Effective removal of uranium ions from drinking water using CuO/X zeolite based nanocomposites: effects of nano concentration and cation exchange

For the first time, effects of CuO nanoparticles concentration (from 1 to 24.2 wt%) in CuO/NaX nanocomposite and replacing various cations (Ag⁺, K⁺, Ca²⁺, and Mg²⁺) with Na⁺ ions in NaX zeolite on removal of uranium ions from drinking water are reported. The removal of uranium was performed under natural conditions of pH, laboratory temperature and the presence of competing cations and anions that are available in tap water of Isfahan city. Characterization of parent NaX zeolite and modified samples were investigated using X-ray fluorescence, X-ray powder diffraction patterns, scanning electron microscopy, and atomic absorption spectroscopy methods. Using Langmuir, Freundlich, and C-models, isotherms of equilibrium adsorption were studied. Results show the removal efficiency and distribution coefficient of NaX zeolite decrease in the presence of other competing anions and cations that exist in drinking water. But, modification of NaX zeolite with various cations and CuO nanoparticles might enhance the ability of X zeolite in removing uranium from drinking water.     

Preparation of highly dispersed copper oxide by thermal destruction of binuclear CuII monofluoroacetate in zeolite Y cavities

Thermal destruction of the binuclear monofluoroacetate complex Cu₂(CH₂FCOO)₄ deposited on zeolite Y was studied by the TG-DTA and ESR methods. Large particles of copper oxide are not formed and fine dispersion of CuO in the matrix is observed due to low temperatures of the destruction of the supported complex (240–250°C) and restriction of the process mainly to large cavities of the zeolite. Published inIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1371–1374, August, 2000.     

Propylene/propane mixture adsorption on faujasite sorbents

The adsorption of propylene and propane on zeolite NaX with and without a saturated (36 wt%) amount of CuCl have been investigated. The single component adsorption isotherms could be well described with a Dual-Site Langmuir model. The dispersion of CuCl results in a decrease of the maximum adsorption capacity of the zeolite for both components. For propylene a strong adsorption via π-complexation with CuCl is present, increasing the adsorption selectivity of the zeolite. The binary mixture (50:50) adsorption was determined via breakthrough/desorption experiments at 318, 358 and 408 K with a partial pressure of the two components between 0.8–54 kPa. For NaX the mixture loading could be well described with the IAS-theory and the single component isotherms, both qualitatively and quantitatively. A transition from an enthalpy controlled adsorption at lower loadings to an entropy affected adsorption at higher loadings was observed. The IAS-theory could only qualitatively describe the trends in the observed mixture adsorption for the CuCl/NaX adsorbent. The dispersion of CuCl in NaX results in a modest improvement of the adsorption selectivity for propylene over propane (from 3–7 to 15–30) but at the expense of a reduced capacity.     

Role of chloroolefins in the formation of copper complexes catalytically active in isomerization of dichlorobutenes

Tetranuclear copper(I) complexes with organic donor ligands were found to be the best precursors of a catalyst for dichlorobutene isomerization. The products of interaction between allyl chloride and a tetranuclear triphenylphosphine complex of copper bromide were investigated by diffraction and spectral analysis. This reaction yields [Cu(PPh₃)Br _n Cl_1−n ]₄ and complexes containing the products of transformation of both triphenylphosphine and allyl chloride. Presented at the First Moscow Workshop on Highly Organized Catalytic Systems. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1830–1834, October, 1997.     

Adsorptive properties of X zeolites modified by transition metal cation exchange

The ionic exchange of the NaX zeolite by Ni²⁺ and Cr³⁺ cations was progressively driven and studied by adsorption of nitrogen and carbon dioxide. For each cation-exchanged X zeolite sample, the development of characteristics such as profile of isotherms, RI criterion, isosteric adsorption heat and microporous volume using both the Dubinin–Radushkevich (DR) equation and the t-plot, was followed through the nitrogen adsorption. Results show that the cationic exchange process, in the case of Cr³⁺ introduced at middle degree, is accompanied by a textural damage for Cr(x)X, in contrast to Ni²⁺-exchanged X zeolites. This degradation occurs without significant presence of mesopores, because the RI criterion values were found to be much lower than 2.2. The CO₂ adsorption isotherms were measured at intervals of 30 K from 273 K and the equilibrium pressures ranged from 0.5 to 600 Torr. The experimental data were correlated by the Toth model. The associated three adjustable parameters were estimated by nonlinear least-squares analysis. The effect of temperature on the model parameters and the Henry’s law slope, K _H , represented by the product of Toth parameters, are discussed.     

