Reaction Chemistry & Engineering最新文献

{"title":"Experimental study on the leaching effect of different chelating agents on the constant metal ions of lignite","authors":"Dawei Chen, Jun Xie, Jingyi Zhang, Yi Wang and Faquan Wang","doi":"10.1039/D4RE00257A","DOIUrl":"10.1039/D4RE00257A","url":null,"abstract":"<p >Chelating agents can increase the porosity of coal by leaching metal ions from it. Therefore, selecting the most suitable chelating agent based on the characteristics of the coal type is crucial when applying chelating agents. In this study, lignite from southwest China was chosen as the sample. Four chelating agents, namely tetrasodium iminodisuccinate (IDS), diethylenetriaminepentaacetic acid (DTPA), tetrasodium aspartate diacetate (ASDA), and tetrasodium glutamate diacetate (GLDA), were evaluated for their impact on the leaching of constant metal ions (CMIs). The leaching effect of CMIs was characterized and analyzed using inductively coupled plasma, scanning electron microscopy, and Brunauer–Emmett–Teller measurements. The results indicated that the ASDA chelating agent was the most effective in leaching Ca<small>²⁺</small>, Mg<small>²⁺</small>, Fe<small>^2+/3+</small>, and Al<small>³⁺</small>. Under the optimal concentration condition of 2500 mg L<small>⁻¹</small>, the leaching effect of CMIs from different chelating agents could be ranked as: ASDA &gt; DTPA &gt; IDS &gt; GLDA. The contact angle of the ASDA chelating agent with the coal sample decreased from 48.2° at 1 s to 26.5° at 20 s. The metal minerals on the surface of the coal dissolved under the action of the ASDA chelating agent, and the micropores on the coal surface transitioned to mesopores and macropores. The pore volume of coal samples increased from 0.0254 cm<small>³</small> g<small>⁻¹</small> to 0.0276 cm<small>³</small> g<small>⁻¹</small>, and the pore size increased from 3.26 nm to 4.06 nm. As the pore size of the coal increased, the permeability also significantly increased.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 9","pages":" 2489-2504"},"PeriodicalIF":3.4,"publicationDate":"2024-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141573551","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":"Scalable preparation of macroporous collagen microgels by air bubble-induced breakup and ice templating†","authors":"Sushant Singh, Wing Yan Chu, Rojin Ostadsharif Memar, Andrew De Carlo, Teodor Veres and Axel Günther","doi":"10.1039/D3RE00595J","DOIUrl":"10.1039/D3RE00595J","url":null,"abstract":"<p >Collagen I, the most abundant protein of the extracellular matrix, has found widespread use in three-dimensional cell culture, and increasingly also in bioprinting and biofabrication applications. However, several limitations remain, such as the capacity to locally recapitulate the multiscale organization of collagen in native tissues. Bioprinting cellular collagen structures with high feature fidelity so far either requires a more rapidly gelling biopolymer to be added or an acellular collagen structure to be defined before the delivery of cells. Here, we report the flow synthesis of macroporous collagen microgels (MCMs) that serve as building blocks for granular bioinks. Obtained bioinks offer excellent printability, provide an avenue to faithfully recapitulate the multiscale collagen organization of native tissues, and overcome the aforementioned limitations. Viscous collagen solutions with concentrations as high as 10 mg ml<small>⁻¹</small> are consistently converted into droplets using a parallelized microfluidic device <em>via</em> air bubble induced droplet breakup into a continuous oil phase. MCMs are obtained by inducing gelation, oil removal, and washing, and incorporating internal pores of tunable size <em>via</em> ice templating at freezing rates between 0.1 and 10 °C min<small>⁻¹</small>. Independent control over the MCM diameter (175–250 μm) and porosity (58–76%) allows the extracellular matrix structure to be tailored to different tissue engineering applications. The wall structures within MCMs share similarities with the highly compacted and recapitulated collagen porosity in native tissues. This approach in the future can be used to 3D print more complicated biomimetic structures that require cell positioning during printing.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 10","pages":" 2584-2598"},"PeriodicalIF":3.4,"publicationDate":"2024-07-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141530555","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 multiscale investigation of polypropylene glycol polymer upcycling to propionaldehyde via catalytic cracking on acid sites of mesoporous Y zeolites†","authors":"Abraham Martinez, Kanan Shikhaliyev, Xuemin Li, Jinyi Han, Kaustav Chaudhuri, Son-Jong Hwang, Jagoda M. Urban-Klaehn, Alexander Kuperman, Anne Gaffney, Jochen Lauterbach and Alexander Katz","doi":"10.1039/D4RE00001C","DOIUrl":"10.1039/D4RE00001C","url":null,"abstract":"<p >We investigate acid-catalyzed upcycling of PPG polymer, emphasizing crucial features on multiple length scales that span reaction engineering on macroscopic length scales down