Pub Date : 2025-04-09DOI: 10.1021/acs.iecr.4c04765
Manjusha C. Padole, Abhijeet Raj
Cement industries contribute significantly to greenhouse gas emissions, including nitrogen oxides (NOx) that pose serious risks to respiratory health and the environment and require effective reduction strategies. This study explores the potential of hydrogen cyanide (HCN) released from spent pot lining (SPL) during its cocombustion with coal in a cement kiln as an effective reducing agent to mitigate NO2 emissions from the plant. A detailed reaction mechanism for the interactions of HCN, HNC, and CN with NO2 is developed to form several possible products, including N2. The study employs a CBS-QB3 composite method and density functional theory (uB3LYP/6–311++G(d,p)) as tools for quantum chemical calculations to analyze the elementary reactions, optimize the structures of intermediate species and transition states, and determine their reaction energetics. The reaction kinetics of all the elementary steps are determined using transition state theory and RRKM methods to determine the preferred reactions among the competing channels. Through reactor simulations using the developed reaction mechanism, the possibility of NO2 reduction by HCN and the most preferred pathway for it are reported. It is found that HCN is highly effective in reducing NO and NO2 to N2 under cement kiln conditions. The results suggest that the utilization of SPL in cement plants together with coal can reduce both coal requirements and NOx emission from the plant.
{"title":"NO2 Reduction by HCN, HNC, and CN during Cofiring of Spent Pot Lining in Cement Plant: A DFT and Reaction Kinetics Study","authors":"Manjusha C. Padole, Abhijeet Raj","doi":"10.1021/acs.iecr.4c04765","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c04765","url":null,"abstract":"Cement industries contribute significantly to greenhouse gas emissions, including nitrogen oxides (NO<sub><i>x</i></sub>) that pose serious risks to respiratory health and the environment and require effective reduction strategies. This study explores the potential of hydrogen cyanide (HCN) released from spent pot lining (SPL) during its cocombustion with coal in a cement kiln as an effective reducing agent to mitigate NO<sub>2</sub> emissions from the plant. A detailed reaction mechanism for the interactions of HCN, HNC, and CN with NO<sub>2</sub> is developed to form several possible products, including N<sub>2</sub>. The study employs a CBS-QB3 composite method and density functional theory (uB3LYP/6–311++G(d,p)) as tools for quantum chemical calculations to analyze the elementary reactions, optimize the structures of intermediate species and transition states, and determine their reaction energetics. The reaction kinetics of all the elementary steps are determined using transition state theory and RRKM methods to determine the preferred reactions among the competing channels. Through reactor simulations using the developed reaction mechanism, the possibility of NO<sub>2</sub> reduction by HCN and the most preferred pathway for it are reported. It is found that HCN is highly effective in reducing NO and NO<sub>2</sub> to N<sub>2</sub> under cement kiln conditions. The results suggest that the utilization of SPL in cement plants together with coal can reduce both coal requirements and NO<sub><i>x</i></sub> emission from the plant.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"58 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143806401","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}
Due to the fast-paced growth of industries, the release of substantial amounts of industrial wastewater, especially organic contaminants like dyes, presents a serious risk to both human health and the environment. However, achieving fast and efficient treatment for wastewater containing organic dyes in an energy-saving manner remains a challenge due to complicated processes and high costs in treatment. Herein, a novel ternary heterojunction (TiO2/Fe2O3/Bi2WO6) by TiO2 and Fe2O3 nanoparticles well-dispersed on Bi2WO6 nanosheets was proposed to ingeniously address these challenges. Under visible light, our TiO2/Fe2O3/Bi2WO6 composite exhibits fast and efficient degradation for the representative dye Rhodamine B, achieving a 98.95% degradation rate in a short time, significantly outperforming individual and binary composites. Ultraviolet–visible and photoluminescence spectroscopy demonstrated the composite’s enhanced visible light absorption and efficient carrier separation. More importantly, the ternary photocatalyst showed excellent stability and reusability, maintaining high performance over multiple cycles. Active species capture identified holes and superoxide radicals as key contributors to the degradation process. This research offers a potential solution for addressing organic dye wastewater by utilizing the improved photocatalytic efficiency of the TiO2/Fe2O3/Bi2WO6 heterojunction.
