Polymers of intrinsic microporosity(PIMs)have received considerable attention for making high-performance membranes for carbon dioxide separation over the last two decades,owing to their highly permeable porous struct...Polymers of intrinsic microporosity(PIMs)have received considerable attention for making high-performance membranes for carbon dioxide separation over the last two decades,owing to their highly permeable porous structures.However,challenges regarding its relatively low selectivity,physical aging,and plasticisation impede relevant industrial adoptions for gas separation.To address these issues,several strategies including chain modification,post-modification,blending with other polymers,and the addition of fillers,have been developed and explored.PIM-1 is the most investigated PIMs,and hence here we review the stateof-the-arts of the modification strategies of PIM-1 critically and discuss the progress achieved for addressing the aforementioned challenges via meta-analysis.Additionally,the development of PIM-1-based thin film composite membranes is commented as well,shedding light on their potential in industrial gas separation.We hope that the review can be a timely snapshot of the relevant state-of-the-arts of PIMs guiding future design and optimisation of PIMs-based membranes for enhanced performance towards a higher technology readiness level for practical applications.展开更多
The long hydrate induction time and limited gas-liquid contact area leads to slow hydrate formation rate and low water-hydrate conversion rate.Porous media are often used to promote hydrate formation because of their ...The long hydrate induction time and limited gas-liquid contact area leads to slow hydrate formation rate and low water-hydrate conversion rate.Porous media are often used to promote hydrate formation because of their large specific surface area.Consequently,we used 3A molecular sieve as a water-carrying solid in this work,and investigated the dynamic renewal of the gas-liquid interface and its effect on hydrate formation.The formation kinetics of ethane hydrate was first measured in an aqueous molecular sieve system.Then the separation of(H_(2)+CH_(4)+C_(2)H_(6)+C_(3)H_(8))gas mixture was conducted via hydrate formation.The results show that the formation rate and gas storage capacity of ethane hydrate can be greatly improved by using aqueous molecular sieve.Compared with a pure water system under the same temperature and pressure,aqueous molecular sieve has obvious advantages in separation effect and energy consumption for separating gas mixtures.展开更多
Zeolitic imidazolate framework-8(ZIF-8)is a typical filler used to fabricate mixed matrix membranes(MMMs)on account of its attractive advantage of high selective permeability for gas separation.However,the performance...Zeolitic imidazolate framework-8(ZIF-8)is a typical filler used to fabricate mixed matrix membranes(MMMs)on account of its attractive advantage of high selective permeability for gas separation.However,the performance is usually affected by filler aggregation due to strong interactions among fillers and weak interactions between the polymer and fillers,However,the performance is usually affected by filler aggregation due to strong interactions among fillers and weak interactions between the polymer and fillers,which will lead to a decrease of selectivity and the performance of gas separation will be strongly influenced.Herein,we modified ZIF-8 with 3-amino-1,2,4-triazole to obtain ZIF-8-NH_(2),Kapton polyamide acid was selected as the polymer matrix.Results showed that the ZIF-8-NH_(2)/Kapton MMMs has a good compatibility interface between ZIF-8 and Kapton because of the covalent bridging,even the filler loading up to 45%(mass).The 45%(mass)of ZIF-8-NH_(2)/Kapton membrane showed 297 barrer(1 barrer=10^(-10)10 cm^(3)·cm·cm^(-2)·s^(-1)·cmHg^(-1),1 cmHg=1333.22 Pa,standard temperature and pressure)of the permeability of H_(2)and 43.9 and 62.2 of selectivities for H_(2)/N_(2)and for H_(2)/CH_(4),respectively,which are beyond the upper limit of Robeson 2008.展开更多
Metal-organic frameworks(MOFs)are a subclass of porous materials that have gained considerable at-tention recently due to their unique properties and potential applications.However,MOFs may exhibit defects affecting t...Metal-organic frameworks(MOFs)are a subclass of porous materials that have gained considerable at-tention recently due to their unique properties and potential applications.However,MOFs may exhibit defects affecting their gas separation performance,limiting their practical applications.This review arti-cle focuses on defects in MOFs and their impact on gas separation.Additionally,the reports explore the potential of De novo and post-synthetic modification(PSM)to improve the gas separation properties by tuning their defects.The PSM of MOFs is discussed in detail,including the different types of modifications and their effects on the MOF properties.Finally,the article discusses the potential of PSM for practical gas separation applications,highlighting recent examples of MOF-based membranes and adsorbents with improved gas separation performance resulting from PSM.It is strategically reasonable to have defects inside the MOFs,but why is it so fascinating in gas separation applications?In this present review,we have tried to uncover the mystery of defects.Overall,this review highlights the importance of defects in MOFs and the potential of PSM strategies to enhance their gas separation properties.展开更多
Gas separation is a critical application of gas hydrates,and accurately predicting separation performance is crucial.In this study,we used thermodynamic calculations to predict the equilibrium phase of gas hydrates fo...Gas separation is a critical application of gas hydrates,and accurately predicting separation performance is crucial.In this study,we used thermodynamic calculations to predict the equilibrium phase of gas hydrates for various mole fractions of CO_(2)+CH_(4)gas mixtures.We also determined the mole fraction of each gas component trapped within the hydrate clathrate.To predict the equilibrium points,we used the SoaveeRedlicheKwong(SRK)equation of state for the gas phase,the nonrandom two-liquid(NRTL)model for the liquid phase,and the CheneGuo model for the hydrate phase.We modified the hydrate fugacity formula and introduced a new function to improve the accuracy of the CheneGuo model.By incorporating experimental equilibrium results from our study and another study,we developed a correlation based on gas mixture composition and temperature,resulting in highly accurate predictions.The use of this new correlation for hydrate fugacity calculation significantly improved precision,as evidenced by an average absolute deviation percent of calculated pressures(AADP)of 1.34%for pure CO_(2)and 1.25%for CH_(4).When considering the 27 data points of different CO_(2)+CH_(4)mixtures,the AADP%was 1.98%.To implement the model to predict equilibrium phases,we used the CheneGuo framework to determine the mole fraction of each gas component in the hydrate mixture.Interestingly,we discovered a linear correlation between the CO_(2)mole fraction in the hydrate and equilibrium pressure,with a slope of approximately 0.001 and a y-intercept of less than one,for all gas compositions.Therefore,we can conclude that low thermodynamic conditions(temperature and pressure)result in a high CO_(2)mole fraction in the hydrate phase and great separation efficiency.展开更多
