Reaction Chemistry & Engineering最新文献

{"title":"Determination of reaction kinetics in three phase CO2 methanation","authors":"Mathias Monning, Asad Asadli, Siegfried Bajohr, Moritz Wolf and Thomas Kolb","doi":"10.1039/D5RE00337G","DOIUrl":"https://doi.org/10.1039/D5RE00337G","url":null,"abstract":"<p >In three phase CO<small>₂</small> methanation, the hydrogenation of the liquid phase dibenzyl toluene (DBT) occurs as a side reaction in the liquid phase. Additionally, DBT decomposition leads to catalyst deactivation by carbon deposition on the catalytic surface. By analyzing the influence of catalyst deactivation on the reaction rates of CO<small>₂</small> methanation and DBT hydrogenation, partial wetting of the catalyst particles is observed. The catalyst surface is not entirely covered by the liquid phase, instead small gas-filled pores remain, within which CO<small>₂</small> methanation occurs in the gas phase. Reaction kinetics under steady state conditions at high reactor temperature is determined for CO<small>₂</small> methanation.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 3","pages":" 723-730"},"PeriodicalIF":3.1,"publicationDate":"2025-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2026/re/d5re00337g?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147335701","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Reactor and kinetic study advances for highly acidic solvolysis-mediated Friedel–Crafts reaction","authors":"Colin Bailey, Connor Donlan, Matthew Glace, Gabrielle Broussard, Someshwar Nagamalla, Lane B. Carasik and Thomas D. Roper","doi":"10.1039/D5RE00379B","DOIUrl":"https://doi.org/10.1039/D5RE00379B","url":null,"abstract":"<p >This study presents a kinetic model that simulates the consumption of 4-hydroxybenzoic acid (4-HBA), the formation of di-isopropyl benzoic acid (DIPBA) <em>via</em> a Friedel–Crafts alkylation reaction, and the generation of key impurities. The model provides valuable insights into reaction dynamics by capturing the intricate interplay between reaction kinetics and competing pathways. In addition, we introduce a cost-effective, scalable reactor design that overcomes the limitations of traditional laboratory-based reactor systems. The reactor system enhances safety, efficiency, and adaptability, making it ideal for large-scale, highly acidic reactions in laboratory settings. Together, this work underscores the insights and limitations of conventional kinetic modeling for solvolysis-mediated Friedel–Crafts reactions and lays the foundation for more efficient and innovative approaches to chemical process development.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 3","pages":" 757-771"},"PeriodicalIF":3.1,"publicationDate":"2025-12-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2026/re/d5re00379b?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147335704","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Product characterization and synergistic studies of in situ co-pyrolysis and catalytic pyrolysis of xylan and polyvinyl chloride","authors":"Tie Liu, Haodong Gao, Yu Liu, Zefeng Deng, Ying Zeng, Shiyuan Xu, Jing Hong, Jiahui Wang and Jiangle Zhang","doi":"10.1039/D5RE00359H","DOIUrl":"https://doi.org/10.1039/D5RE00359H","url":null,"abstract":"<p >Through the co-pyrolysis of PVC and xylan, the HCl released during pyrolysis effectively catalyzes the deoxygenation of oxygenated intermediates (such as aldehydes, ketones, and acids) derived from xylan pyrolysis, thereby suppressing the formation of these coke precursors and reducing char residue. To further enhance the co-pyrolysis efficiency of PVC and xylan, this study employed two types of medium- to high-temperature heterogeneous catalysts for the catalytic pyrolysis of PVC and xylan mixtures. An innovative approach combining self-developed <em>in situ</em> pyrolysis photoionization time-of-flight mass spectrometry with in thermogravimetric infrared spectroscopy was utilized for in-depth investigation. Specifically, a detailed analysis of the catalytic effects and mechanisms during the co-pyrolysis of PVC and xylan was conducted using representative aluminosilicate catalysts (HZSM-5, ZSM-5, USY) and a metal oxide catalyst (ZnO). The results indicate that, compared to the pyrolysis of pure xylan, the relative intensity of polycyclic aromatic hydrocarbons (PAHs) generated from the co-pyrolysis of PVC and xylan decreased (for instance, by 25.4% and 20.6% at <em>m</em>/<em>z</em> = 130 and 180, respectively). Furthermore, both types of heterogeneous catalysts promote PVC pyrolysis to release HCl and effectively lower the formation temperature of co-pyrolysis products from PVC and xylan, with zinc oxide demonstrating the most pronounced catalytic effect. The acid sites of aluminosilicate catalysts facilitate the deoxygenation of xylan, while ZnO promotes the formation of polyene chains from PVC and the dehydrogenation of xylan-derived molecules. Overall, catalytic pyrolysis is a highly promising method for chemical recycling, enabling the transformation of waste plastics and xylan into high-value chemicals or fuels.