Removal of thorium from aqueous solutions by sodium clinoptilolite

Adsorptive behavior of natural clinoptilolite was assessed for removal of thorium from aqueous solutions. Natural zeolite was characterized by X-ray diffraction and X-ray fluorescence. The zeolite sample composed mainly of clinoptilolite. Na-exchanged form of zeolite was prepared and its sorption capacity for removal of thorium from aqueous solutions was examined. The effects of relevant parameters, including initial concentration, contact time, solid to liquid ratio, temperature and initial pH on the removal efficiency were investigated in batch studies. The pH strongly influenced thorium adsorption capacity and maximal capacity was obtained at pH 4.0. Kinetics and isotherm of adsorption were also studied. The pseudo-first-order, pseudo-second-order, Elovich and intra-particle diffusion models were used to describe the kinetic data. The pseudo-second-order kinetic model provided excellent kinetic data fitting (R ² > 0.999) with rate constant of 1.25, 1.37 and 1.44 g mmol⁻¹ min⁻¹ respectively for 25, 40 and 55 °C. The Langmuir and Freundlich models were applied to describe the equilibrium isotherms for thorium uptake and the Langmuir model agrees very well with experimental data. Thermodynamic parameters were determined and are discussed.     

Sorption of lanthanum ions by natural clinoptilolite tuff

The equilibrium and kinetics of sorption of lanthanum ions on natural clinoptilolite tuff are studied. It is demonstrated that sorption of lanthanum ions from diluted solutions occurs in micropores of clinoptilolite, and from concentrated solutions in the mesoporous structure of tuff. The main capacity of zeolite tuff is found in the secondary porous structure. The sorption of lanthanum ions is limited by diffusion in tuff grains. Lanthanum ions are regularly distributed in the tuff phase and interact with the Brønsted centers of large clinoptilolite cavities.     

Na型斜发沸石上Na+-Cu2+离子交换过程动力学

用静态离子交换法研究了Ｎａ型斜发沸石上２Ｎａ＝Ｃｕ＾２＋离子交换动力学，分别测定了液膜扩散常数Ｒ，粒内扩散系数Ｄ和滞留时间Ｔｄ，实验发现，离子交换起始为液膜扩散控制，随后在交换的大部分时间内为粒内扩散控制，并就温度、浓度对离子交换过程速率，Ｃｕ＾２＋平衡交换数量以及滞留时间的影响进行了讨论。     

Ammonium sorption from aqueous solutions by the natural zeolite Transcarpathian clinoptilolite studied under dynamic conditions

The scope of this study is ammonium-ion uptake from synthetic aqueous solutions onto raw and pretreated forms of the natural zeolite Transcarpathian clinoptilolite under dynamic conditions. Hydrogen ions displaced exchangeable cations on the clinoptilolite in distilled water (sodium ions) and hydrochloric acid (sodium, potassium, and calcium ions) and destroyed the zeolite framework structure in the last case. Ammonium uptake onto the zeolite occurs by exchange with Na(+), Ca(2+), and K(+) ions. Although Na(+) ions were observed to be more easily exchanged for both hydrogen and ammonium ions, the role of Ca(2+) ions increased with zeolite saturation by NH(+)(4) ions. The maximum sorption capacity of the clinoptilolite toward NH(+)(4) ions, estimated under dynamic conditions, is significantly higher than that measured under static conditions; proximity of the values of a distribution coefficient and a retardation factor for different conditions (215-265 dm(3)/kg and 979-1107, respectively) allows us to use these parameters to model ammonium uptake onto the clinoptilolite. Slowing down or interruption in filtration resulted in the improvement of ammonium sorption properties of the zeolite. The ammonium removal improves with use of the finer fractions of the clinoptilolite up to 0.35 mm. A recycling study results confirmed the importance of external diffusion for ammonium sorption by the clinoptilolite. Preliminary treatment of the sorbent confirmed the predominant importance of the ion-exchange mechanism. The advantage of prior NaCl treatment of the clinoptilolite in improvement of ammonium removal over the other techniques was shown.     