{"title":"TiO2/Fe2O3/Bi2WO6 Heterojunction with Excellent Carrier Separation Efficiency for Efficient Degradation of Rhodamine B","authors":"Shuyi Gong, Yangrui Zhang, Yikun Chen, Shuchun Zhao, Hualong Peng, Renpan Deng","doi":"10.1021/acs.iecr.4c04020","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c04020","url":null,"abstract":"Due to the fast-paced growth of industries, the release of substantial amounts of industrial wastewater, especially organic contaminants like dyes, presents a serious risk to both human health and the environment. However, achieving fast and efficient treatment for wastewater containing organic dyes in an energy-saving manner remains a challenge due to complicated processes and high costs in treatment. Herein, a novel ternary heterojunction (TiO<sub>2</sub>/Fe<sub>2</sub>O<sub>3</sub>/Bi<sub>2</sub>WO<sub>6</sub>) by TiO<sub>2</sub> and Fe<sub>2</sub>O<sub>3</sub> nanoparticles well-dispersed on Bi<sub>2</sub>WO<sub>6</sub> nanosheets was proposed to ingeniously address these challenges. Under visible light, our TiO<sub>2</sub>/Fe<sub>2</sub>O<sub>3</sub>/Bi<sub>2</sub>WO<sub>6</sub> composite exhibits fast and efficient degradation for the representative dye Rhodamine B, achieving a 98.95% degradation rate in a short time, significantly outperforming individual and binary composites. Ultraviolet–visible and photoluminescence spectroscopy demonstrated the composite’s enhanced visible light absorption and efficient carrier separation. More importantly, the ternary photocatalyst showed excellent stability and reusability, maintaining high performance over multiple cycles. Active species capture identified holes and superoxide radicals as key contributors to the degradation process. This research offers a potential solution for addressing organic dye wastewater by utilizing the improved photocatalytic efficiency of the TiO<sub>2</sub>/Fe<sub>2</sub>O<sub>3</sub>/Bi<sub>2</sub>WO<sub>6</sub> heterojunction.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"183 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143813952","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}
Mo doping optimizes the electronic structure of ReS2. MoxRe(1–x)S2/MoS2 alloy heterojunction exhibits more favorable application prospects in photodetection due to its higher electrical conductivity than ReS2/MoS2 heterojunction. However, alloy heterojunctions are difficult to prepare controllably using conventional vapor-phase chemical vapor deposition (CVD), and the heterojunction growth mechanism remains unclear. Here, a vapor–liquid–solid temperature-gradient process is proposed to grow alloy heterojunctions within predeposited molten Mo precursor droplets. The sulfuration reaction between Re diffusing into the droplet and Mo atoms facilitates the formation of alloy structures. The growth temperatures TRe and TMo in the temperature-gradient significantly affect the growth patterns and morphology evolution of the heterojunction. The MoS2 morphology in vertical alloy heterojunctions becomes triangular as the growth temperature increases. The dimension of the top MoxRe(1–x)S2 alloy is positively correlated with the Re diffusion concentration. Moreover, lateral alloy heterojunctions and single alloys are formed at lower and higher growth temperature differences between TRe and TMo, respectively. These results provide a controllable strategy for the synthesis of isotropic/anisotropic van der Waals TMDC heterojunctions.
