Highly Efficient Extraction of Rhodium(III) from Hydrochloric Acid Solution with Amide-Containing Tertiary Amine Compounds

Extraction of Rh(III) from a HCl solution with N,N-disubstituted amide–containing tertiary amine (ACTA) compounds (N,N-di-n-hexyl(N-methyl-N-n-octyl-ethylamide)amine (MonoAA), N-n-hexyl-bis(N-methyl-N-n-octyl-ethylamide)amine (BisAA), and tris(N-methyl-N-n-octyl-ethylamide)amine (TrisAA)) was investigated. The ACTAs extract Rh(III) more efficiently than tri-n-octylamine (TOA), and the extraction efficiency increases with increasing number of amide groups: TrisAA > BisAA > MonoAA ? TOA. For all ACTAs, the predominant Rh(III) complex extracted from 2 M HCl is probably {[RhCl₅(H₂O)]·(ACTA·H)₂}. The apparent basicity of the ACTAs and TOA varies in the opposite order from that observed for the Rh(III) extraction efficiency. Rh(III) can be readily back-extracted using 10 M HCl solution possessing a high selectivity over similarly loaded Pd(II) and Pt(IV).     

The Solvent Extraction Performance of N,N’-Dimethyl-N,N’-Dibutylmalonamide Towards Platinum and Palladium in Chloride Media

The solvent extraction performance of N,N’-dimethyl-N,N’-dibutylmalonamide (DMDBMA) in 1,2-dichloroethane (1,2-DCE) towards platinum(IV) and palladium(II) in hydrochloric acid media was systematically evaluated. Pt(IV) extraction (%E) increases with the HCl concentration in the aqueous phases, being always higher than 72%, whereas Pd(II) extraction decreases from 65% at 1 M HCl to 22% at 8 M HCl. Several stripping agents for the two metals were tested: Pt(IV) is successfully recovered by a 1 M sodium thiosulfate solution, whereas the best result for Pd(II) was achieved with 0.1 M thiourea in 1 M HCl. The loading capacity of DMDBMA for Pt(IV) is high, and data obtained from successive extraction-stripping cycles suggest a good DMDBMA stability pattern. Attempts to replace 1,2-DCE by more environmentally-friendly diluents showed, in general, worse %E for Pt(IV). The dependence of Pt(IV) distribution coefficients on DMDBMA and chloride ion concentrations, as well as on acidity, are the basis of a proposal for the composition of Pt(IV) extracted species.     

Recovery of Platinum and Palladium from Chloride Solutions by a Thiodiglycolamide Derivative

The liquid-liquid extraction of platinum(IV) and palladium(II) from hydrochloric acid media was carried out using N,N’-dimethyl-N,N’-dicyclohexylthiodiglycolamide (DMDCHTDGA) in 1,2-dichloroethane (1,2-DCE). Pt(IV) is efficiently extracted from 5 M HCl onwards (%E ≥ 97%), whereas Pd(II) is quantitatively recovered from 1 to 8 M HCl solutions. Both Pt(IV) and Pd(II) can be successfully stripped from the loaded organic phases, the former with a 1 M HCl solution, the latter with 0.1 M thiourea in 1 M HCl. The maximum loading capacity of DMDCHTDGA for Pt(IV) could not be determined but it is high, since molar ratios extractant:Pt(IV) within 2 and 3 have been achieved. Data obtained from successive extraction-stripping cycles suggest a good stability profile of DMDCHTDGA towards Pt(IV) recovery. Attempts to replace 1,2-DCE by more environmentally-friendly diluents showed, in general, comparable %E for Pt(IV). The study of the influence of acidity, as well as chloride ion and DMDCHTDGA concentrations, allows a proposal for the composition of the Pt(IV) species formed upon extraction. Results obtained with binary metal ion solutions point out that Pt(IV) and Pd(II) can be efficiently separated from DMDCHTDGA loaded organic phases through sequential selective stripping.     

