Industrial & Engineering Chemistry Research最新文献_第10页

Free Energy Profiles of Monomeric Species in MOFs for Predicting Thermal Stability of MOF–Polymer Systems

IF 3.8 3区工程技术

Industrial & Engineering Chemistry Research Pub Date : 2024-12-08 DOI: 10.1021/acs.iecr.4c0322810.1021/acs.iecr.4c03228

Sanoj Raj, and , Yamil J. Colón*,

{"title":"Free Energy Profiles of Monomeric Species in MOFs for Predicting Thermal Stability of MOF–Polymer Systems","authors":"Sanoj Raj,  and , Yamil J. Colón*, ","doi":"10.1021/acs.iecr.4c0322810.1021/acs.iecr.4c03228","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c03228https://doi.org/10.1021/acs.iecr.4c03228","url":null,"abstract":"Metal–organic frameworks (MOFs) and hybrid MOF–polymer systems have been explored for gas separation applications. The pore surface’s environment and interaction with different monomers can help understand the physical properties of hybrid MOFs–polymer systems. In our work, we have focused on understanding the interaction between the pores of UiO-66/UiO-67 and different monomeric species representative of various polymers (ethyl methyl ether, poly(vinyl alcohol), polyvinyl chloride, and polypropylene), which are similar in structure but have different functional groups. We have used advanced sampling techniques to calculate the free energy profile of monomers traversing through the pores. We find that the free energy barrier for different monomers in UiO-66 and UiO-67 is very different and depends on these monomers’ interaction with the pore environment. The pore-limiting diameter of MOFs, the kinetic diameter of the monomers, and the free energy barrier of monomers traversing through the pores of UiO-66 and UiO-67 were used to understand the stability of these MOF–polymer hybrid systems. We find that UiO-66 with poly(vinyl alcohol), poly(vinyl chloride), and polypropylene is predicted to be stable at room temperature compared to UiO-66 with ethyl methyl ether. UiO-67 hybrid polymer systems are predicted to be unstable at room temperature.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"63 50","pages":"21901–21906 21901–21906"},"PeriodicalIF":3.8,"publicationDate":"2024-12-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142842727","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}

引用次数: 0

Free Energy Profiles of Monomeric Species in MOFs for Predicting Thermal Stability of MOF–Polymer Systems

IF 4.2 3区工程技术

Industrial & Engineering Chemistry Research Pub Date : 2024-12-08 DOI: 10.1021/acs.iecr.4c03228

Sanoj Raj, Yamil J. Colón

{"title":"Free Energy Profiles of Monomeric Species in MOFs for Predicting Thermal Stability of MOF–Polymer Systems","authors":"Sanoj Raj, Yamil J. Colón","doi":"10.1021/acs.iecr.4c03228","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c03228","url":null,"abstract":"Metal–organic frameworks (MOFs) and hybrid MOF–polymer systems have been explored for gas separation applications. The pore surface’s environment and interaction with different monomers can help understand the physical properties of hybrid MOFs–polymer systems. In our work, we have focused on understanding the interaction between the pores of UiO-66/UiO-67 and different monomeric species representative of various polymers (ethyl methyl ether, poly(vinyl alcohol), polyvinyl chloride, and polypropylene), which are similar in structure but have different functional groups. We have used advanced sampling techniques to calculate the free energy profile of monomers traversing through the pores. We find that the free energy barrier for different monomers in UiO-66 and UiO-67 is very different and depends on these monomers’ interaction with the pore environment. The pore-limiting diameter of MOFs, the kinetic diameter of the monomers, and the free energy barrier of monomers traversing through the pores of UiO-66 and UiO-67 were used to understand the stability of these MOF–polymer hybrid systems. We find that UiO-66 with poly(vinyl alcohol), poly(vinyl chloride), and polypropylene is predicted to be stable at room temperature compared to UiO-66 with ethyl methyl ether. UiO-67 hybrid polymer systems are predicted to be unstable at room temperature.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"83 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2024-12-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142793600","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}

