SORPTION OF CESIUM BY HEXACYANOFERRATE COMPOSITES FROM NEUTRAL AND ACIDIC MEDIA

ABSTRACT

Silica-supported copper, cobalt, nickel and zinc hexacyanoferrate(II) composites were prepared by a modified procedure and sorption of cesium by these materials from neutral and acidic media was studied. Distribution coefficient (K_d) values in the range of 10³ to 10⁵ mL/g and capacity values in the range of 1.1 to 2.5 meq/g were obtained in neutral media. A considerable increase in K_d values and capacities was observed for cobalt composites as compared to those for the corresponding unsupported material. High K_d values (10⁴ to 10⁵) were also exhibited in nitric acid media by copper, cobalt and nickel composites but only in the presence of low concentration of hydrazine. The underlying mechanism of the sorption of trace cesium by these composites was found to be true ion exchange. Of all the composites studied, nickel-based materials were found to be most attrition-resistant in agitated test solutions. The behaviour of composites observed in this work is explained from a knowledge of known crystal structure and surface properties of pure compounds.     

Solid–Liquid and Solid–Liquid–Liquid Equilibria in the KI+H2O+i-C3H7OH Ternary System within 10–120°C

The solubility of components, phase equilibria, and critical phenomena in the ternary potassium iodide (KI) +water (H₂O) +isopropyl alcohol (i-C₃H₇OH) system were studied in the range of 10–120°C by the visual polythermal method. Potassium iodide was found to have a salting-out effect at temperatures above 97.0°C, and homogeneous water–isopropanol solutions were delaminated. The formation temperature of the critical tie line of the monotectic state (97.0°C) and the compositions of the solutions corresponding to the critical liquid–liquid solubility points at 104.2, 110.1, 115.6, and 120.1°C were determined. The distribution coefficients of isopropyl alcohol between the organic and aqueous phases in the monotectic state at 100.0, 110.0, and 120.0°C were calculated. The salting-out effect of potassium iodide relative to isopropyl alcohol from aqueous solution is small (the distribution coefficient K_d of isopropanol is 1.8 at 100.0°C) and slightly increases with temperature (K_d is 3.4 at 120.0°C).     

Synthesis,Characterization, and Applications of a New Ion Exchanger Tamarind 4-aminobenzoic Acid (TABA) Resin in Industrial Wastewater Treatment

Chromatographic column separations of toxic metal ions from industrial wastewater were achieved in acid media at optimized (K_d) values with a synthesized cation exchange TABA resin. The prepared TABA resin was characterized by FTIR, elemental, and thermogravimetric analysis. Studies of total ion exchange capacity, resin durability, and swelling were carried out. The distribution coefficient values of metal ions, viz Cu²⁺, Fe²⁺, Zn²⁺, Cd²⁺ and Pb²⁺ at different pH, were also studied using a batch equilibration method. The different factors affecting metal ions adsorption on this substrate, such as treatment time, agitation speed, and temperature, were studied in detail.     

Synthesis of Pre‐Organized Bisdiglycolamides (BisDGA) and Study of their Extraction Properties for Actinides(III) and Lanthanides(III)

Bisdiglycolamides 1–9 were synthesized and studied as extracting agents for An(III) and Ln(III) from nitric acid solutions. Compounds 1d‐3 with rigid spacers as m‐xylylene and 6b‐9 with more flexible alkyl chain linkers, show higher selectivity for Eu(III) extraction over Am(III) than diglycolamides (TBDGA, DMDODGA, TODGA) in (50:50)_%Vol HPT/1‐octanol mixture. Am(III) and Eu(III) extraction kinetics are very fast and back‐extraction with more than 99% efficiency of both cations is possible after four times of contact of the loaded solvent with fresh 0.01 mol/L nitric acid solutions.     

