Pub Date : 2025-03-06DOI: 10.1021/acs.iecr.4c03397
Jong Hyun Rho, Michael Baldea, Elizabeth E. Endler, Monica A. Heredia, Vesna Bojovic, Pejman Pajand
We study the impact of switching from combustion heating to electric heating in integrated processes comprising high-temperature-reaction/separation/recycle sequences, where the heat supporting the reaction(s) is provided mostly or entirely by combusting a byproduct/fuel gas. A canonical process structure is defined. It is shown that the conventional integrated process design with combustion heating presents feedback interactions due to the impact of the downstream units (via the heating value of the fuel gas) on the upstream units. These interactions are absent in the electrified process, with electric heating thus having a “de-integration” effect. An asymptotic analysis is utilized to investigate the dynamic responses of the two process structures. It is demonstrated that the dynamic behavior of the two processes exhibits two time scales, with the faster one corresponding to the evolution of the temperatures of the units with high heat duty and the slow time scale capturing the variables involved in the material balance. A simplified ethylene cracking process example is used to confirm the theoretical findings and their operational implications.
{"title":"Probing the Impact of Electric Heating on the Design, Dynamics, and Operation of Integrated Chemical Processes","authors":"Jong Hyun Rho, Michael Baldea, Elizabeth E. Endler, Monica A. Heredia, Vesna Bojovic, Pejman Pajand","doi":"10.1021/acs.iecr.4c03397","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c03397","url":null,"abstract":"We study the impact of switching from combustion heating to electric heating in integrated processes comprising high-temperature-reaction/separation/recycle sequences, where the heat supporting the reaction(s) is provided mostly or entirely by combusting a byproduct/fuel gas. A canonical process structure is defined. It is shown that the conventional integrated process design with combustion heating presents feedback interactions due to the impact of the downstream units (via the heating value of the fuel gas) on the upstream units. These interactions are absent in the electrified process, with electric heating thus having a “de-integration” effect. An asymptotic analysis is utilized to investigate the dynamic responses of the two process structures. It is demonstrated that the dynamic behavior of the two processes exhibits two time scales, with the faster one corresponding to the evolution of the temperatures of the units with high heat duty and the slow time scale capturing the variables involved in the material balance. A simplified ethylene cracking process example is used to confirm the theoretical findings and their operational implications.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"67 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143561132","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 : 2025-03-06DOI: 10.1021/acs.iecr.4c04273
Jak Tanthana, Vijay Gupta, Paul Mobley, Marty Lail
NAS, a novel water-lean solvent, has demonstrated its technical and economic feasibility through extensive testing and demonstration projects. This study presents results from a recent campaign conducted at Technology Centre Mongstad, Norway, where NAS was evaluated under high CO2 capture rates for both coal- and natural gas-derived flue gases. With minor process modifications, the NAS operated effectively within the existing amine plant. Accurate mass and energy balances were essential for assessing performance, particularly at high capture rates. The capture rates of 97.63% and 99.72% were achieved under coal- and natural gas- derived (NGCC) flue gas conditions, respectively. The specific reboiler duty of 2.59–2.63 GJ/t-CO2 is reported for coal cases and 3.08–4.19 GJ/t-CO2 for NGCC cases. The study found that NAS consistently outperformed traditional 30 wt % MEA in terms of CO2 avoided costs, with reductions ranging from 36 to 38% across various capture rates. These findings highlight the potential of NAS as a promising solution for efficient and cost-effective CO2 capture.
