Mass-transfer in pertraction of butyric acid by phosphonium ionic liquids and dodecane

Transport of butyric acid (BA) through a supported liquid membrane (SLM) containing phosphonium ionic liquid (IL) Cyphos IL-104 and dodecane occurs by two mechanisms. The first is related to the physical solubility of undissociated acid in dodecane in the form of a monomer or dimer and the second to the reactive extraction of acid by IL. Although the model of pertraction indicates that increasing the mean concentration of acid in the feed, c _F,lmv, increases the participation of pertraction based on the physical solubility; in the tested range of c _F,lmv from 0 kmol m⁻³ to 0.45 kmol m⁻³ it does not play an important role and at the highest c _F,lmv value, less than 10 % of the overall BA transport were achieved. The presence of IL in SLM considerably increases the value of the overall mass transfer coefficient in pertraction at low BA concentrations. However, at c _F,lmv > 0.4 kmol m⁻³ its values are similar for SLMs with and without IL. Compared to lactic acid, the pertraction of BA through the same SLM is about five times faster. Reactive transport of BA is connected with the back transport of water via reverse micelles decomposition and formation on the extraction and stripping interfaces.     

Influence of temperature on mass transfer in an incomplete trapping supported liquid membrane extraction of triazole fungicides

The influence of temperature in a supported liquid membrane (SLM) extraction of triazole fungicides was investigated. The mass transfer parameters such as diffusion coefficient, flux and apparent viscosity were determined at temperatures ranging from 5 to 40°C. Increase in temperature led to an increase in diffusion coefficient and flux with a flowing acceptor solution. The apparent viscosity also decreased with an increase in temperature. However, the increase in mass transfer parameters did not result in an overall increase in extraction efficiency with a stagnant or circulation acceptor phase. Stripping of the analytes from the membrane into the acceptor phase as well as the configuration of the extraction unit could have limited the influence of temperature on mass transfer. The partition coefficient of analytes from the acceptor solution to the membrane, K_A, was found to be much higher than that from the donor solution to the membrane K_D, thus triazole compounds preferred to remain in the membrane even with an increased extraction temperature.     

Influence of temperature on mass transfer in an incomplete trapping single hollow fibre supported liquid membrane extraction of triazole fungicides

The influence of temperature in a single hollow fibre supported liquid membrane extraction of triazole fungicides with a stagnant acceptor phase was investigated. The mass transfer parameters such as diffusion coefficient, flux and apparent viscosity were determined at temperature ranging from 278 K to 313 K. Increase in temperature led to an increase in diffusion coefficient and flux. The apparent viscosity also decreased with an increase in temperature. The degree of trapping in the acceptor phase influenced the mass transfer at higher temperature. At lower temperature, the transport of analytes from the donor solution through the donor-membrane interface and through the membrane mainly affected the transport of triazole fungicides. The effect of temperature in a single hollow fibre SLM extraction technique is therefore more pronounced where transport is donor controlled and/or membrane controlled. The partition coefficient of analytes from the acceptor solution to the membrane, K_A was found to be much higher than that of from the donor solution to the membrane K_D, thus least trapped triazole fungicides preferred to remain in the membrane even with an increased extraction temperature.     

Fine‐tuning of electromembrane extraction selectivity using 18‐crown‐6 ethers as supported liquid membrane modifiers

Selectivity of electromembrane extractions (EMEs) was fine‐tuned by modifications of supported liquid membrane (SLM) composition using additions of various 18‐crown‐6 ethers into 1‐ethyl‐2‐nitrobenzene. Gradually increased transfer of K⁺, the cation that perfectly fits the cavity of 18‐crown‐6 ethers, was observed for EMEs across SLMs modified with increasing concentrations of 18‐crown‐6 ethers. A SLM containing 1% w/v of dibenzo‐18‐crown‐6 in 1‐ethyl‐2‐nitrobenzene exhibited excellent selectivity for EMEs of K⁺. The established host–guest interactions between crown ether cavities in the SLM and potassium ions in donor solution ensured their almost exhaustive transfer into acceptor solution (extraction recovery ～92%) within 30 min of EME at 50 V. Other inorganic cations were not transferred across the SLM (Ca²⁺ and Mg²⁺) or were transferred negligibly (NH₄⁺, Na⁺; extraction recovery < 2%) and had only subtle effect on EMEs of K⁺. The high selectivity of the tailor‐made SLM holds a great promise for future applications in EMEs since the range of similar selective modifiers is very broad and may be applied in various fields of analytical chemistry.     

