dongjie Liu, Wenjun Yuan, Fei Chen

Although gas–liquid mass transfer in microchannels has attracted increasing research interest, a comprehensive understanding of how rheological properties influence mass transfer is still lacking. In this study, three-dimensional numerical simulations are performed to investigate oxygen absorption into shear-thinning fluids within a T-junction microchannel. The multiphase mass transfer model employs the Volume-of-Fluid method coupled with a Compressive Continuous Species Transfer formulation, and the rheology behavior is described by the Cross model. The results show that rheological parameters significantly govern various bubble morphologies and hydrodynamics. Specifically, increasing the zero-shear viscosity promotes earlier breakup, whereas increasing the time constant delays breakup. The volumetric mass transfer coefficient k_La is modulated by a factor of 3 across the investigated range of rheological parameters. An enhancement of mass transfer is revealed under higher time constant. This is attributed to the intensified interfacial renewal during the bubble formation stage, which compensates for the reduced transport efficiency in the downstream region caused by longer liquid segments and lower bubble velocities. Furthermore, the contribution of mass transfer flux from the bubble formation region decreases with increasing η₀ and increases with increasing λ, thereby leading to the dominance of mass transfer in the formation region over a relatively short channel length. Finally, a dimensionless predictive model for k_La with a deviation within 20% is established, which captures the effects of flow inertia and rheological properties. These findings provide theoretical guidance for the design and optimization of non-Newtonian microfluidic systems.

尽管微通道中的气液传质引起了越来越多的研究兴趣，但对流变特性如何影响传质的全面理解仍然缺乏。在这项研究中，进行了三维数值模拟，以研究氧气在t结微通道内剪切变薄流体中的吸收。多相传质模型采用流体体积法与压缩连续物质传递公式相结合，流变特性由Cross模型描述。结果表明，流变参数对各种气泡形态和流体力学具有重要的控制作用。具体来说，增加零剪切黏度有利于提前破裂，而增加时间常数则会延迟破裂。在研究的流变参数范围内，体积传质系数kLa被调节为3倍。在较高的时间常数下，传质增强。这是由于气泡形成阶段界面更新加剧，弥补了由于较长的液段和较低的气泡速度导致的下游区域输运效率降低。此外，气泡形成区传质通量的贡献随η0的增大而减小，随λ的增大而增大，从而导致在相对较短的通道长度上，传质在气泡形成区占主导地位。最后，建立了偏差在20%以内的kLa无量纲预测模型，该模型考虑了流动惯性和流变特性的影响。这些发现为非牛顿微流控系统的设计和优化提供了理论指导。

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引用次数: 0

Orthogonal curvilinear coordinates-based high gravity flow-enhanced mass transfer 基于正交曲线坐标的高重力流强化传质

IF 4.3 2区工程技术 Q2 ENGINEERING, CHEMICAL

Chemical Engineering Science

Pub Date : 2026-05-15 Epub Date: 2026-02-04 DOI: 10.1016/j.ces.2026.123517

Yuedi Guo , Menghan Wang , Zhi Qian

High Gravity (HiGee) technology achieves significant improvement in gas–liquid mass transfer efficiency. Conventionally, HiGee’s high mass transfer efficiency is often attributed to increased interfacial area, without considering the critical role of droplet internal flow, resulting in insufficient exploration of the mass transfer mechanisms in distinct zones. Here, we developed a circulation-oscillation coupled flow field model within droplets to address this gap. By introducing an orthogonal curvilinear coordinate system adapted to the flow field structure, we computed the eddy diffusivity at the boundary (

D_{eff} \approx 3.9 \times 10^{- 4} R U_{\infty}

), which reaches up to an order of magnitude of 10² relative to the molecular diffusivity. The average mass transfer coefficient (

\bar{k} = \sqrt{{\bar{D}}_{eff} S}

) in the end-effect zone is approximately three times higher than that in the bulk packing zone, demonstrating the intrinsic differences in mass transfer dynamics between the two zones. Experimental results show that the end-effect zone contributes approximately 50% to the total mass transfer, with model accuracy for the volumetric mass transfer coefficient exceeding 85% in this zone.

