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1.
In this paper, poly(amide-6-b-ethylene oxide) (Pebax1657)/SAPO-34 mixed matrix membranes (MMMs) were prepared by solvent-evaporation method with acetic acid as a novel solvent. CO2, N2, CH4 and H2 permeation properties were investigated, and the physical properties of Pebax/SAPO-34 MMMs were characterized by XRD and SEM. At low SAPO-34 content, it was homogeneously distributed in the Pebax ma- trix, and then precipitated and agglomerated at high SAPO-34 content. The crystallinity of Pebax phase in Pebax/SAPO-34 MMMs decreased initially and then rebounded as a result of phase separation. With the increase of transmembrane pressure difference, CO2 permeability was en- hanced due to the effect of pressure-induced plasticization. Owing to the happening of stratification, the CO2 permeability of Pebax/SAPO-34 MMMs (50 wt% SAPO-34) increased to 338 Barrer from 111 Barrer of pristine Pebax, while the selectivities of CO2/CH4 and CO2/N2 were almost unchanged. Compared with the pristine Pebax, the gas separation performances of Pebax/SAPO-34 MMMs were remarkably enhanced.  相似文献   

2.
Mixed matrix membranes (MMMs) containing graphene-based fillers have attracted considerable attention in the field of gas separation. In this study, two types of graphene derivatives (Graphene (G) and Graphene Oxide (GO)) were embedded into the poly-ether-block-amide (Pebax) based MMM to investigate and compare CO2/N2 separation at various filler loadings (0.3–1 wt%). The morphologies of the prepared neat Pebax and MMMs were characterized by SEM, XRD, FTIR and DSC. Compared with the neat Pebax, the permeability of all gases was increased by adding filler content in the MMMs due to the crystallinity decrement of the polyamide (PA) segment. The best separation performance of the Pebax/G MMMs occurred at 0.7 wt%, where the CO2 permeability increased from 26.51 to 44.78 Barrer (~1.7 times). Also, for the Pebax/GO MMMs, the CO2 permeability was increased up to 58.96 Barrer (~2.2 times) by adding 0.5 wt% filler. This further gas permeation increment for the Pebax/GO sample was attributed to the higher affinity of GO nanosheets to CO2 sorption, which can facilitate CO2 gas transition through the membrane matrix. Moreover, the CO2/N2 ideal selectivity increased from 74.26 for the neat Pebax to 111.95 (~1.5 times) and 120.72 (~1.62 times) by adding 0.7 wt% G (Pebax/G-0.7) and 1 wt% GO (Pebax/GO-1) into Pebax, respectively. As a consequence, graphene derivatives can be recognized as a promising developer of permselectivity (permeability and selectivity) of the MMMs.  相似文献   

3.
Poly(ether-block-amide)/g-PTAP mixed matrix membranes (MMMs) were developed by incorporating different wt.% (1–10%) of a novel 2D g-PTAP nanofiller and its effects on membrane structure and gas permeability were studied. The novel 2D material g-PTAP was synthesized and characterized by various analytical techniques including field-emission scanning electron microscopy (FESEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and Raman spectroscopy. The fabricated MMMs were investigated to study the interaction and compatibility between Pebax and g-PTAP. The MMMs showed an effective integration of g-PTAP nanofiller into the Pebax matrix without affecting its thermal stability. Gas permeation experiments with MMMs showed improved CO2 permeability and selectivity (CO2/N2) upon incorporation of g-PTAP in the Pebax polymer matrix. The maximum CO2 permeability enhancement from 82.3 to 154.6 Barrer with highest CO2/N2 selectivity from 49.5 to 83.5 were found with 2.5 wt.% of nanofiller compared to neat Pebax membranes.  相似文献   