Hexanoic acid as an alternative diluent in a GANEX process: feasibility study

Used nuclear fuel is radiotoxic for mankind and its environment for a long time. However, if it can be transmuted, the radiotoxicity as well as its heat load are reduced. Before a transmutation the actinides within the used fuel need to be separated from the fission, corrosion and activation products. This separation can be achieved by using the liquid–liquid extraction technique. One extraction process that can be used for such a separation is the Group ActiNide EXtraction (GANEX) process. One GANEX process that can successfully accomplish the separation utilizes the diluent cyclohexanone in combination with the extractant tributylphosphate (TBP) (30 % vol) and a second extractant, CyMe₄-BTBP (10 mM). However, there are some issues when using cyclohexanone as diluent. In this work an alternative diluent has therefore been tried in order to determine if it can replace cyclohexanone. The diluent used was hexanoic acid. In a system containing 10–12 mM CyMe₄-BTBP and 30 % vol TBP in hexanoic acid with the aqueous phase 4 M HNO₃, the distribution ratios for americium and curium are unfortunately low (D _Am = 1.1 ± 0.27, D _Cm = 1.6 ± 1.81). The concentration of CyMe₄-BTBP ligand, the extractant of curium and americium, could unfortunately not be increased, because of limited solubility in hexanoic acid. The distribution ratios for fission, corrosion and activation products were low for most metals; however, cadmium, palladium and molybdenum all unfortunately have distributions ratios above 1. To conclude, low americium and curium extractions indicate that hexanoic acid is not a suitable diluent which could replace cyclohexanone in a GANEX process.     

Mathematical modeling for facilitated transport of Ge(IV) through supported liquid membrane containing Alamine 336

A mathematical model was developed for the germanium-facilitated transport from a medium containing tartaric acid using Alamine 336 as a carrier. Modeling was carried out based on the extraction constant (K _ext) obtained from the liquid–liquid extraction (LLX) modeling. The LLX data were achieved from experiments with conditions being Alamine 336 concentrations of 0.1–10% v/v from a solution containing about 1.378 mmol/L Ge (100 mg/L) and tartaric acid as an anionic complexant. The LLX model was attained using the equilibrium-based procedure and fitted to extraction experimental data for various carrier concentrations. This model presented an accurate extraction constant (K _ext = 0.02) used in the facilitated transport modeling. The flat sheet supported liquid membrane (FSSLM) experiments were conducted in the condition of 1.378 mmol/L Ge (100 mg/L), tartaric acid concentration of 2.760 mmol/L, 1 M HCl as a stripping phase and various Alamine 336 concentrations in the range of 0–35% v/v. The FSSLM model was developed according to the Fick’s law, the diffusional transport, and equilibrium equations. According to the model, mass transfer and diffusion coefficients for various concentrations of the carrier were found. In addition, the calculated and experimental values had a good correlation with together showing the validity of the model. This model can be used in the further process simulation such as hollow fiber SLMs.     

