Irene Martínez-Salazar, Ana Orozco-Saumell, M. López Granados, R. Mariscal
The synthesis of dimethyl adipate (DAP), a stable configuration of adipic acid, from biomass-derived cyclopentanone (CPO) and dimethyl carbonate (DMC) constitutes an attractive greener route than petroleum-based industrial processes. Solid basic catalysts such as MgO, Mg5(CO3)4(OH)2·4H2O, KOCH3 and Ca(OCH3)2 have been used achieving a DAP yield up to 30% at 533 K. In addition to the type of catalyst, other operating conditions such as the substrate, reaction time, temperature and CPO concentration have been studied. The methylation of DAP and CPO and the self-aldol condensation of CPO to form dimers and oligomers are reactions that occur in parallel with the production of DAP. It has been established that the main challenge is the self-aldol condensation of CPO. It has been identified that at short reaction times, to prevent methylation, and at dilute concentrations, to avoid CPO self-condensation, the DAP formation rate is much higher than these other competitive reactions. Finally, it should be noted that a DAP productivity up to 3.45 g·gcat−1·h−1 has been achieved under mild conditions.
{"title":"Catalytic Conversion of Cyclopentanone into Dimethyl Adipate over Solid Basic Catalysts with Dimethyl Carbonate","authors":"Irene Martínez-Salazar, Ana Orozco-Saumell, M. López Granados, R. Mariscal","doi":"10.3390/catal14010086","DOIUrl":"https://doi.org/10.3390/catal14010086","url":null,"abstract":"The synthesis of dimethyl adipate (DAP), a stable configuration of adipic acid, from biomass-derived cyclopentanone (CPO) and dimethyl carbonate (DMC) constitutes an attractive greener route than petroleum-based industrial processes. Solid basic catalysts such as MgO, Mg5(CO3)4(OH)2·4H2O, KOCH3 and Ca(OCH3)2 have been used achieving a DAP yield up to 30% at 533 K. In addition to the type of catalyst, other operating conditions such as the substrate, reaction time, temperature and CPO concentration have been studied. The methylation of DAP and CPO and the self-aldol condensation of CPO to form dimers and oligomers are reactions that occur in parallel with the production of DAP. It has been established that the main challenge is the self-aldol condensation of CPO. It has been identified that at short reaction times, to prevent methylation, and at dilute concentrations, to avoid CPO self-condensation, the DAP formation rate is much higher than these other competitive reactions. Finally, it should be noted that a DAP productivity up to 3.45 g·gcat−1·h−1 has been achieved under mild conditions.","PeriodicalId":9794,"journal":{"name":"Catalysts","volume":null,"pages":null},"PeriodicalIF":3.9,"publicationDate":"2024-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139610173","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}
Ningning Zhang, Pablo Domínguez de María, Selin Kara
Biocatalysis holds immense potential for pharmaceutical development as it enables synthetic routes to various chiral building blocks with unparalleled selectivity. Therein, solvent and water use account for a large contribution to the environmental impact of the reactions. In the spirit of Green Chemistry, a transition from traditional highly diluted aqueous systems to intensified non-aqueous media to overcome limitations (e.g., water shortages, recalcitrant wastewater treatments, and low substrate loadings) has been observed. Benefiting from the spectacular advances in various enzyme stabilization techniques, a plethora of biotransformations in non-conventional media have been established. Deep eutectic solvents (DESs) emerge as a sort of (potentially) greener non-aqueous medium with increasing use in biocatalysis. This review discusses the state-of-the-art of biotransformations in DESs with a focus on biocatalytic pathways for the synthesis of active pharmaceutical ingredients (APIs). Representative examples of different enzyme classes are discussed, together with a critical vision of the limitations and discussing prospects of using DESs for biocatalysis.
