Pub Date : 2025-03-04DOI: 10.1021/acs.iecr.4c04447
Zhiyuan Liu, Yanni Liu, Haoran Wang, Zhou Qu, Jinpeng Hou, Hong Meng, Hongwei Fan
Metal–organic framework (MOF) membranes have great potential in efficient helium (He) recovery, but it is highly demanded to improve their separation performance by enhancing molecular sieving. Herein, we explored an orifice-modified MOF-on-MOF bilayer membrane prepared by growing an amino-functionalized ZIF-7 layer on a ZIF-90 layer through an aldehyde-amine condensation reaction. Due to the precise docking between the aperture windows of the crystal cells of such two MOFs, the size-sieving effect was intensified for selective He separation. The resultant membrane exhibits significantly increased selectivities for He/N2 and He/CH4 along with a satisfactory He permeance (∼67 × 10–10 mol·m–2·s–1·Pa–1). Specifically, the He/N2 selectivity of the membrane can reach 16.19, which is about 5 times higher than that of the ZIF-90 membrane (3.24), ranking among the reported He-selective MOF membranes. In addition, a continuous operation for 100 h, subjected to a successive test at room temperature and 150 °C indicates that the membrane has excellent stability. The proposed concept of orifice-modified MOF-on-MOF would provide a new idea for the design and development of advanced MOF-based gas separation membranes.
{"title":"Orifice-Modified MOF-on-MOF Bilayer Membrane for Helium Separation","authors":"Zhiyuan Liu, Yanni Liu, Haoran Wang, Zhou Qu, Jinpeng Hou, Hong Meng, Hongwei Fan","doi":"10.1021/acs.iecr.4c04447","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c04447","url":null,"abstract":"Metal–organic framework (MOF) membranes have great potential in efficient helium (He) recovery, but it is highly demanded to improve their separation performance by enhancing molecular sieving. Herein, we explored an orifice-modified MOF-on-MOF bilayer membrane prepared by growing an amino-functionalized ZIF-7 layer on a ZIF-90 layer through an aldehyde-amine condensation reaction. Due to the precise docking between the aperture windows of the crystal cells of such two MOFs, the size-sieving effect was intensified for selective He separation. The resultant membrane exhibits significantly increased selectivities for He/N<sub>2</sub> and He/CH<sub>4</sub> along with a satisfactory He permeance (∼67 × 10<sup>–10</sup> mol·m<sup>–2</sup>·s<sup>–1</sup>·Pa<sup>–1</sup>). Specifically, the He/N<sub>2</sub> selectivity of the membrane can reach 16.19, which is about 5 times higher than that of the ZIF-90 membrane (3.24), ranking among the reported He-selective MOF membranes. In addition, a continuous operation for 100 h, subjected to a successive test at room temperature and 150 °C indicates that the membrane has excellent stability. The proposed concept of orifice-modified MOF-on-MOF would provide a new idea for the design and development of advanced MOF-based gas separation membranes.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"32 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143546964","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 : 2025-03-03DOI: 10.1021/acs.iecr.4c03938
Yan Liu, Yiming Mo, Youwei Cheng
Chemical reaction networks (CRNs) serve to describe the behavior of complex chemical reaction systems. Analyzing CRNs of a reactive system requires kinetic data that are typically obtained by time-consuming experiments or computational chemistry. Machine learning (ML) has emerged as a promising approach for rapid property prediction based on historical data. However, the accuracy of ML model predictions in kinetics remains a limitation for their application in CRN analysis. In this study, we integrate the cross-attention mechanisms in neural networks and CRN sensitivity and uncertainty analysis to enable the practical application of the ML models in reliable gas-phase CRN analysis. Specifically, a message-passing neural network (MPNN) architecture along with a cross-attention mechanism (CA-MPNN) was developed for accurate prediction of the reaction rate constants with prediction uncertainty. CA-MPNN model outperformed the conventional deep neural network architectures on most of the reaction property data sets. We combined reaction network sensitivity analysis and ML prediction uncertainty analysis to identify influential reactions with high-level uncertainty of the predicted rate constant, which are further calibrated using high-accuracy quantum chemistry methods to mitigate the problem of inaccurate machine learning predictions. Compared with the traditional workflow, this framework significantly reduces up to 80% computational cost to construct a reliable CRN in the demonstrated gas-phase pyrolysis and combustion applications.
