Effects of operating variables on the extraction of uranium from phosphoric acid by factorial design

Extraction of uranium from aqueous phosphoric acid by DEHPA/TOPO is carried out commercially and in pilot plants. The operating variables followed are temperature, concentration of phosphoric acid, and the ratio of DEHPA/TOPO. This study investigates the influence of these operating variables by the statistical method of 2³ Factorial Design on extraction of uranium from phosphoric acid. The mathematical model suggested (K=242.31–7.34C–4.784T+0.164C.T) predicts the effect of variables on the distribution ratio (extraction coefficient). The model is tested by a significance test and represented graphically.     

Emulsion membrane systems for preconcentration of uranium

Various double emulsion systems with liquid membranes containing tri-n-octylphosphine oxide /TOPO/, tri-n-butylphosphate /TBP/, KELEX 100^® and di-2-ethylhexylphosphoric acid /DEHPA/, as carriers for uranium/VI/ pertraction, were studied. The conditions were found at which the systems are most efficient, comparing with solvent extraction. The use of DEHPA as a membrane carrier with solutions of H₂SO₄ and H₃PO₄ encapsulated in the membrane was substanfiated.     

Separation and determination of uranium and radium-226 in phosphorites and their industrial derivatives by extraction chromatography

An extraction chromatographic method based on microporous polyethylene (Microthene) supporting tri-n-octylphosphine oxide (TOPO) was used to separate uranium and²²⁶Ra from phosphorites and their industrial derivatives. Uranium was then determined by fluorimetry and by alpha-spectrometry after electroplating, and radium by precipitation as Ba(Ra)SO₄ and alpha counting with a ZnS(Ag) alpha detector. The method was checked by using an IAEA phosphorite sample having a certified uranium concentration. Some phosphorite, phosphoric acid and plaster samples supplied by an Italian industrial plant were analyzed; uranium isotopes always resulted in radioactive secular equilibrium.     

The influence of cations in phosphoric acid on the extraction of uranium

Commercial phosphoric acid produced by the wet method is not a purecompound. It contains many contaminants. This paper studied the effect ofcertain cations in the commercial phosphoric acid produced by SIAPE wet methodin Homs General Fertilizer Company on the distribution coefficient (K d )ofuranium . The effect of Fe ₃+ , Fe₂+ , Mg₂+, Ca ₂+ , Al ₃+ and V ₅+ on uranium extractionby D2EHPA/TOPO was investigated according to the factorial design method.The results obtained showed that Al ₃+ and Ca ₂+ hada marked beneficial effect on uranium extraction while Mg ₂+ ,Fe ₃+ and V ₅+ had a negligible effect. An increasein Fe ₂+ led to a decrease in the extraction of UO ₃2+ from phosphoric acid.     

Direct uranium extraction from dihydrate and hemi-dihydrate wet process phosphoric acids by liquid emulsion membrane

A new liquid emulsion membrane (LEM) process for uranium extraction from either dihydrate 28-30% P₂O₅ (DH) or hemi-dihydrate 42-45% P₂O₅ (HDH) wet process phosphoric acid is proposed. In this process, the organic component of the LEM is composed of a synergistic mixture of 0.1M di-2-ethyl hexyl phosphoric acid (DEHPA) and 0.025M trioctyl phosphine oxide (TOPO) with 4% Span 80. The internal or the strip acid phase is composed of 0.5M citric acid. The prepared LEM was proved to be stable in 42-45% P₂O₅ acid concentration range and can, therefore, be applied to the phosphoric acid produced by the hemi-dihydrate process. After breakdown of the loaded emulsion, the uranyl citrate in the internal strip phase is separated by adding methanol followed by its calcination to the orange oxide. Most of the reagents used are recycled. The proposed process is characterized by simplicity, practically closed operation cycle in addition to lower capital and operating costs.     