生物催化在医药开发方面具有巨大的潜力，因为它能以无与伦比的选择性合成各种手性构件。其中，溶剂和水的使用对反应的环境影响很大。本着绿色化学的精神，人们已经从传统的高度稀释水性体系过渡到强化的非水性介质，以克服各种限制（如水资源短缺、难处理的废水处理和低底物负荷）。得益于各种酶稳定技术的巨大进步，在非常规介质中进行生物转化的方法层出不穷。深共晶溶剂（DES）作为一种（潜在的）更环保的非水介质，在生物催化中的应用越来越广泛。本综述讨论了 DESs 中生物转化的最新进展，重点是合成活性药物成分 (API) 的生物催化途径。文中讨论了不同酶类的代表性实例，并对使用 DES 进行生物催化的局限性进行了深入探讨，同时还讨论了使用 DES 进行生物催化的前景。
{"title":"Biocatalysis for the Synthesis of Active Pharmaceutical Ingredients in Deep Eutectic Solvents: State-of-the-Art and Prospects","authors":"Ningning Zhang, Pablo Domínguez de María, Selin Kara","doi":"10.3390/catal14010084","DOIUrl":"https://doi.org/10.3390/catal14010084","url":null,"abstract":"Biocatalysis holds immense potential for pharmaceutical development as it enables synthetic routes to various chiral building blocks with unparalleled selectivity. Therein, solvent and water use account for a large contribution to the environmental impact of the reactions. In the spirit of Green Chemistry, a transition from traditional highly diluted aqueous systems to intensified non-aqueous media to overcome limitations (e.g., water shortages, recalcitrant wastewater treatments, and low substrate loadings) has been observed. Benefiting from the spectacular advances in various enzyme stabilization techniques, a plethora of biotransformations in non-conventional media have been established. Deep eutectic solvents (DESs) emerge as a sort of (potentially) greener non-aqueous medium with increasing use in biocatalysis. This review discusses the state-of-the-art of biotransformations in DESs with a focus on biocatalytic pathways for the synthesis of active pharmaceutical ingredients (APIs). Representative examples of different enzyme classes are discussed, together with a critical vision of the limitations and discussing prospects of using DESs for biocatalysis.","PeriodicalId":9794,"journal":{"name":"Catalysts","volume":null,"pages":null},"PeriodicalIF":3.9,"publicationDate":"2024-01-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139612368","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}
E. M. Cepollaro, S. Cimino, M. D'Agostini, Nicola Gargiulo, G. Franchin, L. Lisi
Monoliths manufactured by Direct Ink Writing containing 60% SSZ-13 (SiO2/Al2O3 = 23) and SiO2 with 10% laponite as a binder were investigated as self-standing structured catalysts for NH3-SCR of NOx after a short (4 h) and prolonged (24 h) ion exchange with copper and then compared with pure SSZ-13 exchanged under the same conditions. The catalysts were characterized by morphological (XRD and SEM), textural (BET and pore size distribution), chemical (ICP-MS), red-ox (H2-TPR), and surface (NH3-TPD) analyses. The silica-based binder uniformly covered the SSZ-13 particles, and copper was uniformly distributed as well. The main features of the pure Cu-exchanged SSZ-13 zeolite were preserved in the composite monoliths with a negligible contribution of the binder fraction. NH3-SCR tests, carried out on both monolithic and powdered samples in the temperature range of 70–550 °C, showed that composite monoliths provided very good activity, and that the intrinsic activity of SSZ-13 was enhanced by the hierarchical structure of the composite material.
{"title":"3D-Printed Monoliths Based on Cu-Exchanged SSZ-13 as Catalyst for SCR of NOx","authors":"E. M. Cepollaro, S. Cimino, M. D'Agostini, Nicola Gargiulo, G. Franchin, L. Lisi","doi":"10.3390/catal14010085","DOIUrl":"https://doi.org/10.3390/catal14010085","url":null,"abstract":"Monoliths manufactured by Direct Ink Writing containing 60% SSZ-13 (SiO2/Al2O3 = 23) and SiO2 with 10% laponite as a binder were investigated as self-standing structured catalysts for NH3-SCR of NOx after a short (4 h) and prolonged (24 h) ion exchange with copper and then compared with pure SSZ-13 exchanged under the same conditions. The catalysts were characterized by morphological (XRD and SEM), textural (BET and pore size distribution), chemical (ICP-MS), red-ox (H2-TPR), and surface (NH3-TPD) analyses. The silica-based binder uniformly covered the SSZ-13 particles, and copper was uniformly distributed as well. The main features of the pure Cu-exchanged SSZ-13 zeolite were preserved in the composite monoliths with a negligible contribution of the binder fraction. NH3-SCR tests, carried out on both monolithic and powdered samples in the temperature range of 70–550 °C, showed that composite monoliths provided very good activity, and that the intrinsic activity of SSZ-13 was enhanced by the hierarchical structure of the composite material.","PeriodicalId":9794,"journal":{"name":"Catalysts","volume":null,"pages":null},"PeriodicalIF":3.9,"publicationDate":"2024-01-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139611904","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}
Today, the problem of CO2 emission into the atmosphere is one of the most urgent and complex challenges facing humanity [...]
