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1.
Supported carbon molecular sieve membranes based on a phenolic resin   总被引:7,自引:0,他引:7  
The preparation of a composite carbon membrane for separation of gas mixtures is described. The membrane is formed by a thin microporous carbon layer (thickness, 2 μm) obtained by pyrolysis of a phenolic resin film supported over a macroporous carbon substrate (pore size, 1 μm; porosity, 30%). The microporous carbon layer exhibits molecular sieving properties and it allows the separation of gases depending on their molecular size. The micropore size was estimated to be around 4.2 Å. Single and mixed gas permeation experiments were performed at different temperatures between 25°C and 150°C, and pressures between 1 and 3.5 bar. The carbon membrane shows high selectivities for the separation of permanent gases like O2/N2 system (selectivity≈10 at 25°C). Gas mixtures like CO2/N2 and CO2/CH4 are successfully separated by means of prepared membranes. For example, the membrane prepared by carbonization at 700°C shows at 25°C the following separation factors: CO2/N2≈45 and CO2/CH4≈160.  相似文献   

2.
A thin, gas-tight palladium (Pd) membrane was prepared by the counter-diffusion chemical vapor deposition (CVD) process employing palladium chloride (PdCl2) vapor and H2 as Pd precursors. A disk-shaped, two-layer porous ceramic membrane consisting of a fine-pore γ-Al2O3 top layer and a coarse-pore -Al2O3 substrate was used as Pd membrane support. A 0.5–1 μm thick metallic membrane was deposited in the γ-Al2O3 top layer very close to its surface, as verified by XRD and SEM with a backscattered electron detector. The most important parameters that affected the CVD process were reaction temperature, reactants concentrations and top layer quality. Deposition of Pd in the γ-Al2O3 top layer resulted in a 100- to 1000-fold reduction in He permeance of the porous substrate. The H2 permeation flux of these membranes was in the range 0.5–1.0 × 10−6 mol m−2 s−1 Pa−1 at 350–450°C. The H2 permeation data suggest that surface reaction steps are rate-limiting for H2 transport through such thin membranes in the temperature range studied.  相似文献   

3.
Among several different approaches to form Pd/Ag alloys for hydrogen separation applications, ex situ studies carried out by conventional X-ray point scanning detectors might fail to reveal the key aspects of the phase transformation between Pd and Ag metals. In this respect, in situ time-resolved high-temperature X-ray diffraction (HTXRD) was employed to study the Pd/Ag alloy phase nucleation and growth kinetics. By the use of linear position sensitive detectors, advanced optics and profile fitting with the use of JADE-6.5 software, isothermal phase evolution of the Pd/Ag alloy at 500 °C, 550 °C and 600 °C under hydrogen atmosphere were quantified to elucidate the mechanistic details of the Pd/Ag alloy phase nucleation and growth pattern. Analysis of the HTXRD data by the Avrami model indicated that the nucleation of the Pd/Ag alloy phase was instantaneous where the growth mechanism was through diffusion-controlled one-dimensional thickening of the Pd/Ag alloy layer. The value of the Avrami exponent, n, was found to increase with temperature with the values of 0.34, 0.39 and 0.67 at 500 °C, 550 °C and 600 °C, respectively. In addition, parabolic rate law analysis suggested that the nucleation of the Pd/Ag alloy phase was through a heterogeneous nucleation mode, in which the nucleation sites were defined as the non-equilibrium defects. Indeed, the cross-sectional SEI micrographs indicated that the Pd/Ag alloy phase growth was strongly dependent upon the deposition morphology of the as-synthesized Pd and Ag layers formed by the electroless plating. Based on the Avrami model and the parabolic rate law, the estimated activation energies for the phase transformation were 236.5 kJ/mol and 185.6 kJ/mol and in excellent agreement with the literature values (183–239.5 kJ/mol). Finally, the in situ annealing of the 15.6 μm thick composite Pd/Ag/PSS membrane at 550 °C in hydrogen atmosphere indicated that the Pd/Ag alloy phase formation was not complete even after 500 h. According to the Avrami model, the increase in the hydrogen permeance from 7.1 m3/m2 h atm0.5 to 21.3 m3/m2 h atm0.5 at 550 °C over a period of 500 h corresponded to an 83% Pd/Ag alloy phase formation.  相似文献   

