Dionysia Koufou, Jorid Smets, Rob Ameloot, Simon Kuhn
{"title":"Aerobic oxidation of hydroxymethylfurfural using a homogeneous TEMPO/TBN catalytic system in 3D-printed milli-scale porous reactors","authors":"Dionysia Koufou, Jorid Smets, Rob Ameloot, Simon Kuhn","doi":"10.1007/s41981-023-00264-2","DOIUrl":"10.1007/s41981-023-00264-2","url":null,"abstract":"<div><p>Selective oxidation of hydroxymethylfurfural to diformylfuran was performed in 3D-printed milli-scale porous reactors using pure oxygen in mild operating conditions (T = 60° C, P = 1 atm) and the homogeneous TEMPO/TBN catalytic system. Three different configurations were tested, where a rotation (θ = 22.5°) and/or an inclination (φ = 45°) of the fibers are introduced. An empty tube and a packed bed were also tested as a reference. Out of these designs, the reactor with both parameters varied simultaneously (INSP1) exhibited the highest performance, achieving an efficiency of up to 80%. The maximum conversion of 18.2% was attained for a residence time of 160 s, despite existing mass transfer limitations for this flow rate. The selectivity to DFF was 100% for all the 3D-printed reactors. On the contrary, the packed bed resulted in the highest efficiency, but at the expense of selectivity. Additional oxidation products have been retained in the packing, blocking thus the packed bed after a few hours of operation. The kinetic constant was found based on a (0,1)-order kinetic model from batch experiments. The kinetic information was utilized to evaluate the performance of the 3D-printed porous reactors from a mass transfer and reaction engineering aspect. The 3D-printed reactors were operating almost in kinetic control for total flow rates above 1 mL/min (Ha < 0.3). However, the associated short residence time resulted in small conversion. The 3D-printed reactors show significant potential when operating at higher flow rates. The low conversions can be countered by increasing the residence time, either with multiple passes or by operating them in series.</p></div>","PeriodicalId":630,"journal":{"name":"Journal of Flow Chemistry","volume":"13 2","pages":"169 - 183"},"PeriodicalIF":2.7,"publicationDate":"2023-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://link.springer.com/content/pdf/10.1007/s41981-023-00264-2.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"4266089","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"An eco-friendly and very low catalyst loading continuous condensation of primary amines and 1,3 Di carbonyl compounds: Synthesis of enaminones and enaminoesters by microreactor technology","authors":"Zahra Goodarzi, M. Sadegh Ramezani","doi":"10.1007/s41981-023-00263-3","DOIUrl":"10.1007/s41981-023-00263-3","url":null,"abstract":"<div><p>Herein, an efficient eco-friendly protocol is reported for the continuous synthesis of enaminones using a microreactor device in the presence of a catalytic amount of cerium (III) trichloride (1 mol%) in Propylene carbonate (PC) as a non-toxic solvent. Moreover, continuous separation of the corresponding product, and recycling of the catalyst-solvent system with water is another promising advantage of this technique. Indeed<b>,</b> the separation of the product by water allows any required catalyst and solvent to be reapplied in the next run. In addition, this microfluidic system enabled turnover frequency (TOF) of up to 2940 h<sup>−1</sup> for the corresponding products. The employment of these environment friendly facilitates produce the products with an excellent isolated yield up to 98%. This method performs efficiently, and would extent future applications of continuous organic, inorganic and biochemical reactions in green chemistry.\u0000</p><h3>Graphical Abstract</h3>\u0000 <figure><div><div><div><picture><source><img></source></picture></div></div></div></figure>\u0000 </div>","PeriodicalId":630,"journal":{"name":"Journal of Flow Chemistry","volume":"13 3","pages":"267 - 274"},"PeriodicalIF":2.7,"publicationDate":"2023-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://link.springer.com/content/pdf/10.1007/s41981-023-00263-3.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"4044726","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"5-Hydroxymethylfurfural synthesis from fructose over deep eutectic solvents in batch reactors and continuous flow microreactors","authors":"Chencong Ruan, Hero Jan Heeres, Jun Yue","doi":"10.1007/s41981-023-00262-4","DOIUrl":"10.1007/s41981-023-00262-4","url":null,"abstract":"<p>In this work, a deep eutectic solvent (DES) composed of choline chloride (ChCl) and ethylene glycol (EG) was prepared and applied for the conversion of fructose to 5-hydroxymethylfurfural (HMF), catalyzed by HCl in both laboratory batch reactors and continuous flow microreactors. The effects of reaction temperature, batch time, catalyst loading and molar ratio of ChCl to EG on the fructose conversion and HMF yield were first investigated in the monophasic batch system of ChCl/EG DES. To inhibit HMF-involved side reactions (e.g., its polymerization to humins), methyl isobutyl ketone (MIBK) was used as the extraction agent to form a biphasic system with DES in batch reactors. As a result, the maximum HMF yield could be enhanced at an MIBK to DES volume ratio of 3:1, e.g., increased from 48% in the monophasic DES (with a molar ratio ChCl to EG at 1:3) to 63% in the biphasic system at 80°C and 5 mol% of HCl loading. Based on the optimized results in batch reactors, biphasic experiments were conducted in capillary microreactors under slug flow operation, where a maximum HMF yield of <i>ca.