The separation of gas molecules with similar physicochemical properties is of high importance but practically entails a substantial energy penalty in chemical industry. Meanwhile, clean energy gases such as H_2 and CH...The separation of gas molecules with similar physicochemical properties is of high importance but practically entails a substantial energy penalty in chemical industry. Meanwhile, clean energy gases such as H_2 and CH_4 are considered as promising candidates for the replacement of traditional fossil fuels. However, the technologies for the storage of these gases are still immature. In addition, the release of anthropogenic toxic gases into the atmosphere is a worldwide threat of growing concern. Both in academia and industry, considerable research efforts have been devoted to developing advanced porous materials for the effective and energy-efficient separation, storage, or capture of the related gases. In contrast to conventional inorganic porous materials such as zeolites and activated carbons, metal–organic frameworks(MOFs) are considered as a type of promising materials for gas separation and storage. In this contribution, we review the recent research advance of MOFs in some relevant applications, including CO_2 capture, O_2 purification, separation of light hydrocarbons, separation of noble gases, storage of gases(CH_4,H_2, and C_2 H_2) for energy, and removal of some gaseous air pollutants(NH_3, NO_2, and SO_2). Finally, an outlook regarding the challenges of the future research of MOFs in these directions is given.展开更多
To improve the separation performance of a supersonic gas separation device for the treatment of gas mixture with a single heavy component, a novel structure with shorter settlement distance was constructed and a meth...To improve the separation performance of a supersonic gas separation device for the treatment of gas mixture with a single heavy component, a novel structure with shorter settlement distance was constructed and a method of droplet enlargement was applied. A series of experiments were carried out in the improved separation device under various conditions, using air-ethanol vapor as the medium and micro water droplets as nucleation cen- ters. The effects of the inlet pressure, temperature and relative humidity, the swirling intensity, and mass flow rate of water on the separation performance were investigated. The separation was improved by increasing the inlet pressure and relative humidity. With the decrease of swirling intensity and mass flow rate of water, the separation efficiency increased first and then decreased. The inlet temperature had a slight effect on the separation. The results showed that the separation performance was effectively improved using the proposed structure and method, and the best separation in this study was obtained with the ethanol removal rate about 55% and dew point depression 27 K. The addition of water had little pollution to the air-ethanol vapor system since the water carry-over rate was within the range of -2 %-0 in most cases.展开更多
Three gas separation technologies,chemical absorption,membrane separation and pressure swing adsorption,are usually applied for CO2 capture from flue gas in coal-fired power plants.In this work,the costs of the three ...Three gas separation technologies,chemical absorption,membrane separation and pressure swing adsorption,are usually applied for CO2 capture from flue gas in coal-fired power plants.In this work,the costs of the three technologies are analyzed and compared.The cost for chemical absorption is mainly from $30 to $60 per ton(based on CO2 avoided),while the minimum value is $10 per ton(based on CO2 avoided).As for membrane separation and pressure swing adsorption,the costs are $50 to $78 and $40 to $63 per ton(based on CO2 avoided),respectively.Measures are proposed to reduce the cost of the three technologies.For CO2 capture and storage process,the CO2 recovery and purity should be greater than 90%.Based on the cost,recovery,and purity,it seems that chemical absorption is currently the most cost-effective technology for CO2 capture from flue gas from power plants.However,membrane gas separation is the most promising alternative approach in the future,provided that membrane performance is further improved.展开更多
This paper reports on a new microporous composite silica membrane prepared via acid-catalyzed polymeric route of sol-gel method with tetraethylorthosilicate(TEOS)and a bridged silsesquioxane[1,2-bis(triethoxysilyl)eth...This paper reports on a new microporous composite silica membrane prepared via acid-catalyzed polymeric route of sol-gel method with tetraethylorthosilicate(TEOS)and a bridged silsesquioxane[1,2-bis(triethoxysilyl)ethane, BTESE]as precursors.A stable nano-sized composite silica sol with a mean volume size of^5 nm was synthesized. A 150 nm-thick defect-free composite silica membrane was deposited on disk support consisting of macroporous α-Al2O3 and mesoporousγ-Al2O3 intermediate layer by using dip-coating approach,followed by calcination under pure nitrogen atmosphere.The composite silica membranes exhibit molecular sieve properties for small gases like H2,CO2,O2,N2,CH4 and SF6 with hydrogen permeances in the range of(1-4)×10 -7mol·m -2·s -1·Pa -1(measured at 200°C,3.0×105 Pa).With respect to the membrane calcined at 500°C,it is found that the permselectivities of H 2 (0.289 nm)with respect to N2(0.365 nm),CH4(0.384 nm)and SF6(0.55 nm)are 22.9,42 and>1000,respectively, which are all much higher than the corresponding Knudsen values(H2/N2=3.7,H2/CH4=2.8,and H2/SF6=8.5).展开更多
A rigid aromatic diamine monomer containing di-tert-butylbenzene and dimethyl groups,3,3'-dimethyl-4,4'-diaminophenyl-3",5"-di-tert-butyltoluene,was successfully synthesized by a simple coupling reac...A rigid aromatic diamine monomer containing di-tert-butylbenzene and dimethyl groups,3,3'-dimethyl-4,4'-diaminophenyl-3",5"-di-tert-butyltoluene,was successfully synthesized by a simple coupling reaction using 3,5-di-tert-butylbenzaldehyde and o-toluidine as starting materials.A series of novel polyimides(PI 3a-3c)with large pendant groups were prepared with the obtained diamine monomer and three different commercial aromatic dianhydrides(3,3',4,4'-biphenyltetracarboxylic dianhydride,4,4'-oxydiphthalic anhydride,and 4,4'-(hexafluoroisopropylidene)diphthalic anhydride)by one-step high temperature polycondensation.The prepared polyimides exhibited high solubility and good membrane forming ability:they could be dissolved not only in some high boiling solvents such as DMF,NMP,DMAc,and m-Cresol at room temperature,but also in some low boiling solvents such as CHCl3,CH2Cl2,and THF.Their solubility in most solvents could exceed 10 wt%,and the flexible membranes could be obtained by casting their solutions.The prepared membranes exhibited good gas separation properties.The permeability coefficients of PI 3c for CO2 and O2 were up to 124.6 and 42.8 barrer,respectively,and the selectivity coefficients for CO2/CH4 and O2/N2 were 14.7 and 3.3,respectively.The membranes had light color and good optical transmission.Their optical transmittance at 450 nm wavelength was in the range of 67%-79%,and the cutoff wavelength was in the range of 310-348 nm.They also had good thermal properties with glass transition temperature(Tg)values in the range of 264-302℃.In addition,these membranes possessed good mechanical properties with tensile strength ranging between 77.8-87.4 MPa,initial modulus ranging between 1.69-1.82 GPa,and elongation at break ranging between 4.8%-6.1%.展开更多