Extraction of Soft Metals from Acidic Media with Nitrogen-Donor Ligand TPEN and its Analogs

Abstract

Soft metals were extracted from acidic solution (pH 1 to 4) using two hydrophobic analogs of N,N,N′,N′-tetrakis[2-pyridyl-methyl]-1,2-ethylenediamine (TPEN). N,N,N′,N′-tetrakis[4-(2-butyloxy)-2-pyridyl-methyl]-1,2-ethylenediamine (TBPEN) and N,N,N′,N′-tetrakis(2-quinolinylmethyl)-1,2-ethylenediamine (TQEN) have shown enhanced extraction performance in more acidic media than TPEN. TBPEN showed enhanced extraction of Cd(II) from highly acidic solutions (pH < 2). This is because the distribution of this ligand to the aqueous phase is suppressed by the formation of a metal complex encapsulating Cd(II) with TBPEN. The percent extraction of Cd(II) for TBPEN was 100% at pH 1, whereas TPEN extracts less than 10% of the Cd(II) under these conditions. TBPEN also exhibited selective extraction of a variety of soft metals, such as Au(III), Pt(II), Pd(II), and Cd(II), from the acidic solution at pH 1. These results suggest that a hydrophobic TPEN analog combining alkyl chains to four pyridyl groups is applicable to the practical extraction process of soft metals.     

Liquid-Liquid Extraction of Ruthenium from Chloride Media by N,N'-Dimethyl- N,N'-Dicyclohexylmalonamide

Abstract

Research on the solvent extraction of ruthenium from hydrochloric acid media has been carried out using N,N'-dimethyl-N,N'-dicyclohexylmalonamide (DMDCHMA) dissolved in 1,2-dichloroethane. Ruthenium extraction percentages (%E) ranging from 50% to 80% have been achieved for HCl concentrations between 5 M and 7 M. Extraction curves exhibiting the dependence of the %E ruthenium on HCl concentration in the aqueous phases are presented, the latter solutions being obtained by dissolution of either Ru(III) or Ru(IV) salts. The influence of some experimental parameters on the %E Ru, such as the equilibration time, extractant concentrations, and hydrogen-ion activities, has been thoroughly investigated. Additionally, DMDCHMA is also adequate for extracting Pd(II) from 5 M to 7 M HCl solutions and under similar experimental conditions, %E Rh(III) is below 5%, and Pt(IV), Ir(III), and Ir(IV) cause the formation of third phases. Both Ru and Pd(II) can be successfully stripped from the loaded organic phases with water. A partition scheme to isolate Ru from a number of some associated elements has also been attempted.     

SEPARATION OF PALLADIUM(II) FROM PLATINUM(II), IRIDIUM(III), AND RHODIUM(III) USING CENTRIFUGAL PARTITION CHROMATOGRAPHY

The separation of Pd(II) from Pt(II), Ir(III) and Rh(III) with trioctylphosphine oxide (TOPO) in heptane using centrifugal partition chromatography (CPC) has been investigated for the first time. The extraction of Pd(II) has been studied by CPC and batch solvent extraction. The distribution ratios for Pd(II) determined by both methods agree well. In low HCl concentrations (<0.1 M), the extracted species was PdCl₂.(TOPO)₂, irrespective of the chloride concentration, while at acid concentrations above 0.1 M, the Pd was extracted as the ion pair, 2(TOPO.H⁺).PdCl₄ ^2-. Base line separation of Pd(II) and Pt(II) in CPC was obtained under a variety of chloride and HCl concentration with the average number of theoretical plates being 390 ± 40 at a flow rate of 0.47 ± 0.05 mL/min.     

The Extraction of TcO− 4 and Pd(II) by Dihexyl-N,N-diethylcarbamoylmethylphosphonate from Nitric Acid

Abstract

The extraction behavior of TcO^? ₄ and Pd(II) from aqueous HNO₃ was studied using dihexyl-N,N-diethylcarbamoylmethylphosphonate. Distribution ratios were studied as a function of contact time; concentration of solute, acid, and extractant; and extraction temperature. Extraction measurements of TcO^? ₄ were also made using H₂SO₄ in the aqueous phase. It was found that the extractant dependency for TcO^? ₄ is third power. Distribution measurements for TcO^? ₄ as a function of temperature in the range of 0–50°C led to a calculation of the thermodynamic quantity ΔH. A third-power extractant dependency for Pd(II) is suggested but is not strongly corroborated. Interpretation of Pd(II) data was hindered by slow kinetics (approximately 1 h to reach equilibrium and variations in distribution ratios with aqueous Pd(II) concentration.     