Behaviors of polyelectrolyte AAm/AMPS/bentonite composite hydrogels in uptake of uranyl ions from aqueous solutions

Uranyl ion (UO₂²⁺) sorption properties of polyelectrolyte composite hydrogels made by the polymerization of acrylamide (AAm) with 2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid (AMPS) and clay such as bentonite (Bent) were investigated as a function of composition to find materials with swelling and uranyl ion sorption properties. Highly swollen AAm/AMPS hydrogels and AAm/AMPS/Bent composite hydrogels were prepared by free radical solution polymerization in aqueous solutions of AAm with AMPS as co‐monomer and two multifunctional crosslinkers such as ethylene glycol dimethacrylate (EGDMA) and 1,4 butanediol dimethacrylate (BDMA). Swelling experiments were performed in water at 25°C, gravimetrically. The influence of AMPS content in hydrogels was examined. Uranyl ion adsorption from aqueous solutions was studied by batch sorption technique at 25°C. The effect of uranyl ion concentration and mass of AMPS on the uranyl ion adsorption were examined. Finally, adsorption capacity (the amount of sorbed uranyl ion per gram of dry hydrogel) (q) was calculated to be 0.67 × 10⁻³–2.11 × 10⁻³ mol uranyl ion per gram for the hydrogels. Removal effiency of uranyl ions (RE%) was changed range 9.05–29.92%. The values of partition ratio (K_d) of uranyl ions was calculated to be 0.10–0.43 for AAm/AMPS hydrogels and AAm/AMPS/Bent composite hydrogels, respectively. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Structure and transport properties of the novel (Dy,Er,Gd,Ho,Y)3Fe5O12 and (Dy,Gd,Ho,Sm,Y)3Fe5O12 high entropy garnets

High-entropy, iron-containing, garnet-structured oxides with (Dy,Er,Gd,Ho,Y)₃Fe₅O₁₂ and (Dy,Gd,Ho,Sm,Y)₃Fe₅O₁₂ compositions are synthesized for the first time. A modified Pechini method followed by calcination at 700 °C and sintering at 1300 °C enables obtaining single-phase, homogenous materials of cubic structure with Ia-3d symmetry. High-temperature in-situ X-ray diffraction studies show excellent phase stability of the garnets, as well as moderate thermal expansion coefficient, ca. 11·10^?6 K^-1 in 25?1000 °C temperature range. Raman spectroscopy measurements indicate the presence of local distortion of structural polyhedra, likely associated with the high-entropy effect. The collected Mossbauer spectra confirm distorted character of the lattice. Influenced by the presence of Fe³⁺ in locally distorted octahedra and tetrahedra, the electrical conduction at low temperatures of both oxides remains much lower comparing to Y₃Fe₅O₁₂ (yttrium iron garnet - YIG), as well as to other rare-earth garnets up to 600 °C, where it reaches value similar to YIG.     

SORPTION BEHAVIOR OF PERTECHNETATE ION ON REILLEXTM-HPQ ANION EXCHANGE RESIN FROM HANFORD AND MELTON VALLEY TANK WASTE SIMULANTS AND SODIUM HYDROXIDE/SODIUM NITRATE SOLUTIONS

ABSTRACT

The batch distribution coefficients (K_d, mL solution /g dry resin) for pertechnetate (TcO₄) between Reillex^TMHPQ anion exchange resin and various caustic solutions have been determined. The average K_d value in 1.5 M NaNO₃/l.0 M NaOH solution is (262.2 ± 12.6) mL7sol;g for TcO₄ ^? ranging from 1.0 × 10^TM M to 5.0 × 10^?4 M. Pertechnetate K_d values were measured in a series of NaOH7sol;NaNO₃ solutions. The series are: 1.00 M NaOH with 0.010 to 5.00 M NaNO₃; 0.100 M NaOH with 0,010 to 5.00 M NaNO₃; 0.100 MNaNO₃ with 0.10 to 5.00M NaOH; 1.00MNaNO₃ with 0.10 to 5.00 M NaOH; 1.50 M NaNO₃ with 0.10 to 5.00 M NaOH; 3.50 M NaNO₃ With 0.10 to 5.00 M NaOH. The K_d values are described by the following equation.

This equation was used to predict the K_d values for a series of tank waste simulants. The predicted K_d values are different from the measured values with an average absolute difference of (29 ± 10)%.

