Pub Date : 2025-12-17DOI: 10.1021/acs.iecr.5c03120
Thailan S. P. Lima, Ronnie E. P. Pinto, Ana L. S. Vasconcelos, Bruna V. Ressurreição, Filipe S. Buarque, Ranyere L. Souza, Cleide M. F. Soares, Álvaro S. Lima
Water-free two-phase systems (WFTPSs) represent a promising alternative for separating hydrophobic biomolecules. This study reports novel systems composed of acetonitrile, polymers (polyethylene glycol and polypropylene glycol with different molecular weights), and ionic liquids (IL) based on [C2mim]X (X = acetate, methanesulfonate, and chloride). Phase diagrams were constructed and well described by the Merchuck equation, with high correlation coefficients (R2 = 0.985–0.999). Among the systems investigated, PPG-4000 + [C2mim][OAc] + ACN exhibited the largest biphasic region and the best performance for selective separation of tomato-derived biomolecules. At 308.15 K, lycopene preferentially migrated to the polymer-rich phase with an extraction efficiency of 96.0 ± 3.4%, while ascorbic acid accumulated in the IL-rich phase with 80.7 ± 0.5% recovery, yielding a maximum selectivity of 77.9. Thermodynamic analysis revealed that lycopene transfer was spontaneous (ΔtrG°m < 0), exothermic ΔtrG°m < 0 at 308 K, corresponding to the highest EELYC value (ΔtrH°m = −25.9 kJ mol–1), and entropy-driven (ΔtrS°m = 106 J mol–1 K–1), whereas ascorbic acid migration followed an endothermic and enthalpy-driven mechanism. These findings demonstrate that WFTPSs can be rationally designed for efficient separation of hydrophobic and hydrophilic biomolecules, providing a reproducible, low-cost, and versatile platform for bioseparations. Furthermore, such systems offer potential applications in the food, pharmaceutical, and nutraceutical industries, particularly for the sustainable recovery of antioxidant compounds from agro-industrial residues.
{"title":"Innovative Water-Free Two-Phase Systems Based on Acetonitrile, Polymers, and Ionic Liquids as a Platform for Selective Separation of Lycopene and Ascorbic Acid Present in Tomatoes","authors":"Thailan S. P. Lima, Ronnie E. P. Pinto, Ana L. S. Vasconcelos, Bruna V. Ressurreição, Filipe S. Buarque, Ranyere L. Souza, Cleide M. F. Soares, Álvaro S. Lima","doi":"10.1021/acs.iecr.5c03120","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c03120","url":null,"abstract":"Water-free two-phase systems (WFTPSs) represent a promising alternative for separating hydrophobic biomolecules. This study reports novel systems composed of acetonitrile, polymers (polyethylene glycol and polypropylene glycol with different molecular weights), and ionic liquids (IL) based on [C<sub>2</sub>mim]X (X = acetate, methanesulfonate, and chloride). Phase diagrams were constructed and well described by the Merchuck equation, with high correlation coefficients (<i>R</i><sup>2</sup> = 0.985–0.999). Among the systems investigated, PPG-4000 + [C<sub>2</sub>mim][OAc] + ACN exhibited the largest biphasic region and the best performance for selective separation of tomato-derived biomolecules. At 308.15 K, lycopene preferentially migrated to the polymer-rich phase with an extraction efficiency of 96.0 ± 3.4%, while ascorbic acid accumulated in the IL-rich phase with 80.7 ± 0.5% recovery, yielding a maximum selectivity of 77.9. Thermodynamic analysis revealed that lycopene transfer was spontaneous (Δ<sub>tr</sub><i>G</i>°<sub>m</sub> < 0), exothermic Δ<sub>tr</sub><i>G</i>°<sub>m</sub> < 0 at 308 K, corresponding to the highest EE<sub>LYC</sub> value (Δ<sub>tr</sub><i>H</i>°<sub>m</sub> = −25.9 kJ mol<sup>–1</sup>), and entropy-driven (Δ<sub>tr</sub><i>S</i>°<sub>m</sub> = 106 J mol<sup>–1</sup> K<sup>–1</sup>), whereas ascorbic acid migration followed an endothermic and enthalpy-driven mechanism. These findings demonstrate that WFTPSs can be rationally designed for efficient separation of hydrophobic and hydrophilic biomolecules, providing a reproducible, low-cost, and versatile platform for bioseparations. Furthermore, such systems offer potential applications in the food, pharmaceutical, and nutraceutical industries, particularly for the sustainable recovery of antioxidant compounds from agro-industrial residues.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"248 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145771681","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 : 2025-12-17DOI: 10.1021/acs.iecr.5c03124