{"title":"Investigation of 1T′ MoxRe(1–x)S2/2H MoS2 Heterojunction Morphology Evolution through Vapor–Liquid–Solid Growth Mechanism by Temperature-Gradient CVD","authors":"Tong Cheng, Qi-Bo Wang, Qin-Qin Xu, Zhen-Hua Han, Jian-Zhong Yin","doi":"10.1021/acs.iecr.5c00302","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c00302","url":null,"abstract":"Mo doping optimizes the electronic structure of ReS<sub>2</sub>. Mo<sub><i>x</i></sub>Re<sub>(1–<i>x</i>)</sub>S<sub>2</sub>/MoS<sub>2</sub> alloy heterojunction exhibits more favorable application prospects in photodetection due to its higher electrical conductivity than ReS<sub>2</sub>/MoS<sub>2</sub> heterojunction. However, alloy heterojunctions are difficult to prepare controllably using conventional vapor-phase chemical vapor deposition (CVD), and the heterojunction growth mechanism remains unclear. Here, a vapor–liquid–solid temperature-gradient process is proposed to grow alloy heterojunctions within predeposited molten Mo precursor droplets. The sulfuration reaction between Re diffusing into the droplet and Mo atoms facilitates the formation of alloy structures. The growth temperatures <i>T</i><sub>Re</sub> and <i>T</i><sub>Mo</sub> in the temperature-gradient significantly affect the growth patterns and morphology evolution of the heterojunction. The MoS<sub>2</sub> morphology in vertical alloy heterojunctions becomes triangular as the growth temperature increases. The dimension of the top Mo<sub><i>x</i></sub>Re<sub>(1–<i>x</i>)</sub>S<sub>2</sub> alloy is positively correlated with the Re diffusion concentration. Moreover, lateral alloy heterojunctions and single alloys are formed at lower and higher growth temperature differences between <i>T</i><sub>Re</sub> and <i>T</i><sub>Mo</sub>, respectively. These results provide a controllable strategy for the synthesis of isotropic/anisotropic van der Waals TMDC heterojunctions.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"64 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143798515","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 : 2025-04-08DOI: 10.1021/acs.iecr.5c00489
Xinyi Liu, Zhaoyuan He, Ziyi Huang, Chunrong Tian, Xiaowen Zhao, Lin Ye
In order to protect electronic components from high-temperature impact and also dissipate accumulated heat during use, thermoplastic polyurethane (TPU)-based unidirectional thermal conductive foam with a gradient structure was assembled layer by layer and subsequent scCO2 foaming. Polydopamine (PDA) coating layer was first introduced to the surfaces of boron nitride (BN) with carbon nanotubes (CNTs) as bridging (PBC) through π–π stacking and hydrogen bonding interaction, leading to a high intercalation ratio of TPU molecules between BN layers. The in-plane thermal conductivity (TC) of TPU/60wt%PBC sample reached as high as 4.68 W·m–1·K–1 due to horizontal alignment of uniformly dispersed BN sheets, and excellent flexibility and foldability were also exhibited. Besides, PBC particles were selectively distributed in hard domain (HD), while with increasing TPU hardness and HD region ratio, the effective concentration of PBC in HD decreased, resulting in a drop of TC. Moreover, with increasing PBC content in each layer of TPU/PBC assembled foam, due to decreasing cell size, increasing apparent density, and formation of interconnected 3D thermal conductive network, the in-plane TC of each layer increased gradually and even reached 2.39 W·m–1·K–1 for TPU/40wt%PBC foam layer, resulting in a gradient distribution of cell structure and thermal conductivity. The assembled foam exhibited a tightly integrated structure with blurred interfaces between each layer, and unidirectional thermal conductivity was confirmed by infrared thermography.
{"title":"Construction of Thermoplastic Polyurethane-Based Unidirectional Thermal Conductive Foam with a Gradient Structure","authors":"Xinyi Liu, Zhaoyuan He, Ziyi Huang, Chunrong Tian, Xiaowen Zhao, Lin Ye","doi":"10.1021/acs.iecr.5c00489","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c00489","url":null,"abstract":"In order to protect electronic components from high-temperature impact and also dissipate accumulated heat during use, thermoplastic polyurethane (TPU)-based unidirectional thermal conductive foam with a gradient structure was assembled layer by layer and subsequent scCO<sub>2</sub> foaming. Polydopamine (PDA) coating layer was first introduced to the surfaces of boron nitride (BN) with carbon nanotubes (CNTs) as bridging (PBC) through π–π stacking and hydrogen bonding interaction, leading to a high intercalation ratio of TPU molecules between BN layers. The in-plane thermal conductivity (TC) of TPU/60wt%PBC sample reached as high as 4.68 W·m<sup>–1</sup>·K<sup>–1</sup> due to horizontal alignment of uniformly dispersed BN sheets, and excellent flexibility and foldability were also exhibited. Besides, PBC particles were selectively distributed in hard domain (HD), while with increasing TPU hardness and HD region ratio, the effective concentration of PBC in HD decreased, resulting in a drop of TC. Moreover, with increasing PBC content in each layer of TPU/PBC assembled foam, due to decreasing cell size, increasing apparent density, and formation of interconnected 3D thermal conductive network, the in-plane TC of each layer increased gradually and even reached 2.39 W·m<sup>–1</sup>·K<sup>–1</sup> for TPU/40wt%PBC foam layer, resulting in a gradient distribution of cell structure and thermal conductivity. The assembled foam exhibited a tightly integrated structure with blurred interfaces between each layer, and unidirectional thermal conductivity was confirmed by infrared thermography.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"31 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143798516","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 : 2025-04-08DOI: 10.1021/acs.iecr.5c00624
