Pub Date : 2024-10-14DOI: 10.1021/acs.iecr.4c03239
Mohammad Bahreini, Martin Désilets, Ergys Pahija, Ulrich Legrand, Jiaxun Guo, Arthur G. Fink
Gas diffusion electrodes (GDEs) are promising for scaling up industrial CO2 electrochemical reduction cells. This study introduces a transient numerical model representing an industrial electrolyzer. The model incorporates electrochemical kinetics, homogeneous reaction kinetics, and transport phenomena within the cathode compartment. By integrating a global mass balance over the entire electrolyte, it analyzes time-dependent performance variations such as Faradaic efficiency (FE). This allows us to simulate formate production and understand mass transport limitations within the GDE. Our results demonstrated a 4% increase in FE when the electrolyte flow rate was increased from 120 to 360 mL/min. However, further increasing the flow rate to 830 mL/min showed diminishing returns. Additionally, increasing the KOH concentration in the catholyte from 0.5 to 1 M resulted in a 7–10% increase in FE. A slight further increase was observed when increasing from 3 to 4 M. This analysis provides valuable insights into optimizing electrochemical reduction processes at an industrial scale.
气体扩散电极（GDEs）在扩大工业二氧化碳电化学还原电池的规模方面大有可为。本研究介绍了一种代表工业电解槽的瞬态数值模型。该模型包含电化学动力学、均相反应动力学以及阴极室内的传输现象。通过整合整个电解质的全局质量平衡，该模型可分析随时间变化的性能变化，如法拉第效率（FE）。这使我们能够模拟甲酸盐的产生，并了解 GDE 内部的质量传输限制。我们的结果表明，当电解液流速从 120 mL/min 增加到 360 mL/min 时，FE 增加了 4%。然而，进一步将流速提高到 830 毫升/分钟后，结果表明收益递减。此外，将电解液中的 KOH 浓度从 0.5 M 提高到 1 M，可使 FE 增加 7-10%。这项分析为优化工业规模的电化学还原过程提供了宝贵的见解。
{"title":"Investigation of CO2 Reduction to Formate in an Industrial-Scale Electrochemical Cell through Transient Numerical Modeling","authors":"Mohammad Bahreini, Martin Désilets, Ergys Pahija, Ulrich Legrand, Jiaxun Guo, Arthur G. Fink","doi":"10.1021/acs.iecr.4c03239","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c03239","url":null,"abstract":"Gas diffusion electrodes (GDEs) are promising for scaling up industrial CO<sub>2</sub> electrochemical reduction cells. This study introduces a transient numerical model representing an industrial electrolyzer. The model incorporates electrochemical kinetics, homogeneous reaction kinetics, and transport phenomena within the cathode compartment. By integrating a global mass balance over the entire electrolyte, it analyzes time-dependent performance variations such as Faradaic efficiency (FE). This allows us to simulate formate production and understand mass transport limitations within the GDE. Our results demonstrated a 4% increase in FE when the electrolyte flow rate was increased from 120 to 360 mL/min. However, further increasing the flow rate to 830 mL/min showed diminishing returns. Additionally, increasing the KOH concentration in the catholyte from 0.5 to 1 M resulted in a 7–10% increase in FE. A slight further increase was observed when increasing from 3 to 4 M. This analysis provides valuable insights into optimizing electrochemical reduction processes at an industrial scale.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":null,"pages":null},"PeriodicalIF":4.2,"publicationDate":"2024-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142431549","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-14DOI: 10.1021/acs.iecr.4c01866
Neha A. Padwal, Tobias Mazal, Michael F. Doherty
This article reports innovations in mechanistic modeling and simulation approaches for noncentrosymmetric molecular crystals with two growth units in the unit cell (Z = 2). A simplified steady-state framework considers the kinetics of most likely surface processes to predict nonequilibrium kink densities and step velocities. Kinetic Monte Carlo methods are utilized to simulate the evolution of growing crystal surfaces and capture dynamic step behavior. These approaches are compared quantitatively for their predictions of kink densities and step velocity with respect to interaction anisotropy and supersaturation. The approaches are applied to morphology predictions of an active pharmaceutical ingredient, trimethoprim, followed by a detailed comparative analysis.
