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1.
The recovery of strategic metals such as rare earth elements (REEs) requires the development of new sorbents with high sorption capacities and selectivity. The bi-functionality of sorbents showed a remarkable capacity for the enhancement of binding properties. This work compares the sorption properties of magnetic chitosan (MC, prepared by dispersion of hydrothermally precipitated magnetite microparticles (synthesized through Fe(II)/Fe(III) precursors) into chitosan solution and crosslinking with glutaraldehyde) with those of the urea derivative (MC-UR) and its sulfonated derivative (MC-UR/S) for cerium (as an example of REEs). The sorbents were characterized by FTIR, TGA, elemental analysis, SEM-EDX, TEM, VSM, and titration. In a second step, the effect of pH (optimum at pH 5), the uptake kinetics (fitted by the pseudo-first-order rate equation), the sorption isotherms (modeled by the Langmuir equation) are investigated. The successive modifications of magnetic chitosan increases the maximum sorption capacity from 0.28 to 0.845 and 1.25 mmol Ce g−1 (MC, MC-UR, and MC-UR/S, respectively). The bi-functionalization strongly increases the selectivity of the sorbent for Ce(III) through multi-component equimolar solutions (especially at pH 4). The functionalization notably increases the stability at recycling (for at least 5 cycles), using 0.2 M HCl for the complete desorption of cerium from the loaded sorbent. The bi-functionalized sorbent was successfully tested for the recovery of cerium from pre-treated acidic leachates, recovered from low-grade cerium-bearing Egyptian ore.  相似文献   

2.
The development of new materials is needed to address the environmental challenges of wastewater treatment. The phosphorylation of guar gum combined with its association to chitosan allows preparing an efficient sorbent for the removal of U(VI) from slightly acidic solutions. The incorporation of magnetite nanoparticles enhances solid/liquid. Functional groups are characterized by FTIR spectroscopy while textural properties are qualified by N2 adsorption. The optimum pH is close to 4 (deprotonation of amine and phosphonate groups). Uptake kinetics are fast (60 min of contact), fitted by a pseudo-first order rate equation. Maximum sorption capacities are close to 1.28 and 1.16 mmol U g−1 (non-magnetic and magnetic, respectively), while the sorption isotherms are fitted by Langmuir equation. Uranyl desorption (using 0.2 M HCl solutions) is achieved within 20–30 min; the sorbents can be recycled for at least five cycles (5–6% loss in sorption performance, complete desorption). In multi-component solutions, the sorbents show marked preference for U(VI) and Nd(III) over alkali-earth metals and Si(IV). The zone of exclusion method shows that magnetic sorbent has antibacterial effects against both Gram+ and Gram- bacteria, contrary to non-magnetic material (only Gram+ bacteria). The magnetic composite is highly promising as antimicrobial support and for recovery of valuable metals.  相似文献   

3.
Novel solvent-impregnated resins (SIRs) were prepared by treatment of styrene–divinylbenzene copolymer (LPS-500) with mixtures of the promising polydentante extractant (2-diphenylphosphoryl)-4-ethylphenoxy)methyl)diphenylphosphine oxide (L) and an ionic liquid [C4mim]+[Tf2N]for the extraction chromatography recovery of Nd(III) from nitric acid solutions. It was shown that introduction of the ionic liquid into the SIR composition results in considerable enhancement of the Nd(III) recovery efficiency compared with resin impregnated only by L in slightly acidic media. The influence of the L: ionic liquid molar ratio in the SIRs composition, their percentages, concentration of metal and HNO3 in the eluent, and acid type on the value of synergistic effect and adsorption efficiency of Nd(III) recovery was studied. The SIR containing 40% of mixture of L and [C4mim]+[Tf2N] with molar ratio 2:1 turned out to be the most efficient. The selectivity of Nd(III) separation from light and heavy rare-earth elements was studied and the optimal conditions of Nd(III) adsorption recovery and stripping by this SIR were chosen. It was found that in recovery efficiency of Nd(III) developed SIR exceeded the SIR containing Cyanex 923 (a mixture of monodentate trialkylphosphine oxides) and [C4mim]+[Tf2N].  相似文献   

