Efficient uranium(VI) biosorption on grapefruit peel: kinetic study and thermodynamic parameters

The uranium(VI) biosorption by grapefruit peel was studied from aqueous solutions. Batch experiments was conducted to evaluate the effect of contact time, initial uranium(VI) concentration, initial pH, adsorbent dose, salt concentration and temperature. The equilibrium process was well described by the Langmuir, Redlich–Peterson and Koble–Corrigan isotherm models, with maximum sorption capacity of 140.79 mg g⁻¹ at 298 K. The pseudo second order model and Elovish model adequately describe the kinetic data in comparison to the pseudo first order model and the process involving rate-controlling step is much complex involving both boundary layer and intra-particle diffusion processes. The effective diffusion parameter D _i and D _f values were estimated at different initial concentration and the average values were determined to be 1.167 × 10⁻⁷ and 4.078 × 10⁻⁸ cm² s⁻¹. Thermodynamic parameters showed that the biosorption of uranium(VI) onto grapefruit peel biomass was feasible, spontaneous and endothermic under studied conditions. The physical and chemical properties of the adsorbent were determined by SEM, TG-DSC, XRD and elemental analysis and the nature of biomass–uranium (VI) interactions was evaluated by FTIR analysis, which showed the participation of COOH, OH and NH₂ groups in the biosorption process. Adsorbents could be regenerated using 0.05 mol L⁻¹ HCl solution at least three cycles, with up to 80% recovery. Thus, the biomass used in this work proved to be effective materials for the treatment of uranium (VI) bearing aqueous solutions.     

Binary biosorption of uranium(VI) and nickel(II) from aqueous solution by Ca-pretreated Cystoseira indica in a fixed-bed column

Simultaneous biosorption of uranium(VI) and nickel(II) ions onto Ca-pretreated Cystoseira indica biomass was studied and compared with single uranium or nickel biosorption in a fixed-bed column. Results of single biosorption showed the breakthrough and exhaustion time increase with the increase of the flow rate and inlet metal concentration for both metal ions. Also, it was observed that there was an optimum flow rate of 1.4 mL min⁻¹ (surface loading of 0.792 cm min⁻¹) for both metal ions in the column. Results from both single and binary systems showed the adsorption capacity of C. indica for both metal ions increases with the increasing inlet concentration of each component and C. indica had a stronger affinity for uranium than nickel ions. The binary system results showed that the presence of the second component affected the adsorption of the first one by C. indica so the antagonistic action was observed. Also, the inhibitory effect of uranium ions on the nickel adsorption was greater than nickel ions on the uranium adsorption. The uranium and nickel breakthrough curves under different conditions were described by the Thomas, Yoon-Nelson and Yan models. Among these models, the Yan model appeared to describe the experimental results better.     

Prediction of breakthrough curves for multicomponent adsorption in a fixed-bed column using logistic and Gompertz functions

In order to facilely predict the multicomponent breakthrough curves and avoid the complicated numerical solution, this work proposes two empirical models based on the logistic and Gompertz functions. The S-shaped and bell-like curves correspond to the adsorption and displacement processes respectively. The equilibrium loading of each component can be calculated by integration of the measured breakthrough curves. The effects of the model parameters on the breakthrough curves are investigated. The applicability of the two empirical models is validated by three binary and four ternary adsorption systems, including the gas–solid and liquid–solid adsorption. The residual plot and coefficient of determination (R²) are used to evaluate their fitting quality. The results indicate that the fitting curves agree well with the experimental data and all of the residuals are distributed randomly. The five model parameters (k, τ, k*, τ* and c) are easily obtained by the nonlinear regression. For example, the fitting results are k = 1.37 × 10^?2 min^?1, τ = 292 min, k* = 1.25 × 10^?2 min^?1, τ* = 453 min and c = 85.3 for adsorption of n-butyl acetate and p-xylene on granular activated carbon. On the whole, the Gompertz model is superior to the logistic model in terms of the fitting accuracy. The significance of this work is to provide a simple and practical method for prediction of the multicomponent breakthrough curves.     