{"title":"Modern Modeling and Simulation Approaches for Morphology Predictions of Molecular Crystals","authors":"Neha A. Padwal, Tobias Mazal, Michael F. Doherty","doi":"10.1021/acs.iecr.4c01866","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c01866","url":null,"abstract":"This article reports innovations in mechanistic modeling and simulation approaches for noncentrosymmetric molecular crystals with two growth units in the unit cell (<i>Z</i> = 2). A simplified steady-state framework considers the kinetics of most likely surface processes to predict nonequilibrium kink densities and step velocities. Kinetic Monte Carlo methods are utilized to simulate the evolution of growing crystal surfaces and capture dynamic step behavior. These approaches are compared quantitatively for their predictions of kink densities and step velocity with respect to interaction anisotropy and supersaturation. The approaches are applied to morphology predictions of an active pharmaceutical ingredient, trimethoprim, followed by a detailed comparative analysis.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":null,"pages":null},"PeriodicalIF":4.2,"publicationDate":"2024-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142431550","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Two intumescent flame retardants with UV resistance were specifically designed for low-density polyethylene (LDPE) composites. The mechanical properties, UV resistance, and flame retardancy of these composites were thoroughly evaluated. To delay the premature decomposition of ammonium polyphosphate (APP) under UV radiation, this work employed a coating process using silica gel, melamine formaldehyde resin (MF), and β-cyclodextrin (β-CD) on APP, also known as MCAPP. Furthermore, tris(2-hydroxyethyl) isocyanate (THEIC), which possesses an isocyanate ring, was selected with the purpose of enhancing the absorption of UV radiation and enhancing the fire resistance of LDPE. Finally, the compounds 4-hydroxy-2,2,6,6-tetramethylpiperidine (TMP) and 4-amino-2,2,6,6-tetramethylpiperidine (TEMP), which are hindered amine light stabilizers, were combined with calcium lanceolate (CLS) to create flame-retardant hindered amine light stabilizers (CLS-TMP and CLS-TEMP). CLS-TMP and CLS-TEMP were combined with MCAPP and THEIC to create intumescent flame retardants, which were then incorporated into LDPE to evaluate their flame-retardant properties and UV resistance. The results indicate that the addition of 29.5 wt % (MCAPP/THEIC)/0.5 wt % CLS-TEMP to LDPE increased the limiting oxygen index (LOI) of the composites to 33.2% and achieved a UL-94 vertical flammability rating of V-0. The aging process of the composite samples exhibited a slower progression than that of the control LDPE samples. The sample LDPE/29.5 wt % (MCAPP/THEIC)/0.5 wt % CLS-TEMP showed significant decreases in the rate of shift of both tensile strength and elongation at break. The differences in the LOI before and after the LDPE composites were relatively insignificant after 100 h of UV irradiation.
{"title":"Preparation and Performance of UV-Resistant Intumescent Flame Retardants for Low Density Polyethylene","authors":"Guxia Wang, Tingxuan Dong, Liyang Ding, Yakun Lan, Shuai Yang, Dan Li, Shengwei Guo","doi":"10.1021/acs.iecr.4c03183","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c03183","url":null,"abstract":"Two intumescent flame retardants with UV resistance were specifically designed for low-density polyethylene (LDPE) composites. The mechanical properties, UV resistance, and flame retardancy of these composites were thoroughly evaluated. To delay the premature decomposition of ammonium polyphosphate (APP) under UV radiation, this work employed a coating process using silica gel, melamine formaldehyde resin (MF), and β-cyclodextrin (β-CD) on APP, also known as MCAPP. Furthermore, tris(2-hydroxyethyl) isocyanate (THEIC), which possesses an isocyanate ring, was selected with the purpose of enhancing the absorption of UV radiation and enhancing the fire resistance of LDPE. Finally, the compounds 4-hydroxy-2,2,6,6-tetramethylpiperidine (TMP) and 4-amino-2,2,6,6-tetramethylpiperidine (TEMP), which are hindered amine light stabilizers, were combined with calcium lanceolate (CLS) to create flame-retardant hindered amine light stabilizers (CLS-TMP and CLS-TEMP). CLS-TMP and CLS-TEMP were combined with MCAPP and THEIC to create