ANAEROBIC EXTRACTION OF COBALT IN A PULSE COLUMN

The effects of excluding air (oxygen) from a cobalt solvent extraction circuit were studied for LIX 64N extractant. After solvent extraction of divalent cobalt from ammoniacal solutions with chelating extractants such as LIX 64N, the loaded Co-chelate is believed to oxidize to a stable trivalent complex which resists subsequent stripping with mineral acids. To Improve stripping efficiency, cobalt was extracted and stripped in the absence of oxygen in pulsed, perforated-plate columns that were designed and constructed by the Bureau of Mines. When the ammoniacal cobalt(II) sulfate and LIX 64N solutions were purged, blanketed, and pulsed with argon, cobalt extraction exceeded 99%, and stripping with 1 vol % H₂SO₂ reached 98.5%. The stripped extractant was recycled to the extraction column with no loss of extraction efficiency in six passes through the circuit.     

Stripping of Rh–Sn–Cl‐loaded alkylated 8‐hydroxyquiniline with Na2SO3–HCl

Acidic rhodium(III) chloride solutions pretreated with SnCl₂ at a ratio Sn(II) : Rh(III) = 3 are contacted with an alkylated 8‐hydroxyquinoline (Kelex 100) to prepare loaded organics which subsequently are subjected to stripping with Na₂SO₃–HCl solutions. Rh(III) was found to be stripped selectively involving the following reaction: where H₂Q is the protonated form of kelex 100. Direct characterization of the stripped complex and slope analysis confirmed this stripping reaction. Equilibrium was reached within 20 min. A kinetic analysis found the stripping process to be irreversible and to be controlled most probably by the slow release of SnCl₃^? ligand from the intermediate Rh–Q–SO₃–SnCl₃ organic complex. Copyright © 2004 Society of Chemical Industry     

Solvent extraction of gold(I) from alkaline cyanide solution by dibutylcarbitol (DBC) with n‐octanol

BACKGROUND: Currently, cyanidisation is preferred for the extraction of gold because it has a number of advantages over other methods. Gold(I) can be extracted with various extractants, but there are no reports on the extraction of gold(I) from cyanide solution by dibutylcarbitol (DBC). In this work the extraction of gold(I) from alkaline cyanide solution using DBC with n‐octanol was studied. Several factors affecting the percentage extraction of gold(I), including DBC concentration, diluent concentration, equilibrium time, phase ratio, pH and gold concentration in aqueous phase, were investigated. RESULTS: The results showed that 96.2% of gold(I) could be extracted using an organic phase composed of 40% (v/v) DBC, 50% (v/v) n‐octanol and 10% (v/v) odourless kerosene. The extraction was quite fast and equilibrium could be established within 2 min. Stripping of the gold‐laden organic phase was carried out using sodium sulfite (Na₂SO₃) and sodium thiosulfate (Na₂S₂O₃) solutions, with Na₂S₂O₃ proving better than Na₂SO₃. The percentage stripping of gold(I) was 96.5% when the Na₂S₂O₃ concentration was 4% (w/w), and the stripping capacity of gold(I) exceeded 311.3 mg L^?1 when the phase ratio (A/O) was equal to 0.2. CONCLUSION: Gold(I) can be extracted from aqueous cyanide solution by DBC in the presence of n‐octanol and efficiently stripped by aqueous Na₂S₂O₃ solution. This method has the potential for practical application in the extraction and separation of gold. Copyright © 2008 Society of Chemical Industry     

The hydrochloric acid route for phosphate rock

When phosphate rock is leached with hydrochloric acid, radium can be removed by co-precipitation with Ba_0.4Ca_0.6SO₄ and uranium by extraction with a 5% solution of tributyl phosphate in hexane or Varsol. Phosphoric acid is then separated from calcium chloride solution and other impurities by extraction with undiluted tributyl phosphate. The lanthanides can be precipitated from the raffinate by NH₃, and CaSO₄.2H₂O by H₂SO₄ to regenerate HCl for recycle. The organic phase containing H₃PO₄ can be stripped by NH₃ to yield ammonium phosphate and to regenerate the tributyl phosphate for recycle. Fluorine can be precipitated from the initial leach solution as Na₂SiF₆.     

