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1.
Poly(2,6-dimethyl-1,4-phenylene oxide)(PPO)-silica mixed matrix membranes (MMMs) were synthesized through the in-situ sol–gel method. The effects of the acid–base catalysis conditions and silica loading weight on the gas separation performance of the membranes were investigated. The functional groups, crystalline structure, thermal stability, and morphology of the MMMs were examined using Fourier transform-infrared spectroscopy (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), atomic force microscopy (AFM), and thermogravimetric analysis (TGA), respectively. The results indicate that using the in-situ sol–gel method to synthesize PPO-silica MMMs is beneficial for improving the adhesion between the silica and polymer and for the dispersion of the silica. The additives significantly enhanced the thermal stability of the membranes. Compared with pure PPO membranes, the PPO-silica MMMs prepared with 10 wt.% acid-silica loading exhibited the best H2/CO2 separation properties: H2 permeability was enhanced from 82.1 to 548.7 Barrer, and an H2/CO2 separation ratio of approximately 3.56 was observed.  相似文献   

2.
A novel multilayer mixed matrix membrane (MMM), consisting of poly(phenylene oxide) (PPO), large-pore mesoporous silica molecular sieve zeolite SBA-15, and a carbon molecular sieve (CMS)/Al2O3 substrate, was successfully fabricated using the procedure outlined in this paper. The membranes were cast by spin coating and exposed to different gases for the purpose of determining and comparing the permeability and selectivity of PPO/SBA-15 membranes to H2, CO2, N2, and CH4. PPO/SBA-15/CMS/Al2O3 MMMs with different loading weights of zeolite SBA-15 were also studied. This new class of PPO/SBA-15/CMS/Al2O3 multilayer MMMs showed higher levels of gas permeability compared to PPO/SBA-15 membranes. The permselectivity of H2/N2 and H2/CH4 combinations increased remarkably, with values at 38.9 and 50.9, respectively, at 10 wt% zeolite loading. Field emission scanning electron microscopy results showed that the interface between the polymer and the zeolite in MMMs was better at a 10 wt% loading than other loading levels. The increments of the glass transition temperature of MMMs with zeolite confirm that zeolite causes polymer chains to become rigid.  相似文献   

3.
The effect of MIL 53 (Al) metal organic framework on gas transport properties of poly (4-methyl-1-pentyne) (PMP) was determined based on reverse selectivity. Mixed matrix membranes (MMMs) were fabricated considering various weight percent of MIL 53 particles. The reverse MMMs permselectivities were evaluated through measurement of pure CO2 and H2 permeation together with calculation of CO2/H2 selectivity. The PMP/MIL 53 (Al) MMMs exhibited privileged CO2/H2 permselectivity in comparison with the neat PMP. In addition, CO2 solubility coefficient was significantly increased with increasing the MIL 53 loading, while the H2 solubility coefficient was almost remained unchanged. Moreover with increasing the feed pressure the permeability of CO2 and CO2/H2 selectivity were dramatically enhanced, especially at higher filler loadings. Therefore, it was observed that the reverse selectivity of MMMs was enhanced so that the Robeson upper bound was overcome. The best yielding membranes (PMP/30 wt.% MIL 53) represented the CO2 permeability and CO2/H2 selectivity of 377.24 barrer and 24.91 for pure gas experiments respectively.  相似文献   

4.
The transport properties of gases in polydimethylsiloxane (PDMS)/zeolite A mixed matrix membranes (MMMs) were determined based on pure gas permeation experiments. MMMs were prepared by incorporating zeolite 4A nanoparticles into a PDMS matrix using a new procedure. The permeation rates of C3H8, CH4, CO2, and H2 were evaluated through a dense homogeneous pure PDMS membrane and PDMS/4A MMMs to assess the viability of these membranes for natural gas sweetening and hydrogen purification. SEM investigations showed good adhesion of the polymer to the zeolite in MMMs. Permeation performance of the membranes was also investigated using a laboratory-scale gas separation apparatus and effects of feed pressure, zeolite loading and pore size of zeolite on the gas separation performance of the MMMs were evaluated. The MMMs exhibited both higher selectivity of H2/CH4 and H2 permeability as compared with the neat PDMS membrane, suggesting that these membranes are very promising for gas separations such as H2/CH4 separation.  相似文献   