Pertechnetate k_dvalues for 101-SY, 103-SY, DSS, DSSF-2.33, DSSF-5, DSSF7, 101-AW, and Melton Valley simulants have been determined as a function of time. A first order approach to equilibrium is observed. The K_d values at two hours are (1066±45), (870± 102), (346± 18), (296± 15), (245 ±6), (209± II), (218±5), and (167 ± 5) mL/g, respectively.     

Kinetic Studies on the Exchange of Bivalent Metal Ions on Amberlite IRC‐718—An Iminodiacetate Resin

Abstract

The rate of uptake of alkaline earth metals, copper, and lead have been investigated by a chelating ion exchange resin containing iminodiacetic acid as ligand attached to the copolymer of styrene and divinyl benzene of macroporous matrix structure. It binds alkaline earth metals, Cu, and Pb by the formation of chelate complexes with the carboxylate group of this resin. The experiments discussed in this work have allowed to establish the paramount importance of the presence of this chelating group in obtaining practically useful rates of metal ion uptake. The kinetic parameters like diffusion coefficient (D _o), activation energies (ΔE _a) and entropy of activation have been evaluated under the conditions favoring a particle diffusion control mechanism and the study followed the three models i.e., Nernst Planck, B _t technique and Ash model. K _d values in demineralised water (DMW) were found in the order Cu²⁺ > Pb²⁺ > Mg²⁺ > Sr²⁺ > Ba²⁺ > Ca²⁺.     

Synthesis and characterization of poly(benzimidazolium) membranes for anion exchange membrane fuel cells

Poly(dimethyl benzimidazolium) iodides were synthesized from polybenzimidazole derivatives by permethylation. They were easily changed to OH^?, CO₃ ^2? and HCO₃ ^? ion conducting electrolytes by immersing in 1 M of KOH, K₂CO₃ and KHCO₃. Properties of polymers were changed by the ion exchange process. The anion conducting membranes showed tough and flexible properties. The water uptake, ion exchange capacity and conductivity varied depending on the counter anions. One of the poly(dimethyl benzimidazolium) carbonate membranes, Me-DAB-OBBA-carbonate showed the highest water uptake (59 %) as well as ion conductivity (33.74 mS/cm at 80 °C), and could be a good candidate for an anion exchange membrane for anion exchange membrane fuel cells.     

Advanced visible-light photocatalytic property of biologically structured carbon/ceria hybrid multilayer membranes prepared by bamboo leaves

Biologically structured carbon/cerium dioxide materials are synthesized by biological templates. The microscopic morphology, structure and the effects of different oxidation temperatures on materials are characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD) ultraviolet-visible light spectrum (UV–Vis) and X-ray Photoelectron Spectroscopy (XPS). Moreover, by splitting water under visible light irradiation, the hydrogen production is measured to test the photocatalytic property of these materials. The results show that materials made with bamboo biological templates which are immersed in 0.1 mol L^?1 of cerium nitrate solution, then carbonizated in nitrogen (700 °C) and oxidized in air (500–600 °C), can obtain the biological structure of bamboo leaves. The product is in the composition of hybrid multilayer membrane, which one is carbon membrane form plant cell carbonation and another is ceria membrane by nanoparticle self assembly. The best oxidation temperature is 550 °C and the band gap of carbon/cerium dioxide materials synthesized at this optimum oxidation temperature could be reduced to 2.75 eV. After exposure to visible light for 6 h, the optimal hydrogen production is about 302 μmol g^?1, which is much higher than that of pure CeO₂.     

Synthesis and properties of sulfonated poly(arylene ether nitrile) copolymers containing carboxyl groups for proton‐exchange membrane materials