{"title":"Machine Learning Accelerated Analysis of Chemical Reaction Networks for Gas-Phase Reaction Systems","authors":"Yan Liu, Yiming Mo, Youwei Cheng","doi":"10.1021/acs.iecr.4c03938","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c03938","url":null,"abstract":"Chemical reaction networks (CRNs) serve to describe the behavior of complex chemical reaction systems. Analyzing CRNs of a reactive system requires kinetic data that are typically obtained by time-consuming experiments or computational chemistry. Machine learning (ML) has emerged as a promising approach for rapid property prediction based on historical data. However, the accuracy of ML model predictions in kinetics remains a limitation for their application in CRN analysis. In this study, we integrate the cross-attention mechanisms in neural networks and CRN sensitivity and uncertainty analysis to enable the practical application of the ML models in reliable gas-phase CRN analysis. Specifically, a message-passing neural network (MPNN) architecture along with a cross-attention mechanism (CA-MPNN) was developed for accurate prediction of the reaction rate constants with prediction uncertainty. CA-MPNN model outperformed the conventional deep neural network architectures on most of the reaction property data sets. We combined reaction network sensitivity analysis and ML prediction uncertainty analysis to identify influential reactions with high-level uncertainty of the predicted rate constant, which are further calibrated using high-accuracy quantum chemistry methods to mitigate the problem of inaccurate machine learning predictions. Compared with the traditional workflow, this framework significantly reduces up to 80% computational cost to construct a reliable CRN in the demonstrated gas-phase pyrolysis and combustion applications.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"53 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143539238","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 : 2025-03-03DOI: 10.1021/acs.iecr.4c04775
Shichang Chen, Ran Xu, Junhua Cao, Wenxing Chen
The industrial production of poly(ethylene terephthalate) (PET) melt in these decades has relied on a high-energy-consuming horizontal stirring reactor, especially for industrial-grade PET where the process involves interrupting the melt reaction and a lengthy solid-state polycondensation procedure. A falling film melt polycondensation reactor model was established and used to simulate the production process of industrial-grade PET, and the process was verified in production. On this basis, two new process designs were implemented to produce both clothing-grade and industrial-grade PET. Due to the efficient mass transfer of the falling film reactor, properties such as the molecular weight and terminal carboxyl content of products were improved, along with an increase in production efficiency. The clothing-grade PET production with a falling film reactor reduced electricity consumption by 10–20%. When dual falling film reactors in series replaced the solid-state polycondensation process, the energy and water consumption dropped to surprisingly low levels owing to the elimination of several production stages.
近几十年来，聚对苯二甲酸乙二醇酯（PET）熔体的工业化生产一直依赖于高能耗的水平搅拌反应器，尤其是工业级 PET 的生产过程涉及中断熔体反应和漫长的固态缩聚过程。我们建立了降膜熔融缩聚反应器模型，用于模拟工业级 PET 的生产过程，并在生产中对该过程进行了验证。在此基础上，实施了两种新的工艺设计，以生产服装级和工业级 PET。由于降膜反应器的传质效率高，产品的分子量和末端羧基含量等性能得到了改善，生产效率也得到了提高。使用降膜反应器生产服装级 PET 的耗电量降低了 10-20%。当双降膜反应器串联取代固态缩聚工艺时，由于省去了几个生产阶段，能耗和水耗降到了惊人的低水平。
{"title":"Energy-Saving Processes for Increasing the Molecular Weight via a Falling Film Reactor in Large-Scale Production of PET Fiber","authors":"Shichang Chen, Ran Xu, Junhua Cao, Wenxing Chen","doi":"10.1021/acs.iecr.4c04775","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c04775","url":null,"abstract":"The industrial production of poly(ethylene terephthalate) (PET) melt in these decades has relied on a high-energy-consuming horizontal stirring reactor, especially for industrial-grade PET where the process involves interrupting the melt reaction and a lengthy solid-state polycondensation procedure. A falling film melt polycondensation reactor model was established and used to simulate the production process of industrial-grade PET, and the process was verified in production. On this basis, two new process designs were implemented to produce both clothing-grade and industrial-grade PET. Due to the efficient mass transfer of the falling film reactor, properties such as the molecular weight and terminal carboxyl content of products were improved, along with an increase in production efficiency. The clothing-grade PET production with a falling film reactor reduced electricity consumption by 10–20%. When dual falling film reactors in series replaced the solid-state polycondensation process, the energy and water consumption dropped to surprisingly low levels owing to the elimination of several production stages.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"16 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143538735","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 : 2025-03-03DOI: 10.1021/acs.iecr.4c04567
Han Dong, Pu Zhou, Fan Yang, Enhao Zhang, Yifan Liu, Yefei Tian, Hongye Yuan
The development of metal–organic framework (MOF)-based adsorbents with high uptake capacity and mild regeneration conditions represents a promising avenue for addressing environment-based issues. In this study, we present the successful synthesis of temperature-responsive composite aerogels comprising MOF-808 and poly(N-isopropylacrylamide) (PNIPAM), which forms interpenetrated networks with acrylamide (AM). The resulting thermally responsive PNIPAM/MOF-808 composite aerogels achieved an impressive maximum water capture exceeding 2267 wt % at room temperature, with reversible release observed above 32 °C due to the hydrophilicity–hydrophobicity transition of PNIPAM. Interestingly, the aerogels also exhibit an iodine (I2) capacity of 234 wt % based on the charge transfer mechanism. This study provides a novel strategy for the preparation of efficient and reusable porous adsorbent materials, and it also demonstrates broad application prospects in areas such as water resource management and waste reduction.