今天，向大气层排放二氧化碳的问题是人类面临的最紧迫、最复杂的挑战之一 [...]
{"title":"CO2 Capture, Utilization and Storage: Catalysts Design","authors":"L. Liotta, Hongjing Wu","doi":"10.3390/catal14010080","DOIUrl":"https://doi.org/10.3390/catal14010080","url":null,"abstract":"Today, the problem of CO2 emission into the atmosphere is one of the most urgent and complex challenges facing humanity [...]","PeriodicalId":9794,"journal":{"name":"Catalysts","volume":null,"pages":null},"PeriodicalIF":3.9,"publicationDate":"2024-01-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139616061","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}
In electrocatalytic processes, traditional powder/film electrodes inevitably suffer from damage or deactivation, reducing their catalytic performance and stability. In contrast, self-healing electrocatalysts, through special structural design or composition methods, can automatically repair at the damaged sites, restoring their electrocatalytic activity. Here, guided by Pourbaix diagrams, foam metal was activated by a simple cyclic voltammetry method to synthesize metal clusters dispersion solution (MC/KOH). The metal clusters-modified hydroxylated Ni-Fe oxyhydroxide electrode (MC/NixFeyOOH) by a facile Ni-Fe metal–organic framework-reconstructed strategy, exhibiting superior performance toward the oxygen evolution reaction (OER) in the mixture of MC/KOH and saline–alkali water (MC/KOH+SAW). Specifically, using a nickel clusters-modified hydroxylated Ni-Fe oxyhydroxide electrode (NC/NixFeyOOH) for OER, the NC/NixFeyOOH catalyst has an ultra-low overpotential of 149 mV@10 mA cm−2, and durable stability of 100 h at 500 mA cm−2. By coupling this OER catalyst with an efficient hydrogen evolution reaction catalyst, high activity and durability in overall SAW splitting is exhibited. What is more, benefiting from the excellent fluidity, flexibility, and enhanced catalytic activity effect of the liquid NC, we demonstrate a self-healing electrocatalysis system for OER operated in the flowing NC/(KOH+SAW). This strategy provides innovative solutions for the fields of sustainable energy and environmental protection.
在电催化过程中，传统的粉末/薄膜电极不可避免地会受到损伤或失活，从而降低其催化性能和稳定性。相比之下，自修复电催化剂通过特殊的结构设计或组成方法，可以自动修复受损部位，恢复其电催化活性。在此，我们以 Pourbaix 图为指导，通过简单的循环伏安法活化泡沫金属，合成了金属簇分散液（MC/KOH）。在 MC/KOH 和盐碱水（MC/KOH+SAW）的混合液中，金属簇改性的羟基化 Ni-Fe 氧氢氧化物电极（MC/NixFeyOOH）在氧进化反应（OER）中表现出卓越的性能。具体来说，使用镍簇修饰的羟基化氢氧化镍铁电极（NC/NixFeyOOH）进行氧进化反应，NC/NixFeyOOH 催化剂具有 149 mV@10 mA cm-2 的超低过电位，并且在 500 mA cm-2 下具有 100 小时的持久稳定性。通过将这种 OER 催化剂与高效的氢进化反应催化剂耦合，可在整个声表面波裂解过程中表现出高活性和耐久性。此外，得益于液态 NC 卓越的流动性、灵活性和更强的催化活性效果，我们展示了一种在流动 NC/(KOH+SAW) 中运行的 OER 自修复电催化系统。这一策略为可持续能源和环境保护领域提供了创新解决方案。
