Extraction of Rare Earth Metals Using Liquid Surfactant Membranes Prepared by a Synthesized Surfactant

Abstract

Three surfactants, l-glutamic acid dioleyl ester ribitol (nonionic, 2C ₁₈Δ⁹ GE), l-glutamic acid dioleyl ester quaternary ammonium chloride (cationic, 2C ₁₈Δ⁹ GEC ₂ QA), and dioleyl dimethyl quaternary ammonium chloride (cationic, 2C ₁₈Δ⁹ QA) were synthesized for potential use in liquid membrane operations. These surfactants have strongly hydrophobic, twin oleyl chains as the hydrophobic moiety. Using the synthesized surfactants, extraction of rare earth metals was carried out by liquid surfactant membranes in a stirred tank. The extraction behavior of 12 kinds of rare earth metals was systematically studied with 2-ethylhexyl phosphoric acid mono-2-ethylhexyl ester (commercial name: PC-88A) as a carrier. Different surfactants having an identical hydrophobic moiety can have significantly different behaviors in rare earth extractions by liquid surfactant membranes, where extraction efficiency appears to be governed by the nature of the interfacial microenvironment between oil and water. An interfacial reaction model which takes into account the adsorption of a surfactant at the interface has been proposed to evaluate the permeation rate of rare earth metals by liquid surfactant membranes. It was found that a cationic surfactant strongly enhances the extraction rate of rare earth metals compared with the conventional surfactant, Span 80. The cationic surfactant 2C ₁₈Δ⁹ GEC ₂ QA appears to be one of the best surfactants currently available for rare earth extraction by liquid surfactant membranes.     

Preparation of gold nanoparticles from the metal scrap

The possibility of producing gold nanoparticles from electronic waste (metal scrap) containing gold metal has been demonstrated. After dissolving the metal scrap in chloronitric acid, gold ions are concentrated from aqueous solutions by the flotoextraction method using cationic amphiphile; then, the resulting precursor is reduced in direct micelles of amphiphile. The obtained samples were characterized by the spectroscopic methods, X-ray phase analysis, transmission electron and atomic force microscopies. The catalytic properties of the synthesized gold nanoparticles have been investigated in the reaction of polymerization of pyrrole to polypyrrole.     

多组分废催化剂中钯的分离工艺研究进展

简述了废催化剂中钯分离回收的基本过程和方法,指出多组分废钯催化剂具有很高的回收价值,但存在组分多、分离困难的问题。对于多组分废钯催化剂中钯与贵金属金、银、铂、铑等,以及与非贵金属铜、钴、镍、铁等的分离技术分别进行了简要介绍与评价。结果表明,化学沉淀法、溶剂萃取法、还原法、置换法是目前多组分废钯催化剂常用的回收方法。其中化学沉淀法是使用最多的方法,但存在回收周期长、复杂、成本较高的问题,而溶剂萃取法具有分离效果好、过程简单的优点,成为最具发展前景的方法。因此选择性高、无污染并适合大规模工业化的萃取新工艺成为未来的发展方向。     

Mass Transfer Investigation of Liquid Membrane Transport of Gold (III) by Methyl Isobutyl Ketone Mobile Carrier

Extraction of Au^III ions by an emulsion liquid membrane (ELM) system with methyl isobutyl ketone (MIBK) as the mobile carrier and also liquid‐liquid extraction of Au^III from aqueous solutions have been studied. Experiments on the transport of the gold ions in a liquid‐liquid extraction system and stripping of the extracted ions from the organic phase as well as the extraction by a three‐phase W/O/W emulsion liquid membrane system have been performed. The results showed that even when the distribution coefficient of the diffusing species in the phases is small, the extraction by emulsion liquid membranes would be an effective process. A first‐order extraction rate was proposed and examined for the extraction system.     