The Hafnium-Selective Extraction Fom a Zirconium(Hafnium) Heptafluoride Ammonium Solution Using Organophosphorus-Based Extractants

ABSTRACT

The suitability of the organophosphorus-based extractants, DiOPA, Ionquest 801 and D2EHPA was evaluated for the selective extraction of Zr and Hf from an (NH₄)₃Zr(Hf)F₇ acidic solution using both dispersive and pertraction solvent extraction (SX). A stock solution of (NH₄)₃Zr(Hf)F₇ was dissolved in either HCl or H₂SO₄ (0.1–8 M). The following extraction variables were investigated: type and concentration of the acidic solution, the contact time, and extractant to metal ratio. Subsequently, the stripping was investigated using (NH₄)₂CO₃, CaCl₂, H₂SO₄ and C₂H₂O₄ in the concentration ranges of 0–2 M. During extraction, scrubbing and stripping using D2EHPA, CaCl₂ and C₂H₂O₄, the Zr purity was increased from 97.2% to 99.0%. When extracting from 4 M H₂SO₄ with 9 wt% D2EHPA, a Hf selectivity of 32% was observed where after stripping with C₂H₂O₄ resulted in a 98.7% recovery of Zr. With 1.2 M CaCl₂ as stripping liquor, almost no Hf and 75% Zr stripping was obtained. During the pertraction 72% Hf and 44% Zr extraction was achieved after 180 min when extracting with 9 wt% D2EHPA from 4 M H₂SO₄. Pertraction based stripping with 1.2 M C₂H₂O₄ yielded 75% of both Zr and Hf, while stripping with 2 M CaCl₂ resulted in 58% Hf stripped with almost no Zr stripping.     

Solvent extraction of uranium from acidic sulfate media by Alamine® 336: computer simulation and optimization of the flow‐sheets

BACKGROUND: A series of nine conventional and non‐conventional flow‐sheets have been considered for the recovery of uranium from acidic sulfate solution by liquid–liquid extraction with 0.146 mol L^?1 Alamine^® 336 in kerosene modified with 5% w/w 1‐tridecanol and stripping with a 199 g L^?1 Na₂CO₃ solution. The reference flow‐sheet was a classical counter‐current configuration with four mixers–settlers in the extraction stage and three mixers–settlers in the stripping stage. The others flow‐sheets possessing a total of eight mixers–settlers are unusual combined solvent extraction flow‐sheets with one or two independent extraction stripping loops and with one or two feed inlets. RESULTS: The configuration of the flow‐sheets strongly influences the extraction performance of the process depending on the working conditions (feed, stripping and solvent flow rates). The presence of two independent extraction–stripping loops may allow the delay of the saturation phenomenon encountered in the conventional flow‐sheet and thus, to operate at higher feed flow rates without loss of performance, as far as the residual fraction in the raffinate and the concentration factor in the stripping solution are concerned. Furthermore, the presence of a modification in the non‐conventional flow‐sheets with two independent extraction–stripping loops and two feed inlets leads to interesting configurations for uranium recovery from less concentrated solutions, such as heap leach solutions. CONCLUSION: The use of non‐conventional flow‐sheets is interesting as it allows the process of uranium (VI) recovery by liquid–liquid extraction to be improved. Copyright © 2009 Society of Chemical Industry     

Liquid-Liquid Extraction of Zinc with Aliquat 336-S-Br from Aqueous Bromide Solutions

Abstract

A new solvent extraction system has been developed for zinc in aqueous bromide solution using Aliquat 336-S-Br-xylene solution as an extractant. A 1 mg/ml zinc solution is extracted essentially quantitatively with an equal volume of 5% Aliquat 336-S-Br-xylene solution in 15 sec. The extracted zinc can be stripped from the nonaqueous layer with a series of aqueous solutions including Na₂SO₃ (≥m 1.0 M) NaOH (≥m 0.5 M), NH₃ (≥m 0.5 M), ethylenediamine (≥m 0.3%), and EDTA (≥m0.5%). The extraction is quantitative only from acidic solutions. High aqueous to organic phase ratios can be utilized without loss of extraction efficiency.     

Effect of Possible Interferences on the Extraction of 1-Butanol from Aqueous Solution by the Ethyl Esters of Soybean Oil Fatty Acids

Abstract

The methyl, ethyl, propyl and butyl esters of vegetable and tree oils are effective solvent extractants for 1-butanol from aqueous solution. Early applications of this process will probably involve bacterial mixed solvent fermentations of relatively impure waste and low-valued carbohydrates. Two types of materials, salts and solvents, could be expected to affect the extraction of 1-butanol from such industrial fermentation systems. The effect of four salts, three alcohols, and a ketone were evaluated using factorial experiments. Variations in NaCl, Na₂SO₄, Na₂SO₃, and KHPO₄ from 0 to 0.15 M on the extraction of 0.1 to 4.1% 1-butanol from aqueous solutions at 25,40, and 55 C gave small changes in distribution coefficient. Mild increases occurred with increasing teperature and increasing NaCl, Na₂SO₄, and KH₂PO₄. Mild decreases in 1-butanol extraction occurred with increasing Na₂SO₃. Variations in acetone, ethanol, and 2-propanol concentrations ranging between 0 and 4% w/v at 25, 40 and 55 C gave small changes in distribution coefficient at 1-butanol concentrations ranging between 0.1 and 4.1% w/v had little effect. A slight increase in 1-butanol extraction was observed with increasing 1-pentanol under similar conditions.     