引用次数: 0

Rapid Synthesis of Defect-Free Tubular Co-Gallate MOF Membranes for MeOH/MTBE Separation by Pervaporation 利用渗透蒸发法快速合成用于分离 MeOH/MTBE 的无缺陷管状共棓酸盐 MOF 膜

IF 3.8 3区工程技术

Industrial & Engineering Chemistry Research Pub Date : 2024-12-08 DOI: 10.1021/acs.iecr.4c0347110.1021/acs.iecr.4c03471

Guoshu Gao, Yumeng Zhao, Peng Zhu, Haiou Liu, Xiongfu Zhang*, Yu Guo* and Guohui Yang*,

{"title":"Rapid Synthesis of Defect-Free Tubular Co-Gallate MOF Membranes for MeOH/MTBE Separation by Pervaporation","authors":"Guoshu Gao, Yumeng Zhao, Peng Zhu, Haiou Liu, Xiongfu Zhang*, Yu Guo* and Guohui Yang*, ","doi":"10.1021/acs.iecr.4c0347110.1021/acs.iecr.4c03471","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c03471https://doi.org/10.1021/acs.iecr.4c03471","url":null,"abstract":"The Co-gallate MOF membrane exhibits great potential for separating MeOH/MTBE mixtures due to its regular pore size, exceptional stability, and high hydrophilicity. Nevertheless, the rapid nucleation and growth rate of the Co-gallate crystals in the synthesis solution cause poor nucleation on the substrate surface, which presents a significant challenge for the preparation of continuous Co-gallate membranes. In this study, we presented a cobalt carbonate hydroxide nanowire array (Co-NWA)-induced strategy that enabled the rapid and defect-free synthesis of tubular Co-gallate membranes within just 1 h. The presynthesized Co-NWAs on the substrate played as nucleation centers and anchoring sites, facilitating robust membrane formation. The effects of various synthesis parameters on the crystal morphology and membrane compactness were systematically examined. The optimized Co-gallate membrane demonstrated excellent pervaporation performance, with a permeation flux of 2.03 kg m–2 h–1 and a separation factor of 6711 for a 14.3/85.7 wt % MeOH/MTBE mixture, maintaining high performance for over 100 h, indicative of its remarkable long-term stability. This Co-NWA-induced synthesis strategy presents a promising approach for the industrial-scale application of Co-gallate MOF membranes and the design of other MOF membranes, thereby advancing their utility in requisite liquid separation processes.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"63 50","pages":"22043–22052 22043–22052"},"PeriodicalIF":3.8,"publicationDate":"2024-12-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142842106","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}

引用次数: 0

Bubbles in Sand-Fluidized Bed Gasifiers: Bubble Motion under Inherent Conditional Randomness

IF 3.8 3区工程技术

Industrial & Engineering Chemistry Research Pub Date : 2024-12-08 DOI: 10.1021/acs.iecr.4c0233610.1021/acs.iecr.4c02336

