Selective Separation of Uranium using Alizarin Red S (ARS)-Modified Anion-Exchange Resin or by Flotation of U-ARS Chelate

ABSTRACT

An alizarin red S (ARS)-modified anion-exchange resin was prepared by a simple reaction of ARS with the anion exchanger Doulite A101 and used for the efficient sorption of uranium from aqueous media. The effect of various parameters on the sorption of U(VI) (pH effect, sorption kinetics, resin capacity and breakthrough curves) was investigated. The modified resin sorbs U(VI) over a wide range of pH (2·8–5) with a maximum sorption capacity of 0·68 mmol.g^?1 at pH 3·2 to 4·0. Iron (III), Zr(IV), Ti(IV), Cu(II), and Th(IV) ions are also sorbed to different extents, but Be(II), Bi(III), Ca(II), Mg(II), Pb(II), Hg(II), Zn(II), Cd(II), AI(III), Mn(II), Co(II) and Ni(II) are not sorbed; thus, conditions for separating U(VI) from these metal ions have been identified. For eluting U(VI) from the resin, 0·2 mol.L^?1 HCl was used and the recovery recorded was as high as 99.9%. The use of ARS is extended to float uranium quantitatively and selectively from aqueous media at pH = 4 by using oleic acid as a surfactant. The different parameters affecting the flotation process have also been investigated. Uranium(VI) has been effectively separated from natural water samples and certified uranium ores using both procedures.     

Potentiality of zirconium phosphate synthesized from zircon mineral for uptaking uranium

Zirconium phosphate (ZP), an inorganic ion exchanger, has been synthesized from zircon mineral, characterized, and used as a potential adsorbent for removing U(VI) from nitrate solution with varying background conditions including pH, shaking time, U(VI) initial concentrations, temperature and phase ratio. Batch results for uranium adsorption showed that the adsorption process reached steady-state condition within 30 min., and all the dissolved U(VI) was removed by ZP at pH 5, 298K and at (S/A) 0.1g/25 mL. Uranium adsorption process followed a traditional Langmuir adsorption isotherm, endothermic and spontaneous in nature which emphasized from thermodynamic data. The higher thermal stability of Zr-P amorphous material makes it applicable and efficient adsorbent for removing U(VI).     

Examination of Uranium(VI) Leaching during Ligand Promoted Dissolution of Waste Tank Sludge Surrogates

Abstract

The dissolution of synthetic boehmite (γ-AlOOH) by 1-hydroxyethane-1,1-diphosphonic acid (HEDPA) was examined in a series of batch adsorption/dissolution experiments. Additionally, the leaching behavior of ²³³U(VI) from boehmite was examined as a function of pH and HEDPA concentration. The results are discussed in terms of sludge washing procedures that may be utilized during underground tank waste remediation. In the pH range 4 to 10, complexation of Al(III) by HEDPA significantly enhanced dissolution of boehmite. This phenomenon was especially pronounced in the neutral pH region where the solubility of aluminum, in the absence of complexants, is limited by the formation of sparsely soluble aluminum hydroxides. At pH higher than 10, the dissolution of synthetic boehmite was inhibited by HEDPA, likely due to sorption of Al(III):HEDPA complexes. The addition of HEDPA to equilibrated U(VI)-synthetic boehmite suspensions yielded an increase in the aqueous phase uranium concentration. Partitioning of uranium between the solid and aqueous phase is described in terms of U(VI):HEDPA speciation and dissolution of the boehmite solid phase.     

Synthesis of graphene oxide nanoribbons/chitosan composite membranes for the removal of uranium from aqueous solutions

In this study, a graphene oxide nanoribbons/chitosan (GONRs/CTS) composite membrane was successfully prepared by encapsulating CTS into GONRs, which were unzipped from multi-walled carbon nanotubes. The GONRs/CTS composite membrane so prepared was characterized using scanning electron microscopy, X-Ray diffraction and Fourier transform infrared spectroscopy. The effects of the experimental conditions such as the pH (2‒7), adsorbent dosage (10‒50 mg), experimental time (5 min–32 h), uranium concentration (25‒300 mg∙L⁻¹), experimental temperature (298 K‒328 K) on the adsorption properties of the composite membrane for the removal of U(VI) were investigated. The results showed that the U(VI) adsorption process of the GONRs/CTS composite membrane was pH-dependent, rapid, spontaneous and endothermic. The adsorption process followed the pseudo-secondary kinetics and Langmuir models. The maximum U(VI) adsorption capacity of the GONRs/CTS composite membrane was calculated to be 320 mg∙g⁻¹. Hence, the GONRs/CTS composite membrane prepared in this study was found to be suitable for separating and recovering uranium from wastewater.     

