Liquid-liquid distribution of metals in systems with trioctylmethylammonium dinonyl naphthalenesulfonate

The extraction of copper, nickel, cobalt, zinc, and iron chlorides by the solutions of trioctylmethylammonium dinonyl naphthalenesulfonate in toluene depending on the acidity of aqueous phase was studied. In the range of relatively high acidity (from 3 to 1 M HCl), an increase in the D _M values is observed with a growth in the concentration of hydrogen ions in aqueous phase; that corresponds to the principles of the binary extraction of chloro complex metal-containing acids. With a decrease in the acidity of aqueous phase, an increase in the distribution coefficients of metals is observed due to the change in the extraction mechanism and increase in the fraction of the complexes extracted as metal dinonyl naphthalenesulfonates. In the acidic range, the extractability of metals is mainly determined by the stability of complex metal-containing anions and qualitatively corresponds to the following order: Fe(III) > Cu(II) > Co(II) > Ni(II).     

Role of acid and redox properties on propane oxidative dehydrogenation over polyoxometallates

Cs_2.5H_1.5PV₁Mo₁₁O₄₀ heteropolyoxometallate compounds have been studied for propane oxidative dehydrogenation (ODH) in the 340–400 °C temperature range. Their redox and Brønsted acid properties have been tuned by introducing a redox metal element M such as Co^II, Fe^III, Ga^III, Ni^II, Sb^III or Zn^II in a V:M atom ratio equal to 1:1. This introduction was carried out either directly in the synthesis solution or by usual aqueous cationic exchange of protons of the solid Cs salt. TGA and FT-IR analyses allowed us to determine the extent of metal M substitution for Mo^VI in the Keggin anion and proton replacement by the M cation. It was observed that, under catalytic conditions (C₃:O₂:He=2:1:2, flow rate 15 cm³ min⁻¹, 12 h on stream), the catalysts were stable, with only a small part of the substituted elements (V and/or M) being extracted from the Keggin anion during the reaction. The presence of these metal M cations enabled us to tune the redox and acid properties of the material and to get high selectivity for propene (60–80% at 5 and 10% propane conversion) at a relatively low temperature (300–400 °C). The direct synthesis method was found more efficient than the classical cationic exchange technique for propane ODH.     

Extraction of Lithium Using TBP and the Noncoordinating Cation Exchanger Tetraphenylborate: Principles of Selectivity from Sodium and Higher-Valent Cations

Extraction of lithium, calcium, and some other metal cations using tetraphenylborate/tributyl phosphate mixtures has been studied. The possibility of a qualitative change in the cation exchange extraction series towards the preferential recovery of lowly-charged (singly-charged) metal cations was shown for these systems. A change in the separation factors for singly- over multiply-charged cations in this system, compared to the known commercially available extractants such as alkylphosphoric, carboxylic, and other organic acids, is several orders of magnitude and increases when passing from doubly- to triply-charged metal cations, reaching, for example, values of 10³ and more for the lithium/yttrium couple. It was assumed that the change in the extraction series was caused by the instability of the salts of the multiply-charged metal cations compared to that for the singly-charged cations due to the ionic character of the bond with the extracted metals and structural problems caused by the large volume of the tetraphenylborate anion. The investigated system can serve as a model for the development of a new class of extractants having a higher selectivity for singly-charged metal cations, in particular, for lithium.     

Boron removal from aqueous solutions by ion-exchange resin: Batch studies

In this study, boron removal from aqueous solutions was examined using Dowex 2 × 8 anion exchange resin. The sorption behaviour of resin was investigated as a function of pH, contact-time and temperature, initial boron concentration of solution, resin dosage and effect of other ions. The maximum sorption value for boron was observed at pH 9. The percent removal of boron decreased as temperature and initial boron concentration increased. The presence of other ions in solutions affected the sorption of boron significantly. The Langmuir isotherm was used to describe observed sorption phenomena. The maximum sorption capacity of Dowex 2 × 8 was determined as 16.98 mg B/g at pH 9 and 25°C. The quantitative stripping of boron from resin was obtained with 0.5 M H₂SO₄ or 0.5 M HCl solutions at 25°C. A generalised ion exchange kinetic model was applied to fit the kinetic data obtained by using the Dowex 2 × 8 and the rate-determining step is determined as film-intraparticle diffusion.     