Instability mechanisms of supported liquid membranes for copper (II) ion extraction

The instability of supported liquid membranes (SLMs) for use in copper (II) ion extraction was investigated in this paper. The degradation behavior of these SLMs was monitored in situ by electrochemical impedance spectroscopy (EIS). The electrical properties of a SLM cell can be described by an equivalent circuit, R_s(C_mR_m)Q. The model parameters, membrane resistance (R_m) and membrane capacitance (C_m) can be used to characterize the degradation behavior of SLMs. Experimental data for R_m and C_m indicated that the loss of membrane liquid (ML) during the mass transfer process consists of three stages. Results also suggest that emulsion formation was the dominant instability mechanism for these SLMs. The solubility and osmotic pressure were also shown to not be major factors contributing to the instability although both contributed to the loss of the liquid membrane. The pore size of the polymeric support increased during the first run but remained almost constant in subsequent runs.     

Evaluation of sorption and diffusion behavior of selenium in crushed granite by through-diffusion column tests

Distribution coefficients (K _d), apparent diffusion coefficients (D _a) and retardation factor (Rf) in this work obtained by batch and through-diffusion experiments have been performed, respectively. The accumulative concentration method developed by Crank (The mathematics of diffusion, 12) was applied to realize apparent and effective diffusion coefficient (D _a and D _e) of Se. Besides, a non-reactive radionuclide, HTO, was initially conducted in through-diffusion experiment for assessing the ability of radionuclide retardation. The distribution coefficients (K _d) obtained by batch tests in 14 days under aerobic and anaerobic systems were 6.98 ± 0.35 and 5.21 ± 0.25 mL/g. Moreover, Rf^cal and K _d ^cal of Se obtained from accumulative concentration’s method in through-diffusion test showed an obvious discrepancy with the increase of length/diameter (L/D) ratio. However, it presented an agreement of Rf^H/Se and K _d ^H/Se in a various L/D ratio by comparison of apparent diffusion coefficient’s (D _a) between HTO and Se. It appears that the Rf^H/Se and K _d ^H/Se obtained from the through-diffusion experiments are lower than those derived from the batch experiments. Therefore, it demonstrates that reliable Rf and K _d of Se by through-diffusion experiments could be achieved at a non-reactive radiotracer (HTO) prior to tests and will be more confident in long-term performance assessment of disposal repository.     

Extraction behavior of strontium from nitric acid solution with N,N,N′,N′-Tetraisobutyl diglycolamide

The extraction behaviors of strontium from nitric acid solution were investigated with N,N,N′,N′-tetraisobutyl diglycolamide (TiBDGA). Effects of acidity, diluents, concentration of extractant and temperature on the distribution ratio of strontium (D _Sr) were examined. The stoichiometry of the extracted molecule was Sr²⁺:TiBDGA of 1:3. The apparent extraction equilibrium concentration constant logK _ex was 3.25. The enthalpy change ΔH and entropy change ΔS were ?55.6 kJ mol^-1 and ?124 J mol^-1 K^-1, respectively. The extraction is an exothermic process. Through two strip stages, strontium could be stripped effectively by 0.01 M nitric acid solution.     

Permeation of metal ions through a series of two complementary supported liquid membranes

The permeation of Am³⁺ and Eu³⁺. through two composite supported liquid membranes, SLM, consisting of a series of two complementary SLMs, separated by an aqueous solution, has been studied. The first liquid membrane was a neutral membrane, i.e., a solution of a bifunctional neutral organophosphorous extractant in decalin. The second liquid membrane was an acidic membrane, i.e., a solution of bis(2-ethylhexyl)phosphoric acid in n-dodecane or of dinonylnaphthalene sulphonie acid in decalin. The solid support was a microporous polypropylene film. The composite SLM system had the sequence “Solution A — SLM(A) -Solution B — SLM(B) — Solution A”, where aqueous solution A promotes extraction of th the metal cations into SLM(A) and their stripping from SLM(B), and aqueous solution B promotes stripping of metal cations from SLM(A) and their extraction into SLM(B). SLM(A) and SLM(B) are a neutral or an acidic S/aVis or vice versa. The study has demonstrated that the single-stage character of SLM separations of metal ions in solution can be in principle overcome by repeating the composite SLM arrangement a number of times. The equations describing the concentration variations in the aqueous solutions which are adjacent to the acidic and neutral SLMs are also reported. They allow one to predict quantitatively the degree of enrichment of each aqueous solution as function of time and the degree of separation among different cations achievable with the composite SLM system. The overall permeability of the composite SLM system to a given cation is shown to be a function of the single-membrane permeability coefficients as well as of the volumes of the aqueous solutions and the SLM area.     

