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1.
时飞  李奕帆 《化工进展》2020,39(6):2453-2462
膜分离技术因其低成本、低能耗及高效率的优势被认为是最具有前景的碳捕集技术之一。混合基质膜结合了有机材料与无机材料两方面的优势,是同时提升渗透性和选择性的有效手段。本文从气体在混合基质膜中的传递机制出发,以常见的无孔型与多孔型无机填料为基础,总结了近年来混合基质膜在二氧化碳捕集领域的研究进展,介绍了不同类型的填料在高分子基质中所起到的微结构调节作用,并着重阐述了在混合基质膜制备过程中无机填料与高分子基质之间所存在的相容性问题及其解决方法。最后,提出混合基质膜应在继续致力于填料结构设计、填料分散、构效关系等方面的同时,加强二维填料、微囊填料和促进传递机制等方面的研究。  相似文献   

2.
Porous polyvinylidene fluoride-co-hexafluropropylene (PVDF-HFP) hollow fiber membranes were fabricated through a wet spinning process. In order to improve the membrane structure, composition of the polymer solution was adjusted by studying ternary phase diagrams of polymer/solvent/non-solvent. The prepared membranes were used for sweeping gas membrane distillation (SGMD) of 20 wt% ethylene glycol (EG) aqueous solution. The membranes were characterized by different tests such as N2 permeation, overall porosity, critical water entry pressure (CEPw), water contact angle and collapsing pressure. From FESEM examination, addition of 3 wt% glycerol in the PVDF-HFP solution, produced membranes with smaller finger-likes cavities, higher surface porosity and smaller pore sizes. Increasing the polymer concentration up to 21 wt% resulted in a dense spongy structure which could significantly reduce the N2 permeance. The membrane prepared by 3 wt% glycerol and 17 wt% polymer demonstrated an improved structure with mean pore size of 18 nm and a high surface porosity of 872 m-1. CEPw of 350 kPa and overall porosity of 84% were also obtained for the improved membrane. Collapsing pressure of the membranes relatively improved by increasing the polymer concentration. From the SGMD test, the developed membrane represented a maximum permeate flux of 28 kg·m-2·h-1 which is almost 19% higher than the flux of plain membrane. During 120 h of a long-term SGMD operation, a gradual flux reduction of 30% was noticed. In addition, EG rejection reduced from 100% to around 99.5% during 120 h of the operation.  相似文献   

3.
In this study, poly(vinilydene fluoride-co-hexafluoropropylene)(PVDF-HFP) was used for preparation of hydrophobic membranes using non-solvent induced phase inversion(NIPS) technique. PVDF-HFP copolymer with concentrations of 10 wt% and 12 wt% was prepared to investigate the effect of polymer concentration on pore structure,morphology, hydrophobicity and performance of prepared membranes. Besides, the use of two coagulation baths with the effects of parameters such as coagulant time, polymer type and concentration, and the amount of nonsolvent were studied. The performance of prepared membranes was evaluated based on the permeability and selectivity of oxygen and nitrogen from a gas mixture of nitrogen/oxygen under operating conditions of feed flow rate(1–5 L·min~(-1)), inlet pressure to membrane module(0.1–0.5 MPa) and temperatures between 25 and 45 °C. The results showed that the use of two coagulation baths with different compositions of distillated water and isopropanol,coagulant time, polymer type and concentration, and the amount of non-solvent additive have the most effect on pore structure, morphology, thickness, roughness and crystallinity of fabricated membranes. Porosity ranges for the three fabricated membranes were determined, where the maximum porosity was 73.889% and the minimum value was 56.837%. Also, the maximum and minimum average thicknesses of membrane were 320.85 μm and115 μm. Besides, the values of 4.7504 × 10~(-7) mol· m~(-2)· s~(-1)· Pa~(-1), 0.525 and 902.126 nm were achieved for maximum oxygen permeance, O_2/N_2 selectivity and roughness, respectively.  相似文献   

