Kinetics of Y(III) stripping for the system Y/HCl/Cyanex 272-P507/heptane with constant interfacial area cell with laminar flow

Kinetics and mechanism of stripping of yttrium(III) previously extracted by mixtures of bis(2,4,4-trimethylpentyl)phosphinic acid (Cyanex 272, HA), and 2-ethylhexyl phosphonic acid mono-2-ethylhexl ester (P507, HB) dissolved in heptane have been investigated by constant interfacial-area cell by laminar flow. The corresponding equilibrium stripping equation and equilibrium constant were obtained. The studies of effects of the stirring rate and temperature on the stripping rate show that the stripping regime is dependent on the stripping conditions. The plot of interfacial area on the rate has shown a linear relationship. This fact together with the strong surface activity of mixtures of Cyanex 272 and P507 at heptane-water interfaces makes the interface the most probable locale for the chemical reactions. The stripping rate constant is obtained, and the value is compared with that of the system with Cyanex 272 and P507 alone. It is concluded that the stripping ability with the mixtures is easier than that of P507 due to lower the activation energy of the mixtures. The stripping rate equation has also been obtained, and the rate-determining steps are the two-step interfacial chemical reactions as predicted from interfacial reaction models.

Extraction of rare earths(III) from nitrate medium with di-(2-ethylhexyl) 2-ethylhexyl phosphonate and synergistic extraction combined with 1-phenyl-3-methyl-4-benzoy l-pyrazolone-5

The extraction of trivalent rare earths ( RE) from nitrate solutions with di-(2-ethylhexyl) 2-ethylhexyl phosphonate (DEHEHP, B) and synergistic extraction combined with 1-phenyl-3-methyl-4-benzoyl-pyrazolone-5 (HPMBP, HA) were investigated. The extraction distribution ratios demonstrate a distinct "tetra effect," and Y lies between Tb and Dy when DEHEHP is used as a single extractant for RE. According to the corresponding separation factors (SF12) for adjacent pairs of rare earths, it could be concluded that DEHEHP could be employed for the separation of La from the other rare earths, and Y from light rare earths. The present work has also found that mixtures of HPMBP and DEHEHP have an evident synergistic effect for RE(III). Taking Y( III) as an example, a possible synergistic extraction mechanism is proposed. The enhancement of extraction in the binary system can be explained due to the species Y(NO3) (.) A(2) (.) HA (.) B formed. The synergistic enhancement coefficients ( R), extraction constants, formation constants and thermodynamic functions of the reaction were calculated.

Kinetics and mechanism of Yb(III) extraction and separation from Y(III) with mixtures of bis(2,4,4-trimethylpentyl)phosphinic acid and 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester

The ytterbium(III) extraction kinetics and mechanism with mixtures of bis(2,4,4-trimethylpentyl)phosphinic acid (Cyanex272) and 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester (P507) dissolved in heptane have been investigated by constant interfacial cell with laminar flow. The effects of the stirring rate, temperature, extractant concentration, and pH on the extraction with mixtures of Cyanex272 and P507 have been studied. The results are compared with those of the system with Cyanex272 or P507 alone. It is concluded that the Yb(III) extraction rate is enhanced with mixtures extractant of Cyanex272 and P507 according to their values of the extraction rate constant, which is due to decreasing the activation energy of the mixtures. At the same time, the mixtures exhibits no synergistic effects for Y(III), which provides better possibilities for Yb(III) and Y(III) separations at a proper conditions than anyone alone. Moreover, thermodynamic extraction separation Yb(III) and Y(III) by the mixtures has been discussed, which agrees with kinetics results. Extraction rate equations have also been obtained, and through the approximate solutions of the flux equation, diffusion parameters and thickness of the diffusion film have been calculated.

Extraction and stripping of ytterbium (III) from H2SO4 medium by Cyanex 923

The extraction and stripping of ytterbium (III) from sulfuric acid medium using Cyanex 923 in heptane solution was investigated. The effects of extractant concentration, pH and sulfate ion as well as stripping agents, acidity and temperature on the extraction and stripping were studied. The equilibrium constants and thermodynamic parameters, such as Delta H (10.76 kJ(.)mol(-1)), Delta G (-79.26 kJ(.)mol(-1)) and Delta S (292.41 J(.)K(-1.)mol(-1)), were calculated. The extraction mechanism and the complex species extracted were determined by slope analysis and FrIR spectra. Furthermore, it was found that the extraction of Yb (III) from sulfuric acid medium by Cyanex 923 increased with pH, concentration of SO42-, HSO4-, and extractant concentration, and approximately a quantitative extraction of Yb (III) was achieved at an equilibrium pH near 3.0, and the extracted complex was YbSO4(HSO4)(.)2Cyanex923((o)).