intumescent flame retardants, which were then incorporated into LDPE to evaluate their flame-retardant properties and UV resistance. The results indicate that the addition of 29.5 wt % (MCAPP/THEIC)/0.5 wt % CLS-TEMP to LDPE increased the limiting oxygen index (LOI) of the composites to 33.2% and achieved a UL-94 vertical flammability rating of V-0. The aging process of the composite samples exhibited a slower progression than that of the control LDPE samples. The sample LDPE/29.5 wt % (MCAPP/THEIC)/0.5 wt % CLS-TEMP showed significant decreases in the rate of shift of both tensile strength and elongation at break. The differences in the LOI before and after the LDPE composites were relatively insignificant after 100 h of UV irradiation.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":null,"pages":null},"PeriodicalIF":4.2,"publicationDate":"2024-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142431553","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Severe surface fouling of nanofiltration (NF) has hindered its practical implementation in treating dye-containing wastewater from the textile industry. To address this fouling issue, a novel thin-film nanocomposite NF membrane (TFNx) was proposed by embedding catalytic manganese dioxide (MnO2) nanoparticles within polyamide (PA) rejection layer to realize in situ Fenton-like advanced oxidation self-cleaning. The incorporation of MnO2 nanoparticles was validated to moderately reduce the degree of cross-linking of the PA layer, thereby obtaining an enhanced surface hydrophilicity. The inclusion of MnO2 nanoparticles increased the surface hydrophilicity, resulting in a higher water permeance (TFN10 18.1 ± 0.7 L m–2 h–1 bar–1) that was 57.4% higher than that of the control thin film nanocomposite (TFC) membrane, while a high dye rejection was maintained. In addition, the presence of catalytically capable MnO2 nanoparticles in the Fenton-like reaction led to membrane self-cleaning and demonstrated a better antifouling behavior. The generation of free radicals was triggered by the addition of peroxymonosulfate (PMS). Furthermore, the impacts of operational conditions on membrane self-cleaning performance and operation stability were comprehensively investigated.
纳滤（NF）的严重表面污垢阻碍了其在处理纺织业含染料废水中的实际应用。为了解决这一污垢问题，我们提出了一种新型薄膜纳米复合纳滤膜（TFNx），在聚酰胺（PA）排斥层中嵌入催化二氧化锰（MnO2）纳米颗粒，以实现原位芬顿式高级氧化自清洁。经验证，纳米二氧化锰颗粒的加入可适度降低 PA 层的交联度，从而获得更高的表面亲水性。MnO2 纳米粒子的加入增加了表面亲水性，从而提高了透水性（TFN10 18.1 ± 0.7 L m-2 h-1 bar-1），比对照薄膜纳米复合膜（TFC）高出 57.4%，同时保持了较高的染料抑制率。此外，在类芬顿反应中，催化能力强的 MnO2 纳米粒子的存在导致了膜的自清洁，并表现出更好的防污性能。过氧单硫酸盐（PMS）的加入引发了自由基的生成。此外，还全面研究了操作条件对膜自清洁性能和运行稳定性的影响。
{"title":"Self-Cleaning Thin Film Polyamide Manganese Dioxide Nanocomposite Membrane via Peroxymonosulfate Activation","authors":"Ying Mei, Yushan Huang, Qirui Wang, Yujing Qiu, Yi Yang, Wei Shu, Yongqing Guo, Xiaofei Wang, Yuming Zheng, Xuehui Ge, Xiaocheng Lin","doi":"10.1021/acs.iecr.4c02961","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c02961","url":null,"abstract":"Severe surface fouling of nanofiltration (NF) has hindered its practical implementation in treating dye-containing wastewater from the textile industry. To address this fouling issue, a novel thin-film nanocomposite NF membrane (TFN<i>x</i>) was proposed by embedding catalytic manganese dioxide (MnO<sub>2</sub>) nanoparticles within polyamide (PA) rejection layer to realize in situ Fenton-like advanced oxidation self-cleaning. The incorporation of MnO<sub>2</sub> nanoparticles was validated to moderately reduce the degree of cross-linking of the PA layer, thereby obtaining an enhanced surface hydrophilicity. The inclusion of MnO<sub>2</sub> nanoparticles increased the surface hydrophilicity, resulting in a higher water permeance (TFN10 18.1 ± 0.7 L m<sup>–2</sup> h<sup>–1</sup> bar<sup>–1</sup>) that was 57.4% higher than that of the control thin film nanocomposite (TFC) membrane, while a high dye rejection was maintained. In addition, the presence of catalytically capable MnO<sub>2</sub> nanoparticles in the Fenton-like reaction led to membrane self-cleaning and demonstrated a better antifouling behavior. The generation of free radicals was triggered by the addition of peroxymonosulfate (PMS). Furthermore, the impacts of operational conditions on membrane self-cleaning performance and operation stability were comprehensively investigated.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":null,"pages":null},"PeriodicalIF":4.2,"publicationDate":"2024-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142431548","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-14DOI: 10.1021/acs.iecr.4c02453