4.
An off-line column preconcentration technique using a micro-column of 2,6 diacetylpyridine functionalized Amberlite XAD-4 with inductively coupled plasma mass spectrometry (ICP-MS) as a means of detection has been developed. The aim of the method was to determine rare earth elements (REEs) (La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu) in seawater. Sample solutions (2–10 mL) were passed through the column which was then washed with ultra-pure water to remove residual matrix. The adsorbed cations on the resin were eluted by using 2 mL of 0.1 mol L−1 HNO3 containing 10 ng mL−1 indium as an internal standard. The eluent was analyzed for the metal concentrations using ICP-MS. Sample pH as well as the sample and eluent flow rates were optimized. The sorption capacity of resin was determined by the batch process, by equilibrating 0.05 g of the resin with solutions of 50 mL of 25 mg L−1 of individual metal ions for 4 h at pH 6.0 at 26 °C. The sorption capacities for the resin were found to range between 47.3 μmol g−1 (for Lu) and 136.7 μmol g−1 (for Gd). Limits of detection (3σ), without any preconcentration, ranged from 2 ng L−1 to 10.3 ng L−1 (for Tm and Lu respectively). The proposed method was applied to the determination of REEs in seawater and tap water samples.  相似文献   

5.
Inductively coupled plasma mass spectrometry (ICP-MS) has been used to measure the concentration of trace and rare earth elements (REEs) in soils. Geochemical certified reference materials such as JLk-1, JB-1, and JB-3 were used for the validation of the analytical method. The measured values were in good agreement with the certified values for all the elements and were within 10% analytical error. Beach placer deposits of soils mainly from Odisha, on the east coast of India, have been selected to study selected trace and rare earth elements (REEs), to estimate enrichment factor (EF) and geoaccumulation index (Igeo) in the natural environment. Enrichment factor (EF) and geoaccumulation index (Igeo) results showed that Cr, Mn, Fe, Co, Zn, Y, Zr, Cd and U were significantly enriched, and Th was extremely enriched. The total content of REEs (ƩREEs) ranged from 101.3 to 12,911.3 µg g−1, with an average 2431.1 µg g−1 which was higher than the average crustal value of ΣREEs. A high concentration of Th and light REEs were strongly correlated, which confirmed soil enrichment with monazite minerals. High ratios of light REEs (LREEs)/heavy REEs (HREEs) with a strong negative Eu anomaly revealed a felsic origin. The comparison of the chondrite normalized REE patterns of soil with hinterland rocks such as granite, charnockite, khondalite and migmatite suggested that enhancement of trace and REEs are of natural origin.  相似文献   

6.
Different hypotheses have been tested about the fractionation and bioavailability of rare earth elements (REE) in mangrove ecosystems. Rare earth elements and bioavailability in the mangrove ecosystem have been of significant concern and are recognized globally as emerging pollutants. Bioavailability and fractionation of rare earth elements were assessed in Jazan and AlWajah mangrove ecosystems. Comparisons between rare earth elements, multi-elemental ratios, geo-accumulation index (Igeo), and bio-concentration factor (BCF) for the two mangroves and the influence of sediment grain size types on concentrations of rare earth elements were carried out. A substantial difference in mean concentrations (mg/kg) of REE (La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu) was established, except for mean concentrations of Eu, Gd, Tb, Tm, and Lu. In addition, concentrations of REEs were higher in the Jazan mangrove ecosystem. However, REE composition in the two mangroves was dominated by the lighter REE (LREE and MREE), and formed the major contribution to the total sum of REE at 10.2–78.4%, which was greater than the HREE contribution of 11.3–12.9%. The Post Archean Australian Shale (PAAS) normalized values revealed that lighter REE (LREE and MREE) were steadily enriched above heavy REE. More so, low and negative values of R(H/M) were recorded in the Al Wajah mangrove, indicating higher HREE depletion there. The values of BCF for REEs were less than 1 for all the REEs determined; the recorded BCF for Lu (0.33) and Tm (0.32) were the highest, while the lowest BCF recorded was for Nd (0.09). There is a need for periodic monitoring of REE concentrations in the mangroves to keep track of the sources of this metal contamination and develop conservation and control strategies for these important ecosystems.  相似文献   