{"title":"A Cluster-Type Self-Healing Catalyst for Stable Saline–Alkali Water Splitting","authors":"Haiming Wang, Sheng Chen","doi":"10.3390/catal14010081","DOIUrl":"https://doi.org/10.3390/catal14010081","url":null,"abstract":"In electrocatalytic processes, traditional powder/film electrodes inevitably suffer from damage or deactivation, reducing their catalytic performance and stability. In contrast, self-healing electrocatalysts, through special structural design or composition methods, can automatically repair at the damaged sites, restoring their electrocatalytic activity. Here, guided by Pourbaix diagrams, foam metal was activated by a simple cyclic voltammetry method to synthesize metal clusters dispersion solution (MC/KOH). The metal clusters-modified hydroxylated Ni-Fe oxyhydroxide electrode (MC/NixFeyOOH) by a facile Ni-Fe metal–organic framework-reconstructed strategy, exhibiting superior performance toward the oxygen evolution reaction (OER) in the mixture of MC/KOH and saline–alkali water (MC/KOH+SAW). Specifically, using a nickel clusters-modified hydroxylated Ni-Fe oxyhydroxide electrode (NC/NixFeyOOH) for OER, the NC/NixFeyOOH catalyst has an ultra-low overpotential of 149 mV@10 mA cm−2, and durable stability of 100 h at 500 mA cm−2. By coupling this OER catalyst with an efficient hydrogen evolution reaction catalyst, high activity and durability in overall SAW splitting is exhibited. What is more, benefiting from the excellent fluidity, flexibility, and enhanced catalytic activity effect of the liquid NC, we demonstrate a self-healing electrocatalysis system for OER operated in the flowing NC/(KOH+SAW). This strategy provides innovative solutions for the fields of sustainable energy and environmental protection.","PeriodicalId":9794,"journal":{"name":"Catalysts","volume":null,"pages":null},"PeriodicalIF":3.9,"publicationDate":"2024-01-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139613728","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}
Although the catalytic pyrolysis of low-density polyethylene (LDPE) to produce light olefin has shown potential industrial application advantages, it has generally suffered when using higher pyrolysis temperatures. In this work, Mg-modified Fe-ZSM-5 was used for catalytic conversion of LDPE to obtain light olefin in a fixed bed reactor. The effects of catalyst types, pyrolysis temperatures, and Mg loading on the yield of light olefin were investigated. The 1 wt% Mg loading slightly improved the yield of light olefin to 38.87 wt% at 395 °C, lowering the temperature of the pyrolysis reaction. We considered that the higher light olefin yield of Fe-Mg-ZSM-5 was attributed to the introduction of Mg, where Mg regulated the surface acidity of the catalyst, inhibited the secondary cracking reaction, and reduced coking during the pyrolysis process. Furthermore, the addition of Mg also dramatically reduced the average particle size of Fe oxides from 40 nm to 10 nm, which is conducive to a lower catalytic reaction temperature. Finally, the spent catalyst could be easily regenerated at the conditions of 600 °C in airflow with a heating rate of 10 °C/min for 1 h, and the light olefin yield remained higher than 36.71 wt% after five cycles, indicating its excellent regeneration performance.
