Reaction Chemistry & Engineering最新文献

{"title":"Energy-storage materials with stable structure through carbide slag modification by acid impregnation and manganese doping†","authors":"Caiyun Gao, Xiangli Liu, Yuan Zhang, Fei Jin and Dong Li","doi":"10.1039/D4RE00424H","DOIUrl":"https://doi.org/10.1039/D4RE00424H","url":null,"abstract":"<p >Herein, calcium-based energy-storage materials that directly absorb solar energy were prepared through wet modification of carbide slag (solid waste). It was found that at a carbonization temperature of 700 °C and calcination temperature of 800 °C, the carbonation conversion rate of 50%FA-100 : 10 Mn remains 66.7% after 10 cycles, which is only 6.4% lower than the initial rate. Through ultraviolet spectrophotometry, it was found that after the addition of a small amount of manganese nitrate, the average absorbance of the energy-storage material was 44.14% higher than that of carbide slag. The use of formic acid as a solvent to acidify modified calcium carbide slag for the preparation of energy-storage materials improves the internal structure of the energy-storage materials, which facilitates the entrance of carbon dioxide into the energy-storage material during the diffusion reaction stage to initiate carbonation reaction. The kinetic calculation shows that the activation energy of the modified energy-storage material decreases by 11.3 kJ mol<small>⁻¹</small> in the carbonation reaction stage and 9.25 kJ mol<small>⁻¹</small> in the calcination reaction stage. After the activation energy decreases, the carbonation/calcination reaction is easier to carry out; thus, the reaction time is reduced.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 2","pages":" 428-439"},"PeriodicalIF":3.4,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143107569","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":"Overcoming bottlenecks towards complete biocatalytic conversions and complete product recovery","authors":"Roland Wohlgemuth","doi":"10.1039/D4RE00349G","DOIUrl":"https://doi.org/10.1039/D4RE00349G","url":null,"abstract":"<p >Biocatalysis has become an attractive and powerful technology for resource-efficient conversions of starting materials to products because of selectivity, safety, health, environment and sustainability benefits. One of the key success factors for any synthetic method has traditionally been the yield of the product which has been isolated from the reaction mixture after the conversion and purified to the required purity. The conversion economy and the final product recovery, which determine the isolated yield of a product, are therefore also of key importance for biocatalytic processes, from biocatalytic single-step to multi-step reactions and total synthesis. In order to progress towards complete biocatalytic conversions and to aim at completely recovering and isolating the pure product, relevant thermodynamic, kinetic and other constraints leading to incomplete biocatalytic conversions and incomplete product recovery need to be identified and overcome. The methods and tools for overcoming various types of bottlenecks are growing and can provide valuable guidance for selecting the most suitable approaches towards the goal of achieving 100% yield of the isolated pure product for a specific biocatalytic conversion.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 2","pages":" 278-293"},"PeriodicalIF":3.4,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/re/d4re00349g?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143107602","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":"The scale-up of microwave flow syntheses by recirculation: the chlorine-free preparation of alkyl phenyl-H-phosphinates†","authors":"József Schindler, Dorka Nagy, Rebeka Harján and György Keglevich","doi":"10.1039/D4RE00527A","DOIUrl":"https://doi.org/10.1039/D4RE00527A","url":null,"abstract":"<p >In microwave (MW)-assisted flow syntheses, the size, and hence, the volume of the reactor may be a limiting factor. In this paper, we introduce a novel nonlinear accomplishment by applying recirculation within the flow system. In this way, higher conversions were attained even with a 10 mL reactor cell recirculating larger volumes (25–100 mL) of the reactants. The model reaction was the ionic liquid-catalyzed direct esterification of phenyl-<em>H</em>-phosphinic acid with butyl alcohol. The effect of the flow rate, the absence or presence of the catalyst, and the temperature and volume of the reaction mixture on the conversion were studied in detail. Preparative yields of 64–72% for the butyl phenyl-<em>H</em>-phosphinate with a 5.9–8.6 g h<small>⁻¹</small> productivity were obtained. Comparative thermal experiments confirmed the special role of MW irradiation. The method was then extended to esterification with other alcohols.