CO<Subscript>2</Subscript> adsorption and dehydration behavior of LiNaX,KNaX, CaNaX and CeNaX zeolites

In this study, NaX synthetic zeolite was modified by following the conventional cation exchange method at 70°C. 82, 81, 79 and 48% of sodium were exchanged with Li⁺, K⁺, Ca2⁺ and Ce3⁺, respectively. Thermal analysis data obtained by TG/DSC was used to evaluate the dehydration behavior of the zeolites. The strongest interaction with water and the highest dehydration enthalpy (ΔH) value were found for Li-exchanged form and compared with the other forms. The temperature required for complete dehydration increased with decreasing cation size (cation size: K⁺>Ce³⁺>Ca2⁺>Na⁺>Li⁺). CO₂ adsorption at 5 and 25°C was also studied and the virial model equation was used to analyze the experimental data to calculate the Henry’s law constant, K _o and isosteric heat of adsorption at zero loading Q _st. K _o values decreased with increasing temperature and the highest Qst was obtained for K rich zeolite. It was observed that both dehydration and CO₂ adsorption properties are related to cation introduced into zeolite structure.     

Influence of surface morphology on the oxidation of metal electrodes studied by in-situ grazing incidence x-ray diffractometry

The successful application of in-situ grazing incidence x-ray diffractometry (GIXD) for the investigation of oxidation processes at copper electrodes in pH 12 electrolytes is demonstrated. A penetration/escape depth of about 1 μm could be detected for a smooth polycrystalline copper foil and an x-ray incidence angle of 1.7°. Oxide layers generated at overpotentials less than about 0.5 V in respect to the equilibrium formation potentials of Cu₂O or CuO, respectively, showed a dependence of the crystalline oxide formation on the defect density of the copper substrate. Highly disordered ground or polished specimens exhibited an order of magnitude higher GIXD reflexes from crystalline Cu₂O than electrodeposited copper. Beyond overpotentials of 0.5 V, this epitaxial information for the Cu₂O crystal growth became irrelevant. Further, GIXD turned out to be an appropriate tool to monitor atmospheric corrosion processes under thin humidity films with oxygen access. When oxygen diffusion through the polymer window membrane is allowed, oxygen reduction led to the concurrent formation of a crystalline CuO phase coexisting with amorphous Cu(OH)₂ and Cu₂O, though the potential was kept in the region of Cu₂O. Received: 30 July 1997 / Revised: 28 May 1998 / Accepted: 13 July 1998     

Synthesis of NaX and NaY Zeolites from Tunisian Kaolinite as Base Catalysts: An Investigation of Knoevenagel Condensation

The synthesis of Faujasite‐type zeolites with high purity has been successfully performed from Tunisian kaolinite and the effects of different crystallization parameters on the final products were widely investigated. The alkaline fusion of kaolinite followed by hydrothermal treatment lead to zeolite NaX synthesis whereas the classic hydrothermal transformation of metakaolinite produces NaY zeolite. The results show that an increase in the synthesis temperature and time has improved the crystallization process of the zeolite NaX whereas the SiO₂/Al₂O₃ and the Na₂O/SiO₂ molar ratios were the key parameters to obtain a pure zeolite NaY. The highest specific surface areas obtained with the optimal crystallization conditions were 554 m2 g^?1 and 592 m2 g^?1 for respectively NaX and NaY zeolites. The basic properties of NaX and NaY zeolites were explored in the Knoevenagel condensation of benzaldehyde with ethyl cyanoacetate at 140 °C as a test reaction in the absence of solvent. The influence of ion exchange with cesium cation on the catalytic activity of prepared catalysts was also investigated. It was found that the NaX provided higher activity than that of NaY catalyst due to its lower Si/Al ratio whereas a cesium exchange conferred higher basicity to the prepared Na‐faujasite.     