高重力技术显著提高了气液传质效率。传统上，HiGee的高传质效率往往归因于界面面积的增加，而没有考虑液滴内部流动的关键作用，导致对不同区域传质机制的探索不足。在这里，我们开发了一个循环-振荡耦合流场模型来解决这一差距。通过引入与流场结构相适应的正交曲线坐标系，计算出边界处的涡流扩散系数（Deff≈3.9×10-4RU∞Deff≈3.9×10-4RU∞），相对于分子扩散系数可达102数量级。端效应区平均传质系数（k¯=D¯effSk¯=D¯effS）约为散填料区平均传质系数的3倍，显示了两区传质动力学的内在差异。实验结果表明，端效应区对总传质的贡献约为50%，该区域体积传质系数的模型精度超过85%。

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引用次数: 0

Simulation and experimental study on the flow field, temperature distribution, and dynamic accumulation behavior of bottom dross in a hot-dip galvanizing bath 热镀锌槽底渣流场、温度分布及动态积累行为的模拟与实验研究

IF 4.3 2区工程技术 Q2 ENGINEERING, CHEMICAL

Chemical Engineering Science

Pub Date : 2026-05-15 Epub Date: 2026-02-03 DOI: 10.1016/j.ces.2026.123514

Hongzhu Fei , Nannan Zhao

In the continuous hot-dip galvanization process, zinc dross defects are a key factor affecting the surface quality of galvanized steel sheets, and their formation is related to the operating parameters of the galvanizing bath. In this study, industrial-scale CFD single-phase flow numerical simulations and physical simulation experiments are employed to investigate the effects of steel strip width and speed on the flow field characteristics, temperature distribution of molten zinc, and dynamic accumulation behavior of bottom dross. The results show that the first impact flow drivers the high-temperature molten zinc ejected from the front inductor downward toward the bottom of the galvanizing pot, while the second impact flow transports the low-temperature molten zinc, generated during ingot melting along the pot bottom toward the front wall. As the width of the steel strip decreases, the intensity of the first impact flow weakens, while that of the second impact flow strengthens. Consequently, the low-temperature zones in the molten zinc expand, potentially promoting increased dross formation. Although the steel strip speed does not significantly alter the overall flow field characteristics of the molten zinc, it substantially reduces the amount of suspended dross. Furthermore, the associated reduction in the heat exchange rate lowers the temperature of the molten zinc near the bottom of the zinc pot.

在连续热镀锌过程中，锌渣缺陷是影响镀锌钢板表面质量的关键因素，其形成与镀锌槽的操作参数有关。本文采用工业级CFD单相流动数值模拟和物理模拟实验，研究了钢带宽度和速度对流场特性、锌液温度分布和底部渣滓动态堆积行为的影响。结果表明：第一次冲击流驱动从前端电感器喷出的高温锌液向下流向镀锌锅底部，而第二次冲击流则将铸锭熔化过程中产生的低温锌液沿锅底向前壁输送。随着钢带宽度的减小，第一次冲击流强度减弱，第二次冲击流强度增强。因此，熔融锌中的低温区域扩大，潜在地促进了增加的渣滓形成。虽然钢带速度对锌液的整体流场特性没有明显的改变，但却大大减少了悬浮渣滓的数量。此外，热交换率的降低降低了锌罐底部附近的锌液温度。

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引用次数: 0

Experimental investigation on CO2 hydrate formation and growth in a liquid CO2 droplet system for hydrate-based CO2 sequestration 液滴固碳系统中CO2水合物形成与生长的实验研究