{"title":"Thermal-Responsive PNIPAM/MOF-808 Aerogels for Controllable Water and I2 Capture and Release","authors":"Han Dong, Pu Zhou, Fan Yang, Enhao Zhang, Yifan Liu, Yefei Tian, Hongye Yuan","doi":"10.1021/acs.iecr.4c04567","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c04567","url":null,"abstract":"The development of metal–organic framework (MOF)-based adsorbents with high uptake capacity and mild regeneration conditions represents a promising avenue for addressing environment-based issues. In this study, we present the successful synthesis of temperature-responsive composite aerogels comprising MOF-808 and poly(<i>N</i>-isopropylacrylamide) (PNIPAM), which forms interpenetrated networks with acrylamide (AM). The resulting thermally responsive PNIPAM/MOF-808 composite aerogels achieved an impressive maximum water capture exceeding 2267 wt % at room temperature, with reversible release observed above 32 °C due to the hydrophilicity–hydrophobicity transition of PNIPAM. Interestingly, the aerogels also exhibit an iodine (I<sub>2</sub>) capacity of 234 wt % based on the charge transfer mechanism. This study provides a novel strategy for the preparation of efficient and reusable porous adsorbent materials, and it also demonstrates broad application prospects in areas such as water resource management and waste reduction.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"40 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143539134","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 : 2025-03-03DOI: 10.1021/acs.iecr.4c04321
Jarrett S. Turner, Adam M. Burke, Olivia Smithson, Mohammad I. Hossain, Charles E. Holland, Armin D. Ebner, James A. Ritter
Despite decades of research, the dominant mass transfer mechanisms of N2, O2, and Ar in carbon molecular sieve (CMS) have yet to be well understood. Hence, the objective of this work was to collect experimental data for the uptake and release of N2, O2, and Ar in Shirasagi MSC 3K 172 CMS by volumetric frequency response (VFR) and then contrast these data against several micropore mass transfer models. Data were collected for N2, O2, and Ar in this CMS at 100 and 200 Torr at 25 °C, and at 750 Torr at 20, 30, 40, and 50 °C. Data were measured at 32 different frequencies, spanning 5 × 10–5 to 10 Hz, for each temperature and pressure. The resulting intensity curves, comprising 192 data points, were fit to six different micropore models to identify the dominant mass transfer mechanisms of N2, O2, and Ar in this CMS. These progressively more complex micropore models included the following resistances: single site micropore (SSM) always with Darken loading dependence, single site micropore mouth (SSPM), single site micropore and single site micropore mouth combined (SSC), SSC with Darken loading dependence also applied to the micropore mouth (SSCD), SSCD with an additional more complex Qinglin empirical loading dependence (SSCDQ), and dual site combined with Qinglin loading dependence (DSCDQ). The resulting phase lag curves comprising 192 data points were subsequently predicted by each model. The model that best described the behavior of N2, O2, and Ar in Shirasagi MSC 3K 172 CMS was the DSCDQ model, which consisted of two micropore sites, each with different micropore diffusion resistances but with the same micropore mouth resistance and each resistance with both Darken and Qinglin loading dependencies. The evidence for these two micropore sites came from unique features exhibited only by O2 in the intensity and especially in the phase lag curves and only by the 100 and 200 Torr data. The DSCDQ model was the only one that could capture these features. This result illuminated the power of the VFR technique for discriminating transport mechanisms and the importance of experimentally examining a broad range of conditions with VFR.
