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.     

The Preparation of Metal–Organic-Framework/Boron Phosphate Hybrid Materials for Improved Performances in Proton Exchange Membranes

New types of metal–organic framework based hybrid materials are designed and prepared, which involving the hybridization of various content of boron phosphate (BPO₄) with the precursor of HKUST-1. The structure of obtained HKUST-1/BPO₄ hybrid materials (HB) is fully investigated, and then applied to construct sulfonated poly (ether ether ketone) (SPEEK) based proton exchange membranes (SPEEK/HB). Owing to effective interactions between hybrid materials and SPEEK matrix, the achieved composite membranes reflect a considerable improvement in mechanical and thermal stability, oxidative stability, methanol permeation, and proton conductivity. In particular, the tensile strength of SPEEK/HB-20 composite membrane is 41.3 MPa, which is 1.5 times higher than pristine SPEEK, and the methanol permeability reduced to one-third of SPEEK at the same time. The SPEEK/HB-10 displays the highest proton conductivity of 37.4 mS cm⁻¹ at 80 °C, which is obviously higher than pristine SPEEK. These results reveal that the hybridization of HKUST-1 with BPO₄ provide a promising candidate in the modification of proton exchange membranes (PEMs), and this strategy also possess great application potential in other types of MOFs-based hybrid materials.     

Ion Imprinted Polymer Solid Phase Extraction (IIP‐SPE) for Preconcentrative Separation of Erbium(III) From Adjacent Lanthanides and Yttrium

Abstract

Erbium(III) ion imprinted polymer (IIP) materials were prepared by photochemical polymerization of the ternary complex, Erbium(III)—5,7‐dichloroquinoline‐8‐ol‐4‐vinylpyridine, with methyl methacrylate (functional monomer) and ethylene glycol dimethacrylate (crosslinking monomer) in the presence of 2,2′‐azobisisobutyronitrile (initiator). The synthesis was carried out in 2‐methoxy ethanol (porogen) medium and the resultant material was filtered, dried and powdered to form unleached polymer particles. The imprint ion (erbium(III)) was removed by stirring the above particles with 6 mol/l HCl to obtain leached polymer particles. These leached particles are termed erbium(III) ion imprinted polymer (IIP) particles as it selectively rebind erbium(III) ions. Non‐imprinted/control polymer (CP) particles were similarly prepared without the imprint ion. CP and unleached and leached IIP particles were characterized by XRD, microanalysis, and UV‐visible spectrophotometric studies. Various parameters that influence ion imprinted polymer—solid phase extraction such as pH, weight of polymer particles, preconcentration time, elution time, eluent volume, and aqueous phase volume were varied and optimal conditions for each parameter for quantitative enrichment of erbium(III) were established. The selectivity coefficients of erbium(III) ion over Y, Dy, Ho and Tm were compared with separation factors reported for two of the best liquid—liquid extractants viz. di‐2‐ethylhexyl phosphoric acid and 2‐ethylhexyl‐ethylhexyl phosphate.     

Efficient Separation of Cytosine‐Substituted Mildiomycin Analogue (MIL‐C) from the Fermentation Broth by Ion Exchange

Abstract

Cytosine‐substituted mildiomycin analogue (MIL‐C) was synthesized by supplementing cytosine into the culture medium of Streptoverticillium rimofaciens (one mildiomycin producer) and had a specific and strong inhibitory activity against powdery mildews. In order to facilitate the separation of MIL‐C from this fermentation broth, the cultivation conditions were optimized to increase MIL‐C productivity, and more than 0.9 g/l cytosine was added to the medium to inhibit the biosynthesis of mildiomycin (MIL). According to the ion‐exchange equilibrium and dynamics characteristic of MIL‐C, one weakly cationic resin (DK110) was screened out to separate MIL‐C from fermentation broth with one effective ion‐exchange method. When 2% ammonia aqueous solution was applied as eluent with 2 BVs/h, high recovery yield (97.6%) and purity (70.0%) of MIL‐C were achieved. This novel strategy of combining up‐stream biosynthetic controls and down‐stream purification is very promising for efficient production of this novel nucleoside antibiotic (MIL‐C).     

Combined Ion Exchange—Solvent Extraction (CIESE): A Novel Separation Technique for Inorganic Ions

Abstract

In the present paper a novel separation technique for inorganic ions is described. This has been termed combined ion exchange—solvent extraction (CIESE), because it is assumed that both ion exchange and solvent extraction are operative simultaneously to effect the separations. This concept is illustrated with two examples: the separation of iron(III), Co(II), and Ni(II) on the ion-exchange resins Dowex 50 and Dowex 1 using acetone or tetrahydrofuran—hydrochloric acid mixtures, and the separation of uranium from numerous metal ions on Dowex 50, employing as eluent a medium consisting of tetrahydrofuran—nitric acid. Because this separation principle is superior to methods employing the conventional separation techniques of ion exchange in pure aqueous solutions and of common liquid-liquid extraction, it is expected that it will also find application for the solution of other problems encountered in inorganic analytical chemistry.     