4.
Aerosol flame pyrolysis deposition method was applied to deposit the oxide glass electrolyte film and LiCoO2 cathode for thin film type Li-ion secondary battery. The thicknesses of as-deposited porous LiCoO2 and Li2O–B2O3–P2O5 electrolyte film were about 6 μm and 15 μm, respectively. The deposited LiCoO2 was sintered for 2 min at 700 °C to make partially densified cathode layer, and the deposited Li2O–P2O5–B2O3 glass film completely densified by the sintering at 700 °C for 1 h. After solid state sintering process the thicknesses were reduced to approximately 4 μm and 6 μm, respectively. The cathode and electrolyte layers were deposited by continuous deposition process and integrated into a layer by co-sintering. It was demonstrated that Aerosol flame deposition is one of the good candidates for the fabrication of thin film battery.  相似文献   

5.
Preparation conditions to obtain a dense electrolyte layer on a micro-tubular electrode support were investigated using wet coating and subsequent co-firing techniques. An anode-supported micro-tubular SOFC with 1.5 mm diameter was successfully fabricated by careful control of the co-sintering process of electrolyte/anode support laminates. The densification of the electrolyte layer deposited on the support surface was greatly affected by the shrinkage of tubular support during the co-sintering process. Support shrinkage above 15% was found to produce a fully densified electrolyte layer on the anode support. In contrast, the use of an anode support with shrinkage below 10% constrained gadolinium-doped ceria (GDC) sintering, resulting in a poorly densified GDC microstructure. Finally, we obtained a micro-tubular cell composed of a dense GDC and a porous (La,Sr)(Co,Fe)O3–GDC multi-layered structure on a NiO–GDC micro-tubular anode support. The cell, with a dense and ≈15 μm thick GDC electrolyte layer, was electrochemically evaluated in a temperature range from 450 to 550 °C. This micro-tubular cell with an electrode length of 6.3 mm showed a power density above 0.1, 0.2 and 0.4 W/cm2 at 450, 500 and 550 °C, respectively, in wet H2 fuel flow.  相似文献   

6.
New types of supported Pd membranes were developed for high temperature H2 separation. Sequential combinations of boehmite sol slip casting and film coating, and electroless plating (ELP) steps were designed to synthesize “Pd encapsulated” and “Pd nanopore” membranes supported on -Al2O3 hollow fibers. The permeation characteristics (flux, permselectivity) of a series of unaged and aged encapsulated and nanopore membranes with different Pd loadings were compared to those of a conventional 1 μm Pd/4 μm γ-Al2O3/-Al2O3 hollow fiber membrane. The unaged encapsulated membrane exhibited good performance with ideal H2/N2 separation factors of 3000–8000 and H2 flux 0.4 mol/m2 s at 370 °C and a transmembrane pressure gradient of 4 × 105 Pa. The unaged Pd nanopore membranes had a lower initial flux and permselectivity, but exhibited superior performance with extended use (200 h). At the same conditions the unaged 2.6 μm Pd nanopore membrane had a H2 flux of 0.16 mol/m2 s and separation factor of 500 and the unaged 0.6 μm Pd nanopore membrane had a H2 flux of 0.25 mol/m2 s and separation factor of 50. Both nanopore membranes stabilized after 40 h of operation, in contrast to a continued deterioration of the permselectivity for the other membranes. An analysis of the permeation data reveals a combination of Knudsen and convective transport through membrane defects. A phenomenological, qualitative model of the synthesis and resulting structure of the encapsulated and nanopore membranes is presented to explain the permeation results.  相似文献   

7.
The hydrogen permeation and stability of tubular palladium alloy (Pd–23%Ag) composite membranes have been investigated at elevated temperatures and pressures. In our analysis we differentiate between dilution of hydrogen by other gas components, hydrogen depletion along the membrane length, concentration polarization adjacent to the membrane surface, and effects due to surface adsorption, on the hydrogen flux. A maximum H2 flux of 1223 mL cm−2 min−1 or 8.4 mol m−2 s−1 was obtained at 400 °C and 26 bar hydrogen feed pressure, corresponding to a permeance of 6.4 × 10−3 mol m−2 s−1 Pa−0.5. A good linear relationship was found between hydrogen flux and pressure as predicted for rate controlling bulk diffusion. In a mixture of 50% H2 + 50% N2 a maximum H2 flux of 230 mL cm−2 min−1 and separation factor of 1400 were achieved at 26 bar. The large reduction in hydrogen flux is mainly caused by the build-up of a hydrogen-depleted concentration polarization layer adjacent to the membrane due to insufficient mass transport in the gas phase. Substituting N2 with CO2 results in further reduction of flux, but not as large as for CO where adsorption prevail as the dominating flow controlling factor. In WGS conditions (57.5% H2, 18.7% CO2, 3.8% CO, 1.2% CH4 and 18.7% steam), a H2 permeance of 1.1 × 10−3 mol m−2 s−1 Pa−0.5 was found at 400 °C and 26 bar feed pressure. Operating the membrane for 500 h under various conditions (WGS and H2 + N2 mixtures) at 26 bars indicated no membrane failure, but a small decrease in flux. A peculiar flux inhibiting effect of long term exposure to high concentration of N2 was observed. The membrane surface was deformed and expanded after operation, mainly following the topography of the macroporous support.  相似文献   