Adsorption of Uranium(VI) and Zirconium(IV) from Acid Solutions on Silica Gel

Abstract

Adsorption of uranium(VI) and zirconium(IV) from aqueous solutions on silica gel was investigated by the batch equilibration method. The influence of shaking time and concentrations of nitric acid (i.e., pH of solution) and metal ions in solution were studied. Adsorption of uranium(VI) and zirconium(IV) increases with an increase of pH (decrease of nitric acid concentration) and ion concentrations. The adsorption mechanism of uranium(VI) and zirconium(IV) from aqueous solutions on silica gel is proposed. It is shown that zirconium(IV) and uranium(VI) can be separated if the concentration of nitric acid in solution is higher than 0.01 mol/dm³.     

铁树叶水热炭及其去除溶液中铀U（VI）的研究

本文选用铁树叶为原料,采用温和的水热法制备出生物质炭.采用傅里叶变换红外光谱（FT-IR）探讨材料的成分,研究了溶液的初始pH值、初始铀浓度、温度和时间对吸附铀性能的影响,并从吸附热力学、动力学方面分析水热炭对U（Ⅵ）的吸附过程,探讨其吸附机理.结果表明溶液pH对吸附量的影响尤为显著,当pH为7时达到最大吸附量（54.66mg g-1）;在30 min时达到吸附平衡;吸附量随温度升高而不断增大.动力学研究结果表明铀在水热炭上的吸附符合准二级动力学模型和Langmuir吸附等温方程,Langmuir饱和吸附容量为56.5 mg g-1;热力学研究结果显示△H0=34.67 kJ mol-1,△G0＜0,吸附过程在考察温度范围内为自发的吸热反应过程.     

Superparamagnetic polyvinylpyrrolidone/chitosan/Fe3O4 electrospun nanofibers as effective U(VI) adsorbents

Magnetoactive electrospun fibrous membranes consisting of polyvinylpyrrolidone (PVP), chitosan (CS) and pre-fabricated, double-layer oleic acid-coated magnetite nanoparticles (OA.OA.Fe₃O₄) were fabricated and evaluated as new adsorbent materials for the removal and recovery of uranium (U(VI)) from aqueous solutions. The adsorption has been investigated by batch-type experiments and the solid material has been characterized by X-ray diffraction spectroscopy (XRD), Fourier-transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), transmission electron microscopy/energy dispersive X-ray analysis (TEM/EDX) and vibration sample magnetometry (VSM) measurements prior and after uranium adsorption. The experimental adsorption data were found to be well fitted with the Langmuir isotherm and the pseudo-second order kinetic model. The results indicate that PVP/CS/OA.OA.Fe₃O₄ fibrous adsorbents exhibit good adsorption properties towards U(VI) in aqueous solutions, achieving a q_max value of 0.77 mol kg⁻¹ (183.3 mg g⁻¹) at pH 6.0. The experiments regarding the regeneration and reuse of the magnetoactive adsorbents were carried out using Na₂CO₃, at pH ~11. After four cycles, the percentage relative adsorption remained stable (~100%) whereas the desorption percentage decreased from 31.9% to 21.0%. Generally, the presented results demonstrate that the incorporation of the Fe₃O₄ NPs has a positive effect on the adsorption efficiency of U(VI) from aquatic environments.     

Adsorption of uranium on phosphoric acid-activated peanut shells

ABSTRACT

Phosphoric acid-activated peanut shells (PS) were prepared by hydrothermal treatment at 200–800 °C and denoted as peanut shell-activated carbons (PACs). The PACs were characterized as adsorbent for removing U(VI) from aqueous solutions. The U(VI) adsorption on PACs follows the pseudo-second-order kinetic equation and the Langmuir model. The adsorption capacity depends on solution pH and ionic strength and PAC-800 exhibits the highest adsorption capacity. The increasing U(VI) adsorption could be attributed to C = OOH groups and delocalized π electrons as sorption sites by surface complexation and ion exchange. Therefore, PACs as economic adsorbents could potentially remove U(VI) from aqueous solutions.     

