Evaluation of fine structure of tubular zeolite NaA membrane by FTIR-ATR and FIB-TEM.

A zeolite NaA (LTA) membrane supported by an alumina porous support tube for pervaporation (PV) dehydration of ethanol was characterized by transmission electron microscopy (TEM) using a focused ion beam (FIB) thin-layer specimen preparation technique and by Fourier transform infrared attenuated total reflectance method (FTIR-ATR) using a diamond prism as the waveguide. FIB-TEM clearly presented cross-section images up to about 15 microm depth from the membrane surface. FTIR-ATR monitored the Si-O asymmetric stretching vibration spectrum. The Si-O spectrum was compared with the TEM image and their relationships were discussed. By combining the two methods, we could study the thickness of surface LTA crystals, the grain boundary, the LTA/alumina interface structure and the crystallinity and density of materials inside of the alumina porous support. Consequently, fine structure changes of the LTA membrane corresponding to the hydrothermal synthesis condition could be sensitively detected.     

Evaluation of the dehydration performance of zeolite NaA membrane on porous alumina tube by the alumina X-ray diffraction intensity.

A zeolite NaA (A-type zeolite of ca. 0.4 nm pore size; Linde Type A, LTA) membrane for the dehydration of alcohol was characterized by X-ray diffraction analysis (XRD). Also, the relationship between the X-ray absorption and the EtOH/H2O pervaporation (PV) dehydration performance (water selectivity and permeation flux) of the LTA membrane was first investigated. The LTA membranes used here were gel-synthesized hydrothermally on an alumina porous support tube. Since diffraction lines from the alumina generate from a deeper layer than those of the LTA crystal, and are absorbed by both the surface LTA crystal and materials embedded in the alumina porous support, the alumina (113) diffraction line was intensively monitored to estimate the overall X-ray absorption by the LTA membrane. The intensity of the alumina (113) diffraction line showed a good correlation with the PV dehydration performance of the LTA membrane, that is, lower values with the water selectivity and higher values with the permeation flux. The lower diffraction intensity means stronger X-ray absorption by the LTA membrane. The major factor causing the difference in the X-ray absorption is the thickness or quantity of materials embedded in an alumina porous support, rather than those of the surface LTA crystal. These phenomena can be used conveniently (without real PV experiments) to determine the EtOH/H2O PV dehydration performance of the LTA membrane.     

FTIR-ATR study of the surface of a tubular zeolite NaA membrane ultrasonically reacted with water and acetic acid.

For the dehydration process of biomass alcohol using a zeolite NaA (LTA) membrane supported by an alumina porous support tube, it is very important to understand damage of the surface crystal, which may be caused by acetic acid. Therefore, the surface structure and the chemical composition of the LTA membrane that reacted with water or acetic acid (pH 3-4) were investigated by the Fourier Transform Infrared Attenuated Total Reflectance method (FTIR-ATR), with a diamond prism as the waveguide, scanning electron microscope and an energy-dispersive X-ray analysis. For leaching experiments using water and acetic acid, ultrasonication was applied to promote the leaching rate and to surely prepare damaged membranes as a model experiment. The Si-O asymmetric stretching vibration spectra of the original LTA membranes showed a bimodal peak. LTA membranes after water leaching also showed the same peak. However, for the LTA membrane reacted with acetic acid of pH 3, damage of the surface LTA crystal and the loss of sodium by dissolution were clearly observed. Also, its Si-O spectral shape was broad, which suggests amorphous-like substances secondarily formed on the membrane surface. Sodium acetate was not detected for all LTA membranes reacted with acetic acid. To evaluate surface-damaged and sodium-loss membranes, FTIR-ATR can sensitively detect a Si-O spectral change corresponding to the surface structure and the chemical composition of the LTA membrane.     

间歇式水热合成制备丝光沸石膜及其异丙醇脱水应用

采用市售廉价大孔α-Al₂O₃管作为基质材料,通过热浸渍法在管外表面涂敷晶种,随后在无模板剂体系下,利用新型的间歇式水热合成法制备丝光沸石膜。对比了传统加热和间歇式加热对丝光沸石膜形貌、结构及渗透蒸发异丙醇脱水分离性能的差异。考察了合成液中Na₂O/SiO₂、SiO₂/Al₂O₃和NaF/SiO₂物质的量之比在间歇式水热合成下对丝光沸石膜的影响。研究结果表明,当合成液中Na₂O/SiO₂、SiO₂/Al₂O₃和NaF/SiO₂物质的量之比分别为0.24、16.7和0.25时,制备的丝光沸石膜渗透蒸发异丙醇脱水分离性能最佳,在75℃下,对异丙醇/水(9∶1,w/w)的渗透通量达5.60 kg·m^-2·h^-1,水对异丙醇的分离因数大于10 000。     