Adsorption studies of divalent metal ions with extraction resin containing 1-hexyl-4-ethyloctyl isopropylphosphonic acid

Equilibrium distributions of cobalt(II), nickel(II), zinc(II), cadmium(II), and copper(II) have been studied in the adsorption with extraction resin containing 1-hexyl-4-ethyloctyl isopropylphosphonic acid (HEOPPA) as an extractant from chloride medium. The distribution coefficients are determined as a function of pH. The data are analyzed both graphically and numerically. The extraction of the metal ions can be explained assuming the formation of metal complexes in the resin phase with a general composition ML2(HL)(q). The adsorbed species of the metal ions are proposed to be ML2 and the equilibrium constants are calculated. The efficiency of the resin in the separation of the metal ions is provided according to the separation factors values. The separation of Zn from Ni, Cd, Cu, Co, and Co from Ni, Cd, Cu with the resin is determined to be available. Furthermore, Freundlich's isothermal adsorption equations and thermodynamic quantities, i.e., DeltaG, DeltaH, and DeltaS are determined.

Mass-transfer kinetics of ytterbium extraction with sec-nonylphenoxy acetic acid

The extraction kinetics of ytterbium with sec-nonylphenoxy acetic acid (CA-100) in heptane have been investigated using a constant interfacial area cell with laminar flow. The influence of stirring speed and temperature on the rate indicated that the extraction rate was controlled by the experiment conditions. The plot of interfacial area on the rate showed a linear relationship. This fact together with the low solubility in water and strong surface activity of CA-100 at heptane-water interfaces made the interface the most probable locale for the chemical reactions. The influences of extractant concentration and hydrogen ion concentration on the extraction rate were investigated, and the forward and reverse rate equations for the ytterbium extraction with CA-100 were also obtained. Based on the experimental data, the apparent forward extraction rate constant was calculated. Interfacial reaction models were proposed that agree well with the rate equations obtained from experimental data.

Study on transfer and interfacial kinetics of neodymium and samarium in membrane based extraction

Extraction and interfacial kinetics of Nd3+ and Sm3+ with HER/EHP-kerosene in a hollow fiber membrane extractor were studied. The results show that the extraction reactions in the hollow fiber membrane extractor are the same as those in the liquid-liquid extraction, which can be expressed as a quasi-first-order reaction. The effect of acidity in aqueous phase, concentrations of extractant, Nd3+ and Sm3+ on extraction rate were discussed and the corresponding reaction series were obtained. The reaction equations, reaction rate constants and the separation constant were obtained.

Kinetics and mechanism of Y(III) extraction with CA-100 using a constant interfacial cell with laminar flow

The Yttrium(III) extraction kinetics and mechanism with secnonylphonoxy acetic acid (CA-100) were investigated by a constant interfacial cell with laminar flow. The studies of interfacial tension and solubility of extractant and effects of the stirring rate, temperature, specific interfacial area and species concentration on the extraction rate showed that the extraction regime was dependent on the extraction conditions and the most probable reaction zone was at the liquid-liquid interface. The rate equation of extracting yttrium by CA-100 in heptane was Rf = k[Y3+]((a))[H(2)A(2)]((o))(0.88)[H+]((a))(-1.08).

Extraction kinetics of rare earth elements with sec-octylphenoxy acetic acid

The kinetics of RE (La, Gd, Er, Yb and Y) extraction with sec-octylphenoxy acetic acid was investigated using a constant interfacial area cell with laminar flow at 303 K. The natures of the extracted complexes have some effect on the extraction rate which is controlled by the reaction rate of M(III) and extractant molecules at two-phase interface for Er(III), Yb(III) and Y(III), by a mixed chemical reaction-diffusion for Gd(III) and a diffusion for La( III). The extractant molecules tend to adsorb at the interface. So an interfacial extraction reaction model was derived.

Effect of polyvinylidene fluoride hollow fiber membranes on mass transfer of samarium

The influence of swelling and stripping acidity on the mass transfer coefficient based on water phase and the inner diameters of membranes were studied with P507-HCl-Sm as working system in the two different kinds of hollow fiber membranes. Effects of extractant concentration, H+ concentration in aqueous phase and Sm3+ concentration on extraction rate were discussed and the corresponding reaction series were obtained. According to the investigations on the interfacial kinetics, the reaction kinetics equation and reaction rate constant were obtained.

Separation of zinc(II) from europium(III) by using hollow fiber membrane

Extraction and separation of Eu3+ and Zn2+ in sulfuric acid solution was investigated by hollow fiber membrane with cyanex 302 (bis (2,4,4-trimethylpentyl) monothiophosphinic acid) in counter-currently circulating operation. Reaction mechanism of membrane extraction and effect of extractant concentration and H+ concentration in aqueous phase on the mass transfer coefficient were discussed. It can be concluded that Zn2+ can be extracted completely from Eu3+ sulfate solution according to the kinetics competing difference. In one extractor process, extraction percentage of Zn2+ was not completely and Eu3+ was not extracted. Extraction percentage of Zn2+ reached 94.92%, but Eu3+ only reached 8.59% after 100 minutes extraction in two series connectors and that of Zn2+ and Eu3+ reached 99.9% and 6.53% respectively after 40 minutes extraction in three series connectors.

