Pub Date : 2025-04-23DOI: 10.1021/acs.iecr.5c00313
Caixia Li, Lizhi Liu, Qing Xiong, Di Zhang, Jiaquan Zhang, Huiyong Wang, Juan Du, Baozhan Zheng, Yong Guo
Electrochemical synthesis of H2O2 via a two-electron oxygen reduction reaction (2e– ORR) has emerged as a potential alternative to the traditional anthraquinone method, but developing efficient electrocatalysts with good activity and selectivity is still a challenge. Herein, B/N codoped porous carbon (B/N-MC) was prepared by ZnO template-assisted method. The obtained B/N-MC exhibits excellent catalytic performance for 2e– ORR. When tested in 0.1 M KOH, the B/N-MC has an outstanding Faradaic efficiency over 95% and a higher H2O2 yield rate of 5.5 mol h–1gcat–1, which is 2.1 times higher than that of N-MC without B (2.6 mol h–1gcat–1). DFT calculation results confirm that it is the N/B doping that leads to the electron redistribution of B/N-MC and enhances its adsorption to O2, thus improving the 2e– ORR performance of H2O2 generation. Furthermore, the on-site produced H2O2 on B/N-MC has been successfully used for disinfection and dye degradation, proving its potential for industrial applications. This work provides a new way to improve the performance of carbon-based catalysts by modulating their morphology and electronic structure.
{"title":"Boron/Nitrogen Codoped Porous Carbon: An Efficient Oxygen Reduction Electrocatalyst for H2O2 Production","authors":"Caixia Li, Lizhi Liu, Qing Xiong, Di Zhang, Jiaquan Zhang, Huiyong Wang, Juan Du, Baozhan Zheng, Yong Guo","doi":"10.1021/acs.iecr.5c00313","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c00313","url":null,"abstract":"Electrochemical synthesis of H<sub>2</sub>O<sub>2</sub> via a two-electron oxygen reduction reaction (2e<sup>–</sup> ORR) has emerged as a potential alternative to the traditional anthraquinone method, but developing efficient electrocatalysts with good activity and selectivity is still a challenge. Herein, B/N codoped porous carbon (B/N-MC) was prepared by ZnO template-assisted method. The obtained B/N-MC exhibits excellent catalytic performance for 2e<sup>–</sup> ORR. When tested in 0.1 M KOH, the B/N-MC has an outstanding Faradaic efficiency over 95% and a higher H<sub>2</sub>O<sub>2</sub> yield rate of 5.5 mol h<sup>–1</sup>g<sub>cat</sub><sup>–1</sup>, which is 2.1 times higher than that of N-MC without B (2.6 mol h<sup>–1</sup>g<sub>cat</sub><sup>–1</sup>). DFT calculation results confirm that it is the N/B doping that leads to the electron redistribution of B/N-MC and enhances its adsorption to O<sub>2</sub>, thus improving the 2e<sup>–</sup> ORR performance of H<sub>2</sub>O<sub>2</sub> generation. Furthermore, the on-site produced H<sub>2</sub>O<sub>2</sub> on B/N-MC has been successfully used for disinfection and dye degradation, proving its potential for industrial applications. This work provides a new way to improve the performance of carbon-based catalysts by modulating their morphology and electronic structure.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"13 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143866742","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 synergy between noble metals and metal oxides can effectively improve the catalytic hydrogenation performance. However, precisely controlling the metal–metal oxide interaction remains a significant challenge. In this study, well-defined Pd-SnOx hybrid nanostructures encapsulated in porous silica nanoreactors (Pd-SnOx@pSiO2) were prepared using a microemulsion system comprising water, cetyltrimethylammonium bromide (CTAB), and 1-dodecanethiol (C12–SH). Within the system, CTAB and C12–SH acted as co-surfactants, forming self-assembled micelles, with Pd and Sn ions coordinated to C12–SH. Compared with individual Pd@pSiO2, Pd1-(SnOx)0.75@pSiO2 exhibited significant improvements in catalytic efficient and stability (6 cycles, conversion >99, and 100% selectivity) for the catalytic reduction of 4-nitrophenol. This improvement is ascribed to the synergy between Pd and SnOx, along with the confinement effect provided by the porous silica shells. This research provides a strategy for constructing reactive and stable noble-metal-based catalysts for the hydrogenation of substituted nitroaromatics.