间歇式水热合成制备丝光沸石膜及其异丙醇脱水应用

采用市售廉价大孔α-Al₂O₃管作为基质材料,通过热浸渍法在管外表面涂敷晶种,随后在无模板剂体系下,利用新型的间歇式水热合成法制备丝光沸石膜。对比了传统加热和间歇式加热对丝光沸石膜形貌、结构及渗透蒸发异丙醇脱水分离性能的差异。考察了合成液中Na₂O/SiO₂、SiO₂/Al₂O₃和NaF/SiO₂物质的量之比在间歇式水热合成下对丝光沸石膜的影响。研究结果表明,当合成液中Na₂O/SiO₂、SiO₂/Al₂O₃和NaF/SiO₂物质的量之比分别为0.24、16.7和0.25时,制备的丝光沸石膜渗透蒸发异丙醇脱水分离性能最佳,在75℃下,对异丙醇/水(9:1,w/w)的渗透通量达5.60 kg·m^-2·h^-1,水对异丙醇的分离因数大于10 00...     

23Na NMR study of the mechanism for the dehydration of zeolite NaA

Conclusions Water molecules in partially dehydrated zeolite directly interact with Na⁺ cations. The final three or four water molecules per unit cell removed upon the dehydration of zeolite are apparently bound to Na⁺ cations of the eight-membered windows, while the previous 10 molecules are bound to Na⁺ cations of six-membered windows.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1160–1162, May, 1988.     

Effects of synthesis parameters on zeolite membrane formation and performance by microwave technique

Recently, zeolite membranes on porous supports have been extensively studied in the ethanol–water separation process for further use for gasohol production. This work focuses on a NaA membrane synthesized on an α‐Al₂O₃ support via microwave hydrothermal treatment. Synthesis temperature and time, type of substrate, seed amount and seeding time for the layer growth of the membrane are considered. The formation of as‐synthesized membranes is discussed according to observations by SEM and XRD. In addition, a preliminary study of the performance of the synthesized NaA zeolite membrane was conducted using the pervaporation technique. It was found that, for the synthesized continuous NaA membranes prepared using a 0.5 µm NaA crystal seed concentration of 3 g/l via vacuum seeding, the optimum conditions were 363 K synthesis temperature for 15–20 min via microwave heating. The flux and the separation factor obtained were 1.6 kg/m² h and 1760.5, respectively, for the substrate without an intermediate layer. Interestingly, the substrate with an intermediate layer showed better flux and separation factor at 1.7 kg/m² h and 6532.7, respectively. Copyright © 2007 John Wiley & Sons, Ltd.     

粉煤灰基NaA/NaX双晶型沸石分子筛构建及其协同吸附氨氮性能

以粉煤灰为原料,采用“联合改性三步合成法”——超声辅助碱熔微波晶化法联合废旧玻璃/13X晶种/NaH₂PO₄浸渍三阶段改性合成沸石分子筛(GFS);作为对比,采用传统碱熔水热法合成沸石分子筛(FS);采用“三步合成法”——超声辅助碱熔微波晶化法合成沸石分子筛(WFS)。并采用X射线衍射(XRD)、扫描电镜(SEM)、傅里叶变换红外光谱(FTIR)、能量色散光谱(EDS)、N₂吸附-脱附等方法对材料的组成、形貌和结构进行了表征。结果表明,WFS和GFS较FS具有更高的比表面积和发达的介孔、微孔,且沸石分子筛晶型从NaA单晶型转为NaA/NaX双晶型。氨氮吸附实验结果表明,GFS (56.01 mg·g^-1)较WFS (49.17 mg·g^-1)和FS (39.75 mg·g^-1)吸附性能更优,吸附动力学和热力学数据符合二级动力学模型和Langmuir模型,氨氮吸附过程为以离子交换为主的吸附,且为自发放热过程,低温促进氨氮吸附。     

Growth of a faujasite-type zeolite membrane and its application in the separation of saturated/unsaturated hydrocarbon mixtures