Yi Liu, Shiman Xing, Weiwei Guo, Wangwang Zhu
Data-driven modeling has been widely studied and employed for quality prediction in batch processes. However, existing research and development of this methodology have found it not sufficiently effective in addressing challenges from the batch-to-batch uncertainty and limitation of noisy modeling data. This work proposes a quality prediction method that combines batch correlation information and dynamic data reconciliation (DDR). The method is based on Gaussian process regression and integrated with canonical correlation analysis to capture batch-to-batch characteristics through examining the correlation between batches. Furthermore, DDR is used to dynamically adjust prediction variance, reduce the impact of noisy process data, and improve the prediction accuracy. A numerical case, a batch crystallization process, and a silica modification process have verified that the proposed method is demonstrated effective performance, compared with the candidates.
{"title":"Batch-Wise Self-Corrected Gaussian Process Regression for Quality Prediction in Batch Processes","authors":"Yi Liu, Shiman Xing, Weiwei Guo, Wangwang Zhu","doi":"10.1021/acs.iecr.5c03124","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c03124","url":null,"abstract":"Data-driven modeling has been widely studied and employed for quality prediction in batch processes. However, existing research and development of this methodology have found it not sufficiently effective in addressing challenges from the batch-to-batch uncertainty and limitation of noisy modeling data. This work proposes a quality prediction method that combines batch correlation information and dynamic data reconciliation (DDR). The method is based on Gaussian process regression and integrated with canonical correlation analysis to capture batch-to-batch characteristics through examining the correlation between batches. Furthermore, DDR is used to dynamically adjust prediction variance, reduce the impact of noisy process data, and improve the prediction accuracy. A numerical case, a batch crystallization process, and a silica modification process have verified that the proposed method is demonstrated effective performance, compared with the candidates.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"28 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145771679","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 : 2025-12-17DOI: 10.1021/acs.iecr.5c03864
Sven Dörner, Markus Kinzl, Alexander Mitsos, Dominik Bongartz
Chemical membrane degradation has a significant impact on the lifetime of PEM electrolyzers. For a comprehensive understanding of chemical membrane degradation, cell-level models are useful. However, existing cell-level models ignore the dynamic degradation process of PFSA membranes and do not consider the influence of operating parameters, such as pressure. To address these limitations, we present a dynamic cell-level model in which chemical membrane degradation is represented by the fluoride release rate (FRR). The model is lumped (0D in space), and parameters are estimated with literature data using a pseudo–steady-state approach. The model is then applied to investigate the influence of pressure. The results show increased FRR and H2O2 concentrations at higher pressures due to enhanced O2 crossover. A maximum in the degradation rate arises at intermediate current densities due to the interplay of electro-osmotic drag and back-diffusion, which maximizes in-membrane radical (•OH) concentrations, while at higher current densities washout and Fe2+ limitation reduce them. Time-dependent simulations with full dynamics further indicate that the maximum is reached only after several thousand hours.