Mohammad El Wajeh, Marcel Granderath, Alexander Mitsos, Adel Mhamdi
We present distributed economic nonlinear model predictive control (DeNMPC), employing sequential communication protocols, to optimize the flexible operation of electrified biodiesel production under fluctuating electricity prices. By incorporating buffer tanks for intermediate and final products within the production process, we decouple process dynamics, segmenting it into three distinct subprocesses. The DeNMPC strategy yields significant energy cost savings of 20% compared to steady-state operation while being real-time tractable and ensuring operational feasibility. This stands in contrast to conventional scheduling employing quasi-stationary models, which results in infeasible outcomes. Furthermore, the DeNMPC strategy handles unexpected disturbances in production demand and feed composition, mitigated by the buffer tanks. These tanks prove essential not only for enhancing operational flexibility but also for enabling realizable DeNMPC applications through system decomposition. Additionally, we extend the DeNMPC with two stability formulations from the literature, assessing their suitability and implications within the specific context of the biodiesel production application.
{"title":"Distributed Economic Nonlinear Model Predictive Control for Flexible Electrified Biodiesel Production─Part I: Sequential Architectures","authors":"Mohammad El Wajeh, Marcel Granderath, Alexander Mitsos, Adel Mhamdi","doi":"10.1021/acs.iecr.4c02453","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c02453","url":null,"abstract":"We present distributed economic nonlinear model predictive control (DeNMPC), employing sequential communication protocols, to optimize the flexible operation of electrified biodiesel production under fluctuating electricity prices. By incorporating buffer tanks for intermediate and final products within the production process, we decouple process dynamics, segmenting it into three distinct subprocesses. The DeNMPC strategy yields significant energy cost savings of 20% compared to steady-state operation while being real-time tractable and ensuring operational feasibility. This stands in contrast to conventional scheduling employing quasi-stationary models, which results in infeasible outcomes. Furthermore, the DeNMPC strategy handles unexpected disturbances in production demand and feed composition, mitigated by the buffer tanks. These tanks prove essential not only for enhancing operational flexibility but also for enabling realizable DeNMPC applications through system decomposition. Additionally, we extend the DeNMPC with two stability formulations from the literature, assessing their suitability and implications within the specific context of the biodiesel production application.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":null,"pages":null},"PeriodicalIF":4.2,"publicationDate":"2024-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142431551","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-14DOI: 10.1021/acs.iecr.4c02506
Hamideh Hosseini
Nonthermal plasma (NTP) technology, as an emerging and promising technology, has been exploited for a variety of applications, including material synthesis, surface modification, and the removal of pollutants from air and water. In line with these high-value achievements, a wide range of chemical reactions have been activated by NTP due to its high stability and efficiency. Nevertheless, NTP can be considered an alternative approach for implementing reactions, particularly those that suffer from harsh conditions in conventional techniques. Moreover, the combination of NTP with various catalysts in some chemical reactions has demonstrated significant enhancement in both the conversion of the reactant and the selectivity of the desired product. This review provides an overview of the accomplishment of various chemical reactions, such as oxidation, reduction, copolymerization and polymerization, elimination, addition, isomerization, and rearrangement reactions, in NTP systems. Additionally, it explores the possible mechanisms underlying these reactions by examining the species generated in the plasma atmosphere.