ANION EFFECT ON SELECTIVITY IN SOLVENT EXTRACTION OF ALKALI METAL SALTS BY CROWN ETHERS

ABSTRACT

The influence of the co-extracted anion upon competitive solvent extraction of five alkali metal cations from aqueous solutions into organic diluents by the cis-syn-cis and cis-anti-cis isomers of dicyclohexano-18-crown-6 has been assessed. The anions are bromide, chloride, iodide, nitrate, perchlorate, and thiocyanate and the organic diluents are chloroform and 1-octanol. The extraction efficiency is markedly influenced by the identity of the anion and exhibits some correlation with the inverse of the hydration enthalpy of the anion. Although potassium is the best extracted cation with all anions, the selectivities for potassium over lithium, sodium, rubidium, and cesium are strongly affected by anion variation in chloroform, but not in 1-octanol. The selectivity ordering in chloroform does not correlate with the hydration enthalpy or softness parameter for the anion. Instead it appears to result from variation of the dimensional structure and the availability of specific binding sites in the anion.     

Reactive extraction of 6-aminopenicillanic acid with aliquat-336: Equilibrium and kinetics

The reactive extraction of 6-aminopenicillanic acid (6-APA) from aqueous buffer solution has been studied using a liquid anion exchanger, tricaprylylmethyl ammonium chloride (Aliquat-336) in n-butyl acetate as the solvent. The extraction equilibrium constant and partition coefficient increase with increase in pH up to a limiting value of pH, beyond which extraction decreases due to coextraction of OH^? and buffer anions and hydrolytic decomposition of 6-APA. The experimental data could be predicted from an equilibrium model which takes into account the ideal behaviour of the two liquid phases. The coextraction of the buffer anion under low pH conditions was found to be negligible. The extraction rate measured in a stirred cell of constant interfacial area appears to be dependent on the interfacial mass transfer of the reactive species as well as on the interfacial reaction through its dependence on the concentration of 6-APA in the aqueous and organic phases, respectively.     

EXTRACTION KINETICS OF ZINC BY TRILAURYLAMM0NIUM CHLORIDE AT DIFFERENT CHLORIDE CONCENTRATIONS

The rate of the extraction of zinc by trilaurylammonium chloride (TLAHC1) dissolved in toluene was investigated at different aqueous chloride concentrations, using lithium chloride as bulk electrolyte, ranging from 0.5 mol.dm -3 to 2.0 mol dm -3. The experiments were performed using a modified Lewis cell at 25?°C. The rate of metal extraction was found to increase by increasing the aqueous chloride concentration. The data treatment indicated that ZnCl₂ and ZnCl₄ ^2- are both kinetically active species. The addition reaction with ZnCl₂ is favoured at low chloride concentration while the anion exchange of ZnCl₄ ^2- prevails at high chloride concentration. The addition reaction was explained in terms or interfacial reaction steps. The anion exchange reaction, due to its fast nature, seems to be controlled by diffusion.     

离子液体-磷酸三丁酯体系分离盐湖卤水镁锂

将一种典型的室温离子液体(ionic liquids, ILs)1-辛基-3-甲基咪唑六氟磷酸盐作为替代溶剂用于盐湖卤水萃取锂。在该萃取体系中, 离子液体和磷酸三丁酯(TBP)分别用作萃取介质和萃取剂。详细考察了水相酸度、相比等因素对锂分离效率的影响。初步结果表明:与传统萃取体系相比, 该离子液体萃取体系能极大提高萃取效率。该体系最优条件包括: TBP/ILs=9/1(体积比), 相比O/A=2:1, 水相的pH萃取前不需要调节。在此条件下, 锂和镁的单级萃取效率分别为80.64%和5.30%。经过三级逆流萃取, 锂的萃取率高达99.42%。在温度为80℃, 反萃相比A/O为2的条件下, 锂和镁的单级反萃效率分别为98.78%和99.15%。反萃水相中的镁锂比(Mg/Li)降至3.03, 与初始值相比降低了93.41%。     

离子液体体系用于盐湖卤水提取锂

3种咪唑类离子液体:1-丁基-3-甲基咪唑六氟磷酸盐([C₄mim][PF₆])、1-己基-3-甲基咪唑六氟磷酸盐([C₆mim][PF₆])、1-辛基-3-甲基咪唑六氟磷酸盐([C₈mim][PF₆])被作为绿色溶剂用于盐湖卤水分离镁锂, 建立了以离子液体(ILs)、磷酸三丁酯(TBP)分别为萃取介质和萃取剂的盐湖卤水锂萃取体系, 并与使用传统有机溶剂磺化煤油和氯仿的萃取效果进行了对比。研究发现, 该离子液体体系较使用传统挥发性有机溶剂的萃取体系有更高的萃取率。锂的萃取率随离子液体中烷基碳原子数的减小而增加。详细考察了溶液pH、离子液体浓度、相比对萃取效率的影响, 获得了离子液体体系萃取的最优条件。在最佳萃取条件下, 3种离子液体体系对锂的单级萃取效率均高于80%, 分离系数最高达到100以上。机理研究表明:离子液体体系是以阳离子交换实现对锂的萃取, Li⁺与TBP形成[Li·2TBP]⁺络合物进入有机相。     

Characterization of naphthalene dicarboxylic acids. 3. Separation on Dowex 1-× 8 anion-exchange resin

The 10 isomeric naphthalene dicarboxylic acids have been eluted from a column of Dowex 1 anion exchange resin using potassium bromide 0–1 M. By comparison of their behaviour, it now seems possible that failure to observe these acids in the sub-humic acids of Lawson and co-workers may have been due to use of ions of strength insufficient for their elution.     