Investigation of Uranium(VI) Extraction Mechanisms from Phosphoric and Sulfuric Media by 31P-NMR

Uranium extraction using DEHCNPB (butyl-1-[N,N-bis(2-ethylhexyl)carbamoyl]nonyl phosphonic acid, a bifunctional cationic extractant) has been studied to better understand mechanism differences depending on the original acidic solution (phosphoric or sulfuric). Solvent extraction batch experiments were carried out and the organic phases were probed using ³¹P-NMR. This technique enabled to demonstrate that phosphoric acid is poorly extracted by DEHCNPB ([H₃PO₄]_org < 2mM), using direct quantification in the organic phase by ³¹P-NMR spectra integration. Moreover, in the presence of uranium in the initial phosphoric acid solution, uranyl extraction by DEHCNPB competes with H₃PO₄ extraction.Average stoichiometries of U(VI)-DEHCNPB complexes in organic phases were also determined using slope analysis on uranium distribution data. Uranium seems to be extracted from a phosphoric medium by two extractant molecules, whereas more than three DEHCNPB on average would be necessary to extract uranium from a sulfuric medium. Thus, uranium is extracted according to different mechanisms depending on the nature of the initial solution.     

Uranium extraction enhancement form phosphoric acid by emulsion liquid membrane

This work is mainly concerned with the uranium extraction from phosphoric acid commercially produced by Abu Zaabal Fertilizers and Chemical Co., Egypt. This target would realize a dual purpose where the phosphate ore is considered as an alternative source of uranium besides eliminating its environmental contamination. The applied procedures are that of the new technology of emulsion liquid membrane. Authors have indeed pointed out that the variables explored still leave open to question the roles of stripping at the internal interface as well as the bulk transfer of uranium in the internal phase. For this purpose, two reducing agents are studied as additives to two organic solvent systems; namely the organophosphorous synergistic mixture of D2EHPA/TOPO as well as the tridodecyl amine. The relevant factors have first been optimized upon synthetic uraniferous phosphoric acid solution followed by the application upon the commercial acid after purification. These factors include the concentration of solvent system and the used emulsifier, acid concentration of the external and internal phases besides the nature and concentration of the reductant added to the internal phase. In addition, the permeation time as well as the oxidation state of the external phase was studied. All these factors have indeed been studied under different mixing speeds ranging from 300 up to 1,000 rpm. Ascorbic acid concentration, 1 % as an additive to the internal phosphoric acid phase (40 % P₂O₅) resulted in 95 % uranium extraction efficiency at the lower speed of 600 rpm.     

Study of factors affecting uranium stripping from DEHMA/TOPO solvent by factorial design

Uranium is recovered from wet phosphoric acid by a DEHPA/TOPO mixture. It was found that stripping is the most crucial step in this process. Several studies were undertaken to understand this process in greater depth. This study investigates the main operating variables, mainly concentration of phosphoric acid, temperature and concentration of iron on stripping, by the method of factorial design. A mathematical model was developed to represent the data. Another experiment was undertaken to find out the effect of fluoride ion on stripping. The results agree well with those of earlier investigations, namely that it is beneficial to increase the concentration of phosphoric acid and the temperature. The increase in fluoride ion concentration leads to an enhancement of the stripping distribution ratio.     

The uranium(VI) extraction mechanism of D2EHPA-TOPO from a wet process phosphoric acid

This paper reports the results of an investigation into the solvent extraction of uranium from technical grade phosphoric acid using industrially available extractants as D2EHPA and TOPO diluted in technical grade kerosene. Preliminary tests showed that, the effect of different parameters such as uranium oxidation stage, temperature and the molar ratio of D2EHPA/TOPO on the uranium recovery was in good agreement with those of previous investigations. However, a detailed investigation into the effect of phosphoric acid concentration, organic concentration and acid/organic phase ratios suggested that the mechanism of D2EHPA/TOPO synergism was rather complex and it presented a different character depending on the acid concentration.     

Radiation effects on the extraction of americium(III) with di(2-ethylhexyl) phosphoric acid

Radiation effects on the extraction of Am(III) with di (2-ethylhexyl) phosphoric acid (DEHPA) was studied by exposing DEHPA to gamma rays under various conditions. Gamma irradiation of undiluted DEHPA causes an enhancement of extraction of Am(III) due to the formation of mono (2-ethylhexyl) phosphoric acid (MEHPA) similarly to that of Nd(III). The presence of diluent during irradiation brought about a slight difference from the results in the absence of a diluent. The marked change occurred in Df when the organic solvent was exposed to γ-ray while being mixed with nitric acid solution. An initial slight increase of Df for Am(III) and Nd(III) was followed by a subsequent decrease beyond an absorbed dose of approximately 200 Wh·1⁻¹. This phenomenon was explained by the enhanced decomposition of DEHPA and the subsequent strong hydrolytic and radiolytic decomposition of MEHPA to H₃PO₄ in the aqueous phase, and the complex forming nature of H₃PO₄ with Am(III) and Nd(III).     

