Reaction Chemistry & Engineering最新文献

{"title":"Review of hydrogen ortho–para conversion: experimental data and reaction kinetics†","authors":"Fuyu Jiao, Saif Al Ghafri, Keelan T. O'Neill, Paul S. Stanwix, Guinevere M. Sellner, Einar O. Fridjonsson, Neil Robinson, Eric F. May and Michael L. Johns","doi":"10.1039/D4RE00259H","DOIUrl":"10.1039/D4RE00259H","url":null,"abstract":"<p >Liquid hydrogen is a comparatively high volumetric energy density option for storage and transportation. It however typically requires refrigeration to ∼20 K, which incurs a substantial energy penalty. An additional contribution to this energy consumption is the required exothermic conversion between ortho- and para-hydrogen spin isomers. To realise this conversion in a practical timeframe, the use of a spin conversion catalyst is required. To this end, available reaction data in the literature for the ortho–para forward and backward reaction for the range of catalysts considered is summarised and reviewed. Furthermore, the application of a range of reaction kinetic expressions to this assembled data is considered. Available conversion data for ortho-para conversion is sparse, particularly in the temperature–pressure range relevant to hydrogen liquefaction processes. This is less the case for the reverse para–ortho conversion, presumably a consequence of these data being experimentally easier to access. It can also be concluded, based on the available conversion data, that there is currently no compelling reason to adopt anything more complex than first-order kinetics during hydrogen ortho–para conversion reactor design. Finally, a case study is executed which quantifies the sensitivity of this design to current reaction kinetic parameter uncertainty. This review highlights the sparsity of experimental conversion data at relevant cryogenic conditions and the need for a more comprehensive and fundamental understanding of the origins of the spin conversion catalyst effect and how it is impacted by various deactivation mechanisms.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 11","pages":" 2846-2862"},"PeriodicalIF":3.4,"publicationDate":"2024-08-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142177845","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":"Bayesian-optimization-based design of highly active and stable Fe–Cu/SSZ-13 catalysts for the selective catalytic reduction of NOx with NH3","authors":"Sanha Lim, Hwangho Lee, Hyun Sub Kim, Jun Seop Shin, Jong Min Lee and Do Heui Kim","doi":"10.1039/D4RE00327F","DOIUrl":"10.1039/D4RE00327F","url":null,"abstract":"<p >Catalysts for the selective catalytic reduction of nitrogen oxides (NO<small>_<em>x</em></small>) with NH<small>₃</small> are currently limited by low activity at low temperatures and deactivation under hydrothermal conditions. Herein, we developed a highly active and hydrothermally stable zeolite-based catalyst, Fe–Cu/SSZ-13, using Bayesian optimization (BO). An initial surrogate BO model was constructed and used to identify the optimal Cu and Fe composition through iterative experiments. At each step, the next candidate which optimized the objective function and maximized the acquisition function was selected. The optimized catalyst comprised 2.0 wt% Cu and 2.0 wt% Fe in SSZ-13 zeolite, which was prepared by an incipient wetness impregnation. This catalyst achieved 95.8% NO<small>_<em>x</em></small> conversion at 250 °C and excellent hydrothermal stability, which outperformed the commercial catalyst. Structural characterization demonstrated that its excellent hydrothermal stability resulted from the effect of optimized loading of Fe co-cation. This study highlights the effectiveness of employing BO to design multicomponent catalysts.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 11","pages":" 3029-3037"},"PeriodicalIF":3.4,"publicationDate":"2024-08-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142177847","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":"Modelling the impact of mass transport in a miniplant photoreactor†","authors":"Florian Gaulhofer, Henning Becker, Alexander Peschl and Dirk Ziegenbalg","doi":"10.1039/D4RE00192C","DOIUrl":"10.1039/D4RE00192C","url":null,"abstract":"<p >The scale-up of photoreactions posses challenges due to the non-linear coupling of the radiation field with reaction kinetics and mass transport. A knowledge-based scale-up requires a sufficiently detailed theoretical description of these processes. In this work, a transient, two-dimensional photoreactor model is proposed and used to systematically investigate mass transport limitations in photoreactors, including the effect of transversal mass transport through static mixers and the self-shading effect of the studied homogeneous photoisomerization of a spiropyrane. Simulation results of the proposed photoreactor model indicated that mass transport along the direction of light has a major impact. The transversal dispersion would be increased by a factor of 6 by the installation of static mixers, which would allow for a 1.27 fold increase in conversion in an up-scaled photoreactor. A shrinking of the reaction zone was identified when increasing the light power, eventually limiting the reactor performance. Furthermore, a model-based scale-up study emphasized the importance of mass transport for scaling photoreactors.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 12","pages":" 3231-3247"},"PeriodicalIF":3.4,"publicationDate":"2024-08-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/re/d4re00192c?