4.
Ionic liquid(IL), 1-butyl-3-methylimidazolium hexafluorophosphate([BMIM]PF6) as a new and environmentally friendly diluent was introduced to prepare poly(vinylidene fluoride)(PVDF) membranes via thermally induced phase separation(TIPS). Phase diagram of PVDF/[BMIM]PF6 was measured. The effects of polymer concentration and quenching temperature on the morphologies, properties, and performances of the PVDF membranes were investigated. When the polymer concentration was 15 wt%, the pure water flux of the fabricated membrane was up to nearly 2000 L·m~(-2)·h~(-1), along with adequate mechanical strength. With the increasing of PVDF concentration and quenching temperature, mean pore size and water permeability of the membrane decreased. SEM results showed that PVDF membranes manufactured by ionic liquid(BMIm PF6) presented spherulite structure. And the PVDF membranes were represented as β phase by XRD and FTIR characterization. It provides a new way to prepare PVDF membranes with piezoelectric properties.  相似文献   

5.
Pervaporation has great potential in the separation of many significant mixtures. However, excessive penetration of separation layer into the substrate pores enhances the transport resistance of solvent molecules, which impedes the development of pervaporation membrane. In this study, a facile floating-on-water (FOW) method was used to prepare poly(dimethylsiloxane) (PDMS)/polytetrafluoroethylene (PTFE) composite membranes. The formation of separation layer and preparation of composite membrane were step-by-step completed through this liquid–liquid interface induced method. The PDMS layer thickness could be precisely regulated from 0.5 to 8 μm. Moreover, the pore penetration could be controlled by optimizing pre-crosslinking density, crosslinking time on water and polymer solution volume. The obtained PDMS/PTFE composite membrane exhibited a high flux of 2016 g·m−2·h−1 with the separation factor of 12 when separating ethanol from a 5 wt% ethanol/water mixture. The performance of the membrane could be stable for over 200 h, exhibiting great potential in ethanol perm-selective pervaporation.  相似文献   

6.
Recent advances on mixed matrix membrane for CO2 separation are reviewed in this paper. To improve CO2 separation performance of polymer membranes, mixedmatrixmembranes (MMMs) are developed. The concept of MMM is illustrated distinctly. Suitable polymer and inorganic or organic fillers for MMMs are summarized.Possible interface morphologies between polymer and filler, and the effect of interface morphologies on gas transport properties of MMMs are summarized. The methods to improve compatibility between polymer and filler are introduced. There are eightmethods including silane coupling, Grignard treatment, incorporation of additive,grafting, in situ polymerization, polydopamine coating, particle fusion approach and polymer functionalization. To achieve higher productivity for industrial application,mixed matrix composite membranes are developed. The recent development on hollow fiber and flat mixedmatrix composite membrane is reviewed in detail. Last, the future trend of MMM is forecasted.  相似文献   

7.
Thin film composite (TFC) membranes with nanofillers additives for CO2 separation show promising applications in energy and environment-related fields. However, the poor compatibility between nanofillers and polymers in TFC membranes is the main problem. In this work, covalent organic frameworks (COFs, TpPa-1) with rich —NH— groups were incorporated into polyamide (PA) segment via in situ interfacial polymerization to prepare defect-free TFC membranes for CO2/N2 separation. The formed covalent bonds between TpPa-1 and PA strengthen the interaction between nanofillers and polymers, thereby enhancing compatibility. Besides, the incorporated COFs disturb the rigid structure of the PA layer, and provide fast CO2 transfer channels. The incorporated COFs also increase the content of effective carriers, which enhances the CO2 facilitated transport. Consequently, in CO2/N2 mixed gas separation test, the optimal TFC (TpPa0.025-PIP-TMC/mPSf) membrane exhibits high CO2 permeance of 854 GPU and high CO2/N2 selectivity of 148 at 0.15 MPa, CO2 permeance of 456 GPU (gas permeation unit) and CO2/N2 selectivity of 92 at 0.5 MPa. In addition, the TpPa0.025-PIP-TMC/mPSf membrane also achieves high permselectivty in CO2/CH4 mixed gas separation test. Finally, the optimal TFC membrane showes good stability in the simulated flue gas test, revealing the application potential for CO2 capture from flue gas.  相似文献   