{"title":"Engineering-Scale Demonstration of the High CO2 Capture Rate by the Water-Lean Solvent at Technology Centre Mongstad","authors":"Jak Tanthana, Vijay Gupta, Paul Mobley, Marty Lail","doi":"10.1021/acs.iecr.4c04273","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c04273","url":null,"abstract":"NAS, a novel water-lean solvent, has demonstrated its technical and economic feasibility through extensive testing and demonstration projects. This study presents results from a recent campaign conducted at Technology Centre Mongstad, Norway, where NAS was evaluated under high CO<sub>2</sub> capture rates for both coal- and natural gas-derived flue gases. With minor process modifications, the NAS operated effectively within the existing amine plant. Accurate mass and energy balances were essential for assessing performance, particularly at high capture rates. The capture rates of 97.63% and 99.72% were achieved under coal- and natural gas- derived (NGCC) flue gas conditions, respectively. The specific reboiler duty of 2.59–2.63 GJ/t-CO<sub>2</sub> is reported for coal cases and 3.08–4.19 GJ/t-CO<sub>2</sub> for NGCC cases. The study found that NAS consistently outperformed traditional 30 wt % MEA in terms of CO<sub>2</sub> avoided costs, with reductions ranging from 36 to 38% across various capture rates. These findings highlight the potential of NAS as a promising solution for efficient and cost-effective CO<sub>2</sub> capture.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"46 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143561135","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 : 2025-03-06DOI: 10.1021/acs.iecr.4c03786
Farnaz Tabarkhoon, Mohammad Bazmi, Nicholas A. Welchert, Theodore T. Tsotsis, Malancha Gupta
Silicon carbide (SiCx) thin films are recognized as important materials because of their outstanding characteristics, such as chemical resistance in corrosive environments, a low thermal expansion coefficient, remarkable hardness, and high thermal conductivity. Due to such exceptional properties, these materials find a wide range of applications in the energy, semiconductor, biomedical, and aerospace industries. The current techniques for the production of SiCx films involve preceramic film deposition followed by transfer to a furnace for pyrolysis, which faces challenges such as poor film quality, susceptibility to oxygen contamination, high operating cost, and lengthy processing time. In this study, we fabricate SiCx thin films, instead, by combining preceramic film deposition and pyrolysis in a single reactor. This one-step system improves energy efficiency, minimizes processing time during ceramic film production, and reduces potential contamination. Specifically, we deposited an organosilicon poly(vinylphenyldimethylsilane) film via a low-energy plasma-enhanced chemical vapor deposition (PECVD) technique followed by in situ pyrolysis employing a custom-designed microheater system placed inside the vacuum PECVD chamber. Fourier transform infrared and X-ray energy-dispersive spectroscopy results confirmed that the SiCx film produced via in situ pyrolysis has a lower oxygen content compared to samples that were produced via ex situ pyrolysis after removal from the reactor, thus highlighting the importance of in situ pyrolysis in preventing unwanted oxidation reactions. In summary, the one-pot synthesis technique reduces contamination and oxidation and simplifies the deposition and pyrolysis process, enabling multilayer deposition and pyrolysis in a single batch system with precise control over the composition of each layer.