A series of sulfonated poly(arylene ether nitrile) copolymers containing carboxyl groups were synthesized via a nucleophilic aromatic substitution reaction from phenolphthalein, hydroquinone sulfonic acid potassium salt, and 2,6‐difluorobenzonitrile in N‐methyl pyrrolidone (NMP) with K₂CO₃ as a catalyst. The synthesized copolymers had good solubility in common polar organic solvents and could be easily processed into membranes from solutions of dimethyl sulfoxide, NMP, N,N′‐dimethyl acetylamide, and dimethylformamide. Typical membranes in acid form were gained, and the chemical structures of these membranes were characterized by Fourier transform infrared analysis. The thermal properties, fluorescence properties, water uptake, ion‐exchange capacity, and proton conductivities of these copolymers were also investigated. The results indicate that they had high glass‐transition temperatures in the range 151–187°C and good thermal stability, with the 10 wt% loss temperatures ranging from 330 to 351°C under nitrogen. The copolymers showed characteristic unimodal ultraviolet–visible (UV–vis) absorption and fluorescence emission, and the UV–vis absorption, fluorescence excitation, and emission peaks of the copolymers were obvious. Moreover, the copolymer membranes showed good water uptake and proton conductivities at room temperature and 55% relative humidity because of the introduction of both sulfonic acid groups and carboxyl groups into the copolymers, whose contents were in ranges 18.45–67.86 and 3.4 × 10^?4 to 3.0 × 10^?3 s/cm, respectively. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40213.     

SEPARATION OF COBALT(II) AND NICKEL(II) IONS FROM ACID AQUEOUS SOLUTIONS BY Co IT ION-EXCHANGE INTO γ-TITANIUM PHOSPHATE

ABSTRACT

The Co²⁺-2H⁺, Ni²⁺-2H⁺, and Co²⁺-Ni²⁺-2H⁺ ion exchange processes into γ-Ti(H₂PO₄)(PO₄)2H₂O were studied. Exchange isothenns and titration curves were obtained. Monometallic half ion exchange phases were formed by using MC₂+HCl (M=Co,Ni) solutions. Equilibrium constants, free energy, enthalpy, and entropy of the Co²⁺-2H²⁺ ion exchange reaction were determined. In (Co,Ni)Cl₂ solutions, bimetallic a half ion exchange substitution solid solution is detected. Equilibrium constant of the Co²⁺-Ni²⁺ substitution process in the γ-Ti(Co_xNi_0.5?x.HPO₄)(PO₄)nH₂O phase at 85°C was determined. In (Co,Ni)Cl₂+HCl solutions, total separation of Co²⁺ and Ni²⁺ is obtained.     

The Synthesis of New N2S2‐Macrocyclic Schiff Base Ligands and Investigation of Their Ion Extraction Capability from Aqueous Media

Abstract

Two new macrocyclic Schiff bases, (5) and (7), containing nitrogen‐sulfur donor atoms were designed and synthesized by reaction of α,α′ bis(o‐aminophenylthio)‐1,2‐xylene with glyoxal and phthaldialdehyde, respectively. The liquid‐liquid extraction of metal picrates such as Ag⁺, Hg²⁺, Cd²⁺, Zn²⁺, Cu²⁺, Ni²⁺, Mn²⁺, K⁺, and Na⁺ from aqueous phase to the organic phase was carried out using the novel ligands. The effect of chloroform and dichloromethane as organic solvents over the metal picrate extractions was investigated at 25±0.1°C by using UV‐visible spectrometry. The extractability and selectivity of the tested metal picrates were evaluated. The values of the extraction constants (log K_ex) were determined for the extracted complexes.     

Improvement of Zeolite T Membrane via Clear Solution Gel in Dehydration of Methanol,Ethanol, and 2-Propanol

Using of clear gel solution on synthesis of zeolite membrane can potentially have many benefits. In this research, zeolite T membrane on home-made α-Alumina disc-shaped MF support was successfully synthesized in 120°C for 24 h via secondary growth hydrothermal method using high alkalinity clear gel solution in molar ratio formulation (SiO₂:Al₂O₃:Na₂O:K₂O:H₂O = 55:1:122.7:42.3:2000). The synthesized membrane showed elevated selectivity in dehydration of ethanol/water and 2-propanol/water solutions (between 1000 to more than 10000) and high-water permeation fluxes (between 1.2 to 2.4 kg/m²h at 40°C for 10 wt.% water content). The synthesized MF alumina supports, zeolite T membranes, and crystals used for seeding were characterized by XRD and SEM analyses. These analyses indicated 10 μm dense and defect-free well-intergrowth zeolite T as active layers were formed on the porous media support.     