A series of organosilica sols are prepared by the polymeric sol–gel method using 1,2-bis(triethoxysilyl)ethane(BTESE)as the precursor.Particle size distributions of the BTESE-derived sols are systematically investiga...A series of organosilica sols are prepared by the polymeric sol–gel method using 1,2-bis(triethoxysilyl)ethane(BTESE)as the precursor.Particle size distributions of the BTESE-derived sols are systematically investigated by carefully adjusting the synthesis parameters(i.e.,water ratios,acid ratios and solvent ratios)in the sol process.In certain conditions,increasing the water ratio or the acid ratio tends to cause larger sol sizes and bimodal particle size distributions.However,higher solvent ratios lead to smaller sol sizes and unimodal particle size distributions.The organosilica membranes prepared from the optimized sols show excellent H_2 permeances(up to 4.2×10^(-7)mol·m^(-2)·s^(-1)·Pa^(-1))and gas permselectitivies(H_2/CO_2 is 9.5,H_2/N_2 is 50 and H_2/CH_4 is 68).This study offers significant insights into the relationship between the sol synthesis parameters,sol sizes and membrane performance.展开更多
Mixed matrix hollow fiber membranes（MMHFMs）filled with metal-organic frameworks（MOFs）have great potential for energy-efficient gas separation processes,but the major hurdle is polymer/MOFs interfacial defects and ...Mixed matrix hollow fiber membranes（MMHFMs）filled with metal-organic frameworks（MOFs）have great potential for energy-efficient gas separation processes,but the major hurdle is polymer/MOFs interfacial defects and membrane plasticization.Herein,lab-synthesized MIL-53 was post-functionalized by aminosilane grafting and subsequently incorporated into Ultem-1000 polymer matrix to fabricate high performance MMHFMs.SEM,DLS,XRD and TGA were performed to characterize silane-modified MIL-53（S-MIL-53）and prepared MMHFMs.Moreover,the effect of MOFs loading was systematically investigated first;then gas separation performance of MMHFMs for pure and mixed gas was evaluated under different pressures.MMHFMs containing post-functionalized S-MIL-53 achieved remarkable gas permeation properties which was better than model predictions.Compared to pure HFMs,CO2permeance of MMHFM loaded with 15%S-MIL-53 increased by 157%accompanying with 40%increase for CO2/N2selectivity,which outperformed the MMHFM filled with naked MIL-53.The pure and mixed gas permeation measurements with elevated feed pressure indicated that incorporation of S-MIL-53 also increased the resistance against CO2plasticization.This work reveals that post-modified MOFs embedded in MMHFMs facilitate the improvement of gas separation performance and suppression of membrane plasticization.展开更多
The design and development of highly permeable,selective and stable polymer membranes are great challenges in the gas separation industry.Herein,we constructed two intrinsic microporous polyimides(6FPCA and 6FMCA)deri...The design and development of highly permeable,selective and stable polymer membranes are great challenges in the gas separation industry.Herein,we constructed two intrinsic microporous polyimides(6FPCA and 6FMCA)derived from two isometric diamines(PCA and MCA),which were synthesized by palladium catalyzed C—N coupling reaction.The PCA and MCA diamines contain a hollow beaded structure of 2,2′-paracyclophane as a building block with a specified window size of 3.09Å.The chemical structures of monomers,polyimides were confirmed by NMR,FTIR,and elementary analysis.6FPCA and 6FMCA exhibit good solubility,excellent thermal stability,and mechanical properties.6FPCA exhibits much larger microporosity(434 versus 120 m2·g−1),FFV(0.22 versus 0.15),d-spacing(6.9 versus 5.9Å),and over 10 times higher permeability with a very little decrease in selectivity than the corresponding polyimide(6FpA)with a plane structure,which remarkably increased their separation performance from far below the 2008 Robeson Upper bounds to reach these limitations for O2/N2 and CO2/CH4.Additionally,the 6FPCA also demonstrates good plasticization resistance,moderate aging properties,and high CO2/CH4 mixed-gas separation performance.These results indicate that paracyclophane subunit can be successfully incorporated into polymers to enhance their ultra-microporosity and separation properties,which open a new avenue for developing high performance gas separation membranes with topological ultra-micropores.展开更多
In recent times, membranes have found wide applications in gas separation processes. As most of the industrial membrane separation units use hollow fiber modules, having a proper model for simulating this type of memb...In recent times, membranes have found wide applications in gas separation processes. As most of the industrial membrane separation units use hollow fiber modules, having a proper model for simulating this type of membrane module is very useful in achieving guidelines for design and characterization of membrane separation units. In this study, a model based on Coker, Freeman, and Fleming＇s study was used for estimating the required membrane area. This model could simulate a multicomponent gas mixture separation by solving the governing differential mass balance equations with numerical methods. Results of the model were validated using some binary and multicomponent experimental data from the literature. Also, the artificial neural network （ANN） technique was applied to predict membrane gas separation behavior and the results of the ANN simulation were compared with the simulation results of the model and the experimental data. Good consistency between these results shows that ANN method can be successfully used for prediction of the separation behavior after suitable training of the network展开更多
Gas separation is a key issue in various industrial fields. Hydrogen has the potential for application in clean fuel technologies. Therefore, the separation and purification of hydrogen is an important research subjec...Gas separation is a key issue in various industrial fields. Hydrogen has the potential for application in clean fuel technologies. Therefore, the separation and purification of hydrogen is an important research subject. CO2 capture and storage have important roles in ＂green chemistry＂. As an effective clean technology, gas separation using inorganic membranes has attracted much attention in the last several decades. Membrane processes have many applications in the field of gas separation. Cement is one type of inorganic material, with the advantages of a lower cost and a longer lifespan. An experimental setup has been created and improved to measure twenty different cement membranes. The purpose of this work was to investigate the influence of gas molecule properties on the material transport and to explore the influence of operating conditions and membrane composition on separation efficiency. The influences of the above parameters are determined, the best conditions and membrane type are found, it is shown that cementitious material has the ability to separate gas mixtures, and the gas transport mechanism is studied.展开更多