{"title":"One-Pot Fabrication of Silicon Carbide Thin Films via Plasma-Enhanced Chemical Vapor Deposition (PECVD) Followed by In Situ Pyrolysis","authors":"Farnaz Tabarkhoon, Mohammad Bazmi, Nicholas A. Welchert, Theodore T. Tsotsis, Malancha Gupta","doi":"10.1021/acs.iecr.4c03786","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c03786","url":null,"abstract":"Silicon carbide (SiC<sub><i>x</i></sub>) thin films are recognized as important materials because of their outstanding characteristics, such as chemical resistance in corrosive environments, a low thermal expansion coefficient, remarkable hardness, and high thermal conductivity. Due to such exceptional properties, these materials find a wide range of applications in the energy, semiconductor, biomedical, and aerospace industries. The current techniques for the production of SiC<sub><i>x</i></sub> films involve preceramic film deposition followed by transfer to a furnace for pyrolysis, which faces challenges such as poor film quality, susceptibility to oxygen contamination, high operating cost, and lengthy processing time. In this study, we fabricate SiC<sub><i>x</i></sub> thin films, instead, by combining preceramic film deposition and pyrolysis in a single reactor. This one-step system improves energy efficiency, minimizes processing time during ceramic film production, and reduces potential contamination. Specifically, we deposited an organosilicon poly(vinylphenyldimethylsilane) film via a low-energy plasma-enhanced chemical vapor deposition (PECVD) technique followed by in situ pyrolysis employing a custom-designed microheater system placed inside the vacuum PECVD chamber. Fourier transform infrared and X-ray energy-dispersive spectroscopy results confirmed that the SiC<sub><i>x</i></sub> film produced via in situ pyrolysis has a lower oxygen content compared to samples that were produced via ex situ pyrolysis after removal from the reactor, thus highlighting the importance of in situ pyrolysis in preventing unwanted oxidation reactions. In summary, the one-pot synthesis technique reduces contamination and oxidation and simplifies the deposition and pyrolysis process, enabling multilayer deposition and pyrolysis in a single batch system with precise control over the composition of each layer.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"16 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143570083","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}
Second-generation biodiesel is the dominant biomass-derived liquid fuel produced from nonedible natural or waste oils and fatty acids through selective oxygen removal. Here, we developed a highly selective sulfur-free NiMo/TiO2 catalyst by disentangling electronic and geometric effects to produce second-generation biodiesel via the hydrodeoxygenation of palmitic acid─one of the most common fatty acids in these feedstocks. An unprecedented hexadecane yield of 96.0% (on a mole basis) was achieved over the Ni1Mo1/TiO2 catalyst (with a Ni:Mo ratio of ∼1:1) at 300 °C and 3 MPa H2. Kinetic studies reveal that the competition between hydrodeoxygenation (C–O scission) and decarbonylation (C–C scission) of the intermediate hexadecanol is key to optimizing selectivity. Furthermore, Mo incorporation markedly lowers the apparent activation energy of hydrodeoxygenation─especially in the Ni1Mo1/TiO2 catalyst, which has the lowest Ni–Ni coordination number. Combined with catalyst characterization, these findings elucidate a Mo-induced “Ni coordination environment”-directed reaction pathway: the superb hydrodeoxygenation activity and selectivity of Ni1Mo1/TiO2 stem from its abundant NiMo interfacial sites, where Mo-induced oxygen vacancies synergize with adjacent Ni sites to facilitate the adsorption of O-containing groups and subsequent C–O bond cleavage.
{"title":"Structural and Kinetic Insights into Interfacial Site Effects in NiMo-Catalyzed Hydrodeoxygenation of Palmitic Acid","authors":"Jiachen Fang, Weixiao Sun, Kuan Huang, Xiaohu Ge, Wenyao Chen, Gang Qian, Yueqiang Cao, Jianrong Zeng, Jianbo Ma, Xinggui Zhou, Xuezhi Duan, Jing Zhang, Lilong Jiang","doi":"10.1021/acs.iecr.5c00403","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c00403","url":null,"abstract":"Second-generation biodiesel is the dominant biomass-derived liquid fuel produced from nonedible natural or waste oils and fatty acids through selective oxygen removal. Here, we developed a highly selective sulfur-free NiMo/TiO<sub>2</sub> catalyst by disentangling electronic and geometric effects to produce second-generation biodiesel via the hydrodeoxygenation of palmitic acid─one of the most common fatty