Reaction Chemistry & Engineering最新文献

{"title":"Application of a simple rule for the design of micro- or meso-scale cooled reactors in a heat transfer limited regime","authors":"Kishori Deshpande, Jianping Zeng, Ravindra Dixit, David West and David Jean","doi":"10.1039/D4RE00128A","DOIUrl":"10.1039/D4RE00128A","url":null,"abstract":"<p >Flow chemistry has greatly expanded the reaction toolbox by demonstrating a wide range of individual chemical transformations. For commercial scale processes, it provides an appealing alternative to batch reactors by reducing production costs, increasing product yield and overall process robustness. We describe an approach for continuous processing of a specialty chemical manufactured using a batch process with a typical yield of 150 kg per hour and concomitant adiabatic temperature increase of up to 250 °C. This necessitates controlled feed addition causing longer processing time, lower productivity, and undesirable polymerization reactions. We present a continuous process that addresses the challenges of thermal management and reaction selectivity using flow chemistry thereby enabling up to 12-fold reduction in residence time with a comparable product profile. Fundamental reactor engineering and design principles and associated safety considerations used for designing the reactor and continuous process are described. Guided by this analysis, a continuous process using a ¼ inch tubular reactor is investigated. The results indicate residence time reduction from 6 hours to 30 minutes for comparable feed conversion of 87% and similar product composition. Greater than 90% conversion could not be achieved in the current reactor configuration and associated reactor runaway analysis suggests feed decomposition due to pressure fluctuations or insufficient reactants in the reactor. The analysis highlights the need for designing a reactor with better pressure control using a back pressure regulator and choosing a smaller diameter tube. These insights underscore the importance of applying fundamental reactor engineering principles for designing safe and efficient processes at an industrial scale.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 12","pages":" 3311-3317"},"PeriodicalIF":3.4,"publicationDate":"2024-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142258671","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":"Radio-frequency heating for catalytic propane dehydrogenation†","authors":"Ankush Rout, Somtochukwu Lambert, Aswin Nair, Kailash Arole, Debalina Sengupta, Mark A. Barteau, Benjamin A. Wilhite and Micah J. Green","doi":"10.1039/D4RE00422A","DOIUrl":"10.1039/D4RE00422A","url":null,"abstract":"<p >In this paper, we have demonstrated radio frequency (RF) heating of susceptor nanomaterials coupled with conventional catalysts to enable a new class of heterogeneous catalytic reactors with localized, volumetric heating. The recent emphasis on industrial decarbonization has highlighted the need to reduce greenhouse gas emissions from chemical process heating. Existing industrial scale catalytic reactors use fuel-fired furnaces to achieve high temperatures which contributes to CO<small>₂</small> emissions and requires on-site infrastructure. Compared to conventional heating, this work uses a power-to-chemicals route, where RF fields (1–200 MHz) are utilized to volumetrically heat RF-responsive carbon nanomaterials integrated with the catalyst. With the option of using renewable electricity sources, the greenhouse gas emissions associated with the process can be reduced, thereby contributing to industrial decarbonization. We demonstrate the use of an RF applicator to drive the highly endothermic propane dehydrogenation reaction on a Pt/alumina catalyst using carbon nanotubes as the RF susceptors. The propane conversion and propylene yield using RF heating were similar to those obtained when the reactor was heated externally in an oven (conventional heating (CH)) at 500 °C. After each reaction cycle, the catalyst was successfully regenerated by RF heating in air to remove deposited carbon.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 12","pages":" 3211-3221"},"PeriodicalIF":3.4,"publicationDate":"2024-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/re/d4re00422a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142258668","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":"Spherical CuFeS2@FeSe2 structure as a binder-free electrode and its performance in asymmetric supercapacitors","authors":"Tahereh Nikkhah Amirabad and Ali A. Ensafi","doi":"10.1039/D4RE00144C","DOIUrl":"10.1039/D4RE00144C","url":null,"abstract":"<p >Transition metal chalcogenides (TMCs), such as FeSe<small>₂</small>, FeS<small>₂</small>, and CuS, have attracted considerable attention for energy storage due to their multi-electron transfer capabilities and high capacities. This study presents the synthesis of spherical CuFeS<small>₂</small> through a binder-free hydrothermal process, incorporating selenium powder to form hollow spheres of CuFeS<small>₂</small> encapsulated by FeSe<small>₂</small> nano-planes (CuFeS<small>₂</small>@FeSe<small>₂</small>). Utilizing a modified electrode without a binder and adopting a spherical CuFeS<small>₂</small>@FeSe<small>₂</small> structure significantly enhance the performance of asymmetric supercapacitors. The absence of a binder eliminates potential issues associated with binding agents, ensuring a more efficient charge transfer. The spherical configuration, with FeSe<small>₂</small> layers surrounding and encapsulating the CuFeS<small>₂</small> core, contributes to improved capacitance and stability. The unique structure allows for better utilization of active materials, enhancing the specific capacitance of the electrode. This modified electrode demonstrates remarkable cyclic stability, indicating its potential for long-term practical applications. This unique nanostructure was characterized by field emission scanning electron microscopy (FE-SEM), energy dispersive X-ray spectroscopy (EDX), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS), demonstrating enhanced nanomaterial conductivity. Electrochemical performance analyses, including cyclic voltammetry (CV), galvanostatic charge–discharge (GCD), and electrochemical impedance spectroscopy (EIS), reveal a specific capacity of 1306 A g<small>⁻¹</small> at a current density of 2 A g<small>⁻¹</small> in a three-electrode system. Furthermore, as a positive electrode in an asymmetric supercapacitor device (CuFeS<small>₂</small>@FeSe<small>₂</small>||AC), paired with activated carbon@NF (AC) as a negative electrode, the system achieves an efficient energy density of 152.01 W h kg<small>⁻¹</small> with superior durability, retaining 91.03% capacity after 3000 cycles.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 12","pages":" 3267-3276"},"PeriodicalIF":3.4,"publicationDate":"2024-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142258673","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":"Synthesis of methyl benzoate intensified by p-toluenesulfonic acid-based deep eutectic solvents†","authors":"Dian Jin, Xindi Feng, Li Sun, Zuoxiang Zeng and Zhen Liu","doi":"10.1039/D4RE00352G","DOIUrl":"10.1039/D4RE00352G","url":null,"abstract":"<p >Methyl benzoate (MB) is a chemical raw material used in various fields. However, the conventional approach to synthesizing MB is characterized by difficulties such as equipment corrosion, by-product generation, and recycling challenges. In light of these challenges, this work proposes the utilization of deep eutectic solvents (DESs) as both extractants and catalysts in a reactive extraction process. In particular, <em>p</em>-toluenesulfonic acid-based deep eutectic solvents (PTSA-based DESs) were tested as potential candidates, with choline chloride (ChCl) and imidazole (Im) chosen as hydrogen bonding acceptors (HBAs). The feasibility of DESs consisting of ChCl and PTSA was assessed using the COSMO-RS theory. The optimal process conditions were determined. Under the optimal conditions, the yield of MB reached 93.46%, and the performance of [ChCl–PTSA] remained stable after five cycles. We also used the group contribution method and COSMO-RS to derive separate kinetic models, with activation energies of 43.71 kJ mol<small>⁻¹</small> and 38.71 kJ mol<small>⁻¹</small>. Our work highlights the potential of [ChCl : PTSA] in the industrial production of MB.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 12","pages":" 3179-3190"},"PeriodicalIF":3.4,"publicationDate":"2024-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142258672","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":"Enzyme-catalyzed polyurethane adhesive degradation†","authors":"Angela Romano, Antonella Rosato, Laura Sisti, Giulio Zanaroli, Svajus Joseph Asadauskas, Paulina Nemaniutė, Dalia Bražinskienė, Asta Grigucevičienė and Grazia Totaro","doi":"10.1039/D4RE00253A","DOIUrl":"10.1039/D4RE00253A","url":null,"abstract":"<p >Polyurethanes represent a class of highly versatile synthetic polymers, suitable for a wide range of applications. Their biological degradation is of great interest since it can allow the design of specific formulations by selecting suitable building blocks and it can contribute to the development of sustainable recycling processes. In the current study, a commercial hydrolytic enzyme (cutinase from <em>Humicola insolens</em>, HiC) was investigated for its ability to degrade various polyurethane adhesive formulations, by focusing first on macrodiols, then on specific polyurethanes. The aim was to identify solvent-based polyurethane formulations susceptible to enzymatic hydrolysis. First, a semi-quantitative assay, namely the emulsion turbidity test, was carried out on some macrodiols. Then, weight loss tests were carried out on specific solvent-based polyurethane formulations, and three promising formulations have shown 90, 60 and 40% degradation, after 96 h of incubation with HiC. A study of the enzymatic degradation mechanism of macrodiols and the most degradable polyurethanes was also carried out, through the characterization of the solid residues after the enzymatic degradation by infrared spectroscopy, calorimetric and thermogravimetric analysis, and the identification and/or quantification of the monomers released during the hydrolysis of macrodiols within the liquid fraction (by high-performance liquid chromatography). According to the results, a prevalent exo-type action mode for HiC against some macrodiols was found under the conditions tested, while, from a chemical point of view, the degradation seems to determine, on the polyurethane residues, a general increase in crosslinking.