A microporous zirconia membrane with hydrogen permeance about 5 × 10-8mol·m-2·s-1·Pa-1, H2/CO2 permselectivity of ca. 14, and excellent hydrothermal stability under steam pressure of 100 k Pa was f...A microporous zirconia membrane with hydrogen permeance about 5 × 10-8mol·m-2·s-1·Pa-1, H2/CO2 permselectivity of ca. 14, and excellent hydrothermal stability under steam pressure of 100 k Pa was fabricated via polymeric sol–gel process. The effect of calcination temperature on single gas permeance of sol–gel derived zirconia membranes was investigated. Zirconia membranes calcined at 350 °C and 400 °C showed similar single gas permeance, with permselectivities of hydrogen towards other gases, such as oxygen, nitrogen, methane, and sulfur hexa fluoride, around Knudsen values. A much lower CO2permeance（3.7 × 10-9mol·m-2·s-1·Pa-1）was observed due to the interaction between CO2 molecules and pore wall of membrane. Higher calcination temperature, 500 °C, led to the formation of mesoporous structure and, hence, the membrane lost its molecular sieving property towards hydrogen and carbon dioxide. The stability of zirconia membrane in the presence of hot steam was also investigated. Exposed to 100 k Pa steam for 400 h, the membrane performance kept unchanged in comparison with freshly prepared one, with hydrogen and carbon dioxide permeances of 4.7 × 10-8and ~ 3 × 10-9mol·m-2·s-1·Pa-1, respectively. Both H2 and CO2permeances of the zirconia membrane decreased with exposure time to 100 k Pa steam. With a total exposure time of 1250 h, the membrane presented hydrogen permeance of 2.4 × 10-8mol·m-2·s-1·Pa-1and H2/CO2 permselectivity of 28, indicating that the membrane retains its microporous structure.展开更多
The gas separation properties of free- standing film of polyaniline (PANI) for gas pairs of He/N2, H_2/N_2. CO_2/N_2 and CO_2/CH_4 at room temperature were measured as a function of the protonation state. Variation of...The gas separation properties of free- standing film of polyaniline (PANI) for gas pairs of He/N2, H_2/N_2. CO_2/N_2 and CO_2/CH_4 at room temperature were measured as a function of the protonation state. Variation of the gas permeabilities coefficient of PANI with an insulator to metal transition upon the protonation processes was observed, which might be due to a change in both gas solubility coefficient and diffusion coefficient with the protonation state.展开更多
A review on the polymeric hollow fibers membranes for gas separation has been conducted. In order to deyelop high performance membranes for gas separation, there are a few technology challenges awaiting the chemical e...A review on the polymeric hollow fibers membranes for gas separation has been conducted. In order to deyelop high performance membranes for gas separation, there are a few technology challenges awaiting the chemical engineers to overcome. There are four major challenges, namely: 1) material selection and synthesis; 2) fabrication of hollow fiber membranes with an ultra- thin dense selective layer; 3) materials against plasticization; and 4) aging. In each area, we summarize the scientific accomplishments and technical difficulties.展开更多
A zeolitic imidazolate hybrid membrane(Co-IM-mIM) containing two imidazolate ligands deposited on a macroporous α-alumina support was prepared by pre-depositing and secondary growth technique. XRD, TGA and SEM charac...A zeolitic imidazolate hybrid membrane(Co-IM-mIM) containing two imidazolate ligands deposited on a macroporous α-alumina support was prepared by pre-depositing and secondary growth technique. XRD, TGA and SEM characterizations demonstrate that a stable and thin, but dense and pure-phase Co-IM-mIM membrane can be obtained on the macroporous-alumina discs in Teflon-lined autoclave at 120 °C after pre-depositing by dip-coating at room temperature. No visible cracks, pinholes or other defects were observed on the membrane layer. The gas separation studies of Co-IM-mIM membrane were carried out at 25 °C and 1×10~5 Pa, showing ideal selectivity of 6.95, 5.25, 3.40 for H_2/CO_2, H_2/N_2 and H_2/CH_4, respectively, and a permeance of 17.37× 10^(-6) mol/(m^2·s·Pa) for H_2. The influence of temperature and trans-membrane pressure on hydrogen separation and permeation was also carried out. The gas permeation and selectivity demonstrate that this membrane may have potential applications for efficient H_2 separation.展开更多
Metal-Organic Frameworks(MOFs)have emerged as promising materials for gas adsorption and separation due to their exceptional surface area,tunable porosity,and versatility in functionalization.This paper explores the m...Metal-Organic Frameworks(MOFs)have emerged as promising materials for gas adsorption and separation due to their exceptional surface area,tunable porosity,and versatility in functionalization.This paper explores the mechanisms of gas adsorption in MOFs,including physical adsorption,chemisorption,and synergistic effects,which contribute to their efficiency in capturing and separating gases.The applications of MOFs in key areas such as carbon dioxide capture,hydrogen storage,natural gas separation,and air purification are discussed,highlighting their potential to address pressing environmental and energy challenges.Additionally,the use of MOFs in selective gas separation,membranes,and adsorption-based technologies like Pressure Swing Adsorption(PSA)and Vacuum Swing Adsorption(VSA)is explored,emphasizing their advantages over traditional materials.Despite challenges related to scalability,stability,and cost,MOFs hold great promise for advancing gas separation technologies in the near future,offering more efficient,sustainable,and environmentally friendly solutions.展开更多
基金funding from the European Union’s Horizon 2020 research and innovation program under grant agreement No 872102the China Scholarship Council(CSC,file no.202006240076)-University of Manchester joint studentship for supporting the PhD researchthe special innovation project fund from the Institute of Wenzhou,Zhejiang University(No.XMGL-KJZX-202204)。
文摘Polymers of intrinsic microporosity(PIMs)have received considerable attention for making high-performance membranes for carbon dioxide separation over the last two decades,owing to their highly permeable porous structures.However,challenges regarding its relatively low selectivity,physical aging,and plasticisation impede relevant industrial adoptions for gas separation.To address these issues,several strategies including chain modification,post-modification,blending with other polymers,and the addition of fillers,have been developed and explored.PIM-1 is the most investigated PIMs,and hence here we review the stateof-the-arts of the modification strategies of PIM-1 critically and discuss the progress achieved for addressing the aforementioned challenges via meta-analysis.Additionally,the development of PIM-1-based thin film composite membranes is commented as well,shedding light on their potential in industrial gas separation.We hope that the review can be a timely snapshot of the relevant state-of-the-arts of PIMs guiding future design and optimisation of PIMs-based membranes for enhanced performance towards a higher technology readiness level for practical applications.