</i> 61% could be obtained in 13 min, which is similar to that in batch under otherwise the same conditions. The slight mass transfer limitation in microreactors was confirmed by performing experiments with microreactors of varying length, and comparing the characteristic mass transfer time and reaction time, indicating further room for improvement.</p>","PeriodicalId":630,"journal":{"name":"Journal of Flow Chemistry","volume":"13 2","pages":"155 - 168"},"PeriodicalIF":2.7,"publicationDate":"2023-02-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://link.springer.com/content/pdf/10.1007/s41981-023-00262-4.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"4607263","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Milene M. Hornink, Beatriz G. Rodrigues, Caroline S. Santos, Leandro H. Andrade
{"title":"Continuous one-pot synthesis of new spiro-fused indoles from biobased building blocks using carbamoylation and imidation reactions under ultrasonic irradiation","authors":"Milene M. Hornink, Beatriz G. Rodrigues, Caroline S. Santos, Leandro H. Andrade","doi":"10.1007/s41981-023-00261-5","DOIUrl":"10.1007/s41981-023-00261-5","url":null,"abstract":"<div><p>The application of a flow reactor under ultrasonic irradiation enabled the fast synthesis of new spiro-fused indoles in a one-pot methodology. The exploitation of the reactivity of biobased building blocks, including acrylic acids and formamides, was essential to achieve such highly functionalized molecular targets. A four-step process with a 2–3 min residence time, and no aqueous work-up, created spiro[indoline-succinimides], spiro[indole-pyrrolo-succinimides] and spiro[indole-pyrido-succinimides] with high overall yields.</p><h3>Graphical Abstract</h3>\u0000 <figure><div><div><div><picture><source><img></source></picture></div></div></div></figure>\u0000 </div>","PeriodicalId":630,"journal":{"name":"Journal of Flow Chemistry","volume":"13 2","pages":"201 - 210"},"PeriodicalIF":2.7,"publicationDate":"2023-02-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://link.springer.com/content/pdf/10.1007/s41981-023-00261-5.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"4608223","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Correction to: The applications of organozinc reagents in continuous flow chemistry: Negishi coupling","authors":"Roop Varghese Rubert, Rony Rajan Paul","doi":"10.1007/s41981-023-00259-z","DOIUrl":"10.1007/s41981-023-00259-z","url":null,"abstract":"","PeriodicalId":630,"journal":{"name":"Journal of Flow Chemistry","volume":"13 1","pages":"73 - 73"},"PeriodicalIF":2.7,"publicationDate":"2023-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"4298229","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Effects of two-phase periodic velocity on droplet coalescence inside microchannels","authors":"Wen-qing Li, Xiao-juan Li, An-qi Guan, Zhi-jiang Jin, Jin-yuan Qian","doi":"10.1007/s41981-023-00258-0","DOIUrl":"10.1007/s41981-023-00258-0","url":null,"abstract":"<div><p>A novel method based on periodic change of two-phase velocity for the droplet coalescence in microchannels is proposed. The feasibility of the method is justified by investigating the droplet coalescence in several combinations of the velocity pairs. Once the droplet pairs have been generated, the frequency of the droplet coalescence can be divided into a liquid slug of continuous phase dominated region and a real velocity ratio dominated region. Since the liquid slug between the droplet pairs and the real velocity ratio of the droplet pairs are determined by the flow rate ratios, the critical value of the flow rate ratio is determined to distinguish whether the frequency of the droplet coalescence is liquid slug dominated or real velocity ratio dominated. Compared with the traditional passive method, the droplet pairs are alternatively generated by the periodic change of the two-phase velocity. The velocity gradient of the droplet pairs can be generated spontaneously which avoids the introduction of an expansion structure. The mixing performance inside the coalesced droplet is improved due to the reorganized inner circulation when the droplets is coalesced. The quantitative mixing of the reagents can be achieved to satisfy special application needs by a precise control of the volume of the droplet pairs.</p></div>","PeriodicalId":630,"journal":{"name":"Journal of Flow Chemistry","volume":"13 1","pages":"63 - 72"},"PeriodicalIF":2.7,"publicationDate":"2023-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"4294207","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Continuous dehydration of glycerol to Acrolein based on HPW/TS-COOH catalyzation","authors":"Chen-Xin Su, Jing-Jing Chen, Shao-Yun Wu, Shao-Heng Li, Shou-Quan Zhou, Hui-Dong Zheng, Fu-Weng Zhang","doi":"10.1007/s41981-023-00260-6","DOIUrl":"10.1007/s41981-023-00260-6","url":null,"abstract":"<div><p>Sustainable synthesis of acrolein, a key chemical intermediate, from biomass-derived glycerol is highly attractive. However, conventional catalysts for the dehydration of glycerol suffer from low acrolein selectivity and high deactivation tendency. Herein, a novel green catalyst (HPW/T<sub>0.6</sub> S-COOH) was prepared and employed in the dehydration of glycerol in a continuous flow reactor. The performance of different catalysts and the effects of reaction conditions (reaction temperature, N<sub>2</sub> flow rate, and glycerol concentration) were examined. The HPW/T<sub>0.6</sub> S-COOH catalyst provides the best glycerol conversion of 96.38% and acrolein selectivity of 92.01%. The NH<sub>3</sub>-TPD and pyridine-FTIR results indicate that the Brønsted acid site is more susceptible to acrolein, while the weak strength acid site effectively prevents the further reaction of acrolein, providing practical insights for the rational design of efficient and continuous synthesis of acrolein catalysts.