Separation and recovery of heavy metals from hydrometallurgical effluents by solvent extraction

Summary The possibility of separating and recovering heavy metals from hydrometallurgical effluents by successive solvent extractions has been investigated by two different procedures with liquid waste from the Espindesa Zinc process. The waste (pH value near to 1.5) includes significant amounts of Zn (1.35), Cu (0.12), Co (0.32) and Mn (0.6 g/l) in the presence of big concentrations of macro-constituents (sulphate, chloride, Na) and Fe [8.8 g/l, mostly as Fe(II) salts]. As extractants, Amberlite La-2 (a secondary ammine, as chlorohydrate) and DEHPA (di-2-ethylhexyl-phosphoric acid) at 25% volume in kerosene were selected. The first method includes two extraction stages with LA-2 for Zn and Cu separation (the last one with 60 g/l of chloride ions) and three stages with DEHPA at pH values near to 1.5, 2.0 and 3.5 for isolating Fe, Mn and Co. The second method separates firstly Fe (as ferric salts) with DEHPA. Afterwards, one stage with LA-2 isolates Zn and three stages with DEHPA at pH values near to 2.0, 3.0 and 3.5 lead to fractions rich in Mn, Cu and Co. Reextractions from organic layers with water or HCl at different concentrations lead to purer solutions of the isolated metals. With both methods, the liquid waste can be converted into a saline solution with lesser problems for disposal.     

Toluene/ter-butanol mixed solvent for the selective extraction of Cr(VI) from divalent heavy metals.

A solvent-extraction system comprising toluene/ter-butanol (ter-BuOH) mixed solvent as the organic phase was developed to selectively extract Cr(VI) from acidic chloride media in the presence of divalent metals, namely Cd(II), Co(II), Cu(II), Ni(II) and Zn(II) under 5 M CaCl2 salting-out conditions. Chromium(VI) was selectively extracted as a solvated ion-pair of [ter-BuOH2+ x CrO3Cl-] at ter-BuOH mole fractions of between 0.1 and 0.6 (9.0-57.2% in volume). Divalent metals were extracted at ter-BuOH mole fraction over 0.6 with extraction percents of Co (< 20%), Cu (< 15%), Ni (< 10%) and Zn (< 20%). The concentrations of Ca2+, water and ter-BuOH in the organic phase and ter-BuOH in the aqueous phase were determined to find out the effects on the extraction of Cr(VI). The chemical species of Cr(VI) in acidic chloride media containing 5 M CaCl2 and 0.1 M HCl was confirmed to be the CrO3Cl- species. The effects of the acid, salt concentrations in the aqueous phase and the solvent composition of a mixed organic solvent on the extraction of Cr(VI) were evaluated. Based on the above studies, the extraction mechanism was elucidated and the optimum extraction conditions were determined.     

Methods and techniques for the selective extraction and recovery of oxoanions

An important goal in environmental chemistry is the extraction of metals that are toxic or radioactive from soils and waters. For many such metals, the problem is solved by designing compounds with coordination sites that are specific for that particular metal. For cases such as oxoanions, however, where the inorganic center is already fully coordinated by oxygens, different strategies need to be used. Chromate, phosphate, selenate, pertechnetate, and aluminate are such anions. These species are problematic contaminants in soils and waters because they are either toxic, environmentally undesirable, or radioactive. Furthermore, under both acidic and basic conditions, the coordination positions of these oxoanions are occupied by oxygens. Chromium(VI) as either chromate or dichromate presents a particular problem because it is a strong oxidizing agent. In this review the different methods of extracting this group of pseudotetrahedral oxoanions are discussed, along with the individual advantages and limitations of each strategy.     

Selective reagents for solvent extraction of metals—II. Bis-quinaldic acids

Bis-quinoline-2-carboxylic acids in which the quinoline rings were joined via ether linkages to the 8-position have been synthesized and tested for metal extraction. The reagents extracted Cu²⁺ and Zn²⁺ selectively in the presence of Fe²⁺ and Fe³⁺ from aqueous sulphate solution.     

Selective reagents for solvent extraction of metals—I. Quinaldic acids

Alkyl- and alkoxy-substituted quinoline-2-carboxylic acids were synthesized and tested for metal extraction. Zn²⁺ and Cu²⁺ were extracted from aqueous sulphate solutions by reagents containing 8-alkoxy substituents at lower pH values than were Fe²⁺ or Fe³⁺. Reagents without this substituent were unselective in this respect. A possible explanation for the selectivity may be that the 8-substituent influences the coordination geometry of the metal chelates in favour of tetrahedral complexes.     