Adsorption of uranium (VI) from aqueous solution by tetraphenylimidodiphosphinate

The adsorption of uranium (VI) using tetraphenylimidodiphosphinate (Htpip) was studied. Factors of affecting sorption efficiency have been investigated and results showed the adsorption of uranium (VI) was equilibrium at pH 4.5, time 20 min, adsorbent dosage 0.005 g and initial concentration 50 mg L^?1 reaching 99.86 mg g^?1 of adsorption capacity and 99.86% of removal efficiency. Additionally, the interfering ions studies showed that the adsorbent possessed excellent adsorption selectivity of uranium (VI). The surface morphology of Htpip was investigated by SEM. The adsorption process of uranium (VI) onto Htpip fit the pseudo-second-order kinetic model and the Freundlich isotherm model very well.     

Biosorption characteristics of uranium(VI) from aqueous solution by pummelo peel

The biomass pummelo peel was chosen as a biosorbent for removal of uranium(VI) from aqueous solution. The feasibility of adsorption of U(VI) by Pummelo peel was studied with batch adsorption experiments. The effects of contact time, biosorbent dosage and pH on adsorption capacity were investigated in detail. The pummelo peel exhibited the highest U(VI) sorption capacity 270.71?mg/g at an initial pH of 5.5, concentration of 50???g/mL, temperature 303?K and contacting time 7?h. The adsorption process of U(VI) was found to follow the pseudo-second-order kinetic equation. The adsorption isotherm study indicated that it followed both the Langmuir adsorption isotherm and the Freundlich adsorption isotherm. The thermodynamic parameters values calculated clearly indicated that the adsorption process was feasible, spontaneous and endothermic in nature. These properties show that the pummelo peel has potential application in the removal of the uranium(VI) from the radioactive waste water.     

Experimental and modeling investigation of thorium biosorption by orange peel in a continuous fixed-bed column

In this research work process parameters and breakthrough modeling of thorium biosorption on orange peel in a fixed-bed column has been studied. Some experiments have been done with sorbent diameter, flow rate, bed height and feed inlet concentration. Breakthrough point decreased with decreasing the bed height, increasing feed inlet concentration and increasing flow rate. Meanwhile, sorption capacity increased with decreasing bed height and flow rate. The highest sorption capacity, 87.7 mg/g, occurred in a 0.4–0.8 mm sorbent diameter. The experimental results were fitted by models of Thomas, Yoon–Nelson and Modified Dose–Response (MDR). The MDR model showed better results.     

Adsorption of uranium(VI) from aqueous solution by diethylenetriamine-functionalized magnetic chitosan

In this paper, the modified magnetic chitosan resin containing diethylenetriamine functional groups (DETA-MCS) was used for the adsorption of uranium ions from aqueous solutions. The influence of experimental conditions such as contact time, pH value and initial uranium(VI) concentration was studied. The Langmuir, Freundlich, Sips and Dubinin–Radushkevich equations were used to check the fitting of adsorption data to the equilibrium isotherm. The best fit for U(VI) was obtained with the Sips model. Adsorption kinetics data were tested using pseudo-first-order and pseudo-second-order models. Kinetic studies showed that the adsorption followed the pseudo-second-order kinetic model, indicating that the chemical adsorption was the rate-limiting step. The present results suggest that DETA-MCS is an adsorbent for the efficient removal of uranium(VI) from aqueous solution.     

Effect of flow rate on the sorption breakthrough behaviors of uranium(VI), phosphate,and fulvic acid onto a silica column