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 3","pages":" 608-616"},"PeriodicalIF":3.1,"publicationDate":"2025-12-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147335684","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Recovery of lithium from spent lithium-ion batteries using carbothermal reduction with spent coffee grounds: a parametric optimization using a combined approach of response surface methodology and machine learning","authors":"Yash Srivastava, Rinki Singh, Hemant Goyal and Prasenjit Mondal","doi":"10.1039/D5RE00097A","DOIUrl":"https://doi.org/10.1039/D5RE00097A","url":null,"abstract":"<p >The world today faces the challenge of recovering valuable metals from spent lithium-ion batteries, as improper disposal of battery waste presents significant environmental risks. With the growing demand for lithium resources, the extraction of lithium from waste batteries has become increasingly crucial for resource sustainability and environmental protection. In response to this challenge, this study introduces spent coffee grounds as a novel biomass material for selective lithium extraction through carbothermal reduction with spent cathode powder. During the carbothermal reduction process, lithium in the spent cathode powder is converted into Li<small>₂</small>CO<small>₃</small>, while transition metals such as nickel (Ni), cobalt (Co) and manganese (Mn) are reduced to a lower oxidation state. In this process, the biomass undergoes thermal treatment in an inert atmosphere to generate CH<small>₄</small>, H<small>₂</small>, and CO gases, along with biochar. Biochar and the gaseous products act as effective reducing agents for the metal oxides present in the spent cathode powder. The high fixed carbon content and reactive surface of biochar facilitate solid–solid reduction, while the generated gases such as CO and H<small>₂</small> serve as strong gaseous reducing agents. The reduction residue obtained after carbothermal reduction contains lithium predominantly as lithium carbonate. This lithium carbonate can be efficiently leached using water and subsequently recovered through evaporative crystallization. The effect of parameters such as temperature, the mass ratio of spent coffee grounds to spent cathode powder (BCMR), residence time, and heating rate on leaching efficiency, along with process modeling and optimization, was also investigated using a combined approach of response surface methodology (RSM) and machine learning (ML). The optimized leaching efficiency was observed with the RSM model to be 81.3% and the decision tree model of machine learning to be 80.16% under optimized conditions of a temperature of 587 °C, a BCMR of 0.97, a residence time of 19.4 minutes, and a heating rate of 5.8 °C min<small>⁻¹</small>. The spent coffee grounds, spent cathode powder, reduction residue, and leaching residue were analysed using TGA, SEM-EDX, XRD, and XPS techniques. This approach offers an improved strategy for the valorization of spent coffee grounds in carbothermal reduction, facilitating the selective recovery of lithium from spent lithium-ion batteries, with significant potential for various industrial applications.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 3","pages":" 674-690"},"PeriodicalIF":3.1,"publicationDate":"2025-12-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147335689","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Continuous and sensitive monitoring of LPMO reactions using an optical H2O2 sensor","authors":"Leonor Vieira Carneiro, Anders Ørts Tjell, María Dolores Fernández-Ramos, Torsten Mayr and Daniel Kracher","doi":"10.1039/D5RE00332F","DOIUrl":"https://doi.org/10.1039/D5RE00332F","url":null,"abstract":"<p >We demonstrate the use of an optical sensor to follow the activity of H<small>₂</small>O<small>₂</small>-dependent enzymes in real-time, using <em>quasi</em>-continuous detection of H<small>₂</small>O<small>₂</small>. The sensor enables kinetic measurements of the H<small>₂</small>O<small>₂</small>-consuming enzyme lytic polysaccharide monooxygenase (LPMO) under homogeneous conditions at 1 mL scale conversion assays. By tracking H<small>₂</small>O<small>₂</small> concentration changes over time during 2-minute reaction intervals, we established quantitative assays and determined Michaelis–Menten kinetics for the LPMO from <em>Lentinus similis</em> to cellotetraose, with a <em>K</em><small>_M</small> value of 0.22 ± 0.08 mM and a maximum reaction rate (<em>V</em><small>_max</small>) of 0.97 ± 0.64 μM s<small>⁻¹</small>. This method allows for continuous monitoring without reliance on time-consuming, discontinuous assays or post-reaction sample processing. We evaluate the capabilities of the sensor to monitor enzyme activity, benchmark it against established spectrophotometric methods, and discuss its limitations and advantages. This work provides a method for the real-time assessment of LPMO kinetics but also enables broader application to other redox enzymes that consume or release H<small>₂</small>O<small>₂</small> during the reaction.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 3","pages":" 713-722"},"PeriodicalIF":3.1,"publicationDate":"2025-12-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2026/re/d5re00332f?