acids in these feedstocks. An unprecedented hexadecane yield of 96.0% (on a mole basis) was achieved over the Ni<sub>1</sub>Mo<sub>1</sub>/TiO<sub>2</sub> catalyst (with a Ni:Mo ratio of ∼1:1) at 300 °C and 3 MPa H<sub>2</sub>. Kinetic studies reveal that the competition between hydrodeoxygenation (C–O scission) and decarbonylation (C–C scission) of the intermediate hexadecanol is key to optimizing selectivity. Furthermore, Mo incorporation markedly lowers the apparent activation energy of hydrodeoxygenation─especially in the Ni<sub>1</sub>Mo<sub>1</sub>/TiO<sub>2</sub> catalyst, which has the lowest Ni–Ni coordination number. Combined with catalyst characterization, these findings elucidate a Mo-induced “Ni coordination environment”-directed reaction pathway: the superb hydrodeoxygenation activity and selectivity of Ni<sub>1</sub>Mo<sub>1</sub>/TiO<sub>2</sub> stem from its abundant NiMo interfacial sites, where Mo-induced oxygen vacancies synergize with adjacent Ni sites to facilitate the adsorption of O-containing groups and subsequent C–O bond cleavage.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"9 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143570088","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}
A mixed-valence bimetallic Eu/Zr MOF has been fabricated via a one-step solvothermal method by incorporating Eu3+ ions into the Zr-MOF, thereby making a single-component photocatalyst that can be utilized toward robust photon utilization from the visible light spectrum for the photocatalytic production of green energy like H2 and H2O2. The one-step synthesized bimetallic Eu/Zr-MOF exhibits more visible light captivation properties along with improved charge carrier separation, confined band gap, and excellent ligand-to-metal charge transfer (LMCT) because of the existence of an interconvertible Eu3+/Eu2+ ion pair compared with the pristine MOF counterparts. The addition of Eu ions directed to an upsurge in the electron density around Zr4+ ion, as seen from XPS analysis. Moreover, the introduction of Eu3+ enhanced the exciton segregation, as seen from PL and EIS analyses, thereby leading to superior catalytic performances. An increased photocatalytic H2 generation efficacy of 331.26 μmol h–1 (ACE = 2.42%) was demonstrated by the synthesized EZUNH-2 MOF, which is approximately three times greater than pristine MOFs. As a result, the bimetallic EZUNH-2 MOF can be easily utilized as a robust photocatalyst that has increased inclinations to produce H2O2 at 35.2 μmol h–1, around 4 times more than that of the parent material. Consequently, the one-pot synthesized bimetallic MOF paves a suitable mechanistic pathway for paramount performance toward photocatalytic H2O2 and H2 production.
{"title":"A Visible Light-Responsive Mixed-Valence Bimetallic Eu–Zr MOF-Based Nanoarchitecture toward Efficacious H2O2 and H2 Production","authors":"Srabani Dash, Suraj Prakash Tripathy, Satyabrata Subudhi, Kulamani Parida","doi":"10.1021/acs.iecr.4c04234","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c04234","url":null,"abstract":"A mixed-valence bimetallic Eu/Zr MOF has been fabricated via a one-step solvothermal method by incorporating Eu<sup>3+</sup> ions into the Zr-MOF, thereby making a single-component photocatalyst that can be utilized toward robust photon utilization from the visible light spectrum for the photocatalytic production of green energy like H<sub>2</sub> and H<sub>2</sub>O<sub>2</sub>. The one-step synthesized bimetallic Eu/Zr-MOF exhibits more visible light captivation properties along with improved charge carrier separation, confined band gap, and excellent ligand-to-metal charge transfer (LMCT) because of the existence of an interconvertible Eu<sup>3+</sup>/Eu<sup>2+</sup> ion pair compared with the pristine MOF counterparts. The addition of Eu ions directed to an upsurge in the electron density around Zr<sup>4+</sup> ion, as seen from XPS analysis. Moreover, the introduction of Eu<sup>3+</sup> enhanced the exciton segregation, as seen from PL and EIS analyses, thereby leading to superior catalytic performances. An increased photocatalytic H<sub>2</sub> generation efficacy of 331.26 μmol h<sup>–1</sup> (ACE = 2.42%) was demonstrated by the synthesized EZUNH-2 MOF, which is approximately three times greater than pristine MOFs. As a result, the bimetallic EZUNH-2 MOF can be easily utilized as a robust photocatalyst that has increased inclinations to produce H<sub>2</sub>O<sub>2</sub> at 35.2 μmol h<sup>–1</sup>, around 4 times more than that of the parent material. Consequently, the one-pot synthesized bimetallic MOF paves a suitable mechanistic pathway for paramount performance toward photocatalytic H<sub>2</sub>O<sub>2</sub> and H<sub>2</sub> production.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"14 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143561134","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 : 2025-03-06DOI: 10.1021/acs.iecr.4c04979