Chengyin Lin, Yongyuan Deng, Yuankai Lin, Jun Li, Junling Tu, Riyang Shu
Hydrodeoxygenation (HDO) represents a highly efficient refining pathway to convert lignin-derived phenolic compounds for the production of hydrocarbon fuels, and the selection of a suitable catalyst is pivotal for a high reaction efficiency. In this study, we introduce a novel highly dispersed Pt/Al2O3–TiO2 composite catalyst that is prepared via a photochemical reduction method and employ it for the HDO of lignin-derived phenolic compounds. The catalyst demonstrates a good HDO performance, achieving complete conversion of guaiacol at 260 °C with cyclohexane selectivity of 99.9%. Catalyst characterization results reveal that the Pt/Al2O3–TiO2 catalyst exhibits a high Pt metal dispersion. Besides, the composite support synergistically combines the properties of Al2O3 and TiO2 components, resulting in a high specific surface area, moderate acidity, and abundant oxygen vacancy. These factors facilitate the provision of numerous active metal sites and acid sites those are essential for the HDO reaction. Moreover, the Pt/Al2O3–TiO2 catalyst also shows a high activity on the HDO of various other phenolic compounds. When applied to the upgrading of lignin oil, the catalyst significantly increases the hydrocarbon content from 18.9% to 92.2%, concurrently reducing the oxygen content and substantially increasing the hydrogen content of the lignin oil. The calorific value is significantly enhanced, underscoring the potential of the Pt/Al2O3–TiO2 composite catalyst to upgrade lignin-derived phenolic compounds into high-quality hydrocarbon liquid fuels.
{"title":"Hydrodeoxygenation of Lignin-Derived Phenolic Compounds over Highly Dispersed Pt/Al2O3–TiO2 Composite Catalyst","authors":"Chengyin Lin, Yongyuan Deng, Yuankai Lin, Jun Li, Junling Tu, Riyang Shu","doi":"10.1021/acs.iecr.5c00624","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c00624","url":null,"abstract":"Hydrodeoxygenation (HDO) represents a highly efficient refining pathway to convert lignin-derived phenolic compounds for the production of hydrocarbon fuels, and the selection of a suitable catalyst is pivotal for a high reaction efficiency. In this study, we introduce a novel highly dispersed Pt/Al<sub>2</sub>O<sub>3</sub>–TiO<sub>2</sub> composite catalyst that is prepared via a photochemical reduction method and employ it for the HDO of lignin-derived phenolic compounds. The catalyst demonstrates a good HDO performance, achieving complete conversion of guaiacol at 260 °C with cyclohexane selectivity of 99.9%. Catalyst characterization results reveal that the Pt/Al<sub>2</sub>O<sub>3</sub>–TiO<sub>2</sub> catalyst exhibits a high Pt metal dispersion. Besides, the composite support synergistically combines the properties of Al<sub>2</sub>O<sub>3</sub> and TiO<sub>2</sub> components, resulting in a high specific surface area, moderate acidity, and abundant oxygen vacancy. These factors facilitate the provision of numerous active metal sites and acid sites those are essential for the HDO reaction. Moreover, the Pt/Al<sub>2</sub>O<sub>3</sub>–TiO<sub>2</sub> catalyst also shows a high activity on the HDO of various other phenolic compounds. When applied to the upgrading of lignin oil, the catalyst significantly increases the hydrocarbon content from 18.9% to 92.2%, concurrently reducing the oxygen content and substantially increasing the hydrogen content of the lignin oil. The calorific value is significantly enhanced, underscoring the potential of the Pt/Al<sub>2</sub>O<sub>3</sub>–TiO<sub>2</sub> composite catalyst to upgrade lignin-derived phenolic compounds into high-quality hydrocarbon liquid fuels.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"56 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143798518","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}
Continuous reactors serve as a core component in commercial hydrothermal liquefaction systems, enabling high-capacity biocrude production from sludge. To optimize the reactor configuration and operation conditions, HTL kinetics of sludge were coupled with computational fluid dynamics and finite element methods. The proposed model was used to explore the distributions of biocrude yield, temperature, and stress. With a total length of 0.5 m, the upward-flow serpentine reactor, 325 °C, an inner diameter of 20 mm, and an inlet velocity of 0.0009 m·s–1 provided the highest biocrude yield of 34.39 wt %. Stress concentrations at the bends were observed in the serpentine reactor. Increasing the bending diameter from 14 to 24 mm reduced the maximum equivalent stress from 136.22 to 113.86 MPa, allowing the application of inexpensive stainless steel as the reactor material. The coupled model also provides insights into optimizing the length of a pilot-scale reactor.