IF 4.3 2区工程技术 Q2 ENGINEERING, CHEMICAL

Chemical Engineering Science

Pub Date : 2026-05-15 Epub Date: 2026-02-06 DOI: 10.1016/j.ces.2026.123550

Xingxun Li , Longyan Gao , Shuang Liang , Xuesong Li , Guangjin Chen , Changyu Sun

The hydrate-based CO₂ sequestration has been considered as an effective approach for the long-term carbon storage. When liquid CO₂ is injected into the seabed, it could be sheared into CO₂ droplets. However, existed studies on the CO₂ hydrate formation and growth in the liquid CO₂ droplet system have been lacking. This study focuses on the investigations of morphological evolution processes of the CO₂ hydrate formation and growth kinetics in the liquid CO₂ droplet system. The effects of temperature, pressure, CO₂ saturation and addition of SDS in the surrounding water phase on the evolution of liquid CO₂ hydrate growth process were investigated. The morphological results indicate three liquid CO₂ hydrate growth stages for a single liquid CO₂ droplet located on a platform, namely, the lateral growth of hydrate film on the surface of liquid CO₂ droplet, the growth of hydrate film at the contact edge between the CO₂ droplet and platform and the vertical fibrous hydrate growth in the form of columnar pattern. The higher CO₂ saturation in the surrounding water, higher pressure and lower temperature can contribute to the faster lateral growth kinetics and smoother hydrate film surface. It was confirmed that the formed hydrates cannot exist stably, gradually dissolving into the surrounding water when the driving force for hydrate formation was low. The addition of SDS in the surrounding water could alter the shape of hydrate-coated CO₂ droplet and remarkably promoted the formation of CO₂ hydrates, resulting in the significant vertical fiber-like hydrate growth phenomena.

基于水合物的CO2固存被认为是一种有效的长期碳储存方法。当液态二氧化碳被注入海床时，它可能被剪切成二氧化碳液滴。然而，对液滴体系中CO2水合物的形成和生长的研究还比较缺乏。本研究重点研究了液态CO2液滴体系中CO2水合物形成的形态演化过程和生长动力学。考察了温度、压力、CO2饱和度以及周围水相中加入SDS对液态CO2水合物生长过程演化的影响。形态学结果表明，单个液滴在平台上的液滴水合物生长有三个阶段，即液滴表面水合物膜的横向生长阶段、液滴与平台接触边缘水合物膜的横向生长阶段和垂直纤维状水合物柱状生长阶段。水体中CO2饱和度越高，压力越高，温度越低，水合物膜的横向生长动力学越快，表面越光滑。证实了形成的水合物不能稳定存在，在水合物形成驱动力较低时逐渐溶解到周围水体中。在周围水中加入SDS可以改变水合物包覆CO2液滴的形状，显著促进CO2水合物的形成，形成显著的垂直纤维状水合物生长现象。

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引用次数: 0

Ammonium salt-mediated antisolvent separation of valuable benzene pentacarboxylic and hexacarboxylic acids from the oxidative depolymerization product mixture of lignite 铵盐介导反溶剂分离褐煤氧化解聚产物混合物中有价苯五羧酸和六羧酸

IF 4.3 2区工程技术 Q2 ENGINEERING, CHEMICAL

Chemical Engineering Science

Pub Date : 2026-05-15 Epub Date: 2026-02-07 DOI: 10.1016/j.ces.2026.123556

Minjie Zhang , Qiufeng Wang , Jianxiu Hao , Na Li , Yanpeng Ban , Keduan Zhi , Huacong Zhou , Quansheng Liu