8.
Membrane pollution caused by separating oily wastewater is a big challenge for membrane separation technology. Recently, plant-/mussel-inspired interface chemistry has received more and more attention. Herein, a high antifouling poly (vinylidene fluoride) (PVDF) membrane, coated with tea polyphenols (TP, extracted from green tea) and 3-amino-propyl-triethoxysilane (APTES), was developed to purify oil-in-water emulsions. ATR-FTIR, XPS and SEM were used to demonstrate the evolution of surface biomimetic hybrid coatings. The performances of the developed membranes were investigated by pure water permeability and oil rejection for various surfactant-stabilized oil-in-water emulsions. The experimental results revealed that the membrane deposited with a mass ratio of 0.1/0.2 exhibited ultrahigh pure water permeability (14570 L·m-2·h-1·bar-1, 1 bar=0.1 MPa) and isooctane-in-water emulsion permeability (5391 L·m-2·h-1·bar-1) with high separation efficiency (>98.9%). Even treated in harsh environment (acidic, alkaline and saline) for seven days, the membrane still maintained considerable underwater oleophobic property (148°–153°). The fabricated plant-inspired biomimetic hybrid membranes with excellent performances light a broad application prospect in the field of oily wastewater treatment.  相似文献   

9.
Mixed matrix membranes (MMMs) based on metal–organic framework (MOF) have great promising application in separation of gas mixtures. However, achieving a good interfacial compatibility between polymer and MOF is not straightforward. In this work, focusing on one of the most challenging olefin/paraffin separations: propylene/propane (C3H6/C3H8), we demonstrate that modification of the MOF filler via dopamine polymerization using a double solvent approach strongly improves interfacial compatibility. The resulting membranes show an outstanding separation performance and long-term stability with propylene permeability nearly 90 Barrer and propylene/propane selectivity close to 75. We anticipate that similar MOF modification strategies may help solve the problem of interface defects in the manufacture of MMMs and be extended to other porous fillers.  相似文献   

10.
混合基质膜(MMMs)在气体分离领域具有良好的应用前景,金属有机框架(MOFs)由于具有高孔隙率和有机连接基团,常被用作填料制备MMMs。但由于MOFs与聚合物的界面相容性问题,MMMs的气体分离性能提升受到限制。本文合成了功能化的Zr-MOF(UiO-66-AC),并利用其与聚醚共聚酰胺(Pebax)共同制备了混合基质膜。填料中引入的羰基和羧基等基团提供了MOFs与聚合物基质之间较强的界面相互作用。与纯Pebax膜相比,UiO-66-AC/Pebax MMMs的气体渗透性能得到了显著提高。当填料质量分数为6%时,膜的CO2渗透系数为102.4 Barrer,CO2/N2和CO2/CH4选择性分别为90.6和26.0,CO2/N2分离性能突破了Robeson上限(2008),表明该混合基质膜在CO2的分离应用上具有潜力。  相似文献   

11.
We have developed zeolite 5A and 13X embedded P84 co-polyimide membranes with enhanced permeability and selectivity for the pervaporation dehydration of isopropanol (IPA). It is found that a higher annealing temperature, i.e., is more favorable to improve adhesion between zeolite and polymer phase, and to enhance charge transfer complexes (CTCs) formation. FESEM, DSC and gas permeation results show that zeolite 13X has better compatibility with the matrix polymer than zeolite 5A because of stronger interactions between Na cations in zeolite 13X framework and electron acceptor groups of P84 polyimide. The addition of zeolite into the P84 dense membrane improves water sorption capacity and pervaporation separation performance significantly. Owing to the bigger pore size, larger pore volume, higher sorption capacity and better adhesion, the zeolite 13X incorporated P84 membranes has a much higher permeability than zeolite 5A filled membranes. Interestingly, both have comparably high selectivity possibly because of the effects of chain rigidification and partial pore blockage. The addition of zeolite 13X reduces activation energy for water permeation through the membrane but increases that for IPA permeation. However, the addition of zeolite 5A increases activation energy for both water and IPA permeation. Pervaporation permeability increases with zeolite 13X loading, while the selectivity achieves the maximum at 30 wt% zeolite 13X loading. When the zeolite 13X loading approaches 40 wt%, the adhesion between zeolite and polymer becomes poor and the membrane selectivity declines. A comparison between pervaporation and gas separation results reveals that pervaporation membranes can tolerate a higher degree of interstitial defects than gas separation membranes because of stronger molecular interactions between the feed and the polymer, and the larger molecular size difference between penetrants in the former.  相似文献   