8.
Hydrogen production by steam reforming of methane using catalytic membrane reactors was investigated first by simulation, then by experimentation. The membrane reactor simulation, using an isothermal and plug-flow model with selective permeation from reactant stream to permeate stream, was conducted to evaluate the effect of permselectivity on membrane reactor performance – such as methane conversion and hydrogen yield – at pressures as high as 1000 kPa. The simulation study, with a target for methane conversion of 0.8, showed that hydrogen yield and production rate have approximately the same dependency on operating conditions, such as reaction pressure, if the permeance ratio of hydrogen over nitrogen ((H2/N2)) is larger than 100 and of H2 over H2O is larger than 15. Catalytic membrane reactors, consisting of a microporous Ni-doped SiO2 top layer and a catalytic support, were prepared and applied experimentally for steam reforming of methane at 500 °C. A bimodal catalytic support, which allows large diffusivity and high dispersion of the metal catalyst, was prepared for the enhancement of membrane catalytic activity. Catalytic membranes having H2 permeances in the range of 2–5 × 10−6 m3 m−2 s−1 kPa−1, with H2/N2 of 25–500 and H2/H2O of 6–15, were examined for steam reforming of methane. Increased performance for the production of hydrogen was experimentally obtained with an increase in reaction-side pressure (as high as 500 kPa), which agreed with the theoretical simulation with no fitting parameters.  相似文献   

9.
Poly(N-isopropyl acrylamide) (PNIPAAm) was grafted on a polysulfone UF membrane. The changes of permeability as well as retention of PEG (35 kg/mol) and Dextran (500 kg/mol) between 23 and 60 °C were determined for both grafted and unmodified membranes. The results showed that the viscosity corrected water permeability and solute retention were almost constant for the unmodified membranes within the measured temperature range, the permeability of the grafted membranes increased and the retention of Dextran and PEG decreased with temperature. The variation of changes was most obvious in the temperature range 27–37 °C for the modified membranes due to the lower critical solution temperature (LCST) of PNIPAAm. The location and profile of PNIPAAm inside and on the surface of the membrane were analysed by SEM and FTIR. Depth profile calculation for FTIR spectra showed that PNIPAAm was mostly placed inside the membrane (at a depth of 1.06–1.10 μm from the surface) rather than on the surface. The amount of grafted PNIPAAm was low and did not significantly affect the morphology of the membrane. Therefore, a difference in SEM pictures of modified and unmodified membranes could not be seen. The modified membrane exhibited a clearly different thermal response compared to the unmodified one.  相似文献   

10.
In this experimental work the influence of co-existing gases on the hydrogen permeation through a Ti–Ni–Pd membrane was studied. It was found that nitrogen, carbon dioxide and helium do not influence the hydrogen permeation through the dense membrane. However, carbon monoxide influences the hydrogen flux at each temperature investigated (400–500 °C). The results show that for low CO concentration (i.e. at H2 upstream >80%), the hydrogen flux through the membrane decreases faster than linearly, while, at H2 upstream <80%, the slope is linear but smaller than the theoretical one.  相似文献   

11.
It is desirable to create thin (<25 μm), unsupported, defect-free palladium and palladium alloy foils in a cost-effective manner in order to study intrinsic material properties exclusive of support effects. We have developed a novel technique for producing unsupported palladium films by electroless plating upon mirror-finished stainless steel supports followed by mechanical removal. High quality pure palladium films as thin as 7.2 μm were produced. Single gas steady state permeation experiments were performed using hydrogen and nitrogen to examine permeability and selectivity. The pure palladium membranes showed hydrogen permeabilities comparable to cold-rolled unsupported foils, and high H2/N2 selectivity. Palladium-copper membranes were prepared by sequential electroless plating of copper onto palladium foils followed by in situ annealing. The annealing process produces films of desired composition with permeabilities comparable to those in the literature. The annealing process does not appear to produce defects in the film, and the membranes thus produced have performed 15 days without increased leak rates.  相似文献   

12.
Offwhite pure Fe_2P_2O_7 was synthesized through solid phase reaction using Fe_2O_3 and NH_4H_2PO_4 in argon atmosphere.The reaction products of Fe_2O_3 and NH4_H_2PO_4 at a series of temperatures from 400 to 900℃were characterized by XRD.Comparison and analysis of XRD patterns of resultant products indicated well-crystallized Fe_2P_2O_7 could be obtained over 630℃and Fe_2P_2O_7 prepared at 700℃was triclinic in cell type.Comparison of the cell parameters proved that the as-prepared Fe_2P_2O_7 belonged toβ- Fe_2P_2O_7 in crystal phase and SEM showed its size distribution was 0.5-2μm.  相似文献   

13.
The disruption of lipidic metabolism was considered a good candidate to explain FB1 toxicity mechanism. In the present work we investigated molecular organizational changes induced by FB1–biomembrane interaction possibly involved in mycotoxic effects.