Faujasite type zeolite membranes were synthesized on porous ceramic alumina supports by using direct (in situ) and secondary (seeded) growth methods. In the secondary growth method a seed layer of ZSM-2 nanocrystals (prepared according to a report by Schoeman et al. J. Colloid Interface Sci. 1995, 170, 449–456) was deposited on the surface of the support before the hydrothermal growth. For both in situ and secondary growth, the mixture composition was 4.17 Na₂O:1.0 Al₂O₃:10 TEA (triethanol ammonium):1.87 SiO₂:460 H₂O. X-ray diffraction (XRD), scanning electron microscopy (SEM), and electron microprobe analysis (EPMA), indicate well intergrown 5–30 μm thick FAU films with Si/Al ∼1–1.5. The separation of saturated/unsaturated hydrocarbon mixtures is demonstrated over a range of temperatures (40–160°C). The mixtures examined (and the corresponding equimolar mixture separation factors) are benzene/cyclohexane (160), benzene/n-hexane (144), toluene/n-heptane (45), propylene/propane (6.2), and ethylene/methane (8.4). In all cases, the membranes are unsaturated hydrocarbon permselective. With equimolar feed mixtures (5 kPa/5 kPa benzene/cyclohexane) and in the temperature range 65–160°C, the membranes exhibit separation factor of 20–160 with the benzene flux in the range 10⁻⁴–10⁻³ mol m⁻² s⁻¹. Decreasing the total feed partial pressure (0.31/0.31 kPa benzene/cyclohexane) reduces both separation factor (12) and benzene flux. Similar trend is observed when the benzene/cyclohexane ratio in the feed mixture (0.5/9.5 kPa benzene/cyclohexane) is reduced. A sorption diffusion model based on the Stefan–Maxwell formulation has also been employed to show that the benzene/cyclohexane separation can mainly be attributed to differences of their adsorption properties.     

Mebendazole selective membrane sensor and its application to pharmaceutical analysis.

A PVC membrane sensor for the selective determination of mebendazole (MBZ) was fabricated. The sensor is based on an ion association of MBZ with silicotungstic acid (STA) as ion pair and bis(2-ethylhexyl)phthalate (BEP) as the plasticizing agent in a PVC matrix. The sensor showed a linear response for MBZ for a concentration range 1.0x10(-6)-5.0x10(-2) M with a Nernstian slope of 55.8 mV/decade (limit of detection 6.3x10(-7) M) in the pH range 4-7. It has a fast response time of <30 s. The sensor showed a very good selectivity for MBZ with respect to a large number of ions. The direct determination of MBZ in pharmaceutical formulations gave results that compare well with the data obtained from the standard method.     

Synthesis and characterization of NaA zeolite powder/film deposited on alumina beads by dip-coating method

Linde Type A (LTA) zeolites have been synthesized in the current study by simple sol–gel technique. The crystal growth has been controlled by varying the hydrogel synthesis time and annealing temperature. The resulting products obtained at various crystallization times and temperatures have been studied using X-ray powder diffraction (XRD) method, High resolution transmission electron microscopy images, scanning electron microscopy (SEM) micrographs, energy dispersive study and Brunauer–Emmett–Teller (BET) analysis. The TEM images of the final LTA zeolite annealed at 500 °C revealed the formation of cubic structure. XRD analysis revealed that the crystallinity improved with annealing. BET analysis revealed that the synthesized LTA is a well crystallized 4A zeolite. LTA zeolites were dispersed in poly ethylene glycol in the ratio 3:100 and 5:100 and coated on porous alumina beads for the formation of membrane. The SEM images revealed excellent formation of fine structure LTA zeolite membrane with uniform coating. The membrane consisted of a top layer with thickness of 1.14–2.0 µm. Crystals in the top layer showed cubic morphology and amorphous phase was observed at the grain boundaries present between LTA zeolite and alumina substrate.     

二次合成Y型杂原子分子筛的吸附脱硫研究

采用液-固相同晶取代反应制备骨架含Ga的Y型分子筛(AlY),研究其吸附脱除硫质量分数为500×10^-6模拟燃料中的硫化物。AlY处理含噻吩、四氢噻吩(THT)、4,6-二甲基二苯并噻吩(4,6-DMDBT)、二苯并噻吩(DBT)、苯并噻吩(BT)和4-甲基二苯并噻吩(4-MDBT)的模拟燃料时的吸附容量分别为7.0、17.4、14.5、16.9、6.9 和5.8mg(S)/g吸附剂。采用密度泛函理论(DFT)中的广义梯度近似方法(GGA)计算各分子中硫原子上的电荷数,噻吩、四氢噻吩、4,6-二甲基二苯并噻吩(4,6-DMDBT)、二苯并噻吩(DBT)、苯并噻吩(BT)和4-甲基二苯并噻吩(4-MDBT)中硫原子上电荷数分别为-0.159、-0.298、-0.214、-0.211、-0.193、-0.188。四氢噻吩和4,6-DMDBT中硫原子上的电子密度大于噻吩中硫原子上的电子密度,这就使得四氢噻吩和4,6-DMDBT中的硫原子与吸附位间的作用会明显大于噻吩中的硫原子与吸附位间的作用。采用AlY处理催化裂化汽油时的脱硫率可达68%。     