Metallothionein-cross-linked hydrogels for the selective removal of heavy metals from water

The diverse functional repertoire of proteins promises to yield new materials with unprecedented capabilities, so long as versatile chemical methods are available to integrate biomolecules with synthetic components. As a demonstration of this potential, we have used site-selective strategies to cross-link polymer chains using the N- and C-termini of a metallothionein derived from a pea plant. This arrangement directly relates the swelling volume of the polymer to the folded state of the protein. The material retains the protein's ability to remove heavy metal ions from contaminated water samples, and can be regenerated through the subsequent addition of inexpensive chelators. The change in hydrogel volume that occurs as metal ions are bound allows the detection of contaminants through simple visual inspection. The utility of this bulk property change is demonstrated in the construction of a low-cost device that can report heavy metal contamination with no external power requirements. Most importantly, the generality of the protein modification chemistry allows the immediate generation of new hybrid materials from a wide range of protein sequences.     

Span 80 effect on the solvent extraction for heavy oil recovery

In this study, we used the Span 80 to enhance solvent extraction process, and we explored the mechanism. The results indicated different solvents would obtain different oil recovery, and toluene showed the optimal oil recovery, and the n-heptane showed the lowest oil recovery. The complex solvents could improve oil recovery. Toluene could make the heavy oil show the lowest viscosity (89.6 Pa.S), and n-heptane make the heavy oil show the highest viscosity (176.3 Pa.S). Complex solvents could decrease the heavy oil viscosities. The higher C/H was, the higher heavy oil recovery was, and when the asphaltene and resins content increase, the C/H would increase. The C/H showed the highest value (9.09, by toluene) and the lowest value (8.15). In this study, Span 80 could increase heavy oil C/H ratio, decrease heavy oil viscosity. Span 80 could make the sands surface more hydrophilic, and then the solvent loss would decrease. The oil recovery was high after 10 times recycle use.     

The use of trioctylphosphine oxide for solvent extraction recovery and purification of transplutonium elements

Extraction of trivalent curium, berkelium, californium, einsteinium, and europium with trioctylphosphine oxide (TOPO) from nitric acid solutions as well as extraction of curium and cerium from lactic acid solutions containing DTPA depending on aluminium nitrate concentration have been studied. The distribution of cobalt, nickel, chromium, iron, aluminium, titanium, zirconium, and niobium ions has been studied and coefficients of berkelium purification from the elements studied have been determined under the conditions of extraction-chromatographic recovery of berkelium. The influence of weighed amounts of the same impurities on the yield of berkelium in its extraction-chromatographic separation has been studied. Some examples of the practical application of the extraction-chromatographic techniques using TOPO are given.     

Separation of rhenium from molybdenum and other heavy metals by solvent extraction

Summary Two methods are presented for the extractive separation of rhenium from molybdenum and other heavy metals in hydrochloric acid solution. In the first method, Mo(VI) and Re(VII) are reduced by hydrazine in strong hydrochloric acid solution to Mo(V) and Re(IV). The former is then extracted intoiso-amyl acetate. The Re(IV) remaining in the aqueous phase is oxidised to Re(VII) and determined by known procedures. In the second method, Re(VII) and other ions in 1–1.3N HCl are boiled with hydrazine sulphate for 5 minutes. After adding EDTA to complex Mo(V) and adjusting the solution to 0.33N HCl, rhenium is extracted into chloroform containing 1% tribenzylamine, and is recovered by shaking with water having sufficient ammonia to neutralise the acid and a little hydrogen peroxide.

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Zusammenfassung Zwei Arbeitsweisen für die extraktive Trennung des Rheniums von Molybdän und anderen Schwermetallen in salzsaurer Lösung wurden angegeben. Bei dem ersten Verfahren werden Mo(VI) und Re(VII) mit Hydrazin in stark salzsaurer Lösung zu Mo(V) und Re(IV) reduziert. Ersteres wird dann mit Isoamylacetat extrahiert. Re(IV) verbleibt in der wäßrigen Phase, wird zu Re(VII) oxydiert und auf bekannte Art bestimmt. Beim zweiten Verfahren werden Re(VII) und die anderen Ionen in 1- bis 1,3-n Salzsäure 5 Minuten mit Hydrazinsulfat gekocht. Nachdem man ÄDTA zur Komplexierung des Mo(V) zugesetzt und die Lösung auf 0,33-n an Salzsäure eingestellt hat, wird Rhenium mit einer 1%igen Lösung von Tribenzylamin in Chloroform extrahiert. Die Rückextraktion erfolgt mit Wasser, worin Ammoniak (zur Neutralisation der Säure) und etwas Wasserstoffperoxid gelöst sind.

     

Regeneration of mixed solvent by electrodialysis: selective removal of chloride and sulfate

The applicability of electrodialysis for the selective removal of sulfate and chloride ions from a mixed solvent solution of sodium carbonate is investigated. The mixed solvent consists of 70 wt.% ethylene glycol and 30 wt.% water. Six different ion exchange membranes, the homogeneous membranes Neosepta CM-2, AM-3, AMX and ACM as well as the heterogeneous FuMA Tech CM-A and AM-A, are tested for their chemical and physical resistance to the mixed solvent carbonate solution, their ethylene glycol retention, their electrical resistance in the mixed solvent and their selectivity for sulfate and chloride over carbonate transport.     

