Modification of carbon membranes and preparation of carbon-zeolite composite membranes with zeolite growth

A novel method for the modification of carbon membranes was developed by zeolite growth on the surface of porous carbon tubes using a hydrothermal synthesis method and carbon-zeolite composite membranes were successfully obtained. Zeolite seeds for the zeolite growth were introduced to the inner surface of the tubes by using a slip-casting technique in 1 wt.% seed ethanol solution and continuous and highly intergrown zeolite layers on the seeded tubes were formed by subsequent hydrothermal synthesis. Different types of zeolite layers can be grown on porous carbon tubes by using different types of zeolite seeds. Without zeolite seeds, a zeolite layer could not be formed on the carbon surface. SEM, XRD and pure gas permeation characterization indicates that the carbon-zeolite membranes are continuous and defect-free.     

Maxwell-Stefan理论模拟NaA沸石膜分离一氯甲烷中微量水的渗透特性

通过热浸渍晶种法制备了高质量的NaA沸石膜,并将其应用于蒸汽渗透脱除一氯甲烷中的微量水. 实验结果表明,NaA膜对该体系显示了优异的分离性能,水对一氯甲烷的分离系数高达74831,产品中的水含量从0.2582%(w)降低到0.005%(w). 将基于Maxwell-Stenfan理论和Langmuir理想吸附理论推导的吸附-扩散模型用于模拟水渗透流速与渗透侧真空度和进料温度的关系,预测趋势与实验值吻合很好,且拟合得到的参数与文献报道较接近,表明水蒸汽在NaA沸石膜中的传递为表面扩散机制,水蒸汽的吸附对渗透速率的贡献很大. 水蒸汽的吸附热为-34.15 kJ/mol.     

P型沸石膜的合成及表征

采用水热合成法,详细考察了凝胶碱度对P沸石及其膜的合成的影响,发现凝胶碱度变化对合成晶化产物结构具有决定性影响,确定在实验条件下最佳合成碱度为Na2O/H2O=0.0163~ 0.0212. 在长250 mm、平均孔径3~5 mm的a-Al2O3陶瓷管外表面经二次涂膜,直接原位合成出膜厚约10~12 mm的沸石膜;XRD, SEM及H2, N2单组分气体渗透表征测试表明,载体管上的晶粒均匀规整,互锁状生长,为典型的P型沸石膜, H2和N2在膜内外压差为60~60 kPa范围内(25oC时),渗透速率分别为(3.60~3.99)10-6和(1.13~1.24)10-6 mol/(sm2Pa),同时具有较好的H2/N2选择系数(3.19~3.33).     

SYNTHESIS OF WELL-CRYSTALLIZED ZEOLITE BETA AT LARGE SCALE AND ITS INCORPORATION INTO POLYSULFONE MATRIX FOR GAS SEPARATION

Using a silica source with high specific surface area, aluminum zeolite beta was successfully synthesized in a very short crystallization period through the conventional hydrothermal route. The obtained materials were characterized by means of XRD, TEM, FESEM, EDS, TGA/DTG, and N₂ adsorption/desorption techniques. It is found that the well-crystallized zeolite beta can be rapidly synthesized at 170°C in 9 h and the highly porous silica source used could be completely converted into zeolite beta. No difference results from the silica source used. Moreover, through this synthesis route, it is also possible to conveniently obtain zeolite beta at high yield for manufacturing composite membranes for gas separations. The gas permeation tests show that the incorporation of porous zeolite beta into a polymer has modified the gas permeation properties significantly, indicating industrial application potential of this new type of composite material.     

