Study of nitric acid leachout characteristics from weak base anion exchanger to maintain a specified pH regime during Gd(NO3)3 removal from moderator system of 540 MWe PHWRs

Nitric acid leachout characteristics from weak base anion exchanger (WBA) have been experimentally evaluated as a function of total nitric acid loading at a given flow velocity. An empirical first order model is used to explain the column outlet behaviour. Based on the experimental evaluation, a column configuration of a strong acid cation exchanger (SAC) topped mixed bed of SAC and WBA followed by a 5% nitric acid loaded WBA as the bottom layer of the column has been used to remove Gd(NO₃)₃ from water while maintaining the column outlet pH in the range of 5.0–5.5.     

Effect of Mg2+, Li+, Na+ and K+ on the Electrocrystallization of Nickel from Aqueous Sulfate solutions containing Boric Acid

The effects of metal ions such as Mg²⁺, Li⁺, Na⁺ and K⁺ on the cathodic current efficiency, deposit morphology, crystallographic orientation and polarization behaviour during nickel deposition on stainless steel from aqueous sulfate solutions containing boric acid were investigated. There was virtually no change in current efficiency in presence of these metal ions, but changes were observed in the deposit morphologies and crystal orientations even though all the deposits looked bright, smooth and coherent. Changes were also observed in the polarization behaviour during nickel electrocrystallization in presence and absence of boric acid. An attempt has been made to correlate the effect of these metal ions on various parameters studied.     

Ion exchange in concentrated media. Correlations for variation of selectivity coefficients with medium

An attempt to relate the different values of the ion-exchange selectivity coefficient in different media is made by considering the two phases as ionic solutions where the activity coefficients of species can be evaluated by means of Mikulin's equation.The selectivity coefficients of the NH₄⁺/H⁺, Na⁺/H⁺, and Li⁺/H⁺ exchanges in a sulfonated cation exchanger and of the NO₃⁻/Cl⁻ exchange in a quaternary ammonium anion exchanger have been measured under different conditions characterized by the degree of crosslinking of the ion exchanger, the water activity of the solution, the concentration ratio of two counterions, and the concentration ratio of a third possible counterion.The water activity of the solution is an essential parameter to be controlled, particularly in dilute or moderately concentrated solutions. A representation of the experimental results on the ion-exchange selectivity coefficient is given in terms of two parameters allowing the selectivity coefficient to be predicted even in very concentrated ionic media.     

THE A1-13-PHOSPHATOANTIMONIC ACID SYNTHESIS AND ION EXCHANGE PROPERTIES

Abstract

ABSTRACT The AI-13-phosphatoantimonic acid Al-13-Sb₃P2O₁₄.x H₂O has been prepared starting from K₃Sb₃p₂O₁₄. Thermal behaviour has been studied using TGA and DTA. pH titration curves of Al-13-phosphatoantimonic acid with alkali, hydroxide solutions (Na⁺, K ⁺ and Li⁺) shows a very promising ion exchanger. However, the capacities of the alkali metal were 4.08, 4.32 and 7.2 meq/g for Li⁺, Na⁺ and K⁺ respectively.     

Removal of Co, Cs, and Zr radioisotopes from aqueous solutions using cellulose iminodiacetic acid chelating cum cation-exchanger

The iminodiacetic acid group containing resin acts as a chelating ion exchanger as well as a weakly acidic cation exchanger, depending upon the species present in the solution. Iminodiacetic acid group has been incorporated onto cellulose by a modified Porath's method of functionalization of polysaccharides. The resin has been used for removal of ⁵⁸Co, ¹³⁴Cs, and ⁹⁵Zr radioisotopes from their separate aqueous solutions. ⁹⁵Zr as [Zr(OH)₂(H₂O)₄]⁸⁺ tetrameric species is adsorbed from the aqueous solution at low pH through cation exchange cum chelate formation. ⁵⁸Co as Co²⁺ is complexed with the resin. ¹³⁴Cs as Cs⁺ is exchanged with equivalent amount of H⁺ ions. Cs⁺ was eluted from resin using 0.3N HCl, Co²⁺ with 4N HCl and Zr(IV) with 5N HCl. Final disposal of the resin can be done by encapsulation in the cement concrete.     