{"title":"Dynamic Lumped Cell-Level Model of Chemical Membrane Degradation in PEM Electrolysis: Impact of Pressure and Time Dependence","authors":"Sven Dörner, Markus Kinzl, Alexander Mitsos, Dominik Bongartz","doi":"10.1021/acs.iecr.5c03864","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c03864","url":null,"abstract":"Chemical membrane degradation has a significant impact on the lifetime of PEM electrolyzers. For a comprehensive understanding of chemical membrane degradation, cell-level models are useful. However, existing cell-level models ignore the dynamic degradation process of PFSA membranes and do not consider the influence of operating parameters, such as pressure. To address these limitations, we present a dynamic cell-level model in which chemical membrane degradation is represented by the fluoride release rate (FRR). The model is lumped (0D in space), and parameters are estimated with literature data using a pseudo–steady-state approach. The model is then applied to investigate the influence of pressure. The results show increased FRR and H<sub>2</sub>O<sub>2</sub> concentrations at higher pressures due to enhanced O<sub>2</sub> crossover. A maximum in the degradation rate arises at intermediate current densities due to the interplay of electro-osmotic drag and back-diffusion, which maximizes in-membrane radical (<sup>•</sup>OH) concentrations, while at higher current densities washout and Fe<sup>2+</sup> limitation reduce them. Time-dependent simulations with full dynamics further indicate that the maximum is reached only after several thousand hours.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"44 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145771683","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 : 2025-12-17DOI: 10.1021/acs.iecr.5c02974
Tong Sun, Yanlin Liu, Aolian Wu, Xueqi Yang, Mei Shen
PET fibers are commonly utilized in fiber-reinforced rubber composites due to their excellent properties as a structure backbone. However, the interfacial bonding between PET fibers and rubber is often inadequate, primarily due to the chemical inertness of PET fibers. Traditionally, the RFL impregnation system has been employed for the surface modification of PET fibers. In this study, we introduce a novel environmentally friendly impregnation system named G-SML designed to address these concerns while minimizing environmental impact and ensuring researcher safety. The system activates polyester fibers (PET) by using glycerol triglycidyl ether. Subsequently, the activated fibers were impregnated with a solution comprising sorbitol glycidyl ether (SGE), 2-ethyl-4-methylimidazole (MZ), and styrene–butadiene–vinylpyridine (VP) latex. The primary focus of this investigation was on examining the influence of the SGE/MZ ratio on adhesion between PET and styrene butadiene rubber. Characterization techniques such as attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) and X-ray photoelectron spectroscopy were employed to analyze the surface chemical structure of PET fibers before and after modification. Additionally, we elucidated the mechanism underlying the adhesion between modified fibers and the rubber. Results from H pull-out tests and 180° peeling tests indicated that at an SGE/MZ ratio of 5/4, withdrawal forces reached up to 78 N, while peeling forces achieved 15.3 N/root. Furthermore, optimal adhesive properties, along with enhanced aging stability, were observed at this ratio. This research provides valuable insights into the design and development of environmentally friendly impregnating solutions.