Natural radionuclide-free phosphoric acid production

High-uranium phosphate rock from Itataia, Brazil, was milled for wet-process phosphoric acid production using the dihydrate method. Uranium contained in the phosphoric acid was recovered by solvent extraction. The distribution of long-lived natural radionuclides of the ²³⁸U and ²³²Th decay series involved in these operations was evaluated. ²²⁶Ra, ²²⁸Ra and ²¹⁰Pb were found to predominate in the phosphogypsum, while ²²⁸Th, ²³⁰Th and ²³²Th in the uranium-free phosphoric acid. Thorium is removed from the phosphoric acid by solvent extraction to produce a NORM-free phosphoric acid.     

Single step conversion of UO2 and U3U8 into uranyl sulphate solution

A direct and simple method for the conversion of UO₂ and U₃O₈ powder into uranyl sulphate solution is described, eliminating many tedious chemical steps. UO₂ and U₃O₈ are not soluble in concentrated or dilute sulphuric acid, as uranium in lower oxidation state does not react with sulphuric acid. However, nitric acid oxidizes uranium from lower valency to higher valency state, i.e., tetravalent to the hexavalent uranyl ion in solution. Sufficient amount of sulphuric acid present in the reaction mixture makes it possible for uranyl ions, formed by oxidation of nitric acid, to react with sulphuric acid forming uranyl sulphate.     

A new method of uranium preseparation and concentration for neutron activation analysis

This paper introduces a new type of extractant, sym-dibenzo-16-crown-5-oxyhydroxamic acid (HL). The extraction of UO ₂ ²⁺ , Na⁺, K⁺, Sr²⁺, Ba²⁺ and Br^– were studied with HL in chloroform. The results obtained show that UO ₂ ²⁺ can be quantitatively extracted at pH above 5, whereas the extractions of K⁺, Na⁺, Ba²⁺ and Br^– are negligible in the pH range of 2–7. The dependence of the distribution ratio of U(VI) on both the concentration of the HL and pH are linear, and they have the same slope of 2. This suggests that U(VI) appears to form a 12 complex with ligand.Uranium (VI) can be selectively separated and concentrated from interfering elements such Na, K, Sr and Br by solvent extraction with HL under specific conditions. The recovery of uranium is nearly 100% and the radionuclear purity of uranium is greater than 99.99%. Therefore, it has greatly improved the sensitivity and accuracy for the detection of trace uranium from seawater by neutron activation analysis.     

Kinetic studies on the extraction of uranium(VI) from phosphoric acid medium by bulk liquid membrane containing di-2-ethylhexyl phosphoric acid

To go through the first stage of industrial solvent extraction process in order to recover uranium from phosphate rocks by liquid membrane techniques, as a simple model, the kinetics of facilitated transport of uranium(VI) from a dilute phosphoric acid medium into more concentrated phosphoric acid media as a receiving phase through a bulk liquid membrane containing di-2-ethylhexyl phosphoric acid as a carrier was studied. The influence of phosphoric acid concentration in the source and receiving phases, carrier concentration, type of solvent, stirring speed and temperature were investigated. The kinetic parameters (k _e, k _s, t _max, J _max) were calculated for the interface reactions assuming two consecutive, irreversible first-order reactions. The activation energy values were calculated as 29.40 and 19.51 kJ mol^?1 for extraction and stripping, respectively. The values of calculated activation energy indicated that both the extraction and stripping processes were controlled by mixed regime (both kinetic and diffusion). In addition, the influence of adding trioctyl-phosphine oxide into the membrane phase as a synergic agent on the transport kinetics was determined.     

Extraction of sulfuric acid with TOPO

A study on solvent extraction of sulfuric acid by tri-octylphosphine oxide (TOPO) in n-heptane has been made. Extraction coefficients of H₂SO₄ as a function of H₂SO₄ concentration in aqueous phase, and extractant concentrations in organic phase have been studied. The composition of extracted species, equilibrium constants of extraction reaction have been evaluated. These results are important for interpreting extraction equilibrium data of uranium(VI) or other metal ions with TOPO in sulfuric acid media.     