Adsorption Behaviors of Platinum Group Metals in Simulated High Level Liquid Waste Using Macroporous (MOTDGA-TOA)/SiO2-P Silica-based Absorbent

As fundamental research for separation of platinum group metals (PGMs) from high level liquid waste (HLLW) by macroporous silica-based adsorbent, (MOTDGA-TOA)/SiO₂-P adsorbent was prepared by impregnation of N,N′-dimethyl-N,N′-di-n-octyl-thiodiglycolamide (MOTDGA) and Tri-n-octylamine (TOA) into silica/polymer composite support (SiO₂-P). The adsorption behavior of Ru(III), Rh(III), and Pd(II) in simulated HLLW onto the adsorbent were investigated by the batch method to obtain their corresponding equilibrium and kinetic data. The adsorbent showed strong adsorption for Pd(II) and the adsorption reached equilibrium within 2 hr. High distribution coefficient (K _d) values for Pd(II) were obtained in 0.1–1 M HNO₃ concentration. In addition, the use of both MOTDGA and TOA improved adsorption of Ru(III) and Rh(III) better than individual use of them. Especially, the K _d value for Ru(III) towards (MOTDGA-TOA)/SiO₂-P adsorbent was three times larger than that in the adsorption using only with MOTDGA or TOA as extractant. The adsorptions of Ru(III), Rh(III), and Pd(II) followed the Langmuir adsorption model, and were found to be controlled by the chemisorption mechanism.     

Separation of Ru(III), Rh(III) and Pd(II) from nitric acid solutions using ion-exchange resins bearing carboxylic betaine

To understand the adsorption properties of a styrene–divinylbenzene copolymer functionalized with N,N,N-trimethylglycine, AMP03, the adsorption behaviours for platinoid ions (Ru(III), Rh(III) and Pd(II)) were examined. Furthermore, we performed adsorption experiments using sample solutions by adding triethylamine, thiourea and N,N,N-trimethylglycine. Based on the adsorption data obtained in this study, we performed chromatographic experiments. The results indicated that all platinoid ions in the feed solution completely adsorbed on AMP03, and almost 80% of the adsorbed platinoid ions were recovered. These results show that AMP03 has the potential to recover Ru(III), Rh(III) and Pd(II) from high-level liquid waste.     

Voltammetric behavior of Pd(II) and Ni(II) ions and electrodeposition of PdNi bimetal in N-butyl-N-methylpyrrolidinium dicyanamide ionic liquid

In this study, the voltammetric behavior of Pd(II), Ni(II), and mixtures of Pd(II) and Ni(II) was carried out in room-temperature N-butyl-N-methylpyrrolidinium dicyanamide ionic liquid (BMP-DCA IL). Electrodeposition of PdNi bimetal was achieved by controlled-potential electrolysis at iron wire electrodes from BMP-DCA containing various molar ratios of PdCl₂/NiCl₂. BMP-DCA shows good solubilities to PdCl₂ and NiCl₂, respectively, leading to the convenience for preparing the electrodepositing baths. By tuning the molar ratios of Pd(II)/Ni(II) in the electrodepositing baths and/or the applied potentials, PdNi coatings with various atomic contents of Pd could be obtained. Among these PdNi bimetallic coatings, the PdNi coatings with atomic ratios of ∼80/20 had the highest oxidation current in methanol oxidation reaction (MOR) in 1 M NaOH and exhibited the best poisoning tolerance. Powder X-ray diffraction analysis indicated that two separate metallic phases belonging to Pd and Ni existed in the PdNi coatings. The diffraction signal of Pd was very broad, indicating the tiny crystal size of Pd in the bimetal coatings. The scanning electron spectroscopic micrographs of PdNi coatings demonstrated that the Pd_∼80Ni_∼20 coatings had three-dimensional structures. This morphological characteristic implied that the composition and the surface morphology of the PdNi coatings equivalently contributed to the electrocatalytic activity toward MOR. The Pd_∼80Ni_∼20-coated iron-electrode (Fe/Pd_∼80Ni_∼20) was used to detect methanol and the linearity was observed in 3.53 μM to 758.88 μM using hydrodynamic chronoamperometry where a potential of −0.1 V (vs. Ag/AgCl) was applied.     

Ion-exchange Extraction of Palladium(II) from Chloride Solutions Using a Silica Gel-Immobilized Imidazolium Salt

ABSTRACT

Silica gel with covalently immobilized imidazolium group was obtained by click reaction and characterized by elemental analysis, thermogravimetry, as well as by IR and solid-state ¹³C NMR spectroscopy. The total exchange capacity of the obtained material was calculated to be 0.26 ± 0.02 mM/g. The nature of the salt background of KCl and HCl was shown to have effect on the distribution coefficients of Cu(II), Ni(II), Co(II), Cd(II), and Pd(II) on modified silica gel. In the case of Pd(II) possessing a high distribution coefficient under selected steady-state ion-exchange conditions (0.1 M HCl), dynamic breakthrough curves were obtained for different levels of initial analyte concentration. The addition of equimolar amounts of Fe(III), Al(III), Cu(II), Ni(II), Co(II), and Zn(II) and a change in the total salinity level up to 35 g/L were shown to have no effect on the distribution coefficient of Pd(II) under dynamic ion exchange conditions.     

