Pub Date : 2025-04-02DOI: 10.1021/acs.iecr.4c04684
Jie Zeng, Yifei Wang, Dawei Feng, Qian Liu, Yan Gong, Guangsuo Yu, Fuchen Wang
The liquid film interfacial wave characteristics of vertical and swirling flow are experimentally investigated with the ultrasonic Doppler velocimetry and a high-speed camera under a liquid-phase Reynolds number (Rel) of 5.88 × 103–1.23 × 104, and a correlation for the disturbance wave frequency of swirling flow was developed based on the centrifugal-gravity ratio. The interfacial waves of swirling flow have no apparent periodicity and correlation, similar to the vertical flow. In swirling flow, centrifugal force promotes the accumulation of liquid film mass, reflected in the increase of the substrate liquid film. The circumferential velocity of the swirling flow increases the wall friction stress, reducing the disturbance wave velocity. The superposition of swirling streaks promotes the formation of disturbance waves. Still, the increasing centrifugal force forces the disturbance waves to transfer mass and energy to the ripples, suppressing the formation of disturbance waves. The established correlation for the disturbance wave frequency has a good prediction effect with a mean absolute percentage error of 19.89%.
{"title":"Effect of Centrifugal Force on the Disturbance Wave Characteristics of Decay Swirl Liquid Film","authors":"Jie Zeng, Yifei Wang, Dawei Feng, Qian Liu, Yan Gong, Guangsuo Yu, Fuchen Wang","doi":"10.1021/acs.iecr.4c04684","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c04684","url":null,"abstract":"The liquid film interfacial wave characteristics of vertical and swirling flow are experimentally investigated with the ultrasonic Doppler velocimetry and a high-speed camera under a liquid-phase Reynolds number (<i>Re</i><sub>l</sub>) of 5.88 × 10<sup>3</sup>–1.23 × 10<sup>4</sup>, and a correlation for the disturbance wave frequency of swirling flow was developed based on the centrifugal-gravity ratio. The interfacial waves of swirling flow have no apparent periodicity and correlation, similar to the vertical flow. In swirling flow, centrifugal force promotes the accumulation of liquid film mass, reflected in the increase of the substrate liquid film. The circumferential velocity of the swirling flow increases the wall friction stress, reducing the disturbance wave velocity. The superposition of swirling streaks promotes the formation of disturbance waves. Still, the increasing centrifugal force forces the disturbance waves to transfer mass and energy to the ripples, suppressing the formation of disturbance waves. The established correlation for the disturbance wave frequency has a good prediction effect with a mean absolute percentage error of 19.89%.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"8 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143758209","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 : 2025-04-02DOI: 10.1021/acs.iecr.4c04850
Om Prakash Bamboriya, Mahesh S. Tirumkudulu, Subramanian Ramakrishnan
An understanding of the morphological transformations of drying, particle-laden drops, is important for industrial processes such as spray drying, where drops of particulate suspensions dry rapidly to produce granules. The high drying rates during spray drying produce particle-packed shells saturated with liquid, which may buckle, transforming spherical shells into crumpled granules. The morphology of granules depends on the particle’s mechanical properties and size, interparticle interaction, and drying rates. A recent theory has shown that the morphological transformations are controlled by a dimensionless parameter that measures the competition between the compressive stress generated by capillary forces and the elastic strength of the packing. In this work, we perform experiments on a spray dryer with suspensions containing particles of varying sizes and moduli to test the theoretical predictions. We show remarkable agreement with the theory over many orders of magnitude of the dimensionless parameter. The results provide a fundamental understanding of the morphological changes observed in fast-drying drops containing particles and enable the design of buckle-free granules with desired properties.