7.
The recovery of three rare earth (RE) metals ions [Yb(III), Dy(III) and Nd(III), belonging to heavy, mild and light REs, respectively] was investigated using hybrid chitosan-magnetic nano-based particles functionalized by diethylenetriamine (DETA). The effect of pH on sorption performance was analyzed: the optimum initial pH value was found close to 5 (equilibrium pH value close to 6.5). The nanometric size of sorbent particles (30–50 nm) minimized the contribution of resistance to intraparticle diffusion on the control of uptake kinetics, which is efficiently modeled using the pseudo-second order rate equation: under selected experimental conditions the contact time required for reaching equilibrium was less than 1 h. Sorption isotherms were efficiently modeled using the Langmuir equation: maximum sorption capacities reached about 50 mg metal g?1, regardless of the RE. The temperature had a very limited effect on sorption capacity (in the range 300–320 K). The thermodynamic parameters were determined: the sorption was endothermic (positive values of ΔH°), spontaneous (negative values of ΔG°) and contributed to increasing the disorder of the system (positive values of ΔS°). The three REs have similar sorption properties on DETA-functionalized chitosan magnetic nano-based particles: the selective separation of these elements seems to be difficult. The sorbed metal ions can be removed from loaded sorbents using thiourea, and the sorbent can be recycled for at least five sorption/desorption cycles with a limited loss in sorption performance (by less than 6 %). The saturation magnetization was close to 20 emu g?1; this means that nano-based superparamagnetic particles can be readily recovered by an external magnetic field, making the processing of these materials easy.  相似文献   

8.
Chitosan was modified by grafting 2-pyridyl-ethyl moieties on the biopolymer backbone for the synthesis of a Platinum Group Metal (PGM) sorbent. The sorbent was tested for Pd(II) and Pt(IV) sorption from HCl solutions. Stable for HCl concentrations below 0.5 M, the sorbent reached sorption capacities as high as 3.2 and 2.6 mmol metal g−1 for Pd(II) and Pt(IV), respectively. Metal sorption mainly proceeds by electrostatic attraction in acidic solutions, though a contribution of complexation mechanism cannot be totally rejected. The resistance to intraparticle diffusion is the main controlling mechanism for uptake kinetics. While agitation speed has a limited effect on kinetics, metal concentration and sorbent dosage have a greater effect on the kinetic profiles. The intraparticle diffusivity varies between 3 × 10−11 and 4.5 × 10−10 m2 min−1. Thiourea (combined with HCl solution) is used for Pd(II) and Pt(IV) desorption. The resin could be desorbed and recycled for a minimum of five cycles maintaining high efficiencies of sorption and desorption.  相似文献   

9.
Amorphous cerium phosphate was prepared and characterized. Three-level Box-Behnken design (BBD) was employed to analyze the effect of process variables such as initial pH (2–6), contact time (60–180 min), and sorbent amount (0.05–0.15 g) on the sorption capacity of europium. Analysis of variance (ANOVA) revealed that the main effect of initial pH and sorbent amount has a substantial impact on the sorption of Eu(III). Probability F-value (F = 3 × 10-3) and correlation coefficient (R2 = 0.97) point out that the model is in good accordance with experimental data. The maximum sorption capacity of Eu(III) was found to be 42.14 mg g-1 at initial pH 6, contact time of 180 min, and a sorbent amount of 0.05 g. Sorption isotherm data was well explained by the Langmuir model and monolayer Eu(III) sorption capacity was obtained as 30.40 mg g-1. Kinetic data were well described by the pseudo-second-order model. Thermodynamic data suggested that the process is endothermic and spontaneous.  相似文献   