Exchange and reduction of Cu(2+) ions in clinoptilolite

The ion-exchange and reduction processes for Cu(2+) ions in clinoptilolite from the Caimanes deposit (Moa, Cuba) were studied at different temperatures. The ion-exchange studies were done to determine the kinetic parameters of Cu(2+) removal from solution by this clinoptilolite modified previously to NH(+)(4) form, and thermodynamic parameters of Cu(2+) elution from zeolite using NH(4)Cl solution. The results show that temperature increase favors the exchange and that it is a reversible process. The external diffusion rate appreciably increases with temperature, while, the internal diffusion coefficient rises relatively little. This means that besides ion exchange other processes (such as precipitation of the low-solubility phase and/or salt adsorption) occur, which cause copper removal from solution and affect the intracrystalline diffusion of the ions. For steric reasons the exchange of [Cu(H(2)O)(6)](2+) ions from a solution must occur with a number of water molecules n smaller than 6 (6 > n > or = 0). Cu(2+) reduction by hydrogen and the formation of Cu-particles in the clinoptilolite were verified. The Cu(2+) reduction mechanism is complex, indirect, and sensitive to reduction temperature; consequently, Cu(+)(n) states intermediate between Cu(2+) and Cu(0) should be present in the reduced samples.     

Ion-exchange kinetics in natural heulandite and clinoptilolite

The kinetics of sorption of Ca²⁺ ions from aqueous solution by K⁺-substituted forms of heulandite and clinoptilolite have been studied at 298 K. The K⁺-Ca²⁺ ion exchange in heulandite and clinoptilolite is described by an internal diffusion mechanism. Self-diffusion coefficients were determined for Ca²⁺ ions in these zeolites.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2215–2217, October, 1991.     

尿素在斜发沸石上的自发单层分散

我们发现多种氧化物和盐类可以在载体表面自发单层分散,并存在分散阈值[1].近几年来又探讨了有机物在载体上的分散[2],验证了这一现象的普遍性.尿素是一种特殊物质,作为第一个人工合成的有机物,它同时具有有机物和无机物的性质.因此研究尿素在载体上的分散行为对于关联有机物和无机物的分散性质有重要的意义,也是对自发单层分散理论的充实.而且,尿素作为化肥工业的支柱,研究它的分散状态和分散性质,可以为制备缓释型化肥,提高化肥利用率,减少环境污染提供新的思路.1　实验部分1.1　样品制备　　载体为我国北方产斜发沸石,尿素由北京化工厂生…     

Adsorption of Basic Yellow 28 from aqueous solutions with clinoptilolite and amberlite

The objective of this study was to investigate the adsorption of Basic Yellow 28 that is a cationic dye on clinoptilolite and amberlite XAD-4. Both equilibrium and batch rate adsorption in aqueous solutions of the dyestuff were investigated. Adsorption rate data were analysed using the pseudo-first order kinetic model of Lagergren and the pseudo-second order model to determine adsorption rate constants at 20, 30 and 40 degrees C. The adsorption equilibrium data were analysed using various adsorption isotherm models and the results have shown that adsorption behaviour of Basic Yellow 28 by clinoptilolite and amberlite could be described by either Langmuir or Freundlich models. Langmuir adsorption isotherm constants corresponding to adsorption capacity, Q(0), were found to be 59.6, 52.9 and 56.7 mg/g for clinoptilolite at 20, 30 and 40 degrees C, respectively. Lower adsorption capacities for Basic Yellow 28 on amberlite were obtained. The increase of adsorption rate constants with an increase in temperature for BY 28 adsorption on amberlite indicated chemisorption with dissociation and increased availability of sites due to higher penetration of adsorbing molecules into the pores.     

Thermal Study of Surfactant and Anion Adsorption on Clinoptilolite

The mechanism of surfactant adsorption on various forms of clinoptilolite was studied by DTA, TG and DTG analyses. The examined series of surfactant modified clinoptilolite (SMC) was previously prepared by the adsorption of the surface-active oleylamine on Ca²⁺, Na⁺, H⁺ and mechanochemically treated forms of clinoptilolite. The oleylamine was most strongly adsorbed on H⁺-forms of clinoptilolite due to the largest number and strength of adsorption sites. The surfactant adsorption mechanism on H⁺-form of clinoptilolite was studied by recording the series of variously surfactant-loaded samples. The products of sulphate, dihydrogenphosphate and hydrogenchromate adsorption on SMC were analyzed by DTA, TG and DTG in order to investigate the mechanism of anion adsorption.This revised version was published online in November 2005 with corrections to the Cover Date.     