FB1 was self-aggregated with a critical micellar concentration of 1.97 mM. FB1 (0–81.4 μM), decreased in a dose-dependent manner, the fluorescence anisotropy of TMA-DPH (from 0.349 ± 0.003 to 0.1720 ± 0.0035) in dpPC bilayers, whilst no differences were registered with DPH. At 5.6 μM in the subphase, FB1 increased the lateral surface pressure (π) of a Langmuir film to an extent that depended on the monolayer composition (ΔπdpPC:DOTAP 3:1 > ΔπdpPC:dpPA3:1 > ΔπdpPC), the molecular packing (Δπ decreased linearly as a function of the initial π) and the subphase pH (ΔπpH 2.6 > ΔπpH 7.4 and maximal π allowing the drug penetration πcut-off was 34.3 and 27.7 mN/m at pH 2.63 and 7.4, respectively). FB1 increased the surface potential of dpPC and dpPC:DOTAP monolayers and decreased that of dpPC:dpPA. This suggested that FB1 acquired different orientations and/or foldings depending on the surface electrostatics and the toxin charge state. Moreover, FB1–lipid interactions were transduced into long-range effects at the mesoscopic level affecting the lipidic self-separated lateral domains shape and density.  相似文献   


14.
Dense tubular Ba0.5Sr0.5Co0.8Fe0.2O3−δ (BSCFO) membranes were successfully prepared by the plastic extrusion method. The oxygen permeation flux was determined at different oxygen partial pressures in the shell side and different temperatures between 700 and 900 °C. The oxygen vacancy diffusion coefficients (Dv) at different temperatures were calculated from the dependence of oxygen permeation flux on the oxygen partial pressure term based on the surface current exchange model. No unsteady-state of oxygen permeation flux was observed at the initial stage in our experiments. The reason is the equilibrium time is too short (less than 10 min) to observe the unsteady-state in time. The increase of the helium flow rate can increase the oxygen permeation flux, which is due to the decrease of the oxygen partial pressure in the tube side with increasing of the helium flow rate. The oxygen permeation flux can also be affected by the air flow rate in the shell side when the air flow rate is lower than 150 ml/min. But the oxygen permeation flux is insensitive to the air flow rate when the air flow is higher than 150 ml/min. The membrane tube was operated steadily for 150 h with oxygen permeation flux of 1.12 ml/(cm2 min) at 875 °C. X-ray diffraction (XRD) and energy dispersive spectroscopy (EDS) analysis showed that both the surface exposed to air and the surface exposed to helium of the BSCFO membrane tube after permeation for 150 h are similar to the fresh membrane tube in composition and structure. These results indicated that the membrane tube exhibits high structure stability.  相似文献   

15.
Straight boron nitride nanotubes (BNNTs) with pure hexagonal phase were conveniently prepared by heating the mixture of Mg(BO2)2 · H2O, NH4Cl, NaN3 and Mg powder in an autoclave at 600 °C for 20–60 h. These BNNTs had diameters mainly ranging 30–300 nm and lengths up to 5 μm, and a majority of them had at least one closed end. Besides the traditional end tips, additional cone-like tips were frequently found to be attached on the BNNTs. The effects of temperature, reactants and the possible mechanism of the catalytic formation of the BNNTs are discussed.  相似文献   

16.
A Ni electroless plating process was used with polytetrafluoroethylene (PTFE) fine particles (25–500 μm). Using nonionic hydrocarbon surfactant, PTFE particles were dispersed in the plating bath. The PTFE hydrophobicity was sufficiently high that Ni was deposited partly on the PTFE surface in the initial step. The Ni-PTFE particles were formed into the Ni-PTFE plate by heat treatment at 350 °C after pressing. The Ni-PTFE plate had electrical conductivity and gas permeability, which were influenced by the pore distribution in the plate. Pores with 1 μm diameter might be especially important to impart high gas permeability to the Ni-PTFE plate.  相似文献   