{"title":"Buckling of Spray Drying Drops","authors":"Om Prakash Bamboriya, Mahesh S. Tirumkudulu, Subramanian Ramakrishnan","doi":"10.1021/acs.iecr.4c04850","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c04850","url":null,"abstract":"An understanding of the morphological transformations of drying, particle-laden drops, is important for industrial processes such as spray drying, where drops of particulate suspensions dry rapidly to produce granules. The high drying rates during spray drying produce particle-packed shells saturated with liquid, which may buckle, transforming spherical shells into crumpled granules. The morphology of granules depends on the particle’s mechanical properties and size, interparticle interaction, and drying rates. A recent theory has shown that the morphological transformations are controlled by a dimensionless parameter that measures the competition between the compressive stress generated by capillary forces and the elastic strength of the packing. In this work, we perform experiments on a spray dryer with suspensions containing particles of varying sizes and moduli to test the theoretical predictions. We show remarkable agreement with the theory over many orders of magnitude of the dimensionless parameter. The results provide a fundamental understanding of the morphological changes observed in fast-drying drops containing particles and enable the design of buckle-free granules with desired properties.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"58 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143758210","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 : 2025-04-02DOI: 10.1021/acs.iecr.4c04819
Gang Wang, Shuwen Zhang, Ye Zhu, Xuesong Li, Shiguo Wei, Bing Wang, Yangtian Jing, Changjiang Zuo, Jijun Chen, Jie Zhang, Yufeng Zhou, Jinwei Chen, Ruilin Wang
A novel sulfonated polyimide (SPI-PTDA) is synthesized by introducing low-cost and rigid perylene-3,4,9,10-tetracarboxylic dianhydride (PTDA) into the SPI backbone. A sequence of SPI-PTDA-X membranes with different sulfonation levels has been prepared and characterized. The stable retention time of the SPI-PTDA-75 membrane in aqueous solution at 80 °C is greater than 240 h; its tensile strength (25.83 MPa) is three times that of N212, and the results of the theoretical calculations of molecular ESP indicate the existence of certain interactions within the SPI-PTDA molecule, being responsible for the enhanced mechanical strength of the SPI-PTDA membrane. Additionally, the vanadium ion selectivity of the SPI-PTDA-75 membrane is approximately double that of the N212. The VRFB with the SPI-PTDA-75 membrane demonstrates a Coulombic efficiency (CE) of 97.59% and an energy efficiency (EE) of 80.47% at 120 mA cm–2. The results of 400 charge–discharge cycling tests reveal that the SPI-PTDA-75 membrane maintains strong long-term cycling stability.
{"title":"Low-Cost and High-Performance Sulfonated Polyimide Membrane for Vanadium Redox Flow Battery Application","authors":"Gang Wang, Shuwen Zhang, Ye Zhu, Xuesong Li, Shiguo Wei, Bing Wang, Yangtian Jing, Changjiang Zuo, Jijun Chen, Jie Zhang, Yufeng Zhou, Jinwei Chen, Ruilin Wang","doi":"10.1021/acs.iecr.4c04819","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c04819","url":null,"abstract":"A novel sulfonated polyimide (SPI-PTDA) is synthesized by introducing low-cost and rigid perylene-3,4,9,10-tetracarboxylic dianhydride (PTDA) into the SPI backbone. A sequence of SPI-PTDA-X membranes with different sulfonation levels has been prepared and characterized. The stable retention time of the SPI-PTDA-75 membrane in aqueous solution at 80 °C is greater than 240 h; its tensile strength (25.83 MPa) is three times that of N212, and the results of the theoretical calculations of molecular ESP indicate the existence of certain interactions within the SPI-PTDA molecule, being responsible for the enhanced mechanical strength of the SPI-PTDA membrane. Additionally, the vanadium ion selectivity of the SPI-PTDA-75 membrane is approximately double that of the N212. The VRFB with the SPI-PTDA-75 membrane demonstrates a Coulombic efficiency (CE) of 97.59% and an energy efficiency (EE) of 80.47% at 120 mA cm<sup>–2</sup>. The results of 400 charge–discharge cycling tests reveal that the SPI-PTDA-75 membrane maintains strong long-term cycling stability.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"183 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143758213","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 : 2025-04-02DOI: 10.1021/acs.iecr.5c00311
Ran Chen, Ziyu Zhang, Yining Deng, Jinyan Wang, Yuchun Cui, Yuzeng Zhao, Honghua Ge
Polyethylene terephthalate (PET) is a common packaging plastic that degrades extremely slowly in the environment, with low efficiency in both photodegradation and biodegradation. This study investigates the electrochemical degradation of PET MPs. First, the electrochemical degradation process of PET MPs in aquatic environments was examined. Under the condition of no additional catalyst, the degradation efficiency was measured using a weight loss method, and more efficient electrolysis efficiency was obtained through orthogonal experiment. After 6 h of electrolysis, the weight loss was as high as 68%. The analysis shows that electrolysis temperature is a more critical factor than current density, pH, and surfactant concentration. Second, by studying the changes of soluble organic pollutants in PET MPs and electrolyte with time and temperature during the reaction process, indicating that the increased crystallinity of PET MPs limits the enhancement of degradation efficiency. Furthermore, it was pointed out that the oxidation–reduction reaction of the electrode reaction was enhanced by the surfactant. Combined with the active species analysis, hydroxyl radicals (•OH) and sulfate radicals (SO4•–) play a role in the degradation of PET MPs. The mechanism of electrochemical degradation of PET MPs was hypothesize. The electrochemical degradation method used in this study is characterized by a short treatment time and high efficiency, providing a feasible solution for improving microplastic degradation efficiency, and also provides an effective reference for electrochemical degradation of insoluble pollutants in water.