{"title":"Surface Modification of Fe-ZSM-5 Using Mg for a Reduced Catalytic Pyrolysis Temperature of Low-Density Polyethylene to Produce Light Olefin","authors":"Yincui Li, Ting Liu, S. Deng, Xiao Liu, Qian Meng, Mengxue Tang, Xueying Wu, Huawei Zhang","doi":"10.3390/catal14010078","DOIUrl":"https://doi.org/10.3390/catal14010078","url":null,"abstract":"Although the catalytic pyrolysis of low-density polyethylene (LDPE) to produce light olefin has shown potential industrial application advantages, it has generally suffered when using higher pyrolysis temperatures. In this work, Mg-modified Fe-ZSM-5 was used for catalytic conversion of LDPE to obtain light olefin in a fixed bed reactor. The effects of catalyst types, pyrolysis temperatures, and Mg loading on the yield of light olefin were investigated. The 1 wt% Mg loading slightly improved the yield of light olefin to 38.87 wt% at 395 °C, lowering the temperature of the pyrolysis reaction. We considered that the higher light olefin yield of Fe-Mg-ZSM-5 was attributed to the introduction of Mg, where Mg regulated the surface acidity of the catalyst, inhibited the secondary cracking reaction, and reduced coking during the pyrolysis process. Furthermore, the addition of Mg also dramatically reduced the average particle size of Fe oxides from 40 nm to 10 nm, which is conducive to a lower catalytic reaction temperature. Finally, the spent catalyst could be easily regenerated at the conditions of 600 °C in airflow with a heating rate of 10 °C/min for 1 h, and the light olefin yield remained higher than 36.71 wt% after five cycles, indicating its excellent regeneration performance.","PeriodicalId":9794,"journal":{"name":"Catalysts","volume":null,"pages":null},"PeriodicalIF":3.9,"publicationDate":"2024-01-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139616388","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}
Weihua Mu, Lin Zhu, Shuya Xia, Xue Tan, Liangfei Duan, Guanghao Meng, Guo Liu
Density functional theory (DFT) was employed to explore the reaction mechanism, regio- and diastereoselectivities of nickel-initiated [3+2] cycloaddition between vinylcyclopropane (VCP) and N-tosylbenzaldimine assisted by phosphine ligands. Four different binding modes of the nickel center to VCP substrate were explored during the ring-opening of VCP, among which the C,C_anti and C,C_syn modes were verified to be the most accessible ones. Further explorations about four different phosphine ligand-assisted reactions based on the two most probable binding modes show that the difference in binding mode of bi- and monodentate phosphine ligands can vary the optimal reaction pathway, especially in the [3+2] cycloaddition process between the ring-opened intermediate and N-tosylbenzaldimine. The formation of C–C and C–N bonds between N-tosylbenzaldimine and the ring-opened intermediate through [3+2] cycloaddition is found to be stepwise, with the former acting as the rate-determining step (RDS) in most cases. Computed free energy barriers of RDS transition states on the optimal path I or II not only give out good predictions for reaction rates and half-lives, but also provide reasonable explanations for the major generation of cis-pyrrolidine. Noncovalent interaction analyses of key stationary points suggest the rate is influenced by both electronic effects and steric hindrance, while the diastereoselectivity is mainly controlled by electronic effects.
{"title":"Insights into the Mechanism, Regio-/Diastereoselectivities and Ligand Role of Nickel-Initiated [3+2] Cycloadditions between Vinylcyclopropane and N-Tosylbenzaldimine","authors":"Weihua Mu, Lin Zhu, Shuya Xia, Xue Tan, Liangfei Duan, Guanghao Meng, Guo Liu","doi":"10.3390/catal14010082","DOIUrl":"https://doi.org/10.3390/catal14010082","url":null,"abstract":"Density functional theory (DFT) was employed to explore the reaction mechanism, regio- and diastereoselectivities of nickel-initiated [3+2] cycloaddition between vinylcyclopropane (VCP) and N-tosylbenzaldimine assisted by phosphine ligands. Four different binding modes of the nickel center to VCP substrate were explored during the ring-opening of VCP, among which the C,C_anti and C,C_syn modes were verified to be the most accessible ones. Further explorations about four different phosphine ligand-assisted reactions based on the two most probable binding modes show that the difference in binding mode of bi- and monodentate phosphine ligands can vary the optimal reaction pathway, especially in the [3+2] cycloaddition process between the ring-opened intermediate and N-tosylbenzaldimine. The formation of C–C and C–N bonds between N-tosylbenzaldimine and the ring-opened intermediate through [3+2] cycloaddition is found to be stepwise, with the former acting as the rate-determining step (RDS) in most cases. Computed free energy barriers of RDS transition states on the optimal path I or II not only give out good predictions for reaction rates and half-lives, but also provide reasonable explanations for the major generation of cis-pyrrolidine. Noncovalent interaction analyses of key stationary points suggest the rate is influenced by both electronic effects and steric hindrance, while the diastereoselectivity is mainly controlled by electronic effects.","PeriodicalId":9794,"journal":{"name":"Catalysts","volume":null,"pages":null},"PeriodicalIF":3.9,"publicationDate":"2024-01-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139614536","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}
