THE SEPARATION OF Au(III) AND Pd(II) IN HYDROCHLORIC ACID SOLUTIONS BY STRONG ANION TYPE II EXCHANGE RESINS: THE EFFECT OF COUNTER ION CONCENTRATION AND TEMPERATURE

ABSTRACT

The separation of gold and palladium ions in hydrochloric acid solutions by strong anion Type II exchange resins is studied in batch and column operations. Increases in the hydrochloric acid concentration and the temperature of the adsorption process have the effect of decreasing the adsorption capacity and the separation factor of both metals. A faster kinetics of the adsorption process of both ions results from temperature increase and this effect is higher for gold ions as a result of greater changes in its diffusivity. Although the adsorption capacity of palladium ions is lower at equilibrium conditions, the adsorption isotherms obtained suggest that they are more strongly retained by the polymers.

The high capacities of these resins for both metals permits their use in the preconcentration of gold and palladium but their application in quantitative separation is restricted by the co-elution of up to% of the interfering ion during the desorption process. The best method for ion desorption is sequential elution with% ammonia for palladium recovery followed by 0·5M thiourea in HCI 1M for the recovery of gold.     

Separation of gold(III) ions from copper(II) and zinc(II) ions using thiourea–formaldehyde or urea–formaldehyde chelating resins

Thiourea–formaldehyde (TF) and urea–formaldehyde (UF) chelating resins were synthesized and these resins were used in the separation of gold(III) ions from copper(II) and zinc(II) base metal ions. In the experimental studies, the effect of acidity on gold(III) uptake and gold(III) adsorption capacities by batch method, and loading and elution profiles of gold(III) ions, gold(III), copper(II), and zinc(II), dynamic adsorption capacities and the stability tests of TF and UF resins by column method were examined. By batch method, the optimum acidities were found as pH 2 and 0.5M HCl, and gold(III) adsorption capacities in the solutions including copper(II) and zinc(II) ions were obtained as 0.088 and 0.151 meq Au(III)/g for UF and TF resins, respectively. On the other hand, by column method, the dynamic adsorption capacities were calculated as 0.109 meq Au(III)/g with TF, 0.023 meq Au(III)/g with UF, 0.015 meq Cu(II)/g with TF, 0.0057 meq Cu(II)/g with UF, and under 6.1 × 10^?5 meq Zn(II)/g with TF or UF. TF resin was more effective in the separation and the concentration of gold(III) ions from copper(II) and zinc(II) ions than UF resin. It was seen that sulfur atoms contributed the gold(III) adsorption comparing with oxygen atoms. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

The Uptake of Gold(I) from Ammonia Leaching Solution by Imidazole Containing Polymeric Resins

Abstract

The polymeric resins containing guanylthiourea, 1-methylimidazole, 2-mercapto-1-methylimidazole ligands have been synthesized from vinylbenzyl chloride-divinylbenzene copolymers and used in the removal of Au(I) from ammonium buffer and ammoniacal thiosulphate solutions. The best gold sorption from ammonium buffer that contains 100 g/dm³ NH₃ · H₂O and 5 g/dm³ (NH₄)₂SO₄, is reached in the case of 1-methylimidazole resin (2) (27.9 mg/g) and all three resins do not have a measurable sorption of copper(II) ammine complexes. The resins display a higher affinity towards gold(I) from ammoniacal thiosulphate solutions than from the ammonium buffer solution. The XPS analysis of gold loaded resins suggests the presence of gold at Au(I) oxidation state, most likely in the form of ionic pair Au(NH₃)₂ ⁺OH^? or neutral complex AuNH₃OH and as highly-dispersed metallic gold. The degree of gold desorption is about 50% using 1% potassium cyanide solution in 0.3% hydrogen peroxide solution. Resins retain their capacity towards gold in five consecutive sorption/desorption cycles.     

Analytical Applications of Mixed Ligand Complexes. II. Separation-Gravimetric Determination of Cu(II) as Its Mixed Ligand Complex with 1,10-Phenanthroline and p-Cresotic Acid

Abstract

A method is presented for the gravimetric determination of Cu(II) followed by its separation from Ni(II), Co(II), Mn(II), and other anions and cations by precipitating it as its mixed ligand complex with 1,10-phenanthroline and p-cresotic acid (5-methylsalicylic acid). The precipitate is equivalent to 0.184 times its weight of copper. The method has potential for use in the large-scale separation of copper.     