RUB-13分子筛的合成及其甲醇制烯烃催化性能

采用水热法合成RUB-13分子筛，探讨了有机模板剂（OSDA）、硅源、晶化温度和水硅比等制备条件对RUB-13分子筛晶体结构的影响，考察了RUB-13分子筛在甲醇制烯烃（MTO）反应中的催化性能。结果表明，采用1，2，2，6，6-五甲基哌啶（PMP）为有机模板剂、白炭黑为硅源，在晶化温度为170℃的条件下，选择H₂O/Si比为100和80时可分别合成出高纯度的低硅铝比（Si/Al=100）和高硅铝比（Si/Al=200）的RUB-13分子筛晶体，且晶粒呈棒状形貌。H-Al-B-RUB-13（Si/Al=200）分子筛用于催化甲醇制烯烃反应时，在400℃下表现出高的低碳烯烃选择性（C_2-5⁼选择性达97.8%，丙烯选择性为54.5%），优于传统的H-SAPO-34和H-ZSM-5分子筛催化剂。     

In situ SAXS/WAXS of zeolite microwave synthesis: NaY, NaA, and beta zeolites.

A custom waveguide apparatus is constructed to study the microwave synthesis of zeolites by in situ small-angle X-ray scattering (SAXS) and wide-angle X-ray scattering (WAXS). The WR-284 waveguide is used to heat precursor solutions using microwaves at a frequency of 2.45 GHz. The reaction vessels are designed to include sections of thin-walled glass, which permit X-rays to pass through the precursor solutions with minimal attenuation. Slots were machined into the waveguide to provide windows for X-ray energy to enter and scatter from solutions during microwave heating. The synthesis of zeolites with conventional heating is also studied using X-ray scattering in the same reactor. SAXS studies show that the crystallization of beta zeolite and NaY zeolite is preceded by a reorganization of nanosized particles in their precursor solutions or gels. The evolution of these particles during the nucleation and crystallization stages of zeolite formation depends on the properties of the precursor solution. The synthesis of NaA and NaX zeolites and sodalite from a single zeolite precursor is studied by microwave and conventional heating. Microwave heating shifts the selectivity of this synthesis in favor of NaA and NaX over sodalite; conventional heating leads to the formation of sodalite for synthesis from the same precursor. The use of microwave heating also led to a more rapid onset of NaA zeolite product crystallization compared to conventional heating. Pulsed and continuous microwave heating are compared for zeolite synthesis. The resulting rates of formation of the zeolite products, and the relative amounts of the products determined from the WAXS spectra, are similar when either pulsed or continuous microwave heating is applied in the reactor while maintaining the same synthesis temperature. The consequences of these results in terms of zeolite synthesis are discussed.     

甘油辅助HZSM-5分子筛的制备及其甲烷无氧芳构化催化性能研究

以正硅酸乙酯(TEOS)为硅源,甘油为辅助剂,在水热条件下合成HZSM-5分子筛。考察甘油添加量、晶化时间对HZSM-5分子筛的晶粒尺寸、相对结晶度和酸性等性质及其甲烷无氧芳构化催化性能的影响。利用X射线衍射(XRD)、扫描电镜(SEM)、氨程序升温脱附(NH₃-TPD)等分析手段对不同条件合成的HZSM-5分子筛样品进行表征。结果表明,在添加一定量的甘油辅助剂的条件下,通过调控晶化时间,可以提升HZSM-5分子筛的相对结晶度,在一定程度上抑制无定型SiO₂的产生,增加其酸量。在甲烷无氧芳构化反应中,甘油辅助合成的HZSM-5分子筛催化剂表现出优良的催化性能,与未添加甘油合成的HZSM-5分子筛催化剂相比,甲烷转化率、苯选择性和芳烃选择性均有较大提高,且具有较强的稳定性与容炭能力。     

Characterization of dehydration and hydration behavior of calcium lactate pentahydrate and its anhydrate