Oxidative depolymerization of lignite into valuable chemicals such as benzene polycarboxylic acids (BPCAs) is a potential pathway for the high-value and non-energy utilization of lignite. Up to now, the selective separation of BPCAs from the complex depolymerization product mixtures remains a huge challenge and impedes the development of this route. BPA and BHA are key platform molecules for constructing high performance and functional materials. In this work, based on the differences in physical and chemical properties of BPCAs, ammonium salt-mediated antisolvent separation of BPCAs from the depolymerization products mixture of lignite was developed. The effects of different separation parameters on the separation efficiency were systematically studied. The results showed that the route could selectively separate benzene hexacarboxylic acid (BHA) and benzene pentacarboxylic acid (BPA) from both the simulated solution and the real lignite depolymerization products. For the real system, the separation yields of BHA and BPA were 76.0 % and 90.0 %, respectively. BHA and BPA accounted for 93.0 % among all BPCAs in the separated solution, indicating an enhanced purity compared to the initial depolymerized product mixture. The antisolvent methanol had high selectivity for BHA and BPA, and the separation selectivity could be tuned by optimizing the ammonia dosage, antisolvent methanol dosage, and the pH of the mother solution. As far as we know, this is the first report fulfilling the selective separation of the valuable BHA and BPA from the real complex depolymerized product mixture of lignite. This work contributes new separation route to promote the depolymerization utilization of lignite.

褐煤氧化解聚生成苯多羧酸（BPCAs）等有价值的化学物质是褐煤高价值和非能源利用的潜在途径。到目前为止，从复杂的解聚产物混合物中选择分离双聚物仍然是一个巨大的挑战，阻碍了这一途径的发展。BPA和BHA是构建高性能功能材料的关键平台分子。本研究基于褐煤解聚产物混合物中BPCAs的物理和化学性质的差异，研究了铵盐对BPCAs的反溶剂分离。系统研究了不同分离参数对分离效率的影响。结果表明，该方法可以从模拟溶液和实际褐煤解聚产物中选择性分离出六羧酸苯（BHA）和五羧酸苯（BPA）。在实际体系中，BHA和BPA的分离率分别为76.0 %和90.0 %。分离后的溶液中BHA和BPA占所有BPCAs的93.0 %，与初始解聚产物混合物相比，纯度有所提高。抗溶剂甲醇对BHA和BPA具有较高的选择性，可通过优化氨用量、抗溶剂甲醇用量和母液pH来调节分离选择性。据我们所知，这是第一个从真正复杂的褐煤解聚产物混合物中实现有价值的BHA和BPA选择性分离的报道。本研究为促进褐煤解聚利用提供了新的分离途径。

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引用次数: 0

Dual-network microgels system with thermal crosslinking behavior for high-temperature steam channeling control in heavy oil reservoirs 具有热交联特性的双网络微凝胶体系用于稠油油藏高温蒸汽窜流控制

IF 4.3 2区工程技术 Q2 ENGINEERING, CHEMICAL

Chemical Engineering Science

Pub Date : 2026-05-15 Epub Date: 2026-02-11 DOI: 10.1016/j.ces.2026.123570

Jianing Yu , Xu Li , Haifeng He , Zhimin Peng , Ansheng Chen , Jinglun Qian , Liming Zheng , Jingyang Pu

Heavy oil development faces challenges due to high viscosity and steam channeling during thermal recovery. Conventional plugging agents like foams and gels often suffer from thermal instability and low injectivity. This study developed a thermally crosslinkable dual-network microgel system (3AC-PL) for steam channeling control. The system consists of polymer microgels-synthesized from acrylamide (AM), 2-acrylamido-2-methylpropanesulfonic acid (AMPS), α-olefin sulfonate (AOS), and carboxymethyl cellulose (CMC)-and crosslinkers including polyethyleneimine (PEI) and L-lysine hydrochloride (Lys-HCl). Characterized by FTIR, SEM, TG-DSC, and rheology, 3AC-PL demonstrated controlled swelling, excellent thermal/salt resistance, and strong viscoelasticity between 130–160°C. Microfluidic experiments confirmed that the microgel effectively blocked high-permeability channels, diverted steam into low-permeability zones, and increased oil recovery from 63.53 % to 95.20 %. Molecular dynamics simulations further revealed sequential crosslinking mechanisms and the role of hydrogen bonding in network stability. This work presents a promising dual-network microgel system that integrates molecular-level understanding with practical performance, offering an effective solution for managing steam channeling in high-temperature heavy oil reservoirs.