5.
NU-1000 and graphene nanosheet (GNs) with different loadings have been used as fillers to prepare mixed matrix membranes (MMMs) with polyethersulfone (PES). The high performance of the MMMs has been successfully fabricated for the evaluation of gas separation at 1 bar and various temperatures (20, 40, 60 °C). The successful fabrication of the MMMs were confirmed by using SEM, FTIR, AFM, and XRD. The crystalline nature of GNs and NU-1000 in the MMMs are evidenced by XRD, which confirms the successful fabrication of the MMMs. In addition, the thermal stability of the MMMs was enhanced with the increase of the GNs. Separation performance of H2 was superior to CO2, N2 and CH4 separation on the MMMs which is a critical for producing energy. The best gas separation results in terms of both permeability and selectivity were obtained with 0.03% GNs and 10% NU-1000. PG3N membrane presented maximum H2/CO2, H2/N2 and H2/CH4 selectivity of 5, 4.2, 3.3 at 20 C, respectively. With an increase in temperature, the permeability increased, while the selectivity of all the MMMs decreased. The MMMs exhibited excellent gas separation capability, which offers unique opportunities for potential large-scale practical applications.  相似文献   

6.
In this study, a ‘green” method has been discovered by utilizing the amino functional poly(ethylene oxide) (PEO) and epoxy functional PEO with low molecular weights to synthesis cross-linked membranes for enhancing H2 purification and CO2 capture performance by retarding the crystallinity of semi-crystalline polymer of PEO. The cross-linking reaction can happen simply by mixing two materials without using any solvent. The reaction has been characterized by Fourier transform infrared-attenuated total reflectance (FTIR-ATR), X-ray photoelectron spectroscopy (XPS), solid-state 13C nuclear magnetic resonance (NMR) and the gel content test. Furthermore, X-ray diffraction (XRD) and differential scanning calorimeter (DSC) confirm the amorphous structure of cross-linked PEO membranes, which should benefit the gas transport. The gas transport properties and the plasticizing phenomenon of CO2 have been examined in detail. Interestingly, the investigation on CO2 plasticization phenomenon reveals that the cross-linked PEO membrane should be plasticized immediately after the pressure load. The pressure dependence of CO2 permeability in the pressure range from 0.25 atm to 30 atm can be separated into two stages based on the permeability increment although the CO2 permeability continuously increases with the loading pressure. The gas transport results illustrate that CO2 has much larger permeability than that of any tested gas (including H2, N2 and CH4) attributing to the CO2-philic characteristic of ethylene oxide (EO) groups in the cross-linked PEO membrane. The good permeability and selectivity make the developed PEO membrane promising for H2 purification and CO2 capture applications.  相似文献   

7.
We have demonstrated, for the first time, a polymer blend comprising poly(vinylidene fluoride) (PVDF) and a room-temperature ionic liquid (RTIL) that shows a high CO2 permeability of 1778 Barrer with CO2/H2 and CO2/N2 selectivity of 12.9 and 41.1, respectively. The low viscosity RTIL, 1-ethyl-3-methylimidazolium tetracyanoborate ([emim][B(CN)4]) possesses a high CO2 solubility, and plays a significant role in CO2 separation, whereas PVDF provides the mechanical strength to the blend membranes. A series of PVDF/[emim][B(CN)4] polymer blends with different compositions were tested for their gas separation performance involving H2, N2 and CO2 in both pure gas and mixed gas conditions. Both optical observation and Maxwell predictions confirm the heterogeneous nature of the PVDF/[emim][B(CN)4] system. However, compared to miscible ionic liquid based blends, where molecular level interactions may restrain chain flexibility and reduce gas permeability, heterogeneous PVDF/RTIL blend systems show far superior gas transport properties. Most of these blend membranes outperform most reported materials and their gas transport and separation capabilities fall within the attractive region bound by the “2008 Robeson Upper Limit” for CO2/H2 and CO2/N2 gas pairs, and are also very stable at trans-membrane pressure up to 5 atm. Therefore, they are potential materials for H2 purification and CO2 capture from hydrogen production and flue gas.  相似文献   