电化学提锂技术中电极材料和电极体系的研究进展

锂及其化合物具有广泛的应用前景,锂资源需求越来越大,因此,开发能实现高储量、低品位的（浓）海水/卤水锂资源高效提取的方法具有重要意义。近年来,电化学提锂技术因其高选择性、低能耗和环境友好等特点而成为研究热点。本文针对电化学提锂技术中锂吸附电极材料的选择/制备和电极体系构建两方面的研究进展进行了归纳分析。在锂吸附电极材料的选择/制备上,基于高锂离子选择性的LiFePO₄、LiMn₂O₄和LiNi_1/3Co_1/3Mn_1/3O₂电极被逐渐开发应用。在电极体系构建上,与具有阴离子可逆交换性能的AgCl、ZnCl₂和聚吡咯对电极所构成的电极体系可避免副反应发生,能耗较低;不含其他对电极材料的“摇椅式”结构电极体系可降低电极成本,提高提锂效率。此外,指出了目前电化学提锂技术尚存在的不足,未来可从电极材料制备、提锂过程优化、装备设计三方面进行研究,以推进电化学提锂技术的发展与应用。     

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.     

从浓缩盐湖卤水中萃取分离锂的实验研究

采用溶剂萃取法,对中国青海某盐湖浓缩后的高镁锂比老卤中的锂进行分离提取,系统考察了萃取剂浓度、萃取相比、卤水酸度等因素对锂萃取率的影响。对富锂有机相进行反萃取,考察了反萃取相比、反萃剂盐酸浓度等条件对锂负载有机相反萃取的影响。萃取工艺对从高镁锂比盐湖卤水中分离锂具有较好的应用前景。     

Dilute solution properties of naphthalene-labelled acrylamide/N,N-dimethyl maleimido propyl ammonium propane sulphonate copolymer

The aqueous solution properties of an ampholytic naphthalene-labelled acrylamide/N,N-dimethyl maleimido propyl ammonium propane sulphonate copolymer, poly(ADMMAPS)/NA, are examined in this study by measuring reduced and intrinsic viscosities. The intrinsic viscosity of the poly(ADMMAPS)/NA is related to the type and concentration of the salt added. This behaviour, resulting from the associations of the polymer chains, is in contrast with cationic and anionic polyelectrolytes. Smaller anions, such as F^-, with a common cation (K⁺) are found to be the most difficult to be bound to the sulphonate group, indicating that a lower intrinsic viscosity of the poly(ADMMAPS)/NA would be found in aqueous KF solution. Smaller cations, such as Li⁺, with a common anion (Cl^-) are found to be the most difficult to be bound to the quaternary ammonium group, indicating that a lower intrinsic viscosity of the poly(ADMMAPS)/NA would be found in LiCl salt aqueous solution. Because a naphthalene label was introduced into the polymer, the behaviour of the solution properties of the poly(ADMMAPS)/NA could be clearly defined in term of macroscopic and microscopic analysis. The models proposed in this study can account for the poly(ADMMAPS)/NA solution viscosities. © 1998 SCI.     

Chemistry of organosulphur compound types occurring in heavy oil sands : 5. Reaction of thiophene and tetrahydrothiophene with aqueous Group VIIIB metal species at high temperature

As part of a study of organosulphur compounds in heavy oil sands, the interaction of thiophene (1) and tetrahydrothiophene (10) with aqueous solutions of Group VIIIB metal species at 200–240 °C has been investigated. Thiophene was the more reactive and the greatest degree of reaction was observed with the second- and third-row members of the Group VIIIB metals. Aqueous Pt(IV) gave most reaction for both substances. Desulphurization of the sulphur compounds was significant, although conversion to more complex organic substances, including dithienyls and benzothiophene, account for > 50 wt % of the total reaction for most metal species. The presence of CO₂ in the products showed that water was involved in the reaction. Reactions with thiophene produced only minor amounts of C₁---C₄ hydrocarbons, but significant quantities were obtained from reactions with tetrahydrothiophene.     

The anodic behaviour of zinc in aqueous KOH solution—I. Passivation experiments at very high current densities

The anodic behaviour of zinc in aqueous potassium hydroxide has been investigated at very high cds (1–10 A/cm²). Galvanostatic experiments have been made in aqueous KOH (1–12·8 M) for reaction times 0·1 s–0·2 ms.

The relationship between the cd and the passivation time follows a √ t relationship. The forms of the overpotential/time curves indicate changes in the ohmic component of the total polarization.