Wei Wang, Xiaoyi Shen, Yan Liu, Mingyu Han, Yuchun Zhai
In this study, a novel fluoride removal adsorbent of the Zr4+-doped Mg–Al-layered double hydroxide (MgAlZr-LDH) was synthesized by a facile hydrothermal method, and the adsorbents before and after adsorption were characterized by SEM, XRD, FTIR, and XPS. The results of the adsorption experiments showed that adsorption reached equilibrium within 10 min. The adsorption kinetics and thermodynamics fitting indicated that the adsorption process followed the pseudo-second-order kinetic model and the Langmuir isotherm model. Its capacity for fluoride could reach up to 51.92 mg·g–1 at room temperature. Additionally, the adsorbent is effective across a wide pH range and exhibits good selectivity for fluoride. Its adsorption capacity still remained above 75% after 5 reusability cycles. Additionally, the defluorination mechanism is proposed, including electrostatic attraction, ion exchange, and ligand exchange. MgAlZr-LDH can be used as an effective adsorbent for removing fluoride from wastewater and has promising application prospects.
{"title":"A Novel Fluoride Removal Adsorbent of a Zr4+-Doped Mg–Al-Layered Double Hydroxide: Synthesis and Fluoride Removal Performance","authors":"Wei Wang, Xiaoyi Shen, Yan Liu, Mingyu Han, Yuchun Zhai","doi":"10.1021/acs.iecr.4c04979","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c04979","url":null,"abstract":"In this study, a novel fluoride removal adsorbent of the Zr<sup>4+</sup>-doped Mg–Al-layered double hydroxide (MgAlZr-LDH) was synthesized by a facile hydrothermal method, and the adsorbents before and after adsorption were characterized by SEM, XRD, FTIR, and XPS. The results of the adsorption experiments showed that adsorption reached equilibrium within 10 min. The adsorption kinetics and thermodynamics fitting indicated that the adsorption process followed the pseudo-second-order kinetic model and the Langmuir isotherm model. Its capacity for fluoride could reach up to 51.92 mg·g<sup>–1</sup> at room temperature. Additionally, the adsorbent is effective across a wide pH range and exhibits good selectivity for fluoride. Its adsorption capacity still remained above 75% after 5 reusability cycles. Additionally, the defluorination mechanism is proposed, including electrostatic attraction, ion exchange, and ligand exchange. MgAlZr-LDH can be used as an effective adsorbent for removing fluoride from wastewater and has promising application prospects.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"212 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143561138","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 : 2025-03-06DOI: 10.1021/acs.iecr.4c04170
Maximilian Fleck, Rei Katsuta, Timm Esper, Niels Hansen, Joachim Gross
This study extends the transferable anisotropic Mie potential (TAMie) to primary alkylamines. The force field parameters are fitted by minimizing the squared deviations of vapor pressures and liquid densities from experimental data of n-propylamine and n-butylamine. The physically based PC-SAFT equation of state was used as a surrogate model to approximate simulation results and additionally utilized in a linear multifidelity Gaussian process model extrapolating to temperatures that are difficult to simulate directly with Monte Carlo simulations. In the parameter optimization procedure, the deviation between simulation and experiment was approximated with Gaussian processes to determine those force field parameters, which cannot be mapped to the PC-SAFT representation. For propylamine and butylamine, the optimized force field leads to mean absolute relative deviations of 0.55% and 0.59% for liquid densities and 0.95% and 0.34% for vapor pressures in the range of reduced temperature 0.55 ≤ T/Tc ≤ 0.85 and 0.55 ≤ T/Tc ≤ 0.9. The transferability to higher alkylamines was tested for n-hexylamine to n-octylamine. Individual parameter sets are provided for methylamine and ethylamine. Dynamic properties such as the shear viscosity of pure substances are predicted in fair agreement with experimental data, even though no dynamic property was included in the parametrization. The phase behavior of binary mixtures of primary amines with alkanes is investigated, and the predictions of the TAMie model are found to be in very good agreement with experimental data.