{"title":"Numerical Simulation of Hydrothermal Liquefaction of Sludge in Continuous Reactors: Integration of Kinetics, Fluid Dynamics, and Stress Analyses","authors":"Lili Qian, Chenzheng Ma, Wei Huang, Hao Chen, Shuang Wang, Heng Gu","doi":"10.1021/acs.iecr.4c03708","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c03708","url":null,"abstract":"Continuous reactors serve as a core component in commercial hydrothermal liquefaction systems, enabling high-capacity biocrude production from sludge. To optimize the reactor configuration and operation conditions, HTL kinetics of sludge were coupled with computational fluid dynamics and finite element methods. The proposed model was used to explore the distributions of biocrude yield, temperature, and stress. With a total length of 0.5 m, the upward-flow serpentine reactor, 325 °C, an inner diameter of 20 mm, and an inlet velocity of 0.0009 m·s<sup>–1</sup> provided the highest biocrude yield of 34.39 wt %. Stress concentrations at the bends were observed in the serpentine reactor. Increasing the bending diameter from 14 to 24 mm reduced the maximum equivalent stress from 136.22 to 113.86 MPa, allowing the application of inexpensive stainless steel as the reactor material. The coupled model also provides insights into optimizing the length of a pilot-scale reactor.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"242 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143798511","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}
In this study, a series of puffball carbon-supported catalysts were synthesized to facilitate the hydrodeoxygenation (HDO) of the lignin model compound vanillin (VAN) into 2-methoxy-4-methylphenol (MMP). The Co-ZIF/BC catalyst, prepared by loading ZIF-67 onto puffball carbon support, achieved a VAN conversion rate of 96.28% and a selectivity of 86.57% for MMP under reaction conditions of 240 °C and 1.5 MPa of H2 for 4 h. Based on the characterization results, it was found that the Co-ZIF/BC catalyst exhibited high crystal defects, a large specific surface area, and mesopore volume, as well as strong Lewis acid sites. Additionally, the Co–N bonds formed between Co nanoparticles and nitrogen increased the electron density on the catalyst surface. The abundant surface Co0 species enhanced hydrogen adsorption and dissociation, providing more active sites, which facilitated the activation of reactants and improved the efficiency of the catalytic reaction. The use of abundant and low-cost puffball materials in the preparation of the Co-ZIF/BC catalyst not only reduced production costs but also supported the sustainability of the catalytic process, aligning with the principles of green chemistry.
{"title":"Metal–Organic Frameworks and Biomass: Mutual Partners on Designing Environmentally Friendly Catalysts for Catalytic Conversion of Lignin-Derived Substances","authors":"Changyong Li, Mengqing Zhou, Yun Zheng, Shengchun Hu, Liangliang Zhang, Changzhou Chen, Jianchun Jiang","doi":"10.1021/acs.iecr.5c00201","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c00201","url":null,"abstract":"In this study, a series of puffball carbon-supported catalysts were synthesized to facilitate the hydrodeoxygenation (HDO) of the lignin model compound vanillin (VAN) into 2-methoxy-4-methylphenol (MMP). The Co-ZIF/BC catalyst, prepared by loading ZIF-67 onto puffball carbon support, achieved a VAN conversion rate of 96.28% and a selectivity of 86.57% for MMP under reaction conditions of 240 °C and 1.5 MPa of H<sub>2</sub> for 4 h. Based on the characterization results, it was found that the Co-ZIF/BC catalyst exhibited high crystal defects, a large specific surface area, and mesopore volume, as well as strong Lewis acid sites. Additionally, the Co–N bonds formed between Co nanoparticles and nitrogen increased the electron density on the catalyst surface. The abundant surface Co<sup>0</sup> species enhanced hydrogen adsorption and dissociation, providing more active sites, which facilitated the activation of reactants and improved the efficiency of the catalytic reaction. The use of abundant and low-cost puffball materials in the preparation of the Co-ZIF/BC catalyst not only reduced production costs but also supported the sustainability of the catalytic process, aligning with the principles of green chemistry.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"65 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143806407","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}
CuO-ZnO-TiO2 was prepared by ultrasound-assisted coprecipitation. Its catalytic performance in the liquid-phase oxidation of cumene with oxygen to cumene hydroperoxide (CHP) was studied. Under the reaction conditions of CuO:ZnO:TiO2 molar ratio of 3:1:1.33, feed ratio (catalyst/cumene) of 7.5 mg/mL, reaction temperature of 85 °C, reaction time of 7 h, and oxygen flow rate of 15 mL/min, the conversion of cumene was 37.2% and the selectivity of CHP was 94.5%. Characterization by XRD, SEM, TEM, EDS, and N2 adsorption/desorption showed 3CuO-ZnO-TiO2 was concentrated with a particle size of about 50 nm, specific area of about 110 m2/g with a pore volume of 0.0048 cm3/g, and high dispersion of active components. XPS and O2-TPD characterization indicated that 3CuO-ZnO-TiO2 contains a large amount of lattice oxygen and reactive oxygen species. DFT simulation indicated ROO· is more easily generated and more likely to bind to the CuO-ZnO surface to facilitate oxidation of cumene to cumene peroxides.