{"title":"Electrochemical Degradation of PET Microplastics and Its Mechanism","authors":"Ran Chen, Ziyu Zhang, Yining Deng, Jinyan Wang, Yuchun Cui, Yuzeng Zhao, Honghua Ge","doi":"10.1021/acs.iecr.5c00311","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c00311","url":null,"abstract":"Polyethylene terephthalate (PET) is a common packaging plastic that degrades extremely slowly in the environment, with low efficiency in both photodegradation and biodegradation. This study investigates the electrochemical degradation of PET MPs. First, the electrochemical degradation process of PET MPs in aquatic environments was examined. Under the condition of no additional catalyst, the degradation efficiency was measured using a weight loss method, and more efficient electrolysis efficiency was obtained through orthogonal experiment. After 6 h of electrolysis, the weight loss was as high as 68%. The analysis shows that electrolysis temperature is a more critical factor than current density, pH, and surfactant concentration. Second, by studying the changes of soluble organic pollutants in PET MPs and electrolyte with time and temperature during the reaction process, indicating that the increased crystallinity of PET MPs limits the enhancement of degradation efficiency. Furthermore, it was pointed out that the oxidation–reduction reaction of the electrode reaction was enhanced by the surfactant. Combined with the active species analysis, hydroxyl radicals (<sup>•</sup>OH) and sulfate radicals (SO<sub>4</sub><sup>•–</sup>) play a role in the degradation of PET MPs. The mechanism of electrochemical degradation of PET MPs was hypothesize. The electrochemical degradation method used in this study is characterized by a short treatment time and high efficiency, providing a feasible solution for improving microplastic degradation efficiency, and also provides an effective reference for electrochemical degradation of insoluble pollutants in water.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"61 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-04-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143758211","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 : 2025-04-01DOI: 10.1021/acs.iecr.4c03784
Andrew Z. Haddad, Akanksha K. Menon, Ravindra Revanur, Jennifer Klare, Jeffrey J. Urban, Robert Kostecki
Forward osmosis (FO) desalination using thermoresponsive ionic liquid (IL)–water mixtures is a promising technology for treating nontraditional water sources. However, its demonstration has primarily been at the lab-scale, with water flux and recovery values that are not representative of realistic applications. In this work, the performance of tetrabutyl-phosphonium trifluoroacetate (P4444TFA), as well as a new dual draw of P4444TFA with tetrabutyl-ammonium trifluoroacetate (N4444TFA) is characterized. The dual draw combines the higher osmolality of one IL with the lower critical solution temperature (LCST) of the second IL to outperform its constituents at the same total concentration of IL in water (70 wt %). Experiments were first performed in a lab-scale coupon tester to understand the effects of draw osmotic pressure and viscosity on water flux through the membrane. Bench-scale experiments were then performed in an element tester with a 1 m2 membrane area to evaluate the performance of IL-based FO for the desalination of produced water feed from oil and gas. Specifically, 10 kg of IL-water draw solution was used with 3 kg of real produced water feed, resulting in water recoveries of 60% with initial and final water fluxes of 14 LMH and 3 LMH, respectively. The bench-scale experimental results were used as inputs for a cost analysis, yielding a levelized cost of water (LCOW) of $1.18 per m3. This reveals the potential of IL-based draw solutions for cost-effective desalination of challenging feedwaters using FO.