Transport of U(VI) from sulphuric acid medium across supported liquid membrane (SLM) containing di-(2-ethylhexyl) phosphoric acid (D2EHPA)/n-dodecane as a carrier

This paper reports on the supported liquid membrane (SLM) based transport studies of U(VI) from sulphate medium using di-(2-ethylhexyl) phosphoric acid/n-dodecane as carrier. Polytetrafluoroethylene membrane was used as solid support and H₂SO₄ as receiver phase. The effects of various parameters such as receiver phase concentration, feed acidity, carrier concentration, U(VI) concentration, membrane thickness and membrane pore size on U(VI) transport had been investigated. With increase in H₂SO₄ concentrations and pH of feed solution there is an increase in U(VI) transport across the SLM. Similarly with increase in membrane thickness the U(VI) transport decrease whereas in case of pore size variation reverse results are obtained. The membrane thickness variation results showed that the U(VI) transport across the SLM is entirely diffusion controlled and the diffusion coefficient the D _(o) was calculated as 1.36 × 10^?7 cm² s^?1. Based on optimized condition, a scheme had been tested for selective recovery of U(VI) from ore leach solution containing a large number of other metal ions.     

A novel Np–Pu separation procedure based on extraction with di-(chlorophenyl)-dithiophosphinic acid in nitric solution

The extraction behavior of Pu(III), Pu(IV), Np(IV) and Np(V) with di(chlorophenyl)-dithiophosphinic acid (DCPDTPA) in toluene from nitric acid solutions was studied systematically. In aqueous solution with high nitric acid concentration, the extraction capability (represented by distribution ratio D) for Pu and Np in different valences with DCPDTPA comes as D _Np(IV) > D _Pu(IV) > D _Np(V) > D _Pu(III). A new radiochemical procedure for Np/Pu separation based on DCPDTPA extraction was proposed and tested with simulated samples. The recoveries of Np and Pu are as high as 80 % after the whole separation procedure, with the decontamination factor of trivalent lanthanide fission product element (e.g. Eu) greater than 1.5 × 10⁴. The decontamination factor of Pu–Np is 2.0 × 10³, while the decontamination factor of Np–Pu is greater than 4.8 × 10³ after additional purification.     

Removal of uranium from sulfate leach liquor of salcrete deposits using tri-n-octyl amine

A uranyl sulfate leach liquor obtained by uranium leaching of a technological sample of salcrete deposits of Gabal Qatrani ore was subjected to uranium extraction using the liquid–liquid technique. Uranium was effectively extracted from sulfate leach liquor by [(10 %) tri-n-octylamine (TOA)] dissolved in xylene as a diluent. The extraction efficiency was markedly enhanced as the concentration of TOA increases from 1 to 10 %. The relevant factors controlling the extraction process of uranium using tri-n-octylamine were studied. These factors include the effect of diluents used, TOA concentration, contact time, settling time and phase ratio (O/A) v/v. The optimum extraction conditions were chosen. Stripping of uranium from the loaded TOA has been carried out using 5 % Na₂CO₃ as an effective stripping agent. More than 97 % of uranium was extracted by 10 % TOA, at contact time 10 min, settling time 5 min, phase ratio (V_O/V_A) 1/1 and at room temperature. The feasibility of using the TOA for preconcentration-separation of uranium was assessed by stripping studies. The loaded uranium onto TOA has been stripped by 100 % when using 5 % Na₂CO₃ as an efficient eluting agent at 15 min contact time, 5 min settling time and phase ratio (O/A) 2/1.     