基金supported by National Natural Science Foundation of China (22278424, 22127812)Distinguished Youth Foundation of the Tianshan Program of Xinjiang Uygur Autonomous Region (2022TSYCJC0013)Science Foundation of China University of Petroleum-Beijing (2462023YJRC002)
文摘The long hydrate induction time and limited gas-liquid contact area leads to slow hydrate formation rate and low water-hydrate conversion rate.Porous media are often used to promote hydrate formation because of their large specific surface area.Consequently,we used 3A molecular sieve as a water-carrying solid in this work,and investigated the dynamic renewal of the gas-liquid interface and its effect on hydrate formation.The formation kinetics of ethane hydrate was first measured in an aqueous molecular sieve system.Then the separation of(H_(2)+CH_(4)+C_(2)H_(6)+C_(3)H_(8))gas mixture was conducted via hydrate formation.The results show that the formation rate and gas storage capacity of ethane hydrate can be greatly improved by using aqueous molecular sieve.Compared with a pure water system under the same temperature and pressure,aqueous molecular sieve has obvious advantages in separation effect and energy consumption for separating gas mixtures.
基金funded by National Natural Science Foundation of China(22278023)Beijing Municipal Science and Technology Planning Project(Z221100002722002)+1 种基金Beijing Natural Science Foundation(2222015)the long-term from the Ministry of Finance and the Ministry of Education of China.
文摘Zeolitic imidazolate framework-8(ZIF-8)is a typical filler used to fabricate mixed matrix membranes(MMMs)on account of its attractive advantage of high selective permeability for gas separation.However,the performance is usually affected by filler aggregation due to strong interactions among fillers and weak interactions between the polymer and fillers,However,the performance is usually affected by filler aggregation due to strong interactions among fillers and weak interactions between the polymer and fillers,which will lead to a decrease of selectivity and the performance of gas separation will be strongly influenced.Herein,we modified ZIF-8 with 3-amino-1,2,4-triazole to obtain ZIF-8-NH_(2),Kapton polyamide acid was selected as the polymer matrix.Results showed that the ZIF-8-NH_(2)/Kapton MMMs has a good compatibility interface between ZIF-8 and Kapton because of the covalent bridging,even the filler loading up to 45%(mass).The 45%(mass)of ZIF-8-NH_(2)/Kapton membrane showed 297 barrer(1 barrer=10^(-10)10 cm^(3)·cm·cm^(-2)·s^(-1)·cmHg^(-1),1 cmHg=1333.22 Pa,standard temperature and pressure)of the permeability of H_(2)and 43.9 and 62.2 of selectivities for H_(2)/N_(2)and for H_(2)/CH_(4),respectively,which are beyond the upper limit of Robeson 2008.
基金support through the National Research Foundation of Korea(NRF)grant funded by the Ko-rean government(MSIT)(Nos.NRF-2022R1C1C1003313 and NRF-2020M3H4A3106356)supported by the Technology Innovation Program(No.20010846)+2 种基金funded by the Ministry of Trade,Industry&Energy(MOTIE,Korea)supported by the“Regional Innovation Strategy(RIS)”through the National Research Foundation of Korea(NRF)funded by the Ministry of Education(MOE)(No.2023RIS-007)support through the Korea Environ-ment Industry&Technology Institute,funded by the Korea Ministry。
文摘Metal-organic frameworks(MOFs)are a subclass of porous materials that have gained considerable at-tention recently due to their unique properties and potential applications.However,MOFs may exhibit defects affecting their gas separation performance,limiting their practical applications.This review arti-cle focuses on defects in MOFs and their impact on gas separation.Additionally,the reports explore the potential of De novo and post-synthetic modification(PSM)to improve the gas separation properties by tuning their defects.The PSM of MOFs is discussed in detail,including the different types of modifications and their effects on the MOF properties.Finally,the article discusses the potential of PSM for practical gas separation applications,highlighting recent examples of MOF-based membranes and adsorbents with improved gas separation performance resulting from PSM.It is strategically reasonable to have defects inside the MOFs,but why is it so fascinating in gas separation applications?In this present review,we have tried to uncover the mystery of defects.Overall,this review highlights the importance of defects in MOFs and the potential of PSM strategies to enhance their gas separation properties.