{"title":"Forward Osmosis Desalination Using Thermoresponsive Ionic Liquids: Bench-Scale Demonstration and Cost Analysis","authors":"Andrew Z. Haddad, Akanksha K. Menon, Ravindra Revanur, Jennifer Klare, Jeffrey J. Urban, Robert Kostecki","doi":"10.1021/acs.iecr.4c03784","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c03784","url":null,"abstract":"Forward osmosis (FO) desalination using thermoresponsive ionic liquid (IL)–water mixtures is a promising technology for treating nontraditional water sources. However, its demonstration has primarily been at the lab-scale, with water flux and recovery values that are not representative of realistic applications. In this work, the performance of tetrabutyl-phosphonium trifluoroacetate (P<sub>4444</sub>TFA), as well as a new dual draw of P<sub>4444</sub>TFA with tetrabutyl-ammonium trifluoroacetate (N<sub>4444</sub>TFA) is characterized. The dual draw combines the higher osmolality of one IL with the lower critical solution temperature (LCST) of the second IL to outperform its constituents at the same total concentration of IL in water (70 wt %). Experiments were first performed in a lab-scale coupon tester to understand the effects of draw osmotic pressure and viscosity on water flux through the membrane. Bench-scale experiments were then performed in an element tester with a 1 m<sup>2</sup> membrane area to evaluate the performance of IL-based FO for the desalination of produced water feed from oil and gas. Specifically, 10 kg of IL-water draw solution was used with 3 kg of real produced water feed, resulting in water recoveries of 60% with initial and final water fluxes of 14 LMH and 3 LMH, respectively. The bench-scale experimental results were used as inputs for a cost analysis, yielding a levelized cost of water (LCOW) of $1.18 per m<sup>3</sup>. This reveals the potential of IL-based draw solutions for cost-effective desalination of challenging feedwaters using FO.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"24 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143758212","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 : 2025-04-01DOI: 10.1021/acs.iecr.5c00482
Valquiria Lilith Braga das Neves, Layanne Guedes Silva de Araújo, Rílvia Saraiva de Santiago-Aguiar
Microplastic pollution is a growing environmental concern, requiring the development of efficient recycling processes to mitigate its impact and ensure proper waste disposal. Chemical recycling has emerged as a promising strategy; however, conventional techniques often rely on hazardous solvents, long reaction times, and extreme operating conditions, like high temperatures and pressures. In this context, protic ionic liquids (PILs) have gained attention as sustainable alternatives due to their thermal stability, reusability, and ability to optimize reaction conditions. This study investigates the hydrolysis of polyethylene terephthalate (PET) microplastics using low-toxicity PILs as solvents. The depolymerization efficiency was evaluated using four PILs: choline formate ([ChFor]), triethanolammonium acetate ([TEAA]), 1,5-diazabicyclo [4.3.0] non-5-ene acetate ([DBNH][OAc]), and tetramethylammonium formate ([TeMA][For]). These PILs were synthesized and characterized by FTIR and 1H NMR spectroscopy to confirm their structures. Cytotoxicity assays using Artemia salina classified these compounds as low or nontoxic (LC50 > 250 μg/mL). The results demonstrated that all studied PILs were capable of depolymerizing PET. Among them, [DBNH][OAc] exhibited the highest efficiency, achieving 99.67% PET conversion and 92.52% terephthalic acid (TPA) yield at 110 °C within 30 min. Structural characterization confirmed the production of TPA, supporting its potential reintegration into industrial applications and preventing recontamination by microplastics.
{"title":"Chemical Recycling of Polyethylene Terephthalate (PET) Driven by the Use of Protic Ionic Liquids: A Strategy to Mitigate Microplastic Pollution","authors":"Valquiria Lilith Braga das Neves, Layanne Guedes Silva de Araújo, Rílvia Saraiva de Santiago-Aguiar","doi":"10.1021/acs.iecr.5c00482","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c00482","url":null,"abstract":"Microplastic pollution is a growing environmental concern, requiring the development of efficient recycling processes to mitigate its impact and ensure proper waste disposal. Chemical recycling has emerged as a promising strategy; however, conventional techniques often rely on hazardous solvents, long reaction times, and extreme operating conditions, like high temperatures and pressures. In this context, protic ionic liquids (PILs) have gained attention as sustainable alternatives due to their thermal stability, reusability, and ability to optimize reaction conditions. This study investigates the hydrolysis of polyethylene terephthalate (PET) microplastics using low-toxicity PILs as solvents. The depolymerization efficiency was evaluated using four PILs: choline