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1.
This study investigated the effect of annealing time and temperature on gas separation performance of mixed matrix membranes (MMMs) prepared from polyethersulfone (PES), SAPO‐34, and 2‐hydroxy 5‐methyl aniline (HMA). A postannealing period at 120°C for a week extensively increased the reproducibility and stability of MMMs, but for pure PES membranes no post‐annealing was necessary for stable and reproducible performance. The effect of operation temperature was also investigated. The permeabilities of H2, CO2, and CH4 increased with increasing permeation temperature from 35°C to 120°C, yet CO2/CH4 and H2/CH4 selectivities decreased. PES/SAPO‐34/HMA ternary and PES/SAPO‐34 binary MMMs exhibited the highest ideal selectivity and permeability values at all temperatures, respectively. For H2/CO2 pair, when temperature increased from 35°C to 120°C, selectivity increased from 3.2 to 4.6 and H2 permeability increased from 8 to 26.5 Barrer for ternary MMM, demonstrating the advantage of using this membrane at high temperatures. The activation energies were in the order of CH4 > H2 > CO2 for all membranes. PES/SAPO‐34/HMA membrane had activation energies higher than that of PES/SAPO‐34 membrane, suggesting that HMA acts as a compatibilizer between the two phases. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40679.  相似文献   

2.
Poor adhesion between hydrophobic polymers and hydrophilic inorganic fillers is a challenge that encumbers a high separation performance of mixed matrix membrane (MMM). In this study, Titanium(IV) oxide (TiO2) nanoparticles were functionalized using ethylenediamine (EDA) before embedment in poly(ether sulfone) (PES) polymer matrix. MMMs were synthesized through dry phase inversion technique. Membranes morphology and nanoparticles dispersion was drastically enhanced posterior amine modification indicating an improved adhesion between the polymer and filler particles. Membranes thermal stability was likewise improved as higher degradation temperatures were perceived for PES/EDA–TiO2 MMMs. Gas separation evaluation for pure carbon dioxide (CO2) and methane (CH4) gases revealed a remarkably enhanced separation performance upon amine‐grafting of TiO2 as EDA‐TiO2 MMMs exhibited a higher separation performance as compared to MMMs with pristine TiO2. The highest ideal separation factor achieved was 41.52 with CO2 permeability of 10.11 Barrer at an optimum loading of 5% wt of EDA‐TiO2 which is threefold higher as compared to neat PES membrane and approximately twofold higher than MMMs with pristine TiO2, respectively, at the same filler loading. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45346.  相似文献   

3.
Separation of the radioisotope 85Kr from 136Xe is an important target during used nuclear fuel recycling. We report a detailed study on the Kr and Xe adsorption, diffusion, and membrane permeation properties of the silicoaluminophosphate zeolite SAPO‐34. Adsorption and diffusion measurements on SAPO‐34 crystals indicate their potential for use in Kr‐Xe separation membranes, but also highlight competing effects of adsorption and diffusion selectivity. SAPO‐34 membranes are synthesized on α?alumina disk and tubular substrates via steam assisted conversion seeding and hydrothermal growth, and are characterized in detail. Membrane transport measurements reveal that SAPO‐34 membranes can separate Kr from Xe by molecular sieving, with Kr permeabilities around 50 Barrer and mixture selectivity of 25–30 for Kr at ambient or slight sub‐ambient conditions. The membrane transport characteristics are modeled by the Maxwell‐Stefan equations, whose predictions are in very good agreement with experiment and confirm the minimal competing effects of adsorption and diffusion. © 2016 American Institute of Chemical Engineers AIChE J, 63: 761–769, 2017  相似文献   

4.
Modified ultra-porous ZIF-8 particles were used to prepare novel ZIF-8/Pebax 1657 mixed matrix membranes (MMMs) on PES support for separation of CO2 from CH4 using spin coating method. TEM and SEM were used to characterize modified ZIF-8 particles. SEM was also used to investigate the morphology of synthesized MMMs. The MMMs with thinner selective layer showed higher CO2 permeability and lower CO2/CH4 selectivity in permeation tests compared to MMMs with thicker selective layer. The plasticization was recognized as the main reason for rise in CO2 permeability and drop in CO2/CH4 selectivity of thinner MMMs. The gas sorption results showed that the high permeability of CO2 in MMMs is mainly due to the high solubility of this gas in MMMs, leading to high CO2/CH4 solubility selectivity for MMMs. The fractional free volume and void volume fraction of MMMs increased as the thickness of membrane decreased. Applying higher mixed feed pressures and permeation tests temperatures resulted in increase in CO2 permeability and decrease in CO2/CH4 selectivity. At highest testing temperature (60 °C), the CO2 permeability of synthesized MMMs with thinner selective layer remarkably increased.  相似文献   