The present study assesses, using a theoretical approach, the performances of two widely used fixed-bed reactors for the ethanol-to-butadiene (ETB) one-stage (Lebedev) process: multibed adiabatic reactors (MBAR) with inter-bed heating and a multitubular reactor (MTR). The mathematical model consists of mass and heat conservation equations at catalyst particle and particle bed scales, coupled with a published kinetic model specific for a modified MgO–SiO2 catalyst. The process simulations at the level of catalyst particle have shown that the inter-phase concentration and temperature gradients are negligible, the only physical step with a limiting influence on process kinetics being the internal diffusion. A simplified version of the reactor model was also formulated, including empirical expressions developed in the study for the calculation of internal effectiveness factors. The reactor simulations highlighted that the MBAR with inter-bed heating by injection of hot reactants provides worse butadiene (BD) yields as a consequence of reduced reaction times (due to reactant by-pass of catalyst beds). The MBAR with inter-bed heating using heat exchangers provides better performances but inferior to those of MTR if the number of catalyst beds is less than six. A preliminary optimization study for the MBAR and MTR is also presented. The results showed that the maximization of BD yield has the drawback of a low BD production rate, whereas the maximization of BD production rate corresponds to a relatively low BD yield and high ethanol and inert recycles. A trade-off between the two extreme cases can be attained by maximizing the income generated by reactor operation.
{"title":"An Analysis of Fixed-Bed Catalytic Reactors Performances for One-Stage Butadiene Synthesis from Ethanol","authors":"A. Brosteanu, I. Banu, G. Bozga","doi":"10.3390/catal14010083","DOIUrl":"https://doi.org/10.3390/catal14010083","url":null,"abstract":"The present study assesses, using a theoretical approach, the performances of two widely used fixed-bed reactors for the ethanol-to-butadiene (ETB) one-stage (Lebedev) process: multibed adiabatic reactors (MBAR) with inter-bed heating and a multitubular reactor (MTR). The mathematical model consists of mass and heat conservation equations at catalyst particle and particle bed scales, coupled with a published kinetic model specific for a modified MgO–SiO2 catalyst. The process simulations at the level of catalyst particle have shown that the inter-phase concentration and temperature gradients are negligible, the only physical step with a limiting influence on process kinetics being the internal diffusion. A simplified version of the reactor model was also formulated, including empirical expressions developed in the study for the calculation of internal effectiveness factors. The reactor simulations highlighted that the MBAR with inter-bed heating by injection of hot reactants provides worse butadiene (BD) yields as a consequence of reduced reaction times (due to reactant by-pass of catalyst beds). The MBAR with inter-bed heating using heat exchangers provides better performances but inferior to those of MTR if the number of catalyst beds is less than six. A preliminary optimization study for the MBAR and MTR is also presented. The results showed that the maximization of BD yield has the drawback of a low BD production rate, whereas the maximization of BD production rate corresponds to a relatively low BD yield and high ethanol and inert recycles. A trade-off between the two extreme cases can be attained by maximizing the income generated by reactor operation.","PeriodicalId":9794,"journal":{"name":"Catalysts","volume":null,"pages":null},"PeriodicalIF":3.9,"publicationDate":"2024-01-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139615901","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}
Moran Dahan, L. Fadeev, Hagay Hayun, M. Gozin, Y. Gelbstein, B. A. Rosen
Solid oxide fuel cells are characterized by a high efficiency for converting chemical energy into electricity and fuel flexibility. This research work focuses on developing durable and efficient anodes for solid oxide fuel cells (SOFCs) based on exsolving nickel from the perovskite structure. A-site-deficient La- and Ni-doped strontium titanates (La0.2Sr0.7Ti0.95Ni0.05O3−δ, LSTN) were synthesized using four different techniques and mixed with Ce0.8Gd0.2O2−δ (GDC) to form the SOFC anode. The synthesis routes of interest for comparison included solid-state, sol-gel, hydrothermal, and co-precipitation methods. LSTN powders were characterized via XRD, SEM, TPR, BET and XPS. In situ XRD during reduction was measured and the reduced powders were analyzed using TEM. The impact of synthesis route on SOFC performance was investigated. All samples were highly durable when kept at 0.5 V for 48 h at 800 °C with H2 fuel. Interestingly, the best performance was observed for the cell with the LSTN anode prepared via co-precipitation, while the conventional solid-state synthesis method only achieved the second-best results.