{"title":"An Overview of Chemical Reactions Activated by Plasma","authors":"Hamideh Hosseini","doi":"10.1021/acs.iecr.4c02506","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c02506","url":null,"abstract":"Nonthermal plasma (NTP) technology, as an emerging and promising technology, has been exploited for a variety of applications, including material synthesis, surface modification, and the removal of pollutants from air and water. In line with these high-value achievements, a wide range of chemical reactions have been activated by NTP due to its high stability and efficiency. Nevertheless, NTP can be considered an alternative approach for implementing reactions, particularly those that suffer from harsh conditions in conventional techniques. Moreover, the combination of NTP with various catalysts in some chemical reactions has demonstrated significant enhancement in both the conversion of the reactant and the selectivity of the desired product. This review provides an overview of the accomplishment of various chemical reactions, such as oxidation, reduction, copolymerization and polymerization, elimination, addition, isomerization, and rearrangement reactions, in NTP systems. Additionally, it explores the possible mechanisms underlying these reactions by examining the species generated in the plasma atmosphere.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":null,"pages":null},"PeriodicalIF":4.2,"publicationDate":"2024-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142431546","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-14DOI: 10.1021/acs.iecr.4c02589
Junjie Li, Ye Gao, Jiansong Wang, Lei Niu, Yuanzheng Ge, Yulong Zhang, Mingyang Chen, Junbo Gong
Ammonium sulfate is a widely used nitrogen fertilizer, with a significant market share in agricultural production. However, its poor powder characteristics and excessively fast release rate greatly hinder its development. This study investigates the effects of the abrasion and dissolution processes on the morphology of ammonium sulfate crystals. Furthermore, through a study of the cooling rate, stirring rate, and heating methods, a technique was developed to produce spherical ammonium sulfate particles through a single heating step without the use of organic solvents. The resulting spherical ammonium sulfate product exhibits excellent powder properties, good sphericity, and high flowability. More importantly, compared to cubic particles, the dissolution rate of the spherical product decreases by approximately 20%, and the caking ratio decreases by about 30% at the same humidity, demonstrating its anticaking and sustained-release performance.
{"title":"Preparation of (NH4)2SO4 Spherical Particles with Functions of Sustained-Release and Anticaking by an Organic Solvent-Free Process","authors":"Junjie Li, Ye Gao, Jiansong Wang, Lei Niu, Yuanzheng Ge, Yulong Zhang, Mingyang Chen, Junbo Gong","doi":"10.1021/acs.iecr.4c02589","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c02589","url":null,"abstract":"Ammonium sulfate is a widely used nitrogen fertilizer, with a significant market share in agricultural production. However, its poor powder characteristics and excessively fast release rate greatly hinder its development. This study investigates the effects of the abrasion and dissolution processes on the morphology of ammonium sulfate crystals. Furthermore, through a study of the cooling rate, stirring rate, and heating methods, a technique was developed to produce spherical ammonium sulfate particles through a single heating step without the use of organic solvents. The resulting spherical ammonium sulfate product exhibits excellent powder properties, good sphericity, and high flowability. More importantly, compared to cubic particles, the dissolution rate of the spherical product decreases by approximately 20%, and the caking ratio decreases by about 30% at the same humidity, demonstrating its anticaking and sustained-release performance.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":null,"pages":null},"PeriodicalIF":4.2,"publicationDate":"2024-10-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142431552","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Zinc (Zn) is commonly used as a promoter in Cu-based catalysts to boost the production of organosilane monomers during the Rochow-Müller reaction. However, the effect of Zn on the phase change of Cu-based catalysts in the reaction process is not yet fully understood. In this study, we prepared two Zn-modified CuO catalysts using simple ball milling (Zn–CuO) and physical mixing (Zn+CuO) methods. We found that adding Zn into CuO enhanced the adsorption of methyl chloride on the CuO surface, thereby promoting the sequential phase transformation of CuO to Cu2O and then to Cu and further to CuCl. Moreover, CuCl, as a key intermediate phase, could diffuse into Si powder and form Cu3Si under high-temperature conditions. Compared to CuO and Zn+CuO, Zn–CuO underwent a faster phase transformation, facilitating the generation of the active Cu3Si phase and enhancing the dimethyldichlorosilane selectivity and Si conversion. This study has clarified the role of the Zn promoter in the phase transformation of CuO catalysts in the Rochow-Müller reaction. Understanding this mechanism is crucial to designing more efficient catalysts.