文摘Gas separation is a critical application of gas hydrates,and accurately predicting separation performance is crucial.In this study,we used thermodynamic calculations to predict the equilibrium phase of gas hydrates for various mole fractions of CO_(2)+CH_(4)gas mixtures.We also determined the mole fraction of each gas component trapped within the hydrate clathrate.To predict the equilibrium points,we used the SoaveeRedlicheKwong(SRK)equation of state for the gas phase,the nonrandom two-liquid(NRTL)model for the liquid phase,and the CheneGuo model for the hydrate phase.We modified the hydrate fugacity formula and introduced a new function to improve the accuracy of the CheneGuo model.By incorporating experimental equilibrium results from our study and another study,we developed a correlation based on gas mixture composition and temperature,resulting in highly accurate predictions.The use of this new correlation for hydrate fugacity calculation significantly improved precision,as evidenced by an average absolute deviation percent of calculated pressures(AADP)of 1.34%for pure CO_(2)and 1.25%for CH_(4).When considering the 27 data points of different CO_(2)+CH_(4)mixtures,the AADP%was 1.98%.To implement the model to predict equilibrium phases,we used the CheneGuo framework to determine the mole fraction of each gas component in the hydrate mixture.Interestingly,we discovered a linear correlation between the CO_(2)mole fraction in the hydrate and equilibrium pressure,with a slope of approximately 0.001 and a y-intercept of less than one,for all gas compositions.Therefore,we can conclude that low thermodynamic conditions(temperature and pressure)result in a high CO_(2)mole fraction in the hydrate phase and great separation efficiency.
基金supported from the Natural Science Foundation of China (Grant Nos. 21771012, 21601008 and 21576006)the National Natural Science Fund for Innovative Research Groups (Grant No. 51621003)the China Postdoctoral Science Foundation (Grant No. 2016M600879)
文摘The separation of gas molecules with similar physicochemical properties is of high importance but practically entails a substantial energy penalty in chemical industry. Meanwhile, clean energy gases such as H_2 and CH_4 are considered as promising candidates for the replacement of traditional fossil fuels. However, the technologies for the storage of these gases are still immature. In addition, the release of anthropogenic toxic gases into the atmosphere is a worldwide threat of growing concern. Both in academia and industry, considerable research efforts have been devoted to developing advanced porous materials for the effective and energy-efficient separation, storage, or capture of the related gases. In contrast to conventional inorganic porous materials such as zeolites and activated carbons, metal–organic frameworks(MOFs) are considered as a type of promising materials for gas separation and storage. In this contribution, we review the recent research advance of MOFs in some relevant applications, including CO_2 capture, O_2 purification, separation of light hydrocarbons, separation of noble gases, storage of gases(CH_4,H_2, and C_2 H_2) for energy, and removal of some gaseous air pollutants(NH_3, NO_2, and SO_2). Finally, an outlook regarding the challenges of the future research of MOFs in these directions is given.
基金Supported by the Natural Science Foundation of Liaoning Province, China （20052193） and Ph.D. Programs Foundation of Ministry of Education o f China （20070141045）.
文摘To improve the separation performance of a supersonic gas separation device for the treatment of gas mixture with a single heavy component, a novel structure with shorter settlement distance was constructed and a method of droplet enlargement was applied. A series of experiments were carried out in the improved separation device under various conditions, using air-ethanol vapor as the medium and micro water droplets as nucleation cen- ters. The effects of the inlet pressure, temperature and relative humidity, the swirling intensity, and mass flow rate of water on the separation performance were investigated. The separation was improved by increasing the inlet pressure and relative humidity. With the decrease of swirling intensity and mass flow rate of water, the separation efficiency increased first and then decreased. The inlet temperature had a slight effect on the separation. The results showed that the separation performance was effectively improved using the proposed structure and method, and the best separation in this study was obtained with the ethanol removal rate about 55% and dew point depression 27 K. The addition of water had little pollution to the air-ethanol vapor system since the water carry-over rate was within the range of -2 %-0 in most cases.
基金Supported by the National High Technology Research and Development Program of China (2007AA03Z229)the Fundamental Research Funds for the Central Universities (2009ZM0185)
文摘Three gas separation technologies,chemical absorption,membrane separation and pressure swing adsorption,are usually applied for CO2 capture from flue gas in coal-fired power plants.In this work,the costs of the three technologies are analyzed and compared.The cost for chemical absorption is mainly from $30 to $60 per ton(based on CO2 avoided),while the minimum value is $10 per ton(based on CO2 avoided).As for membrane separation and pressure swing adsorption,the costs are $50 to $78 and $40 to $63 per ton(based on CO2 avoided),respectively.Measures are proposed to reduce the cost of the three technologies.For CO2 capture and storage process,the CO2 recovery and purity should be greater than 90%.Based on the cost,recovery,and purity,it seems that chemical absorption is currently the most cost-effective technology for CO2 capture from flue gas from power plants.However,membrane gas separation is the most promising alternative approach in the future,provided that membrane performance is further improved.
基金Supported by the National Natural Science Foundation of China(20906047)the State Key Laboratory of Chemical Engineering(SKL-ChE-09A01)the State Key Laboratory of Materials-Oriented Chemical Engineering(ZK201002)
文摘This paper reports on a new microporous composite silica membrane prepared via acid-catalyzed polymeric route of sol-gel method with tetraethylorthosilicate(TEOS)and a bridged silsesquioxane[1,2-bis(triethoxysilyl)ethane, BTESE]as precursors.A stable nano-sized composite silica sol with a mean volume size of^5 nm was synthesized. A 150 nm-thick defect-free composite silica membrane was deposited on disk support consisting of macroporous α-Al2O3 and mesoporousγ-Al2O3 intermediate layer by using dip-coating approach,followed by calcination under pure nitrogen atmosphere.The composite silica membranes exhibit molecular sieve properties for small gases like H2,CO2,O2,N2,CH4 and SF6 with hydrogen permeances in the range of(1-4)×10 -7mol·m -2·s -1·Pa -1(measured at 200°C,3.0×105 Pa).With respect to the membrane calcined at 500°C,it is found that the permselectivities of H 2 (0.289 nm)with respect to N2(0.365 nm),CH4(0.384 nm)and SF6(0.55 nm)are 22.9,42 and>1000,respectively, which are all much higher than the corresponding Knudsen values(H2/N2=3.7,H2/CH4=2.8,and H2/SF6=8.5).