4.
In this study, graphene nanosheets (GNs) were incorporated into polyethersulfone (PES) by phase inversion approach for preparing PES-GNs mixed matrix membranes (MMMs). To investigate the impact of filler content on membrane surface morphology, thermal stability, chemical composition, porosity and mechanical properties, MMMs were constructed with various GNs loadings (0.01, 0.02, 0.03, and 0.04 wt%). ?The performance of prepared MMMs was tested for separation and selectivity of CO2, N2, H2 and CH4 gases at various pressures from 1 to 6 bar and temperature varying from 20 to 60 °C. It was observed that, compared to the pristine PES membrane, the prepared MMMs significantly improved the gas separation and selectivity performance with adequate mechanical stability. The permeability of CO2, N2, H2 and CH4 for the PES + 0.04 wt% GNs increases from 9 to 2246, 11 to 2235, 9 to 7151, and 3 to 4176 Barrer respectively, as compared with pure PES membrane at 1 bar and 20 °C due to improving the membrane absorption and porosity. In addition, by increasing the pressure, the permeability and selectivity of CO2, N2, H2 and CH4 are increased due to the increased driving force for the transport of gas via membranes. Furthermore, the permeability of CO2, N2, H2 and CH4 increased by increasing the temperature from 20 to 60 °C due to the plasticization in the membranes and the improvement in polymer chain movement. This result proved that the prepared membranes can be used for gas separation applications.  相似文献   

5.
Mixed matrix membranes (MMMs) made from inorganic fillers and polymers is a kind of promising candidate for gas separation. In this work, two‐dimensional MXene nanosheets were synthesized and incorporated into a polyether‐polyamide block copolymer (Pebax) matrix to fabricate MMM for CO2 capture. The physicochemical properties of MXene nanosheets and MXene/Pebax membranes were studied systematically. The introduction of MXene nanosheets provided additional molecular transport channels and meanwhile enhanced the CO2 adsorption capacity, thereby enhancing both the CO2 peremance and CO2/N2 selectivity of Pebax membrane. The optimized MXene/Pebax membrane with a MXene loading of 0.15 wt % displayed a high separation performance with a CO2 permeance of 21.6 GPU and a CO2/N2 selectivity of 72.5, showing potential application in CO2 capture.  相似文献   

6.
《先进技术聚合物》2018,29(4):1334-1343
The aminated graphene oxide (GO) was prepared by the functionalization of pristine GO with ethylenediamine and then dispersed into the poly(amic acid) (the precursor of polyimide [PI]) solution followed by the chemical imidization to successfully fabricate the PI/amine‐functionalized GO mixed matrix membranes (MMMs) using in‐situ polymerization method. Chemical structure and morphology of the GO before and after amine modification were characterized by scanning electron microscopy, Raman spectrum, Fourier transform infrared, and X‐ray photoelectron spectroscopy. Scanning electron microscopy indicated that fine dispersion of GO throughout PI matrix was achieved, which indicates that the in‐situ polymerization approach can enhance the interfacial interaction between the GO and the PI matrix, and then improve the dispersion of carbon material in the polymer matrix. Compared with the conventional solution mixture method, the MMMs prepared with in‐situ polymerization method showed excellent CO2 permeability and CO2/N2 selectivity. The MMMs doped with 3 wt.% aminated GO exhibited maximum gas separation performance with a CO2 permeability of 12.34 Barrer and a CO2/N2 selectivity of 38.56. These results suggest that the amino groups on GO have strong interaction with the CO2 molecules, which can significantly increase the solubility of polar gas. Our results provide an easy and efficient way to prepare MMMs with good mechanical behavior and excellent gas separation performance.  相似文献   