{"title":"Application, Characterization, and Simulation of CuO-ZnO-TiO2 for Catalytic Oxidation of Cumene to Cumene Hydroperoxide","authors":"Yicheng Zhang, Siyu Wu, Yuetong Ma, Fei Zha, Xiaohua Tang, Yue Chang, Haifeng Tian, Xiaojun Guo","doi":"10.1021/acs.iecr.4c04387","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c04387","url":null,"abstract":"CuO-ZnO-TiO<sub>2</sub> was prepared by ultrasound-assisted coprecipitation. Its catalytic performance in the liquid-phase oxidation of cumene with oxygen to cumene hydroperoxide (CHP) was studied. Under the reaction conditions of CuO:ZnO:TiO<sub>2</sub> molar ratio of 3:1:1.33, feed ratio (catalyst/cumene) of 7.5 mg/mL, reaction temperature of 85 °C, reaction time of 7 h, and oxygen flow rate of 15 mL/min, the conversion of cumene was 37.2% and the selectivity of CHP was 94.5%. Characterization by XRD, SEM, TEM, EDS, and N<sub>2</sub> adsorption/desorption showed 3CuO-ZnO-TiO<sub>2</sub> was concentrated with a particle size of about 50 nm, specific area of about 110 m<sup>2</sup>/g with a pore volume of 0.0048 cm<sup>3</sup>/g, and high dispersion of active components. XPS and O<sub>2</sub>-TPD characterization indicated that 3CuO-ZnO-TiO<sub>2</sub> contains a large amount of lattice oxygen and reactive oxygen species. DFT simulation indicated ROO· is more easily generated and more likely to bind to the CuO-ZnO surface to facilitate oxidation of cumene to cumene peroxides.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"16 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143798513","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 : 2025-04-08DOI: 10.1021/acs.iecr.5c00008
Deyin Gu, Changshu Li, Yinghua Song, Hui Xu, Ting yao
In this work, an impeller with a fractal structure design was introduced in the laminar mixing of high-viscosity fluids to facilitate chaotic advection. Power consumption characteristics, mixing time, Kolmogorov entropy, and 0–1 test were applied to characterize the mixing performance and chaotic mixing characteristics. Visualization experiment, Poincaré section, and trajectories of massless particles were employed to investigate the structure of the flow field. The findings showed that the fractal structure design introduced in the impeller blades provided a reduction in power consumption, power number, and mixing time and an improvement in the Kolmogorov entropy and chaotic mixing degree, while additional energy conservation, less mixing time, and a higher chaotic mixing degree were achieved by increasing the fractal iteration number in the impeller blades. Poincaré section showed the isolated mixing regions (IMRs) and chaotic mixing regions (CMRs) in the flow field, and the phenomenon can also be confirmed by visualization experiment. The particles within the IMRs did not undergo material exchange but rather exhibited movement solely within the designated regions. In addition, the trajectories of massless particles suggested that the fractal structure design of impeller blades facilitated structural instability of the IMRs, stimulated fluid particles to escape from the IMRs into the CMRs, and induced chaotic advection in the flow field.