Kinetics of the sorption of metal ions from sea water on clinoptilolite

Based on a study of the sorption kinetics of metal ions from sea water onto granular clinoptilolite and powdered clinoptilolite incorporated into a grain of a highly permeable inert support it has been shown that the rate of the sorption processes is limited principally by diffusion in the microgranules of zeolite. For the Tedzami clinoptilolite studied the characteristic dimensions of the microgranules are 15–20 m and are commensurate with the dimensions of microcrystals determined independently.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 263–267, February, 1990.We thank E. V. Venetsianov, L. S. Kamenetskii and M. V. Veksler for assistance in the investigation.     

NH 型斜发沸石吸附钾离子

研究了NH4 型斜发沸石对盐水中钾离子的吸附行为,考察了竞争阳离子等对铵型斜发沸石吸附钾离子的影响。结果表明,NH4 型斜发沸石对钾离子具有较强的选择吸附性与较大的饱和吸附容量,受钾离子初始浓度的影响,NH4 型斜发沸石吸附钾离子的行为在沸石相K 平衡分数YK 为0.5时发生较大转折。竞争阳离子的存在在不同程度上抑制了铵型斜发沸石对钾离子的吸附,特别是钾离子与钠离子的相对比例直接影响NH4 型斜发沸石对混合液中钾离子的选择交换能力。     

Characterization of modified clinoptilolite

Samples of clinoptilolite were modified using insoluble hexacyanoferrate from aqueous solution. The modified samples were characterized by elemental analysis, powder X-ray diffraction, solid state NMR and vibrational spectroscopy. The sorption properties of modified clinoptilolite were studied, too. Higher affinity for¹³⁷Cs sorption in comparison with the natural clinoptilolite has been proved.     

Uranium adsorption characteristic and thermodynamic behavior of clinoptilolite zeolite

Summary Natural zeolite, clinoptilolite was tested for its ability to remove uranium from aqueous solutions. Influence parameters to the sorption process, such as initial uranium concentration, pH, contact time and temperature were investigated. Distribution coefficients of uranium on clinoptilolite were measured by batch technique. Experimental isotherms evaluated from the distribution coefficients were fit to Langmuir, Freundlich and Dubinin-Radushkevich (D-R) models. Values of ΔH and ΔS were found as 0.93 and 56.09 J/mole, respectively. It was observed that the adsorption process is endothermic. Kinetics of uranium sorption was investigated at different time intervals at 30 °C. The reaction rate and diffusion constant were calculated.     

Sorption of Silver and Chemiluminescent Activity of Clinoptilolite

Sorption conditions of ions and colloidal particles of silver by a zeolite (clinoptilolite) and clays, and specific features of distribution of absorbed silver in clinoptilolite grains were studied. Temperature dependences of the intensity of heterogeneous chemiluminescence from samples of natural clinoptilolite and its modified forms were obtained. The activation energies of the luminescence-active chemisorption of oxygen on electron-donor centers of the zeolite surface and relative amount of centers were determined.     

Iodide adsorption on the surface of chemically pretreated clinoptilolite

The possibility to use the monoionic Ag⁺-form (eventually Hg⁺- and Hg²⁺- forms) of clinoptilolite of domestic origin for radioactive iodide elimination from waters has been studied. The capacity of the monoforms of clinoptilolite towards iodide exceeds many times that of the capacity of clinoptilolite in natural form. Due to the low solubility product of AgI, Hg₂I₂ and HgI₂ iodides generate precipitates on the zeolite surface. Rtg analyses of the silver form of clinoptilolite after sorption of iodide demonstrate the formation of new crystals on the zeolite surface. The influence of interfering anions on the adsorption capacity of silver clinoptilolite towards iodide was investigated, too. Kinetic curves of iodide desorption from the surface of silver and mercury clinoptilolite were compared. Simultaneously, adsorption isotherms for the systems aqueous iodide solution/Ag^–, Hg-clinoptilolite were determined.     