{"title":"Gaussian Process-Supported Optimization of the Transferable Anisotropic Mie Potential Force Field for Primary Alkylamines","authors":"Maximilian Fleck, Rei Katsuta, Timm Esper, Niels Hansen, Joachim Gross","doi":"10.1021/acs.iecr.4c04170","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c04170","url":null,"abstract":"This study extends the transferable anisotropic Mie potential (TAMie) to primary alkylamines. The force field parameters are fitted by minimizing the squared deviations of vapor pressures and liquid densities from experimental data of <i>n</i>-propylamine and <i>n</i>-butylamine. The physically based PC-SAFT equation of state was used as a surrogate model to approximate simulation results and additionally utilized in a linear multifidelity Gaussian process model extrapolating to temperatures that are difficult to simulate directly with Monte Carlo simulations. In the parameter optimization procedure, the deviation between simulation and experiment was approximated with Gaussian processes to determine those force field parameters, which cannot be mapped to the PC-SAFT representation. For propylamine and butylamine, the optimized force field leads to mean absolute relative deviations of 0.55% and 0.59% for liquid densities and 0.95% and 0.34% for vapor pressures in the range of reduced temperature 0.55 ≤ <i>T</i>/<i>T</i><sub><i>c</i></sub> ≤ 0.85 and 0.55 ≤ <i>T</i>/<i>T</i><sub><i>c</i></sub> ≤ 0.9. The transferability to higher alkylamines was tested for <i>n</i>-hexylamine to <i>n</i>-octylamine. Individual parameter sets are provided for methylamine and ethylamine. Dynamic properties such as the shear viscosity of pure substances are predicted in fair agreement with experimental data, even though no dynamic property was included in the parametrization. The phase behavior of binary mixtures of primary amines with alkanes is investigated, and the predictions of the TAMie model are found to be in very good agreement with experimental data.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"36 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143561133","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 : 2025-03-06DOI: 10.1021/acs.iecr.4c03523
Chunyi Li, Akriti Sarswat, Susan E. Henkelis, Tina M. Nenoff, Ryan P. Lively, Jessica M. Rimsza
The design and realization of highly selective nanoporous materials are necessary to target critical separations across industries. By leveraging pore size, pore shape, and linker functionalization, the design of nanoporous solid adsorbents will enable the rapid production of energy efficient separation materials for high-value gas mixtures. This study uses a combination of modeling, synthesis, and gas adsorption testing to investigate a new class of small-pore isostructural rare-earth (RE) 2,5-dihydroxyterephthalic acid (DOBDC) metal–organic frameworks (MOFs) (RE: Pr-, Gd-, Er-, Yb; DOBDC = 2,5-dihydroxyterephthalic acid) and their adsorption selectivity for acetylene/ethylene mixtures. Density functional theory simulations identified that selective binding of acetylene over ethylene in the Gd-, Er-, and Yb-DOBDC MOFs was due to hydrogen-bonding between acetylene and the linker hydroxyl. Adsorption experiments validated the computational results by identifying mechanisms that control the acetylene/ethylene adsorption selectivity and high acetylene adsorption. Furthermore, dynamic column breakthrough experiments with the Gd-DOBDC MOF validated the simulations and indicated that ethylene can be separated from acetylene in a mixture containing 1 vol % acetylene and 39 vol % ethylene (balance argon). The results highlight the complexity of gas binding in functional porous materials and how combining modeling and experiment enables a fundamental understanding of gas–framework interactions that can be leveraged for the design of future separation materials.