Nicolas Torres Brauer, and , Hugo de Lasa*,

{"title":"Bubbles in Sand-Fluidized Bed Gasifiers: Bubble Motion under Inherent Conditional Randomness","authors":"Nicolas Torres Brauer,  and , Hugo de Lasa*, ","doi":"10.1021/acs.iecr.4c0233610.1021/acs.iecr.4c02336","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c02336https://doi.org/10.1021/acs.iecr.4c02336","url":null,"abstract":"Fluidized biomass gasification can be employed for agricultural waste conversion, including the production of syngas and biochar. Syngas is a valuable, renewable, and clean energy source, while biochar is a good supplement for soil remineralization. Fluidized bed biomass gasifiers are strongly influenced in their performance by bubble flow dynamics. In 2023, Chemical Reactor Engineering Centre (CREC) researchers, at the University of Western Ontario, introduced a phenomenological probabilistic predictive model (PPPM), which takes into consideration bubble motion randomness, and it was established on the basis of both theoretical principles and experimental data. Computational particle fluid dynamics (CPFD), and in particular, a multiphase particle-in-cell (MP-PIC) model, are considered in the present study to predict bubble sizes, bubble velocities, and bed pressure drops. MP-PIC simulations, yielding bubble rising velocity (BRV) and bubble axial chord (BAC) data, based on more than a +80,000 bubble population were considered to confirm inherently constrained bubble randomness motion. Results show that even if there are unavoidable and random variations in local bed density, bubble motion, and bubble interactions, simulated bubbles consistently fall within MP-PIC behavioral bands. It is anticipated that the observed fluid dynamic probabilistic trends, as obtained with both the MP-PIC and the PPPM, could be used in the future to improve sand-fluidized bed drag correlations and the scale-up of lab-scale gasifiers for agricultural waste gasification while accounting for the unavoidable conditional inherent randomness in bubble motion.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"63 50","pages":"21696–21707 21696–21707"},"PeriodicalIF":3.8,"publicationDate":"2024-12-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142850366","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}

引用次数: 0

Analysis Tool for Gas and Vapor Solubility in Glassy Polymers: The Dual Nonequilibrium Lattice Fluid (d-NELF)

IF 4.2 3区工程技术

Industrial & Engineering Chemistry Research Pub Date : 2024-12-07 DOI: 10.1021/acs.iecr.4c02070

Matteo Minelli, Ferruccio Doghieri

{"title":"Analysis Tool for Gas and Vapor Solubility in Glassy Polymers: The Dual Nonequilibrium Lattice Fluid (d-NELF)","authors":"Matteo Minelli, Ferruccio Doghieri","doi":"10.1021/acs.iecr.4c02070","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c02070","url":null,"abstract":"In view of the physically sounding ideas it is founded on, as well of its simplicity and stand-alone character, the dual-mode sorption model (DMS) has been almost universally used in past decades to analyze and compare gas sorption data in polymeric matrixes below the glass transition temperature. The elements the DMS analysis is based on are here revised with the help of results developed within the nonequilibrium lattice fluid (NELF) model to derive meaningful relations between DMS model parameters and equilibrium and nonequilibrium structure property characteristics of the NELF approach. The result is a stand-alone and simple-to-use new tool for the analysis of solubility data in glassy polymers which allows for the use of a limited amount of data to retrieve the nonequilibrium structure property characteristic of the polymer matrix. The model can then be used to compare the solubility of different gases in the same glassy polymer, based just on equilibrium binary interaction parameters, or to distinguish the gas or vapor solubility properties of different nonequilibrium structures in the same polymer species, based on pertinent values of excess-free volume and compressibility.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"13 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2024-12-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142788729","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}

引用次数: 0

Analysis Tool for Gas and Vapor Solubility in Glassy Polymers: The Dual Nonequilibrium Lattice Fluid (d-NELF)

IF 3.8 3区工程技术

Industrial & Engineering Chemistry Research Pub Date : 2024-12-07 DOI: 10.1021/acs.iecr.4c0207010.1021/acs.iecr.4c02070