Acid natural clinoptilolite: structural properties against adsorption/separation of n-paraffins

The employment of an acid natural clinoptilolite (AZH-1) in the adsorption and separation of n-paraffins has been evaluated. Natural clinoptilolite, NZ, was the raw material used to prepare the sodium-exchanged clinoptilolite (AZ) starting from which the AZH-1 sample was obtained by acid treatment. The structural stability of the samples after the applied treatments was demonstrated. The nitrogen adsorption experiments indicated that the acid sample has a homogeneous porous distribution and a considerable increase in the micropore volume with respect to NZ and AZ. The employment of the inverse gas chromatography at infinite dilution (IGCID) allowed studying the adsorption and separation of n-paraffin mixtures on AZH-1. It was also confirmed that the diffusion on AZH-1 took place in an unblocked structure through the A channel of ten members with minimal interactions. The IGCID results demonstrated the capacities of the acid Cuban natural zeolite in the adsorption and separation of n-paraffin mixtures.     

Ion exchange studies on natural and modified zeolites and the concept of exchange site accessibility

In the present study natural and Na-rich form of clinoptilolite are examined, in respect to ion exchange of Pb2+, Cu2+, Cr3+, and Fe3+. Equilibrium and kinetic studies performed, under the same normality (0.01 N). Equilibrium studies demonstrate that Na+ enrichment of clinoptilolite is beneficial in respect to metal uptake for all metals, except Cr3+, which is shown to have the same equilibrium behavior in both materials. Kinetic study shows that diffusion coefficients are in the range of 0.16 to 9 x 10(-9) cm2/s, and are not always improved in Na-rich form of clinoptilolite. The effect of temperature on diffusion coefficients is also examined, and Arrhenius activation energy is determined to be in the range of 3.02 to 13.9 kcal/mol, for all metals and materials, except Cu2+, which have extremely low activation energy in the natural sample, equal to 0.04 kcal/mol.     

Removal of toxic hexavalent chromium by polyaniline modified clinoptilolite nanoparticles

In this work clinoptilolite nanoparticles were modified with conducting polyaniline by the polymerization of anilinium cations in and out side of the clinoptilolite channels and a nanocomposite of polyaniline/clinoptilolite was obtained. Cations (Na⁺, K⁺, Mg²⁺, Ca²⁺...) in the natural clinoptilolite structure were exchanged with anilinium cations by the treatment of clinoptilolite nanoparticles in an acidic solution of aniline monomer. The cation exchange process was confirmed by elemental analysis of nitrogen and carbon atoms of anilinium cations in clinoptilolite dry powder after treatment. The polyaniline/clinoptilolite nanocomposite was obtained by the oxidative polymerization of anilinium cations within the clinoptilolite structure. The polyaniline/clinoptilolite nanocomposite was characterized utilizing FT-IR and X-ray diffraction measurements and was used for the removal of Cr(VI) from aqueous solutions in chromate anion form as an important water pollutant. The effect of a number of parameters such as initial concentration of Cr(VI), amount of nanocomposite and contact time on the removal efficiency of Cr(VI) by polyaniline/clinoptilolite nanocomposite were determined and optimized. It was found that after 5 min of exposure of nanocomposite powder with Cr(VI) solutions in the concentration range of 25 to 100 ppm, more than 98% of chromate anions can be removed and the Cr(VI) removal capacity per one gram of nanocomposite is about 0.3 mmol of Cr(VI).     

Sorption of Water-Soluble Copper(II) Compounds on Clinoptilolite

Copper(II) sorption on clinoptilolite from aqueous solutions with different pH was studied. The results were analyzed using the calculated distribution of water-soluble copper(II) species at different pH. The best conditions of copper(II) sorption on clinoptilolite from aqueous solutions were determined.     

Cesium exchange reaction on natural and modified clinoptilolite zeolites

Cesium cation exchange reaction with K, Na, Ca and Mg ions on natural and modified clinoptilolite has been studied. Batch cation-exchange experiments were performed by placing 0.5 g of clinoptilolite into 10 ml or 20 ml of 1·10⁻³M CsCl solution for differing times. Two type deposits of clinoptilolite zeolites from, Nižny Hrabovec (NH), Slovakia and Metaxades (MX), Greece were used for ion-exchange study. The distribution coefficient (K _d ) and sorption capacity (Γ) were evaluated. For the determination of K, Na, Ca and Mg isotachophoresis method, the most common cations in exchange reaction was used. Cesium sorption was studied using ¹³⁷Cs tracer and measured by γ-spectrometry.