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 12","pages":" 3133-3145"},"PeriodicalIF":3.4,"publicationDate":"2024-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/re/d4re00253a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142177818","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":"Synthetic and mechanistic studies of the multicomponent reaction of 2-(phenylethynyl)benzaldehyde, primary amine and diphenylphosphine oxide†","authors":"Kármen Szabó, Zsolt Kelemen, Pál Tamás Szabó and Erika Bálint","doi":"10.1039/D4RE00387J","DOIUrl":"10.1039/D4RE00387J","url":null,"abstract":"<p >The synthesis of potentially biologically active phosphinoyl functionalized <em>N</em>-(2-(phenylethynyl)benzyl)amine, 1,2-dihydro-isoquinoline and 2<em>H</em>-isoindoline <em>via</em> a multicomponent reaction of 2-(phenylethynyl)benzaldehyde, amine and diphenylphosphine oxide is described for the first time. Depending on the catalyst and the conditions used, the same one-pot three-component reaction can selectively lead to the mentioned three different products. The formation of the cyclic products was investigated by a comprehensive catalyst screening, as well as by quantum chemical calculations. It was found that for the synthesis of phosphinoyl functionalized <em>N</em>-(2-(phenylethynyl)benzyl)amine, there is no need to use any catalyst. For the complete formation of isoquinoline ring containing phosphine oxide, zirconium(<small>IV</small>) chloride was the most efficient catalyst and 2<em>H</em>-isoindol-1-ylphosphine oxide was synthesized selectively by a silver acetate catalyst. Furthermore, dihydro-isoquinolin-1-ylphosphine oxide was converted into the thermodynamically more stable 2<em>H</em>-isoindol-1-ylphosphine oxide.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 12","pages":" 3222-3230"},"PeriodicalIF":3.4,"publicationDate":"2024-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142177820","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":"A simplified chemical kinetic model with a reaction mechanism based on a multidimensional average error iteration method for ammonia and ammonia/hydrogen combustion†","authors":"Daiyao Yue, Chongkai Zhao, Rui Sun, Jieyu Jiang, Chunjie Sui, Xin Zhong and Bin Zhang","doi":"10.1039/D4RE00274A","DOIUrl":"10.1039/D4RE00274A","url":null,"abstract":"<p >Ammonia (NH<small>₃</small>) is emerging as a promising fuel due to its high energy density, high hydrogen content, and zero carbon emissions from combustion. The study of chemical kinetics in NH<small>₃</small> combustion offers theoretical approaches to address its low reactivity and high nitrogen oxide (NO<small>_<em>x</em></small>) emissions, especially in binary fuels with hydrogen (H<small>₂</small>), which have been shown to positively affect NH<small>₃</small> combustion systems. However, existing NH<small>₃</small>/H<small>₂</small> models have various defects under different conditions. In this study, we develop a simplified NH<small>₃</small>/H<small>₂</small> chemical kinetics model that is comprehensively validated using a large amount of representative experimental literature data, including ignition delay time, laminar flame speeds, and species concentration profiles. The model is analyzed using an innovative multidimensional average error iteration method, ensuring that the overall average error remains within 5%. Subsequently, the model is simplified by removing unnecessary components and reaction steps through the direct relation graph with error propagation method, reducing computational consumption. The combustion results of the pure NH<small>₃</small> and NH<small>₃</small>/H<small>₂</small> mixtures under most conditions are highly consistent with those of the new model. By conducting sensitivity and productivity analyses, we determined the key reactions controlling fuel reactivity under different H<small>₂</small> ratios and the important interactions between intermediate products are described in detail. Additionally, the different reaction directions of NH<small>₃</small> and the principle of NO<small>_<em>x</em></small> generation under high H<small>₂</small> conditions are elucidated through these analyses and reaction pathway diagrams.