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 2","pages":" 371-378"},"PeriodicalIF":3.4,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143107565","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":"Effect of the presence of CO2 on the stability of the methanol-to-olefins reaction catalyzed by Zn/SAPO-34 zeolite","authors":"Haobin Hu, Ke Ma, Zhenyu Cheng, Xinyu Qi, Haiyan Song, Zhijun Li, Yufeng Wang, Penghui Zhang, Chengyi Dai and Xiaoxun Ma","doi":"10.1039/D4RE00464G","DOIUrl":"https://doi.org/10.1039/D4RE00464G","url":null,"abstract":"<p >The methanol-to-olefins reaction is a viable and promising technological route to replace increasingly scarce petroleum resources. SAPO-34 zeolite is an ideal catalyst for the methanol-to-olefins reaction due to its suitable acidity and pore structure. However, a single zeolite catalyst has limited performance, and in this work, metal species were introduced on SAPO-34 molecular sieves to achieve higher low-carbon olefin selectivity through the modulation of acidity. However, since the introduction of metals promotes aromatic cycling, it allows the creation of carbonaceous precursors and reduces the catalyst lifetime. Therefore, the introduction of CO<small>₂</small> into the carrier gas inhibited the generation of carbonaceous precursors and thus prolonged the catalyst life. The presence of the metal species and their effects on SAPO-34's pores and structure were characterized by XPS, the change in acid amount was determined by NH<small>₃</small>-TPD, and the adsorption strength of the catalyst for CO<small>₂</small> was determined by CO<small>₂</small>-TPD, revealing the active sites of the catalyst. High low-carbon olefin selectivity and long catalyst life were also achieved, with low-carbon olefin selectivity of 88.0%.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 3","pages":" 667-675"},"PeriodicalIF":3.4,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143489382","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":"Integrating continuous flow reaction and work-up: chiral amine resolution, separation and purification using a novel coalescing filter system†","authors":"Bethan M. Rowley, Lisa A. Thompson, Luke A. Power, James Daglish, Emma Parks, James Birbeck, Steve Marsden, Nikil Kapur and A. John Blacker","doi":"10.1039/D4RE00442F","DOIUrl":"10.1039/D4RE00442F","url":null,"abstract":"<p >To maximize the benefits of a continuous flow reaction, a continuous work-up is also needed. Herein, we present a process design and novel equipment for a continuous amine resolution reaction, integrated with liquid–liquid (L–L) extraction, back-extraction into a different solvent, and crystallisation purification for product isolation. The reaction, in iso-propyl acetate, flows through a heated fixed-bed reactor with solid supported <em>Candida antarctica</em> lipase which catalyses the resolution of (<em>rac</em>)-1-phenylethylamine to give the (<em>R</em>)-amide in 50% conversion and 96% enantiomeric excess (ee). This is separated from the unreacted (<em>S</em>)-amine co-product by mixing with an acidic aqueous stream and separating the phases using our recently reported coalescence filter separator. The aqueous stream is neutralised by mixing with base and back-extracted into methyl-THF solvent before separating the phases using a membrane separator. Finally, a solid amine salt is isolated by filtration, achieved by mixing the free base with an organic acid to cause crystallisation to give the (<em>S</em>)-1-phenylethylamine in 43% yield and &gt;99% ee from racemate. The work illustrates how typical reactions, work-up and purification steps that involve multiple phases can be telescoped together using both new and commercially available laboratory equipment. This continuous system uses mild reaction conditions, green solvents and minimises their use for reduced waste.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 2","pages":" 392-397"},"PeriodicalIF":3.4,"publicationDate":"2024-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC11603407/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142764873","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":"Upcycling polymethyl methacrylate to methacrylic acid†","authors":"Yanfa Zhuang, Nooshin Saadatkhah, Tien-Dat Nguyen, Jacopo De Tommaso, Clive Yi Jie Ng, Chunyu Wang, Abdellah Ajji and Gregory S. Patience","doi":"10.1039/D4RE00341A","DOIUrl":"https://doi.org/10.1039/D4RE00341A","url":null,"abstract":"<p >Waste polymethyl methacrylate (PMMA) has become a more prominent contributor to global plastic waste in the aftermath of the COVID-19 pandemic. Recycling PMMA relies either on mechanical recycling or thermal depolymerization. Mechanical properties deteriorate after several mechanical recycling cycles. Depolymerization technologies operate in an inert atmosphere and require costly monomer purification downstream. Therefore, neither chemical nor mechanical recycling of PMMA is economically viable. Here, we demonstrate a sustainable recycling method through catalytic hydrolysis to upcycle PMMA while reaching higher product purity. PMMA reacts over zeolites and produces methacrylic acid instead of methyl methacrylate offering technical, economical, and market benefits. Direct hydrolysis of PMMA over an H-type zeolite with an SiO<small>₂</small>/Al<small>₂</small>O<small>₃</small> ratio of 80 produced methacrylic acid with a yield of 56% and a selectivity of 58%. Coke formed within the framework of large-pore zeolites, causing reversible deactivation of medium–strong acid sites and Brønsted acid sites. The catalytic decarboxylation of methacrylic acid primarily produces acetone and CO, and six-membered glutaric anhydride forms in solid residues.