7.
《Arabian Journal of Chemistry》2020,13(12):8979-8994
Mixed matrix membranes (MMMs) fabricated with porous metal organic frame works have enhanced the separation performance of polymer membranes. In this context microporous 3D Tb(BTC)(H2O).(DMF)1.1 MOF was incorporated into pristine Matrimid® with loadings of 10, 20 and 30 weight percentages. SEM micrographs indicated proper distribution of filler in the Matrimid and no interfacial voids were observed. Gas permeation studies evidenced the CO2 permeability to be 13.2 (82.32%) and 18.34 (153.31%) and 25.86 Barrer for 10, 20 and 30 wt% MMMs respectively. The 257.18% increase in CO2 permeability of 30 wt% MMM than methane was attributed to polar nature of CO2, its smaller kinetic diameter, condensability, and larger solubility within the Matrimid matrix than non – polar and larger CH4 molecules.Addition of filler influenced the pure gas selectivity of all MMMs positively. So, 30 wt% MMM exhibited the highest 58.04% increase in selectivity that was attributed to the molecular sieving property of the filler and the size exclusion phenomena as followed by CH4 and CO2. The high values of mixed and pure gas selectivity were obtained upon increasing filler concentration. The commercial applicability of these MMMs was tested by checking their selectivity under increased feed concentrations of CO2 and checking permeability and selectivities at high temperatures. The study depicted that, competitive sorption of gases, prevalence of size exclusion phenomena and polymer chains relaxation at higher temperature were responsible for low gas selectivity. MMM with 30 wt% of MOF lied close to Robson’s Upper bound 2008 that indicated its good separation potential.  相似文献   

8.
Graphene oxide nanoparticles (GO) were firstly functionalized using p-phenylenediamine and then utilized as nanofillers to prepare poly(ether-block-amide) (Pebax®-1657)/poly(vinyl alcohol) (PVA-60000)-based mixed-matrix membranes. The modified GO as well as the fabricated mixed matrix membranes underwent some characterization analyses, including FTIR, TGA, XRD, FESEM, and EDX. The influence of amine-modified nanoparticles content (2, 4, and 6 wt%), and feed pressure on CO2, CH4, and N2 permeabilitis and ideal CO2/CH4 and CO2/N2 selectivities values of the MMMs were investigated. The permeation experiments demonstrated that Pebax/PVA (10 and 15 wt%) blend membranes caused an increase in CO2 permeability owing to the high affinity of polar CO2 molecules to polar PVA segments. Moreover, the incorporation of 6 wt% amine-functionalized GO into the Pebax/PVA (10 wt%) and Pebax/PVA (15 wt%) blend polymer raised the CO2 permeability and CO2/CH4 and CO2/N2 selectivity by nearly 43%, 28%, and 37%, respectively, due to the higher CO2 adsorption capacity of the amine-functionalized GO.  相似文献   

9.
Mixed-matrix membranes (MMMs) with combination of two distinct dimensional nanofillers (such as 1D-3D, 2D-3D, or 3D-3D, etc.) have drawn special attention for gas separation applications due to their concerted effects on gas permeation and mechanical properties. An amine-functionalized 1D multiwalled carbon nanotube (NH2-MWCNT) with exceptional mechanical strength and rapid gas transport was crosslinked with an amine-functionalized 3D metal-organic framework (UiO-66-NH2) with high CO2 affinity in a Schiff base reaction. The resultant crosslinked mixed-dimensional nanostructure was used as a nanofiller in a polysulfone (PSf) polymer matrix to explore the underlying synergy between 1D and 3D nanostructures on the gas separation performance of MMMs. Cross-sectional scanning electron microscopy and mapping revealed the homogenous dispersion of UiO-66@MWCNT in the polymer matrix. The MMM containing 5.0 wt. % UiO-66@MWCNT demonstrated a superior permeability 8.3 Barrer as compared to the 4.2 Barrer of pure PSf membrane for CO2. Moreover, the selectivity (CO2/CH4) of this MMM was enhanced to 39.5 from the 28.0 observed for pure PSf under similar conditions of pressure and temperature.  相似文献   

10.
A novel composite membrane consisting of an interconnected MOF scaffold coated with cross‐linked poly(ethylene glycol) (PEG) has been developed. As a result of its unique structure, the membrane shows an exceptional 18‐fold permeability enhancement as compared to pristine PEG membranes, without compromising the selectivity. This performance is unattainable with current mixed‐matrix membranes (MMMs). Our optimized membrane has a permeability of 2700 Barrer with a CO2/N2 selectivity of 35, which surpasses the latest Robeson upper bound.  相似文献   