Matteo Minelli, and , Ferruccio Doghieri*,

{"title":"Analysis Tool for Gas and Vapor Solubility in Glassy Polymers: The Dual Nonequilibrium Lattice Fluid (d-NELF)","authors":"Matteo Minelli,  and , Ferruccio Doghieri*, ","doi":"10.1021/acs.iecr.4c0207010.1021/acs.iecr.4c02070","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c02070https://doi.org/10.1021/acs.iecr.4c02070","url":null,"abstract":"In view of the physically sounding ideas it is founded on, as well of its simplicity and stand-alone character, the dual-mode sorption model (DMS) has been almost universally used in past decades to analyze and compare gas sorption data in polymeric matrixes below the glass transition temperature. The elements the DMS analysis is based on are here revised with the help of results developed within the nonequilibrium lattice fluid (NELF) model to derive meaningful relations between DMS model parameters and equilibrium and nonequilibrium structure property characteristics of the NELF approach. The result is a stand-alone and simple-to-use new tool for the analysis of solubility data in glassy polymers which allows for the use of a limited amount of data to retrieve the nonequilibrium structure property characteristic of the polymer matrix. The model can then be used to compare the solubility of different gases in the same glassy polymer, based just on equilibrium binary interaction parameters, or to distinguish the gas or vapor solubility properties of different nonequilibrium structures in the same polymer species, based on pertinent values of excess-free volume and compressibility.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"63 50","pages":"22087–22103 22087–22103"},"PeriodicalIF":3.8,"publicationDate":"2024-12-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142842185","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}

引用次数: 0

Study on the Dissolution Behavior of UO2 in the Na2CO3–H2O2 System Using a Flow-Through Dissolution Device

IF 4.2 3区工程技术

Industrial & Engineering Chemistry Research Pub Date : 2024-12-07 DOI: 10.1021/acs.iecr.4c03554

Meng Zhang, Haofan Fang, Mingjian He, Caishan Jiao, Hongtao Zhao, Chaobo Shang

{"title":"Study on the Dissolution Behavior of UO2 in the Na2CO3–H2O2 System Using a Flow-Through Dissolution Device","authors":"Meng Zhang, Haofan Fang, Mingjian He, Caishan Jiao, Hongtao Zhao, Chaobo Shang","doi":"10.1021/acs.iecr.4c03554","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c03554","url":null,"abstract":"The CARBEX process, proposed in 2008, is a spent nuclear fuel (SNF) reprocessing process that relies on the alkaline environment of a Na2CO3–H2O2 system. In this work, we focused on the dissolution stage of the CARBEX process using a flow-through dissolution device to investigate the dissolution behavior of UO2 in the Na2CO3–H2O2 system and provide the dissolution rates of UO2 under different concentrations of Na2CO3 and H2O2. In addition, the 60Co-γ radiation source was used to simulate the radioactive environment during spent fuel reprocessing and to investigate the effect on the UO2 dissolution behavior in irradiation. The results show that the radiolysis products of water molecules react with excess H2O2 in solution to further generate •HO2. At the same time, H2O2 can also quench reductive radioactive dissolution products, increasing the oxidizing nature of the solution and thereby enhancing the dissolution rate of UO2 in a Na2CO3–H2O2 system. Finally, the dissolution process of UO2 in the Na2CO3–H2O2 system under irradiation conditions was summarized.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"86 1","pages":""},"PeriodicalIF":4.2,"publicationDate":"2024-12-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142788731","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}

引用次数: 0

Study on the Dissolution Behavior of UO2 in the Na2CO3–H2O2 System Using a Flow-Through Dissolution Device

IF 3.8 3区工程技术

Industrial & Engineering Chemistry Research Pub Date : 2024-12-07 DOI: 10.1021/acs.iecr.4c0355410.1021/acs.iecr.4c03554

Meng Zhang, Haofan Fang, Mingjian He, Caishan Jiao*, Hongtao Zhao* and Chaobo Shang,