{"title":"Volumetric Frequency Response Investigation of the Mass Transfer Mechanisms of N2, O2, and Ar in Carbon Molecular Sieve","authors":"Jarrett S. Turner, Adam M. Burke, Olivia Smithson, Mohammad I. Hossain, Charles E. Holland, Armin D. Ebner, James A. Ritter","doi":"10.1021/acs.iecr.4c04321","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c04321","url":null,"abstract":"Despite decades of research, the dominant mass transfer mechanisms of N<sub>2</sub>, O<sub>2</sub>, and Ar in carbon molecular sieve (CMS) have yet to be well understood. Hence, the objective of this work was to collect experimental data for the uptake and release of N<sub>2</sub>, O<sub>2</sub>, and Ar in Shirasagi MSC 3K 172 CMS by volumetric frequency response (VFR) and then contrast these data against several micropore mass transfer models. Data were collected for N<sub>2</sub>, O<sub>2</sub>, and Ar in this CMS at 100 and 200 Torr at 25 °C, and at 750 Torr at 20, 30, 40, and 50 °C. Data were measured at 32 different frequencies, spanning 5 × 10<sup>–5</sup> to 10 Hz, for each temperature and pressure. The resulting intensity curves, comprising 192 data points, were fit to six different micropore models to identify the dominant mass transfer mechanisms of N<sub>2</sub>, O<sub>2</sub>, and Ar in this CMS. These progressively more complex micropore models included the following resistances: single site micropore (SSM) always with Darken loading dependence, single site micropore mouth (SSPM), single site micropore and single site micropore mouth combined (SSC), SSC with Darken loading dependence also applied to the micropore mouth (SSCD), SSCD with an additional more complex Qinglin empirical loading dependence (SSCDQ), and dual site combined with Qinglin loading dependence (DSCDQ). The resulting phase lag curves comprising 192 data points were subsequently predicted by each model. The model that best described the behavior of N<sub>2</sub>, O<sub>2</sub>, and Ar in Shirasagi MSC 3K 172 CMS was the DSCDQ model, which consisted of two micropore sites, each with different micropore diffusion resistances but with the same micropore mouth resistance and each resistance with both Darken and Qinglin loading dependencies. The evidence for these two micropore sites came from unique features exhibited only by O<sub>2</sub> in the intensity and especially in the phase lag curves and only by the 100 and 200 Torr data. The DSCDQ model was the only one that could capture these features. This result illuminated the power of the VFR technique for discriminating transport mechanisms and the importance of experimentally examining a broad range of conditions with VFR.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"10 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143539239","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 : 2025-03-03DOI: 10.1021/acs.iecr.4c04180
Sajjad Kohzadi, Ali Haghtalab
The activity coefficient in electrolyte systems is a key measure of deviations from ideal behavior, essential for simulating the thermodynamic properties of these systems. Accurate modeling and prediction of this coefficient are crucial for understanding the interactions of electrolyte solutions and optimizing industrial and chemical processes. This study introduces the OP-NRTL-NRF (One Parameter Non-Random Two-Liquid, Non-Random Factor) local composition model specifically designed for binary aqueous electrolyte systems. This model redefines interaction parameters based on fundamental principles and simplifies the traditional approach by correlating the mean activity coefficient with a single adjustable correction factor rather than relying on extensive experimental data and multiple parameters. By redefining the binary interaction parameter, this model establishes relationships that describe the variation of excess Gibbs energy in the central cells of anions, cations, and water molecules. The observed changes in Gibbs energy within water molecular cells indicate the formation of hydration bonding structures and ion pairs. This model, optimized for 85 binary aqueous electrolyte systems at 298.15 K using a data set of 1819 experimental points, shows excellent agreement with experimental results and accurately predicts osmotic coefficient values. Additionally, the model has been extended to ternary systems and has been used to calculate the solubility of electrolytes in water solvent for 10 ternary systems, comprising 110 experimental solubility points, at 298.15 K. The results demonstrate good agreement with experimental data, and the model’s ability to predict the behavior of ternary electrolyte systems is reliable.