{"title":"Porous Silica Nanoreactors Encapsulating Pd-SnOx Hybrid Nanostructures for the Catalytic Reduction of 4-Nitrophenol","authors":"Kaijie Li, Qin Wang, Qifan Zhao, Hongbo Yu, Hongfeng Yin","doi":"10.1021/acs.iecr.4c04838","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c04838","url":null,"abstract":"The synergy between noble metals and metal oxides can effectively improve the catalytic hydrogenation performance. However, precisely controlling the metal–metal oxide interaction remains a significant challenge. In this study, well-defined Pd-SnO<sub><i>x</i></sub> hybrid nanostructures encapsulated in porous silica nanoreactors (Pd-SnO<sub><i>x</i></sub>@pSiO<sub>2</sub>) were prepared using a microemulsion system comprising water, cetyltrimethylammonium bromide (CTAB), and 1-dodecanethiol (C<sub>12</sub>–SH). Within the system, CTAB and C<sub>12</sub>–SH acted as co-surfactants, forming self-assembled micelles, with Pd and Sn ions coordinated to C<sub>12</sub>–SH. Compared with individual Pd@pSiO<sub>2</sub>, Pd<sub>1</sub>-(SnO<sub><i>x</i></sub>)<sub>0.75</sub>@pSiO<sub>2</sub> exhibited significant improvements in catalytic efficient and stability (6 cycles, conversion >99, and 100% selectivity) for the catalytic reduction of 4-nitrophenol. This improvement is ascribed to the synergy between Pd and SnO<sub><i>x</i></sub>, along with the confinement effect provided by the porous silica shells. This research provides a strategy for constructing reactive and stable noble-metal-based catalysts for the hydrogenation of substituted nitroaromatics.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"71 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-04-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143866353","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 : 2025-04-22DOI: 10.1021/acs.iecr.5c00131
Xiang Guo, Jinshuo Qiao, Hang Zhai, Cheng Zou, Sitong Chen, Rong zheng Ren, Wang Sun, Zhenhua Wang, Kening Sun
Direct carbon solid oxide fuel cells (DC-SOFCs) are energy-conversion devices that can be utilized to directly convert the chemical energy in carbon into electrical energy. However, the development of DC-SOFCs is hindered by the inefficient mass transfer process on the anode surface. Herein, B-site Cu-substituted (PrBa)0.95Fe1.8–xTi0.2CuxO6−δ (PBFTCx, x = 0–0.3) materials are synthesized via the sol–gel combustion method and evaluated as anode materials for DC-SOFCs. These Cu@PBFTCx (x = 0–0.3) anode materials show significantly improved CO adsorption capacities and oxygen ion conductivities, leading to improved catalytic performance in DC-SOFCs. Among the Cu-doped samples, Cu@PBFTC0.2 shows the most enhanced CO adsorption capacity and the highest ion conductivity in air. A single cell assembled with a Cu@PBFTC0.2 anode exhibits excellent performance when using nanoactivated carbon as a fuel, achieving a peak power density of 518.98 mW cm–2 at 800 °C. This work demonstrates the excellent potential for utilizing Cu@PBFTCx materials as DC-SOFC anodes.
{"title":"In Situ Exsolvation of Cu Nanoparticles to Enhance Anode Catalysis in Direct Carbon Solid Oxide Fuel Cells","authors":"Xiang Guo, Jinshuo Qiao, Hang Zhai, Cheng Zou, Sitong Chen, Rong zheng Ren, Wang Sun, Zhenhua Wang, Kening Sun","doi":"10.1021/acs.iecr.5c00131","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c00131","url":null,"abstract":"Direct carbon solid oxide fuel cells (DC-SOFCs) are energy-conversion devices that can be utilized to directly convert the chemical energy in carbon into electrical energy. However, the development of DC-SOFCs is hindered by the inefficient mass transfer process on the anode surface. Herein, B-site Cu-substituted (PrBa)<sub>0.95</sub>Fe<sub>1.8–x</sub>Ti<sub>0.2</sub>Cu<sub><i>x</i></sub>O<sub>6−δ</sub> (PBFTC<sub><i>x</i></sub>, <i>x</i> = 0–0.3) materials are synthesized via the sol–gel combustion method and evaluated as anode materials for DC-SOFCs. These Cu@PBFTC<sub><i>x</i></sub> (<i>x</i> = 0–0.3) anode materials show significantly improved CO adsorption capacities and oxygen ion conductivities, leading to improved catalytic performance in DC-SOFCs. Among the Cu-doped samples, Cu@PBFTC<sub>0.2</sub> shows the most enhanced CO adsorption capacity and the highest ion conductivity in air. A single cell assembled with a Cu@PBFTC<sub>0.2</sub> anode exhibits excellent performance when using nanoactivated carbon as a fuel, achieving a peak power density of 518.98 mW cm<sup>–2</sup> at 800 °C. This work demonstrates the excellent potential for utilizing Cu@PBFTC<sub><i>x</i></sub> materials as DC-SOFC anodes.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"91 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143862428","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 : 2025-04-22DOI: 10.1021/acs.iecr.4c04292
Bo Song, Tao Liu, Mingyan Zhao, Yan Cui, Junghui Chen, Zoltan K. Nagy, Rolf Findeisen