8.
In this study, novel sodium titanate (Na2Ti3O7) nanotube/Nafion® composite membranes were prepared by a solution casting method. The properties of these composite membranes were studied using Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM). Additionally, the water uptake, methanol permeability, proton conductivity, and selectivity of the composite membranes were measured to evaluate the applicability of these membranes in DMFCs. It was found that the addition of Na2Ti3O7 nanotubes enhanced the water uptake and reduced the methanol permeability of the composite membranes. The proton conductivity and methanol permeability depend on the Na2Ti3O7 nanotube content. Using the selectivity, the optimal nanotube contents was found to be 5 wt%. The new composite membrane was found to have significantly higher selectivity than a pure Nafion® membrane and thus has good potential to outperform Nafion® in DMFCs.  相似文献   

9.
Industrial hydrogen production may prefer CO2-selective membranes because high-pressure H2 can therefore be produced without additional recompression. In this study, high performance CO2-selective membranes are fabricated by modifying a polymer–silica hybrid matrix (PSHM) with a low molecular weight poly(ethylene glycol) dimethyl ether (PEGDME). The liquid state of PEGDME and its unique end groups eliminate the crystallization tendency of poly(ethylene glycol) (PEG). The methyl end groups in PEGDME hinder hydrogen bonding between the polymer chains and significantly enhance the gas diffusivity. In pure gas tests, the membrane containing 50 wt% additive shows CO2 gas permeability and CO2/H2 selectivity of 1637 Barrers and 13 at 35 °C, respectively. In order to explore the effect of real industrial conditions, the gas separation performance of the newly developed membranes has been studied extensively using binary (CO2/H2) and ternary gas mixtures (CO2/H2/carbon monoxide (CO)). Compared to pure gas performance, the second component (H2) in the binary mixed gas test reduces the CO2 permeability. The presence of CO in the feed gas stream decreases both CO2 and H2 permeability as well as CO2/H2 selectivity as it reduces the concentration of CO2 molecules in the polymer matrix. The mixed gas results affirm the promising applications of the newly developed membranes for H2 purification.  相似文献   

10.
The present study explores the fundamental science of estimating sorption of gases in membranes comprised of inorganic porous fillers within a polymer matrix with a novel semi-empirical correlation. The sorption properties of H2, C3H8, CO2 and CH4 were determined in polydimethylsiloxane (PDMS)/zeolite 4A mixed matrix membranes (MMMs) to assess the viability of these membranes for hydrogen purification and natural gas sweetening. Zeolite filling in MMMs results an increase in solubility over neat PDMS membrane. In addition, incorporation of zeolite 4A to PDMS membrane improved H2 permeation and H2/CH4 selectivity. The results confirmed that zeolite 4A can significantly improve the separation properties of poorly H2-selective PDMS membrane from 0.7 up to 11 and this overcomes the Robeson upper-bound limitation. This improvement was explained referring the Flory–Huggins interaction parameter within MMMs.  相似文献   