SYNTHETIC INORGANIC ION-EXCHANGE MATERIALS. XXXXI. ION EXCHANGE EQUILIBRIA OF ALKALI METAL IONS/HYDROGEN IONS ON TIN(IV) ANTIMONATE

Ion exchange equilibria of alkali metal ions (Li⁺, Na⁺, K⁺,, Rb⁺, and Cs⁺)H⁺, systems have been studied in MNO-j-HNOj media with ionic strength of 0.1 at 30, 45 and 60 °C on tin(IV) antimonate as a cation exchanger. The ion exchange isotherms have been measured for both forward and backward reactions by the batch technique. The isotherms showed S-shaped curves for all exchange systems studied. The selectivity coefficients (logarithmic scale) vary with the equivalent fraction X_M of alkali metal ions in the exchanger and give two linear functions of X_M with a break point (X_M= 0.14, except 0.04 for Li⁺, /H⁺) indicating two different exchanging sites. The selectivity sequence, Na⁺, ? K⁺, ? Rb⁺, ? Cs⁺, ? ? Li, holds in the range of Xu= (0 - 0.04) and the sequence, Cs < Rb ⁺, ? K ⁺, ? Na ⁺, < Li ⁺, applies when X_M is higher than 0.14.

Hypothetical thermodynamic data on “zero loading” of the ion exchange reaction was evaluated.     

Selectivity and competitive mechanism of cation exchange resin for Fe,Mg, and Al ions in phosphoric acid

The presence of iron, magnesium, and aluminum elements as the primary impurities in wet-process phosphoric acid (WPA) adversely affects the industrial phosphoric acid and subsequent phosphorus chemical products. This study aims to investigate the selectivity and competition mechanism of Sinco-430 cation exchange resin for Fe, Mg, and Al ions in phosphoric acid solution. By studying the effects of different process conditions on the removal efficiency, the suitable conditions for the static removal of metal ions from Fe-Mg, Al-Mg, and Fe-Al binary systems were determined: solid–liquid mass ratio (S/L) of 0.3, phosphoric acid concentration of 27.61 wt.%, system temperature of 50°C, and rotational speeds of 200, 400, and 200 rpm, respectively. By calculating the selectivity coefficients of the resin for metal ions under different experimental conditions and mutual replacement experiments, the semi-empirical formulas for the selectivity coefficients were derived and order of selectivity was determined as follows: Mg²⁺ > Fe²⁺ > Al³⁺. Visual MINTEQ 3.1 software and density functional theory (DFT) calculations demonstrated that at low pH, the main forms of Fe, Mg, and Al present in phosphoric acid were FeH₂PO₄⁺, Mg²⁺, and AlH₂PO₄²⁺, respectively. This finding explained the differences in selectivity of the resin for Fe, Mg, and Al. The dynamic removal of metal ions from phosphoric acid was investigated. The order of metal ion selectivity of the resin by the dynamic method is the same as that of the static method, and the dynamic exchange behaviour was most consistent with the Yan model.     

Amino acid sensing by impedance of porous monolith-type ion exchanger

A biological and chemical sensor with rapid response at the microlevel is required for health and environmental monitoring. To develop a high-performance sensor, we use a porous monolith-type ion exchanger having three-dimensional acceptors to sense chemical substances. This porous monolith-type ion exchanger has an open-cellular structure with 5-50-μm diameter pores. The concentration of amino acids in the solution can be detected by measuring the impedance of the monolith-type ion exchanger. The novel ion exchanger has a high-exchange rate and high-electrical conductivity compared with that of the conventional ion-exchange resins. It is found that the impedance of the porous ion exchanger varies widely, depending on the amino acids such as glycine, asparatic acid, lysine, and phenylalanine. The impedance of anion exchanger had the highest value for phenylalanine with a benzene ring. OH-ion conduction is suppressed possibly due to the phenylalanine molecules stabilized by the hydrophobic interaction with the anion exchanger. In addition, we succeeded in sensing amino acid ions with concentration as low as 10⁻⁷ mol. The porous ion exchanger has the potential of a high-performance device for biological and chemical sensing.     