12.
《分离科学与技术》2012,47(18):2451-2473
Abstract

In the production of pure alcohol, pervaporation is developing into an important technology. In this study, in order to improve the performance of the pervaporation process, a mixed-matrix polymer-zeolite membrane is developed. In the preparation of these membranes, cellulose acetate as base polymer, acetone or DMF as solvent, and 13X or 4A zeolites as fillers were used. To test the performance of homogeneous and mixed-matrix membranes, a laboratory-scale pervaporation setup was constructed. The effect of the following experimental parameters on the selectivity and flux were experimentally studied to determine the optimum values of operating conditions and to understand the separation mechanism in the indicated ranges: feed concentration, 70–90 wt%; feed temperature, 30–70°C; feed flow rate, 32–76 L/h. It was observed that the addition of zeolite to the membrane matrix improves the flux value twofold with respect to its homogeneous membranes with some loss in their selectivity. For example, for a feed concentration of 74 wt% EtOH at 50°C and 1 mmHg, the flux value for the unfilled membrane is 0.6 L/m2·h, and for a 30% zeolite-filled membrane, the flux is increased to 1.33. For these cases, the selectivities are 7.76 and 5.0 for the unfilled and filled membranes, respectively. TEM micrographs of the mixed-matrix membranes show a homogeneous distribution of zeolite particles which produce a cavelike porous structure in the matrix. The combined effect of this modified morphology and zeolite selectivity is the possible reason for the observed pervaporation performances of mixed-matrix membranes.  相似文献   

13.
李杰  王乃鑫  纪树兰 《化工进展》2014,33(11):2982-2990
渗透汽化优先透醇膜分离技术可有效解决燃料乙醇和丁醇生产中发酵产率较低的瓶颈问题,受到广泛关注。膜材料的选择与改性以及膜结构的构建是提高透醇性能的关键。有机/无机杂化膜可以实现有机和无机材料的优势互补,被认为是未来分离膜领域最重要的发展方向之一。本文扼要回顾了用于优先透醇渗透汽化分离的有机无机杂化材料,结合本文作者课题组的研究工作,重点阐述了杂化粒子的结构、粒径、界面相容性、纳微分散、负载量等因素对渗透汽化传递过程的作用机制,进一步对近年来发展的成膜新方法进行了总结。在此基础上,提出今后有机/无机杂化渗透汽化优先透醇膜研究的主要方向是发展新型纳米级、超疏水并与有机聚合物具有高度界面相容性的无机粒子,以及构建高负载量的纳微结构与超亲醇表面。  相似文献   

14.
In this study, the effects of 1-Ethyl-3-methylimidazolium tetrafluoroborate ionic liquid on CO2/CH4 separation performance of symmetric polysulfone membranes are investigated. Pure polysulfone membrane and ionic liquid-containing membranes are characterized. Field emission scanning electron microscopy (FE-SEM) is used to analyze surface morphology and thickness of the fabricated membranes. Energy dispersive spectroscopy (EDS) and elemental mapping, Fourier transform infrared (FTIR), thermal gravimetric (TGA), X-ray diffraction (XRD) and Tensile strength analyses are also conducted to characterize the prepared membranes. CO2/CH4 separation performance of the membranes are measured twice at 0.3 MPa and room temperature (25 °C). Permeability measurements confirm that increasing ionic liquid content in polymer-ionic liquid membranes leads to a growth in CO2 permeation and CO2/CH4 selectivity due to high affinity of the ionic liquid to carbon dioxide. CO2 permeation significantly increases from 4.3 Barrer (1 Barrer=10-10 cm3(STP)·cm·cm-2·s-1·cmHg-1, 1cmHg=1.333kPa) for the pure polymer membrane to 601.9 Barrer for the 30 wt% ionic liquid membrane. Also, selectivity of this membrane is improved from 8.2 to 25.8. mixed gas tests are implemented to investigate gases interaction. The results showed, the disruptive effect of CH4 molecules for CO2 permeation lead to selectivity decrement compare to pure gas test. The fabricated membranes with high ionic liquid content in this study are promising materials for industrial CO2/CH4 separation membranes.  相似文献   