The use of calcium lactate pentahydrate (CLP) as an additional filler-binder for direct compaction of tablets has been reported to result in a short disintegration time and rapid drug release. The aim of this study was to understand the dehydration and hydration behavior of CLP and calcium lactate anhydrate (CLA) under various conditions of storage temperature and relative humidity. The removal and acquisition of crystal water were investigated by using differential scanning calorimetry (DSC), thermogravimetry-differential thermal analysis (TG-DTA), powder X-ray diffraction (PXRD) and scanning electron microscopy (SEM). The PXRD results indicated that CLP exists as a crystalline solid and CLA as an amorphous solid. Dehydration of CLP resulted in aggregated particles of CLA with an increase in average particle size. The dehydration and hydration kinetics of CLP were analyzed with the Hancock-Sharp equation on the basis of the isothermal DSC data. The dehydration of CLP followed a zero-order mechanism (Polany-Winger equation). In contrast, the surface roughness of CLA was significantly decreased by hydration. The hydration of CLA followed a three-dimensional diffusion model (Ginstling-Brounshtein equation).     

Preparation of a novel composite electrode based on N-doped TiO_2-coated Na Y zeolite membrane and its photoelectrocatalytic performance

For the first time the preparation of the N-doped TiO_2-coated NaY zeolite membrane(N-doped TiO_2/NaY zeolite membrane) as an electrode material for photoelectrocatalysis has been achieved and reported.The XRD, SEM, UV–vis and XPS techniques were used to characterize the structure of the N-doped TiO_2/NaY zeolite membrane. The results verified that the surface of the N-doped TiO_2/NaY zeolite membrane was coated by TiO_2 nanoparticles of ca. 20 nm size and exhibited a distinct red-shift in the UV–vis spectra compared to N-doped TiO_2. The photoelectrocatalysis performance of the N-doped TiO_2/NaY zeolite membrane electrode was evaluated by phenol degradation. The results revealed it is a promising novel electrode material for application of photoelectrocatalysis in the removal of organic contaminants in waste water.     

Nb-P/SBA-15催化剂的制备及其对果糖水解制5-羟甲基糠醛的催化性能

果糖催化脱水制5-羟甲基糠醛（5-HMF）是生物质转化制高附加值化合物过程中的一个重要反应。采用自制的介孔SBA-15,浸渍法制备了Nb/SBA-15催化剂,再经磷酸化处理制得Nb-P/SBA-15催化剂,研究了该催化剂在果糖脱水制5-HMF反应中的性能。SEM、TEM、BET和XRD表征结果表明,Nb/SBA-15和Nb-P/SBA-15完好地保留了SBA-15的微观结构,其内孔道直径为10 nm,铌酸在孔内表面分布均匀;负载铌和磷酸化后,孔壁变薄。NH₃-TPD结果显示,Nb/SBA-15经磷酸预处理后,不仅弱酸性位有所增加,而且产生了中强酸和强酸性位,使得在含水两相体系果糖脱水反应中,Nb-P/SBA-15比Nb/SBA-15具有更高的催化活性和5-HMF选择性。同时考察了反应温度、溶剂比例、反应时间对果糖脱水的影响,结果表明,以水/MIBK（V/V=1/2）为溶剂时,160 ℃下反应1.5 h,果糖转化率和5-HMF收率分别高达96.1%和92.6%。Nb-P/SBA-15经循环使用四次后仍具有较好的催化活性,表明该催化剂具有较高的耐水稳定性。     

Adsorption phenomena at high pressures and temperatures 1. Method of investigation; adsorption of nitrogen on NaA zeolite

A simple precision volumetric-gravimetric setup was elaborated and created for determining the equilibrium and kinetic parameters of adsorption in the 1–160 MPa pressure range and the 300–600 K temperature range. The isotherms of adsorption of nitrogen on crystalline NaA zeolite in the indicated temperature and pressure range were measured. A method was proposed for determining the pore volume of zeolites based on conducting adsorption measurements at high pressures of the gas phase. The isosteric heats of adsorption of nitrogen on NaA zeolite at 305, 334, and 373 K were estimated.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1233–1238, June, 1990.     

Adsorption phenomena at high pressures and temperatures 4. Isotherms of excess and absolute adsorption of Kr on NaA zeolite

The problem of conversion of an isotherm of excess adsorption measured experimentally into values of the total amount of the adsorbate (absolute adsorption) has been formulated. Five isotherms of excess adsorption of krypton on NaA zeolite were measured (at 334–500 K) at equilibrium pressures of -160 MPa. The corresponding isotherms of the total amount were calculated and the temperature dependences of the parameters of an equation describing the isotherms of excess adsorption were identified. It was shown that at high temperatures and pressures, krypton atoms diffuse into the -cavities of the NaA zeolite.For Part 3, seeRuss. Chem. Bull., 1996, 45, 534 (Engl. Transl.).Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1138–1142, May, 1996.