{"title":"Deciphering the Promoting Effect of Zn on CuO for Dimethyldichlorosilane Production via the Rochow-Müller Reaction","authors":"Yuanlong Cui, Yongxia Zhu, Baofang Jin, Kangjun Wang, Jiajian Gao, Lili Zhang, Guangwen Xu, Ziyi Zhong, Fabing Su","doi":"10.1021/acs.iecr.4c02149","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c02149","url":null,"abstract":"Zinc (Zn) is commonly used as a promoter in Cu-based catalysts to boost the production of organosilane monomers during the Rochow-Müller reaction. However, the effect of Zn on the phase change of Cu-based catalysts in the reaction process is not yet fully understood. In this study, we prepared two Zn-modified CuO catalysts using simple ball milling (Zn–CuO) and physical mixing (Zn+CuO) methods. We found that adding Zn into CuO enhanced the adsorption of methyl chloride on the CuO surface, thereby promoting the sequential phase transformation of CuO to Cu<sub>2</sub>O and then to Cu and further to CuCl. Moreover, CuCl, as a key intermediate phase, could diffuse into Si powder and form Cu<sub>3</sub>Si under high-temperature conditions. Compared to CuO and Zn+CuO, Zn–CuO underwent a faster phase transformation, facilitating the generation of the active Cu<sub>3</sub>Si phase and enhancing the dimethyldichlorosilane selectivity and Si conversion. This study has clarified the role of the Zn promoter in the phase transformation of CuO catalysts in the Rochow-Müller reaction. Understanding this mechanism is crucial to designing more efficient catalysts.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":null,"pages":null},"PeriodicalIF":4.2,"publicationDate":"2024-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142430488","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2024-10-13DOI: 10.1021/acs.iecr.4c02289
Kavya Pradeepan, Kaiprathu Anjali, Shun Nishimura
Lanthanide metal–organic frameworks (Ln-MOFs) have attracted considerable interest in heterogeneous catalysis due to their tunable channel sizes, stable network structures, and diverse active sites. Here, a series of lanthanum (La)-based MOFs were synthesized in the presence of various amine modulators of ethylene diamine (ED), 1,4-diazabicyclo[2.2.2]octane (DABCO), butylamine (BA), triethylamine (TEA), and heptylamine (HA) under identical conditions. These modulators play a crucial role in both the nucleation and growth processes of the La-MOFs. The impact of these modulators on crystallinity, porosity, acidity, thermal stability, bonding, morphology, and oxidation state of the metal was investigated. Textural analysis confirmed that the MOFs possess identical crystalline structures but different morphologies. The catalytic performance of the as-prepared La-MOF catalysts was evaluated for levulinic acid (LA) esterification. La-MOF-DABCO exhibited the highest yield, producing 92% ethyl levulinate (EL) in 2 h at 190 °C. Kinetic parameters indicated an activation energy of 20.7 kJ mol–1 and a reaction order of 0.5 with respect to LA. Thermodynamic analysis classified the reaction as endergonic, nonspontaneous, and more ordered. The study illuminated the influence of Brønsted–Lewis acid sites of La-MOF on catalytic esterification, highlighting a modulator-driven approach to MOF synthesis and its potential in heterogeneous catalysis. These findings offer insights for modeling and simulation studies in industrial applications.
{"title":"Amine-Modulated Lanthanum-Based Metal–Organic Frameworks for Levulinic Acid Conversion to Alkyl Levulinate","authors":"Kavya Pradeepan, Kaiprathu Anjali, Shun Nishimura","doi":"10.1021/acs.iecr.4c02289","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c02289","url":null,"abstract":"Lanthanide metal–organic frameworks (Ln-MOFs) have attracted considerable interest in heterogeneous catalysis due to their tunable channel sizes, stable network structures, and diverse active sites. Here, a series of lanthanum (La)-based MOFs were synthesized in the presence of various amine modulators of ethylene diamine (ED), 1,4-diazabicyclo[2.2.2]octane (DABCO), butylamine (BA), triethylamine (TEA), and heptylamine (HA) under identical conditions. These modulators play a crucial role in both the nucleation and growth processes of the La-MOFs. The impact of these modulators on crystallinity, porosity, acidity, thermal stability, bonding, morphology, and oxidation state of the metal was investigated. Textural analysis confirmed that the MOFs possess identical crystalline structures but different morphologies. The catalytic performance of the as-prepared La-MOF catalysts was evaluated for levulinic acid (LA) esterification. La-MOF-DABCO exhibited the highest yield, producing 92% ethyl levulinate (EL) in 2 h at 190 °C. Kinetic parameters indicated an activation energy of 20.7 kJ mol<sup>–1</sup> and a reaction order of 0.5 with respect to LA. Thermodynamic analysis classified the reaction as endergonic, nonspontaneous, and more ordered. The study illuminated the influence of Brønsted–Lewis acid sites of La-MOF on catalytic esterification, highlighting a modulator-driven approach to MOF synthesis and its potential in heterogeneous catalysis. These findings offer insights for modeling and simulation studies in industrial applications.