Synthesis and characterization of a new guar gum 4‐hydroxybenzoic acid resin and its use for the separation of heavy metal ions in industrial effluents

Hydroxybenzoic acid group has been incorporated onto guar gum by modified Porath's method of functionalization of polysaccharides. The newly synthesized guar gum 4‐hydroxybenzoic acid (GHBA) resin was characterized by Fourier‐transform infrared spectroscopy, elemental analysis, ion‐exchange capacity, column reusability, and physicochemical properties. The distribution coefficient (K_d) values and effect of pH on chelation of these metal ions using batch method were studied. The separations of mixture of Fe²⁺, Zn²⁺, Cu²⁺, Cd²⁺, and Pb²⁺ metal ions on GHBA resin on the basis of their distribution coefficient at various pH were also achieved using column chromatography. The effect of experimental parameters such as pH, treatment time, agitation speed, temperature, adsorbent dose, initial metal ion concentration, and flow rate on the removal of metal ions has been also studied. GHBA resin is effective adsorbents for the removal of different toxic metal ions from aqueous solutions and follows the order: Fe²⁺ > Zn²⁺ > Cu²⁺ > Cd²⁺ > Pb²⁺. POLYM. ENG. SCI. 2013. © 2012 Society of Plastics Engineers     

Solvent Extraction of Au(III) by the Chloride Salt of the Amine Alamine 304 and Its Application to a Solid Supported Liquid Membrane System

Abstract

The extraction of Au(III) by the chloride salt of the amine Alamine 304 (R₃NH⁺Cl^?) in xylene from hydrochloric acid solutions has been investigated. The analysis of metal distribution data by numerical calculations suggested the formation of the species R₃NH⁺AuCl₄ ^? in the organic phase with formation constant log K _ext = 5.44. The results obtained on Au(III) distribution have been implemented in a solid‐supported liquid membrane system, where in NaSCN solutions were found to be the most effective to strip the metal from the organic solution. Influence of membrane composition, metal concentration on gold transport, and the selectivity of the system have also been studied.     

Evaluation of a (E,E)‐Dioxime Containing Two 15‐Membered Dioxatrithiamacrocycles and its Mononuclear Ni(II) Complex as Ag+ Extractants

Abstract

A macrocyclic vic‐dioxime (1) and its mononuclear Ni(II) complex (2) were studied as extractant. The aqueous solutions of Ag⁺, Mn²⁺, Pb²⁺, Ni²⁺, Cu²⁺, Cd²⁺, and Zn²⁺ picrates were used for extraction experiments. The solutions of the ligands in two different organic solvents were used as organic phases. The metal picrate extractions were carried out at 25±0.1°C by using UV‐visible spectrometry. The most effective transport was observed for Ag⁺ picrate among the tested metal picrates. The effect of pH on the extraction of Ag⁺ picrate was evaluated with the ligands. The ratio of extracted Ag‐complex to chloroform phase was 2:1 (L:M) for (2). In other cases the ratios were 1:1 for both (1) and (2). Molar ratio method was also used to demonstrate the composition. The values of the extraction constants (log K_ex) were determined for the extracted Ag‐complexes.     

Ion‐Exchange Separation of Pu from Macro Concentration of Th in HNO3 Medium

Abstract

Sorption behavior of Th and Pu from anion‐ as well as cation‐exchange resin was investigated from nitric acid medium by both batch and column methods. The anion‐exchange studies involved anionic nitrate complexes of Pu⁴⁺ and Th⁴⁺ sorbed onto DOWEX 1x4 resin (50–100 mesh), and the cation‐exchange studies involved the sorption of Pu³⁺ and Th⁴⁺ onto BIORAD AG 50Wx8 (50–100 mesh) or DOWEX 50Wx4 (50–100 mesh) resin. The batch data gave a separation factor (K _d,Pu/K _d,Th) of 22 for the anion‐exchange method and 0.017 for the cation‐exchange method at 3 and 2 M HNO₃, respectively. A two‐stage ion‐exchange separation method was developed for the quantitative separation of Pu (8 g/L) from a macro amount of Th (200 g/L) in nitric acid medium. The first step involved the quantitative sorption of plutonium from the mixture while about 90% of Th could be washed in 6 column volumes. The plutonium, eluted (as Pu³⁺) using 0.5 M HNO₃ + 0.2 M hydrazinium nitrate (HN) + 0.2 M hydroxyl ammonium nitrate (HAN), and the residual (～10%) Th were subsequently loaded onto a cation‐exchange column in the second step. Greater than 99% Pu was recovered with 2 M HNO₃ (in ～8 column volumes) containing 0.2 M HN + 0.2 M HAN. The final elution of thorium from the cation‐exchange column was achieved in about 6 column volumes of 1 M α‐hydroxy isobutyric acid. A (Pu, Th)O₂ fuel scrap sample was dissolved in 16 M HNO₃ containing 0.005 M HF and was used subsequently as the feed for the anion‐exchange column. The eluted Pu was subsequently loaded onto a cation‐exchange column for final purification. The recovery of plutonium and thorium was found to be >99% and >98%, respectively, while the respective decontamination factors were estimated to be 215 and 292.     