锰氧化物负载沸石固定床离子交换柱去除铀(VI)的研究

The adsorption of uranium (VI) on the manganese oxide coated zeolite (MOCZ) from aqueous solution was investigated in a fixed-bed column. The experiments were conducted to investigate the effects of bed height, flow rate, particle size, initial concentration of uranium (VI), initial pH, presence of salt and competitive ions. The U-uptake by MOCZ increased with initial uranium (VI) concentration and bed height, but decreased as the flow rate and particle size increased. In the presence of salt and competitive ions, the breakthrough time was shorter. The ad-sorption capacity reached a maximum at pH of 6.3. The Thomas model was applied to the experimental data to de-termine the characteristic parameters of the column for process design using linear regression. The breakthrough curves calculated from the model were in good agreement with the experimental data. The BDST model was used to study the influence of bed height on the adsorption of uranium (VI). Desorption of uranium (VI) in the MOCZ column was investigated. The column could be used for at least four adsorption-desorption cycles using 0.1 mol•L－1 NaHCO3 solution as the elution. After desorption and regeneration with deionized water, MOCZ could be reused to adsorb uranium (VI) at a comparable capacity. Compared to raw zeolite, MOCZ showed better capacity for uranium (VI) removal.     

Adsorption of Uranium from Dilute Aqueous Solution on Inorganic Adsorbents

Abstract

The adsorption of uranium from a dilute aqueous solution by a large number of inorganic adsorbents has been investigated. A mixture of aluminum hydroxide, ferric hydroxide, and activated carbon in the weight ratio 1:3:4 has shown a high adsorbability for uranium. The separation of uranium from a dilute aqueous solution by this mixed adsorbent under various temperatures and pH values has been studied. The adsorbability was found to exhibit a maximum at pH 4.0 to 5.5 and to decrease with increasing temperature. A number of eluting solutions for the desorption of uranium from the mixed adsorbent were also tested; 1 N (NH₄)₂ CO ₃ was found to be the most suitable eluting solution (93% recovery of uranium).     

Extraction of Uranium(VI) and Plutonium(IV) with Tetra-Alkylcarbamides

ABSTRACT

The use of tetra-alkylcarbamides as novel extractants for the separation of uranium(VI) and plutonium(IV) by solvent extraction from spent nuclear fuels is investigated in this study. Batch extraction experiments show that tetra-alkylcarbamides strongly extract U(VI) with high distribution ratios. Plutonium(IV) can be co-extracted with U(VI) at high nitric acid concentration, while high U(VI)/Pu(IV) selectivities can be reached at lower acidity. Loading capacity experiments with high uranium concentrations show that alkyl chains longer than butyl are necessary to avoid third phase formation. Nevertheless, the viscosity of uranium-loaded solvents gets too high with alkyl chains longer than pentyl. Overall, this study shows that with TPU extractant (with four pentyl chains), an efficient co-extraction of uranium and plutonium can be reached (D_U,Pu > 1) for a concentration of nitric acid higher than 4 mol?L^?1, while the partition between uranium(VI) and plutonium(IV) could be operated even at 2 mol?L^?1 nitric acid without redox chemistry.     

茶渣吸附U(Ⅵ)的特性

通过静态吸附实验,考察了铀溶液初始pH、初始浓度以及吸附时间、吸附剂粒度、温度对茶渣吸附U(Ⅵ)的影响,分析了吸附过程的动力学行为及等温吸附特性,并通过红外光谱和扫描电镜探讨了吸附机理。结果表明:pH对茶渣吸附U(Ⅵ)的影响较大,pH为2和6时吸附量分别为13.90、43.19 mg·g^-1。茶渣吸附U(Ⅵ)的过程较慢,吸附过程需要12 h才能达到平衡。吸附过程的准二级动力学方程的拟合效果优于准一级动力学方程。吸附量随铀溶液浓度的增加而增大,而吸附率则相反。铀溶液初始浓度为10~100 mg·L^-1,相应的吸附量为9.40~70.05 mg·g^-1,吸附率为94.04%~70.05%。茶渣吸附U(Ⅵ)的动力学行为更符合准二级动力学方程,等温吸附数据对Freundlich方程的拟合度较高。茶渣粒度及温度对茶渣吸附U(Ⅵ)的影响不大。茶渣吸附U(Ⅵ)的过程中,起主要作用的基团有羟基、羰基、硝基、P-O、Si-O。     

Uranium(VI) Removal from Aqueous Solution by Poly(Amic Acid)-Modified Marine Fungus