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.     

Synergistic Enhancement of the Extraction of Trivalent Lanthanides and Actinides by Tetra‐(n‐Octyl)Diglycolamide from Chloride Media

Abstract

This work describes a unique synergistic enhancement of the extraction of trivalent actinides and lanthanides by extraction chromatographic resins containing tetra‐n‐octyldiglycolamide (TODGA) from hydrochloric acid containing anionic metal chlorides. The presence of mg/L quantities of trivalent Fe, Ga, In, Tl, or Bi in HCl leads to several orders of magnitude enhancement of the extraction of trivalent actinides and lanthanides. The synergistic effect persists, even when the amount of metal chloride exceeds the capacity of the resin. The application of this synergistic enhancement for the separation of actinium from stainless steel and the preconcentration of americium and plutonium from large soil samples will be described.     

Amberlite XAD‐2 Impregnated with Cyanex302 for Separation of Traces of Thorium(IV)

Abstract

Amberlite XAD‐2 resin impregnated with Cyanex302 has been used to separate and preconcentrate thorium(IV) from associated elements prior to its spectrophotometric determination. The impregnated resin (HL‐XAD‐2) was characterized by IR spectra. A column packed with HL‐XAD‐2 was used to understand sorption and desorption behaviour of thorium(IV). The effect of various parameters such as acidity of aqueous phase, nature and concentration of eluting agents, eluent volume and its flow rate were evaluated to optimize conditions for isolation of thorium(IV). Adsorption characteristics of thorium(IV) on HL‐XAD‐2 in batch studies indicated that the data fit well in Langmuir and Freundlich adsorption isotherm models. The maximum sorption capacity of the modified resin for thorium(IV) was 8.48 mmol g^?1 while the limit of detection (3σ_B) was 0.75 µg dm^?3. A preconcentration factor greater than 100 was achieved. The influence of diverse ions on extraction of thorium(IV) was examined and the method developed was applied for the separation of thorium(IV) from synthetic mixtures and monazite sand. The method is reproducible with a relative standard deviation (R.S.D.) of 0.6%.     

Extraction of Neptunium (IV) Ions into 30% Tri‐Butyl Phosphate from Nitric Acid

The distribution of Np(IV) between 0.08–4.5 M HNO_3(aq,eqm) and ～30% tributyl phosphate has been modelled, accounting for the formation of 1:1 and 1:2 nitrate complexes and Np(IV) hydrolysis in the aqueous phase and the extraction of Np(NO₃)₄(TBP)₂ into TBP. The potential formation and extraction of NpOH(NO₃)₃(TBP)₂ and Np(NO₃)₄(TBP)₂.HNO₃ species, including spectroscopic evidence, and oxidations of Np(IV) to Np(V) and Np(VI) in the solvent phase have also been considered. The model highlights some key gaps in the available thermodynamic data.     

Studies Related to the Processing of U–Zr and U–Pu–Zr Metallic Fuels Using Tri-iso-amyl Phosphate (TiAP) as Extractant

Metallic fuel is reprocessed by a compact nonaqueous pyrochemical process. The present study explores the possible uses of an aqueous reprocessing-based method as an alternative to the pyro-processing of metallic fuels. Solvent extraction studies in the batch mode were carried out for both U–Zr- and U–Pu–Zr-based metal alloy systems. Earlier studies carried out in our laboratory have established that Tri-iso-amyl Phosphate (TiAP) is a promising extractant for the reprocessing of spent fuels. In the present study, the distribution data has been generated for the extraction of uranium and zirconium as a function of equilibrium aqueous phase metal ion and nitric acid concentration with TiAP and Tri-n-butyl Phosphate (TBP)-based solvents. These studies indicate the formation of a third phase with zirconium in the presence of uranium with TBP under certain experimental conditions whereas it was not encountered with the TiAP system. Flow sheet for the co-extraction and co-stripping of heavy metal ions by 1.1M TiAP and 1.1M TBP in n-dodecane from U–Zr as well as U–Pu–Zr feed solutions in stage-wise mode has been evaluated. Percentage extraction and stripping of metal ions were calculated stage-wise and the results are discussed.     