SELECTIVE EXTRACTION OF PALLADIUM(II) FROM CHLORIDE SOLUTIONS WITH NONYLTHIOUREA DISSOLVED IN CHLOROFORM

ABSTRACT

The extraction of Palladium(II) [Pd(II)] from hydrochloric acid solutions with nonylthiourea (NTH) dissolved in chloroform at a constant ionic strength of 1.0?M has been studied. The extraction of Pd(II) has been investigated as a function of the concentration of the extractant, chloride ion, and proton concentrations as well as extraction temperature. The distribution data have been treated graphically and numerically. The analysis of the experimental data has shown that Pd(II) is extracted as PdCl₂·(NTH) and PdCl₂·(NTH)₂ species with the respective extraction constants of log?K ₁₁=5.0±0.1 and log?K ₁₂=9.1±0.1. The back-extraction of Pd(II) from the organic phase using different stripping reagents has been examined. The selectivity of NTH for Pd(II) against Pt(IV), Rh(III), Cu(II), Fe(III), and Zn(II) has also been investigated.     

Feasibility of Using Di-Dodecyl-Di-Octyl Diglycolamide for Partitioning of Minor Actinides from Fast Reactor High-Level Liquid Waste

The unsymmetrical diglycolamide, di-dodecyl-di-octyl diglycolamide (D³DODGA) is a modifier-free extractant proposed for partitioning of trivalent actinides from nitric acid medium. D³DODGA has been evaluated for the feasibility of using it in the absence of a phase modifier, for the partitioning of minor actinides from fast reactor high-level liquid waste (FR-HLLW). The extraction behavior of various metal ions present in the simulated FR-HLLW was studied in a solution of 0.1 M D³DODGA/n-dodecane from nitric acid medium. The distribution ratio of about 20 metal ions was measured as a function of concentration of nitric acid and other interfering ion. The extraction was found to be strongly dependent on the oxidation state of the metal ion. The extraction of Am(III) from 3–4 M nitric acid medium was quantitative in a single contact. However, it was accompanied by the quantitative extraction of fission products such as trivalent lanthanides (Ln(III)), Y(III), and Zr(IV). The extraction of Sr(II), Pd(II), and Ru(III) in 0.1 M D³DODGA/n-dodecane was not insignificant, but quite low. The extraction of Ba(II), Ni(II), Mo(VI), and Fe(III) was marginal and the extraction of Co(II), Sb(III), Mn(II), and Cs(I) in 0.1 M D³DODGA/n-dodecane was negligible. Our results indicated that 0.1 M D³DODGA/n-dodecane is a promising candidate for the separation of trivalent actinides from fast reactor high-level liquid waste containing significant quantities of trivalent lanthanides and actinides.     

Extraction of Copper(II) with N′,N′-Dialkylhydrazides of Benzoic and Phenylacetic Acids

This article is concerned with the study of the extraction of Cu(II), Co(II), Ni(II), and Zn(II) with N′,N′-dialkylhydrazides of benzoic and phenylacetic acids. The applied reagents are able to extract Cu(II) from ammoniac media efficiently. The influence of the length and structure of alkyl chains on the extraction of Cu(II) has been analyzed. It is shown that N′,N′-dibytil- and N′,N′-dihexylhydrazides of benzoic acid exhibit the most promise for extracting Cu(II) from ammoniac media, and N′,N′-dihexylhydrazide of phenylacetic acid as an extractant is worse than the analogous benzoic acid derivative. Copper stripping has been studied for various concentrations of H₂SO₄, and the copper extraction constants have been calculated. The data obtained indicate that the degree of Cu(II) extraction decreases with increasing concentration of ammonium salts.     