Comparative extraction efficiencies of tri-<Emphasis Type="Italic">n</Emphasis>-butyl phosphate and <Emphasis Type="Italic">N,N</Emphasis>-dihexyloctanamide for uranium recovery using supercritical CO<Subscript>2</Subscript>

Extraction of uranium from tissue paper, synthetic soil, and from its oxides (UO₂, UO₃ and U₃O₈) was carried out using supercritical carbon dioxide modified with methanol solutions of extractants such as tri-n-butyl phosphate (TBP) or N,N-dihexyl octanamide (DHOA). The effects of temperature, pressure, extractant/nitric acid (nitrate) concentration, and of hydrogen peroxide on uranium extraction were investigated. The dissolution and extraction of uranium in supercritical CO₂ modified with TBP, from oxide samples followed the order: UO₃ ≫ UO₂ > U₃O₈. Addition of hydrogen peroxide in the modifier solution enhanced the dissolution/extraction of uranium in dynamic mode. DHOA appeared better than TBP for recovery of uranium from different oxide samples. Similar enhancement in uranium extraction was observed in static mode experiments in the presence of hydrogen peroxide. Uranium estimation in the extracted fraction was carried out by spectrophotometry employing 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol (Br-PADAP) as the chromophore.     

以脉冲萃取柱利用三异辛胺从高浓度铀溶液中回收铀

利用三异辛胺(TOA)纯化Gattar小型试验工厂的高浓度铀溶液(洗脱液的铀浓度7 g·L^-1),研究了脉冲萃取柱的性能。利用实验室级脉冲萃取柱进行了实验室规模的溶剂萃取实验和后续实验。结果表明,在室温、pH=1和有机相与水相的比例(V_O/V_A)约为1.8：1时,加入二(2-乙基己基)磷酸(D2EHPA)使其与TOA的比例(V_D2EHPA/V_TOA)为2：3,可使萃取克服Cl-的抑制效应,提高效率。将结论用于考察试验工厂级萃取柱的流体力学和传质性能,结果表明用脉冲萃取柱萃取铀可以达到97%的萃取效率,具有可行性。     

以脉冲萃取柱利用三异辛胺从高浓度铀溶液中回收铀

利用三异辛胺（TOA）纯化Gattar小型试验工厂的高浓度铀溶液（洗脱液的铀浓度7 g·L^-1）,研究了脉冲萃取柱的性能。利用实验室级脉冲萃取柱进行了实验室规模的溶剂萃取实验和后续实验。结果表明,在室温、pH=1和有机相与水相的比例（V_O/V_A）约为1.8∶1时,加入二（2-乙基己基）磷酸（D2EHPA）使其与TOA的比例（V_D2EHPA/V_TOA）为2∶3,可使萃取克服Cl^-的抑制效应,提高效率。将结论用于考察试验工厂级萃取柱的流体力学和传质性能,结果表明用脉冲萃取柱萃取铀可以达到97%的萃取效率,具有可行性。     

Liquid–liquid extraction of uranium from Egyptian phosphoric acid using a synergistic D2EHPA–DBBP mixture

Extraction of uranium from Egyptian phosphoric acid with synergistic mixture of di-2-ethylhexylphosphoric acid (D2EHPA) and di-butyl butyl phosphonate (DBBP) is reported in this paper. The influence of various factors such as D2EHPA concentration, DBBP concentration, phosphoric acid concentration, contact time, aqueous: organic phase’s ratio (aq:org) and temperature on the degree of extraction has been established. The data on the effect of temperature on the extraction showed that the enthalpy change is −23.12 kJ/mol. Uranium extracted by D2EHPA–DBBP is further subjected to a second cycle of extraction and scrubbing impurities. The uranium is finally converted to a high purity UO₃ product using precipitation with hydrogen peroxide and heat treatment at 375 °C.     

Extraction of uranium (VI) from sulfuric acid solution with TOPO

The extraction of uranium(VI) from sulfuric acid medium with tri-octylphosphine oxide (TOPO) in n-heptane was studied. Accompanied with the increase in the concentration of H₂SO₄, the distribution coefficient of uranium(VI) increased in the region of dilute sulfuric acid. When the concentration of H₂SO₄ surpassed 3.5 mol·dm⁻³, the distribution coefficient of uranium(VI) was at maximum. This result was due to the competition extraction between uranium(VI) and H₂SO₄. From the data, the composition of extracted species and the equilibrium constant of extraction reaction have been evaluated, which were (TOPOH)₂UO₂(SO₄)₂ (TOPO) and 10^7.6±0.15, respectively.