Five column experiments have been carried out to investigate the effect of flow rate on the breakthrough curves (BTCs) of phosphate, fulvic acid, and uranium(VI) onto a silica column. Both BTCs of phosphate and fulvic acid, and three BTCs of uranium(VI) in the presence and absence of phosphate or fulvic acid at high flow rate published in the previous paper [1] were compared with corresponding initial parts of BTCs at low flow rate in this paper. Each BTC in this paper was expressed as both C/C_o–t and C/C_o–V/V_o plots, where C and C_o are the concentrations in the influent and the effluent respectively, t and V are the time and the effluent volume from the start of injection of pulse solution respectively, V_o is the pore volume of the SiO₂ column. Based on the experimental results and the relationship among V, t, and flow rate F, it was found that there are advantages to using C/C_o–V/V_o plot as BTC to study the effect of flow rate. Based on these comparisons of C/C_o–V/V_o plots at different flow rates and the theoretical analysis from the Bohart–Adams sorption model, it was found that the right shift (increase in V/V_o of breakthrough), the left shift (decrease in V/V_o of breakthrough), and the non-shift (non-change in V/V_o of breakthrough) of initial parts of BTCs with increasing flow rate are certain to occur instead of only left shift and that three different trends of shifts can be mainly attributed to different rate-controlling mechanisms of sorption process.     

Adsorption of uranium(VI) from aqueous solution by novel dibutyl imide chelating resin

Journal of Radioanalytical and Nuclear Chemistry - The main structure of polystyrene-divinylbenzene (PSD) was synthesized by suspension method, and chlorinated resin (PSD-Cl) obtained by...     

Liquid-liquid extraction of molybdenum(VI) and uranium(VI) by LIX 622

The order of extraction of Mo(VI) from 1M acid solutions by 5% (v/v) LIX 622 (HL) in benzene is HCl>HNO₃>HClO₄>H₂SO₄, and extraction decreases with increasing concentration of HCl and H₂SO₄, and increases slightly with increasing concentration of HNO₃ and HClO₄. The extracted species is shown to be MoO₂L₂ as established by IR data of organic extracts and the extracted species in the solid form. Extraction is almost quantitative at and above 10% LIX 622, and is found to be independent of [Mo(VI)] in the range of 10^–4 to 10^–3 M. The diluents CCl₄, CHCl₃ and C₆H₆ are found to be superior to solvents of high dielectric constant for extraction of Mo(VI). Extraction of uranium(VI) by 10% (v/v) LIX 622 in benzene was found to increase with increasing equilibrium pH (3.0 to 6.0), and becomes quantitative at pH 5.9. Tributyl phosphate acts as a modifier up to 2% (v/v). Thorium(IV) is almost not extracted by LIX 622 or its mixture. Separation of Mo(VI) and U(VI) is feasible.     

Microdetermination of uranium (VI)

Summary A new method has been evolved for the separation and estimation of UO₂ ²⁺ from Cu²⁺, Zn²⁺, Ag⁺, Pb²⁺, Ga³⁺, In³⁺, Tl³⁺, La³⁺, Ti⁴⁺, Zr⁴⁺ and Th⁴⁺ with the sodium salt of benzilic acid as precipitating and chelating agent andn-butanol as solvent for solvent extraction. All these cations except UO₂ ²⁺ are precipitated by benzilic acid; UO₂ ²⁺ forms a deep yellow complex extractable byn-butanol. The uranium can be determined in the organic phase spectrophotometrically at 430 nm. The pH range over which the separation can be carried out is 2.6–4.0. Few anions and cations interfere.

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Zusammenfassung Eine neue Methode der Trennung und Bestimmung von UO₂ ²⁺ neben Cu²⁺, Zn²⁺, Ag⁺, Pb²⁺, Ga³⁺, In³⁺, Tl²⁺, La³⁺, Ti⁴⁺, Zr⁴⁺ und Th⁴⁺ wurde ausgearbeitet. Das Natriumsalz der Benzilsäure dient als Färbungs- und Komplexbildungsmittel und n-Butanol zur Extraktion. Alle angeführten Kationen mit Ausnahme von UO₂ ²⁺ werden von Benzilsäure gefällt; UO^{2 2+} bildet einen tiefgelben, mit n-Butanol extrahierbaren Komplex und kann in der organischen Phase spektrophotometrisch bei 430 nm bestimmt werden. Die Trennung kann bei pH 2,6 bis 4,0 durchgeführt werden. Nur wenige Anionen und Kationen stören.