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142177846","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":"Closed-loop identification of enzyme kinetics applying model-based design of experiments†","authors":"Leon Hennecke, Lucas Schaare, Mirko Skiborowski and Andreas Liese","doi":"10.1039/D4RE00127C","DOIUrl":"10.1039/D4RE00127C","url":null,"abstract":"<p >Accurate kinetic models for enzyme catalysed reactions are integral to process development and optimisation. However, the collection of useful kinetic data is heavily dependent on the experimental design and execution. In order to reduce the limitations associated with traditional statistical design and manual experiments, this study introduces an integrated, automated approach to identifying kinetic models based on model-based optimal experimental design. The immobilised formate dehydrogenase of <em>Candida boidinii</em> catalyses the enzymatic reduction of NAD<small>⁺</small> to NADH and is used as a model system. Continuous collection of UV/Vis data under steady-state conditions is employed to determine the kinetic parameters in a packed bed reactor. Automation of the experimental work was utilised in Python to compensate for the need for more time-consuming data collection. A completely automated closed-loop system was created and appropriate kinetic models for anticipating process dynamics were identified. The automated platform was able to identify the correct kinetic model out of eight candidate models with only 15 experiments. Further extension of the design space improved model discrimination and led to a properly parameterized kinetic model with sufficeintly high parameter precision for the conditions under examination.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 11","pages":" 2984-2993"},"PeriodicalIF":3.4,"publicationDate":"2024-08-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142177849","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":"Experimental and computational study of a packed bed bioreactor for the continuous production of succinic acid","authors":"Ioannis Zacharopoulos, Min Tao, Constantinos Theodoropoulos","doi":"10.1039/d4re00280f","DOIUrl":"https://doi.org/10.1039/d4re00280f","url":null,"abstract":"In this work we present a packed bed bioreactor system packed, with immobilised cells in sodium alginate beads, for the biological conversion of glycerol to succinic acid. We simulate this continuous bioreactor system by constructing a partial differential equation, multi-phase, convection-diffusionmodel, which uses the intrinsic kinetics for the fermentation of glycerol with A. succinogenes. The model is validated, by conducting a series of fermentation experiments at different operating conditions and is subsequently used to successfully predict the dynamics and the species profiles throughout the length of the bioreactor. The model is then exploited for optimising the continuous bioprocess. The computed optimal conditions are experimentally validated. The succinic acid concentration at the end effluent of the bioreactor reached 51.16 g/L, with the substrate being fully consumed. The maximum succinic acid productivity was calculated to be 2.15 g/L/h, a value which is the highest recorded for the bioproduction of succinic acid with glycerol.","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":"29 1","pages":""},"PeriodicalIF":3.9,"publicationDate":"2024-08-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142177848","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":"Current research status on the structural properties and modification of LiFePO4 cathode materials","authors":"Guo Xiaoying, Bao Yuanyuan, Li Wei, Zhao Siqin and Huang Chao","doi":"10.1039/D4RE00263F","DOIUrl":"10.1039/D4RE00263F","url":null,"abstract":"<p >With the current global economy developing at a rapid pace, research into lithium-ion batteries has become a focal point in many major areas. Lithium iron phosphate, also known as LiFePO<small>₄</small> or LFP, is one of the most promising cathode materials for commercial lithium batteries. Its advantages include low cost, environmental friendliness, long cycle life, good thermal stability, and more. Its high-rate charge–discharge capability is limited by its low electronic conductivity and lithium ion diffusion coefficient. Thus, this work describes the structural features of LiFePO<small>₄</small> cathode materials, focuses on their modification (coating, ion doping, morphological control methods), and concludes by anticipating the direction of future research in this field.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 11","pages":" 2830-2845"},"PeriodicalIF":3.4,"publicationDate":"2024-08-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142177885","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":"Optimization of reaction parameters for the synthesis of natural aroma esters by factorial design†","authors":"Adrian Ioan Dudu, Csaba Paizs and Monica Ioana Toşa","doi":"10.1039/D4RE00265B","DOIUrl":"10.1039/D4RE00265B","url":null,"abstract":"<p >In this study, the synthesis of aroma esters by the direct esterfication of carboxylic acids with aromatic alcohols mediated by lipase B from <em>Candida antarctica</em> encapsulated in a sol–gel matrix in a solvent-free system is presented. Vacuum was used in order to remove the resultant water. The reaction parameters were optimized by factorial design experiments considering four factors (acid excess, temperature, vacuum and time) on two levels. As a result, the conversions were significantly increased (for example, from an isolation yield of 49.4% to 94.3% for cinnamyl butyrate). A semi-preparative experiment was further set up for cinnamyl butyrate preparation. The green chemistry metrics, such as the <em>E</em>-factor of 4.76 and mass intensity of 6.04, demonstrated that the newly developed enzymatic process is suitable for industrial application based on green chemistry principles.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 11","pages":" 2994-3002"},"PeriodicalIF":3.4,"publicationDate":"2024-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/re/d4re00265b?