Computer simulation of flow‐sheets for the solvent extraction of uranium: a new route to delay the effect of chemical degradation of the organic phase during uranium recovery from acidic sulfate media

BACKGROUND: The extractants used in solvent extraction processes undergo degradation under thermal, chemical and radiolytical stresses. In the case of uranium plants, tri‐n‐octylamine, used as an extractant, slowly degrades into di‐n‐octylamine. Such degradation causes a gradual depletion of the uranium extraction isotherms and as a result, of the efficiency of uranium recovery from feed solutions. The present work highlights a new route to delay this depletion of the extraction efficiency, merely by optimizing the flow‐sheets involved in the process. Five flow‐sheets have been compared for uranium recovery from acidic sulfate media by a solution of 0.146 mol L⁻¹ tri‐n‐octylamine in kerosene modified with 5% w/w 1‐tridecanol and stripping with a 199 g L⁻¹ Na₂CO₃ solution. These five flow‐sheets include the classical counter‐current flow‐sheet with four mixers–settlers in extraction and three mixers–settlers in stripping and four unusual combined solvent extraction flow‐sheets with two independent extraction stripping loops and with one or two feed inlets. RESULTS: Computer simulation supplied evidence of the strong influence of the studied flow‐sheets on the sturdiness of the process. More precisely, the unusual combined solvent extraction flow‐sheets appeared to be significantly more efficient than the classical counter‐current one and it is shown that an advantage of this can be to delay the negative impact of gradual degradation of tri‐n‐octylamine on uranium recovery efficiency from acidic sulfate media. CONCLUSION: The replacement of classical counter‐current flow‐sheets with a unique extraction‐stripping loop in unusual combined flow‐sheets with two or more independent extraction‐stripping loops and with one or more feed inlets is a fruitful approach to delay the periodic addition of fresh tri‐n‐octylamine necessary for counter‐balancing the progressive degradation of the extraction solvent and, as a result, to delay the gradual depletion of the efficiency of uranium recovery. Copyright © 2009 Society of Chemical Industry     

Separation of Simulated Mixed Mo(VI) and V(V) From HNO3 and HCl Solutions by Selective Extraction and Stripping with Tri-N-Butyl Phosphate as Extractant

Equilibrium study was carried out to determine the optimum conditions required for Mo(VI) extraction from HNO₃ solutions and subsequently, simulated mixed Mo(VI), and V(V) were extracted from HNO₃ (pH = 1.0) and 6.0 mol L^?1 HCl solutions with TBP dissolved in n-hexane. The variation of pH (selective extraction) and selective stripping were investigated as methods of separation of Mo(VI) and V(V). The latter method was found inefficient for separations from HNO₃ solutions (pH = 1.0) except supplemented with selective stripping (back-extraction with 2.0 mol L^?1 H₂SO₄/14.5 mol L^?1 NH₄OH). While from 6.0 mol L^?1 HCl, selective stripping was adequate to quantitatively strip in turns the Mo(VI) and V(V) co-extracted into the TBP phase. About 100% of the co-extracted V(V) from the HCl medium was stripped in a two-stage process, in contrast to a single-stage required for Mo(VI) of the same result. The selective stripping method was found to be better because an initial appreciable co-extraction had occurred prior to stripping separation. Based on analytical and spectra data, the extracted complexes from HNO₃ and HCl media were formulated as ((MoO₂)_7–8n(VO₂)_2n · (NO₃)₁₆) ^(16–18)n- · m TBP (where n>m) and (MoO₂Cl₂ · VO₂ Cl) · xTBP, respectively.     