Determination of some basic constants of sec-octylphenoxy acetic acid

In this work some basic constants of extractant Sec-Octylphenoxy acetic acid (CA-12) such as solubility (S) in water, dissociation constant (K-a) in aqueous solution, dimerization constant( K-2) and distribution constant (K-d) between water and haptane have been determined by two phase titration method. The results are as follows: S = 1.40 x 10(-4) mol/L, K-a = 3.02 x 10(-4), K-2 = 3.56 x 10(2), K-d = 4.06 x 10(2) (25 +/-0.5 degreesC).

Solvent extraction of scandium(III) by Cyanex 923 and Cyanex 925

The extraction equilibria of Sc(III), Zr(IV), Ti(IV), Th(IV), Fe(III) and Lu(III) from sulphuric or hydrochloric acid media by Cyanex 923 (mixture of straight chain alkylated phosphine oxides) and Cyanex 925 (mixture of branched chain alkylated phosphine oxides) were studied at various aqueous acidities. The extractant Cyanex 923 demonstrated better scandium loading and selectivity for TI(IV). Fe(III) and Lu(III) than Cyanex 925. The effects of extractant concentration on the extractions of sulphuric acid and Sc(III) by Cyanex 923 were examined. The stoichiometries of the extraction reactions were postulated based on slope analysis. The experimental results indicate that Cyanex 923 can be employed to recover scandium directly from the hydrolytic mother solution arising from TiO2 production via the sulphate process. The parameters studied were scandium loading capacity, phase ratio, concentrations of Ti(IV) scrubbing and Sc(III) stripping agents. A new solvent extraction technology of scandium recovery was developed. The purity of the final Sc(III) product is above 95% with a yield > 94%. (C) 1998 Elsevier Science B.V.

Extraction and separation of heavy rare earth (III) with Extraction Resin containing di(2,4,4-trimethyl pentyl) phosphinic acid (Cyanex 272)

Extraction resins, of the type of;levextrel, (which is a collective term for styrene/divinylbenzene based copolymers of predominantly macroporous structure that contain a selective extractant) are important for the recovery and separation of metal ions, as they combine features of solvent extraction and ion exchange resins. This paper presents the results of the adsorption of heavy rare earth ions (Ho(III), Er(III), Tm(III), Yb(III), Lu(III) and Y(III)) from hydrochloric acid solutions at 0.2 mol/L ionic strength and 50 degrees C by the extraction resin containing di (2,4,4-trimethyl pentyl) phosphinic acid (Cyanex 272) and the chromatographic separation of (Er(III), Tm(III) and Yb(III)). Technological separation products, with purity and yield of Tm2O3 >99.97%, >80%, Er2O3 >99.9%, >94% and Yb2O3 >99.8%, >80% respectively, have been obtained from a feed having the composition Tm2O3 60%, Er2O3 10%, and Yb2O3 3%, the others 27%. The distribution coefficients, extraction equilibrium constants and separation factors have been determined as a function of acidity, loading of the resin and rare earths, flow rates and column ratios. The resolutions and efficiencies of separation of Er/Tm/Yb each other have been calculated. The stoichiometry of the extraction of rare earth ions has been suggested as well.

SOLVENT-EXTRACTION OF SC(III), ZR(IV), TH(IV), FE(III), AND LU(III) WITH THIOSUBSTITUTED ORGANOPHOSPHINIC ACID EXTRACTANTS

The solvent extraction of Sc(III), Zr(IV), Th(IV), Fe(III) and Lu(III) with Cyanex 302 (bis(2,4,4-trimethylpentyl)monothiophosphinic acid) and Cyanex 301 ( bis(2,4,4-trimethylpentyl) dithiophosphinic acid) in n-hexane from acidic aqueous solutions has been investigated systematically. The effect of equilibrium aqueous acidity on the extraction with these reagents was studied. The separation of Th(IV), Fe(III) and Lu(III) from Sc(III), or the separation of other metals from Lu(III) with Cyanex 302, can be achieved by controlling the aqueous acidity. However, Cyanex 301 exhibited a poor selectivity for the above metals, except for Lu(III). The extraction of these metals with Cyanex 272, Cyanex 302 and Cyanex 301 has been compared. The stripping percentages of Sc(III) for Cyanex 302 and Cyanex 301 in a single stage are near 78% and 75% with 3.5 mol/L and 5.8 mol/L sulphuric acid solutions, respectively. The effects of extractant concentration and temperature on the extraction of Sc(III) were investigated. The stoichiometry of the extraction of Sc(III) with Cyanex 302 was determined. The role of different components of Cyanex 302 in the extraction of Sc(III) was discussed.