{"title":"Study on the Dissolution Behavior of UO2 in the Na2CO3–H2O2 System Using a Flow-Through Dissolution Device","authors":"Meng Zhang, Haofan Fang, Mingjian He, Caishan Jiao*, Hongtao Zhao* and Chaobo Shang, ","doi":"10.1021/acs.iecr.4c0355410.1021/acs.iecr.4c03554","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c03554https://doi.org/10.1021/acs.iecr.4c03554","url":null,"abstract":"The CARBEX process, proposed in 2008, is a spent nuclear fuel (SNF) reprocessing process that relies on the alkaline environment of a Na2CO3–H2O2 system. In this work, we focused on the dissolution stage of the CARBEX process using a flow-through dissolution device to investigate the dissolution behavior of UO2 in the Na2CO3–H2O2 system and provide the dissolution rates of UO2 under different concentrations of Na2CO3 and H2O2. In addition, the 60Co-γ radiation source was used to simulate the radioactive environment during spent fuel reprocessing and to investigate the effect on the UO2 dissolution behavior in irradiation. The results show that the radiolysis products of water molecules react with excess H2O2 in solution to further generate •HO2. At the same time, H2O2 can also quench reductive radioactive dissolution products, increasing the oxidizing nature of the solution and thereby enhancing the dissolution rate of UO2 in a Na2CO3–H2O2 system. Finally, the dissolution process of UO2 in the Na2CO3–H2O2 system under irradiation conditions was summarized.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"63 50","pages":"21662–21671 21662–21671"},"PeriodicalIF":3.8,"publicationDate":"2024-12-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142850449","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}

引用次数: 0

New Approach Lagrangian for Numerical Analysis Within L-V One Equilibrium Stage of a Distillation Column Using the SPH Method

IF 3.8 3区工程技术

Industrial & Engineering Chemistry Research Pub Date : 2024-12-07 DOI: 10.1021/acs.iecr.4c0331310.1021/acs.iecr.4c03313

Jazmín Cortez-González, Rodolfo Murrieta-Dueñas*, Carlos Enrique Alvarado-Rodríguez, Juan Gabriel Segovia-Hernández, Salvador Hernández and Roberto Gutiérrez-Guerra,

{"title":"New Approach Lagrangian for Numerical Analysis Within L-V One Equilibrium Stage of a Distillation Column Using the SPH Method","authors":"Jazmín Cortez-González, Rodolfo Murrieta-Dueñas*, Carlos Enrique Alvarado-Rodríguez, Juan Gabriel Segovia-Hernández, Salvador Hernández and Roberto Gutiérrez-Guerra, ","doi":"10.1021/acs.iecr.4c0331310.1021/acs.iecr.4c03313","DOIUrl":"https://doi.org/10.1021/acs.iecr.4c03313https://doi.org/10.1021/acs.iecr.4c03313","url":null,"abstract":"This paper presents a numerical analysis of liquid–vapor equilibrium in a sieve tray of a distillation column using the Smoothed Particle Hydrodynamics (SPH) method. This Lagrangian approach provides a comprehensive understanding of the hydrodynamics, heat transfer, and liquid–vapor interactions within the tray, considering variations in deck area (85%, 90%, and 95%). The study examines flow patterns, flow regimes, weeping phenomena, and heat transfer within the tray. Results indicate that with a reduced deck area, the bubble regime predominates, leading to higher weeping rates and lower temperature uniformity between phases. Conversely, increasing the deck area to 90% or 95% shifts the regime to steam jet and spray, reduces weeping, and enhances phase interaction, thereby improving heat transfer and equilibrium stage efficiency. The study also highlights the effectiveness of the SPH method in simulating complex flow behavior within sieve trays.","PeriodicalId":39,"journal":{"name":"Industrial & Engineering Chemistry Research","volume":"63 50","pages":"21974–21990 21974–21990"},"PeriodicalIF":3.8,"publicationDate":"2024-12-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142850537","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}

引用次数: 0

New Approach Lagrangian for Numerical Analysis Within L-V One Equilibrium Stage of a Distillation Column Using the SPH Method

IF 4.2 3区工程技术

Industrial & Engineering Chemistry Research Pub Date : 2024-12-07 DOI: 10.1021/acs.iecr.4c03313

Jazmín Cortez-González, Rodolfo Murrieta-Dueñas, Carlos Enrique Alvarado-Rodríguez, Juan Gabriel Segovia-Hernández, Salvador Hernández, Roberto Gutiérrez-Guerra

引用次数: 0