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147335700","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Multiple Brønsted acidic sites in nitrogen-rich dicyandiamide immobilized on silica gel as a heterogeneous catalyst for efficient conversion of fructose into 5-hydroxymethylfurfural","authors":"Duy Quoc Mai, Nam Phuong Duong Thai, Diep Dinh Le, Dao Anh Le Nguyen, Trinh Hao Nguyen and Phuong Hoang Tran","doi":"10.1039/D5RE00516G","DOIUrl":"https://doi.org/10.1039/D5RE00516G","url":null,"abstract":"<p >5-Hydroxymethylfurfural (HMF) has received increasing attention as a crucial intermediate for the production of high-value-added chemicals and biofuels. Therefore, strategies for the synthesis of HMF have been widely explored by designing various catalysts. In this study, acidic nitrogen-rich dicyandiamide immobilized on silica gel (SiO<small>₂</small>-DCDA-SO<small>₃</small>H) was synthesized using a simple and practical method to enhance the dehydration of fructose into HMF. Various modern techniques were used to characterize the catalyst. Besides, the effect of temperature, catalyst mass, substrate, initial substrate concentration, and solvent, and its reusability and large-scale production were assessed to find the optimal conditions. The catalyst exhibited excellent catalytic activity with an impressive yield of HMF (95.2% ± 4.3%) from fructose at 160 °C after 120 min in dimethyl sulfoxide (DMSO). Moreover, this catalyst may be exploited as a promising catalyst for laboratory-scale synthesis of HMF and has potential to be implemented in industry given that it demonstrates strong reusability and scalability.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 3","pages":" 746-756"},"PeriodicalIF":3.1,"publicationDate":"2025-12-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147335703","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"ANN-based prediction of equilibrium gas composition and carbon yield in methane pyrolysis and reforming methods","authors":"Robert Cherbański, Tomasz Kotkowski, Stanisław Murgrabia, Eugeniusz Molga and Andrzej Stankiewicz","doi":"10.1039/D5RE00322A","DOIUrl":"https://doi.org/10.1039/D5RE00322A","url":null,"abstract":"<p >We investigate the potential of artificial neural networks (ANNs) to approximate the equilibrium gas-phase composition and carbon yield in methane pyrolysis (MP), dry reforming of methane (DRM), steam methane reforming (SMR), and partial oxidation of methane (POM). Unlike the conventional thermodynamic approach, which relies on the Gibbs free energy minimization, the ANN-based method provides a data-driven alternative. Using supervised learning, the model captures the complex, nonlinear relationships between process parameters, such as temperature, pressure, and reactant ratios, and the resulting equilibrium product compositions. This approach not only circumvents the computationally intensive nature of Gibbs energy minimization but also enables rapid predictions across a broad range of operating conditions. The study evaluates the performance of a representative ANN architecture and compares its predictions with conventional thermodynamic calculations to assess the method's accuracy and generalization capability. The results demonstrate that the trained ANN predicts the gas-phase compositions and carbon yields very well, even when all input variables are interpolated. Moreover, the ANN performs the same task several thousand times faster than the conventional method. Overall, the results demonstrate the potential of ANNs as efficient tools for accelerating equilibrium calculations in methane conversion processes. The developed and validated approach can be considered a useful tool for predicting the equilibrium gas composition and carbon yield in methane pyrolysis and reforming processes. The SI provides the synaptic weights necessary for the practical application of ANNs to calculate the equilibrium gas composition and carbon yield in MP, DRM, SMR, and POM over a wide range of temperatures, pressures, and initial reactant compositions.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 3","pages":" 691-706"},"PeriodicalIF":3.1,"publicationDate":"2025-11-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2026/re/d5re00322a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147335690","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Highly selective synthesis of 2-cyclopentylidenecyclopentanone via cyclopentanone self-condensation over MgAl-LDO(NO3−)","authors":"Xue Luo, Jiahui Liu, Danhui Li, Lili Zhao and Hualiang An","doi":"10.1039/D5RE00305A","DOIUrl":"https://doi.org/10.1039/D5RE00305A","url":null,"abstract":"<p >Cyclopentanone self-condensation to 2-cyclopentylidenecyclopentanone is one of the key steps in synthesizing high-density fuels. In this study, MgAl-LDO(NO<small>₃</small><small>⁻</small>) catalysts, prepared <em>via</em> coprecipitation, demonstrated good catalytic performance. Meanwhile, Mg<small>₂</small>Al-LDO(NO<small>₃</small><small>⁻</small>) catalysts with different Mg/Al ratios were explored. Characterization by XRD, NH<small>₃</small>-TPD and CO<small>₂</small>-TPD revealed that Mg<small>₂</small>Al-LDO(NO<small>₃</small><small>⁻</small>) possessed appropriate acid–base active sites, correlating with its enhanced catalytic performance. Under optimized reaction conditions, cyclopentanone conversion reached 85.9% with 98.8% selectivity toward 2-cyclopentylidenecyclopentanone. Furthermore, the reusability of the catalyst was investigated. XRD, SEM, and N<small>₂</small> adsorption–desorption analyses indicated that structural changes in the Mg<small>₂</small>Al-LDO(NO<small>₃</small><small>⁻</small>) catalyst led to its deactivation. GC-MS analysis of the reaction system identified the primary by-product as 2,5-dicyclopentylidenecyclopentanone. Based on these findings, a plausible reaction network is proposed.