5.
Mixed matrix membranes (MMMs) were prepared by solvent evaporation method using Pebax-1074 polymer as matrix and inorganic zeolite SAPO-23 as dopant. The morphology, surface functional groups, microstructure, thermal stability, and separation performance of MMMs were analyzed by scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray diffraction, thermogravimetric analysis, and gas permeation, respectively. The effects of dopant loading amount, permeation temperature, and permeation pressure on the structure and properties of MMMs were investigated. The results showed that the introduction of SAPO zeolite reduced the crystallinity of the MMMs and improved the CO2/N2 selectivity. Under the conditions of 30°C and 0.15 MPa, the MMMs prepared by incorporating with 5% SAPO zeolite in content exhibited the highest CO2/N2 selectivity of 72.0 together with the CO2 permeability of 98.2 Barrer.  相似文献   

6.
Interfacial void‐free mixed‐matrix membranes (MMMs) of polyimide (PI)/zeolite were developed using 13X and Linde type A nano‐zeolites and tested for gas separation purposes. Fabrication of a void‐free polymer‐zeolite interface was verified by the decreasing permeability developed by the MMMs for the examined gases, in comparison to the pure PI membrane. The molecular sieving effect introduced by zeolite 13X improved the CO2/N2 and CO2/CH4 selectivity of the MMMs. Separation tests indicated that the manufactured nanocomposite membrane with 30 % loading of 13X had the highest permselectivity for the gas pairs CO2/CH4 and CO2/N2 at the three examined feed pressures of 4, 8 and 12 atm.  相似文献   

7.
In theory, the combination of inorganic materials and polymers may provide a synergistic performance for mixed‐matrix membranes (MMMs); however, the filler dispersion into the MMMs is a crucial technical parameter for obtaining compelling MMMs. The effect of the filler distribution on the gas separation performance of the MMMs based on Matrimid®‐PEG 200 and ZIF‐8 nanoparticles is demonstrated. The MMMs were prepared by two different membrane preparation procedures, namely, the traditional method and non‐dried metal‐organic framework (MOF) method. In CO2/CH4 binary mixtures, the MMMs were tested under fixed conditions and characterized by various methods. Finally, regardless of the MMM preparation procedure, the incorporation of 30 wt % ZIF‐8 nanoparticles allowed to increase the CO2 permeability in MMMs. The ZIF‐8 dispersion influenced significantly the separation factor.  相似文献   

8.
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   

9.
With global appeal to green and efficient utilization of energies, metal‐organic frameworks based mixed matrix membranes are standing out in applications such as gas and liquid separation because of the integration of size/shape selectivity of MOFs with processability and mechanical stability of polymers. In the present work, a novel MIL‐68(Al) (MIL = Material of Institute Lavoisier) based mixed matrix membrane (MMM) was developed by adding porous MIL‐68(Al) into Matrimid for the separation of CO2/CH4 mixture. The MIL‐68(Al)/Matrimid MMM displays a high CO2 permselectivity. For the separation of an equimolar CO2/CH4 mixture at 373 K and 1 bar, the CO2 permeability and the CO2/CH4 selectivity are 284.3 Barrer and 79.0, respectively, which far exceed the Robeson upper bound limit and those of the previously reported MMMs. Both the operation pressure and temperature have great influence to the separation performance of the MIL‐68(Al)/Matrimid MMM. Further, the MIL‐68(Al)/Matrimid MMM shows a high stability in the long‐term separation of CO2/CH4. These properties recommend the MIL‐68(Al)/Matrimid MMM as a promising candidate for the purification of natural gases. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43485.  相似文献   