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142177850","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":"Wireless μLED packed beds for scalable continuous multiphasic photochemistry†","authors":"Esai Daniel Lopez, Patricia Zhang Musacchio and Andrew R. Teixeira","doi":"10.1039/D4RE00241E","DOIUrl":"10.1039/D4RE00241E","url":null,"abstract":"<p >Photochemical and photocatalytic reactions are a powerful emerging tool in the green synthesis of organic molecules. In contrast to thermochemical reactions, they promise greater energy efficiency, milder reaction conditions, and a decrease in the number of synthesis steps. Unfortunately, conventional batch photochemical systems are not inherently scalable, making translation to industrial applications challenging. Fundamentally, this is most clearly attributed to the penetration depth of light, as constrained by the Beer–Lambert relationship: as the size of the reactor is increased, the depth of light penetration into liquid medium decreases exponentially. Small-diameter plug flow reactors with external illumination have recently been employed industrially to 1) transition photochemistry from batch to continuous flow, and 2) overcome light penetration challenges by employing millimeter-scale optical paths; however these often present with substantial pressure drops and scalability challenges. In this work, a fixed bed reactor is packed with wireless μLEDs (μLED-PBR) and engineered to scale the oxidation of α-terpinene using a homogeneous rose-bengal photosensitizer. Utilizing μLEDs as packing allows for internal volumetrically scalable illumination from 250 or 500 μLEDs. Not only is the μLED packing efficient at delivering photons, but it also statically induces turbulence and mixing of the biphasic streams within the reactor. Unlike tubular plug flow reactors, the μLED-PBR design is volumetrically scalable. During operation, a co-current trickle flow regime was established with a 29 μm liquid film flowing over the μLEDs. In stark contrast to those typical in small channel tubular flow reactors, the packed bed experienced negligible hydrodynamic pressure drop penalties. The photochemical space time yield of the reactor normalized to the power consumption for the μLED-PBR was three orders of magnitude greater than other externally illuminated thin film flow reactors for the same chemistry: 1411 mmol W<small>⁻¹</small> per day compared to 1.34 mmol W<small>⁻¹</small> per day.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 11","pages":" 2963-2974"},"PeriodicalIF":3.4,"publicationDate":"2024-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/re/d4re00241e?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142177851","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":"Dual jet-mixing reactor for fully continuous synthesis of core@shell Au@Ag nanocomposites†","authors":"Pinaki Ranadive, Faiz Khan, Jessica O. Winter and Nicholas Brunelli","doi":"10.1039/D3RE00417A","DOIUrl":"10.1039/D3RE00417A","url":null,"abstract":"<p >The wide-scale production of nanomaterials would benefit from scalable synthetic methods. One class of promising nanomaterials consists of a core@shell structure in which one type of material is used for the core and a second material is grown on the surface to produce a shell. Although these materials are commonly realized in batch, core@shell structures have not yet been widely translated to scalable manufacturing processes. In this work, we investigate the continuous flow synthesis of Au@Ag core@shell nanomaterials using sequential jet-mixing reactors (JMRs). Connecting the two JMRs overcomes challenges with particle instability when the processes are separated. Using synthesis conditions typical for batch methods in the JMR resulted in a non-uniform particle size distribution. Through investigating the synthesis conditions of the Au core, the key parameters affecting the synthesis of well-defined nanoparticles are identified as the concentration of the reducing agent and the inclusion of bovine-serum albumin (BSA) to limit particle aggregation. The concentration of the reducing agent is adjusted to achieve a high yield of Au NPs. The adjusted concentration enabled continuous synthesis of Au@Ag core@shell nanoparticles using BSA as the stabilizing ligand in a dual jet mixing reactor system. Overall, this work provides insights on integrating sequential processes for the synthesis of core@shell nanomaterials.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 11","pages":" 2915-2924"},"PeriodicalIF":3.4,"publicationDate":"2024-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/re/d3re00417a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141949281","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":"Environmental sustainability assessment as a driver for selection of the manufacturing processes of a bispecific T-cell engager","authors":"Monica Gabriela, Benjamin T. Smith, Bart Connors, Marc Leslie, Adam Hartwick, Kevin Gant and Margaret M. Faul","doi":"10.1039/D4RE00266K","DOIUrl":"10.1039/D4RE00266K","url":null,"abstract":"<p >A focus on environmental sustainability is important in selection of our commercial drug substance manufacturing processes. During clinical development of a bispecific T-cell engager (BITE) molecule we developed two processes to manufacture this important biologic: (1) a stirred tank process and (2) a continuous manufacturing process. We will describe the challenges and opportunities of developing and producing this novel biologic modality, while also minimizing the environmental impact. We will highlight the metrics and methods used to measure and improve the environmental performance of the processes, such as carbon emissions, water consumption, waste generation, and energy efficiency. The benefits of adopting a life-cycle management approach and leveraging continuous manufacturing technologies to enhance the sustainability of the process during development will be discussed and the results compared to the stir tank process to enable the identification of the optimal process for manufacturing of this innovative BITE molecule.</p>","PeriodicalId":101,"journal":{"name":"Reaction Chemistry & Engineering","volume":" 10","pages":" 2773-2783"},"PeriodicalIF":3.4,"publicationDate":"2024-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141949276","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}