Electrodeposition of Au–Sn alloys from acid Au(III) baths

A bath for the electrodeposition of white gold alloys of interest for the electroforming of hollow jewellery is proposed and investigated. The system was an acidic Au(III)–Sn(IV) bath for the electrodeposition of Au–Sn alloys. The electrochemical investigations were based on cyclic voltammetry, linear-sweep voltammetry, galvanostatic electrodeposition experiments and in situ Raman spectroscopy. The electrode kinetics of alloy formation were elucidated by stripping voltammetry. The effects of cathodically adsorbed CN^– were studied by in situ Raman spectroscopy. Electrodeposited foils were studied from the crystallographic, compositional and morphological points of view. Codeposition of Au and Sn gives rise to a single phase of approximately equiatomic composition over a current density interval of 10 to 40 mA cm^–2. This orthorhombic phase is structurally the same as the phase of the equilibrium Au–Sn system, but its stoichiometry and lattice parameters are different. The equilibrium two-phase , structure can be obtained by heat-treatment.     

New Multi‐Dentate Ion‐Selective AXAD‐16‐MOPPA Polymer for the Preconcentration and Sequential Separation of U(VI), Th(IV) from Rare Earth Matrix

Abstract

A new class of multi‐dentate ligand anchored polymeric resin has been synthesized by grafting Amberlite XAD‐16 with [2‐(1‐Methyl‐3‐oxo‐2‐phenyl‐2, 3‐dihydro‐1H‐pyrazol‐4‐ylcarbamoyl)‐ethyl]‐phosphinic acid (AXAD‐16‐MOPPA). The modification steps involved during the grafting process are characterized by FT‐IR spectroscopy, ³¹P and ¹³C‐CPMAS (cross‐polarized magic angle spin) NMR spectroscopy, CHNPS elemental analysis and thermogravimetric analysis. The influence of various physio‐chemical parameters on the quantitative extraction of metal ions by the resin phase are studied and optimized by both static and dynamic methods. The developed grafted polymer shows greater selectivity for actinide ions like U(VI) and Th(IV) when compared to the lanthanides with greater distribution ratio values in highly acidic matrices. However, the lanthanides compete for the active sites in near neutral conditions. But the sorbed actinide ions and lanthanide elements can be separated by the sequential elution methodology. Moreover, the polymer exhibits faster metal ion phase exchange kinetics, where with a high sample flow rate of 25 mL min^?1 quantitative analyte sorption is achievable during the extraction chromatographic column operation for all the analytes. It also offers good ion‐selectivity and greater preconcentration factor values of 400 for U(VI) and 333 for Th(IV) in 4M HNO₃ conditions. The resin shows very high sorption capacity values of 1.45 mmol g^?1 for U(VI), 1.39 mmol g^?1 for Th(IV), and 1.31 mmol g^?1 for La(III) at near neutral conditions. Finally, the developed grafted resin has been successfully applied in extracting Th(IV) from matrix monazite sand which comprises large rare earth matrix, U(VI) from seawater and also U(VI) and Th(IV) from simulated nuclear spent fuel mixtures. The analytical data obtained from triplicate measurements are within 3.5% rsd, reflecting the reproducibility and reliability of the developed method.     

Ion Exchange of the Organometallic Aqua‐Ion fac‐[99mTc(CO)3(H2O)3]+ from Aqueous Solutions

Dynamic (column) studies on the ion exchange of triaquatricarbonyltechnetium(I) cation, fac‐[^99mTc(CO)₃(H₂O)₃]⁺ (1), in the system: amphoteric ion exchange resin (Purolite S‐950) ‐ aqueous HNO₃ solutions (0.05–2 M) corroborate the +1 charge of 1. Stability constants of fac‐[^99mTc(CO)₃(H₂O)_3?nCl_n]^1?n complexes, determined from the distribution coefficients in the system anion exchanger (Dowex 1X4) ‐ aqueous HCl solutions (0.1–12 M) differ from the literature values determined at a constant ionic strength. This difference, resulting from the decrease in the activity of water with increasing HCl concentration, may be a measure of the effect of non‐constant ionic strength on ion‐exchange equilibria. Weak acidic properties of 1 in aqueous solution at n.c.a. (no carrier added) level (pK_a ?9) have been demonstrated by paper electrophoresis.     

Evaluation of Amberlite IRC‐718 Chelating Ion Exchange Resin in Loading‐Elution‐Regeneration Cycles for the Separation and Recovery of Strontium from Alkaline Radioactive Waste

The separation and recovery of radiostrontium from simulated alkaline reprocessing waste solution has been studied using Amberlite IRC‐718, a chelating resin containing iminodiacetic acid groups. The breakthrough behavior of strontium has been determined by conducting an extended column run. The column loading performance has been correlated with batch equilibration results. Efficient elution of loaded strontium has been achieved using dilute nitric acid. Satisfactory column performance has been demonstrated in repeated loading‐elution‐regeneration cycles. Finally, the characteristics of used resin have been determined to ascertain its efficacy for further use.     