Boric acid recovery using polymer filtration: Studies with alkyl monool,diol, and triol containing polyethylenimines

Three water‐soluble polymers containing linear alkyl monool, 1,2‐diol, and 1,2,3‐triol groups, mostly on the primary amines of polyethylenimine, were synthesized, characterized, and tested for their ability to recover boric acid. The boron‐binding capacities of these polymers and the backbone polyethylenimine were determined by titration, ultrafiltration, and inductively coupled plasma/atomic emission spectroscopy analysis. At low boron concentrations, the 1,2,3‐triol polymer performed better than the 1,2‐diol, whereas at high boron concentrations, the 1,2‐diol outperformed the 1,2,3‐triol. ¹¹B‐NMR spectroscopy and retention studies with various salt concentrations indicated that boron interacted with these two polymers by means of ion pairing with the protonated amines and by borate ester formation. For the monool and the polyethylenimine backbone, the mechanism for boron binding was ion pairing only. These polymers are under consideration for the selective recovery and recycling of enriched boric acid used in the primary coolant loop of pressurized water nuclear reactors. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1590–1604, 2005     

Enhancement of uranyl ion uptake by prestructuring of acrylamide–maleic acid hydrogels

Acrylamide–maleic acid (AAm–MA) hydrogels were prepared by gamma‐irradiation of their aqueous solutions. UO₂⁺² ion uptake on P(AAm–MA) hydrogels was investigated using two types of gel systems prepared by a simple irradiation method and a prestructured reaction. It has been observed that gels prestructured with UO₂⁺² ions adsorbed approximately 15–20% more UO₂⁺² ions than gels prepared in pure water (the usual method). It was also found that the uranyl ion adsorption capacity of hydrogels increased with an increasing amount of maleic acid in the gel system and an increasing concentration of uranyl ion in the solution. A possible interaction mechanism between the groups in the copolymeric gels and UO₂⁺² ion has been proposed based on the stoichiometry and the spectroscopic evidence. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 284–289, 2000     

Removal of nitrogen containing reducing agents from water coolant systems using ion exchange resin and membranes

Oxidizing environment prevailing in water coolant systems aggravates the corrosion of structural materials. Reducing agents are added to the reactor coolant systems to control the oxidants and mitigate material corrosion. Maintenance of required concentration of the reducing agents in the system and their removal after completing the processes can be done using ion exchange resins as well as ion exchange membranes. In this article, a comparative study on the efficacy in removing the reducing agents from aqueous solutions by the cation exchange resin and membranes such as sulfonated polysulfone and nafion is evaluated. Some of the membranes were synthesized in the laboratory and characterized by SEM, FTIR and pure water flux studies. Nitrogen containing reducing agents such as hydrazine, hydroxylamine, and ammonium hydroxide have been chosen for the study. Results indicate that strong acid cation exchange (SAC) resin taken in a column and sulfonated polysulfone (SPSf) membrane as a stack are found to be equally efficient in purification of coolant system from the added reducing agents. Uptake of metal ions was observed to be higher on SAC resin column in presence of reducing agent. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44588.     

Ion Exchange Kinetics of Heavy Metal Ions on Organic–Inorganic Composite Cation Exchanger Poly-o-toluidine Zr(IV) Tungstate

To study the ion exchange kinetics of heavy metal ions on the organic–inorganic composite cation exchanger poly-o-toluidine Zr(IV) tungstate, Nernst–Planck was computer simulated. Simulated numerical results for counter ions (Cu, Zn, Cd and Pb) of equal valence and four different ionic mobilities are presented to understand the ionic diffusion process. These results are based on the fractional attainment of equilibrium U(τ), of the counter ions under study. The forward (M²⁺–H⁺) and reverse (H⁺–M²⁺) ion exchange processes are justified as the particle diffusion phenomenon. The self-diffusion coefficient (D _o ), energy of activation (E _a ), and entropy of activation (?S*) have also been estimated to understand the ion exchange process occurring over the surface of this cation exchanger and indicated that the ion exchange process is feasible and spontaneous. It is concluded that the difference in activation energies and entropy of activation may facilitate the separation of metal ions. The regeneration capability of this cation exchanger was also explained.     