Creatinine adsorption capacity of electrospun polyacrylonitrile (PAN)‐zeolite nanofiber membranes for potential artificial kidney applications

Innovative dialysis membranes are needed for dialysis, which is the primary treatment for patients with end stage renal disease. In this study, we developed a polyacrylonitrile zeolite nanofiber composite membrane using an electrospinning process to adsorb uremic toxins through molecular sieve mechanism. Scanning electron microscope images revealed that the average diameter of the fiber fabricated with 10 wt % polyacrylonitrile was 673 nm and that of polyacrilonitirle‐zeolite membranes were 277?419 nm. The creatinine adsorption behavior of 500‐KOA (L), 720‐KOA (Farrierite), 840‐NHA (ZSM‐5), and 940‐HOA (Beta) zeolite powders were investigated. Among all the zeolites, 940‐HOA zeolites showed the best performance. The creatinine adsorption capacity of 940‐zeolite powders increased from 2234 µg/g in 50 µmol/L creatinine solution to 25423 µg/g in 625 µmol/L creatinine solution. The speed of adsorption was very quick; 0.025 g of 940‐zeolite powders can eliminate 91% of 2 µmol creatinine in 5 min. The zeolites incorporated inside the membrane had higher creatinine adsorption capacity than free zeolites. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42418.     

Analysis of transient permeation fluxes into and out of membranes for adsorption measurements

A relationship between the integrated fluxes into and out of a membrane following a positive or negative step change in feed concentration was derived. This analysis allows adsorption isotherms in the transport pathways through membranes to be determined from transient permeation responses to step concentration changes in the feed without measuring the retentate response. For Fickian diffusion through a membrane with Langmuir adsorption and zero coverage at the permeate boundary, the difference between the time-integrated flux into and flux out of the membrane is shown to be three times the time-integrated difference between the steady-state flux and the flux out. For Maxwell-Stefan diffusion, this ratio of integrated flux differences is 3 at low coverages and decreases towards 2 at saturation coverage. Mass transfer resistance at the permeate boundary increases the Fickian ratio above 3, and the ratio increases with decreasing Sherwood number. The ratio of integrated flux differences is shown to be identical to the steady-state replenishment time divided by the time lag. Thus, the ratio can be calculated directly from the steady-state concentration profile and the concentration-dependent diffusion coefficient. Surface diffusion through zeolite membranes was analyzed to demonstrate the calculation of the flux relationship for specific adsorption and diffusion models, but the method developed can be applied to membrane permeation in general.     

Preparation of zeolite‐incorporated poly(dimethyl siloxane) membranes for the pervaporation separation of isopropyl alcohol/water mixtures

ZSM‐5 zeolite‐incorporated poly(dimethyl siloxane) membranes were prepared, and the molecular dispersion of the zeolite in the membrane matrix was confirmed with scanning electron microscopy. After the swelling of the membranes was studied at 30°C, the membranes were subjected to the pervaporation separation of isopropyl alcohol/water mixtures at 30, 40, and 50°C. The effects of the zeolite loading and feed composition on the pervaporation performances of the membranes were analyzed. Both the permeation flux and selectivity increased simultaneously with increasing zeolite content in the membrane matrix. This was examined on the basis of the enhancement of hydrophobicity, selective adsorption, and the establishment of molecular sieving action. The membrane containing the highest zeolite loading (30 mass %) had the highest separation selectivity (80.84) and flux (6.78 × 10^?2 kg m^?2 h^?1) at 30°C with 5 mass % isopropyl alcohol in the feed. From the temperature dependence of the diffusion and permeation values, the Arrhenius activation parameters were estimated. A pure membrane exhibited higher activation energy values for permeability (E_p) and diffusivity (E_D) than zeolite‐incorporated membranes, and signified that permeation and diffusion required more energy for transport through the pure membrane because of its dense nature. Obviously, the zeolite‐incorporated membranes required less energy because of their molecular sieving action, which was attributed to the presence of straight and sinusoidal channels in the framework of the zeolite. For the zeolite‐incorporated membranes, the activation energy values obtained for isopropyl alcohol permeation were significantly lower than the water permeation values, and this suggested that the zeolite‐incorporated membranes had higher selectivity toward isopropyl alcohol. The E_p and E_D values ranged between 21.81 and 31.12 kJ/mol and between 15.27 and 41.49 kJ/mol, respectively. All the zeolite‐incorporated membranes exhibited positive values of the heat of sorption, and this suggested that the heat of sorption was dominated by Henry's mode of sorption. sorption. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1377–1387, 2005     