Hybrid Properties of Alginate‐PEI Adsorbent for Chromium (VI) Removal from Aqueous Solutions

Abstract

An adsorbent consisting of polyethyleneimine (PEI) immobilized in calcium alginate gel beads was synthesized and evaluated for Cr⁶⁺ removal. An evaluation of the synthesis process showed the importance of the PEI molecular weight on the immobilization efficiency. Polyethyleneimine of 70,000 Da molecular weight displayed the highest immobilization percentage at 52%. Batch kinetics and equilibrium tests showed that alginate‐PEI (APEI) resin displayed considerable affinity for negatively charged Cr⁶⁺ complexes at low pH conditions ranging from pH 1.5‐pH 3. The results also indicated the reduction of Cr⁶⁺ to less toxic Cr³⁺ species by the APEI adsorbent. The column adsorption experiments showed the ability of APEI resin to treat a 10 mg/L Cr⁶⁺ solution with pH influent adjustment from pH 1.5 to pH 3 to concentrations that satisfy effluent standards for Cr⁶⁺ (<0.1 mg/L) and total Cr (<0.5 mg/L). Finally, comparisons with a highly aminated commercial resin Chitopearl CS‐03 highlighted the unique ability of the hybrid APEI beads with its amine and carboxylic groups for the adsorption of Cr⁶⁺ as well as the retention of generated Cr³⁺ ions.     

Separation of Actinides(III) from Lanthanides(III) in Simulated Nuclear Waste Streams using 6,6′‐Bis‐(5,6‐dipentyl‐[1,2,4]triazin‐3‐yl)‐[2,2′]bipyridinyl (C5‐BTBP) in Cyclohexanone

Abstract

An extraction system comprising 6,6′‐bis‐(5,6‐dipentyl‐[1,2,4]triazin‐3‐yl)‐[2,2′]bipyridinyl (C5‐BTBP) dissolved in cyclohexanone was investigated. The main purpose of this investigation was to extract and separate actinides(III) from lanthanides(III), both of which are present in the waste from the reprocessing of spent nuclear fuel. The system studied showed high distribution ratios for the actinides(III) and a high separation factor between actinides and lanthanides (SF_Am/Eu around 150). The extraction kinetics were fast with equilibrium being reached in 5 minutes. The effects of temperature on the extraction and the stoichiometry of the extracted complex were investigated. The extraction of californium(III) was studied and it was found that the BTBP molecule has a higher affinity for californium than for americium (SF_Cf/Am around 4). This system could be used to separate actinides(III) from lanthanide fission products with high efficiency, if used in conjunction with a pre‐equilibrium step.     

Moisture stability of ethane-selective Ni(II), Fe(III), Zr(IV)-based metal–organic frameworks

Metal–organic frameworks (MOFs) combined with selective adsorption capacity of ethane over ethylene and good moisture stability are highly urged by adsorption industrial community. Here, the moisture stability mechanism of Zr-bptc, UiO-66, PCN-245, and Ni(bdc)(ted)_0.5 were investigated by moisture stability experiments, and computational simulation of metal node-linker breaking energy caused by water. Results show that the moisture stability follows the order of Zr-bptc > UiO-66 > PCN-245 > Ni(bdc)(ted)_0.5. The different moisture stability for these MOFs is likely attributed to the bond strength between metal center and ligands, the coordination number of metal center, the hydrophobicity of framework, as well as the degree of interpenetrated framework. Additionally, comparing with ethylene-selective MOFs, ethane-selective MOFs have fewer coordinatively unsaturated metal sites. Breakthrough experiments indicated that Zr-bptc is the promising material for ethane/ethylene separation.     

Removal of As(V) and Cr(VI) Ions from Aqueous Solution using a Continuous,Hybrid Field‐Gradient Magnetic Separation Device

Abstract

A continuous flow colloidal affinity magnetic separation device is used for the removal of As(V) and Cr(VI) from aqueous solutions. Langmuir isotherms fit the adsorption behavior of the individual ions on Orica MIEX^® ion exchange particles. In a mixture of equal weight percent As(V) and Cr(VI), the adsorption of As(V) begins only above a critical cut‐off concentration, implying preferential adsorption of the higher valence ion at the available sites. Cr(VI) is removed selectively from the mixture in the continuous flow device, consistent with the presence of a higher concentration of the higher valence ion in the proximity of a charged (anion‐exchange) surface.