formate ([ChFor]), triethanolammonium acetate ([TEAA]), 1,5-diazabicyclo [4.3.0] non-5-ene acetate ([DBNH][OAc]), and tetramethylammonium formate ([TeMA][For]). These PILs were synthesized and characterized by FTIR and <sup>1</sup>H NMR spectroscopy to confirm their structures. Cytotoxicity assays using <i>Artemia salina</i> classified these compounds as low or nontoxic (LC<sub>50</sub> > 250 μg/mL). The results demonstrated that all studied PILs were capable of depolymerizing PET. Among them, [DBNH][OAc] exhibited the highest efficiency, achieving 99.67% PET conversion and 92.52% terephthalic acid (TPA) yield at 110 °C within 30 min. Structural characterization confirmed the production of TPA, supporting its potential reintegration into industrial applications and preventing recontamination by microplastics.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"75 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143745619","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}
Propane dehydrogenation (PDH) over platinum-based bimetallic catalysts has received widespread attention as an on-purpose technology for producing propylene. However, catalysts prepared using the traditional impregnation method usually show a weak interaction between the support and active Pt sites. Moreover, catalysts undergo structural changes in a high-temperature-reducing atmosphere, resulting in decreased activity during the reaction. To enhance the metal–support interaction, Zn-doped mesoporous silica nanoparticle (Zn-MSN) supports were prepared using a one-step synthesis to support Pt species. The addition of Zn altered the surface properties of the MSN support, increasing the number of surface hydroxyl groups and thereby improving the dispersion of [Pt(NH3)4]2+ on the catalyst surface through electrostatic interactions. The Pt/2.0Zn-MSN catalyst, with highly stable and dispersed Pt clusters, showed the highest PDH activity, with an initial propane conversion and propylene selectivity of 51.3% and 98.7%, respectively. It also showed strong resistance to coke deposition and had the lowest deactivation rate of 0.008 h–1.
{"title":"Propane Dehydrogenation Over the Catalyst with Stable and Dispersed Pt Clusters on Zn-MSN Support","authors":"Jiaxin Song, Yiou Shan, Xiaoqiang Fan, Xuehua Yu, Lian Kong, Xia Xiao, Zean Xie, Zhen Zhao","doi":"10.1021/acs.iecr.5c00198","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c00198","url":null,"abstract":"Propane dehydrogenation (PDH) over platinum-based bimetallic catalysts has received widespread attention as an on-purpose technology for producing propylene. However, catalysts prepared using the traditional impregnation method usually show a weak interaction between the support and active Pt sites. Moreover, catalysts undergo structural changes in a high-temperature-reducing atmosphere, resulting in decreased activity during the reaction. To enhance the metal–support interaction, Zn-doped mesoporous silica nanoparticle (Zn-MSN) supports were prepared using a one-step synthesis to support Pt species. The addition of Zn altered the surface properties of the MSN support, increasing the number of surface hydroxyl groups and thereby improving the dispersion of [Pt(NH<sub>3</sub>)<sub>4</sub>]<sup>2+</sup> on the catalyst surface through electrostatic interactions. The Pt/2.0Zn-MSN catalyst, with highly stable and dispersed Pt clusters, showed the highest PDH activity, with an initial propane conversion and propylene selectivity of 51.3% and 98.7%, respectively. It also showed strong resistance to coke deposition and had the lowest deactivation rate of 0.008 h<sup>–1</sup>.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"38 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143745621","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 : 2025-04-01DOI: 10.1021/acs.iecr.4c04958
Yubin Li, Yuxin Kang, Antai Kang, Xiangyang Liu, Sha Li, Li Qiu, Weimin Zhang, Ruifeng Li, Xiaoliang Yan
Ni–Fe alloy catalysts represent promising alternatives for dry reforming of methane (DRM). However, the strong affinity of Fe for oxygen caused progressive Fe segregation on the alloy, leading to a decline in catalytic properties. Herein, we explored an efficient approach to create highly dispersed CeO2 clusters on an Al2O3 support for anchoring the stable Ni3Fe1 alloy using the oxygen spillover effect. CH4 and CO2 conversions as well as the H2/CO ratio were maintained at 73.7%, 81.6%, and 0.87 at 700 °C, respectively, on the optimal Ni3Fe1/1CeO2–16Al2O3. This catalyst featured plentiful oxygen vacancies, strong interactions between the metal and support, and moderate CO2 activation centers. These collective effects enable the oxygen spillover from FeOx toward the proximate vacancies on CeO2. These oxygen species were consumed along with the generation of vacancies by carbon species. The oxygen spillover effect could not only stabilize the alloy structures but alleviate carbon deposition in DRM.