Speciation of mercury in soil and sediment by selective solvent and acid extraction

In order to characterize the mercury hazard in soil, a sequential extraction scheme has been developed to classify mercury species based on their environmental mobility and/or toxicity for either routine lab analysis or on-site screening purposes. The alkyl mercury species and soluble inorganic species that contribute to the major portion of potential mercury toxicity in the soil are extracted by an acidic ethanol solution (2% HCl+10% ethanol solution) from soil matrices as "mobile and toxic" species. A High-Performance Liquid Chromatography (HPLC) system coupled with Inductively Coupled Plasma Mass Spectrometry (ICP-MS) detection has been developed to further resolve the species information into soluble inorganic species (Hg(2+)), methylmercury(II) (MeHg(+)) and ethylmercury(II) (EtHg(+)) species. Alternatively, these species can be separated into "soluble inorganic mercury" and "alkyl mercury" sub-categories by Solid-Phase Extraction (SPE). A custom Sulfydryl Cotton Fiber (SCF) material is used as the solid phase medium. Optimization of the SCF SPE technique is discussed. Combined with a direct mercury analyzer (DMA-80), the SCF SPE technique is a promising candidate for on-site screening purposes. Following the ethanol extraction, the inorganic mercury species remaining in soil are further divided into "semi-mobile" and "non-mobile" sub-categories by sequential acid extractions. The "semi-mobile" mercury species include mainly elemental mercury (Hg) and mercury-metal amalgams. The non-mobile mercury species mainly include mercuric sulfide (HgS) and mercurous chloride (Hg(2)Cl(2)).     

Synthesis of calix[4]arene-based dipodal receptors: Competitive solvent extraction and liquid bulk membrane transport for selective recovery of Cu2+

A series of new p-tert-butylcalix[4]arene-based dipodal receptors are synthesised in high yields. The calix[4]arene units of all the receptors have been found to be present in cone conformation. To optimise the good extraction ability and high transport rate, we synthesised the receptors that differ from each other in their end groups. These receptors extract Cu²⁺  ion selectively from the buffered aqueous medium containing a mixture of metal ions. The receptor bearing four sp³ nitrogens has by far the greater ability to extract Cu²⁺  than the other receptors. All these receptors were effectively used for Cu²⁺  ion transport from the aqueous buffered source phase to the aqueous receiving phase.

     

Competitive solvent extraction of alkaline earth metals by ionizable nano-baskets of calixarene

The competitive solvent extraction of alkaline earth metals using different nano-baskets was investigated. The novelty of this work is to study the correlations between the isomer structure of calixarenes and their extraction properties. The objective was to quantify the effects of aryl groups in the ionisable pendant moieties, calixarene conformation, steric orientations (cis- and trans-) and relative positions (ortho- and para-) of pendant moieties upon the extraction efficiency, pH_1/2 and the selectivity of calix[4]arene complexes. Alkaline earth metals were extracted from aqueous solutions into chloroform by di-ionisable calix[4]arenes and were measured using ion chromatography. The results revealed that alternation of aryl group in the pendant moieties, changing their orientation from cis- to trans-analogues as well as from ortho- to para- analogues, showed no changes in the selectivity, the extraction efficiency and the pH_1/2 of calix[4]arene complexes. Changing the scaffold of calixarene's ring to the cone, 1,2-alternate and partial-cone conformers altered their complexation ability towards alkaline earth metals and their extraction efficiency.     

Kinetic modelling of cadmium removal from phosphoric acid by non-dispersive solvent extraction

In this work it is reported that the kinetic modelling of the separation of cadmium from phosphoric acid by non-dispersive solvent extraction. Using Cyanex 302 as selective extractant, the extraction step was carried out in a hollow fibre module containing polypropylene fibres, whereas the concentration step required a ceramic module with tubular channels due to the high acidity of the backextraction agent. Application of the methodology previously reported by the authors led to the development of a kinetic model with three design parameters, i.e., equilibrium constant of the extraction reaction (K'_e = 6 × 10³ mol⁻²/l⁻²), membrane mass transport coefficient of the extraction module K_me=8.33×10⁻⁸ m/s) and of the backextraction module (K_ms=3.33×10⁻⁸ m/s), that described satisfactorily the behaviour of the separation-concentration system. Thus, in this work a new application of the non-dispersive solvent extraction technology is presented, characterising at the same time the behaviour and parameters of a new type of contactor, i.e., a tubular ceramic module.     