Fusarium sp. #ZZF51, marine-derived mangrove endophytic fungus, was chemically modified by poly(amic acid) to enhance its potential of uranium(VI) biosorption in aqueous solution. Compared with uranium(VI) removal of the pristine biomass, the maximum uranium(VI) adsorption capacity of the modified biomass increased 9.5-fold under the optimal condition of pH 5.0, S/L 0.4, and equilibrium time 180 min. Kinetic study showed that the process follows the pseudo-second-order kinetic model, which indicates that chemical reaction controls the adsorption rate. The thermodynamic experimental data fit well with Langumir, Freundlich, and Temkin isotherms, and their R ² values are 0.954, 0.963, and 0.986, respectively. FTIR spectroscopic analysis of the native, modified, and uranium-loaded biomass demonstrated the involvement of carboxyl, amide, and hydroxyl groups on the surface of fungus Fusarium sp. #ZZF51 cell wall in the adsorption of uranium(VI).     

EXTRACTION OF PLUTONIUM (III) BY TBP IN PRESENCE OF URANIUM

ABSTRACT

The distribution ratio (D) values for the extraction of plutonium (III) from nitric acid medium into 30% TBP in n-dodecane saturated with uranium(VI) (0% to 80%) were determined. For a fixed saturation of TBP with uranium, the D values for Pu(III) were found to increase with increase in nitric acid concentration (1M to 5M). At a fixed nitric acid concentration, the D values were found to decrease with increase in loading of TBP with uranium. The D values for the extraction of Pu(III) using 20% TBP in n-dodecane and 30% TBP in n-paraffin at 80% uranium saturation were also determined The distribution data was least squares analysed against concentration of HNO₃ as well as percentage saturation of TBP with uranium and the coefficients obtained are reported. For all these extraction systems, D values for U(VI) were also determined.     

Note: Effect of Temperature in the Extraction of Uranium and Plutonium by Triisoamyl Phosphate

Abstract

The extraction of uranium(VI) by triisoamyl phosphate (TiAP) has been studied to derive the thermodynamic parameters such as entropy change and the free-energy change. The extraction of U(VI) and Pu(IV) has also been studied with 1.1 M solutions of tri-n-butyl phosphate (TBP), tri-n-amyl phosphate (TAP), and TiAP as a function of temperature. While the enthalpy of U(VI) extraction was found to be exothermic, the enthalpy for the extraction of Pu(IV) was always found to be endothermic. The temperature at which the distribution ratios of U(VI) and Pu(IV) cross each other (the temperature of inversion) has been derived for TBP, TAP, and TiAP, and the results reveal the lowest temperature of inversion occurs for TiAP. The results indicate the advantage of TiAP as an extractant in avoiding plutonium reflux during the PUREX process involving high plutonium feed solutions, in addition to lower aqueous solubility, freedom from the third-phase formation problem, lower degradation, and better economics.     

Application of Supported Liquid Membranes for Removal of Uranium from Groundwater

Abstract

The separation of uranium from Hanford site groundwater was studied by hollow-fiber supported liquid membranes, SLM. The carrier bis(2,4,4-trimethylpentyl)phosphinic acid, H[DTMPeP], contained in the commercial extractant Cyanex^TM 272 was used as membrane carrier, because of its selectivity for U over calcium and magnesium. The water soluble complexing agent, 1-hydroxyethane-1,1-diphosphonic acid, HEDPA, was used as stripping agent. Polyproylene hollow-fibers and n-dodecane were used as polymeric support and diluent, respectively. Laboratory scale hollow-fiber modules were employed in a recycling mode, using as feed synthetic groundwater at pH 2, to confirm the capability of the proposed SLM system to separate and concentrate U(VI) in the strip solution. Information was obtained on the U(VI) concentration factor and on the long-term performance of the SLMs. Encouraging results were obtained both with a conventional module and with a module containing a carrier solution reservoir. Industrial scale modules were used at Hanford to test the SLM separation of U(VI) from real contaminated groundwater. The uranium concentration was reduced from approximately 3,500 ppb to about 1 ppb in a few hours.     