{"title":"Effect of Oxygen Spillover on Stable Ni3Fe1 Alloy for High-Performance Dry Reforming of Methane","authors":"Yubin Li, Yuxin Kang, Antai Kang, Xiangyang Liu, Sha Li, Li Qiu, Weimin Zhang, Ruifeng Li, Xiaoliang Yan","doi":"10.1021/acs.iecr.4c04958","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c04958","url":null,"abstract":"Ni–Fe alloy catalysts represent promising alternatives for dry reforming of methane (DRM). However, the strong affinity of Fe for oxygen caused progressive Fe segregation on the alloy, leading to a decline in catalytic properties. Herein, we explored an efficient approach to create highly dispersed CeO<sub>2</sub> clusters on an Al<sub>2</sub>O<sub>3</sub> support for anchoring the stable Ni<sub>3</sub>Fe<sub>1</sub> alloy using the oxygen spillover effect. CH<sub>4</sub> and CO<sub>2</sub> conversions as well as the H<sub>2</sub>/CO ratio were maintained at 73.7%, 81.6%, and 0.87 at 700 °C, respectively, on the optimal Ni<sub>3</sub>Fe<sub>1</sub>/1CeO<sub>2</sub>–16Al<sub>2</sub>O<sub>3</sub>. This catalyst featured plentiful oxygen vacancies, strong interactions between the metal and support, and moderate CO<sub>2</sub> activation centers. These collective effects enable the oxygen spillover from FeO<sub><i>x</i></sub> toward the proximate vacancies on CeO<sub>2</sub>. These oxygen species were consumed along with the generation of vacancies by carbon species. The oxygen spillover effect could not only stabilize the alloy structures but alleviate carbon deposition in DRM.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"28 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143745618","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 : 2025-04-01DOI: 10.1021/acs.iecr.5c00412
Patrycja Mruc, Dorota Antos
Chiral chromatography (CCh) is often a cost driver in the large-scale separation of enantiomers. To improve the economics of the separation process, we developed the concept of coupling CCh with achiral chromatography (ACh). In this concept, the CCh step is used to enrich the enantiomeric mixture with the target enantiomer, while in the ACh step, the enriched mixture is separated to obtain the product with a desired purity. The ACh separation is driven by the phenomenon of self-disproportionation of enantiomers (SDE), which relies on formation of homochiral and heterochiral associates that can be separated in an achiral environment, whereas the CCh separation occurs in the presence of a chiral stationary phase (CSP). The coupled ACh-CCh process is operated in a cyclic mode for which cyclic steady state is attained. To demonstrate the concept of the process and develop a generic methodology for its design, a model mixture consisting of enantiomers of methyl p-tolyl sulfoxide was used, with S-p-tolyl sulfoxide as the target enantiomer. For both ACh and CCh, the influence of the operating variables, including mobile phase composition, loading density, and enantiomeric excess (ee) of the feed mixture, on the separation performance was examined. On the basis of the experimental data, a dynamic model was formulated, calibrated, and used to support the process design and assess the performance of both the standalone ACh and CCh as well as their coupling in various configurations. The amount of product obtained in a single cycle of ACh-CCh was markedly higher compared to that obtained in the standalone CCh, which provided the benefit of reducing consumption of the costly CSP. This benefit was enhanced with increasing ee of the feed mixture. For example, for racemic mixtures, the mass of the product per cycle of ACh-CCh was 1.5 times higher, for mixtures with ee = 70% it was 4 times higher, and for mixtures with ee = 85% it was 5.7 times higher compared to the standalone CCh. Furthermore, for mixtures with a high ee, a marked improvement in process productivity was obtained, e.g., for mixtures with ee = 70%, the productivity of ACh-CCh was twice higher, for ee = 85% it was 2.5 times higher compared to the standalone CCh.