Recovery of Gold and Silver from Ores by Hydrometallurgical Processing

Abstract

The Bureau of Mines has played an important role in the revival of precious-metal mining in the Western United States. During the past 30 years, many techniques used by industry to recover gold and silver were pioneered and developed by the Bureau of Mines. In 1952, technology was developed to strip gold from granular activated carbon and allow the carbon to be reused. In 1969, the heap leaching concept was applied to low-grade gold and silver ores and mine wastes. Heap leaching in conjunction with carbon adsorption-desorption permits very low value material to be economically processed. In 1970, an oxidation treatment based on hypochlorite was developed to increase the recovery of gold from carbonaceous gold ores by cyanidation. In the early 1950's, attempts were made to employ carbon-in-pulp technology to recover gold from ores, but the fixed price of gold and increasing operational costs made cyanidation unprofitable. The Bureau of Mines and Homestake Mining Co. jointly operated a carbon-in-pulp pilot plant, and the technology was used in full-scale production at the Homestake Mine in 1972. In 1973, a pressure stripping method, which decreased the time needed for the stripping step, was developed to desorb gold and silver from carbon. An alcohol desorption method, developed in 1976, also decreased the carbon stripping time. In 1979, an agglomeration pretreatment was developed that permitted clayey precious metal ores to be heap-leached. Almost all precious-metal-mining companies use at least one of the above techniques in production facilities.     

Preparation of the Sulfonamide Containing Block Copolymer as Polymeric Sorbent for Removal of Mercury from Aqueous Solutions

A new sulfonamide containing polymeric sorbent for the removal of mercury ions from waste waters was prepared starting from poly(glycidyl methacrylate)-b-poly(ethylene glycol)-b-poly(glycidyl methacrylate) (PGMA- b -PEG- b -PGMA) triblock copolymer prepared by using the ATRP method. Epoxy groups on the block copolymer were functionalized with amino groups. Ammonia-functionalized PGMA- b -PEG- b -PGMA was treated with excess of benzenesulfonyl chloride to obtain a sulfonamide-based polymeric sorbent. The sulfonamide containing the polymeric sorbent with a 3.5 mmol · g^?1 total nitrogen content is able to selectively sorb mercury from aqueous solutions. The mercury sorption capacity of the resin is around 3.12 mmol g^?1 under non-buffered conditions. Experiments performed in identical conditions with several metal ions revealed that Cd(II), Pb(II), Zn(II), Fe(III), and Fe(II) also were extractable in quantities (0–0.45 mmol/g). The sorbed mercury can be eluted by repeated treatment with 4 M HNO₃ without hydrolysis of the sulfonamide groups.     

Liquid-Liquid Extraction of Vanadium(V) and Niobium(V) with Tris(2-ethylhexyl)phosphate: Mutual Separation of Vanadium(V), Niobium(V), and Tantalum(V), and Analysis of Steel Samples

Abstract

Tris(2-ethylhexyl)phosphate (TEHP) dissolved in toluene is used for selective extraction of vanadium(V) and niobium(V) from hydrochloric and hydrobromic acid solution. Vanadium is determined spectrophotometrically after backextraction from TEHP, whereas unstripped niobium is determined in the TEHP phase with thiocyanate. The probable extractable species is VOCl₃·2TEHP or NbOCl₃·2TEHP/NbOBr₃·2TEHP. The method permits mutual separation of vanadium(V), niobium(V), and tantalum(V), and provides analysis of vanadium and niobium in alloys with a high degree of accuracy and precision.     

Binding Properties of a Polymer Having Amidoxime Groups with Proton and Metal Ions

Abstract

The proton-binding behavior of a polymer having amidoxime groups was examined by the potentiometric titration method. Adsorptive properties of the polymer for UO₂(VI), Mg(II), Fe(II), Ni(III), Co(II), Ni(II), Cu(II), and Zn(II) were also examined at very low concentrations in the 1–9 pH range. The amidoxime polymer possesses adsorptive affinities of the following order: (Mg(II), Ca(II)) < Zn(II) < Co(II) < Ni(II) < Cu(II) < UO₂(VI). These adsorptive affinities are reasonably explained by the proton-binding and the metal ion-complexing abilities of the ligand, and are discussed from the standpoint of uranium recovery from seawater.     