Determination of organically-associated trace metals in estuarine sea-water by solvent extraction and atomic-absorption spectrometry

Chloroform extraction of trace metals (Ni, Cu, Mo, Mn, Cd and Pb) in estuarine sea-water was studied at pH 8 and pH 3, on the basis that the metals would be associated with dissolved organic matter (DOM), which has recently been characterized by reversed-phase liquid chromatography. Ni, Cu, Mo and Mn were extracted more at pH 8 than at pH 3. Cd and Pb were not associated with the DOM at either pH 8 or 3. The percentage of the total dissolved trace metals in sea-water associated with DOM varied from 0 to 14%. The metals extracted into chloroform at pH 8 were assumed to be associated with neutral or weakly basic DOM while at pH 3 they could be associated with either the neutral (or weakly basic) DOM or two types of acidic DOM.     

Interfacial phenomena in solvent extraction of metals: Extraction of palladium(II)

4-Octylphenylamine, decyl isonicotiniate, decyl nicotiniate, decyl 2-hydroxyethyl sulphide and its analg with partly fluorinated alkyl group were used for palladium(II) extraction from 3M HCl. The adsorption of these compounds at toluene/HCl solution was also studied and interpreted. 4-Octylphen adsorbs at the hydrocarbon/HCl solution at much lower concentration range than other extractants and can be used as a phase transfer catalyst. The addition of 4-octylphenylamine increases the extraction rate with esters of pyridine carboxylic acids and decreases the time needed to obtain the equilibrium of extraction.     

A back-extraction procedure for the dithiocarbamate solvent extraction method. Rapid determination of metals in seawater matrices

Summary A ligand exchange liquid/liquid extraction method using dithiocarbamate complexes is elaborated for the graphite furnace atomic absorption spectrometry (GF-AAS) of seawater and marine interstitial water. Palladium is used for the exchange. This metal ensures a rapid and quantitative back-extraction. It simultaneously works as matrix modifier in the GF-AAS analysis. The proposed method is evaluated in the analysis of lead, copper, nickel, and cadmium in CASS-II marine reference seawater and samples from the North Sea. A microanalytical variant of the method is applied in marine interstitial water analysis down to sample volumes of 500 l.     

Membrane-based microchannel device for continuous quantitative extraction of dissolved free sulfide from water and from oil

Underground fluids are important natural sources of drinking water, geothermal energy, and oil-based fuels. To facilitate the surveying of such underground fluids, a novel microchannel extraction device was investigated for in-line continuous analysis and flow injection analysis of sulfide levels in water and in oil. Of the four designs investigated, the honeycomb-patterned microchannel extraction (HMCE) device was found to offer the most effective liquid–liquid extraction. In the HMCE device, a thin silicone membrane was sandwiched between two polydimethylsiloxane plates in which honeycomb-patterned microchannels had been fabricated. The identical patterns on the two plates were accurately aligned. The extracted sulfide was detected by quenching monitoring of fluorescein mercuric acetate (FMA). The sulfide extraction efficiencies from water and oil samples of the HMCE device and of three other designs (two annular and one rectangular channel) were examined theoretically and experimentally. The best performance was obtained with the HMCE device because of its thin sample layer (small diffusion distance) and large interface area. Quantitative extraction from both water and oil could be obtained using the HMCE device. The estimated limit of detection for continuous monitoring was 0.05 μM, and sulfide concentrations in the range of 0.15–10 μM could be determined when the acceptor was 5 μM FMA alkaline solution. The method was applied to natural water analysis using flow injection mode, and the data agreed with those obtained using headspace gas chromatography-flame photometric detection. The analysis of hydrogen sulfide levels in prepared oil samples was also performed. The proposed device is expected to be used for real time survey of oil wells and groundwater wells.     

Preconcentration and matrix isolation of heavy metals through a two-stage solvent extraction in a flow system

Metal ions (Cd, Cu, Pb, Co and Ni) in trace amounts were isolated from sample matrices and concentrated by extraction in a flow system. The sample flow was first mixed with buffer and reagent (carbamates) and the combined aqueous flow was next segmented with trichlorotrifluoroethane (Freon 113). The metal complexes were extracted into the organic phase in a 2-m long coil which was followed by a separator with a teflon membrane. The organic phase passed on to a second segmentor where an acidic, aqueous mercury(II) solution was added. Back-extraction to the aqueous solution took place in a 1-m long coil. The Freon was removed in a second membrane separator and the aqueous phase was collected and analyzed by graphite-furnace atomic absorption spectrometer. The enrichment factors were of the order of 15–20 and the recoveries were 90–100% from the sub-μg l^?1 level up to 20–50 μg l^?1. The recoveries decrease at concentrations above 50 μg l^?1, presumably because of slow dissolution of precipitated complexes in the sample solutions. The observed recoveries for copper were generally somewhat lower, being in the range 80–90%.