To facilitate quality-by-design (QbD) of seeded cooling crystallization, a novel surrogate modeling and process optimization method is proposed in this paper, based on the design of experiments (DoE) with sensitivity analysis on the process operating conditions. To overcome the deficiency of the crystal growth kinetic model related to the population balance equation, which could not reflect the explicit relationship between the process operating conditions (e.g., initial solution supersaturation and cooling rate) and product crystal size distribution (CSD), a surrogate model is established by using the Gaussian process regression (GPR) approach, based on experimental data from a permitted range of operating conditions. Correspondingly, a swarm-based metaheuristic algorithm named beluga whale optimization (BWO) is adopted to determine proper hyperparameters in the surrogate model. By analyzing the global sensitivity analysis (GSA) of product CSD with respect to these operation conditions, a sensitivity-based DoE is developed to reduce the number of batch experiments required for implementation. Based on the established surrogate model, a comprehensive quality criterion is introduced to optimize these operating conditions, which takes into account the information entropy of product CSD together with the desired product yield and size range. The seeded cooling crystallization process of the β-form l-glutamic acid is tested to verify the effectiveness and merits of the proposed modeling and optimization method.
{"title":"Surrogate Modeling with Sensitivity-Based Experiment Design and Process Optimization of Seeded Cooling Crystallization: A Case Study on β-Form LGA","authors":"Bo Song, Tao Liu, Mingyan Zhao, Yan Cui, Junghui Chen, Zoltan K. Nagy, Rolf Findeisen","doi":"10.1021/acs.iecr.4c04292","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c04292","url":null,"abstract":"To facilitate quality-by-design (QbD) of seeded cooling crystallization, a novel surrogate modeling and process optimization method is proposed in this paper, based on the design of experiments (DoE) with sensitivity analysis on the process operating conditions. To overcome the deficiency of the crystal growth kinetic model related to the population balance equation, which could not reflect the explicit relationship between the process operating conditions (e.g., initial solution supersaturation and cooling rate) and product crystal size distribution (CSD), a surrogate model is established by using the Gaussian process regression (GPR) approach, based on experimental data from a permitted range of operating conditions. Correspondingly, a swarm-based metaheuristic algorithm named beluga whale optimization (BWO) is adopted to determine proper hyperparameters in the surrogate model. By analyzing the global sensitivity analysis (GSA) of product CSD with respect to these operation conditions, a sensitivity-based DoE is developed to reduce the number of batch experiments required for implementation. Based on the established surrogate model, a comprehensive quality criterion is introduced to optimize these operating conditions, which takes into account the information entropy of product CSD together with the desired product yield and size range. The seeded cooling crystallization process of the β-form <span>l</span>-glutamic acid is tested to verify the effectiveness and merits of the proposed modeling and optimization method.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"63 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143862297","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}
Heat exchangers often face challenges such as uneven flow distribution, low heat transfer efficiency, and excessive pressure loss, which hinder energy utilization and operational performance. To address these issues, this study employs topology optimization and parameter optimization methods to enhance the flow and heat transfer performance of heat exchanger tube bundles. First, a shape sensitivity analysis is conducted to identify key regions influencing performance, revealing that the intervals of 60–100 and 260–300° exhibit the highest sensitivity. The topology-optimized structure demonstrates significant improvements, with a 6.40% increase in flow performance, a 0.63% enhancement in heat transfer efficiency, and a 7.54% boost in overall performance compared to the original structure with an average deformation of 0.05 mm. Parameter optimization, while yielding slightly lower performance gains, produces more regular and industrially feasible structures. The study highlights the advantages of topology optimization in exploring a broader design space without being constrained by predefined parameters, offering a more efficient approach to performance enhancement. By integrating sensitivity analysis and optimization techniques, this research provides theoretical guidance for the structural design of heat exchangers, contributing to improved energy efficiency and operational stability in industrial applications.