11.
Sulfonated-silica/Nafion® composite membranes were prepared in a sol–gel reaction of (3-Mercaptopropyl)trimethoxysilane (SH-silane) followed by solution casting, and then oxidated using 10 wt% H2O2 solution. The chemical and physical properties of the composite membranes were characterized by using FT-IR, XPS, 29Si NMR and SEM analyses. Experimental results indicated that the optimum oxidation condition was 60 °C for 1 h. The performance of the silica–SO3H/Nafion® composite membranes was evaluated in terms of methanol permeability, proton conductivity and cell performance. The silica–SO3H/Nafion® composite membranes have a higher selectivity (C/P ratio = 26,653) than that of pristine Nafion® (22,795), perhaps because of their higher proton conductivity and lower methanol permeability. The composite membrane with 0.6 wt% silica–SO3H/Nafion® performed better than pristine Nafion®. The current densities were measured as 62.5 and 70 mA cm−2 at a potential of 0.2 V with a composite membrane that contained 0 and 0.6 wt% silica–SO3H, respectively. The cell performance of the DMFC was improved by introducing silica–SO3H. The composite membrane with 0.6 wt% of silica–SO3H yielded the maximum power density of 15.18 mW cm−2. The composite membranes are suitable for DMFC applications with high selectivity.  相似文献   

12.
Gas permeability through synthesized polydimethylsiloxane (PDMS)/zeolite 4A mixed matrix membranes (MMMs) were investigated with the aid of artificial neural network (ANN) approach. Kinetic diameter and critical temperature of permeating components (e.g. H2, CH4, CO2 and C3H8), zeolite content and upstream pressure as input variables and gas permeability as output were inspected. Collected data of the experimental operation was used to ANN training and optimum numbers of hidden layers and neurons were obtained by trial-error method. The selected ANN architecture (4:10:1) was used to predict gas permeability for different inputs in the domain of training data. Based on the results, the predicted values demonstrate an excellent agreement with the experimental data, with high correlation (R2 = 0.9944) and less error (RMSE = 1.33E−4). Furthermore, using sensitivity analysis, kinetic diameter and critical temperature were found as the most significant effective variables on gas permeability. As a result, ANN can be recommended for the modeling of gas transport through MMMs.  相似文献   

13.
In this work, we proposed a mixed matrix membrane prepared by using a glycerol modified guar gum (GGP) polymer matrix incorporated with graphene oxide (GO). The influence of varying GO concentration on the gas separation performance was investigated and 2 wt% was found to be the optimum concentration for high performance. The 2 wt% GO mixed matrix membranes were further modified with Pd nanoparticles. When GO, and Pd nanoparticles were mixed, CO2 permeability increased by 49.94%, while the permeability of H2 gas molecules decreased by 98.11%, respectively, compared to the pristine GGP membrane. The selectivity of CO2/H2 was obtained as 18.27. The glass transition temperature of the membrane increased from 85 to 95.2 °C, tensile strength and elongation of the break were significantly improved by 29.09% and 84.37% through the addition of Pd and GO into the membrane. The scanning electron microscopy revealed a dense top surface after GO nanosheets incorporation. Further, the thermogravimetric analysis proposes that the modified membrane is thermally stable than GGP. Henceforth, the study suggests GO incorporation and Pd nanoparticles modification of guar gum membrane is a promising gas separation membrane with potentially high selectivity for CO2 gas.  相似文献   

14.
The novel contribution of the current study is to employ adaptive neuro-fuzzy inference system (ANFIS) for evaluation of H2-selective mixed matrix membranes (MMMs) performance in various operational conditions. Initially, MMMs were prepared by incorporating zeolite 4A nanoparticles into polydimethylsiloxane (PDMS) and applied in gas permeation measurement. The gas permeability of CH4, CO2, C3H8 and H2 was used for ANFIS modeling. In this manner, the H2/gas selectivity as the output of the model was modeled to the variations of feed pressure, nanofiller contents and the kind of gas, which were defined as input (design) variables. The proposed method is based on the improvement of ANFIS with genetic algorithm (GA) and particle swarm optimization (PSO). The PSO and GA were applied to improve the ANFIS performance. To determine the efficiency of PSO-ANFIS, GA-ANFIS and ANFIS models, a statistical analysis was performed. The results revealed that the PSO-ANFIS model yields better prediction in comparison to two other methods so that root mean square error (RMSE) and coefficient of determination (R2) were obtained as 0.0135 and 0.9938, respectively. The RMSE and R2 values for GA-ANFIS were 0.0320 and 0.9653, respectively, and for ANFIS model were 0.0256 and 0.9787, respectively.  相似文献   