C4烷烃在ZSM-5分子筛和Y分子筛上的吸附和扩散研究

采用气相色谱法研究了正丁烷和异丁烷在ZSM-5分子筛和Y分子筛上的扩散性能。烃分子的吸附平衡常数随温度的升高而降低，而扩散系数随温度的升高而增大。研究发现，烃分子的有效分子直径和分子形状是决定其扩散快慢的主要因素，同时分子筛孔道的大小对烃分子的扩散也存在影响，分子筛孔道越大，烃分子的扩散越快。     

Performance of zeolite powder and tubular membrane having different Si/Al ratio for removing As(III) in aqueous phase

Three different types of zeolite having pore sizes in the range 0.26‐0.74 nm, (NaP, NaA, and NaY) powders and membranes are synthesized with different Si:Al ratio on low cost clay alumina tubular support. The results of the permeation and separation studies showed that the NaP zeolite powder and membrane removes maximum As(III) from the water solution (more than 80%) compared to other zeolites. The removal of As(III) to achieve drinking water standard, by zeolite membrane, in a single step process does not seem to have been reported before the present investigation. These are the novelty achieved.     

SSZ-13沸石粒径及硅铝比对甲醇制烯烃反应性能的影响

通过调控合成配方,以水热合成法制备一系列不同粒径及硅铝比的SSZ-13沸石,考察沸石孔道结构、酸性质与催化性能之间的关系。采用XRD、SEM、XRF、N₂吸附-脱附以及²⁷Al MAS NMR对沸石样品进行详细的表征,并评价其甲醇制烯烃反应(MTO)催化性能。结果表明,小晶粒SSZ-13沸石相对结晶度高、晶粒尺寸均一;在MTO中,小晶粒SSZ-13沸石的MTO催化寿命大幅高于大晶粒SSZ-13沸石;减小晶粒尺寸可改善分子扩散效率,在此基础上提高沸石的酸密度可增加其活性稳定性。     

Synthesis and Characterization of Ceramic Membranes (W‐Type Zeolite Membranes)

In this article, effects of synthesis parameters (synthesis temperature, synthesis time, and number of layers) on W‐type zeolite membranes synthesized over flat SUS supports for O₂/SF₆ gas separation were experimentally investigated. Experiments were carried out at these levels of synthesis temperature: 165°C, 185°C, and 200°C; synthesis time: 6, 12, and 18 h and number of layers: 1 and 2. Permeation measurements, XRD and SEM analysis were used for characterization of the synthesized membranes. The results showed that increasing synthesis temperature from 165°C up to 185°C increases separation factor of O₂/SF₆, however, further increasing decreases the separation performance. The same trend was observed for synthesis time for the single layer synthesized zeolite W membrane, although for the double layer synthesized zeolite W membrane, separation factor increased with increasing synthesis time. Repetition of layering has a net positive effect on separation factor of O₂/SF₆, and negative effect on permeation flux through the membranes. This behavior was attributed to the dual effect of synthesis temperature and synthesis time on selectivity. More zeolite crystals are deposited and larger crystals are formed at higher synthesis temperatures and longer synthesis times. Well W‐type zeolite membrane was synthesized at 185°C for 18 h with two repeating layers with a high separation factor of 20.1.     

Pervaporation of n‐butanol aqueous solution through ZSM‐5‐PEBA composite membranes

Composite membranes were prepared by incorporating ZSM‐5 zeolite into poly(ether‐block‐amide) (PEBA) membranes. These composite membranes were characterized by TGA, XRD, and SEM. The results showed that the zeolite could distribute well in the polymer matrix. And when the zeolite content reached 10%, the agglomeration of zeolite in the membranes was found. The composite membranes were used to the pervaporative separation of n‐butanol aqueous solution. The effect of zeolite content on pervaporation performance was investigated. With the contribution of preferential adsorption and diffusion of n‐butanol in the polymer matrix and zeolite channel, the 5% ZSM‐5‐PEBA membrane showed enhanced selectivity and flux. The effects of liquid temperature and concentration on separation performance were also investigated. All the composite membranes demonstrated increasing separation factor and permeation flux with increasing temperature and concentration. Incorporation of ZSM‐5 could decrease the activation energy of n‐butanol flux of the composite membrane. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