Poly(oligo-oxyethylene methacrylate-co-alkali metal acrylamidocaproate) as a single ion conductor

Summary The new single ion conductors, poly(oligo-oxyethylene methacrylate-co-alkali metal acrylamidocaproic acid) ((CH₂CCH₃COO(CH₂CH₂O)₉H)_x–(CH₂CHCONH(CH₂)₅ COO-M⁺)_1-x), M⁺=Li⁺, Na⁺, K⁺, were synthesized and the effects of the cation and the temperature on ionic conductivity were investigated. The alkyl spacer in the alkali metal acrylamidocaproate was introduced to increase the flexibility of the side chain for the complex formation between the ionic groups and the oxygens in PEO unit. The room temperature(30°C) conductivity of the K single ion conductor was found to be 5x10^-7 S/cm which is the highest value reported for the single ion conductors having carboxylate groups without any additives. The pseudo-activation energy in the VTF equation was not dependent on the type of the cation, which indicates that the ion hopping rate is higher than the string renewal rate in these single ion conductors.     

Dissolution mechanism of colemanite in sulphuric acid solutions

Boron compounds are very important raw materials in many branches of industry and their uses have been increasing and expanding continuously. Colemanite, one of the most common boron minerals, has a monoclinic crystal structure with a chemical formula of 2CaO·3B₂O₃·5H₂O and is used usually in the production of boric acid. The present study concerns and investigation of the dissolution mechanism of colemanite in H₂SO₄ solution and the effect of acid concentration, the effect of SO₄⁻² ion on the dissolution process, using H₂SO₄, HCI+H₂SO₄ and H₂SO₄+Na₂SO₄ solutions. The analysis of the experimental data shows that increasing H₃O⁺ acid concentration increased the dissolution rate, but increasing SO₄⁻² concentration reduced dissolution rate because of the precipitation of a solid film of CaSO₄ and CaSO₄·H₂O.     

Synthesis and properties of a cellulose exchanger with the crown ether diaminodibenzo-17-crown-5 as anchor group

A new cellulose exchanger was synthesized from “o-aminophenolcellulose” by diazotation and coupling with diaminodibenzo-17-crown-5. The distribution coefficients for Ca²⁺, Sr²⁺, Ba²⁺, Na⁺ and K⁺ were determined in water/methanol mixtures as a function of the water content. Separation of Ca²⁺, Na⁺ and K⁺ and fractionation of the calcium isotopes ⁴⁸Ca and ⁴⁰Ca were investigated. The enrichment factor ε = 4.9 · 10^?3 for ⁴⁸Ca²⁺ is appreciably higher than that found for cation exchange resins with ? SO₃H groups, but lower than that reported for certain cryptands.     

Characterization and adsorption behavior of newly synthesized sodium bis(2-ethylhexyl) sulfosuccinate–cerium (IV) phosphate (AOT–CeP) cation exchanger

A new cationic exchange material, sodium bis(2-ethylhexyl) sulfosuccinate (AOT) with cerium (IV) phosphate (AOT–CeP) has been synthesized. The characterization of the ion exchanger was performed by using infra red spectroscopy (IR), X-ray diffraction (XRD), scanning electron microscopy (SEM), thermo gravimetric analysis/differential thermo gravimetric analysis (TGA/DTA/DTG) and elemental analysis. The ion exchange properties like ion exchange capacity, elution and concentration behavior of AOT–CeP were determined by taking the material into a column and elution of H⁺ was done by NaNO₃. The thermal stability of the ion exchanger was studied by determining ion exchange capacity after heating to different temperatures for one hour. The adsorption studies on AOT–CeP demonstrated that the material is selective for Cu²⁺, Pb²⁺, Cd²⁺, Zn²⁺ and Hg²⁺ ions. AOT–CeP was found to be effective for the separation of Cu²⁺, Pb²⁺, Cd²⁺, Zn²⁺ and Hg²⁺ ions in the presence of alkali metals/alkaline earth metals. This cationic exchanger was also effective for the removal of Cu²⁺, Pb²⁺, Cd²⁺, Zn²⁺ and Hg²⁺ ions in the presence of acid and other transition metal ions. Thus, AOT–CeP can be used for the removal of these ions from the waste water during its treatment.     