10.
A method is described for the selective extraction of chromium(III) from aqueous solutions and natural water samples, based on the use of two newly synthesized solid-phase extractors via silica gel-immobilized-vanillin derivatives (I,II). Experimental conditions for effective adsorption of trace levels of Cr(III) were optimized with respect to different experimental parameters using batch and column procedures in detail. The optimum pH values for the separation of Cr(III) simultaneously on the newly sorbents were both 4.0 and complete elution of Cr(III) from the sorbents surface was carried out using 2.0 mL of 0.5 mol L− 1 HCl. The sorption capacity of phase I towards Cr(III) was found to be 0.700 mmol g− 1 where the sorption capacity of phase II was 0.538 mmol g− 1. The detection limits (3σ) of the method defined by IUPAC were found to be 0.87 and 0.64 ng mL− 1 with enrichment factors of 100 and 75 for phases I and II, respectively. The method has been applied for the determination of Cr(III) in biological materials and water samples with satisfactory results.  相似文献   

11.
The liquid-phase adsorption of toluene in cyclohexane and hexane solutions on modified activated carbons was evaluated; the energy involved in the interaction between these solutions and the solids was determined by immersion enthalpies of pure solvents and their mixtures, and the contribution of the system constituents was calculated by differential enthalpies. The thermal treatment generated modifications that favored adsorption and interaction with the evaluated solutions, since it increased the textural parameters and the basic character of the samples. Cyclohexane could create greater competition with the adsorption sites compared to hexane, but it favored the increase in adsorption capacities (0.416 to 1.026 mmol g−1) and the interactions with the solid evaluated through the immersion enthalpies. The immersion enthalpies of pure solvents (−16.36 to −112.7 J g−1) and mixtures (−25.65 to −104.34 J g−1) had exothermic behaviors that were decreasing due to the possible displacement of solvent molecules when increasing the solute concentration in the mixtures. The differential enthalpies for toluene were negative (−18.63 to −2.14 J), mainly due to the π–π interaction with the solid, while those of the solvent–solid component tended to be positive values (−4.25 to 55.97 J) due to the displacement of the solvent molecules by those of toluene.  相似文献   

12.
A series of solid-phase uranium extractants were prepared by post-synthesis impregnation of a mesoporous silica support previously functionalized with octyl chains by direct silanization. Five materials were synthesized with 0, 0.2, 0.3, 0.4 and 0.5 mmol of the amidophosphonate ligand DEHCEBP per gram of functionalized solid, and the effect of the ligand concentration on the uranium extraction efficiency and selectivity of the materials was investigated. Nitrogen adsorption–desorption data show that with increasing ligand loadings, the specific surface area and average pore volume decrease as the amidophosphonate ligand fills first the micropores and then the mesopores of the support. Acidic uranium solutions with a high sulfate content were used to replicate the conditions in ore treatment leaching solutions. Considering the extraction kinetics, the equilibration time was found to increase with the ligand concentration, which can be explained by the clogging of micropores and the multilayer arrangement of the DEHCEBP molecules in the materials with their highest ligand contents. The fact that the equilibrium ligand/uranium ratio is about 2 mol/mol regardless of the ligand concentration in the material suggests that all the ligand molecules remain accessible for extraction. The maximum uranium extraction capacities ranged from 30 mg∙g−1 at 0.2 mmol∙g−1 DEHCEBP to 54 mg∙g−1 in the material with 0.5 mmol∙g−1 DEHCEBP. These materials could therefore potentially be used as solid-phase uranium extractants in acidic solutions with high sulfate concentrations.  相似文献   