{"title":"Influence of the La0.2Sr0.7Ti0.95Ni0.05O3 (LSTN) Synthesis Method on SOFC Anode Performance","authors":"Moran Dahan, L. Fadeev, Hagay Hayun, M. Gozin, Y. Gelbstein, B. A. Rosen","doi":"10.3390/catal14010079","DOIUrl":"https://doi.org/10.3390/catal14010079","url":null,"abstract":"Solid oxide fuel cells are characterized by a high efficiency for converting chemical energy into electricity and fuel flexibility. This research work focuses on developing durable and efficient anodes for solid oxide fuel cells (SOFCs) based on exsolving nickel from the perovskite structure. A-site-deficient La- and Ni-doped strontium titanates (La0.2Sr0.7Ti0.95Ni0.05O3−δ, LSTN) were synthesized using four different techniques and mixed with Ce0.8Gd0.2O2−δ (GDC) to form the SOFC anode. The synthesis routes of interest for comparison included solid-state, sol-gel, hydrothermal, and co-precipitation methods. LSTN powders were characterized via XRD, SEM, TPR, BET and XPS. In situ XRD during reduction was measured and the reduced powders were analyzed using TEM. The impact of synthesis route on SOFC performance was investigated. All samples were highly durable when kept at 0.5 V for 48 h at 800 °C with H2 fuel. Interestingly, the best performance was observed for the cell with the LSTN anode prepared via co-precipitation, while the conventional solid-state synthesis method only achieved the second-best results.","PeriodicalId":9794,"journal":{"name":"Catalysts","volume":null,"pages":null},"PeriodicalIF":3.9,"publicationDate":"2024-01-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139615129","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}
Sulfonic resins can replace homogeneous sulfonic acids in the oxidation of alcohols with the H2O2/KBr system. The performance of different resins was tested with methyl 9(10)-hydroxystearate, a secondary fatty alcohol. The structural features of the resin were more important than the acid strength for the catalytic performance of this reaction. The optimization of the reaction conditions allows the recovery of the resin, although regeneration is required due to the active role of KBr, and a significant loss of sulfonic groups can be detected after nine runs. In the case of primary fatty alcohols, the oxidation leads to carboxylic acids, which are esterified with the starting alcohol under the acidic conditions. For cyclic secondary alcohols, the steric hindrance around the hydroxyl group seems to be important for the efficiency of the oxidation to ketone.
{"title":"Sulfonic Resins as Catalysts for the Oxidation of Alcohols with H2O2/KBr","authors":"Vicente Dorado, C. Herrerías, Jose M. Fraile","doi":"10.3390/catal14010074","DOIUrl":"https://doi.org/10.3390/catal14010074","url":null,"abstract":"Sulfonic resins can replace homogeneous sulfonic acids in the oxidation of alcohols with the H2O2/KBr system. The performance of different resins was tested with methyl 9(10)-hydroxystearate, a secondary fatty alcohol. The structural features of the resin were more important than the acid strength for the catalytic performance of this reaction. The optimization of the reaction conditions allows the recovery of the resin, although regeneration is required due to the active role of KBr, and a significant loss of sulfonic groups can be detected after nine runs. In the case of primary fatty alcohols, the oxidation leads to carboxylic acids, which are esterified with the starting alcohol under the acidic conditions. For cyclic secondary alcohols, the steric hindrance around the hydroxyl group seems to be important for the efficiency of the oxidation to ketone.","PeriodicalId":9794,"journal":{"name":"Catalysts","volume":null,"pages":null},"PeriodicalIF":3.9,"publicationDate":"2024-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139616653","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}
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