to zeolite catalyst design on the nanoscale. We modified a previously described semi-batch reactor configuration to minimize coking and enhance recovered selectivities by incorporating rapid quenching of reaction products (instead of slower quenching with a condenser, which facilitates sequential coupling reactions), and decreased the initial carrier-gas residence time in the bed consisting of mixed catalyst and PPG polymer, further reducing the deposition of solid residues in the used catalyst. Our results highlight the importance of tight interfacial contact between the catalyst surface and the initial PPG polymer reactant, which is achieved <em>via</em> a pretreatment that removes adsorbed water, for drastically increasing the propionaldehyde selectivity, particularly for the large surface-area mesoporous catalysts. Our best catalyst consisted of mesoporous Y zeolite synthesized at an alkalinity of 0.16 M and exhibited nearly the same high propionaldehyde selectivity of approximately 95% (86% propionaldehyde yield) for a PPG polymer with molecular weights of 425 and 2000 Daltons (Da), suggesting the absence of mass transport restrictions. We also deconvolute the catalyst attribute between extra-framework aluminum (Al<small>_EF</small>) content and mesopore external surface area that most sensitively controlled propionaldehyde selectivity. This was performed by synthetically incorporating Al<small>_EF</small> content into our optimum catalyst, at a high and low alumina dispersion. The high dispersion alumina catalyst consisted of a uniform 10 nm-thick alumina layer covering the interior pores of the mesoporous Y catalyst, whereas the low dispersion alumina catalyst had a completely phase-separated alumina phase, commensurate in size to the zeolite particles. Our results demonstrate that Al<small>_EF</small> content in the catalyst decreases propionaldehyde yield by increasing the amount of solid residues in the catalyst post reaction, and had a minor effect on the propionaldehyde selectivity. These results point to a Brønsted rather than Lewis acid-catalyzed mechanism of catalysis for PPG polymer upcycling to propionaldehyde. In summary, our study demonstrates the most sensitive controlling attribute of the zeolite catalyst for selective propionaldehyde synthesis is its mesoporosity (as reflected in the mesopore volume and surface area) and that the multiscale details of the catalyst and reactor design also have profound consequences in achieving high propionaldehyde selectivity and yield.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 9","pages":" 2469-2482"},"PeriodicalIF":3.4,"publicationDate":"2024-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141504212","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":"Autonomous reaction self-optimization using in-line high-field NMR spectroscopy†","authors":"Nour El Sabbagh, Margherita Bazzoni, Yuliia Horbenko, Aurélie Bernard, Daniel Cortés-Borda, Patrick Giraudeau, François-Xavier Felpin and Jean-Nicolas Dumez","doi":"10.1039/D4RE00270A","DOIUrl":"10.1039/D4RE00270A","url":null,"abstract":"<p >Autonomous self-optimization in flow is a powerful approach to efficiently optimize chemical transformations in a high dimensional space. Self-optimizing flow reactors combine automated flow devices with feedback optimization algorithms, which are powered by process analytical technology. In this contribution, we introduce the concept of autonomous self-optimizing flow reactors guided by in-line high-field NMR spectroscopy. We designed an autonomous experimental setup, combining an automated flow reactor with a high-field NMR spectrometer and a feedback optimization algorithm. User-friendly interfaces were developed for straightforward input of experimental parameters and precise control of equipment. Using 1D <small>¹</small>H NMR spectroscopy with a solvent suppression method, we achieved accurate quantitative measurements. Self-optimization utilizing the Nelder–Mead algorithm to maximize either the yield or the throughput of a formal [3 + 3] cycloaddition was conducted through the fine-tuning of the residence time, stoichiometry, and catalyst loading as input variables. The integration of high-field NMR within autonomous flow systems promises enhanced precision and efficiency in chemical synthesis optimization, particularly for complex reaction mixtures, setting the stage for advances in chemical synthesis.