10.
A simple method of pore modification complied with defect removal polymer zeolite mixed matrix membrane was developed by in situ carbon (C) deposition. The C deposition was achieved by the controlled decomposition of polymer matrix by heat treatment. In this study, polyetherimide/silicoaluminophosphate‐34 mixed matrix membrane (MMM) was fabricated on clay‐alumina support tube, followed by carbonization of the polymer matrix for gas separation application. MMM without heat treatment were also synthesized for comparison by conventional method. The membranes were characterized by X‐ray diffraction, field emission scanning electron microscopy, and X‐ray photoelectron spectroscopy. Due to carbonization, in situ C nanoparticles were deposited in to the interfacial pores, and filler particles were oriented in preferable direction. The presence of C?O, C? N, and graphitic carbon in the matrix, may be an indication of partial carbonization and restoration of adherence of polymer with substrate. The separation factor for CO2/CH4 achieved 39.15 with a permeance value of 23.01 × 10?8mol/(m2 s Pa) for CO2 at 30 °C and 200 kPa feed pressure. For the first time, this work shows an improvement toward permeability of MMM by simple carbonization of polymer matrix with commendable values as compare to the reported literature. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45508.  相似文献   

11.
Facilitated mixed‐matrix membranes (MMMs) containing Cu‐metal organic frameworks (Cu‐MOFs) with high CO2 selectivity on an asymmetric polysulfone support were fabricated and examined the effect of gas separation performance using different matrices. An amorphous poly(2‐ethyl‐2‐oxazoline) (POZ) and semicrystalline poly(amide‐6‐b‐ethylene oxide) (PEBAX®MH 1657) block copolymer were chosen as the polymeric matrix and the effect of the matrix on CO2 separation for MMMs containing Cu‐MOFs was investigated. The interaction of CO2 in different matrix was investigated theoretically using the density functional theory method, and it was found that the amide segment in PEBAX would contribute more to the CO2 solubility than ether segment. The morphological changes were investigated by differential scanning calorimetry, field emission scanning electron microscope and X‐ray diffractometer. The ideal selectivity of CO2/N2 was enhanced significantly with the addition of a Cu‐MOF, and the values are higher in the Cu‐MOF/PEBAX MMM compared with that in a POZ based asymmetric MMM. Improvement in the CO2/N2 selectivity of a Cu‐MOF/PEBAX MMM was achieved via facilitated transport by the CO2‐selective Cu‐MOFs due to both their high adsorption selectivity of CO2 over N2 and the decreased crystallinity of PEBAX due to the presence of the Cu‐MOFs, which would provide a synergic effect on the CO2 separation. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 132, 42853.  相似文献   

12.
Mixed‐matrix membranes (MMMs) have shown great advantages but still face some challenges, such as the trade‐off between permeability and selectivity, stability, and the lack of efficient ways to enhance them simultaneously. Here, the fabrication of MMMs with metal‐organic frameworks derived porous carbons (MOF‐PCs) as fillers which exhibit selective‐facilitating CO2 transport passage originating from interactions between fillers and CO2 is showed. With the aid of the developed multicalcination method, MOF‐PCs with variable N‐contents were prepared and incorporated into PPO‐PEG matrix for the first time to prepare MMMs, which show excellent separation performance for CO2/CH4 mixture with a tunable separation performance by combining different N‐contents and surface areas of MOF‐PCs. Moreover, the developed MMMs have hydrothermal and chemical stability. This work not only presents a series of MMMs with both good separation properties and stability, it also provides useful information for guiding the fabrication of high performance MMMs for practical application. © 2018 American Institute of Chemical Engineers AIChE J, 64: 3400–3409, 2018  相似文献   

13.
Polyether‐block‐amide (Pebax)/graphene oxide (GO) mixed‐matrix membranes (MMMs) were prepared with a solution casting method, and their gas‐separation performance and mechanical properties were investigated. Compared with the pristine Pebax membrane, the crystallinity of the Pebax/GO MMMs showed a little increase. The incorporation of GO induced an increase in the elastic modulus, whereas the strain at break and tensile strength decreased. The apparent activation energies (Ep) of CO2, N2, H2, and CH4 permeation through the Pebax/GO MMMs increased because of the greater difficulty of polymer chain rotation. The Ep value of CO2 changed from 16.5 kJ/mol of the pristine Pebax to 23.7 kJ/mol of the Pebax/GO MMMs with 3.85 vol % GO. Because of the impermeable nature of GO, the gas permeabilities of the Pebax/GO MMMs decreased remarkably with increasing GO content, in particular for the larger gases. The CO2 permeability of the Pebax/GO MMMs with 3.85 vol % GO decreased by about 70% of that of the pristine Pebax membrane. Rather than the Maxwell model, the permeation properties of the Pebax/GO MMMs could be described successfully with the Lape model, which considered the influence of the geometrical shape and arrangement pattern of GO on the gas transport. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42624.  相似文献   