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 3","pages":" 772-780"},"PeriodicalIF":3.1,"publicationDate":"2025-11-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147335705","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Oxygen-vacancy-engineered BiO2−x/Bi2O3 heterojunctions for synergistic photo-tribocatalytic degradation and broad-spectrum antibacterial performance","authors":"Tianlei Wang, Ziheng Wei, Xueping Wang, Lei Zhang, Wei Zhao and Changsheng Yue","doi":"10.1039/D5RE00410A","DOIUrl":"https://doi.org/10.1039/D5RE00410A","url":null,"abstract":"<p >Limitations of photocatalytic technology, such as a high recombination rate of photogenerated carriers and limited spectral response range, restrict the degradation capability of photocatalytic materials, hindering the practical application. In this paper, BiO<small>_{2−<em>x</em>}</small>/Bi<small>₂</small>O<small>₃</small> heterojunctions are successfully constructed by precisely controlling hydrothermal time and temperature, and the synergistic enhancement catalytic mechanism, involving oxygen vacancy regulation, heterojunction design, and the coupling of photo- and tribo-energy, is systematically revealed. The sample synthesized at 170 °C for 6 h possesses the highest oxygen vacancy concentration, a reasonable Bi<small>³⁺</small>/Bi<small>⁵⁺</small> ratio and a narrow band structure. Under photo-tribocatalysis, the optimized sample achieves 99% degradation of methylene blue within 2 h, maintaining a degradation efficiency retention rate of 94% after three consecutive cycles. Furthermore, the sample exhibits excellent broad-spectrum antibacterial performance, achieving bactericidal rates exceeding 90% against <em>Bacillus pasteurii</em>, <em>Saccharomyces cerevisiae</em> and <em>Bacillus mucilaginosus</em>. Additionally, density functional theory calculations that the mechanical stress induced by friction can optimize the migration rate and pathways of carriers at the heterogeneous interface, thereby enhancing the catalytic degradation activity. Therefore, this work comprehensively provides both theoretical foundations and experimental support for the development of new high-efficiency catalytic degradation materials.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 3","pages":" 731-745"},"PeriodicalIF":3.1,"publicationDate":"2025-11-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147335702","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Modular continuous flow synthesis of zidovudine (AZT): a two-stage integrated process enabling safe azidation and enhanced sustainability in HIV drug manufacturing","authors":"Yan Chen, Rongkun Jiang, Fang Zhao, Yufang Xu, Xuhong Qian and Weiping Zhu","doi":"10.1039/D5RE00370A","DOIUrl":"https://doi.org/10.1039/D5RE00370A","url":null,"abstract":"<p >AIDS is one of the deadliest global epidemics. Zidovudine (<strong>AZT</strong>), the first FDA-approved HIV treatment, is a key component of antiretroviral therapy. The current industrial synthesis of <strong>AZT</strong> exhibits several drawbacks: low selectivity of hydroxyl protection, hazardous azidation, and prolonged reaction times/extended processing durations, contributing to suboptimal efficiency, safety hazards, and environmental burden. To address these limitations, we developed a modular continuous flow process for the synthesis of <strong>AZT</strong>. We actively addressed the solvent and reagent compatibility issues and balanced the yield of integrated reactions. This process integrated hydroxyl protection and cyclization in module A, followed by azidation and hydroxyl deprotection in module B, with seamless filtration connecting the two modules. The integrated platform achieves a 69% overall yield across four transformations, reducing the batch time of 2550 minutes to a residence time of 108 minutes. Compared to traditional batch processes, the continuous flow system enhances the selectivity of hydroxyl protection, enables safer handling of azidation reactions, significantly reduces the <em>E</em>-factor from 375 to 210 while increasing the space–time yield (STY) to 17.39 g L<small>⁻¹</small> h<small>⁻¹</small>, resulting in a 289-fold performance gain over the batch process.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 3","pages":" 665-673"},"PeriodicalIF":3.1,"publicationDate":"2025-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147335688","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}