PREPARATION AND TESTING OF CARBON/SILICALITE-1 COMPOSITE MEMBRANES

Methods for preparation of carbon/silicalite-1 composite membranes have been developed. First, silicalite-1 membranes were prepared by in-situ hydrothermal synthesis on both porous alumina and metal disks. Preparation of the carbon/silicalite-1 composite membranes was accomplished by polymerizing furfuryl alcohol on the surface of the silicalite-1 membrane, followed by carbonizing the polymer layer in an inert atmosphere at 773 K. The pure silicalite-1 membrane showed no selectivity for single gases, indicating the presence of intercrystalline diffusion and viscous flow as the dominant transport mechanism. The carbon/zeolite composite membrane exhibited ideal selectivities for He/N₂, CO₂/N₂, and N₂/CH₄ of 11.99, 17.12, and 3.58 at room temperature. No permeation of n-butane and i-butane for the composite membrane was detected up to temperatures of 453 K, indicating that the pore size for the composite membrane was approximately 0.4 nm. By carefully oxidizing the carbon layer in air at 623 K, the pore size of the composite membrane was adjusted such that n-butane permeation could be detected. No permeation of i-butane was apparent, suggesting that the pore size of the composite membrane had been enlarged to approximately 0.5 nm. Further oxidation of the carbon layer produced a finite n-/i-C₄H₄ ideal selectivity, indicating that the pore size of the membrane was now larger than 0.55 nm. Therefore, selective oxidation of the carbon layer can be used to control the pore size of the composite membrane.     

Enhancement of NaA zeolite membrane properties through organic cation addition

Thin NaA zeolite membranes, with uniform and small crystals, were prepared on the tubular -Al₂O₃ support by adding a small amount of tetramethylammonium hydroxide (TMAOH) in the clear synthesis solution. The as-synthesized NaA zeolite membranes were characterized by XRD and SEM. The permeation properties of the membranes were evaluated by pervaporation and gas permeation. The effects of TMAOH amount on membrane formation and permeation properties were investigated. By addition of suitable amount of TMAOH in the clear synthesis solution, the crystals size of NaA zeolite could be remarkably reduced from about 10 μm to 3–4 μm, and the membrane thickness correspondingly reduced from about 16 μm to 5 μm. The thinner membrane prepared by adding TMAOH in the clear synthesis solution, with uniform and small crystal, displayed higher perm-selective properties than that without adding TMAOH. For the as-synthesized NaA zeolite membrane prepared with adding suitable amount of TMAOH (x = 1), the separation factor (water/isopropanol) was 4700 and the flux was 1.67 kg/(m² h), which were higher than that without adding TMAOH of 339 and 1.08 kg/(m² h), respectively. The ideal separation factor of H₂/N₂ was 6.60, higher than that without adding TMAOH of 3.41.     

催化裂化催化剂生产过程中分子筛粉碎技术的应用

在催化裂化催化剂生产过程中为了提高超稳分子筛的有效利用率,提升产品质量,使用了一系列超稳分子筛粉碎技术。对超稳分子筛聚集的原因及粉碎技术进行了对比分析,重点分析了介质超细研磨粉碎技术对催化剂质量指标的影响。造成超稳分子筛粒子聚集的主要原因是NaY分子筛合成过程中粒子间相互吸附,后续分子筛交换改性工序对分子筛粒度分布影响较小。介质超细研磨机和干磨粉碎技术对粉碎超稳分子筛效果明显,能够有效降低分子筛粒径,在催化裂化催化剂生产过程中介质超细研磨机的应用效果较好。经粉碎后的超稳分子筛能够明显降低催化裂化催化剂的磨损指数,提高微反活性。     