15.
SAPO-34 zeolite membranes show high efficiency for CO2/CH4 separation but suffer from the reduction of separation performance when exposed to humid atmosphere. In this work, n-dodecyltrimethoxysilane (DTMS) was used to modify the hollow fibers supported SAPO-34 membranes to increase the external surface hydrophobicity and thus sustain their performance under moisture environment. The modified membranes were fully characterized. Their separation performance was extensively investigated in both dry and wet gaseous systems and compared with the un-modified ones. The un-modified SAPO-34 membrane exhibited a high separation selectivity of 160 and CO2 permeance of 1.18×10-6 mol·m-2·s-1·Pa-1 for separation of dry CO2/CH4 at 298 K. However, its separation selectivity declined to 0.9 and the CO2 permeance was only about 1.7×10-8 mol·m-2·s-1·Pa-1 for wet CO2/CH4 at same temperature. High temperature (e.g. 353 K) could reduce the effect of moisture to improve SAPO-34 separation selectivity, but further increasing temperature (e.g. 373 K) led to decrease in CO2/CH4 separation selectivity. A significant decrease of selectivity was observed at higher pressure drop. The modified SAPO-34 membrane showed decreased CO2 permeance but increased separation selectivity for dry CO2/CH4 gas mixture, and super performance for wet CO2/CH4 gas mixture due to the improved hydrophobicity of membrane surface. A separation selectivity of 65 and CO2 permeance of 4.73×10-8 mol·m-2·s-1·Pa-1 for wet CO2/CH4 mixture can be observed at 353 K with a pressure drop of 0.4 MPa. Furthermore, the modified membrane exhibited stable separation performance during the 120-hour test for wet CO2/CH4 mixture at 353 K. The hydrophobic modification paves a way for SAPO-34 membranes in real applications.  相似文献   

16.
To improve the pervaporation selectivity of poly(acrylic acid) sodium (PAAS) membranes incorporated with NaA zeolite, the interface compatibility between zeolite nanocrystals and the polymer matrix was improved by modifying NaA zeolite using 3‐aminopropyltriethoxysilane (APTES). Both X‐ray photoelectron spectra and FTIR confirmed the chemical modification, while the results of zeolite particle size analysis and scanning electron microscopy revealed the improved dispersion of the modified zeolite. Transmission electron microscopy images of these hybrid membranes indicated that the interface between the polymer and modified zeolite phases had improved. The effects of loaded NaA zeolite on the pervaporation performance of hybrid membranes were investigated. The selectivity of hybrid membranes made from APTES‐modified zeolite was higher than that using the original zeolite under the same conditions, because fewer voids resulted from the incompatibility between the zeolite and PAAS and the structure was more homogenous. Based on the Arrhenius plots, the activation energies of water and the ethanol ratio were lower for modified zeolite hybrid membranes, because water molecules experienced less restrictive passage through the membranes compared with the original zeolite‐based hybrid membrane. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013  相似文献   

17.
Branched polyethyleneimine (PEI) functionalized UiO-66 were synthesized and used as fillers to fabricated mixed-matrix membranes (MMMs) for CO2/CH4 separation. The purpose of introducing amino-functional groups in the filler is to improve the interfacial compatibility of the filler with the polymer through the formation of hydrogen bonds with the carbonyl group of 6FDA-ODA. Additionally, the amino group can facilitate CO2 transport through a reversible reaction, enhancing the CO2/CH4 separation properties of MMM. The chemical structure and morphology of fillers and membranes were characterized by employing X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectrometer (FTIR), X-ray diffraction (XRD), thermogravimetric (TGA), Derivative thermogravimetry (DTG) and scanning electron microscope (SEM). Furthermore, the effects of filler loading and feed pressure on CO2 permeability and CO2/CH4 selectivity have been investigated. MMMs present higher gas separation performance than pure 6FDA-ODA due to the presence of amino groups and the improvement of interface morphology. In particular, the MMM with 15 wt% loading of UiO-66-PEI shows optimum CO2 permeability of 28.23 Barrer and CO2/CH4 selectivity of 56.49. Therefore, post-synthetic modification of UiO-66 particle with PEI is a promising alternative to improved membrane performance.  相似文献   