Liquid–Liquid Extraction of Silver From Chloride Media by N,N′-Tetrasubstituted Dithiomalonamide Derivatives

N,N′-dimethyl-N,N′-diphenyldithiomalonamide (DMDPHDTMA) and N,N′-dimethyl-N,N′-dicyclohexyldithiomalonamide (DMDCHDTMA) were synthesized and tested as extractants for silver in chloride solutions. Even when relatively low concentrations are used, both compounds effectively extract Ag(I) from 2–5 M chloride concentrated aqueous phases. Ag(I) is successfully stripped by a stabilized sodium thiosulfate solution. Results obtained from sequential cycles of extraction-stripping suggest that both extractants exhibit a high Ag(I) loading capacity. The effects of the equilibration time, concentrations of extractant, chloride and hydrogen ions on Ag(I) extraction have been investigated. The chemical reactions involved on Ag(I) extraction are proposed. There is no selectivity of DMDPHDTMA or DMDCHDTMA for Ag(I) when Cu(II) and Fe(III) co-exist in the chloride aqueous solution.     

Palladium Isolation and Purification from Nitrate Media: Efficient Process Based on Malonamides

ABSTRACT

Solvents based on malonamides have been described to be very efficient and selective for liquid-liquid extraction of Pd(II) from nitrate media. The present study details the possibility to selectively extract Pd(II) over common metallic cations, Cu(II), Ni(II), Co(II), Zn(II), Nd(III), Fe(III) and Al(III) using N,N’-dimethyl,N,N’-dibutyltetradecylmalonamide (DMDBTDMA) in toluene. The lowest selectivity was obtained considering Fe(III) and Nd(III), the extraction of all other cations being negligible. Pd(II) distribution and selectivity regarding Fe(III) have been fine-tuned using the aqueous HNO₃ concentration as the sole parameter, so that extraction, scrubbing and stripping steps can be simply designed without the need for other specific metal chelating reagents and/or aqueous media and without the extensive generation of aqueous effluents. DMDBTDMA was also benchmarked with other classical Pd(II) extractants such as tributylphosphate (TBP), dihexylsulfide (DHS), tetraoctyl diglycolamide (TODGA) and bis(2-ethylhexyl)sulfoxide (BESO) in toluene and in n-heptane. Overall, this study reveals that malonamides are very well positioned and should be considered for further processing of aqueous nitrate wastes containing Pd contaminated with common base metals.     

Fatty Imidazolines: A Novel Extractant for the Recovery of Palladium(II) from Hydrochloric Acid Solutions

The extraction of palladium(II) from hydrochloric acid solutions with a novel highly basic extractant, a mixture of homologous 1-[2-(alkanoylamino)ethyl]-2-alkyl-2-imidazolines (AAI) in toluene with 15% (v/v) of n-octanol was studied. Palladium(II) is rapidly and most effectively extracted with AAI hydrochloride at the low hydrochloric acid (chloride ions) concentration (up to 1 M) and can be completely separated from Fe(III), Cu(II), and Co(II). The palladium(II) extraction at the optimum acidity occurs via an anion-exchange mechanism with the formation of ionic associates (LH)₂PdCl₄ (K _ex = (1.5 ± 0.2) · 10⁴ at 0.5 M HCl) and is accompanied by the dimerization of palladium(II) in the organic phase with the formation of ionic associates (LH)₂Pd₂Cl₆ (K _dim = (3.9 ± 0.4) · 10^?4 at 0.5 M HCl). The anion-exchange extraction of palladium(II) at the acidity of 0.5 M HCl is temperature independent in the range 20–49°C. Complete stripping of palladium(II) can be performed using a 5% solution of thiourea in 0.1 M HCl.     

Separation of Precious Metals through a Trioctylamine Liquid Membrane

Abstract

The extraction behavior of precious metals (PMs) from HCl media has been studied using trioctylamine (TOA) in kerosene. The extraction sequence of PMs was found to be Au(III) > Pd(II), Pt(IV), Ir(IV) > Ir(III). Ru. Transport of PMs was performed through a supported liquid membrane (SLM) impregnated with TOA as a mobile carrier from the HCl feed solution into the HClO₄ or HNO₃ product solution. Selective transport; and recovery of PMs from certain mixtures were accomplished across the TOA-SLM on the basis of differences in extraction equilibria and kinetics.     

Enantioselective Reaction of Imines and Benzyl Nitriles Using Palladium Pincer Complexes with C2‐Symmetric Chiral Bis(imidazoline)s

Enantioselective reactions of a wide variety of benzyl nitriles with N‐tosylimines catalyzed by novel chiral 1,3‐bis(imidazolin‐2‐yl)benzene‐palladium(II) [Phebim‐Pd(II)] complexes have afforded the respective products in high yield with good enantioselectivity. A reaction mechanism is proposed based on X‐ray crystal structures of palladium complexes.