基金This work was finanially supported by the Key Research Project of Jiangsu Province(No.BE2017645)Scientifc Research and Innovation Project for Graduate Students in Jiangsu Province(No.KYCX19-1757)。and a Project Funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions of China。
文摘A rigid aromatic diamine monomer containing di-tert-butylbenzene and dimethyl groups,3,3'-dimethyl-4,4'-diaminophenyl-3",5"-di-tert-butyltoluene,was successfully synthesized by a simple coupling reaction using 3,5-di-tert-butylbenzaldehyde and o-toluidine as starting materials.A series of novel polyimides(PI 3a-3c)with large pendant groups were prepared with the obtained diamine monomer and three different commercial aromatic dianhydrides(3,3',4,4'-biphenyltetracarboxylic dianhydride,4,4'-oxydiphthalic anhydride,and 4,4'-(hexafluoroisopropylidene)diphthalic anhydride)by one-step high temperature polycondensation.The prepared polyimides exhibited high solubility and good membrane forming ability:they could be dissolved not only in some high boiling solvents such as DMF,NMP,DMAc,and m-Cresol at room temperature,but also in some low boiling solvents such as CHCl3,CH2Cl2,and THF.Their solubility in most solvents could exceed 10 wt%,and the flexible membranes could be obtained by casting their solutions.The prepared membranes exhibited good gas separation properties.The permeability coefficients of PI 3c for CO2 and O2 were up to 124.6 and 42.8 barrer,respectively,and the selectivity coefficients for CO2/CH4 and O2/N2 were 14.7 and 3.3,respectively.The membranes had light color and good optical transmission.Their optical transmittance at 450 nm wavelength was in the range of 67%-79%,and the cutoff wavelength was in the range of 310-348 nm.They also had good thermal properties with glass transition temperature(Tg)values in the range of 264-302℃.In addition,these membranes possessed good mechanical properties with tensile strength ranging between 77.8-87.4 MPa,initial modulus ranging between 1.69-1.82 GPa,and elongation at break ranging between 4.8%-6.1%.
基金Supported by the National Natural Science Foundation of China(21276123,21490581)the National High Technology Research and Development Program of China(2012AA03A606)+1 种基金the "Summit of the Six Top Talents" Program of Jiangsu Province(2011-XCL-021)the Open Research Fund Program of Collaborative Innovation Center of Membrane Separation and Water Treatment(2016YB01)
文摘A series of organosilica sols are prepared by the polymeric sol–gel method using 1,2-bis(triethoxysilyl)ethane(BTESE)as the precursor.Particle size distributions of the BTESE-derived sols are systematically investigated by carefully adjusting the synthesis parameters(i.e.,water ratios,acid ratios and solvent ratios)in the sol process.In certain conditions,increasing the water ratio or the acid ratio tends to cause larger sol sizes and bimodal particle size distributions.However,higher solvent ratios lead to smaller sol sizes and unimodal particle size distributions.The organosilica membranes prepared from the optimized sols show excellent H_2 permeances(up to 4.2×10^(-7)mol·m^(-2)·s^(-1)·Pa^(-1))and gas permselectitivies(H_2/CO_2 is 9.5,H_2/N_2 is 50 and H_2/CH_4 is 68).This study offers significant insights into the relationship between the sol synthesis parameters,sol sizes and membrane performance.
基金the financial support from the National Natural Science Foundation of China(No.21436009)
文摘Mixed matrix hollow fiber membranes（MMHFMs）filled with metal-organic frameworks（MOFs）have great potential for energy-efficient gas separation processes,but the major hurdle is polymer/MOFs interfacial defects and membrane plasticization.Herein,lab-synthesized MIL-53 was post-functionalized by aminosilane grafting and subsequently incorporated into Ultem-1000 polymer matrix to fabricate high performance MMHFMs.SEM,DLS,XRD and TGA were performed to characterize silane-modified MIL-53（S-MIL-53）and prepared MMHFMs.Moreover,the effect of MOFs loading was systematically investigated first;then gas separation performance of MMHFMs for pure and mixed gas was evaluated under different pressures.MMHFMs containing post-functionalized S-MIL-53 achieved remarkable gas permeation properties which was better than model predictions.Compared to pure HFMs,CO2permeance of MMHFM loaded with 15%S-MIL-53 increased by 157%accompanying with 40%increase for CO2/N2selectivity,which outperformed the MMHFM filled with naked MIL-53.The pure and mixed gas permeation measurements with elevated feed pressure indicated that incorporation of S-MIL-53 also increased the resistance against CO2plasticization.This work reveals that post-modified MOFs embedded in MMHFMs facilitate the improvement of gas separation performance and suppression of membrane plasticization.
基金financially supported by the National Natural Science Foundation of China (Nos. 22078245 and 21861016)YLU-DNL Fund (No. 2022009)
文摘The design and development of highly permeable,selective and stable polymer membranes are great challenges in the gas separation industry.Herein,we constructed two intrinsic microporous polyimides(6FPCA and 6FMCA)derived from two isometric diamines(PCA and MCA),which were synthesized by palladium catalyzed C—N coupling reaction.The PCA and MCA diamines contain a hollow beaded structure of 2,2′-paracyclophane as a building block with a specified window size of 3.09Å.The chemical structures of monomers,polyimides were confirmed by NMR,FTIR,and elementary analysis.6FPCA and 6FMCA exhibit good solubility,excellent thermal stability,and mechanical properties.6FPCA exhibits much larger microporosity(434 versus 120 m2·g−1),FFV(0.22 versus 0.15),d-spacing(6.9 versus 5.9Å),and over 10 times higher permeability with a very little decrease in selectivity than the corresponding polyimide(6FpA)with a plane structure,which remarkably increased their separation performance from far below the 2008 Robeson Upper bounds to reach these limitations for O2/N2 and CO2/CH4.Additionally,the 6FPCA also demonstrates good plasticization resistance,moderate aging properties,and high CO2/CH4 mixed-gas separation performance.These results indicate that paracyclophane subunit can be successfully incorporated into polymers to enhance their ultra-microporosity and separation properties,which open a new avenue for developing high performance gas separation membranes with topological ultra-micropores.