{"title":"Investigation of Structure-Performance Relationship of Heat Exchanger using Topology Optimization","authors":"Shilin Gao, Yajie Gou, Jintao Xing, Jing Li, Xudong Duan","doi":"10.1021/acs.iecr.5c00917","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c00917","url":null,"abstract":"Heat exchangers often face challenges such as uneven flow distribution, low heat transfer efficiency, and excessive pressure loss, which hinder energy utilization and operational performance. To address these issues, this study employs topology optimization and parameter optimization methods to enhance the flow and heat transfer performance of heat exchanger tube bundles. First, a shape sensitivity analysis is conducted to identify key regions influencing performance, revealing that the intervals of 60–100 and 260–300° exhibit the highest sensitivity. The topology-optimized structure demonstrates significant improvements, with a 6.40% increase in flow performance, a 0.63% enhancement in heat transfer efficiency, and a 7.54% boost in overall performance compared to the original structure with an average deformation of 0.05 mm. Parameter optimization, while yielding slightly lower performance gains, produces more regular and industrially feasible structures. The study highlights the advantages of topology optimization in exploring a broader design space without being constrained by predefined parameters, offering a more efficient approach to performance enhancement. By integrating sensitivity analysis and optimization techniques, this research provides theoretical guidance for the structural design of heat exchangers, contributing to improved energy efficiency and operational stability in industrial applications.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"7 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143862429","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 low activity and rapid coke deposition issues are challenging for the nonmetal and metal catalysts in the direct dehydrogenation (DDH) of ethylbenzene to styrene, respectively. To address these issues, the synergistic effect between nonmetal and metal species was explored in this paper by successively loading Pt species and phosphorus oxynitride (PNO) on Al2O3 support to fabricate PNO/Pt/Al2O3 catalyst. The XPS, TEM, NH3-TPD, and CO2-TPD characterizations revealed an obvious strong interaction between Pt and P, increasing the loading amount of PNO and significantly modifying the electronic properties of the Pt species. The catalytic performance results showed that PNO/Pt/Al2O3 not only exhibited higher catalytic activity with XEB of 56.68% than that of PNO/Al2O3 (39.55%) and Pt/Al2O3 (41.65%) but also displayed better coke resistance than Pt/Al2O3 at high-concentration of ethylbenzene feed. DFT calculations confirmed that the interaction between Pt and PNO led to the obviously reduced energy barriers for α-C–H and β-C–H bond breaking, which therefore enhanced the catalytic activity.
{"title":"Phosphorus Oxynitride Modified Pt/Al2O3 Catalyst with High Activity and Coke Resistance over Direct Dehydrogenation of Ethylbenzene","authors":"Yuan Ma, Baining Lin, Lukai Luo, Chaojun Guo, Le Xie, Yonghua Zhou","doi":"10.1021/acs.iecr.5c00042","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c00042","url":null,"abstract":"The low activity and rapid coke deposition issues are challenging for the nonmetal and metal catalysts in the direct dehydrogenation (DDH) of ethylbenzene to styrene, respectively. To address these issues, the synergistic effect between nonmetal and metal species was explored in this paper by successively loading Pt species and phosphorus oxynitride (PNO) on Al<sub>2</sub>O<sub>3</sub> support to fabricate PNO/Pt/Al<sub>2</sub>O<sub>3</sub> catalyst. The XPS, TEM, NH<sub>3</sub>-TPD, and CO<sub>2</sub>-TPD characterizations revealed an obvious strong interaction between Pt and P, increasing the loading amount of PNO and significantly modifying the electronic properties of the Pt species. The catalytic performance results showed that PNO/Pt/Al<sub>2</sub>O<sub>3</sub> not only exhibited higher catalytic activity with <i>X</i><sub>EB</sub> of 56.68% than that of PNO/Al<sub>2</sub>O<sub>3</sub> (39.55%) and Pt/Al<sub>2</sub>O<sub>3</sub> (41.65%) but also displayed better coke resistance than Pt/Al<sub>2</sub>O<sub>3</sub> at high-concentration of ethylbenzene feed. DFT calculations confirmed that the interaction between Pt and PNO led to the obviously reduced energy barriers for α-C–H and β-C–H bond breaking, which therefore enhanced the catalytic activity.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"126 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143862302","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 : 2025-04-22DOI: 10.1021/acs.iecr.5c00269
Meifeng Zhu, Jin Cheng, Qing Wang, Mingyang Zhu, Yiting Lin, Cheng Lian, Honglai Liu
Lithium-ion batteries encompass multiple electrochemical interfaces. At the electrode–electrolyte interface, the structure of the electric double layer (EDL), especially the ion distribution, directly influences the characteristics and efficiency of the electrochemical process. A fast and accurate description of ion distribution is essential for advancing EDL research and improving the performance of quasi-solid-state polymer electrolytes (QPEs). However, experimental methods currently struggle to directly measure the density distribution of the EDL, and traditional molecular simulations are known for their long computational times. In this article, we have developed fluid density functional theory (FDFT), tailored specifically for the QPE system. The use of polymers increases the ionic density at the interface due to the occupying effect. The thickness of EDL is affected by different polymers’ polymerization degrees. Furthermore, the addition of additives increases the concentration of Li+ on the surface of the lithium metal anode. With the application of FDFT and the theoretical direction of the design of QPEs, this paper further develops the design method and puts forward some theoretical suggestions.