13.
The possibilities of the sorption-spectroscopic determination of the sum of rare-earth elements have been studied on an example of La, Gd, and Yb as representatives of the light, middle, and heavy rare earth elements. The determination is carried out after the sorption from solutions with pH 3 onto the surface polyacrylonitrile fiber loaded with a Chel-100 ion exchanger followed by complexation with Chlorophosphonazo III. A dynamic version of the sorption-spectroscopic determination of the sum of La, Gd, and Yb has been developed for the concentration range 5–30 ng/mL with a detection limit of 3 ng/mL. The method was tested in the analysis of model solutions of CaCl2, FeCl3, and TiCl4; RSD < 20%.  相似文献   

14.
This research focuses on removal of Fe(III) from aqueous solution using chitosan–magnetite nanocomposites as potential sorbent. The presence of nanosized magnetic particles within the nanocomposites was confirmed by TEM and SAED analysis. The particles with diameter 508 μm and 84 μm, follow Frendlich sorption isotherm at 30 °C, and the Frendlich constants (KF, 1/n) have been found to be 5.974 mg g−1, 2.66 and 35.98 mg g−1, 1.385, respectively. Out of various kinetic models, the experimental data for dynamic uptake of Fe(III) is best fitted on ‘pseudo-second order’ kinetic model. The linear nature of plots between log (% sorption) and log (time) is indicative of intra-particle diffusion. For the particles with diameters 508 μm and 84 μm, the value of kid was found to be 1.78 mg l−1 min−0.5 and 2.13 mg l−1 min−0.5. The sorption mean free energy from the Dubinin–Radushkevic isotherm was found to be 7.04 kJ mol−1 indicating chemical nature of sorption. The increase in chitosan content in sorbent particles is found to enhance the Fe(III) uptake. The various thermodynamic parameters have also been evaluated. Finally, the presence of Cu2+ ions in the sorbate is found to decrease the uptake of Fe(III).  相似文献   

15.
The usage of a variety of sorbents has been shown as promising matrix removal/preconcentration strategies for the determination of rare earth elements (REEs) in various natural water samples by inductively coupled plasma atomic emission spectrometry (ICP-AES). The sorption efficiency of various zeolites (clinoptilolite, mordenite, zeolite Y, zeolite Beta), ion-exchangers (Amberlite CG-120, Amberlite IR-120, Rexyn 101, Dowex 50W X18) and chelating resins (Muromac, Chelex 100, Amberlite IRC-718) towards REEs was investigated in terms of solution pH, shaking time and sorbent amount. The results have shown that most of the materials can take up REEs at a wide pH range. The experiments were continued with clinoptilolite, zeolite Y and Chelex 100 and it was demonstrated that all three materials displayed very fast kinetics for REE sorption (higher than 96% in 1 min). Desorption from the sorbents was realized with 2.0 M HNO3 for clinoptilolite and 0.1 M HNO3 for zeolite Y and Chelex 100. Only the lower concentration range (0.01-2.0 mg l−1) of matrix-matched standards were used in quantitation although the calibration graphs were linear at least up to 10.0 mg l−1 for all REEs studied. The limit of detection (3 s) without preconcentration was 0.1, 1.0, and 0.2 μg l−1 for Eu, La, and Yb, respectively. The validity of the method with the selected sorbents was checked through spike recovery experiments.  相似文献   