15.
It has been shown that hydrogen, which can be used for energy storage, can be produced efficiently by the membrane based Hybrid Sulfur (HyS) process. During the HyS electrolysis step, SO2 and H2O are converted to H2 and H2SO4, which implies that membranes to be used for this process should have both a high proton conductivity and acid stability. In this study ionic and ionic-covalently cross-linked polybenzimidazole (PBI) blended membranes were investigated and compared with Nafion®212 in terms of their acid stability. Characterization of the membranes, which included monitoring the change in weight, swelling, SEM/EDX, TEM, TGA-MS, FTIR and IEC before and after H2SO4 treatment showed that all tested membranes were stable in 80 wt% H2SO4 at 80 °C for 120 h. Subsequent HyS electrolysis showed that the blend membranes performed better than Nafion®115 at current densities below 0.3 A/cm2, while performing similar above 0.3 A/cm2.  相似文献   

16.
Polymeric membranes offer economic separation processes but are less explored for H2 separation application. This work aims to unveil the H2 separation potential of polymeric membrane by developing PVA-based reverse selective composite membrane. CO2-selective PEBAX was blended at different PVA:PEBAX ratio. The effect of PEBAX blending on membrane morphology, crystallinity and gas separation behavior was studied. Incorporation of PEBAX at <50 wt% resulted in composite with improved CO2 permeability but selectivity loss. Blending of >60 wt% PEBAX enhanced both permeance and selectivity of the resulted composite as the host matrix was dominated by this PEO containing material thus greatly enhancing polymer chain mobility and promoting CO2-solubility. The best composite which contains 60 wt% PEBAX exhibited CO2 permeability of 20.0 Barrer and CO2/H2 selectivity of 7.6. This performance surpasses the Robeson's boundary and unleashes the potential of tailoring the properties of polymeric nanocomposite membrane for H2 separation application through facile PVA/PEBAX blending.  相似文献   

17.
Two types of advanced nano-composite materials have been formed by incorporating as-synthesized wet-state zeolitic imidazolate frameworks-8 (ZIF-8) nano-particles into a polybenzimidazole (PBI) polymer. The loadings of ZIF-8 particles in the two membranes (i.e., 30/70 (w/w) ZIF-8/PBI and 60/40 (w/w) ZIF-8/PBI) are 38.2 vol % and 63.6 vol %, respectively. Due to different ZIF-8 loadings, variations in particle dispersion, membrane morphology and gas separation properties are observed. Gas permeation results suggest that intercalation occurs when the ZIF-8 loading reaches 63.6 vol %. The incorporation of ZIF-8 particles significantly enhances both solubility and diffusion coefficients but the enhancement in diffusion coefficient is much greater. Mixed gas tests for H2/CO2 separation were conducted from 35 to 230 °C, and both membranes exhibit remarkably high H2 permeability and H2/CO2 selectivity. The 30/70 (w/w) ZIF-8/PBI membrane has an H2/CO2 selectivity of 26.3 with an H2 permeability of 470.5 Barrer, while the 60/40 (w/w) ZIF-8/PBI membrane has an H2/CO2 selectivity of 12.3 with an H2 permeability of 2014.8 Barrer. Mixed gas data show that the presence of CO or water vapor impurity in the feed gas stream does not significantly influence the membrane performance at 230 °C. Thus, the newly developed H2-selective membranes may have bright prospects for hydrogen purification and CO2 capture in realistic industrial applications such as syngas processing, integrated gasification combined cycle (IGCC) power plant and hydrogen recovery.  相似文献   