{"title":"Structurally Driven Selective Adsorption of Hydrocarbons by Metal Substitution in Isostructural Rare-Earth Metal–Organic Frameworks","authors":"Chunyi Li, Akriti Sarswat, Susan E. Henkelis, Tina M. Nenoff, Ryan P. Lively, Jessica M. Rimsza","doi":"10.1021/acs.iecr.4c03523","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c03523","url":null,"abstract":"The design and realization of highly selective nanoporous materials are necessary to target critical separations across industries. By leveraging pore size, pore shape, and linker functionalization, the design of nanoporous solid adsorbents will enable the rapid production of energy efficient separation materials for high-value gas mixtures. This study uses a combination of modeling, synthesis, and gas adsorption testing to investigate a new class of small-pore isostructural rare-earth (RE) 2,5-dihydroxyterephthalic acid (DOBDC) metal–organic frameworks (MOFs) (RE: Pr-, Gd-, Er-, Yb; DOBDC = 2,5-dihydroxyterephthalic acid) and their adsorption selectivity for acetylene/ethylene mixtures. Density functional theory simulations identified that selective binding of acetylene over ethylene in the Gd-, Er-, and Yb-DOBDC MOFs was due to hydrogen-bonding between acetylene and the linker hydroxyl. Adsorption experiments validated the computational results by identifying mechanisms that control the acetylene/ethylene adsorption selectivity and high acetylene adsorption. Furthermore, dynamic column breakthrough experiments with the Gd-DOBDC MOF validated the simulations and indicated that ethylene can be separated from acetylene in a mixture containing 1 vol % acetylene and 39 vol % ethylene (balance argon). The results highlight the complexity of gas binding in functional porous materials and how combining modeling and experiment enables a fundamental understanding of gas–framework interactions that can be leveraged for the design of future separation materials.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"17 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143570085","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The shuttle effect of electrolyte-soluble lithium polysulfides hinders the practical application of high theoretical energy density Li–S batteries. Usually, introducing an interlayer between the S-based cathode and separator can act as a functional secondary current collector, which not only provides a physical barrier but also captures and reuses the escaped active S species from the cathode, thus achieving high S utilization. Herein, multitransition metal phosphides [(Mn/Co/Fe)Fe–P or (Mn/Co/Ni)Fe–P] with strong chemical interaction and catalytic effect to lithium polysulfides are employed to decorate commercial polypropylene (PP). Especially in the case of (Mn/Co/Fe)Fe–P, the corresponding particles with a small size of ∼50 nm guarantee strong lithium polysulfide adsorption and fast Li+ diffusion, thus effectively confining the active S species in the cathode region during Li–S battery operation. As a result, the Li–S battery with (Mn/Co/Fe)Fe–P/PP delivers a specific capacity of 870.41 mA h g–1 at 3 C, which retains 345.32 mA h g–1 after 1000 cycles, corresponding to a capacity decay of 0.06% per cycle. In addition, the symmetrical Li||Li cell with (Mn/Co/Fe)Fe–P/PP exhibits stable performance for almost 1000 cycles, which further demonstrates the possibility of (Mn/Co/Fe)Fe–P/PP to tune Li+ plating/stripping behaviors and hinder Li dendrites.