{"title":"A Local Composition OP-NRTL-NRF Model for Correlation Mean Activity Coefficients in Aqueous Electrolyte Systems from Thermodynamic Properties","authors":"Sajjad Kohzadi, Ali Haghtalab","doi":"10.1021/acs.iecr.4c04180","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c04180","url":null,"abstract":"The activity coefficient in electrolyte systems is a key measure of deviations from ideal behavior, essential for simulating the thermodynamic properties of these systems. Accurate modeling and prediction of this coefficient are crucial for understanding the interactions of electrolyte solutions and optimizing industrial and chemical processes. This study introduces the OP-NRTL-NRF (One Parameter Non-Random Two-Liquid, Non-Random Factor) local composition model specifically designed for binary aqueous electrolyte systems. This model redefines interaction parameters based on fundamental principles and simplifies the traditional approach by correlating the mean activity coefficient with a single adjustable correction factor rather than relying on extensive experimental data and multiple parameters. By redefining the binary interaction parameter, this model establishes relationships that describe the variation of excess Gibbs energy in the central cells of anions, cations, and water molecules. The observed changes in Gibbs energy within water molecular cells indicate the formation of hydration bonding structures and ion pairs. This model, optimized for 85 binary aqueous electrolyte systems at 298.15 K using a data set of 1819 experimental points, shows excellent agreement with experimental results and accurately predicts osmotic coefficient values. Additionally, the model has been extended to ternary systems and has been used to calculate the solubility of electrolytes in water solvent for 10 ternary systems, comprising 110 experimental solubility points, at 298.15 K. The results demonstrate good agreement with experimental data, and the model’s ability to predict the behavior of ternary electrolyte systems is reliable.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"190 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143532917","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 : 2025-03-03DOI: 10.1021/acs.iecr.4c04674
Guojun Lv, Linfang Jiang, Yan Chen, Xuyang Zou, Xubin Zhang, Fumin Wang
The addition of an additional mesoporous/macroporous templating agent inevitably has an adverse effect on the economy and greenness of the seed-assisted synthesis process for hierarchical zeolites; hence, the development of an efficient seed-assisted method for the synthesis of hierarchical zeolite without the addition of an additional additive is appealing. Herein, we reported the preparation of hierarchical TS-1 zeolite with a large amount of mesopores using a liquid–solid mixture seed-assisted method and its application as a heterogeneous catalyst in the oxidative desulfurization reactions. The characterization results disclosed that the liquid–solid mixture seed was more conducive to the formation of hierarchical TS-1 zeolite than liquid seed alone and solid seed alone. The formation process of hierarchical TS-1 zeolite with different crystallization times was investigated in detail, and accordingly, a possible two-stage crystallization mechanism was proposed. In addition, the synthesized hierarchical TS-1 zeolite showed remarkably enhanced catalytic activity in the oxidative desulfurization of dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT) in comparison to the conventional microporous TS-1 zeolite. This work provides some guidance for the development of a more efficient and greener seed-assisted synthesis method for hierarchical zeolites without the addition of any additional mesoporous/macroporous templating agent.