Extraction chromatographic method of preconcentration and separation of lead (II) with high molecular mass liquid cation exchanger

A selective method has been developed for the extraction chromatographic separation of lead (II) with Versatic 911 (liquid cation exchanger) coated on silanised silica gel. Lead (II) has been extracted from 0.1 M acetate buffer at the range of pH 4.5-6.5. The effects of pH, flow-rate, stripping agents on extraction and elution have been investigated. Exchange capacity of the prepared exchanger at different temperatures with respect to lead (II) has been determined. The extraction equilibrium constant (K_ex) and different standard thermodynamic parameters have also been calculated by temperature variation method. The effect of pH on R_f values in ion exchange paper chromatography has been investigated. In order to investigate the sorption isotherm, two equilibrium models, the Freundlich and Langmuir isotherms, were analyzed. Lead (II) has been separated from synthetic binary and multi-component mixtures containing various metal ions associated with it in ores and alloy samples. The method effectively permits sequential separation of lead (II) from synthetic quaternary mixture containing its congeners Cu (II), Sn (II), Hg (II) and Cu (II), Cd (II), Bi (III) of the same analytical group. The method was found effective for removal and recovery of lead (II) from industrial waste and standard alloy samples following its preconcentration on the column. A plausible mechanism for the extraction of lead (II) has been suggested.     

Liquid—Liquid Extraction of Goid(III) with Diluted Tributyl Phosphate

Abstract

A new method is developed for the. solvent extraction of gold with diluted tributyl phosphate. In this method, 50% tributyl phosphate in toluene extracts gold quantitatively from 3 M hydrochloric acid containing 2 M lithium chloride as the salting-out agent. Gold from the organic phase is stripped with 1 M ammonium hydroxide and determined photometrically as its complex with stannous chloride. It is possible to extract gold in the presence of a large number of ions.     

Bis[4-(methylthio)phenylmethyleneaminophenyl] disulfide, 2-[4-(methylthio)phenyl]-2,3-dihydro-1,3-benzothiazole,and its nickel(II) and cobalt(II) complexes: Synthesis,adsorption on gold surface and electrochemical characterization

2-[4-(Methylthio)phenyl]-2,3-dihydro-1,3-benzothiazole (1) and bis[4-(methylthio)phenylmethylene-aminophenyl] disulfide (2) were synthesized. Novel coordination compounds of Ni(II) and Co(II) with 2-[4-(methylthio)phenylmethyleneamino]thiophenol, M(1)₂ (M=Co (3); M=Ni (4)), were prepared by reacting 1 with M(OAc)₂·6H₂O or MCl₂·6H₂O in EtOH solution. The structure of 2 was proved by X-ray crystallography. Electrochemical behavior of 1–4 in CH₃CN solution and at the surface of a gold electrode was studied by cyclic voltammetry. The modification of the electrode by ligand 1 and its complexes with Ni²⁺ and Co²⁺ is described in detail. Two procedures were used to obtain a self-assembled monolayer of a metal complex on the gold surface: the adsorption of prepared coordination compound 3 or 4 on the electrode and the initial modification of the electrode with ligand 1 followed by the formation of a coordination complex between the ligand adsorbed on the electrode and a metal salt occurring in solution. On the basis of the electrochemical data, it was found that the structure of complexes formed on the surface differs from that of the complexes produced in solution.     

Ion-Exchange Behavior of Mercury(II) in Mixed Solvents: Separation from Zinc(ll), Cadmium(ll), Gold(lll), and Thallium(lll)

Abstract

Distribution coefficients of Zn(II), Cd(II), Au(III), Hg(II), T1(I), and Tl(III) between cation- and anion-exchangers Amberlite IR-120 and Amberlite IR-400, and aqueous solutions containing nitric or hydrochloric acid and organic solvents have been determined. The organic solvents were methanol, acetone, and tetrahydrofuran. The separation of Hg(II) from Zn(II), Cd(II), Au(III), and Tl(III) has been proposed in mixed solvents with high separation factors. Some of these separations have been actually performed using column method.     