{"title":"Strong Interfacial Adhesion and Good Heat Stability of PET/Rubber Composites Modified by Developing New Eco-Friendly Dipping System","authors":"Tong Sun, Yanlin Liu, Aolian Wu, Xueqi Yang, Mei Shen","doi":"10.1021/acs.iecr.5c02974","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c02974","url":null,"abstract":"PET fibers are commonly utilized in fiber-reinforced rubber composites due to their excellent properties as a structure backbone. However, the interfacial bonding between PET fibers and rubber is often inadequate, primarily due to the chemical inertness of PET fibers. Traditionally, the RFL impregnation system has been employed for the surface modification of PET fibers. In this study, we introduce a novel environmentally friendly impregnation system named G-SML designed to address these concerns while minimizing environmental impact and ensuring researcher safety. The system activates polyester fibers (PET) by using glycerol triglycidyl ether. Subsequently, the activated fibers were impregnated with a solution comprising sorbitol glycidyl ether (SGE), 2-ethyl-4-methylimidazole (MZ), and styrene–butadiene–vinylpyridine (VP) latex. The primary focus of this investigation was on examining the influence of the SGE/MZ ratio on adhesion between PET and styrene butadiene rubber. Characterization techniques such as attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) and X-ray photoelectron spectroscopy were employed to analyze the surface chemical structure of PET fibers before and after modification. Additionally, we elucidated the mechanism underlying the adhesion between modified fibers and the rubber. Results from H pull-out tests and 180° peeling tests indicated that at an SGE/MZ ratio of 5/4, withdrawal forces reached up to 78 N, while peeling forces achieved 15.3 N/root. Furthermore, optimal adhesive properties, along with enhanced aging stability, were observed at this ratio. This research provides valuable insights into the design and development of environmentally friendly impregnating solutions.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"82 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145771678","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 : 2025-12-16DOI: 10.1021/acs.iecr.5c04330
Guangliang Jia, Xiaojuan Lai, Xinli Jiang, Yunchao Chang, Daoming Zheng, Meiling Fan, Lei Wang, Jihua Cai
To improve the utilization rate of thickening agents used for oil recovery in high-temperature and high-salinity oil reservoirs, a water-soluble copolymer APDM was prepared via the copolymerization of acrylamide with functional monomer acrylic acid, 2-acrylamido-2-methylpropanesulfonic acid (AMPS), octadecyldimethylallyl ammonium chloride (DMAAC-18), and N-vinylpyrrolidone (NVP) using the free-radical polymerization method. Then, hydrophobic copolymer HPAD and ACDM copolymer without DMAAC-18 and NVP were synthesized under the same conditions. The APDM copolymer was characterized by using infrared spectroscopy and proton nuclear magnetic resonance, and the salt resistance, viscoelastic properties, temperature resistance, and shear resistance of APDM, HPAD, and ACDM were determined. The results showed that APDM exhibits superior temperature resistance, shear strength, and thickening properties compared with those of HPAD and ACDM. APDM also demonstrates salt-thickening behavior in low-concentration saline solutions as the low salinity charge stimulates hydrophobic micelle microregions, facilitating solubilization of hydrophobic monomers and formation of supramolecular aggregates. The hydrophobic microporous network formed by DMAAC-18, the solubilization effect of NVP, and the charge-shielding effect of the sulfonic acid group in AMPS synergistically enhance the environmental adaptability of APDM. Rheological tests revealed apparent viscosities of 57.49 and 62.16 mPa·s for a 0.5 wt % APDM solution in deionized water and a 20,000 mg/L NaCl solution, respectively, after shearing for 1 h at 140 °C and 170 s–1. Furthermore, 0.5 wt % APDM in 2 × 104 mg/L CaCl2 and MgCl2 solutions exhibited apparent viscosities above 50 mPa·s at temperatures below 130 °C, showing excellent temperature and shear resistance. Therefore, the APDM copolymer is suitable for application as a thickener in high-salinity reservoirs.