Enhanced adsorptive removal of Cr(VI) in aqueous solution by polyethyleneimine modified palygorskite

Polyethyleneimine (PEI) modified palygorskite (Pal) was used for the adsorption of Cr(VI) in aqueous solution. The absorbent was characterized by Fourier transform infrared spectroscopy (FT-IR) and thermogravimetric analysis (TGA). Characterized results confirmed that the Pal has been successfully modified by PEI. The modification of PEI increased the Cr(VI) adsorption performance of the Pal by the adsorption combined reduction mechanism, and amino groups of the adsorbent play the main role in the enhanced Cr(VI) adsorption. The maximum adsorption capacity was 51.10 mg·g⁻¹ at pH 4.0 and 25 °C. The adsorption kinetics of Cr(VI) on the adsorbent conforms to the Langmuir isotherm model. The maximum adsorption occurs at pH 3, and then the adsorption capacity of PEI-Pal was decreased with the increase of pH values. The adsorption kinetics of Cr(VI) on PEI-Pal was modeled with pseudo-second-order model. The addition of Cl⁻, SO₄²⁻ and PO₄³⁻ reduced the Cr(VI) adsorption by competition with Cr(VI) for the active sites of PEI-Pal. The Cr(VI) saturated PEI-Pal can be regenerated in alkaline solution, and the adsorption capacity can still be maintained at 30.44 mg·g⁻¹ after 4 cycles. The results demonstrate that PEI-Pal can be used as a potential adsorbent of Cr(VI) in aqueous solutions.     

Pseudo-Emulsion Based Hollow Fiber Strip Dispersion Technique (PEHFSD): Optimization,Modelling and Application of PEHFSD for Recovery of U(VI) from Process Effluent

Abstract

Pseudo emulsion based hollow fiber strip dispersion technique (PEHFSD) is the first of its kind ever explored in radioactive environment for the extraction of uranium from acidic process streams. Permeation of U(VI) was investigated as a function of various experimental variables such as hydrodynamic conditions (flow rates of pseudo-emulsion and feed phase), concentration of U(VI) in the feed phase, concentration of tri-n-butylphosphate (TBP), HNO₃ concentration in feed phase, O/A ratio and 0.01 M HNO₃ as stripping agent in pseudo-emulsion phase. The mass transfer coefficient was calculated from the experimental results and a model has been presented for determining mass transfer characteristics. PEHFSD has been demonstrated for separation/recovery of uranium from oxalate supernatant waste generated during plutonium precipitation by oxalic acid. PEHFSD and HFSLM (hollow fiber supported liquid membrane) performance has been compared in order to analyze the efficiency of the technique.     

Adsorption characteristics of U(Ⅵ)on tea waste

通过静态吸附实验,考察了铀溶液初始pH、初始浓度以及吸附时间、吸附剂粒度、温度对茶渣吸附U(Ⅵ)的影响,分析了吸附过程的动力学行为及等温吸附特性,并通过红外光谱和扫描电镜探讨了吸附机理。结果表明:pH对茶渣吸附U(Ⅵ)的影响较大,pH为2和6时吸附量分别为13.90、43.19 mg·g^-1。茶渣吸附U(Ⅵ)的过程较慢,吸附过程需要12 h才能达到平衡。吸附过程的准二级动力学方程的拟合效果优于准一级动力学方程。吸附量随铀溶液浓度的增加而增大,而吸附率则相反。铀溶液初始浓度为10~100 mg·L^-1,相应的吸附量为9.40~70.05 mg·g^-1,吸附率为94.04%~70.05%。茶渣吸附U(Ⅵ)的动力学行为更符合准二级动力学方程,等温吸附数据对Freundlich方程的拟合度较高。茶渣粒度及温度对茶渣吸附U(Ⅵ)的影响不大。茶渣吸附U(Ⅵ)的过程中,起主要作用的基团有羟基、羰基、硝基、P—O、Si—O。     

Extraction Behavior of Uranium(VI) with Polyurethane Foam

Abstract

The extraction of uranium(VI) from aqueous solution with polyether-based polyurethane (PU) foam was studied. The effects of the kinds and concentrations of nitrate salts, uranium(VI) concentration, temperature, nitric acid concentration, pH, the content of poly(ethylene oxide) in the polyurethane foam, and the ratio of PU foam weight and solution volume on the extraction of uranium(VI) were investigated. The interferences of fluoride and carbonate ions on the extraction of uranium(VI) were also examined, and methods to overcome both interferences were suggested. It was found that no uranium was extracted in the absence of a nitrate salting-out agent, and the extraction behaviors of uranium(VI) with polyurethane foam could be explained in terms of an etherlike solvent extraction mechanism. In addition, the percentage extraction of a multiple stage was also estimated theoretically.