{"title":"Multiple Electrochemical Interfaces in Lithium-Ion Batteries: A Fluid Density Functional Theory Study","authors":"Meifeng Zhu, Jin Cheng, Qing Wang, Mingyang Zhu, Yiting Lin, Cheng Lian, Honglai Liu","doi":"10.1021/acs.iecr.5c00269","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c00269","url":null,"abstract":"Lithium-ion batteries encompass multiple electrochemical interfaces. At the electrode–electrolyte interface, the structure of the electric double layer (EDL), especially the ion distribution, directly influences the characteristics and efficiency of the electrochemical process. A fast and accurate description of ion distribution is essential for advancing EDL research and improving the performance of quasi-solid-state polymer electrolytes (QPEs). However, experimental methods currently struggle to directly measure the density distribution of the EDL, and traditional molecular simulations are known for their long computational times. In this article, we have developed fluid density functional theory (FDFT), tailored specifically for the QPE system. The use of polymers increases the ionic density at the interface due to the occupying effect. The thickness of EDL is affected by different polymers’ polymerization degrees. Furthermore, the addition of additives increases the concentration of Li<sup>+</sup> on the surface of the lithium metal anode. With the application of FDFT and the theoretical direction of the design of QPEs, this paper further develops the design method and puts forward some theoretical suggestions.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"15 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143857879","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 direct epoxidation of allyl chloride (ALC) to produce epichlorohydrin as a green and sustainable production technology is gaining global attention due to the significant reduction in wastewater and residues compared to traditional methods. This study conducted epoxidation experiments of ALC in a fixed-bed reactor using a titanium silicalite-1 supported catalyst to reveal the catalytic characteristics and kinetics. The effects of the operating conditions on the reaction performance are studied using the single-factor variable method. The results indicate that decreasing the liquid hourly space velocity, increasing the temperature, solvent amount, and feed ratio influence the reaction rates of the main epoxidation reaction and the side ring-opening reaction, leading to the tendency of increasing hydrogen peroxide (HP) conversion and decreasing epichlorohydrin selectivity. The optimal HP conversion and epichlorohydrin selectivity reached 96.34% and 95.88%, respectively. Based on the Eley–Rideal and Langmuir–Hinshelwood mechanism, kinetic modeling of the surface reaction as a rate-controlling step is constructed. Under the condition of eliminating external and internal diffusion limitations, kinetic data reflecting the intrinsic catalytic reaction rate are measured. The predicted reaction rates based on the Eley–Rideal model with HP being adsorbed show good agreement with the experimental data and accurately describe the intrinsic kinetic behavior of ALC epoxidation. This work provides theoretical support for the design and optimization of reactors for the direct epoxidation of ALC, thereby promoting the development and application of environmentally friendly production processes.