{"title":"Synthesis and Salt-Thickening Mechanism of Hydrophobic Association Copolymers Based on Functional Monomer Synergy","authors":"Guangliang Jia, Xiaojuan Lai, Xinli Jiang, Yunchao Chang, Daoming Zheng, Meiling Fan, Lei Wang, Jihua Cai","doi":"10.1021/acs.iecr.5c04330","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c04330","url":null,"abstract":"To improve the utilization rate of thickening agents used for oil recovery in high-temperature and high-salinity oil reservoirs, a water-soluble copolymer APDM was prepared via the copolymerization of acrylamide with functional monomer acrylic acid, 2-acrylamido-2-methylpropanesulfonic acid (AMPS), octadecyldimethylallyl ammonium chloride (DMAAC-18), and <i>N</i>-vinylpyrrolidone (NVP) using the free-radical polymerization method. Then, hydrophobic copolymer HPAD and ACDM copolymer without DMAAC-18 and NVP were synthesized under the same conditions. The APDM copolymer was characterized by using infrared spectroscopy and proton nuclear magnetic resonance, and the salt resistance, viscoelastic properties, temperature resistance, and shear resistance of APDM, HPAD, and ACDM were determined. The results showed that APDM exhibits superior temperature resistance, shear strength, and thickening properties compared with those of HPAD and ACDM. APDM also demonstrates salt-thickening behavior in low-concentration saline solutions as the low salinity charge stimulates hydrophobic micelle microregions, facilitating solubilization of hydrophobic monomers and formation of supramolecular aggregates. The hydrophobic microporous network formed by DMAAC-18, the solubilization effect of NVP, and the charge-shielding effect of the sulfonic acid group in AMPS synergistically enhance the environmental adaptability of APDM. Rheological tests revealed apparent viscosities of 57.49 and 62.16 mPa·s for a 0.5 wt % APDM solution in deionized water and a 20,000 mg/L NaCl solution, respectively, after shearing for 1 h at 140 °C and 170 s<sup>–1</sup>. Furthermore, 0.5 wt % APDM in 2 × 10<sup>4</sup> mg/L CaCl<sub>2</sub> and MgCl<sub>2</sub> solutions exhibited apparent viscosities above 50 mPa·s at temperatures below 130 °C, showing excellent temperature and shear resistance. Therefore, the APDM copolymer is suitable for application as a thickener in high-salinity reservoirs.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"6 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145771694","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 : 2025-12-16DOI: 10.1021/acs.iecr.5c03417
Ikuo Ushiki, Mizuki Hironaka
Supercritical CO2 is a sustainable solvent used for separation and purification. Recovering VOCs via adsorption from supercritical CO2 is of great interest, highlighting the need for effective adsorbents. This research examined the adsorption equilibria of ethyl acetate, a representative volatile organic compound (VOC), on MSU-H mesoporous silica under supercritical CO2 conditions. Experimental equilibrium adsorption data were collected using a fixed-bed apparatus over temperatures T = (313 to 353) K and pressures P = (10.0 to 15.0) MPa. The resulting data could be modeled using the Dubinin–Astakhov (DA) equation, enabling a quantitative assessment of key parameters, such as the saturated adsorption capacity and characteristic adsorption energy. The results indicated that MSU-H exhibits a much higher adsorption capacity for ethyl acetate than activated carbon, approximately four times greater under identical pressure and temperature conditions. This is mainly due to strong interactions between the silanol groups on MSU-H’s surface and the polar VOC molecules. Additionally, this study offers a thorough and systematic analysis of how pressure, temperature, and CO2 density influence adsorption equilibria on MSU-H. The findings demonstrate distinct density-dependent behavior, where increasing CO2 density reduces ethyl acetate uptake due to competitive adsorption and solvation effects─an aspect not previously explored. The detailed assessment of these thermodynamic factors provides new quantitative insights into the impact of operating conditions and emphasizes the excellent adsorption performance of mesoporous silica, laying a solid theoretical foundation for designing and optimizing supercritical CO2-based VOC recovery processes.