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Résumé On développe une nouvelle méthode pour la séparation et l'évaluation de UO₂ ²⁺ dans Cu²⁺, Zn²⁺, Ag⁺, Pb²⁺, Ga³⁺, In³⁺, Tl³⁺, La³⁺, Ti⁴⁺, Zr⁴⁺ et Th⁴⁺, par le sel de sodium de l'acide benzilique comme agent précipitant et chélatant et le N-butanol comme solvant pour l'extraction par solvant. Tous ces cations, sauf UO₂ ²⁺, précipitent par l'acide benzilique; UO₂ ²⁺ forme un complexe jaune intense que l'on peut extraire par le N-butanol. On peut doser l'uranium en phase organique par spectrophotométrie à 430 nm. La séparation peut s'effectuer dans le domaine de pH de 2,6 à 4,0. Peu d'anions et de cations interfèrent.

     

Adsorption of U(VI) ions from low concentration uranium solution by thermally activated sodium feldspar

The thermally activated sodium feldspar (TASF), a novel material, was prepared by calcinating the micron sodium feldspar (SF) at 450 °C for 45 min. The TASF and the SF were characterized using X-ray diffraction and mercury injection porosimetry, and the TASF was found to have larger specific surface area and larger porosity than SF. The effects of the initial pH, temperature, contact time and initial U(VI) ions concentration on the adsorption of U(VI) ions from the low concentration uranium solution by TASF were investigated. The maximum adsorption efficiency of TASF for 0.5 mg/L uranium solution amounted to 95.49 % when the initial pH was 5.0, the temperature, 318 K, and and the contact time, 600 min. The relationship between the adsorption capacity q _e and equilibrium concentration C _e can well be described by Freundlich equation. Adsorption isotherm and the analysis by FT-IR coupled with SEM revealed that U(VI) ions were adsorbed onto the surface of TASF in multimolecular or cluster states, and that the intraparticle diffusion occurred in spontaneous process. The basic thermodynamic parameters including free energy change, entropy change and enthalpy change were calculated to comprehend the intrinsic features and spontaneous nature of the adsorption process. The FT-IR spectroscopic characterization for the TASF indicated that many groups were involved in the adsorption process of U(VI) ions, and the –OH group played a more important role. The experimental results suggested that TASF had great adsorption efficiency and strong potentiality of enrichment and recovery for the low concentration U(VI).     

Representation of breakthrough curves for fixed-bed adsorbers and reactors using moments of the impulse response

An approximate expression for breakthrough curves (step responses) in isothermal packed-bed adsorbers and reactors is obtained by using the first two moments of the impulse response in a leading term of a Laguerre polynomial series expansion. The approximation is expressed in terms of an incomplete gamma function which can readily be obtained either by Romberg integration or from tabulated values. The approximation agrees well with analytical solutions for both long and short packed-beds. It is shown that the leading term of the Laguerre series is a better approximation to analytical solutions for short beds than the Hermite polynomial expansion and is at least equal to the latter in case of long columns.     

Extraction of uranium(IV) and uranium(VI) by primary and tertiary-amines from sulphate solutions

In developing a method for possible low level isotopic enrichment, which uses to advantage the equilibrium isotope effect observed during U(1V)-U(VI) electron exchange reaction in sulphate solutions, details of a solvent extraction process involving high concentration of a mixture of U(IV) and U(VI) and at low acid concentrations, are described. The extraction behaviour of uranium under these conditions is discussed. During the extraction with amines, U(IV) tended to get oxidised in sulphate solutions.     

Extraction of uranium(VI) by bis(hexylsulfinyl)methane

The extraction of uranium(VI) with bis(hexylsulfinyl)methane (BHxSM) from nitric acid aqueous solution has been investigated. It was found that the extraction increased with increasing nitric acid concentration up 8.5 mol/l and then decreased. Extraction distribution ratio also increased with the bis(hexylsulfinyl)methane concentration. The extraction species appear to be UO₂(NO₃)₂ ^.2BHxSM. The influences of temperature, salting-out concentration and oxalate concentration on the extraction equilibrium were also investigated, and the enthalpy of the extraction reaction was obtained. The result shows that the reaction of uranium(VI) extraction with BHxSM is an exothermic one.