{"title":"Reaction Characteristics and Kinetics of Allyl Chloride Epoxidation Catalyzed by Supported Titanium Silicalite-1 in a Fixed-Bed Reactor","authors":"Fuqiang Qi, Zhentao Zhang, Junling Yang, Zhenqun Wu, Jinfang Zhi, Guanyue Gao","doi":"10.1021/acs.iecr.4c04526","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c04526","url":null,"abstract":"The direct epoxidation of allyl chloride (ALC) to produce epichlorohydrin as a green and sustainable production technology is gaining global attention due to the significant reduction in wastewater and residues compared to traditional methods. This study conducted epoxidation experiments of ALC in a fixed-bed reactor using a titanium silicalite-1 supported catalyst to reveal the catalytic characteristics and kinetics. The effects of the operating conditions on the reaction performance are studied using the single-factor variable method. The results indicate that decreasing the liquid hourly space velocity, increasing the temperature, solvent amount, and feed ratio influence the reaction rates of the main epoxidation reaction and the side ring-opening reaction, leading to the tendency of increasing hydrogen peroxide (HP) conversion and decreasing epichlorohydrin selectivity. The optimal HP conversion and epichlorohydrin selectivity reached 96.34% and 95.88%, respectively. Based on the Eley–Rideal and Langmuir–Hinshelwood mechanism, kinetic modeling of the surface reaction as a rate-controlling step is constructed. Under the condition of eliminating external and internal diffusion limitations, kinetic data reflecting the intrinsic catalytic reaction rate are measured. The predicted reaction rates based on the Eley–Rideal model with HP being adsorbed show good agreement with the experimental data and accurately describe the intrinsic kinetic behavior of ALC epoxidation. This work provides theoretical support for the design and optimization of reactors for the direct epoxidation of ALC, thereby promoting the development and application of environmentally friendly production processes.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"24 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143862298","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 : 2025-04-22DOI: 10.1021/acs.iecr.4c04608
Jae Hwan Choi, Chan Kim, Jong Min Lee
As interest in polyethylene terephthalate (PET) recycling grows, research into PET hydrogenolysis has expanded, yet reactor design studies remain limited. This work presents a mathematical model for a three-phase slurry bubble column reactor, chosen for its suitability in high-pressure and viscous conditions. Using hydrodynamic correlations and a GPU-based optimization solver, the model simulates and optimizes reactor performance. Results reveal that viscosity, influenced by polymer molecular weight and solvent ratio, critically impacts PET conversion rates. Catalyst size and feed proportion also significantly affect conversion via changes in axial dispersion, mass transfer, and reaction kinetics. These findings underscore the importance of optimizing viscosity and other reactor parameters to improve the efficiency of PET hydrogenolysis, supporting more effective industrial recycling strategies.
{"title":"Modeling and Optimization of PET Hydrogenolysis in a Slurry Bubble Column Reactor","authors":"Jae Hwan Choi, Chan Kim, Jong Min Lee","doi":"10.1021/acs.iecr.4c04608","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c04608","url":null,"abstract":"As interest in polyethylene terephthalate (PET) recycling grows, research into PET hydrogenolysis has expanded, yet reactor design studies remain limited. This work presents a mathematical model for a three-phase slurry bubble column reactor, chosen for its suitability in high-pressure and viscous conditions. Using hydrodynamic correlations and a GPU-based optimization solver, the model simulates and optimizes reactor performance. Results reveal that viscosity, influenced by polymer molecular weight and solvent ratio, critically impacts PET conversion rates. Catalyst size and feed proportion also significantly affect conversion via changes in axial dispersion, mass transfer, and reaction kinetics. These findings underscore the importance of optimizing viscosity and other reactor parameters to improve the efficiency of PET hydrogenolysis, supporting more effective industrial recycling strategies.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"27 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-04-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143857873","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 : 2025-04-21DOI: 10.1021/acs.iecr.5c01051
Xiao-Xuan Peng, Ze-Peng Bai, Kang Wu, Hua Zou, Hang-Tian Zhang, Jie-Xin Wang
The escalating global demand for poly(butylene terephthalate) (PBT), as one of the five major engineering plastics, has led to severe ecological crises and significant resource consumption. In this work, we employ 1,4-butanediol dispersions of ultrasmall zinc oxide nanoparticles (ZnO NPs) with an average size of 2.8 nm and excellent dispersity as catalysts for the highly efficient glycolysis of PBT using 1,4-butanediol. Specifically, complete depolymerization of PBT and approximately 98% yield of bis(4-hydroxybutyl) terephthalate (BHBT) are achieved within 45 min at 200 °C by only a minimal amount of ZnO NPs (0.1 wt %). More importantly, 95% PBT conversion can still remain after five cycles, exhibiting high recyclability of ZnO NPs. The possible reaction mechanism for glycolysis of PBT in 1,4-butanediol over ZnO NPs is proposed, and the reaction kinetics is also studied with an activation energy of 149.7 kJ/mol. Furthermore, ZnO NPs also show outstanding catalytic activity in the methanolysis of PBT, reaching over 97% yield of dimethyl terephthalate (DMT) within 60 min at 160 °C. This work provides a sustainable pathway for efficient recycling and reuse of PBT and broadens its market prospect.
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