{"title":"Enhanced Adsorption of Polar VOCs on MSU-H Mesoporous Silica under Supercritical CO2 Conditions","authors":"Ikuo Ushiki, Mizuki Hironaka","doi":"10.1021/acs.iecr.5c03417","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c03417","url":null,"abstract":"Supercritical CO<sub>2</sub> is a sustainable solvent used for separation and purification. Recovering VOCs via adsorption from supercritical CO<sub>2</sub> is of great interest, highlighting the need for effective adsorbents. This research examined the adsorption equilibria of ethyl acetate, a representative volatile organic compound (VOC), on MSU-H mesoporous silica under supercritical CO<sub>2</sub> conditions. Experimental equilibrium adsorption data were collected using a fixed-bed apparatus over temperatures <i>T</i> = (313 to 353) K and pressures <i>P</i> = (10.0 to 15.0) MPa. The resulting data could be modeled using the Dubinin–Astakhov (DA) equation, enabling a quantitative assessment of key parameters, such as the saturated adsorption capacity and characteristic adsorption energy. The results indicated that MSU-H exhibits a much higher adsorption capacity for ethyl acetate than activated carbon, approximately four times greater under identical pressure and temperature conditions. This is mainly due to strong interactions between the silanol groups on MSU-H’s surface and the polar VOC molecules. Additionally, this study offers a thorough and systematic analysis of how pressure, temperature, and CO<sub>2</sub> density influence adsorption equilibria on MSU-H. The findings demonstrate distinct density-dependent behavior, where increasing CO<sub>2</sub> density reduces ethyl acetate uptake due to competitive adsorption and solvation effects─an aspect not previously explored. The detailed assessment of these thermodynamic factors provides new quantitative insights into the impact of operating conditions and emphasizes the excellent adsorption performance of mesoporous silica, laying a solid theoretical foundation for designing and optimizing supercritical CO<sub>2</sub>-based VOC recovery processes.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"155 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145771682","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 : 2025-12-16DOI: 10.1021/acs.iecr.5c03794
Sunghyun Yoon, Jui Tu, Li-Chiang Lin, Yongchul G. Chung
Accurate and efficient prediction of multicomponent adsorption equilibria across pressures, temperatures, and compositions remains a central challenge for designing energy-efficient, adsorption-based separation processes. Traditional approaches, including model fitting and ideal adsorbed solution theory (IAST), often fail to balance accuracy, computational efficiency, and transferability under process-relevant conditions. Here, we introduce a material-to-process modeling framework that integrates macrostate probability distributions (MPDs) from flat-histogram Monte Carlo simulations with rigorous cyclic process optimization. MPDs directly capture the joint occupancy distributions of adsorbates, producing a reweightable landscape that enables high-fidelity mixture adsorption equilibria without repeated simulations or model assumptions. We show that coupling this statistical mechanical foundation with process modeling delivers accurate and computationally efficient evaluations for binary and ternary gas mixture separations. This integration establishes MPD-based modeling as a generalized method for predictive multicomponent adsorption equilibria, accelerating the discovery and design of adsorbent materials for carbon capture and other separation challenges.
{"title":"Integrating Macrostate Probability Distributions with Swing Adsorption Modeling for Binary/Ternary Gas Separation","authors":"Sunghyun Yoon, Jui Tu, Li-Chiang Lin, Yongchul G. Chung","doi":"10.1021/acs.iecr.5c03794","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c03794","url":null,"abstract":"Accurate and efficient prediction of multicomponent adsorption equilibria across pressures, temperatures, and compositions remains a central challenge for designing energy-efficient, adsorption-based separation processes. Traditional approaches, including model fitting and ideal adsorbed solution theory (IAST), often fail to balance accuracy, computational efficiency, and transferability under process-relevant conditions. Here, we introduce a material-to-process modeling framework that integrates macrostate probability distributions (MPDs) from flat-histogram Monte Carlo simulations with rigorous cyclic process optimization. MPDs directly capture the joint occupancy distributions of adsorbates, producing a reweightable landscape that enables high-fidelity mixture adsorption equilibria without repeated simulations or model assumptions. We show that coupling this statistical mechanical foundation with process modeling delivers accurate and computationally efficient evaluations for binary and ternary gas mixture separations. This integration establishes MPD-based modeling as a generalized method for predictive multicomponent adsorption equilibria, accelerating the discovery and design of adsorbent materials for carbon capture and other separation challenges.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"117 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145777606","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 : 2025-12-16DOI: 10.1021/acs.iecr.5c03710
Mei Wu, Xi-Bao Zhang, Xue-Gang Li, Zheng-Hong Luo
CO2-to-methanol (CTM) is an important route for carbon utilization. Autothermal reactors (ATRs) can utilize reaction heat more efficiently than conventional water-cooled reactors, but their feasibility and economics for CTM remain underexplored. This study proposes a cocurrent ATR for the CTM process (AT-CTM) and compares its performance with the water-cooled (WC-CTM) process at a single-pass production scale of 2,000 and 5,400 t·a–1 with recycle streams. The syngas-to-methanol (STM) process and a counter-current ATR are also studied. STM exhibits the highest single-pass methanol yield and carbon conversion but also the highest hot spot temperature. AT-CTM achieves methanol yield and CO2 conversion comparable to WC-CTM while operating at an inlet temperature 100 °C lower and reducing annual utilities costs by 150 k$. For the AT-CTM process, a C/H ratio of 3 offers the trade-off between CO2 conversion and economic cost, and an inlet temperature of 100 °C maximizes methanol production with low utilities demand.