Liquid‐Liquid Extraction of Tetravalent Hafnium from Acidic Chloride Solutions using Bis(2,4,4‐trimethylpentyl) Dithiophosphinic Acid (Cyanex 301)

Abstract

Liquid‐liquid extraction studies of tetravalent hafnium from acidic chloride solutions have been carried out with bis(2,4,4‐trimethylpentyl) dithiophosphinic acid (Cyanex 301) as an extractant diluted in kerosene. Increase of acid concentration decreases the percentage extraction of metal. Plot of log D vs. log [HCl] gave a straight line with a negative slope of 2±0.1 indicating the exchange of two moles of hydrogen ions for every mole of Hf(IV) extractacted into the organic phase. Extraction of Hf(IV) increases with increase of extractant concentration. The plot of log D vs. log [HA] is linear with slope 2±0.1, indicating the association of two moles of extractant with the extracted metal species. The addition of sodium salts enhanced the percentage extraction of metal, and followed the order NaSCN>Na₂SO₄> NaNO₃>NaCl. Stripping of metal from the loaded organic (LO) with HCl and H₂SO₄ indicated sulphuric acid as the best stripping agent. Increase of temperature increases the percentage extraction of metal indicating the process is endothermic. Regeneration and recycling capacity of Cyanex 301, extraction behavior of associated elements such as Zr(IV), Ti(IV), Al(III), Fe(III), and IR spectra of the Hf(IV)‐Cyanex 301 complex was studied.     

Studies on the Development of a Flow-Sheet for AHWR Spent Fuel Reprocessing Using TBP

The present paper describes the results of solvent extraction studies carried out in batch mode to collect data on distribution of uranium, plutonium, and thorium using 5% TBP in n-dodecane. Extraction studies are carried out from feed solutions having bulk thorium containing aluminum and fluoride ions in ～3.00–4.00 M nitric acid at concentration levels anticipated in feed solutions during Advanced Heavy Water Reactor (AHWR) spent fuel reprocessing. Studies are carried out under varied experimental conditions. Parameters such as organic to aqueous phase ratio during extraction, concentration of nitric acid for scrubbing co-extracted thorium from loaded organic phase etc., are studied in detail. Hydroxylamine nitrate is selected for reductive stripping of plutonium in preliminary studies. Reagent mixture containing 0.30 M HAN + 0.60 M HNO₃ and 0.20 M N₂H₄ is found to be optimum for plutonium partitioning. This paper also describes the extraction and stripping of uranium and plutonium in co-current mode. The extraction behavior of relevant fission products is studied from a simulated feed solution. A preliminary study on a few commercially available reducing agents is also included. These data are useful in developing a flow-scheme for the recovery of uranium and plutonium from spent fuel originating from AHWR.     

Uranium Solvent Extraction and Separation From Vanadium in Alkaline Solutions

Quaternary amine could be used to extract uranium from alkaline leach solutions, but third phase formation prevented its application. In this paper, isodecanol was used as the modifier for Aliquat 336 in Shellsol D70 to extract uranium from a carbonate leach solution. The formation of third phase was eliminated. More than 98% of uranium was extracted using 3% (w/v) Aliquat 336 and 3% (w/v) isodecanol in Shellsol D70 from a carbonate leach solution containing 95 mg/L U and 25 mg/L V at pH 10.3 and room temperature in a single contact. The separation factor of uranium over vanadium increased with increasing pH of the auqueous solution and reached 280 at pH 11, indicating a good separation of the two metals. The co-extracted vanadium was scrubbed from the loaded organic solution at pH 11 using a solution containing 50 g/L Na₂CO₃. Over 90% of uranium was stripped from the loaded organic soluiton using an acidic solution containing 150 g/L ammonium sulphate in a single contact. It was also found that to obtain high uranium extraction, the chloride concentration should be controlled to less than 1 g/L in the aqueous phase.     

Polarographic and voltammetric measurements of disproportionation of uranium(V) in sulphate and other complexing media on mercury electrodes

The rate of disproportionation of uranium(V) was studied at a hme using single sweep and cyclic voltammetry in sulphate solutions at an almost constant ionic strength (I = 1.2-1.0 mol1^?1) as a function of pH and concentration of uranium(VI). The rate constant of disproportionation of uranium(V) in 0.4 M Na₂SO₄ recalculated for the activity of hydrogen ion equal unity is k₀ = 6.3 × 10⁵ mol^?21²s^?1. Also standard rate constants k_s were determined.In preliminary dc polarography experiments in other complexing media as citrate, tartarate and oxalate a higher increase of the limiting current than in sulphate was found for the same pH values pointing to the assumption that in these media the disproportionation reaction of uranium(V) might proceed still faster than in sulphate solutions.     