Solvent-Extraction Behavior of Cobalt(II), Nickel(II), Copper(II), and Palladium(II) with Tri-n-butylphosphate

Abstract

A systematic study of the extraction behavior of cobalt(II), nickel(II), copper(II), and palladium(II) with TBP from thiocyanate system in various ranges of acid concentrations has been performed. The thiocyanate medium leads to enhanced extractions in all these cases compared to those in the previously used chloride medium. For palladium, the chloride and nitrate systems have been critically examined. Sixty-two per cent extraction occurs from 4 M hydrochloric acid using 100% TBP in a single run and the extraction becomes quantitative (>99%) after four successive equilibrations. A simpler method has been proposed for rapid extraction of palladium(II) as the thiocyanate complex. Quantitative extraction occurs in the presence of 1.2% thiocyanate solution from 0.5 to 2 M hydrochloric acid (initial) up to pH 8.0. The extractable species of cobalt(II), nickel(II), copper(II), and palladium(II) from thiocyanate medium are probably similar and of the type [M(CNS)₄]^2? [K·TBP·3H₂O]₂ ⁺ (buffer solution) and [M(CNS)₄]^2? [H·TBP·3H₂O]⁺ ₂ (acid solution). A simple extraction scheme has been worked out for the separation of palladium(II) from iron(III), cobalt(II), nickel, manganese(II), copper(II), and platinum.     

LIQUID-LIQUID EXTRACTION OF GOLD(III) AND ITS SEPARATION OVER COPPER(II), IRON(III), AND ZINC(II) USING THIOUREA DERIVATIVES FROM CHLORIDE MEDIA

ABSTRACT

Selective liquid-liquid extraction of Au(III) from aqueous chloride media (1 mol/L NaCl) into cumene by thiourea derivatives namely 2a-c (N-thiocarbamoylbenzamidine derivatives), 3a-f (N-benzoylthiourea derivatives) has been investigated in detail. Marked differences in the metal extraction are noted using these organic compounds with respect to their structural variation. The extraction behaviour of Au(III) with extractants 2a-c and 3a-f followed the order : 2b> 2a>2c and 3e≈ 3c≈ 3d >3a >3f≈3b, respectively. The organic reagent 2a and 3c were selected for further detailed studies owing to their better strippability behaviour. Optimum conditions such as structure of the organic extractant, aqueous phase pH, diluent, time of equilibration, metal concentration, extractant concentration, effect of other metal cations were established for extraction separation of Au(III). Experimental data have been treated graphically and numerically by means of the computer programme LETAGROP-DISTR, and can be explained by assuming the formation of the species AuCl₃L and AuCl₃L₂ for 2a-c and AuCl₃L₂ for 3a-f derivatives. The lack of interference from even appreciable amounts of possible base metals such as Cu(II), Zn(II) and Fe(III) may be considered an outstanding advantage of the method for separation of gold from these metals using 2a and 3c.     

Activated carbon sorbent with thioetheric sites—preparation and characterization

An activated carbon sorbent containing thioetheric sites (ACTS) was prepared by modification of the activated carbon with 2,2′-thiodiethanol. The specific surface area, pore volume, concentration of oxygen-containing groups and sulfur content of the sorbent were determined. The sorption behavior towards ions of some precious metals—Au(III), Pt(IV), Pd(II) and heavy metals—Ni(II), Zn(II), Fe(III), Cu(II), Pb(II), Cd(II) and Co(II) was studied. Selectivity towards gold, palladium and platinum in the pH range 1–9 was observed. The capacity for gold was 80 mg g⁻¹. The sorption of Au(III) at pH 1 is not affected by milligram amounts of Ni(II), Zn(II), Fe(III), Cu(II), Pb(II), Cd(II) and Co(II). The sorbed gold species is Au(0).     

Extraction of Gold and Silver by Thiourea-Based Reagents

Abstract

The synthesis and properties of some novel solvent extractants that are highly selective for gold and silver in very acidic chloride solutions are described. In this paper we also report on the study of one of these reagents; Dodecyl-thiourea (DTH), which has shown to be a very selective extractant for Au(III) and Ag(I) in the presence of Cu(II) and Fe(III). The extraction of Au and Ag was found to be fast. The Gold-DTH extraction data were explained by the formation of AuCl₃.(DTH)₃ species while silver forms AgCl.(DTH)₂ complex. The extractant has been also tested for practical application by determining the loading and stripping isotherms.     