11.
Incompatibility between filler and polymer chains accompanied by particle agglomeration has a detrimental effect on the performance of mixed matrix membranes (MMMs). To obviate intermolecular forces of different additives, functional groups (-COOH, –NCO, and –NH2) were grafted on the surface of multi-walled carbon nanotubes (MWCNTs) which were then incorporated as fillers in the poly(ether-block-amide) (PEBA) polymeric matrix in the range of 0.1–1 wt% loading. CO2 permeability and ideal CO2/N2 and CO2/CH4 selectivity of MMMs was compared with the neat membrane, and the results revealed favorable enhancement and surpassed CO2/N2 Robeson's upper bound under 4–10 bar in the range of 15–55 °C. Mixed gas separation performance of MMMs, which is of vital importance in industrial applications, was also investigated. The results indicate that MWCNT-NCO created superior grafts with the polymer chains, and MMMs with this additive had a better gas separation performance with high mechanical and thermal stability.  相似文献   

12.
In this work, the films of poly(ether-block-amide) (Pebax 1657) and hydrophilic/hydrophobic silica nanoparticles (0–10 wt%) were coated on a poly(vinyl chloride) (PVC) ultrafiltration membrane to form new mixed matrix composite membranes (MMCMs) for CO2/N2 separation. The membranes were characterized by SEM, FTIR, DSC and XRD. Successful formation of a non-porous defect-free dense top layer with ~4 μm of thickness and also uniform dispersion of silica nanoparticles up to 8 wt% loading in Pebax matrix were confirmed by SEM images. The gas permeation results showed an increase in the permeance of all gases and an increase in ideal CO2/N2 selectivity with the increase in silica nanoparticle contents. Comparison between the incorporation of hydrophilic and hydrophobic silica nanoparticle into Pebax matrix revealed that the great enhancement of CO2 solubility is the key factor for the performance improvement of Pebax + silica nanoparticle membranes. The best separation performance of the hydrophilic silica nanoparticle-incorporated Pebax/PVC membrane for pure gases (at 1 bar and 25 °C) was obtained with a CO2 permeability of 124 barrer and an ideal CO2/N2 selectivity of 76, i.e., 63 and 35% higher than those of neat Pebax membrane, respectively. The corresponding values for hydrophobic silica nanoparticle-incorporated Pebax/PVC membrane were 107 barrer for CO2 permeability and 61 for ideal CO2/N2 selectivity. Also the performances of MMCMs improved upon pressure increase (1–10 bar) owing to the shift in plasticizing effect of CO2 towards the higher pressures. In addition, an increase in permeabilities with a decrease in ideal selectivity was observed upon temperature increase (25–50 °C) due to the intensification of chain mobility.  相似文献   