18.
Membrane separation is a high-efficiency, energy-saving, and environment-friendly separation technology. Covalent organic framework (COF)-based mixed-matrix membranes (MMMs) have broad application prospects in gas separation and are expected to provide new solutions for coal-bed methane purification. Herein, a high-throughput screening method is used to calculate and evaluate COF-based MMMs for CH4/N2 separation. General design rules are proposed from thermodynamic and kinetic points of view using the computation-ready, experimental COFs. From our database containing 471,671 generated COFs, 5 COF membrane materials were screened with excellent membrane selectivities, which were then used as the filler of MMMs for separation performance evaluation. Among them, BAR-NAP-Benzene_CF3 combined with polydimethylsiloxane and styrene-b-butadiene-b-styrene show high CH4 permeability of 4.43×10-13 mol·m·s-1·Pa-1·m-2 and high CH4/N2 selectivity of 9.54, respectively. The obtained results may provide reasonable information for the design of COF-based membranes for the efficient separation of CH4/N2.  相似文献   

19.
《分离科学与技术》2012,47(12):1908-1914
3A-filled hydrophilic polyurethane (PU) membranes were prepared by incorporating zeolite 3A into PU for pervaporation separation of acetaldehyde and water mixtures (acetaldehyde concentration 2 wt%–20 wt%). The composite membranes were characterized by Fourier transform infrared spectroscopy and X-ray diffraction. The morphology and thermal stability of these membranes were also investigated. The effects of zeolite 3A on the sorption, diffusion, and pervaporation performance were evaluated. The swelling study showed that 3A-PU membrane had higher swelling degree in acetaldehyde aqueous solution than in pure water. And the swelling degree of the composite membrane in acetaldehyde solution increased with the 3A content. The permeation flux and water/acetaldehyde separation factor first increased and then decreased with increasing 3A content. The reason may be that a proper quantity of 3A will enlarge the free volume fraction of PU while excessive 3A lead to its poor dispersion. The highest permeation flux of the composite membrane could reach 223 g · m?2 · h?1 and the maximum water/acetaldehyde selectivity achieved 7.5. The calculation of sorption selectivity and diffusion selectivity showed that diffusion played a more important role in this process.  相似文献   

20.
Pervaporation (PV) is an emerging separation technique for liquid mixture. Mixed matrix membranes (MMMs) often demonstrate trade-off relationship between separation factor and flux. In this study, by changing the organic linkers (2-methyl imidazolate, imidazole-2-carboxaldehyde, 2-ethyl imidazolate), ZIF-8, ZIF-90 and MAF-6 were prepared and filled in polydimethylsiloxane (PDMS) membranes for dealcoholization of 5% (mass) n-butanol solution, and the membranes properties and pervaporation performances were adjusted. Compared with the pure PDMS membrane, the addition of ZIF-8 resulted in a 9% increase in flux (1136 g·m-2·h-1) and a 22.5% increase in separation factor (28.3), displaying anti-trade-off effect. For the MAF-6/PDMS MMMs (2.0% mass loading), the pervaporation separation index (PSI) and separation factor were 32347 g·m-2·h-1 and 58.6 respectively (increased by 34% and 154% in contrast with that of the pure PDMS membrane), and the corresponding permeation flux was 552 g·m-2·h-1, presenting great potential in the removal butanol from water. It was deduced that the large aperture size combined with moderate hydrophobicity of metal-organic frameworks (MOFs) favor the concurrent increase in permeability and selectivity.  相似文献   

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