{"title":"Enhanced Lithium Polysulfide Conversion via the Second Current Collector Based on Multitransition-Metal-Phosphides for Li–S Batteries","authors":"Liqing He, Kaiquan He, Tengfei Cheng, Wanggang Fang, Chaoqun Shang","doi":"10.1021/acs.iecr.5c00371","DOIUrl":"https://doi.org/10.1021/acs.iecr.5c00371","url":null,"abstract":"The shuttle effect of electrolyte-soluble lithium polysulfides hinders the practical application of high theoretical energy density Li–S batteries. Usually, introducing an interlayer between the S-based cathode and separator can act as a functional secondary current collector, which not only provides a physical barrier but also captures and reuses the escaped active S species from the cathode, thus achieving high S utilization. Herein, multitransition metal phosphides [(Mn/Co/Fe)Fe–P or (Mn/Co/Ni)Fe–P] with strong chemical interaction and catalytic effect to lithium polysulfides are employed to decorate commercial polypropylene (PP). Especially in the case of (Mn/Co/Fe)Fe–P, the corresponding particles with a small size of ∼50 nm guarantee strong lithium polysulfide adsorption and fast Li<sup>+</sup> diffusion, thus effectively confining the active S species in the cathode region during Li–S battery operation. As a result, the Li–S battery with (Mn/Co/Fe)Fe–P/PP delivers a specific capacity of 870.41 mA h g<sup>–1</sup> at 3 C, which retains 345.32 mA h g<sup>–1</sup> after 1000 cycles, corresponding to a capacity decay of 0.06% per cycle. In addition, the symmetrical Li||Li cell with (Mn/Co/Fe)Fe–P/PP exhibits stable performance for almost 1000 cycles, which further demonstrates the possibility of (Mn/Co/Fe)Fe–P/PP to tune Li<sup>+</sup> plating/stripping behaviors and hinder Li dendrites.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"67 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143570087","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The calcium looping (CaL) process is a promising carbon capture technology for CO2 capture from point source emitters. A key challenge in the CaL process is the loss of sorbent capacity over successive capture-regeneration cycles due to sintering, which affects long-term stability. This study addresses this issue by a novel approach of incorporating MgO, Al2O3, and ZrO2 as promoters into calcium-based sorbents synthesized using the solution combustion synthesis (SCS) method. Sorbents were developed in mono-, bi-, and trimetallic configurations using soluble metal nitrates as precursors. Among the tested sorbents, Ca/(Zr–Al) demonstrated the highest CO2 uptake of 0.46 g of CO2/g of sorbent, while Ca/(Mg–Zr–Al) achieved 0.43 g of CO2/g of sorbent. Both configurations exhibited exceptional stability, maintaining over 90% of their initial capacity after 50 cycles at elevated temperatures. These results highlight the effectiveness of bi- and trimetallic sorbents in enhancing the performance and durability of the CaL process.
{"title":"CO2 Capture with Mg-, Al-, and Zr- Assisted CaO-Based Sorbents in the Calcium Looping Process Under Mild and Realistic Conditions","authors":"Aakash Vijayaraghavan Ramesh, Seyed Mojtaba Hashemi, Nader Mahinpey","doi":"10.1021/acs.iecr.4c04749","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c04749","url":null,"abstract":"The calcium looping (CaL) process is a promising carbon capture technology for CO<sub>2</sub> capture from point source emitters. A key challenge in the CaL process is the loss of sorbent capacity over successive capture-regeneration cycles due to sintering, which affects long-term stability. This study addresses this issue by a novel approach of incorporating MgO, Al<sub>2</sub>O<sub>3</sub>, and ZrO<sub>2</sub> as promoters into calcium-based sorbents synthesized using the solution combustion synthesis (SCS) method. Sorbents were developed in mono-, bi-, and trimetallic configurations using soluble metal nitrates as precursors. Among the tested sorbents, Ca/(Zr–Al) demonstrated the highest CO<sub>2</sub> uptake of 0.46 g of CO<sub>2</sub>/g of sorbent, while Ca/(Mg–Zr–Al) achieved 0.43 g of CO<sub>2</sub>/g of sorbent. Both configurations exhibited exceptional stability, maintaining over 90% of their initial capacity after 50 cycles at elevated temperatures. These results highlight the effectiveness of bi- and trimetallic sorbents in enhancing the performance and durability of the CaL process.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"58 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143561136","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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