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 1","pages":" 237-250"},"PeriodicalIF":3.4,"publicationDate":"2024-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142844656","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 hierarchical surrogate approach to biomass ethanolysis reaction kinetic modelling†","authors":"Ailís O'Shea, Conall McNamara, Prajwal Rao, Mícheál Howard, Mohammad Reza Ghanni and Stephen Dooley","doi":"10.1039/D4RE00378K","DOIUrl":"https://doi.org/10.1039/D4RE00378K","url":null,"abstract":"&lt;p &gt;The reaction mechanism and kinetics of the sulfuric acid catalysed ethanolysis of glucose, cellulose, xylan, and corncob were investigated using a combination of experiments and empirical reaction mechanism modelling. The experimental study was carried out in ethanol at various temperatures between 150 °C and 200 °C. Ethanol mediates the depolymerisation and formation of ethyl levulinate from the carbohydrates in the substrates. Ethanol itself is converted to the corresponding ether in a parallel acid-catalysed condensation reaction. The complementary synergistic thermal and combustion properties of the main components in the resulting mixture, ethyl levulinate, diethyl ether, and ethanol, create the potential for the use of the product mixture as a tailored drop-in biofuel. The concentrations of the main species in the product mixtures from the reaction experiments were used to build a hierarchical surrogate kinetic model based on feedstock composition. The reaction mechanism provided to the surrogate kinetic model is informed by a comparative experimental mechanistic study of the ethanolysis of glucose and fructose. The study shows that the major reaction species formed from glucose ethanolysis are ethyl glucoside and ethyl levulinate, whereas fructose ethanolysis primarily forms 5-hydroxymethylfurfural, 5-ethoxymethylfurfural, ethyl fructoside and ethyl levulinate. The study shows that fructose produces a higher yield of ethyl levulinate than glucose and that fructose does so at a rate approximately ten times faster than glucose. The rate of formation of both ethyl levulinate and diethyl ether increases with increasing temperature. The maximum yields (mass%) of ethyl levulinate achieved from the ethanolysis of glucose, cellulose, xylan, and corncob are 39.3, 39.1, 7.9, and 18.6%, respectively. Ethyl levulinate yields reach a maximum steady state value for each feedstock that is independent of temperature. The conversion of the model compounds, glucose, cellulose, and xylan, to ethyl levulinate in the presence of ethanol and sulfuric acid is a catalytic process. However, for corncob, the yield of ethyl levulinate is dependent on the concentration of sulfuric acid in the reaction. This effect is also observed in the mass fraction of diethyl ether formed, indicating that the hydrogen cation supplied by sulfuric acid is not being fully replenished in the corncob ethanolysis process. A corncob : acid mass ratio of 10 : 1 is identified as a sufficient sulfuric acid concentration to achieve a maximum steady state yield of ethyl levulinate. An empirical analysis of the experimental data show that the apparent activation energies of the global reaction of glucose to ethyl levulinate and ethanol to diethyl ether are 21.5 and 23.0 kcal mol&lt;small&gt;&lt;sup&gt;−1&lt;/sup&gt;&lt;/small&gt;, respectively. The hierarchical surrogate kinetic model for the ethanolysis of corncob based on its composition of cellulose, hemicellulose, and lignin was developed and has an overall &lt;","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 2","pages":" 344-359"},"PeriodicalIF":3.4,"publicationDate":"2024-11-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143107564","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":"Ammonia decomposition over low-loading ruthenium catalyst achieved through “adiabatic” plasma reactor†","authors":"Minhazur Rahman Shawon, Chinwendu Umeojiakor, Anthony Griffin, Jeffrey Aguinaga, Jiachun Wu, Derek Patton, Zhe Qiang, Hossein Toghiani and Yizhi Xiang","doi":"10.1039/D4RE00509K","DOIUrl":"https://doi.org/10.1039/D4RE00509K","url":null,"abstract":"<p >Electrified catalytic processes for ammonia (NH<small>₃</small>) decomposition have been considered as essential technologies for distributed CO<small>_<em>x</em></small>-free hydrogen