Role of boric acid in the formation of poly(vinyl alcohol)-iodine complexes in undrawn films

The role of boric acid in the formation of poly(vinyl alcohol) (PVA)-iodine complexes in undrawn films has been investigated by using wide-angle X-ray diffraction (WAXD) and high-resolution solid-state ¹³C NMR spectroscopy. From UV-vis absorption spectroscopy, it is confirmed that boric acid is necessary for the formation of the complexes in films that are treated with I₂/KI aqueous solutions at relatively low I₂ concentrations. The WAXD profiles indicate that, irrespective of the presence of iodine, crystallite sizes perpendicular to the chain axis become smaller by the addition of boric acid in the swelling media. Moreover, small crystallites and surficial parts of larger crystallites may be partially dissolved in the swelling process with water and boric acid suppresses the re-crystallization in the drying process with or without iodine. The ¹³C spin-lattice relaxation time analysis reveals that there exist two components called the mobile and the less mobile components in the films and the latter component, which contains the complexes and the crystalline component, is increased in the fraction by the presence of boric acid. The evaluation of the CH resonance line shows that some of the intermolecular hydrogen bonds are broken by boric acid, which increases the intramolecular hydrogen bonds. The CH₂ lineshape analysis also reveals that the gauche fraction is appreciably increased in the less mobile component by the addition of boric acid. These facts suggest that boric acid may promote the formation of PVA-iodine complexes particularly in the surficial areas of the crystallites probably by reducing the molecular mobility of the PVA chains by causing cross-linking among them.     

Influence of interlayer cations on the water sorption and swelling–shrinkage of MX80 bentonite

The potential of water sorption and swelling–shrinkage in the expansive clays is practically defined by the nature of interlayer cations. The purpose of this paper is to estimate the effects of the cation saturation (Mg⁺, Ca⁺, Li⁺, Na⁺, and K⁺) on the swelling–shrinkage behaviour of the MX80 bentonite.The MX80 bentonite (a “commercial clay”) was treated with concentrated solutions (1 N) of sodium, calcium, magnesium, potassium, and lithium chlorides. This treatment was made three times with constant agitation for 1 h. Then, the clay was washed three times with distilled water. The scanning transmission electron microscopy (STEM) and inductively coupled plasma atomic emission microscopy (ICP-AES) analyses were used to verify the efficiency of the cation saturation.Finally, two techniques were employed to estimate the effect of the cation saturation on the swelling–shrinkage behaviour of the bentonite: the first one uses an isothermal system of water adsorption, where the water activity is controlled by a supersaturated salt solution. In the second, environmental scanning electron microscopy (ESEM), coupled with a digital image analysis (DIA) program, was used to estimate the swelling–shrinkage potential at different water activities. The swelling–shrinkage isotherms were always estimated on isolated aggregates.The isotherms of water adsorption and swelling–shrinkage of the bentonite MX80 show that the amount of adsorbed water and the swelling–shrinkage potential depend directly on the interlayer cation. For example, the sodium bentonite presents an excellent capacity to swell while the lithium bentonite does not swell significantly at the aggregate scale. In addition, other textural properties may be modified by the cation saturation, such as the specific surface, the particle size, porosity, etc.     

Highly Efficient and Selective Transport of Cu(II) with a Cooperative Carrier Composed of Tetraaza-14-Crown-4 and Oleic Acid through a Bulk Liquid Membrane

Tetraaza-14-crown-4 and oleic acid was successfully applied for transport of Cu(II) in chloroform bulk liquid membrane. The uphill moving of Cu(II) during the liquid membrane transport process has occurred. The main effective variable such as the type of the metal ion acceptor in the receiving phase and its concentration, tetraaza-14-crown-4 and oleic acid concentration in the organic phase on the efficiency of the ion-transport system were examined. By using L-cysteine as a metal ion acceptor in the receiving phase, the maximum amount of copper (II) transported across the liquid membrane was achieved to 96 ± 1.5% after 140 minutes. The selectivity of copper ion transport from the aqueous solutions containing Pb²⁺, Tl⁺, Ag⁺, Co²⁺, Ni²⁺, Mg²⁺, Zn²⁺, Hg²⁺, Cd²⁺ and Ca²⁺ ions were investigated. In the presence of CH₃COONH₄ and Na₄P₂O₇ as suitable masking agents in the source phase, the interfering effects of Pb⁺² and Cd²⁺ were diminished drastically.