Highly Efficient and Selective Transport of Au(III) through a Bulk Liquid Membrane using Potassium-dicyclohexyl-18-crown-6 as Carrier

Abstract

The facilitated transport of Au(III) through a chloroform bulk liquid membrane containing potassium-dicyclohexyl-18-crown-6 as a selective ion carrier was designed. Au(III) as [AuBr₄]^?, quantitatively transported across the liquid membrane. In the receiving phase, L-cysteine acts as a specific stripping agent. The amount of Au(III) transported through the liquid membrane after 120 minutes was (96.2±1.3)%. The type of halide and its concentration, pH of source and receiving phase and also the type of stripping agents were optimized. The selectivity and efficiency of gold(III) transport from aqueous solutions containing various metal ions were investigated. The presence of EDTA in the source phase diminished drastically the competitive effect of interfering metals ion.     

Synthesis and Surface Active Properties of Gemini Cationic Surfactants and Interaction with Anionic Azo Dye (AR52)

A homologous series of new gemini cationic surfactants were synthesized and characterized using micro elemental analysis, FTIR, ¹H-NMR and mass spectra. The surface activities of these amphiphiles were determined based on the data of surface tension. Critical micelle concentration, effectiveness of the surface tension reduction, efficiency of adsorption, maximum surface excess, minimum surface area and critical packing parameter were evaluated. The effect of cationic micelles on solubilization of anionic azo dye, sulforhodamine B (Acid Red 52) in aqueous micellar solution of the synthesized gemini cationic surfactants was studied at pH 6.9 ± 0.5 and 25 °C. The results showed that the solubility of dye rose with increasing surfactant concentration as a consequence of some association between the dye and the micelles. It was also observed that the aggregation of surfactant and dye takes place at a surfactant concentration below the CMC of the individual surfactant. The partition coefficients between the bulk water and surfactant micelles as well as the Gibbs energies of distribution of dye between the bulk water and surfactant micelles were calculated using a pseudo-phase model. The effect of the hydrophobic chain length of Gemini cationic surfactants on the distribution parameters was also reported. The results show favorable solubilization of dye in cationic micelles.     

Rare Earth Metal Extraction by Liquid Surfactant Membranes Containing a Calixarene Carboxylate Derivative: Permeation Acceleration Effect of Sodium Ions

ABSTRACT

Calixarene carboxylate derivatives were used as a mobile carrier for rare earth permeation in a liquid surfactant membrane (LSM) system. The effect of alkali metal ions on the extraction behavior of rare earth metals in both liquid-liquid extraction and LSM systems has been studied. The addition of sodium ions considerably enhanced the extraction ability of rare earth metals in the extraction equilibrium. Furthermore, the presence of alkali metal ions in the material solution affected the rate of rare earth permeation in LSMs. The most accelerative transport of rare earth metals by LSMs was achieved by the addition of sodium ions. This acceleration effect of sodium ions was predominant in a tetracarboxylate calixarene whose cavity size just fits the ionic diameter of sodium ions. The sodium-loaded calix[4]arene derivative showed good performance as an effective mobile carrier for rare earth metals in the presence of sodium ions.     

The effect of surfactants on the kinetics of diazocoupling between p-methoxybenzenediazonium ions and α-naphthylamine

The effect of anionic, cationic and non-ionic surfactants on the reaction rate between p-methoxybenzenediazonium ions and α-naphthylamine is examined.Strong catalytic activity is shown by the micelles of sodium lauryl sulphate, while limited variations of the rate of reaction could be detected in the presence of micelles of Triton X-100 and cetyltrimethylammonium bromide.     

负载型纳米金催化剂的研究进展

金是一种高化学惰性金属,其纳米粒子具有独特的结构和性质,在催化、光电传感器和生物医药等领域应用广泛。研究表明,负载在金属氧化物等载体上的纳米金粒子具有很高的催化活性,特别是在CO低温催化氧化中,催化效率明显高于其他类型贵金属。纳米金催化剂的研究已经具有了相当的深度和广度,在工业催化和环境保护等领域显现出重要的发展前景和商机。     

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.     