1,5-Bis(2,5-Difluorophenyl)-3-Mercaptoformazan. A New Tetrafluorinated Dithizone Analogue

Abstract

1,5-Bis(2,5-difluorophenyl)-3-mercaptoformazan (2,2′, 5.5′-tetrafluorodithizone, F₄ H₄ Dz) has been synthesized; its electronic spectra was found to be significantly different from that of dithizone. Its pH_½ in chloroform (8.4) and in carbon tetra-chloride (7.4) are lower than the corresponding values (10.6 and 8.8, respectively) for dithizone. The partition coefficient of the reagent is remarkably decreased in chloroform (270) and in carbon tetrachloride (160) due to the presence of fluorine atoms, compared to the corresponding values (10⁴.89 and 10⁴.18, respectively) for dithizone. The extraction constants of its complexes with Cd(II), Cu(II), Pb(II), Co(II), Hg(II), and Zn(II) were found to be higher than the corresponding values of dithizone complexes, thus enabling their extraction from more acidic solutions. The new reagent seems also to be slightly more sensitive for Bi(III), Cd(II), Co(II), Cu(II), and Hg(II).     

A New Sorbent for Selective Separation of Metal: Polyethylenimine Methylenephosphonic Acid

Abstract

A new sorbent, the polyethylenimine methylenephosphonic acid (PEIMPA), was synthesized from commercially available polyethylenimine. After characterization by (¹H, ¹³C, ³¹P) NMR, elementary analysis, UV/VIS and FTIR, the new ion exchange polymer PEIMPA has been investigated in liquid – solid extraction of a mixture of Cd(II), Co(II), Cu(II), Fe(III), Ni(II), Pb(II), and Zn(II) cations from a mineral residue of zinc ore dissolved in nitric acid. The selectivity of this polymer was studied as a function of pH. PEIMPA can sorb much higher amounts of Fe ion than Cd, Co, Cu, Ni, Pb, and Zn ions. The recovery of Fe(III) is almost quantitative. Because of this remarkable affinity, the PEIMPA resin has the potential for application in several fields. Further studies of the polymer are in progress.     

The Extraction Ability and Sensitivity of Porphyrazine Derivatives Towards Some Transition Metal Cations

The synthesis of novel metal-free and magnesium porphyrazines, peripherally substituted with dithia-dioxa (S₂O₂) and tetrathia (S₄) 14-membered macrocycles were performed by cyclotetramerization of (6Z)-1,3,4,9,10,12-hexahydro-2,5,8,11-benzo-dioxadithiacyclotetradecine-6,7-dicarbodinitrile (3) or (6Z)-1,3,4,9,10,12-hexahydro 2,5,8,11-benzotetrathiacyclotetradecine-6,7-dicarbodinitrile (5). The metal-free porphyrazines have been obtained by known route. The structure of compounds were characterized by elemental analysis and ¹H, ¹³C NMR, IR, UV-vis, and MS spectral data. The solvent extraction properties of the synthesized compounds towards some metal cations, such as Ag(I), Hg(II), Cu(II), Mn(II), Cr(III), Ni(II), Pb(II), and Zn(II) have been investigated. The effect of Cu²⁺, Mn²⁺, Ni²⁺, Pb²⁺, Sr²⁺, Al³⁺, Zn²⁺, Ba²⁺, Cd²⁺, Co²⁺, Hg²⁺, and Ag⁺ ions on the absorption spectra of the compounds were investigated by means of spectrophotometric method. Magnesium porphyrazine with S₂O₂ (6) interacted within Hg²⁺ ion specifically of all the tested metal ions.     

Separation and Recovery of Silver(I) Ions from Base Metal Ions by Thiourea- or Urea-Formaldehyde Chelating Resin

Abstract

In the present work, thiourea-formaldehyde (TF) and urea-formaldehyde (UF) chelating resins have been synthesized and they have been used in the adsorptions of Ag(I), Cu(II), and Zn(II) metal ions by batch and column methods. The effect of initial acidity of Ag(I) solution and the adsorption capacities of TF and UF resins by batch method and the separation of Ag(I) ions from Cu(II) and Zn(II) base metal ions by the column method were examined experimentally. The adsorption capacities of TF and UF resins were found as 58.14 and 47.39 mg Ag(I)/g by batch method and 30.7 and 4.66 mg Ag(I)/g, 0.80 and 0.121 mg Cu(II)/g, and under 0.002 mg Zn(II)/g by the column method, respectively. It was found that Ag(I) ions showed higher affinity towards TF resin than UF resin, compared with Cu(II) or Zn(II) ions, and Ag(I) could be separated more effectively by TF resin from Cu(II)and Zn(II) ions.