Adsorption properties of BEA zeolites and their aluminum phosphate extrudates for purification of isomaltose

The disaccharide isomaltose is produced via an enzymatic reaction and is adsorbed to BEA zeolite. This reaction integrated adsorption can be achieved as fluidized bed as well as fixed bed. We investigated isotherms, adsorption enthalpies and sorption kinetics of BEA zeolite and extrudates with a novel aluminum phosphate sintermatrix. These extrudates contain 50% (w/w) of BEA 150 zeolites (Si/Al = 75) as primary crystals. BET-surface for extrudates is 245 m²⋅g⁻¹ and 487 m²⋅g⁻¹ for zeolite. Extrudates show a monomodal macropore structure with a maximum at 90 nm. All isotherms show a type I shape. For lower equilibrium concentrations, which occur during the enzymatic reaction, Henry’s law is applied and compared to a Langmuir model. Adsorption equilibrium constant K _i,L calculated from Langmuir for extrudates at 4 °C is 64.7 mL⋅g⁻¹ and more than twice as high as obtained from Henry’s law with K _i is 26.8 mL⋅g⁻¹. Adsorption on extrudates at 4 °C is much stronger than on zeolite crystals where the Henry coefficient K _i is 17.1 mL⋅g⁻¹. Adsorption enthalpy Δh _Ad calculated from van’t Hoff plot with the Henry equation is −44.3 kJ⋅mol⁻¹ for extrudates and −29.6 kJ⋅mol⁻¹ for zeolite crystals. Finally, the kinetics for ad- and desorption were calculated from the initial slope. The diffusion rate for ad- and desorption on extrudates were in the same range while adsorption on zeolites is three orders of magnitudes faster than desorption.     

Dehydrogenation activities of highly dispersed transition metal oxides on NaY zeolite

Highly dispersed α-Fe_2O_3/NaY,NiO/NaY,and CuO/NaY catalyst systems were pre-pared by impregnation method.Dispersion thresholds of the transition metal oxides on NaY" zeolitewere determined by XRD phase analysis.The dispersion capacities of the transition metal oxides on NaYzeolite are much lower than that estimated on the basis of a closed packed monolayer in the micropores.The catalytic activity and selectivity of the highly dispersed oxide catalyst systems for ethylben-zene and cyclohexane dehydrogenation reactions were reported.     

Vapor‐Phase Aldolization of n‐Butyraldehyde to 2‐Ethyl‐2‐Hexenal over Solid‐Base Catalysts

Vapor‐phase aldol condensation of n‐butyraldehyde to 2‐ethyl‐2‐hexenal was studied at 1 atm and 150～ 300°C in a fixed‐bed, integral‐flow reactor by using NaX, KX, γ‐Al₂O₃ and Na/NaOH/γ‐Al₂CO₃ catalysts. Ion exchange of NaX zeolite with potassium acetate solution results in a decrease of crystallinity and apparent lowering of surface area, whereas the basic strength is enhanced. Treatment of γ‐Al₂O₃ with NaOH and Na causes a large decrease of the surface area but strong enhancement of the catalyst basicity. The catalytic activity on the basis of unit surface area is in the order Na/NaOH/γ‐Al₂O₃ < KXU < KXW < NaX >γ‐Al₂O₃, in accordance with the relative catalyst basic strength. The molar ratio of trimeric to dimeric products increases with increasing the reaction temperature and the catalyst basic strength except for Na/NaOH/γ‐Al₂O₃. Very high selectivity of 2‐ethyl‐2‐hexenal (>98.5%) was observed for reactions over NaX zeolite at 150°C. Based on the FT‐IR and the catalytic results, the reaction paths are proposed as follows: self‐aldol condensation of n‐butyraldehyde, followed by dehydration produces 2‐ethyl‐2‐hexenal, which then reacts with n‐butyraldehyde and successively dehydrates to 2,4‐diethyl‐2,4‐octadienal and 1,3,5‐triethylbenzene. For the reaction over NaX, the calculated Arrhenius frequency factor and activation energy are 314 mol/g·h and 32.6 kJ/mol, respectively.     