13.
The goal of this work is to explore new polyimide materials that exhibit both high permeability and high selectivity for specific gases. Copolyimides offer the possibility of preparing membranes with gas permeabilities and selectivities not obtainable with homopolyimides. A series of novel fluorinated copolyimides were synthesized with various diamine compositions by chemical imidization in a two-pot procedure. Polyamic acids were prepared by stoichiometric addition of solid dianhydride in portions to the diamine(s). The gas permeation behavior of 2,2′-bis(3,4′-dicarboxyphenyl) hexafluoropropane dianhydride(6FDA)-2,6-diamine toluene (2,6-DAT)/1,3-phenylenediamine (mPDA) polyimides was investigated. The physical properties of the copolyimides were characterized by IR, DSC and TGA. The glass transition temperature increased with increase in 2,6-DAT content. All the copolyimides were soluble in most of the common solvents. The gas permeability coefficients decreased with increasing mPDA content. However, the permselectivity of gas pairs such as H2/N2, O2/N2, and CO2/CH4 was enhanced with the incorporation of mPDA moiety. The permeability coefficients of H2, O2, N2, CO2 and CH4 were found to decrease with the increasing order of kinetic diameters of the penetrant gases. 6FDA-2,6-DAT/mPDA (3:1) copolyimide and 6FDA-2,6-DAT polyimide had high separation properties for H2/N2, O2/N2, CO2/CH4. Their H2, O2 and CO2 permeability coefficients were 64.99 Barrer, 5.22 Barrer, 23.87 Barrer and 81.96 Barrer, 8.83 Barrer, 39.59 Barrer, respectively, at 35°C and 0.2 MPa (1 Barrer = 10−10 cm3 (STP)·cm·cm−2·s−1·cmHg−1) and their ideal permselectivities of H2/N2, O2/N2 and CO2/CH4 were 69.61, 6.09, 63.92 and 53.45, 5.76, 57.41, respectively. Moreover, all of the copolyimides studied in this work exhibited similar performance, lying on or above the existing upper bound trade-off lines between permselectivity and permeability. They may be utilized for commercial gas separation membrane materials. __________ Translated from Acta Polymerica Sinica, 2008, 8 (in Chinese)  相似文献   

14.
Poly (ether-b-amide) (PEBA) mixed matrix membranes (MMMs) filled by different amounts of nano ZnO (up to 1 wt %) were synthesized and their gas separation performance was evaluated for CO2, CH4 and N2 pure gas and their binary mixtures. The ZnO-filled PEBA MMMs were characterized using ATR-FTIR, FESEM, AFM, TGA, DMTA, XRD and Mechanical tensile strength analyses. Generally, it was revealed that 0.5 wt % loading of ZnO into the polymer matrix caused a ZnO−PEO interaction; while ZnO–ZnO self-association hindered the interaction for the MMMs with other loadings of ZnO. As a result, PEBA-ZnO 0.5 wt % MMM possessed a higher glass transition temperature (Tg). Therefore, the CO2 permeability through PEBA-ZnO 0.5 wt % enhanced 27% than simple PEBA membrane. Moreover, all the fabricated MMMs were simulated by molecular simulation. Grand Canonical Monte Carlo (GCMC) and Molecular Dynamics (MD) methods were also applied to simulate the structural and gas transport properties of the membranes. The RDF, XRD, Tg, FFV and density analysis were compared with experimental results. Also, a binary mixture of CO2:CH4 (10:90) was used to determine CO2 permeability and CO2/CH4 selectivity, which were considerably reduced compared to single gas experiments. Moreover, the solubility of the binary gas mixture, the energy distribution and density distribution of both gases within the simulated cell were calculated by molecular simulation.  相似文献   

15.
Mixed‐matrix membranes (MMMs) comprising Matrimid and a microporous azine‐linked covalent organic frameworks (ACOF‐1) were prepared and tested in the separation of CO2 from an equimolar CO2/CH4 mixture. The COF‐based MMMs show a more than doubling of the CO2 permeability upon 16 wt % ACOF‐1 loading together with a slight increase in selectivity compared to the bare polymer. These results show the potential of COFs in the preparation of MMMs.  相似文献   

16.
Three phase Pebax~? MH 1657/PEG-ran-PPG/CuBTC(polymer/liquid/solid) was successfully deposited as a selective layer on a porous Polysulfone(PSF) support. In fact, the beneficial properties of PEG(high selectivity) with those of PPG(high permeability, amorphous) have been combined with superior properties of mixed matrix membrane(MMMs). The membranes were characterized by DSC, TGA and SEM, while CuBTC was characterized by CO_2 and CH_4adsorption test. Statistically based experimental design(central composite design, CCD) was applied to analyze and optimize the effect of PEG-ran-PPG(10–50 wt%) and CuBTC(0–20 wt%) mass contents on the CO_2 permeance and CO_2/CH_4 ideal selectivity. Based on the regression coefficients of the obtained models, the CO_2 permeance was notably influenced by PEG-ran-PPG,while CuBTC has the most significant effect on the CO_2/CH_4 ideal selectivity. Under the optimum conditions(PEG-ran-PPG: 32.76 wt% and CuBTC: 20 wt%), nearly 620% increase in the CO_2 permeance and43% enhancement in the CO_2/CH_4 ideal selectivity was observed compared to the neat Pebax. The effect of pressure(3, 9 and 15 bar) on the pure and mixed gas separation performance of the composite membranes was also investigated. The high solubility of CO_2 in the membranes resulted in the enhancement of CO_2 permeability with increase in gas pressure.  相似文献   