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 10","pages":" 2599-2609"},"PeriodicalIF":3.4,"publicationDate":"2024-06-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141504213","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":"Efficient synthesis of glycerol carbonate over a commercially available 4A molecular sieve via an integrated vacuum reactive distillation process†","authors":"Jiayin Huang, Anwei Wang, Chunsheng Zhao, Yu Fan, Shanshan Cao, Zheng Tian and Weiyou Zhou","doi":"10.1039/D4RE00213J","DOIUrl":"10.1039/D4RE00213J","url":null,"abstract":"<p >Various heterogeneous catalysts have been investigated in the transesterification of glycerol with ethylene carbonate to glycerol carbonate in a batch reactor, and a commercially available 4A molecular sieve exhibited relatively high catalytic performance for its surface strong basic and acidic sites. Further, an integrated vacuum reactive distillation process was developed for the transesterification in the presence of the 4A molecular sieve. The produced ethylene glycol could be efficiently removed from the reaction system to overcome the equilibrium, and excellent glycerol conversion (99%) and glycerol carbonate selectivity (&gt;99%) were obtained under the optimal reaction conditions. The recycling and the scale-up experiments demonstrate the excellent practical potential of the present process, thus providing an efficient reaction process for the preparation of glycerol carbonate.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 9","pages":" 2452-2459"},"PeriodicalIF":3.4,"publicationDate":"2024-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141504149","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":"Understanding heterogeneous growth mechanisms at graphene edges: a theoretical study on acetylene deposition and mechanistic analysis†","authors":"C. Giudici, G. Contaldo, M. Ferri, L. Pratali Maffei, M. Bracconi, M. Pelucchi and M. Maestri","doi":"10.1039/D4RE00096J","DOIUrl":"10.1039/D4RE00096J","url":null,"abstract":"<p >This study aims to bridge significant knowledge gaps in the understanding of graphene growth mechanisms. We enhance current kinetic models through a detailed investigation of C<small>₂</small>H<small>₂</small> deposition processes on solid graphene surfaces. These processes represent key elementary reaction steps in the complex heterogeneous network responsible for pyrocarbon formation during chemical vapor deposition and infiltration processes. Unlike previous methodologies that relied on analogies with gas-phase systems, our research meticulously explored the actual system, providing a comprehensive overview of the reactions involved in graphene growth at both armchair and zigzag edges. Utilizing transition state theory, we calculate accurate, temperature-dependent rate constants for all elementary reactions in graphene edge growth. This sheds light on the mechanisms and kinetics of pyrocarbon growth, including the potential for structural defect formation. Findings are compared with analogous gas-phase reactions responsible for soot particle formation, assessing the impact of surface interactions. A lumping technique is applied to reduce the complexity of species and reactions while preserving the accuracy of the chemical description. As such, this approach offers valuable insights into relevant pathways paving the way towards a deep understanding of the chemistry of the pyrolysis of hydrocarbons aiming to produce nanomaterials with targeted properties.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 9","pages":" 2505-2519"},"PeriodicalIF":3.4,"publicationDate":"2024-06-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/re/d4re00096j?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141504214","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":"Optimization of parameters during phosphoric acid production using response surface methodology: toward a biomimetic process†","authors":"Mehdi Abdelouahhab, Sliman Manar and Rachid Benhida","doi":"10.1039/D4RE00150H","DOIUrl":"10.1039/D4RE00150H","url":null,"abstract":"<p >In order to improve the performance and efficiency of a process, understanding the influence of various variables on a desired output or response is a common task in engineering challenges. This paper aims to investigate the effect of three parameters – namely the free H<small>₂</small>SO<small>₄</small> rate, the solid rate, and the percentage of P<small>₂</small>O<small>₅</small> in the ranges of 2.4–5.8%, 32–37%, and 28–32%, respectively – on the reactive crystallization phase during the phosphoric acid production. The experiments were carried out using a filterability workbench and a semi-continuous reactor that replicated the operating conditions of the dihydrate process. The investigation conducted using the factorial and Box–Behnken methods enabled the optimization and determination of operational significant conditions affecting the filterability of the phosphoric slurry to be thoroughly evaluated and controlled. Overall, response surface methodology (RSM) has several advantages over classical one-variable-at-a-time optimization, including the ability to assess the interaction effect between variables on the response of interest and the ability to generate large amounts of data from a limited number of experiments. Furthermore, the desirability function approach has been successfully implemented for the identification of the optimal conditions, and phosphogypsum crystals offering high and low filterabilities were characterized and compared. Finally, we anticipate that our paper will serve as a foundation for the explanation of how the natural giant gypsum crystals of Naica and Pulpí were formed.