17.
The liquid-phase alkylation of phenol with 1-dodecene was carried out over WOx/ZrO2 solid acid catalysts. The catalysts were prepared by wet impregnation method using zirconium oxyhydroxide and ammonium metatungstate. Catalysts with different WO3 loading (5–30 wt.%) were prepared and calcined at 800 °C and catalyst with 15% WO3 was calcined from 700–850 °C. All the catalysts were characterized by surface area, XRD, and FTIR. The catalyst with 15% WO3 calcined at 800 °C (15 WZ-800) was found to be the most active in the reaction. The effect of temperature, molar ratio and catalyst weight on dodecene conversion and products selectivity was studied in detail. Under the optimized reaction conditions of 120 °C, phenol/1-dodecene molar ratio 2 and time 2 h, the catalyst 15 WZ-800 gave >99% dodecene conversion with 90% dodecylphenol selectivity. Comparison of the catalytic activity of 15 WZ-800 with sulfated zirconia calcined at 500 °C (SZ-500) and Hβ zeolite showed that activity of SZ-500 was lower than that of 15 WZ-800, while Hβ zeolite showed negligible activity. It is observed that the presence of water in the reaction mixture was detrimental to the catalytic activity of WOx/ZrO2. The catalyst 15 WZ-800 also found to be an efficient catalyst for alkylation of phenol with long-chain olefins like 1-octene and 1-decene.  相似文献   

18.
Homogeneous membranes were prepared by casting the solution of blended chitosan and polyvinyl alcohol (PVA) on a glass plate. The percent weight of chitosan in the membrane was varied from 0 to 100%. The membrane thickness was in the range of 15–30 μm. The membranes were heat treated at 150 °C for an hour. After that the membranes were crosslinked by glutaraldehyde and sulfuric acid in acetone aqueous solution. The membranes were tested at 30–60 °C for dehydration performance of 50–95% isopropanol aqueous solutions. At around 90% of isopropanol in the feed mixture, permeate flux increased whereas the percent of water in permeate tended to decrease when the feed temperature increased for all membranes, except that the water content in permeate from the membrane containing 75 wt.% chitosan remained constant. The swelling degree in water and the total flux increased with increasing chitosan content in membranes. The effect of temperature on permeate flux followed the Arrhenius relationship. The permeate flux decreased when isopropanol in the feed increased for all membranes. However, water content in permeate and isopropanol concentration in the feed formed complex relationship for different chitosan content membranes. Sorption did not appear to have significant effects on separation. The membrane containing chitosan 75% performed the best. For a feed solution containing 90% isopropanol at 60 °C, the permeate flux was 644 g/m2 h with water content of nearly 100% in the permeate. At 55% isopropanol in the feed at 60 °C, the permeate flux was 3812 g/m2 h. In the range of 55–95% of isopropanol in the feed, the water content in permeate was more than 99.5%. This membrane showed very excellent performance with good mechanical strength. It is promising to develop this membrane for industrial uses.  相似文献   

19.
20.
Nanoparticles are expected to be applicable to inhalation as carrier but there exist disadvantages because of their size. Their deposition dose to the lung will be small. To overcome this problem and utilize nanoparticles for inhalation, we have prepared nanocomposite particles as drug carriers targeting lungs. The nanocomposite particles are prepared as drug-loaded nanoparticles–additive complex to reach deep in the lungs and to be decomposed into nanoparticles when they deposit into lung. In this study, we examined the effect of preparation condition – inlet temperature, size of primary nanoparticles and weight ratio of primary nanoparticles – on the property of nanocomposite particles.

When the size of primary nanoparticles was 400 nm and inlet temperature was 90 °C, only the nanocomposite particles containing between 45 and 55% of primary nanoparticles could be decomposed into nanoparticles in water. On the other hand, when the inlet temperature was 80 °C, nanocomposite particles were decomposed into nanoparticles independent of the weight ratio of primary nanoparticles. Also, the aerodynamic diameter of the nanocomposite particles was between 1.5 and 2.5 μm, independent of the weight ratio of primary nanoparticles.

When the size of primary nanoparticles was 200 nm and inlet temperature was 70 °C, nanocomposite particles were decomposed into nanoparticles independent of the weight ratio of primary nanoparticles. Also, the aerodynamic diameters of them were almost 2.0 μm independent of the weight ratio of primary nanoparticles. When the nanocomposite particles containing nanoparticles with the size of 200 nm are prepared at 80 °C, no decomposition into nanoparticles was observed in water.

Fine particle values, FPF, of the nanocomposite particles were not affected by the weight ratio of primary nanoparticles when they were prepared at optimum inlet temperature.  相似文献   


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