稠油开发面临着热采过程中高粘度和蒸汽窜流的挑战。泡沫和凝胶等传统堵漏剂通常存在热不稳定性和低注入性的问题。本研究开发了一种热交联双网络微凝胶系统（3AC-PL），用于蒸汽窜流控制。该体系由丙烯酰胺（AM）、2-丙烯酰胺-2-甲基丙磺酸（AMPS）、α-烯烃磺酸盐（AOS）和羧甲基纤维素（CMC）合成的聚合物微凝胶和聚乙烯亚胺（PEI）和l -赖氨酸盐酸盐（Lys-HCl）等交联剂组成。通过FTIR， SEM， TG-DSC和流变学表征，3AC-PL在130-160°C之间具有控制膨胀，优异的耐热/耐盐性和强粘弹性。微流控实验证实，微凝胶有效封堵高渗透通道，将蒸汽分流至低渗透层，将采收率从63.53%提高到95.20%。分子动力学模拟进一步揭示了顺序交联机制和氢键在网络稳定性中的作用。这项工作提出了一种有前途的双网络微凝胶体系，它将分子水平的理解与实际性能相结合，为高温稠油油藏的蒸汽窜流管理提供了有效的解决方案。

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引用次数: 0

Tracing Structural Evolution of Maillard-Derived Carbon Skeletons for Advanced Zinc-Ion Hybrid Supercapacitors 先进锌离子混合超级电容器maillard衍生碳骨架的结构演化

IF 4.3 2区工程技术 Q2 ENGINEERING, CHEMICAL

Chemical Engineering Science

Pub Date : 2026-05-15 Epub Date: 2026-02-11 DOI: 10.1016/j.ces.2026.123588

Qian Shen, Gong Chen, Qihui Zhao, Junyuan Yang, Xinru Men, Li Guo, Yunhe Zhao

Biomass-derived carbon materials are promising for energy storage due to their sustainability and low cost, but often suffer from limited surface area, poor porosity, and insufficient active sites. To address these issues, nitrogen-doped carbon (BC-GA) with a groove-nested porous structure was synthesized via Maillard reaction between glucose and glycine at 550 °C, followed by KOH etching and calcination. This process enabled uniform nitrogen doping and surface modification, while creating a hierarchical pore structure tailored to match the size of solvated Zn²⁺ ions (0.86 nm). When applied in symmetric supercapacitors (BC-GA//BC-GA), the material exhibited a synergistic dual–mechanism storage behavior, delivering a specific capacitance of 103.1F g⁻¹ at 2 A g⁻¹ and retaining 65% at 16 A g⁻¹. In zinc-ion hybrid supercapacitors (BC-GA//ZnSO₄(aq)//Zn), it achieved a high energy density of 165 Wh kg⁻¹ and a power density of 400 W kg⁻¹, simultaneously demonstrating practical ability to power an electronic watch. This work offers a new strategy for enhancing biomass carbon through reaction and etching control.

由于其可持续性和低成本，生物质衍生的碳材料在储能方面很有前景，但通常存在表面积有限、孔隙度差和活性位点不足的问题。为了解决这些问题，通过葡萄糖和甘氨酸在550℃的美拉德反应合成了具有凹槽嵌套多孔结构的氮掺杂碳（BC-GA），然后进行KOH蚀刻和煅烧。该工艺实现了均匀的氮掺杂和表面改性，同时创建了适合溶剂化Zn2+离子尺寸（0.86 nm）的分层孔结构。当应用于对称超级电容器（BC-GA//BC-GA）时，该材料表现出协同的双机制存储行为，在2 ag−1时提供103.1F g−1的比电容，在16 ag−1时保持65%。在锌离子混合超级电容器（BC-GA//ZnSO4(aq)//Zn）中，它实现了165 Wh kg−1的高能量密度和400 W kg−1的功率密度，同时展示了为电子表供电的实际能力。这项工作为通过反应和蚀刻控制提高生物质碳提供了一种新的策略。