Adsorption and adsorption-induced deformation of NaX zeolite under high pressures of carbon dioxide

Isotherms of carbon dioxide adsorption and adsorption-induced deformation of pelletized crystalline NaX zeolite at pressures of 0.2--5.4 MPa and temperatures of 195--423 K are measured. The adsorption deformation is positive at low zeolite micropore filling (a < 1 mmol g^-1) at all temperatures, i.e., the zeolite suffers expansion. Further, as the amount of the adsorbed substance increases, the adsorption deformation curves pass first through a maximum and then through a minimum. In the range of high fillings (a > 7 mmol g^-1) the NaX zeolite shows dramatic expansion.     

Chromium uptake from tricomponent solution in zeolite fixed bed

Removal of Cr³⁺,Ca²⁺,Mg²⁺ and K⁺ in equilibrium isotherms and in tricomponent solutions (Cr/Ca/K, Cr/Ca/Mg and Cr/Mg/K) were investigated in NaX and NaY packed beds at 30^∘C. The equilibrium selectivity was obtained as Cr⁺³ > Mg²⁺ > Ca²⁺≈K⁺ for zeolite NaY and Ca^{2 +}≫Cr^{3 +} > Mg^{2 +}≈K⁺ for zeolite NaX. The breakthrough curves showed sequential ion exchange where chromium ions are able to replace the competing cations. Some mass transfer parameters, such as length of unused bed and overall mass transfer coefficient, were investigated. Chromium retention was also investigated through a mass balance. Based on the breakthrough results, it was concluded that chromium-uptake mechanism was hardly influenced by the competition and interaction between the entering ions. NaY showed a higher affinity towards Cr³⁺ for both equilibrium and dynamic systems and its sites were more efficiently used in the ion exchange process. Chromium was less retained in NaX due to the high selectivity towards calcium ions.     

以开孔的二维MFI纳米片为构筑单元制备沸石片膜

以食人鱼溶液(体积比为3∶1的95%～98%(w/w)H_2SO_4和30%(w/w)H_2O_2混合液)处理多层MFI(ML-MFI)除去有机结构导向剂(OSDA),经超声剥离和沉降纯化后得到了开孔的MFI沸石纳米片。采用X射线衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)、N_2吸附-脱附、傅立叶变换红外光谱(FT-IR)和热重分析(TGA)等手段对得到的MFI沸石纳米片进行表征,发现食人鱼溶液处理可移除ML-MFI中的OSDA,再经超声剥离得到可分散、开孔的MFI沸石纳米片。将MFI沸石纳米片用简单抽滤的方式沉积到自制Al_2O_3载体上,不经二次生长得到了连续的沸石纳米片膜。单组分气体渗透性能测试结果表明,制备的MFI沸石纳米片膜对正/异丁烷的理想选择性为4.1～5.8,正丁烷的渗透速率为2.2×10~(-7)～4.1×10~(-7) mol·m~(-2)·s~(-1)·Pa~(-1)。     

Introduction of vanadium species in <Emphasis Type="Italic">β</Emphasis> zeolite by solid-state reaction: spectroscopic study of V speciation and molecular mechanism

V-containing β zeolites were prepared by solid-state reaction between V₂O₅ and β zeolite. The zeolite structure was analysed by XRD and N₂ physisorption. The V speciation was studied by chemical analysis and different spectroscopies (FT-IR, ²⁷Al-NMR, UV-Vis, EPR, photoluminescence). After calcination of V₂O₅-β zeolite mechanical mixtures at 500°C, three kinds of V species were identified: (i) oligomeric vanadates with octahedral V⁵⁺ easily removed by treatment with NH₄OAc, (ii) isolated vanadyl (V=O)²⁺ ions in axially distorted octahedral or square pyramidal environment, interacting with framework and/or extraframework Al nuclei and (iii) isolated V⁵⁺ in tetrahedral and octahedral environments, localized in framework defect sites. The amount of the latter species is higher when water vapor is present during calcination and when parent β zeolite contains a high concentration of defect sites generated by a strong acid pretreatment. Isolated V⁵⁺ are easily reduced to tetrahedral V⁴⁺ or to square pyramidal (V=O)²⁺. Possible models of the mechanism of formation of V species by solid-state reaction and further reduction are proposed.     

Description of NaX zeolite deformation during adsorption of xenon

The equation describing the experimental data of NaX zeolite deformation during adsorption of xenon at pressures of 0.001–7 MPa and temperatures of 252–333 K was obtained on the basis of the generalized Lennard-Jones pair interaction potential. The temperature dependences of the constants in the equation were determined. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1887–1890, October, 1999.     