Separation of Cobalt and Nickel by Liquid Surfactant Membranes Containing a Synthesized Cationic Surfactant

ABSTRACT

Separation of cobalt(II) and nickel(II) by using a hydroxyoxime extractant has been investigated both in liquid-liquid extraction and in a liquid surfactant membrane(LSM) system. In the liquid-liquid equilibrium extraction studies, hydroxyoximes showed significant extractability for nickel ions, although LIX 84 was found to have exceptional chelating affinity for nickel ions. In the LSM system functionalized by hydroxyoxime, the cobalt ions were efficiently separated from nickel ions as a result of slower permeation of nickel chelates across the emulsion membrane. More complete cobalt recovery was achieved in the LSMs dosed with LIX 860 than when the same carrier was applied to the liquid-liquid extraction system. Furthermore, cobalt permeation rate was enhanced threefold when a quaternary ammonium type of cationic surfactant was used as an emulsifier due to carrier interaction with surfactant at the reaction interface. The permeation mechanism of ions in LSMs was elucidated by an interfacial reaction model which took into account the adsorption of the carrier and surfactant at the reaction interface.     

Effective and Selective Recovery of Precious Metals by Thiourea Modified Magnetic Nanoparticles

Adsorption of precious metals in acidic aqueous solutions using thiourea modified magnetic magnetite nanoparticle (MNP-Tu) was examined. The MNP-Tu was synthesized, characterized and examined as a reusable adsorbent for the recovery of precious metals. The adsorption kinetics were well fitted with pseudo second-order equation while the adsorption isotherms were fitted with both Langmuir and Freundlich equations. The maximum adsorption capacity of precious metals for MNP-Tu determined by Langmuir model was 43.34, 118.46 and 111.58 mg/g for Pt(IV), Au(III) and Pd(II), respectively at pH 2 and 25 °C. MNP-Tu has high adsorption selectivity towards precious metals even in the presence of competing ions (Cu(II)) at high concentrations. In addition, the MNP-Tu can be regenerated using an aqueous solution containing 0.7 M thiourea and 2% HCl where precious metals can be recovered in a concentrated form. It was found that the MNP-Tu undergoing seven consecutive adsorption-desorption cycles still retained the original adsorption capacity of precious metals. A reductive adsorption resulting in the formation of elemental gold and palladium at the surface of MNP-Tu was observed.     

Hemoglobin Extraction Using Cosurfactant-Free Nonionic Microemulsions

ABSTRACT

Oil-continuous microemulsions provide an effective medium as a liquid membrane for extraction of proteins due to high solubilization and low miscibility in aqueous feed. Unlike the use of reverse micelles, this new method employs a preformulated cosurfactant-free nonionic microemulsion of high water content. The use of nonionic microemulsions for hemoglobin extraction demonstrates the potential for effective separation of proteins, amino acids, and other biochemicals. The extraction can be controlled by adjusting pH and microemulsion composition. It is enhanced by the addition of an appropriate liquid ion exchanger. The extraction results cannot be explained only in terms of ionic interactions.     

Biosorbents based on pine sawdust and malt sprouts for preconcentration and ICP-OES determination of nonferrous,heavy, and precious metals in the environmental samples

Pine sawdust and malt sprouts modified with orthophosphoric acid and carbamide have been proposed for solid-phase extraction (SPE) of nonferrous, heavy, and precious metals and their subsequent determination in the environmental samples by inductively coupled plasma optical emission spectrometry (ICP-OES). Modified adsorbents were characterized by SEM, TGA, and FT-IR and compared with native matrixes. SPE of some nonferrous and precious metal ions by biosorbents was studied. Depending on the SPE conditions, it was possible to separate nonferrous and heavy metals from alkali and alkaline earth metals. The proposed adsorbents are effective for preconcentration of nonferrous and heavy metals from natural waters and precious metals from solutions after digestion of geological samples.     

Extraction of Gold (III) Ions from Aqueous Solutions Using Polyamine Type Surfactant Liquid Membrane

Experimental results of extraction of gold (III) ions from aqueous solutions by a polyamine type liquid membrane are presented. The effects of various parameters such as concentration of gold ions in the external phase, concentration of carrier, concentration of the internal phase reagents, pH of the external phase and the speed of agitation on the extraction rate were studied. The results show that by proper selection of the extraction conditions, nearly all of the Au (III) ions present in a highly concentrated feed solution was extracted within a few minutes.     