</p></div>","PeriodicalId":630,"journal":{"name":"Journal of Flow Chemistry","volume":"13 2","pages":"143 - 154"},"PeriodicalIF":2.7,"publicationDate":"2023-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"4575192","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Lisa Schulz, Philipp Stähle, Sven Reining, Mathias Sawall, Norbert Kockmann, Thorsten Röder
{"title":"Multivariate curve resolution for kinetic modeling and scale-up prediction","authors":"Lisa Schulz, Philipp Stähle, Sven Reining, Mathias Sawall, Norbert Kockmann, Thorsten Röder","doi":"10.1007/s41981-022-00252-y","DOIUrl":"10.1007/s41981-022-00252-y","url":null,"abstract":"<p>An imine synthesis was investigated in a nearly isothermal oscillating segmented flow microreactor at different temperatures using non-invasive Raman spectroscopy. Multivariate curve resolution provided a calibration-free approach for obtaining kinetic parameters. The two different multivariate curve resolution approaches, soft and hard modeling, were applied and contrasted, leading to similar results. Taking heat and mass balance into account, the proposed kinetic model was applied for a model-based scale-up prediction. Finally, the reaction was performed in a 0.5 L semi-batch reactor, followed by in-line Raman spectroscopy and off-line gas chromatography analysis. The successful scale-up was demonstrated with a good agreement between measured and predicted concentration profiles.</p>","PeriodicalId":630,"journal":{"name":"Journal of Flow Chemistry","volume":"13 1","pages":"13 - 19"},"PeriodicalIF":2.7,"publicationDate":"2023-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://link.springer.com/content/pdf/10.1007/s41981-022-00252-y.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"4790674","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Continuous flow synthesis of phenyl glucosazone and its conversion to 2H-1,2,3-Triazole building blocks","authors":"Maria Molnar, Marcus Baumann","doi":"10.1007/s41981-022-00255-9","DOIUrl":"10.1007/s41981-022-00255-9","url":null,"abstract":"<div><p>A continuous flow approach for the generation of phenyl glucosazone from glucose and phenyl hydrazine is reported giving the pure target in 53% isolated yield. This thermal process generates the target product as an insoluble material that causes reactor fouling via adhering to the reactor walls. To overcome this issue a segmented flow approach was realised whereby streams of air and the reaction solution were combined in a T-piece and directed through the heated reactor coil. The resulting micro-mixing prevented reactor fouling and blocking and allowed for multi-hour reactions to generate the desired target in high yield. The value of the phenyl glucosazone product was demonstrated via its oxidative cyclisation into 2<i>H</i>-phenyl-1,2,3-triazoles which represent important heterocyclic scaffolds.\u0000</p></div>","PeriodicalId":630,"journal":{"name":"Journal of Flow Chemistry","volume":"13 2","pages":"211 - 215"},"PeriodicalIF":2.7,"publicationDate":"2023-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://link.springer.com/content/pdf/10.1007/s41981-022-00255-9.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"4649363","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"The applications of organozinc reagents in continuous flow chemistry: Negishi coupling","authors":"Roop Varghese Rubert, Rony Rajan Paul","doi":"10.1007/s41981-022-00253-x","DOIUrl":"10.1007/s41981-022-00253-x","url":null,"abstract":"<div><p>The design and implementation of flow technique helps organic chemists to resolve numerous challenges that are encountered during various catalytic reactions. Flow technologies, which offer solutions for technical and/or chemical issues, have gained popularity over the last two decades in the field of organic chemistry. The selectivity, efficiency, and safety of the entire process has been accelerated by flow reactors as they improve mass and heat transfer, speeds up the mixing of the reaction, and they offer exact control of the reaction parameters. This review mainly describes the utilization of flow chemistry in reactions involving organiozinc reagent, particularly Negishi coupling. The Negishi coupling of organozinc reagent is a valuable tool for the formation of C-C bond with functional group tolerance and are used extensively in total synthesis. This review also portrays a comparative study of organozinc reagents prepared using different procedures. A study of the effect of different catalysts over the same reaction is also carried out. An overview of different flow techniques that are employed has also been incorporated.</p></div>","PeriodicalId":630,"journal":{"name":"Journal of Flow Chemistry","volume":"13 3","pages":"217 - 246"},"PeriodicalIF":2.7,"publicationDate":"2023-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"4496032","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}