16.
A new grafted polymer has been developed by the chemical modification of Amberlite XAD-16 (AXAD-16) polymeric matrix with [(2-dihydroxyarsinoylphenylamino)methyl]phosphonic acid (AXAD-16-AsP). The modified polymer was characterized by a combination of 13C CPMAS and 31P solid-state NMR, Fourier transform-NIR-FIR-Raman spectroscopy, CHNPS elemental analysis, and thermogravimetric analysis (TGA). The distribution studies for the extraction of U(VI), Th(IV), and La(III) from acidic solutions were performed using an AXAD-16-AsP-packed chromatographic column. The influences of various physiochemical parameters on analyte recovery were optimized by both static and dynamic methods. Accordingly, even under high acidities (>4 M), good distribution ratio (D) values (102–104) were achieved for all the analytes. Metal ion desorption was effective using 1 mol L–1 (NH4)2CO3. From kinetic studies, a time duration of <15 min was sufficient for complete metal ion saturation of the resin phase. The maximum metal sorption capacities were found to be 0.25, 0.13, and 1.49 mmol g–1 for U(VI); 0.47, 0.39, and 1.40 mmol g–1 for Th(IV); and 1.44, 1.48, and 1.12 mmol g–1 for La(III), in the presence of 2 mol L–1 HNO3, 2 mol L–1 HCl, and under pH conditions, respectively. The analyte selectivity of the grafted polymer was tested in terms of interfering species tolerance studies. The system showed an enrichment factor of 365, 300, and 270 for U(VI), Th(IV), and La(III), and the limit of analyte detection was in the range of 18–23 ng mL–1. The practical applicability of the polymer was tested with synthetic nuclear spent fuel and seawater mixtures, natural water, and geological samples. The RSD of the total analytical procedure was within 4.9%, thus confirming the reliability of the developed method.  相似文献   

17.
Hydrophilic glycolmethacrylate gels with side chains containing thiol groups show high sorption selectivity for Hg, Sb, Bi, As, Ag, Cu and Pt, even in 1–3 M solutions of sulfuric or hydrochloric acid. The preparation of the sorbent Spheron Thiol and the distribution coefficients for 13 ions as a function of pH are described; within the optimal pH range the distribution coefficients exceed 104. The sorption capacity of the resin reached ca. 0.5–1.0 mmol Hg g-1 in 0.05 M HCl and equilibrium was achieved within 5 min, except for arsenic and platinum in insufficiently acidic solutions.  相似文献   

18.
Liquid chromatography coupled on-line to a sequential ICP/AES system is applied for the determination of 14 rare-earth elements (REEs) in samples with widely different concentrations of REEs and matrix elements. The REEs are separated on a cation-exchanger by applying an α- hydroxyisobutyric acid gradient. The determination limits were the same as those obtained by continuous nebulization of single-element standard solutions. The chromatographic separation precludes mutual spectral interferences between the REEs. The practical value of the method developed is demonstrated by the determination of REE impurities in Specpure rare-earth oxides, by its demonstrated potential to evaluate real spectral interferences, and by the analysis of geological samples (natural phosphates) with relatively low total REE contents. The detection limits of REEs in these natural phosphates ranged between 0.005 and 0.4 μg g?1.  相似文献   

19.
The mechanism of Pd(II) and198Au(III) sorption on 4(benzylcellulose)phenylthiocarbamoylamine has been investigated. The data obtained from the sorption dependence on medium acidity and temperature, from isotherms, IR spectra and diffuse reflectance spectra led to the conclusion that the physical sorption of the two elements is accompanied by the formation of chelates. The sorbent might be employed for the concentration of Pd(II) and Au(III) from dilute solutions.  相似文献   

20.
The interphase distribution of microamounts of La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Y, and Sc perchlorates between aqueous HClO4 solutions and solutions of bidentate phosphorylmethyl-substituted butylphenylphosphinates Oct2P(O)CH2P(O)Ph(OBu) (compound I) and Ph2P(O)CH2P(O)Ph(OBu) (compound II) in 1,2-dichloroethane is studied. The stoichiometry of extracted complexes is determined, and the efficiency of metal ion extraction into the organic phase is considered as a function of the HClO4 concentration in the aqueous phase and the nature of the organic solvent. The possibility of concentrating rare-earth elements (REE)(III) and scandium(III) from HClO4 solutions with the complexing sorbent synthesized by noncovalent immobilization of I and II compounds on a macroporuos polymer matrix is shown.  相似文献   

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