{"title":"Investigation on the Chaotic Mixing Mechanism of High-Viscosity Fluids with Laminar Flow in an Irregular Impeller Stirred Tank","authors":"Deyin Gu, Changshu Li, Yinghua Song, Hui Xu, Ting yao","doi":"10.1021/acs.iecr.5c00008","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c00008","url":null,"abstract":"In this work, an impeller with a fractal structure design was introduced in the laminar mixing of high-viscosity fluids to facilitate chaotic advection. Power consumption characteristics, mixing time, Kolmogorov entropy, and 0–1 test were applied to characterize the mixing performance and chaotic mixing characteristics. Visualization experiment, Poincaré section, and trajectories of massless particles were employed to investigate the structure of the flow field. The findings showed that the fractal structure design introduced in the impeller blades provided a reduction in power consumption, power number, and mixing time and an improvement in the Kolmogorov entropy and chaotic mixing degree, while additional energy conservation, less mixing time, and a higher chaotic mixing degree were achieved by increasing the fractal iteration number in the impeller blades. Poincaré section showed the isolated mixing regions (IMRs) and chaotic mixing regions (CMRs) in the flow field, and the phenomenon can also be confirmed by visualization experiment. The particles within the IMRs did not undergo material exchange but rather exhibited movement solely within the designated regions. In addition, the trajectories of massless particles suggested that the fractal structure design of impeller blades facilitated structural instability of the IMRs, stimulated fluid particles to escape from the IMRs into the CMRs, and induced chaotic advection in the flow field.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"43 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143806408","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}
CuO-ZnO-TiO2 was prepared by ultrasound-assisted coprecipitation. Its catalytic performance in the liquid-phase oxidation of cumene with oxygen to cumene hydroperoxide (CHP) was studied. Under the reaction conditions of CuO:ZnO:TiO2 molar ratio of 3:1:1.33, feed ratio (catalyst/cumene) of 7.5 mg/mL, reaction temperature of 85 °C, reaction time of 7 h, and oxygen flow rate of 15 mL/min, the conversion of cumene was 37.2% and the selectivity of CHP was 94.5%. Characterization by XRD, SEM, TEM, EDS, and N2 adsorption/desorption showed 3CuO-ZnO-TiO2 was concentrated with a particle size of about 50 nm, specific area of about 110 m2/g with a pore volume of 0.0048 cm3/g, and high dispersion of active components. XPS and O2-TPD characterization indicated that 3CuO-ZnO-TiO2 contains a large amount of lattice oxygen and reactive oxygen species. DFT simulation indicated ROO· is more easily generated and more likely to bind to the CuO-ZnO surface to facilitate oxidation of cumene to cumene peroxides.
{"title":"Application, Characterization, and Simulation of CuO-ZnO-TiO2 for Catalytic Oxidation of Cumene to Cumene Hydroperoxide","authors":"Yicheng Zhang, Siyu Wu, Yuetong Ma, Fei Zha*, Xiaohua Tang, Yue Chang, Haifeng Tian and Xiaojun Guo, ","doi":"10.1021/acs.iecr.4c0438710.1021/acs.iecr.4c04387","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c04387https://doi.org/10.1021/acs.iecr.4c04387","url":null,"abstract":"<p >CuO-ZnO-TiO<sub>2</sub> was prepared by ultrasound-assisted coprecipitation. Its catalytic performance in the liquid-phase oxidation of cumene with oxygen to cumene hydroperoxide (CHP) was studied. Under the reaction conditions of CuO:ZnO:TiO<sub>2</sub> molar ratio of 3:1:1.33, feed ratio (catalyst/cumene) of 7.5 mg/mL, reaction temperature of 85 °C, reaction time of 7 h, and oxygen flow rate of 15 mL/min, the conversion of cumene was 37.2% and the selectivity of CHP was 94.5%. Characterization by XRD, SEM, TEM, EDS, and N<sub>2</sub> adsorption/desorption showed 3CuO-ZnO-TiO<sub>2</sub> was concentrated with a particle size of about 50 nm, specific area of about 110 m<sup>2</sup>/g with a pore volume of 0.0048 cm<sup>3</sup>/g, and high dispersion of active components. XPS and O<sub>2</sub>-TPD characterization indicated that 3CuO-ZnO-TiO<sub>2</sub> contains a large amount of lattice oxygen and reactive oxygen species. DFT simulation indicated ROO· is more easily generated and more likely to bind to the CuO-ZnO surface to facilitate oxidation of cumene to cumene peroxides.</p>","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"64 15","pages":"7670–7678 7670–7678"},"PeriodicalIF":3.8,"publicationDate":"2025-04-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143832699","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：