{"title":"Liquid–Solid Mixture Seed-Assisted Synthesis of Hierarchical TS-1 Zeolite for Efficient Oxidative Desulfurization","authors":"Guojun Lv, Linfang Jiang, Yan Chen, Xuyang Zou, Xubin Zhang, Fumin Wang","doi":"10.1021/acs.iecr.4c04674","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c04674","url":null,"abstract":"The addition of an additional mesoporous/macroporous templating agent inevitably has an adverse effect on the economy and greenness of the seed-assisted synthesis process for hierarchical zeolites; hence, the development of an efficient seed-assisted method for the synthesis of hierarchical zeolite without the addition of an additional additive is appealing. Herein, we reported the preparation of hierarchical TS-1 zeolite with a large amount of mesopores using a liquid–solid mixture seed-assisted method and its application as a heterogeneous catalyst in the oxidative desulfurization reactions. The characterization results disclosed that the liquid–solid mixture seed was more conducive to the formation of hierarchical TS-1 zeolite than liquid seed alone and solid seed alone. The formation process of hierarchical TS-1 zeolite with different crystallization times was investigated in detail, and accordingly, a possible two-stage crystallization mechanism was proposed. In addition, the synthesized hierarchical TS-1 zeolite showed remarkably enhanced catalytic activity in the oxidative desulfurization of dibenzothiophene (DBT) and 4,6-dimethyldibenzothiophene (4,6-DMDBT) in comparison to the conventional microporous TS-1 zeolite. This work provides some guidance for the development of a more efficient and greener seed-assisted synthesis method for hierarchical zeolites without the addition of any additional mesoporous/macroporous templating agent.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"49 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143532922","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 : 2025-03-03DOI: 10.1021/acs.iecr.4c03996
Shouzheng Yuan, Ju Jiang, Qiang Zhou, Xiao Chen
Filtered two-fluid models (fTFMs) are usually employed to predict the flow behavior in large fluidized bed reactors. In fTFMs, other than the filtered drag force, the filtered solid stress also plays crucial roles, particularly at larger filter sizes. However, many traditional filtered closures have been developed using full-periodic domain data sets, which overlook the influence of wall boundaries. In practical fluidized reactors, wall boundaries can significantly impact the evolution of heterogeneous structures, potentially reducing the accuracy of filtered solid phase stress closures. This work improves the performance of existing filtered solid stress closure by introducing the impact of the wall boundary. The newly proposed closure is systematically evaluated in various posteriori validations, including a turbulent bed and two fast beds by coarse-grid two-fluid model simulations.
{"title":"Solids Stress Closure Accounting for Wall Effects in Gas–Solid Fluidized Beds","authors":"Shouzheng Yuan, Ju Jiang, Qiang Zhou, Xiao Chen","doi":"10.1021/acs.iecr.4c03996","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c03996","url":null,"abstract":"Filtered two-fluid models (fTFMs) are usually employed to predict the flow behavior in large fluidized bed reactors. In fTFMs, other than the filtered drag force, the filtered solid stress also plays crucial roles, particularly at larger filter sizes. However, many traditional filtered closures have been developed using full-periodic domain data sets, which overlook the influence of wall boundaries. In practical fluidized reactors, wall boundaries can significantly impact the evolution of heterogeneous structures, potentially reducing the accuracy of filtered solid phase stress closures. This work improves the performance of existing filtered solid stress closure by introducing the impact of the wall boundary. The newly proposed closure is systematically evaluated in various posteriori validations, including a turbulent bed and two fast beds by coarse-grid two-fluid model simulations.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"30 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143532916","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 : 2025-03-03DOI: 10.1021/acs.iecr.4c04232
Anwen Dai, Jun Zhang, Anjin Li
Heterogeneous nucleation technology can promote the growth of fine particulate matter, making it easier to remove. To investigate the particle size distribution characteristics of fine particulate matter during heterogeneous growth in a growth tube, this study couples the particle growth process with fluid dynamics and explores the interaction between supersaturation distribution and particle flow. The effects of temperature difference and flow velocity on the spatial distribution of particle size are revealed. The results show that, along the axial direction, particle size remains constant at first and then gradually increases; along the radial direction, particle size increases rapidly before decreasing sharply near the wall; ineffective regions exist both at the inlet and wall, where particles cannot be activated to grow; the temperature difference and flow velocity not only influence particle growth efficiency but also affect the extent of these ineffective regions. This study provides a theoretical basis for optimizing the design of growth tubes, enhancing nucleation regions, and improving the utilization of vapor resources.