Spectroscopic study of ternary copper(II) complexes on a silica surface

The formation of ternary surface complexes of copper(II) with one or two molecules of 2,2′-bipyridine (bpy) or α-picolinic acid (Hpic), which were obtained after adsorption on the silica surface in different ways, was studied by electronic and ESR spectroscopy. Coordination of the ligands, which were preliminarily adsorbed by copper ions, afforded only 1∶1 ternary surface complexes. In both cases, coordinatively more saturated ternary surface complexes were formed only when Cu(bpy)₂ ²⁺ and Cu(pic)₂ were adsorbed on the SiO₂ surface from solutions. The compositions and structures of the ternary surface complexes containing bipyridine ligands are temperature independent, whereas in the picolinate-containing ternary surface complexes, the coordination spheres of the adsorbed complexes are rearranged as the temperature changes. Presented at the First Moscow Workshop on Highly Organized Catalytic Systems (June 19, 1997). Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1765–1771, October, 1997.     

Adsorption of carbon dioxide and nitrogen on zeolite rho prepared by hydrothermal synthesis using 18-crown-6 ether

Zeolite rho was prepared by hydrothermal synthesis using an 18-crown-6 ether (18C6) as a structure-directing agent, and the effects of the calcination temperature for removal of 18C6 on the physicochemical properties and CO₂-adsorption properties were investigated. CO₂ adsorption on zeolite rho calcined at 150 °C was lower than that on samples calcined at temperatures above 300 °C. For samples calcined above 300 °C, CO₂ adsorption increased with increasing calcination temperature up to 400 °C. It is thought that the pore volume for adsorption of CO₂ increased as a result of 18C6 removal, resulting in increasing CO₂ adsorption. A decrease in CO₂ adsorption for calcination from 400 °C to 500 °C was observed. The particle size of zeolite rho increased with increasing 18C6 molar ratio. Particle sizes of 1.0-2.1 μm and 1.4-2.6 μm were found by field-emission scanning electron microscopy and dynamic light-scattering, respectively. The particle size is controlled in these regions by adjusting the 18C6 molar ratio. XRD showed that zeolite rho samples with 18C6 molar ratios of 0.25-1.5 had high crystallinity. The adsorbed amount of CO₂ is almost constant, at 3.4 mmol-CO₂ g⁻¹, regardless of the 18C6 molar ratio. However, CO₂ selectivity, which is the CO₂/N₂ adsorption ratio, decreased. The amount of CO₂ adsorbed on zeolite rho is lower than that on zeolite NaX, but higher than that on SAPO-34. The CO₂/N₂ adsorption ratio for zeolite rho was higher than those for SAPO-34 and zeolite NaX.     

含氟体系中高性能T型分子筛膜的合成

含氟体系中,在负载晶种的大孔莫来石支撑体表面快速合成了高性能且取向生长的T型分子筛膜。采用XRD、SEM和MAS NMR等手段对分子筛膜层和粉末进行表征。讨论了添加物、氟硅比、合成温度和合成时间等条件对膜生长与分离性能的影响,并阐述了含氟体系中T型分子筛膜快速晶化的机理。碱金属氟盐的加入促进了T型分子筛晶体层的晶化速率,并对晶体层形貌产生了一定的影响。膜应用于75℃、水/异丙醇(10∶90,w/w)体系的平均渗透通量和分离因子分别为(4.91±0.18)kg·m-2·h-1和7 060±1 130。     

含氟体系中高性能T型分子筛膜的合成

含氟体系中,在负载晶种的大孔莫来石支撑体表面快速合成了高性能且取向生长的T型分子筛膜。采用XRD、SEM和MASNMR等手段对分子筛膜层和粉末进行表征。讨论了添加物、氟硅比、合成温度和合成时间等条件对膜生长与分离性能的影响,并阐述了含氟体系中T型分子筛膜快速晶化的机理。碱金属氟盐的加入促进了T型分子筛晶体层的晶化速率,并对晶体层形貌产生了一定的影响。膜应用于75℃、水/异丙醇（10：90,w/w）体系的平均渗透通量和分离因子分别为（4.91±0.18）kg·m^-2·h^-1和7060±1130。