文摘In recent times, membranes have found wide applications in gas separation processes. As most of the industrial membrane separation units use hollow fiber modules, having a proper model for simulating this type of membrane module is very useful in achieving guidelines for design and characterization of membrane separation units. In this study, a model based on Coker, Freeman, and Fleming＇s study was used for estimating the required membrane area. This model could simulate a multicomponent gas mixture separation by solving the governing differential mass balance equations with numerical methods. Results of the model were validated using some binary and multicomponent experimental data from the literature. Also, the artificial neural network （ANN） technique was applied to predict membrane gas separation behavior and the results of the ANN simulation were compared with the simulation results of the model and the experimental data. Good consistency between these results shows that ANN method can be successfully used for prediction of the separation behavior after suitable training of the network
基金supported by Federal Ministry of Food,Agriculture and Consumer Protection,Agency for Renewable Resources in Germany(No.22010502)
文摘Gas separation is a key issue in various industrial fields. Hydrogen has the potential for application in clean fuel technologies. Therefore, the separation and purification of hydrogen is an important research subject. CO2 capture and storage have important roles in ＂green chemistry＂. As an effective clean technology, gas separation using inorganic membranes has attracted much attention in the last several decades. Membrane processes have many applications in the field of gas separation. Cement is one type of inorganic material, with the advantages of a lower cost and a longer lifespan. An experimental setup has been created and improved to measure twenty different cement membranes. The purpose of this work was to investigate the influence of gas molecule properties on the material transport and to explore the influence of operating conditions and membrane composition on separation efficiency. The influences of the above parameters are determined, the best conditions and membrane type are found, it is shown that cementitious material has the ability to separate gas mixtures, and the gas transport mechanism is studied.
基金Supported by the National Natural Science Foundation of China(21276123,21490581)the National High Technology Research and Development Program of China(2012AA03A606)+3 种基金State Key Laboratory of Materials-Oriented Chemical Engineering(ZK201002)the Natural Science Research Plan of Jiangsu Universities(11KJB530006)the "Summit of the Six Top Talents" Program of Jiangsu Provincea Project Funded by the Priority Academic Program development of Jiangsu Higher Education Institutions(PAPD)
文摘A microporous zirconia membrane with hydrogen permeance about 5 × 10-8mol·m-2·s-1·Pa-1, H2/CO2 permselectivity of ca. 14, and excellent hydrothermal stability under steam pressure of 100 k Pa was fabricated via polymeric sol–gel process. The effect of calcination temperature on single gas permeance of sol–gel derived zirconia membranes was investigated. Zirconia membranes calcined at 350 °C and 400 °C showed similar single gas permeance, with permselectivities of hydrogen towards other gases, such as oxygen, nitrogen, methane, and sulfur hexa fluoride, around Knudsen values. A much lower CO2permeance（3.7 × 10-9mol·m-2·s-1·Pa-1）was observed due to the interaction between CO2 molecules and pore wall of membrane. Higher calcination temperature, 500 °C, led to the formation of mesoporous structure and, hence, the membrane lost its molecular sieving property towards hydrogen and carbon dioxide. The stability of zirconia membrane in the presence of hot steam was also investigated. Exposed to 100 k Pa steam for 400 h, the membrane performance kept unchanged in comparison with freshly prepared one, with hydrogen and carbon dioxide permeances of 4.7 × 10-8and ~ 3 × 10-9mol·m-2·s-1·Pa-1, respectively. Both H2 and CO2permeances of the zirconia membrane decreased with exposure time to 100 k Pa steam. With a total exposure time of 1250 h, the membrane presented hydrogen permeance of 2.4 × 10-8mol·m-2·s-1·Pa-1and H2/CO2 permselectivity of 28, indicating that the membrane retains its microporous structure.
文摘The gas separation properties of free- standing film of polyaniline (PANI) for gas pairs of He/N2, H_2/N_2. CO_2/N_2 and CO_2/CH_4 at room temperature were measured as a function of the protonation state. Variation of the gas permeabilities coefficient of PANI with an insulator to metal transition upon the protonation processes was observed, which might be due to a change in both gas solubility coefficient and diffusion coefficient with the protonation state.
文摘A review on the polymeric hollow fibers membranes for gas separation has been conducted. In order to deyelop high performance membranes for gas separation, there are a few technology challenges awaiting the chemical engineers to overcome. There are four major challenges, namely: 1) material selection and synthesis; 2) fabrication of hollow fiber membranes with an ultra- thin dense selective layer; 3) materials against plasticization; and 4) aging. In each area, we summarize the scientific accomplishments and technical difficulties.
基金Project(21376274)supported by the National Natural Science Foundation ChinaProject(2015BAL04B02)supported by the National Key Technology R&D Program of China
文摘A zeolitic imidazolate hybrid membrane(Co-IM-mIM) containing two imidazolate ligands deposited on a macroporous α-alumina support was prepared by pre-depositing and secondary growth technique. XRD, TGA and SEM characterizations demonstrate that a stable and thin, but dense and pure-phase Co-IM-mIM membrane can be obtained on the macroporous-alumina discs in Teflon-lined autoclave at 120 °C after pre-depositing by dip-coating at room temperature. No visible cracks, pinholes or other defects were observed on the membrane layer. The gas separation studies of Co-IM-mIM membrane were carried out at 25 °C and 1×10~5 Pa, showing ideal selectivity of 6.95, 5.25, 3.40 for H_2/CO_2, H_2/N_2 and H_2/CH_4, respectively, and a permeance of 17.37× 10^(-6) mol/(m^2·s·Pa) for H_2. The influence of temperature and trans-membrane pressure on hydrogen separation and permeation was also carried out. The gas permeation and selectivity demonstrate that this membrane may have potential applications for efficient H_2 separation.
文摘Metal-Organic Frameworks(MOFs)have emerged as promising materials for gas adsorption and separation due to their exceptional surface area,tunable porosity,and versatility in functionalization.This paper explores the mechanisms of gas adsorption in MOFs,including physical adsorption,chemisorption,and synergistic effects,which contribute to their efficiency in capturing and separating gases.The applications of MOFs in key areas such as carbon dioxide capture,hydrogen storage,natural gas separation,and air purification are discussed,highlighting their potential to address pressing environmental and energy challenges.Additionally,the use of MOFs in selective gas separation,membranes,and adsorption-based technologies like Pressure Swing Adsorption(PSA)and Vacuum Swing Adsorption(VSA)is explored,emphasizing their advantages over traditional materials.Despite challenges related to scalability,stability,and cost,MOFs hold great promise for advancing gas separation technologies in the near future,offering more efficient,sustainable,and environmentally friendly solutions.