14.
《分离科学与技术》2012,47(7):1138-1143
Fine crystals of SAPO-34 were synthesized by preparation of sol-gel precursor and hydrothermal process. The produced crystalline phase and the crystal shapes were analyzed by XRD patterns and SEM images. The core-shell adsorbent was prepared by the formation of the fine layer of SAPO-34 on the surface of the inert ceramic particles using the same synthesis parameters and hydrothermal conditions by in situ crystallization. The prepared core-shell SAPO particles were tested in dynamic adsorption experiments of a mixture of 5% CO2 and 95% CH4 at 298 K and 0.1 MPa, and their performance was compared with pure powders of SAPO-34 in the same adsorption operational conditions. The longer breakthrough time, sharper breakthrough curves, and higher CO2 adsorbed amount were observed using core-shell SAPO-34 particles as adsorbent rather than using pure particles of SAPO-34. It is concluded that the production of a thin layer of SAPO-34 on cheap and inert porous ceramic particles is preferred rather than using higher amounts of SAPO-34 powders pelleted or binded with inert material in dynamic adsorption processes for the separation of CO2 from natural gas.  相似文献   

15.
Nowadays, new methods for gas‐separation processes are being quickly developed. The separation of CH4/CO2 and CH4/H2 is usually the subject of most related research studies, especially in the membrane gas‐separation process, because of their important role in industry. In this study, we attempted to improve the separation properties of a polysulfone/zeolite 4A mixed‐matrix membrane by modifying the zeolite particle surface. The method included a simple ion‐exchange reaction of magnesium chloride with ammonium hydroxide that yielded the formation and precipitation of magnesium hydroxide whiskers on the surface of the zeolites. The whiskers could omit most of the nonselective voids by interlocking the polymer chains through them and, consequently, improve the permeability, selectivity, and elastic modulus of the membranes. X‐ray diffraction, energy‐dispersive X‐ray spectroscopy, scanning electron microscopy (SEM), Fourier transform infrared spectroscopy, and dynamic mechanical analysis proved all the changes recorded after the particle and membrane treatments. SEM images showed the petal‐like morphology of the whiskers that formed on the surface of the particles after the reaction against the smooth surface of the untreated zeolite. At a 30 wt % loading of particles in the polymeric matrix, the selectivities for H2/CH4 and CO2/CH4 increased by 69 and 56%, respectively; in contrast, the H2 and CO2 permeabilities decreased by 2.5 and 10%, respectively. The modulus of elasticity for the treated membrane also increased by 14 and 30% compared to those of the pure and untreated membranes, respectively. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44329.  相似文献   

16.
Novel facilitated‐transport mixed‐matrix membrane (MMM) were prepared through the incorporation of polydopamine (PDA) microspheres into a poly(amide‐b‐ethylene oxide) (Pebax MH 1657) matrix to separate CO2–CH4 gas mixtures. The Pebax–PDA microsphere MMMs were characterized by Fourier transform infrared spectroscopy, scanning electron microcopy, X‐ray diffraction, differential scanning calorimetry, and thermogravimetric analysis. The PDA microspheres acted as an adhesive filler and generated strong interfacial interactions with the polymer matrix; this generated a polymer chain rigidification region near the polymer–filler interface. Polymer chain rigidification usually results in a larger resistance to the transport of gas with a larger molecular diameter and a higher CO2–CH4 selectivity. In addition, the surface of PDA microspheres contained larger numbers of amine, imine, and catechol groups; these were beneficial to the improvement of the CO2 separation performance. Compared with the pristine Pebax membrane, the MMM with a 5 wt % PDA microsphere loading displayed a higher gas permeability and selectivity; their CO2 permeability and CO2–CH4 selectivity were increased by 61 and 60%, respectively, and surpassed the 2008 Robeson upper bound line. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44564.  相似文献   