Studies on the separation of 90Y from 90Sr by solvent extraction and supported liquid membrane using TODGA: role of organic diluent

Solvent extraction and supported liquid membrane transport studies on Y(III) and Sr(II) were carried out using both nitric as well as hydrochloric acid feed conditions using N,N,N′,N′-tetra-octyldiglycolamide (TODGA) in several organic diluents. The solvent extraction studies indicated extremely large separation factor (SF) values with chloroform, carbon tetrachloride, 1-decanol and hexone when 6 M HNO₃ was used as the feed. On the other hand, the SF values were 1–2 orders of magnitude lower when the nitric acid concentration was 3 M HNO₃. Significantly large SF values were also obtained from 6 M HCl when xylene, carbon tetrachloride, n-dodecane and hexone were used as the diluent. Though mass transfer was not very promising in the supported liquid membrane studies with most of the diluent systems, quantitative Y(III) transport was observed with 0.1 M TODGA in xylene with negligible Sr(II) transport suggesting possibility of obtaining carrier free ⁹⁰Y. The purity of the radiotracer was checked by half-life method.     

Development of negligible depletion hollow fiber membrane-protected liquid-phase microextraction for simultaneous determination of partitioning coefficients and acid dissociation constants

A new method based on negligible depletion hollow fiber-protected liquid-phase microextraction coupled with high-performance liquid chromatography (HPLC) was developed for the simultaneous determination of partitioning coefficients (K_OW) and acid dissociation constants (pK_a), by using phenol, 4-chlorophenol and 2,4-dichlorophenol as model compounds. A 37-mm length polypropylene hollow fiber membranes (600 μm inner diameter, 200 μm wall-thickness, 0.2 μm pore size, ∼70% porosity) with two-end sealed were filled with 1-octanol by ultrasonic agitation to prepare the extraction device. The extraction device was deployed in sample solutions, prepared by spiking target analytes in 1-octanol saturated aqueous solutions (500 mL), for negligible depletion extraction. After equilibrium was reached (∼5 h), the 1-octanol in the lumen of the hollow fiber membrane was collected for HPLC determination of the target analytes. As the depletion of the analytes in aqueous samples was negligible, the distribution coefficient (D_OW) could be calculated based on the measured equilibrium concentration in 1-octanol (C_O) and the initial concentration (C_W) in the aqueous sample of the target analyte (D_OW = C_O/C_W). The D_OW values measured at various pH values were nonlinearly regressed with pH to obtain the K_OW and pK_a values of a compound. Results showed that the measured values of the K_OW and pK_a of these model compounds agreed well with literature data.     

Synthesis and characterization of N,N,N′,N′-tetraalkyl-4-oxaheptanediamide as extractant for extraction of uranium(VI) and thorium(IV) ions from nitric acid solution

Tridentate ligand N,N,N′,N′-tetraoctyl-4-oxaheptanediamide(TOOHA) and other three analogous diamides have been prepared and characterized by using NMR spectra and element analysis. The extraction of UO₂ ²⁺ and Th⁴⁺ with the present extractants was investigated at 293 ± 1 K from nitric acid solutions. n-Octane was found to be the most suitable diluent in the present study compared with other diluents tested. Extraction distribution ratios (D) of U(VI) and Th(IV) have been studied as a function of aqueous concentrations of HNO₃, extractant concentrations. The results indicated that U(VI) is mainly extracted as UO₂(NO₃)₂·2TOOHA. In the case of Th⁴⁺ ion, the possible compositions of extracted species in organic phase were presumed to be Th(NO₃)₄·2TOOHA and Th(NO₃)₄·3TOOHA. In addition, the influence of concentration of sodium nitrate as salting-out agent on the distribution ratio of U(VI) and Th(IV) with TOOHA was also evaluated.     