Removal of toxic metal ions by using composite cation-exchange material

Polyanilinezirconium(IV) arsenate composite cation exchange material was synthesized under different experimental conditions by the incorporation of polyaniline into the matrices of inorganic precipitate (zirconium(IV)arsenate). The experimental parameters such as concentration, mixing volume ratio, and pH were established for the synthesis of the material. Ion-exchange material that was synthesized at pH 1.0 showed an ion exchange capacity of 1.33 meq g⁻¹ for Na⁺ ions. The composite material exhibits improved ion-exchange capacity along with chemical and thermal stability. The exchanger was characterized based on FTIR, TGA, XRD, and SEM analysis. The X-ray diffraction study shows semi-crystalline nature of the material. The distribution coefficient studies (K_d) of metal ions on the material were performed in diverse solvent systems. Based on K_d values the material was found to be selective for Pb(II) and Hg(II) ions. Some analytically important binary separations of metal ions in synthetic mixtures viz. Ba²⁺-Pb²⁺, Pb²⁺-Ni²⁺, Cd²⁺-Hg²⁺, Ni²⁺-Hg²⁺, Zn²⁺-Pb²⁺, Ca²⁺-Bi³⁺, Al³⁺-Hg²⁺, and Ca²⁺-Pb²⁺ were achieved on the columns of polyanilinezirconium(IV) arsenate cation exchanger. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis and characterization of PPY/K[Fe(CN)3(OH)(en)] nanocomposite: Study of photocatalytic,sorption, electrical,and thermal properties

This work involves the synthesis of nanocomposite of Polypyrrole (PPY) with photoadduct {K[Fe(CN)₃(OH)(en)]} via in‐situ oxidative chemical polymerisation. Photoadduct is synthesized by irradiating equimolar mixture of potassium hexacyanoferrate (III) and ethylenediamine (en) and is then reduced to nanosize by high energy ball mill. Successful synthesis of nanophotoadduct is confirmed by elemental analyser, UV–Vis, and FTIR. The nanocomposite of PPY and photoadduct has been characterised by SEM, TEM, FTIR, XRD, TGA, UV–Vis spectroscopy, I–V characteristics, and dielectric analysis for structural, thermal, optical, electrical, and dielectric properties. The average particle size of nanophotoadduct and nanocomposite has been found to be 80 and 84 nm, respectively. The thermal stability of nanocomposite is enhanced. The nanocomposite shows high value of dielectric constant (5 × 10³ at10³ Hz) and ac conductivity (7.0 × 10⁸ Sm^?1 at 10⁶ Hz) as compared with pure PPY. The high value of dielectric constant can make the material suited for energy storage applications. The nanocomposite shows higher photocatalytic activity as compared with pure PPY and a high value of distribution coefficient (K_d) has been obtained for Pb²⁺, Zn²⁺, and Cd²⁺ ions, hence, can act as an efficient material for removal of dyes and heavy metal ions in waste water. Thus, photoadduct of K₃[Fe(CN)₆] and ethylenediamine(en), a new kind of filler, has succeeded in improving the properties of PPY with respect to thermal stability, high dielectric constant, high ac conductivity, efficient photocatalytic activity, and high K_d value for toxic metal ions. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43487.