17.
《分离科学与技术》2012,47(8):1261-1271
Membrane composed of PC as base of polymer matrix with different ratio of multiwall carbon nano tubes (MWCNTs) as nanofillers and poly ethylene glycol (PEG) as second polymer was prepared by solution casting method. Both raw-MWCNTs (R-MWCNTs) and functionalized carboxyle-MWCNTs (C-MWCNTs) were used in membrane preparation. The MWCNTs loading ratio and pressure effects on the gas transport properties of membranes were examined in relation to pure He, N2, CH4, and CO2 gases. Results showed that the use of C-MWCNT instead of R-MWCNTs in mixed matrix membranes (MMMs) fabrication with base of PC provides better performance and also it increases (CO2/CH4) and (CO2/N2) selectivities to 27.38 and 25.42 from 25.45 and 19.24, respectively (at 5 wt% of MWCNTs). PEG as the second rubbery polymer was utilized to improve the separation performance and mechanical properties. In blend MMMs, highest (CO2/CH4) selectivity at 2 bar pressure increased to 35.64 for PC/PEG/C-MWCNT blend MMMs which was 27.28 for PC/MWCNTs MMMs at 10 wt%. Increase of feed pressure led to gas permeability and gas pair selectivity improvement in approximately all of membranes. Analysis of mechanical properties showed improvement in tensile modules with the increase of MWCNTs loading ratio and use of PEG in prepared MMMs.  相似文献   

18.
Ethanediamine‐modified zeolitic imidazolate framework (ZIF)‐8 particles (ZIF‐8‐NH2) is synthesized and incorporated in the poly(vinyl alcohol) (PVA) matrix to fabricate novel PVA/ZIF‐8‐NH2 mixed matrix membranes (MMMs) for pervaporation dehydration of ethanol. The PVA/ZIF‐8‐NH2 MMMs exhibit enhanced membrane homogeneity and separation performance because of the higher hydrophilicity and restricted agglomeration of the particles, as compared to corresponding MMMs loaded with unmodified particles. The effect of ZIF‐8‐NH2 loading in the MMMs is studied and the MMM with a 7.5 wt % ZIF‐8‐NH2 loading shows the best pervaporation performance for ethanol dehydration at 40°C. Various characterization techniques (Fourier transform infrared, scanning electron microscope, contact angle, sorption test, etc.) are used to investigate the MMMs loaded with ZIF‐8 and ZIF‐8‐NH2 particles. The impact of operation conditions on pervaporation performance is also performed. The performance benchmarking shows that the MMMs have superior separation factors and comparable flux to most other PVA hybrid membranes. © 2016 American Institute of Chemical Engineers AIChE J, 62: 1728–1739, 2016  相似文献   

19.
The application of thin‐film composite mixed‐matrix membranes (TFC‐MMMs) for gas separation is widely considered as an efficient separation technology. The principal methods for the preparation of TFC‐MMMs are dip‐coating, phase inversion, and interfacial polymerization comprising different types of support layers. These methods influence the CO2 permeation over the selective and support layers. A comprehensive review is provided for capturing new details of progress achieved in developing TFC‐MMMs with detailed performance of gas separation in the previous few years. Various preparation techniques of TFC‐MMMs and their effect on the gas separation performance of the prepared membranes are described.  相似文献   

20.
Poly vinyl chloride/multi wall carbon nano tubes (PVC/MWCNTs) mixed matrix membranes (MMMs) were prepared for gas separation. Raw and functionalized MWCNTs (R-MWCNTs and C-MWCNTs) were utilized in membranes preparation. The C-MWCNT shows better performance compared to raw ones. Membrane (CO2/CH4) selectivity was increased from 39.21 to 52.18 at 2 bar pressure by MWCNT loading ratio. The modified membranes with styrene butadiene rubber (SBR-MMMs) showed 63.52 and 34.70 selectivity for (CO2/CH4) and (CO2/N2) at 2 bar pressure. Mechanical properties analysis exhibited tensile module improvement utilizing blending modification. Increase of feed pressure led to membrane gas permeability decreasing. But gas pair selectivity follows a nearly constant behavior for MMMs and increasing behavior for blend MMMs.  相似文献   

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