Thermal Stability of Silica-Zirconia Membranes

The thermal stability, phase transformation, surface morphology, pore size distribution and permeation of the defect-free silica-zirconia membrane were investigated by using X-ray diffraction （XRD）, atomic force microscopy （AFM）, gas adsorption analyzer （BET）, and gas permeation apparatus, respectively. Using silica as the stabilizing agent, the defect-free membrane was much more stable than pure zirconia. The crystal transformation of zirconia in the silica-stabilized membrane could be prohibited by the interaction between silica and zireonia. ZrO2 crystals were kept tetragonal below 900℃, the size of which did not change with temperature between 700℃ and 900℃. It was further verified by the AFM observation, pore size analysis and permeation study. This thermal stability makes the silica-zirconia membrane a good choice as the intermediate layer for zeolite and Pd-based membranes.     

Preparation and permeation characterization of β‐zeolite‐incorporated composite membranes

In this work, several β‐zeolite‐incorporated polymer composite membranes were fabricated with the solution‐casting method. The zeolite loadings were 10, 20, and 30 wt %, respectively. Scanning electron microscopy characterization showed that the zeolite particles could be uniformly distributed in the whole polymer matrix. Gas permeation results demonstrated that after the incorporation of the same β‐zeolite, the polyimide exhibited a significant increase in gas permeability but a decrease in permselectivity, and both were quite pronounced at high zeolite loadings; this resulted from the loose structure that formed. The poly(ether sulfone) composite membranes showed obvious increases in both permeability and selectivity, and the permeability increase was considerably greater at higher zeolite loadings. The permselectivity increase could possibly be attributed to the pore sieving and preferential adsorption of β‐zeolite entities for the test gases as the heat treatment may have resulted in the formation of a defect‐free microstructure. However, breakthrough of the upper‐bound line was not achieved for these composite membranes, as reflected by Robeson plots. Our results suggest that changes in membrane performance not only are attributable to the properties and content of β‐zeolite particles but also depend on the heterogeneous microstructure created by zeolite entities. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Transient measurements of adsorption and diffusion in H-ZSM-5 membranes

A transient permeation method presented here not only determines the adsorption and diffusion properties of the pores that are the transport pathways through zeolite membranes, but nondestructively estimates the effective thickness of the membrane. Transient responses of the permeate concentration to step changes in the feed were measured on two H-ZSM-5 tubular membranes and modeled assuming Maxwell-Stefan diffusion and Langmuir adsorption. The adsorption isotherms determined from these transient measurements at 298 K of N₂ and CO₂ were nearly identical to those measured by calorimetry on H-ZSM-5 powders. The CH₄ isotherm at 298 K was similar to isotherms measured by calorimetry and gravimetric techniques on Na-ZSM-5 and silicalite powders. The similarity of the isotherms indicates that transport of these light gases occurs mainly through zeolite pores. The Maxwell-Stefan diffusion coefficients D_MS depended on concentration and were higher for higher feed partial pressures. Average D_MS values for the two membranes were 7.5, 5 and 1.5×10⁻¹⁰ m²/s for N₂, CH₄, and CO₂, respectively; these are in the same range and order as diffusion coefficients measured in zeolite crystals.     

Zeolite filled P84 co-polyimide membranes for dehydration of isopropanol through pervaporation process

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

Micropore size estimation on gas separation membranes: A study in experimental and molecular dynamics

The effect of the gas molecular size and its affinity to the pore surface on gas permeation properties through the ceramic membranes was studied by both the gas permeation experiments and gas permeation simulations using a nonequilibrium molecular dynamics (MD) technique. A modified gas permeation model equation based on the gas translation (GT) mechanism was presented. MD simulation revealed that the effective diffusion length in a micropore depended on the gas molecular size, and the pre‐exponential coefficient of a modified GT model equation showed good correlation with the kinetic diameter of the gas molecules. Also presented is a simple method to estimate the mean pore size of microporous membranes. The estimated pore sizes were consistent with observed kinetic diameter dependencies of gas permeance for real silica membranes. The pore size of a Deca‐Dodecasil 3R (DDR) zeolite membrane was also reasonably estimated at ～0.4 nm from the reported gas permeation data. © 2012 American Institute of Chemical Engineers AIChE J, 59: 2179–2194, 2013