Within the time range investigated no evidence was found for a change in the mode of passivation.

The effect of an increase of temperature was to increase the passivation time: the magnitude of the increase was greater than expected from the increase in the diffusion coefficient alone.     

Back extraction of platinum metals from liquid membranes in an electric field

A new method for back extraction of platinum metals from the salts of tertiary amines and quaternary onium bases in the organic phase is proposed. This method allows the back extraction of platinum metals into diluted solutions of mineral acids over one stage. The method involves the passing of direct current through a system in which the extract containing a platinum metal is a liquid membrane. This method allows a practically complete back extraction of the anions PtCl₆ ^2-, RuNOCl₅ ^2- and Ru₂OCl₁₀ ^4- (the latter passes into the aqueous phase without breaking the dimer anion). It was found that when PtCl₆ ^2-, PdCl₄ ^2- and Ru₂OCl₁₀ ^4- are in a liquid membrane based on Oct₃NHCl in 1.2-dichloroethane, under the action of an electric field all these anions are transferred into aqueous 1 M HCl (E > 85%). To provide maximum back extraction of platinum metal anions, it is necessary to use small concentrations of extractants in 1.2-dichloroethane (0.1 M for Oct₃NHCl and 0.03–0.04 M both for Oct₄NCl and Ph₄PCl) over the period of the back extraction. Cyclic voltametry has demonstrated the determining role of chloroions in current transport through the interface of phases I and II.     

改性剂种类对蒙脱土结构和性能的影响

为增加蒙脱土(montmorillonite,MMT)和有机物的相容性和研究插层剂种类对MMT结构和性能的影响,采用Cu,Co和Ni无机金属阳离子,十二烷基磺酸钠、十二烷基硫酸钠、α-烯烃磺酸盐和十二烷基苯磺酸钠等有机阴离子表面活性剂及十六烷基氯化吡啶、十六烷基三甲基溴化铵、十二烷基三甲基溴化铵等有机阳离子表面活性剂作为改性剂,对蒙脱土进行一次改性和二次改性,制备出一系列改性蒙脱土.研究了改性剂种类、插层方式、插层次序对插层效果的影响.X射线衍射分析表明:一次改性时,插层剂均能进入蒙脱土的层间,改性土的层间距由1.04nm增加到1.7～3.52nm;二次改性时,先阳离子后阴离子的插层顺序有利于层间距增大(4.14nm),还可利用配位作用将二次改性剂引入金属离子一次改性MMT中,使层间距增大.改性机理研究认为:阳离子改性机理为层间离子交换,而阴离子改性机理是改性剂和MMT表面形成了氢键.沉降实验表明一次改性土和二次改性土在有机溶剂中分散能力有所增强.     

Extraction of Lanthanides(III) with N,N′-Bis(Diphenylphosphinyl-Methylcarbonyl)Diaza-18-Crown-6 in the Presence of Ionic Liquids

The extraction of microquantities of La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, and Y from nitric acid solutions into an organic phase containing N,N′-bis(diphenylphosphinyl-methylcarbonyl)diaza-18-crown-6 and ionic liquid (IL) 1-butyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide (BMImTf₂N) has been studied. The effect of HNO₃ concentration in the aqueous phase and that of the extractant and IL concentration in the organic phase on the extraction of metal ions is considered. The stoichiometry of the extracted complexes has been determined. A considerable synergistic effect was observed in the presence of IL in the organic phase containing a neutral organophosphorus ligand. This effect is connected with the hydrophobic nature of the IL anion. The partition of IL between the equilibrium organic and aqueous phases is the dominant factor governing the extractability of lanthanide (III) ions in the extraction system. The potentialities of polymeric resin impregnated with compound I and BMImTf₂N for the preconcentration of lanthanides(III) from nitric acid solutions are demonstrated.     

The Partition Behavior of Zn(II) using Halide Ions Extractants in Aqueous Peg‐Based Two‐Phase Systems

Abstract

The partition behavior of Zn(II) has been studied in aqueous polyethylene glycol PEG(1550) – (NH₄)₂SO₄ two‐phase system using halide ions (Cl^?, Br^? and I^?) as extracting agents, at two different values of salt stock solution pH. The efficiency of extractants increase in this order: Cl^?>Br^?>I^?. The extracted species were estimated from the distribution coefficients' values determined as a function of halide ions concentration, and the “conditional extraction constants” were calculated. The experimental results suggest that the Zn(II) partition in presence of halide ions in such systems is the result of two competitive processes. The IR spectra of solidified PEG‐rich phases show that the passing of metal species into PEG‐rich phases bring a supplementary water contribution, which makes the extraction process to occurs until it reaches an “equilibrium state”, dependent on the hydrophobicity of these phases and not on the type of extracted metal species.