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 9","pages":" 2436-2451"},"PeriodicalIF":3.4,"publicationDate":"2024-06-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141504215","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 synthesis of hexanitrostilbene using a difunctional electrochemical reactor†","authors":"Yuqiu Wang, Guangyuan Zhang, Shuaijie Jiang, Ming Lu and Pengcheng Wang","doi":"10.1039/D4RE00110A","DOIUrl":"10.1039/D4RE00110A","url":null,"abstract":"<p >The adoption of electrochemical reactors has effectively mitigated the environmentally detrimental challenges in industrial manufacturing processes. A novel method for the eco-friendly synthesis of hexanitrostilbene using a difunctional electrochemical reactor is introduced, facilitating effective blending of feedstock and transformation of C–C bonds into C<img>C bonds simultaneously. The effectiveness has been confirmed by significant improvements in yield, increasing from 36% to 58.5% when exposed to 8 mA current for 30 min. Moreover, the purity rose from 86% to 98.2%, accompanied by a notable elevation in the decomposition temperature of hexanitrostilbene.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 9","pages":" 2419-2426"},"PeriodicalIF":3.4,"publicationDate":"2024-06-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141513508","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":"Automated self-optimization of continuous crystallization of nirmatrelvir API†","authors":"Kakasaheb Y. Nandiwale, Robert P. Pritchard, Cameron T. Armstrong, Steven M. Guinness and Kevin P. Girard","doi":"10.1039/D4RE00272E","DOIUrl":"10.1039/D4RE00272E","url":null,"abstract":"<p >Continuous flow crystallization is an attractive mode of operation, due to its ability to generate consistent product quality while requiring a smaller footprint and lower production costs than its batch counterpart. We present a novel combination of a custom/in-house automated continuous crystallization platform integrated with self-optimization algorithms. We demonstrate the automated optimization of continuous crystallization of nirmatrelvir (PF-07321332), one of the active ingredients in Paxlovid™, a potent, selective, and orally bioavailable inhibitor of SARS-CoV-2 M<small>^pro</small>. The continuous crystallization platform consists of three mixed suspension mixed product removal (MSMPR) crystallizers in series and includes an in-house designed automation user interface integrated with lab equipment. The platform also has an iterative design of experiments (DoE) based on mixed-integer nonlinear programming (MINLP) self-optimization algorithms. We implement automated controls for the lab equipment, including a flow sonication cell as the nucleation device, feed pumps, temperature controller units (TCUs), thermocouples, pressure sensors, stirrers, and coriolis mass flow meters. We enable integration of variety of <em>in situ</em> process analytical technologies (PATs) <em>via</em> open platform communications unified architecture (OPC UA), including Mettler Toledo ParticleTrack™ with FBRM® (Focused Beam Reflectance Measurement) technology and Blaze™ Metrics imaging probe for the data visualization and real time process understanding.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 9","pages":" 2460-2468"},"PeriodicalIF":3.4,"publicationDate":"2024-06-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141530556","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":"Design and preparation of four-component eutectogels as a green and efficient catalyst for the one-pot multi-component synthesis of 1,2,4,5-tetrasubstituted and 2,4,5-trisubstituted imidazole derivatives under solvent-free conditions†","authors":"Phat Ngoc Nguyen, Trung-Nhan Dong Tran, Nhat Minh Nguyen, Viet-Hoang Nguyen Le, Linh Dieu Nguyen, Phuong Hoang Tran and Hai Truong Nguyen","doi":"10.1039/D4RE00169A","DOIUrl":"10.1039/D4RE00169A","url":null,"abstract":"<p >In the past few years, there has been a prominent surge in the exploration of the synthesis of imidazole derivatives in synthetic organic chemistry. This growing interest arises from the wide range of potential applications offered by these compounds across various fields, encompassing industrial chemistry, pharmaceuticals, and medicinal chemistry. This study demonstrates an innovative synthesis of four-component eutectogels (ETGs), in particular ETG-Zr<small>⁴⁺</small>, for the production of imidazole derivatives. The ETG-Zr<small>⁴⁺</small> catalyst was characterized using FT-IR spectroscopy, SEM, TGA, and XRD, demonstrating its potential as a sustainable catalyst for the synthesis of poly-functionalized imidazole derivatives. The application of ETG-Zr<small>⁴⁺</small> as a catalyst afforded 1,2,4,5-tetraphenyl-1<em>H</em>-imidazole derivatives in 70–92% yields and 2,4,5-trisubstituted imidazole derivatives in 61–76% yields. Notably, the catalyst exhibits the advantage of reusability and promotes eco-friendly approaches <em>via</em> a one-pot, multi-component reaction pathway.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 9","pages":" 2393-2410"},"PeriodicalIF":3.4,"publicationDate":"2024-06-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141504216","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}