production. Here we show that efficient NH<small>₃</small> decomposition can be achieved over low-loading Ru/Al<small>₂</small>O<small>₃</small> using an adiabatic dielectric barrier discharge (DBD) plasma reactor. Specifically, we demonstrate that the activity of NH<small>₃</small> decomposition in the adiabatic plasma reactor is up to 4.9 times higher than that under nonadiabatic conditions. The NH<small>₃</small> conversion was 73% (in the adiabatic plasma reactor) over the 0.05 wt% Ru/Al<small>₂</small>O<small>₃</small> catalysts at a plasma power of 19 W, whereas, the conversion is only 15% when performed in the nonadiabatic plasma reactor, moreover, the catalyst was almost inactive in the thermal catalytic NH<small>₃</small> decomposition. Additionally, nearly 100% NH<small>₃</small> conversion was achieved over the 0.5 wt% Ru/Al<small>₂</small>O<small>₃</small> catalyst at 19 W or over higher Ru loading catalysts at lower powers. We suggested that more efficient NH<small>₃</small> decomposition was attributed to the enhanced synergy between plasma-activated radicals ·NH<small>_<em>x</em></small> and vibrationally excited NH<small>^v</small><small>₃</small>, and the catalytically active Ru sites when using the adiabatic plasma reactor – in contrast to the nonadiabatic counterpart.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 2","pages":" 320-331"},"PeriodicalIF":3.4,"publicationDate":"2024-11-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143107562","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 ethylphenols and xanthenes via reaction of calcium carbide and phenol: experimental and theoretical studies†","authors":"Xin Liu, Yuxin Yan, Zhenyu Liu and Qingya Liu","doi":"10.1039/D4RE00397G","DOIUrl":"https://doi.org/10.1039/D4RE00397G","url":null,"abstract":"<p >Calcium carbide (CaC<small>₂</small>) is a platform chemical for various organic synthesis, and monomeric phenol (PhOH) is expected to be produced <em>via</em> biomass conversion in the near future. This work explores their downstream product during reaction at 300–400 °C without additional solvent and catalyst. The reaction matrix was investigated by density functional theory (DFT) calculation and characterization of the solid product. Results indicate that in addition to ethylphenols, xanthenes are unexpectedly formed with a yield of 26.0% at 350 °C. DFT calculation indicates that PhOH is firstly alkylated by CaC<small>₂</small> to form vinylphenol or dehydrated intermolecularly to form diphenyl ether. Xanthenes are then formed through two pathways: dehydration of vinylphenol with PhOH and then cyclization; alkylation and cyclization of diphenyl ether with CaC<small>₂</small>-derived acetylene. Ethylphenols are formed through hydrogenation of vinylphenol where PhOH provides hydrogen. Vinylphenol hydrogenation for ethylphenols exhibits a competitive advantage over vinylphenol dehydration for xanthenes. X-ray diffraction (XRD) of the solid product indicates that CaC<small>₂</small> is converted to calcium phenoxide. Isomolecular electrostatic potential maps suggest that calcium phenoxide exerts a catalytic effect on the alkylation and dehydration reactions. This work provides a novel protocol for xanthene synthesis and an <em>in situ</em> efficient utilization method of the acetenyl group.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 1","pages":" 191-202"},"PeriodicalIF":3.4,"publicationDate":"2024-11-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142844651","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":"Selective separation of Li, Ni, Co and Mn from model spent Li ion battery cathode materials by dry processing using the combination of chlorination and oxidation†","authors":"Yuuki Mochizuki and Naoto Tsubouchi","doi":"10.1039/D4RE00328D","DOIUrl":"https://doi.org/10.1039/D4RE00328D","url":null,"abstract":"<p >The volatilization of Li, Ni, Co, and Mn during chlorination treatment of LNO, LCO, and LMO (model materials for used LIB cathode materials) was investigated with the aim of developing technology for selectively separating and recovering valuable elements by dry methods from used LIB cathode materials. Based on the characterization results for each species, oxidation treatment was performed on LNO, LCO, and LMO after chlorination, and the selective separation of Li from Ni, Co, and Mn was investigated. Volatilization of Li, Ni, Co, and Mn from LNO, LCO, and LMO occurred at over 700 °C during chlorination, and it was difficult to perform selective volatilization separation of the LIB constituent elements. It was found that when LNO, LCO, and LMO were treated by chlorination at up to 600 °C and then heated in air up to 1300 °C, Li could be selectively separated from Ni, Co, and Mn.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 2","pages":" 332-343"},"PeriodicalIF":3.4,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143107563","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}