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引用次数: 0

Theoretical modelling and kinetic analysis on microwave accelerated crystallization of ZSM-5 ZSM-5微波加速结晶理论建模及动力学分析

IF 4.3 2区工程技术 Q2 ENGINEERING, CHEMICAL

Chemical Engineering Science

Pub Date : 2026-05-15 Epub Date: 2026-02-01 DOI: 10.1016/j.ces.2026.123484

Yan Zhang , Zhenyu Zhao , Yushan Guo , Jing Shi , Kaixu Shen , Hong Li , Jiawei Teng , Xin Gao

Microwave technology can accelerate zeolite crystallization, thereby reducing synthesis time and energy consumption. However, there is little quantitative information on the underlying micro-mechanisms of the acceleration effect, thus hindering the rational design of microwave-assisted ZSM-5 synthesis processes. Therefore, this study elucidated the mechanism of microwave-accelerated ZSM-5 crystallization by developing a real-time Raman-based monitoring method for temperature-dependent kinetic analysis. ZSM-5 samples prepared via conventional hydrothermal method and microwave heating were compared, with the crystallization process divided into nucleation and crystal-growth stages for kinetic analysis. Combined with dielectric spectroscopy characterization, the regulation of microwave-induced acceleration was revealed, followed by the establishment and isothermal experimental validation of a theoretical model to describe microwave-selective heating effects. The results show that to achieve the target crystallinity of 95%, the conventional heating method requires 110 min, while microwave heating shortens this time to 40 min. Microwave acceleration primarily enhances the pre-exponential factor of the crystallization process, which can be attributed to the selective promotion of molecular kinetic energy in ionic precursors, highlighting the effects of ionic concentration and microwave field intensity. A 1.5-fold increase in ionic content enhances ionic migration by 28.6%, shortening nucleation time from 25 min to 14 min. Furthermore, increasing the microwave electric field from 0.34 V/m to 0.60 V/m raises the nucleation rate from 0.033 min⁻¹ to 0.071 min⁻¹. The mechanistic insights into microwave-accelerated ZSM-5 crystallization, along with the developed kinetic monitoring method and quantitative model, provide theoretical support for the development of large-scale microwave-assisted zeolite synthesis processes.

微波技术可以加速沸石结晶，从而减少合成时间和能耗。然而，关于加速效应的微观机制的定量信息很少，从而阻碍了微波辅助ZSM-5合成工艺的合理设计。因此，本研究通过开发一种基于拉曼的实时监测方法进行温度依赖性动力学分析，阐明了微波加速ZSM-5结晶的机理。比较了传统水热法制备的ZSM-5样品和微波加热法制备的ZSM-5样品，并将结晶过程分为成核阶段和晶体生长阶段进行动力学分析。结合介电光谱表征，揭示了微波诱导加速的规律，建立了描述微波选择性加热效应的理论模型并进行了等温实验验证。结果表明，要达到95%的目标结晶度，常规加热方法需要110 min，而微波加热将此时间缩短至40 min。微波加速主要增强了结晶过程的指前因子，这可归因于离子前驱体中分子动能的选择性提升，突出了离子浓度和微波场强度的影响。离子含量增加1.5倍，离子迁移率提高28.6%，成核时间从25 min缩短到14 min。此外，将微波电场从0.34 V/m增加到0.60 V/m，使成核速率从0.033 min−1提高到0.071 min−1。对微波加速ZSM-5结晶机理的认识，以及所建立的动力学监测方法和定量模型，为大规模微波辅助沸石合成工艺的开发提供了理论支持。

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