{"title":"Design and Performance Evaluation of a Co-Current Autothermal Multi-Tubular Fixed-Bed Reactor for CO2-to-Methanol Synthesis","authors":"Mei Wu, Xi-Bao Zhang, Xue-Gang Li, Zheng-Hong Luo","doi":"10.1021/acs.iecr.5c03710","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c03710","url":null,"abstract":"CO<sub>2</sub>-to-methanol (CTM) is an important route for carbon utilization. Autothermal reactors (ATRs) can utilize reaction heat more efficiently than conventional water-cooled reactors, but their feasibility and economics for CTM remain underexplored. This study proposes a cocurrent ATR for the CTM process (AT-CTM) and compares its performance with the water-cooled (WC-CTM) process at a single-pass production scale of 2,000 and 5,400 t·a<sup>–1</sup> with recycle streams. The syngas-to-methanol (STM) process and a counter-current ATR are also studied. STM exhibits the highest single-pass methanol yield and carbon conversion but also the highest hot spot temperature. AT-CTM achieves methanol yield and CO<sub>2</sub> conversion comparable to WC-CTM while operating at an inlet temperature 100 °C lower and reducing annual utilities costs by 150 k$. For the AT-CTM process, a C/H ratio of 3 offers the trade-off between CO<sub>2</sub> conversion and economic cost, and an inlet temperature of 100 °C maximizes methanol production with low utilities demand.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"38 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145771693","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 : 2025-12-16DOI: 10.1021/acs.iecr.5c04099
Mahla Mahmoudi, Lingyang Ding, Gisele Azimi
The rapid growth of electric vehicle adoption is intensifying demand for lithium-ion batteries (LIBs), resulting in a rising volume of spent batteries and the need for efficient recycling strategies to recover critical metals. Supercritical fluid extraction (SCFE) using supercritical carbon dioxide (sc-CO2) offers a sustainable route for metal recovery, particularly when combined with chelating and reducing agents. This study develops a phenomenological modeling framework by integrating Sovová’s broken and intact cell (BIC) model with the shrinking-core model to describe the extraction kinetics of Li, Co, Mn, and Ni from real NMC111 black mass. The BIC model successfully predicted extraction curves with deviations below 1.1%, identifying a Type A pattern dominated by rapid surface extraction followed by intraparticle diffusion. Shrinking-core analysis confirmed ash-layer diffusion as the rate-determining step, with apparent activation energies ranging from 4.8 to 14.9 kJ/mol. Comparison with Chrastil empirical solubility modeling validated the predictive accuracy of the BIC approach, highlighting stable solubility behavior for Li and Co and stronger sensitivity for Mn and Ni. By bridging macroscopic kinetics with mechanistic insights, this work establishes a predictive framework for optimizing SCFE processes, advancing environmentally responsible and scalable recycling of strategic metals from end-of-life LIBs.