Emulsion liquid membrane for selective extraction of Bi(III)

Di(2-ethylhexyl)phosphoric acid was used as extractant of bismuth ions from nitrate medium by emulsion liquid membrane, with Triton X-100 as the biodegradable surfactant in n-pentanol bulk membrane. The novelties and innovative points of this work are the application of emulsion liquid membrane for selective and efficient extraction of bismuth ions as wel as the relevant optimization procedures. The extraction of bismuth ions was evaluated by the yield of extraction. The experimental parameters were evaluated and optimized, including the ratio of di(2-ethylhexyl)phosphoric acid mass concentration to Triton X-100 (1.0%:0.5%), nature of diluent (n-pentanol), nature and concentration of stripping solution (sulfuric acid, 0.5 mol·L?1), stirring speed (1800 r·min?1) and equilibrium time of extraction (20 min), initial feed solution of bismuth (350 mg·L?1) and the volume ratio of internal stripping phase to membrane phase (14). The experimental parameters of kinetic extraction reveal that the bismuth ions can be extracted by 100%.     

LIQUID MEMBRANE TRANSPORT OF CEPHALOSPORIN ANTIBIOTICS: EFFECT OF SOLUTE CHEMICAL NATURE ON CARRIER SPECIFICITY

Cephalosporin antibiotics were transported from a dilute aqueous solution (feed phase) through a bulk liquid membrane containing Aliquat-336 as an anion exchange carrier in n-butyl acetate as the solvent to another aqueous solution (receiving phase) of lower pH. Under appreciable pH gradient of the feed and receiving phases, facilitated uphill transport could be obtained. Under the optimal pH condition, the intial solute flux across the bulk liquid membrane could be correlated well with the hydrophobicity of the solutes. A linear correlation exists between the initial solute flux and hydrophobicity, indicating that the solute of higher hydrophobic nature are transported at a higher rate in the bulk liquid membrane involving the specific carrier. The correlation appears to be derived from a linear dependenc of solute hydrophobicity on equilibrium constant of the reactive extraction system being exploited in the bulk liquid membrane.     

Selective Extraction of Precious Metal Ions with Novel Trident Molecules Containing Pyridyl Groups

Trident molecules containing pyridyl groups have been prepared for use as novel extraction reagents to investigate their physicochemical properties for dissolution into the aqueous phase and their ability, together with their corresponding monomeric analogues, to extract precious metal ions. Differences in their behavior were related to the pK _a values of the trident molecules and the position of the nitrogen atom in the pyridyl groups. The trident molecules exhibit the ability to selectively extract silver from mixtures of other precious metals. The extraction mechanism and the coordination site of the silver ion with a 2-pyridyl derivative were determined by slope analysis and peak shift of the ¹H-NMR spectra of the extraction reagent before and after silver loading.     

反胶团技术应用研究进展

反胶团具有独特的优良性能,有着十分广阔的应用前景,近年来正越来越多地受到关注。该文介绍了反胶团理论的最新研究进展,综述了反胶团技术在酶催化反应、萃取分离、纳米粒子的制备等方面的应用研究进展, 提出了反胶团技术目前存在的问题,并对其应用前景作了展望。引用文献22篇。     

Modeling and Experimental Data for the Reverse Micellar Extraction of Proteins Using a New Surfactant

ABSTRACT

In this study the reverse micellar extraction of α-chymotrypsin using bis(2,4,4-trimethylpentyl) sodium dithiophosphinate as the surfactant has been investigated. Experiments were performed to determine the effects of pH and salt concentration on the reverse micellar extraction and backward extraction of α-chymotrypsin in isooctane/decanol mixtures. The results showed that both pH and salt concentration influence the reverse micellar extraction of α-chymotrypsin. The pH affects the extraction of the protein through changing the sign and number of the charges carried by protein molecules and thereby affects their interactions with the charged head groups of the surfactant molecules. It was found that at high pH values the hydrogen ions compete with positively charged protein molecules and exchange with the counterions of the surfactant molecules, and as a result destroy the reverse micelles. This effect was exploited for the backward extraction of protein molecules from the reverse micellar phase. A model has been developed to correlate the experimental data of reverse micellar extraction of proteins. In the model the reverse micelles were treated as noninteractive ion-exchange sites. The activity coefficient of the protein molecules in reverse micelles was represented by the model proposed by Pitzer. It has been shown that the model can correlate the experimental data obtained in this work and those reported in other studies.