A new regenerable process for the recovery of SO2

Increasing demand for regenerable processes with SO₂ recovery is to be expected. Advantages and limitations of the earlier developed citrate and adipate absorption/ steam stripping process are compared with those of the Wellman-Lord (sulphite) process. On the basis of comprehensive laboratory studies, a new process is proposed which supplements the citrate and adipate process. In this new process, the absorbent is a concentrated sodium phosphate buffer and the loaded buffer is regenerated by evaporation. The main buffer component is Na₂HPO₄, but NaH₂PO₄ is added in order to obtain a more complete stripping of SO₂ during regeneration. The new process promises excellent absorption properties for SO₂ with extremely low oxidation losses, regeneration with few incrustation problems and appreciable energy savings.     

Purification of nickel sulphate solutions containing iron,copper, cobalt,zinc and manganese

Acidic nickel-bearing solution containing iron, cobalt, manganese, zinc and copper was processed through a solvent extraction and precipitation technique to obtain a pure nickel sulphate solution. Iron was extracted using 0.2M Cyanex-272 (partially neutralised) as the extractant. Stripping of iron from the loaded organic has also been studied. After iron recovery through solvent extraction the raffinate still contained 0·25 g dm^?3 of iron which was quantitatively separated by a lime precipitation technique. During this iron precipitation there was no loss of cobalt and nickel but copper, manganese and zinc were coprecipitated to some extent. From the iron-free nickel sulphate solution the other impurities were extracted using the same extractant (Cyanex-272) in a single stage. The metal ions from the loaded organic were stripped using a 0·5% (v/v) H₂SO₄ solution in a single stage. The entire operation needs only seven stages: two stages for iron extraction, three stages for iron stripping from the loaded organic, and one stage each for extraction and stripping of other impurities. In the entire operation the loss of nickel was less than 0·5%.     

用Na2SO4提高牛眼透明质酸回收率的研究

通过NaCl和Na     

Studies on the Recovery of Uranium from Phosphoric Acid Medium Using Synergistic Mixture of 2-Ethyl Hexyl Hydrogen 2-Ethyl Hexyl Phosphonate and Octyl(phenyl)-N,N-diisobutyl Carbamoyl Methyl Phosphine Oxide

Abstract

This paper describes the extraction of uranium from aqueous phosphoric acid medium using 2-ethyl hexyl hydrogen 2-ethyl hexyl phosphonate (PC88A) and octyl (phenyl)-N,N-diisobutylcarbamoylmethylphosphine oxide (CMPO) individually as well as their synergistic mixture in different diluents. The extraction parameters such as variation in concentration of either of the extractants, concentration of H₃PO₄ and uranium in the aqueous phase are investigated to optimize the extraction conditions. Results indicate that the synergistic mixture, 0.9 M PC88A + 0.1 M CMPO in xylene, can be used for the extraction of uranium from the phosphoric acid medium. The loaded uranium from the synergistic organic phase can be stripped using 0.5 M solution of (NH₄)₂CO₃. This synergistic mixture is used to recover uranium from a typical wet process phosphoric acid sample and the recovery is found to be better than 90%.     

Integration of reverse osmosis and membrane crystallization for sodium sulphate recovery

Reverse osmosis and membrane crystallization are evaluated in this work as stand-alone and integrated technologies for the recovery of Na₂SO₄ from aqueous solutions. When SO₂ is removed from flue gases by absorption in an aqueous solution and reacts with NaOH, a reusable product (i.e., Na₂SO₄) of industrial interest can be obtained.For stand-alone reverse osmosis, the effect of the concentration of the feed solution and pressure is studied. For membrane crystallization, the influence of the concentration and flow rate of the feed and osmotic solutions on the process performance has been determined. The characterization of the obtained crystals shows that Na₂SO₄·10H₂O is obtained. From the experimental results, the potential for integration of reverse osmosis and membrane crystallization is simulated. It was concluded that using a reverse osmosis unit prior to the membrane crystallization unit minimizes the total membrane area in comparison with the stand-alone processes.     

Modeling of the Extraction Equilibrium of Copper from Sulfate Solutions with Acorga M5640

The extraction equilibrium of copper from sulfate media with the aldoxime Acorga M5640 in ShellSol D70 has been investigated. The distribution results were interpreted by taking into account the nonideality of the aqueous phase. The activity of copper and hydrogen ions in the target systems CuSO₄/H₂SO₄/Na₂SO₄ and CuSO₄/H₂SO₄/Fe₂(SO₄)₃/ZnSO₄ were calculated through the speciation of the aqueous solutions and by applying the Pitzer model. The experimental pH values were found in good agreement with the predicted pH values. A model considering the dimerization of the aldoxime extractant was proposed to predict the distribution ratio and the copper loading isotherms. The extraction constant at infinite dilution and the apparent dimerization constant were evaluated from the experimental data and were found to be 10^{3.06 ± 0.07} and 51 ± 9 M^?1, respectively, at 25°C.