{"title":"Phenomenological Modeling of Supercritical CO2 Extraction for Critical Metal Recovery from NMC Black Mass","authors":"Mahla Mahmoudi, Lingyang Ding, Gisele Azimi","doi":"10.1021/acs.iecr.5c04099","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c04099","url":null,"abstract":"The rapid growth of electric vehicle adoption is intensifying demand for lithium-ion batteries (LIBs), resulting in a rising volume of spent batteries and the need for efficient recycling strategies to recover critical metals. Supercritical fluid extraction (SCFE) using supercritical carbon dioxide (sc-CO<sub>2</sub>) offers a sustainable route for metal recovery, particularly when combined with chelating and reducing agents. This study develops a phenomenological modeling framework by integrating Sovová’s broken and intact cell (BIC) model with the shrinking-core model to describe the extraction kinetics of Li, Co, Mn, and Ni from real NMC111 black mass. The BIC model successfully predicted extraction curves with deviations below 1.1%, identifying a Type A pattern dominated by rapid surface extraction followed by intraparticle diffusion. Shrinking-core analysis confirmed ash-layer diffusion as the rate-determining step, with apparent activation energies ranging from 4.8 to 14.9 kJ/mol. Comparison with Chrastil empirical solubility modeling validated the predictive accuracy of the BIC approach, highlighting stable solubility behavior for Li and Co and stronger sensitivity for Mn and Ni. By bridging macroscopic kinetics with mechanistic insights, this work establishes a predictive framework for optimizing SCFE processes, advancing environmentally responsible and scalable recycling of strategic metals from end-of-life LIBs.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"16 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145771696","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 : 2025-12-15DOI: 10.1021/acs.iecr.5c03494
Deping Xia, Wei Wang, Jingzhou Liu, Hualin Lin, Sheng Han
The Mg/Al hydrotalcite with different morphologies was prepared under mild conditions through a coprecipitation process. The sulfur- and phosphorus-free MA2 nanosheets were used in combination with MoDTC to improve the low load-bearing capacity and unsatisfactory tribological properties of organic molybdenum in PAO8. Especially, the 2.0 wt % MA2 nanosheets combined with 2.0 wt % MoDTC demonstrated the highest friction performances in PAO8. The results indicated that the synergistic effect between MA2 and MoDTC contributes to the formation of a stable tribofilm composed of MoS2, MgO, Al2O3, MoO3, Fe2(SO4)3, Fe2O3, and Fe3O4. This tribofilm not only could effectively protect the friction interface and provide friction-reducing and antiwear effects but also possess high film-forming rates (PB value) and load-bearing capacity.
{"title":"Enhancement of Tribological Properties Enabled by a Synergistic Effect between Mg/Al Hydrotalcite and MoDTC","authors":"Deping Xia, Wei Wang, Jingzhou Liu, Hualin Lin, Sheng Han","doi":"10.1021/acs.iecr.5c03494","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c03494","url":null,"abstract":"The Mg/Al hydrotalcite with different morphologies was prepared under mild conditions through a coprecipitation process. The sulfur- and phosphorus-free MA2 nanosheets were used in combination with MoDTC to improve the low load-bearing capacity and unsatisfactory tribological properties of organic molybdenum in PAO8. Especially, the 2.0 wt % MA2 nanosheets combined with 2.0 wt % MoDTC demonstrated the highest friction performances in PAO8. The results indicated that the synergistic effect between MA2 and MoDTC contributes to the formation of a stable tribofilm composed of MoS<sub>2</sub>, MgO, Al<sub>2</sub>O<sub>3</sub>, MoO<sub>3</sub>, Fe<sub>2</sub>(SO<sub>4</sub>)<sub>3</sub>, Fe<sub>2</sub>O<sub>3</sub>, and Fe<sub>3</sub>O<sub>4</sub>. This tribofilm not only could effectively protect the friction interface and provide friction-reducing and antiwear effects but also possess high film-forming rates (<i>P</i><sub>B</sub> value) and load-bearing capacity.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"1 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-12-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145752936","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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