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":null,"pages":null},"PeriodicalIF":4.2,"publicationDate":"2024-10-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142431554","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The involvement of liquid–liquid heterogeneous intensification in chemical processes is indispensable due to the presence of phase interfaces that impose limitations on mixing efficiency. Herein, a submerged rotating packed bed (SRPB) was developed to intensify liquid–liquid heterogeneous mixing under a dramatic centrifugal environment. The packing was submerged in continuous liquid to potentially match the heat-sensitive reaction systems. The liquid–liquid heterogeneous dispersion phenomena were photographed using a microscope, and the heterogeneous mixing efficiency was investigated using a sodium hydroxide and aspirin system as the chemical probe. As rotational speed was increased from 300 to 1500 r/min, the Sauter mean diameter of the aqueous phase was remarkably reduced from 110.65 to 19.57 μm, proving that SRPB could effectively disperse the liquid–liquid heterogeneous reaction system. Benefiting from the rotating packing, the segregation index (XS) and micromixing time (tm) respectively decreased in the range of 0.33–0.11 and 3.98–1.36 ms, indicating that the mixing efficiency was significantly enhanced under the centrifugal field of SRPB. The increase in the total volume flow rate reduced XS and tm, which could stem from the enlarged heterogeneous interfaces by forming multiple composite droplets at large volume flow rates. Compared with conventional RPB, the XS of SRPB (0.09–0.35) was slightly lower than that of RPB (0.1–0.4), and the tm of SRPB (1.36–3.98) was remarkably lower than that of RPB (1–10), proving the superiority of SPRB in promoting heterogeneous mixing.
{"title":"Liquid–Liquid Heterogeneous Mixing Characteristics in a Submerged Rotating Packed Bed","authors":"Xi-Fan Duan, Zhen-Yu Yang, Yan-Bin Li, Abdelgadir Bashir Banaga, Liangliang Zhang, Guang-Wen Chu, Jian-Feng Chen","doi":"10.1021/acs.iecr.4c02676","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c02676","url":null,"abstract":"The involvement of liquid–liquid heterogeneous intensification in chemical processes is indispensable due to the presence of phase interfaces that impose limitations on mixing efficiency. Herein, a submerged rotating packed bed (SRPB) was developed to intensify liquid–liquid heterogeneous mixing under a dramatic centrifugal environment. The packing was submerged in continuous liquid to potentially match the heat-sensitive reaction systems. The liquid–liquid heterogeneous dispersion phenomena were photographed using a microscope, and the heterogeneous mixing efficiency was investigated using a sodium hydroxide and aspirin system as the chemical probe. As rotational speed was increased from 300 to 1500 r/min, the Sauter mean diameter of the aqueous phase was remarkably reduced from 110.65 to 19.57 μm, proving that SRPB could effectively disperse the liquid–liquid heterogeneous reaction system. Benefiting from the rotating packing, the segregation index (<i>X</i><sub>S</sub>) and micromixing time (<i>t</i><sub>m</sub>) respectively decreased in the range of 0.33–0.11 and 3.98–1.36 ms, indicating that the mixing efficiency was significantly enhanced under the centrifugal field of SRPB. The increase in the total volume flow rate reduced <i>X</i><sub>S</sub> and <i>t</i><sub>m</sub>, which could stem from the enlarged heterogeneous interfaces by forming multiple composite droplets at large volume flow rates. Compared with conventional RPB, the <i>X</i><sub>S</sub> of SRPB (0.09–0.35) was slightly lower than that of RPB (0.1–0.4), and the <i>t</i><sub>m</sub> of SRPB (1.36–3.98) was remarkably lower than that of RPB (1–10), proving the superiority of SPRB in promoting heterogeneous mixing.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":null,"pages":null},"PeriodicalIF":4.2,"publicationDate":"2024-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142415445","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
京公网安备 11010802042870号
京ICP备2023020795号-1
扫码关注我们
求助内容：
应助结果提醒方式：