{"title":"Coupling Achiral and Chiral Chromatography for Efficient Separation of Enantiomeric Mixtures","authors":"Patrycja Mruc, Dorota Antos","doi":"10.1021/acs.iecr.5c00412","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c00412","url":null,"abstract":"Chiral chromatography (CCh) is often a cost driver in the large-scale separation of enantiomers. To improve the economics of the separation process, we developed the concept of coupling CCh with achiral chromatography (ACh). In this concept, the CCh step is used to enrich the enantiomeric mixture with the target enantiomer, while in the ACh step, the enriched mixture is separated to obtain the product with a desired purity. The ACh separation is driven by the phenomenon of self-disproportionation of enantiomers (SDE), which relies on formation of homochiral and heterochiral associates that can be separated in an achiral environment, whereas the CCh separation occurs in the presence of a chiral stationary phase (CSP). The coupled ACh-CCh process is operated in a cyclic mode for which cyclic steady state is attained. To demonstrate the concept of the process and develop a generic methodology for its design, a model mixture consisting of enantiomers of methyl <i>p</i>-tolyl sulfoxide was used, with S-<i>p</i>-tolyl sulfoxide as the target enantiomer. For both ACh and CCh, the influence of the operating variables, including mobile phase composition, loading density, and enantiomeric excess (ee) of the feed mixture, on the separation performance was examined. On the basis of the experimental data, a dynamic model was formulated, calibrated, and used to support the process design and assess the performance of both the standalone ACh and CCh as well as their coupling in various configurations. The amount of product obtained in a single cycle of ACh-CCh was markedly higher compared to that obtained in the standalone CCh, which provided the benefit of reducing consumption of the costly CSP. This benefit was enhanced with increasing ee of the feed mixture. For example, for racemic mixtures, the mass of the product per cycle of ACh-CCh was 1.5 times higher, for mixtures with ee = 70% it was 4 times higher, and for mixtures with ee = 85% it was 5.7 times higher compared to the standalone CCh. Furthermore, for mixtures with a high ee, a marked improvement in process productivity was obtained, e.g., for mixtures with ee = 70%, the productivity of ACh-CCh was twice higher, for ee = 85% it was 2.5 times higher compared to the standalone CCh.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"25 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143758048","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 : 2025-04-01DOI: 10.1021/acs.iecr.4c04311
Reza Monjezi, Alexandra Bouriakova, Karen Leus, Pascal Van Der Voort, Dirk Poelman, Geraldine J. Heynderickx, Rino Morent, Joris W. Thybaut
Ozone-assisted catalytic oxidation (OzCO) and conventional catalytic oxidation (CCO) of alkanes such as propane and methane were investigated over Mn/Hydroxyapatite at 50–450 °C using the innovative LoPOx setup, which enables precise control of the reactor total pressure. Utilizing ozone as the oxidant decreased the required oxidation temperature by up to 300 °C compared to CCO, enabling full propane conversion below 100 °C, with a maximum CO2 selectivity amounting to 85%. Kinetic analysis revealed distinct propane OzCO stages, transitioning from OzCO-driven conversion (<100 °C) to gas-phase ozonation (100–200 °C), followed by gas-phase ozonation and CCO (200–400 °C), and ultimately CCO (>400 °C). A comparative assessment of propane and methane oxidation revealed that, despite the presence of highly reactive oxygen species, the high C–H bond dissociation energy of methane significantly limited its oxidation. Consequently, although the presence of O3 effectively enabled low-temperature propane oxidation, it was insufficient for methane abatement under similar conditions.
{"title":"Ozone-Assisted Catalytic Alkane Oxidation over Mn/Hydroxyapatite Catalyst at a Precisely-Controlled Total Pressure","authors":"Reza Monjezi, Alexandra Bouriakova, Karen Leus, Pascal Van Der Voort, Dirk Poelman, Geraldine J. Heynderickx, Rino Morent, Joris W. Thybaut","doi":"10.1021/acs.iecr.4c04311","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c04311","url":null,"abstract":"Ozone-assisted catalytic oxidation (OzCO) and conventional catalytic oxidation (CCO) of alkanes such as propane and methane were investigated over Mn/Hydroxyapatite at 50–450 °C using the innovative LoPOx setup, which enables precise control of the reactor total pressure. Utilizing ozone as the oxidant decreased the required oxidation temperature by up to 300 °C compared to CCO, enabling full propane conversion below 100 °C, with a maximum CO<sub>2</sub> selectivity amounting to 85%. Kinetic analysis revealed distinct propane OzCO stages, transitioning from OzCO-driven conversion (<100 °C) to gas-phase ozonation (100–200 °C), followed by gas-phase ozonation and CCO (200–400 °C), and ultimately CCO (>400 °C). A comparative assessment of propane and methane oxidation revealed that, despite the presence of highly reactive oxygen species, the high C–H bond dissociation energy of methane significantly limited its oxidation. Consequently, although the presence of O<sub>3</sub> effectively enabled low-temperature propane oxidation, it was insufficient for methane abatement under similar conditions.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"50 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143745617","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}
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