Échelle d'acidité dans l'hydrogénodifluorure de potassium (KHF2) fondu à 250°C: Détermination électrochimique

In molten potassium hydrogenodifluoride (KHF₂) fully ionized into K⁺ and HF₂^?, at 250°C, the HF₂^? ion is slightly dissociated according to the equilibrium: HF₂^?HF+F^?. This is a solvent acid base equilibrium, HF being the strongest acid and F^? the strongest base in this system. By means of a voltammetric study we showed that the hydrogen electrode may be used as an acidity indicator electrode in the whole acidity range of the melt. By analysis of the equilibrium potential variation in acidic and in basic media, the HF₂^? dissociation constant (melt autoprotolysis constant): K_D = {HF} {F^?} was determined The experimental value: K_D=10^?2.05 mol² kg^?2 is compared with a calculated one, issued from thermodynamic data. Results obtained with other electrodes (LaF₃ monocrystal electrode and copper electrode) were discussed and compared with those obtained with the hydrogen electrode.     

Potassium europium molybdate phosphate

The new compound K₂Eu(MoO₄)(PO₄) has been synthesized. The compound is isostructural to the known potassium lanthanide molybdate phosphates (Ln = Nd, Sm, Dy, Yb, Lu). It crystallizes in space group Ibca (no. 73) with the unit cell parameters a = 19.734 Å b = 12.301 Å c = 6.978 Å V = 1693.8 Å, R _p = 2.19%, R _wp = 2.97%. K₂Eu(MoO₄)(PO₄) decomposes above 1000°C and has a rather high luminescence intensity. The ⁵D₀-⁷F_2,4 electric dipole transitions are noticeably stronger than the ⁵D₀-⁷F_1,3 magnetic dipole transitions because of the noncentrosymmetric coordination environment of the europium ions in the complex molybdate phosphate.     

The nucleation study on the cationic miniemulsion polymerization of octamethylcyclotetrasiloxane (D4)

The nucleation of the cationic miniemulsion polymerization of octamethylcyclotetrasiloxane (D₄) has been investigated in detail in this work. The particle size was traced by dynamic laser scattering in the polymerization process using different concentration of dodecylbenzenesulfonic acid (DBSA) as both the initiator and surfactant. The results reveal the progressively decreasing particle sizes with the steadily increasing monomer conversion. The descending particle sizes can be explained by the existence of homogeneous nucleation of hydroxyl-terminated polydimethylsiloxane (PDMS) oligomers in addition to the primary droplet nucleation. A linear relationship between the natural logarithm of the average particle diameter (lnd(t)) and the natural logarithm of the monomer conversion (lnf(t)) is then deduced based on the theory, which has been validated by the experimental data. The slope of lnd(t)~lnf(t) line relies on the parameter of K which is the ratio of PDMS oligomers entering water phase to all PDMS oligomers produced. The influence of DBSA concentration on the K and the fraction of homogeneous nucleation (F(H)) has been then obtained. Both of the values of K and F(H) increase with the increasing DBSA concentrations.     

Simulation of a hybrid fermentation-separation process for production of butyric acid

Simulation of a hybrid fermentation-separation process for the production of butyric acid (BA) based on published data was done. A unit consisting of a bioreactor with immobilized cells in the fibrous bed and of separation by pertraction through supported liquid membranes (SLM) was considered. Productivities of the unit volume of a fixed bed bioreactor in continuous and fed-batch fermentation at pH 5.5 and 6.0 were used. Concentration of BA in the bioreactor outlet stream was assumed to be in the interval from 0.11 kmol m⁻³ to 0.45 kmol m⁻³. Data on the pertraction through SLM with phosphonium ionic liquid (IL) and bulk liquid membrane with trioctylamine (TOA) as carriers were used. A strong increase in the required membrane area was found for both carriers at the pH of pertraction above 4. pH values of fermentation and pertraction should be optimized independently. It is advantageous to have pH of the feed into the pertraction unit of about 4. Dependences of the membrane area on the pertraction efficiency are nearly linear and not very sharp, especially for IL, what enables working at the pertractor efficiency exceeding 90 %. Application of phosphonium IL is promising compared to classical extractant TOA because of lower demand of the membrane area in a large interval of BA concentrations in the pertractor feed.