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 12","pages":" 3153-3171"},"PeriodicalIF":3.4,"publicationDate":"2024-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142177817","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":"Carbonylations in flow: tube-in-tube reactor vs. gas–liquid slug flow†","authors":"Agnieszka Ładosz, Astrid Friedli, Arnaud Lhuillery and Georg Rueedi","doi":"10.1039/D4RE00287C","DOIUrl":"10.1039/D4RE00287C","url":null,"abstract":"<p >In order to improve the performance of carbonylation reactions in flow, we compared the tube-in-tube system to a gas–liquid two-phase setup. We found that the two-phase slug flow reactor significantly improved the yield and throughput of the reactions tested. First, we performed a reference reaction, methoxycarbonylation of 4-chlorobenzonitrile, using conditions described in the literature and obtained 57% calculated yield in the biphasic setup and 16% in the tube-in-tube setup, with side product formation of 1% and 8% respectively. The reaction was further optimized in both apparatuses, improving the yield in the biphasic setup to 86%, while the tube-in-tube method was limited to about 34%. Finally, a 1.5 g scale-up of a project-relevant building block yielded 73% of the product in the tube-in-tube setup <em>vs.</em> 92% when two-phase flow was used, with more than a ten-fold increase in throughput in the biphasic method. Using gas–liquid flow enabled higher yield and throughput due to direct contact of gas and liquid, better control of CO equivalents and intensification of process conditions: higher temperature, pressure and concentration in the system and significant reduction of residence time.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 12","pages":" 3172-3178"},"PeriodicalIF":3.4,"publicationDate":"2024-09-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142177821","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":"Boosting the kinetics of PET glycolysis†","authors":"Maria Schlüter, Ryota Enomoto, Shin Makino, Lisa Weihs, Cyra Lina Stamm, Kerstin Wohlgemuth and Christoph Held","doi":"10.1039/D4RE00235K","DOIUrl":"10.1039/D4RE00235K","url":null,"abstract":"<p >Glycolysis is the most promising chemical recycling method to depolymerize poly(ethylene terephthalate) (PET) with ethylene glycol (EG) into the monomer bis(2-hydroxyethyl) terephthalate (BHET). Boosting the depolymerization kinetics while staying under comparatively mild and green reaction conditions is required to bring glycolysis to industrial scale utilization. This work suggests achieving this goal by a combined pressure, temperature and co-solvent addition approach. By using the environmentally friendly γ-valerolactone (GVL) as a suitable co-solvent in the traditional PET glycolysis system, and slight temperature and pressure elevation, the kinetics was boosted by almost two orders of magnitude compared to the standard literature process. A kinetic model was employed to describe the kinetics as a function of temperature and GVL concentration. The optimized condition allowed nearly full conversion after 2 minutes only.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 11","pages":" 3038-3046"},"PeriodicalIF":3.4,"publicationDate":"2024-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/re/d4re00235k?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142177822","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":"Complete kinetic model and process reengineering of glyoxal oxidation by nitric acid in a capillary microreactor†","authors":"Junnan Wang, Wei Zhan, Yating Li, Ting Wang, Chengxiang He, Chunying Zhu, Youguang Ma and Taotao Fu","doi":"10.1039/D4RE00313F","DOIUrl":"10.1039/D4RE00313F","url":null,"abstract":"<p >The oxidation of glyoxal by nitric acid to glyoxylic acid is a complex process with parallel and consecutive side reactions. The complete reaction kinetics has not been thoroughly reported before. In this work, a continuous flow microreactor system, consisting of micromixers, preheating capillary loops, a capillary microreactor and quenching device, is designed to achieve oxidation under homogeneous conditions. A complete kinetic model is established and all kinetic parameters are obtained. The effects of the molar ratio of nitric acid to glyoxal, reaction temperature and concentration of nitric acid on the reaction are investigated systematically. Based on the process reengineering of existing devices, two schemes of segmented feeding (nitric acid in several segments) and recirculating feeding (incompletely reacted material is returned to the reactor for reaction) are proposed. Finally, the optimal reaction conditions are determined. At 68 °C (the initial molar ratio of nitric acid to glyoxal was 1.26, with a final molar ratio of 1.4 after segmented feeding at once, the molar ratio of sodium nitrite to glyoxal is 0.15, and the mass concentration of nitric acid is 35%), the yield of glyoxal acid is 89.2% and the selectivity is 95.9%. This work refines the kinetic data for the oxidation reaction of glyoxal nitrate. It is of theoretical importance for optimising reaction performance (temperature and residence time regulation strategies) and reactor design.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 11","pages":" 3016-3028"},"PeriodicalIF":3.4,"publicationDate":"2024-09-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142177823","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}