18.
Metal organic frameworks (MOFs) with marvelous properties have aroused enormous attention for different application especially gas adsorption and separation. In this regard, fabrication of MOF hybrids with carbon based materials is new strategy to upgrade MOF performance. In this study CuBTC (Copper benzene-1,3,5-tricarboxylic acid)/graphene oxide (GO) composite was synthesized and characterized by BET, SEM, TGA, XRD and FT-IR techniques. Then CuBTC and CuBTC/GO composite were incorporated into polysulfone (PSF) polymer to construct mixed matrix membranes (MMMs). The obtained membranes were characterized by SEM, TGA, XRD and tensile tests and their gas permeability was measured. The results were compared to those of CuBTC/PSF MMMs. It was revealed that CuBTC/GO composite as filler showed superior performance relative to CuBTC. For instance, 15 wt% loading of CuBTC/GO in PSF represented outstanding gas separation behavior while the same loading of CuBTC in PSF deteriorated performance of MMM. Well particle dispersion and favorable polymer-filler interaction were responsible for such observed difference. A high H2/CH4 and H2/N2 selectivity of 80.03 and 70.46 were recorded for CuBTC/GO in PSF (15 wt%) compared to 44.56 and 40.92 for CuBTC in PSF (15 wt%).  相似文献   

19.
This work has been focused on the characterization of the methanol permeability and fuel cell performance of composite Nafion/PVA membranes in function of their thickness, which ranged from 19 to 97 μm. The composite membranes were made up of Nafion® polymer deposited between polyvinyl alcohol (PVA) nanofibers. The resistance to methanol permeation of the Nafion/PVA membranes shows a linear variation with the thickness. The separation between apparent and true permeability permits to give an estimated value of 4.0 × 10−7 cm2 s−1 for the intrinsic or true permeability of the bulk phase at the composite membranes. The incorporation of PVA nanofibers causes a remarkable reduction of one order of magnitude in the methanol permeability as compared with pristine Nafion® membranes. The DMFC performances of membrane-electrode assemblies prepared from Nafion/PVA and pristine Nafion® membranes were tested at 45, 70 and 95 °C under various methanol concentrations, i.e., 1, 2 and 3 M. The nanocomposite membranes with thicknesses of 19 μm and 47 μm reached power densities of 211 mW cm−2 and 184 mW cm−2 at 95 °C and 2 M methanol concentration. These results are comparable to those found for Nafion® membranes with similar thickness at the same conditions, which were 210 mW cm−2 and 204 mW cm−2 respectively. Due to the lower amount of Nafion® polymer present within the composite membranes, it is suggested a high degree of utilization of Nafion® as proton conductive material within the Nafion/PVA membranes, and therefore, significant savings in the consumed amount of Nafion® are potentially able to be achieved. In addition, the reinforcement effect caused by the PVA nanofibers offers the possibility of preparing membranes with very low thickness and good mechanical properties, while on the other hand, pristine Nafion® membranes are unpractical below a thickness of 50 μm.  相似文献   

20.
The SO2 transport properties of Nafion® and sPEEK membranes were measured using an electrochemical reaction cell to investigate their application in the electrochemical hybrid sulfur process. The permeability of SO2 in the membranes was determined from a combined theory based on Faraday's law and Fick's law where the electrochemical reaction rate of SO2 in the downstream membrane is the same as its diffusion flux through the membrane. Both Nafion® and sPEEK membranes show higher SO2 diffusion coefficients at higher temperatures. For sPEEK membranes, increasing the degree of sulfonation resulted in increasing permeability, as more water was imbibed in the membranes with higher degrees of sulfonation. Activation energy was extracted from the temperature-dependence of the diffusion coefficients for both membranes. The sPEEK membranes exhibited similar diffusion coefficients to those of Nafion®, even at high sulfonation degrees of 70%. Besides SO2 permeability, proton conductivity and mechanical properties were measured for comparison between the 2 polymer membranes. Although the proton conductivity of the sPEEK was slightly lower than the Nafion® membrane, it was very competitive considering its higher mechanical strength and much lower cost.  相似文献   

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