17.
Defect‐free mixed‐matrix membranes (MMMs) were prepared by incorporating hydrophilic metal‐organic polyhedra (MOPs) into cross‐linked polyethylene oxide (XLPEO) for efficient CO2 separation. Hydrophilic MOPs with triethylene glycol pendant groups, which were assembled by 5‐tri(ethylene glycol) monomethyl ether isophthalic acid and CuII ions, were uniformly dispersed in XLPEO without particle agglomeration. Compared to conventional neat XLPEO, the homogenous dispersion of EG3‐MOPs in XLPEO enhanced CO2 permeability of MMMs. Upon increasing the amount of EG3‐MOPs, the membrane performance such as CO2/N2 selectivity was steadily improved because of unsaturated CuII sites at paddle‐wheel units, which was confirmed by Cu K‐edge XANES and TPD analysis. Therefore, such defect‐free MMMs with unsaturated metal sites would contribute to enhance CO2 separation performance.  相似文献   

18.
In the early stage of membrane technology development in gas separation, utilization of polymeric membranes has gained attention due to their robustness and ease of fabrication. However, the performance of polymeric membranes is limited by the trade-off between permeability and selectivity. Meanwhile, inorganic membrane is capable to exhibit great enhancement in separation performance but unfortunately its fabrication process is hard and costly. Thus, development of mixed matrix membranes (MMMs) by incorporating inorganic fillers into the polymer matrix has become a potential alternative to overcome the limitations of polymeric and inorganic membranes in gas separation. Nevertheless, fabrication of defect-free MMMs with improved separation performance and without compromising the mechanical and thermal stability is extremely difficult and challenging. In the current review paper, various types of inorganic fillers for MMMs fabrication and recent reported efforts to tailor the underlying problems on MMMs fabrication were discussed. The future outlook to advance the performance of MMMs in gas separation especially for CO2/CH4 separation was highlighted.  相似文献   

19.
A SAPO-34 membrane separated CO2/H2 and H2/CH4 mixtures at feed pressures up to 1.7 MPa. Strong CO2 adsorption inhibited H2 adsorption and decreased H2 permeances significantly, especially at low temperatures, so that CO2 preferentially permeated and CO2/H2 selectivities were higher at low temperatures. At 253 K, CO2/H2 separation selectivities were greater than 100 with CO2 permeances of 3 × 10−8 mol m−2 s−1 Pa−1. The CO2/H2 separation exceeded the upper bounds (selectivity–permeability plot) for polymer membranes. The SAPO-34 membrane separated H2 from CH4 because CH4 is close to the SAPO-34 pore size and has a lower diffusivity than H2. The H2/CH4 separation selectivity had a small maximum with temperature, and decreased slightly with feed pressure and CH4 feed concentration.  相似文献   

20.
Zeolite ZIF-8 has been etched with acid to form microporous ZIF-8-E crystals. These were then introduced into a polyethersulfone (PES) membrane matrix to enhance its CO2/N2 separation performance. Open through pores of size about 100 nm formed in the ZIF-8 crystals allow the ingrowth of polyethersulfone chains, ensuring a reduction in the number of nonselective voids, thereby achieving better interaction between ZIF-8-E and PES. As a result, the CO2/N2 separation performance of the ZIF-8-E/PES membrane increased significantly, showing a CO2 permeability of 15.7 Barrer and a CO2/N2 ideal selectivity of 6.5.  相似文献   

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