{"title":"Numerical Simulation of Size Distribution of Polydisperse Fine Particles during Heterogeneous Condensation in Water Vapor Environment","authors":"Anwen Dai, Jun Zhang, Anjin Li","doi":"10.1021/acs.iecr.4c04232","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c04232","url":null,"abstract":"Heterogeneous nucleation technology can promote the growth of fine particulate matter, making it easier to remove. To investigate the particle size distribution characteristics of fine particulate matter during heterogeneous growth in a growth tube, this study couples the particle growth process with fluid dynamics and explores the interaction between supersaturation distribution and particle flow. The effects of temperature difference and flow velocity on the spatial distribution of particle size are revealed. The results show that, along the axial direction, particle size remains constant at first and then gradually increases; along the radial direction, particle size increases rapidly before decreasing sharply near the wall; ineffective regions exist both at the inlet and wall, where particles cannot be activated to grow; the temperature difference and flow velocity not only influence particle growth efficiency but also affect the extent of these ineffective regions. This study provides a theoretical basis for optimizing the design of growth tubes, enhancing nucleation regions, and improving the utilization of vapor resources.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"46 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143539133","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 : 2025-03-03DOI: 10.1021/acs.iecr.4c03157
Jarlon Conceição da Costa, Isabela Conceição Sales, Bruna Vida da Ressureição, Luciano Morais Lião, Gerlon de Almeida Ribeiro Oliveira, Álvaro Silva Lima, Luiz Mário N Góis, Silvana Mattedi
Recently, ionic liquids (ILs) have been applied in extraction and separation processes due to their chemical and physical properties arising from the cations and anions that form these liquids. In aqueous two-phase systems (ATPSs), ILs can be used as phase formers and assist in the separation and purification processes of biomolecules, such as phenolics and terpenes present in clove oil. In this work, the effect of temperature (288.2, 298.2, and 308.2 K) and the alkyl chain size of protic ionic liquid (PIL) anion in ATPSs based on PIL + acetonitrile (ACN) + water at 101.2 kPa is evaluated. The NRTL and UNIQUAC models were used to predict the LLE data. The increase in the temperature and the alkyl chain compressed the biphasic region of the phase diagram. In the proposed systems, partitioning data were obtained for commercial biomolecules present in clove oil (eugenol, eugenyl acetate, and α-humulene). Phenolics (eugenol and eugenyl acetate) were partitioned to the PIL-rich phase. In contrast, α-humulene (terpene) was partitioned into the ACN-rich phase. It was observed that increasing temperature increases or maintains almost constant the recovery of biomolecules in the bottom phase (RB) from similar tie-line length (TLL). Additionally, eugenol and eugenyl acetate can be partially isolated (selectivity: S = 2.17) at 298.2 K. Finally, the highest values achieved for bottom phase recoveries for the target biomolecules were achieved using ATPS formed by [2HEA][Bu] + ACN + water (TLL ≈ 53 and 57.57 < RB < 93.54). PILs can be used as a salting-out agent to form biphasic phase systems with acetonitrile and separate biomolecules where reasonable recovery rates were verified.
{"title":"Effect of Temperature on Aqueous Two-Phase Systems Based on Acetonitrile and Protic Ionic Liquids: Phase Diagram and Partitioning of Commercial Biomolecules Present in Clove Oil","authors":"Jarlon Conceição da Costa, Isabela Conceição Sales, Bruna Vida da Ressureição, Luciano Morais Lião, Gerlon de Almeida Ribeiro Oliveira, Álvaro Silva Lima, Luiz Mário N Góis, Silvana Mattedi","doi":"10.1021/acs.iecr.4c03157","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c03157","url":null,"abstract":"Recently, ionic liquids (ILs) have been applied in extraction and separation processes due to their chemical and physical properties arising from the cations and anions that form these liquids. In aqueous two-phase systems (ATPSs), ILs can be used as phase formers and assist in the separation and purification processes of biomolecules, such as phenolics and terpenes present in clove oil. In this work, the effect of temperature (288.2, 298.2, and 308.2 K) and the alkyl chain size of protic ionic liquid (PIL) anion in ATPSs based on PIL + acetonitrile (ACN) + water at 101.2 kPa is evaluated. The NRTL and UNIQUAC models were used to predict the LLE data. The increase in the temperature and the alkyl chain compressed the biphasic region of the phase diagram. In the proposed systems, partitioning data were obtained for commercial biomolecules present in clove oil (eugenol, eugenyl acetate, and α-humulene). Phenolics (eugenol and eugenyl acetate) were partitioned to the PIL-rich phase. In contrast, α-humulene (terpene) was partitioned into the ACN-rich phase. It was observed that increasing temperature increases or maintains almost constant the recovery of biomolecules in the bottom phase (<i>R</i><sub>B</sub>) from similar tie-line length (TLL). Additionally, eugenol and eugenyl acetate can be partially isolated (selectivity: <i>S</i> = 2.17) at 298.2 K. Finally, the highest values achieved for bottom phase recoveries for the target biomolecules were achieved using ATPS formed by [2HEA][Bu] + ACN + water (TLL ≈ 53 and 57.57 < <i>R</i><sub>B</sub> < 93.54). PILs can be used as a salting-out agent to form biphasic phase systems with acetonitrile and separate biomolecules where reasonable recovery rates were verified.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"39 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143532918","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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