Sorption of Pb(II), Cd(II) and Zn(II) by iminodiacetate chelating resins in non-competitive and competitive conditions

Two chelating resins (CRs) bearing iminodiacetate (IDA) groups derived from acrylonitrile - divinylbenzene (AN-DVB) copolymers having 10 and 15 wt.% nominal cross-linking degrees and a high mobility of the functional groups caused by the presence of a longer spacer between the matrix and the IDA groups were synthesized and tested as sorbents for heavy metal ions like: Pb(II), Cd(II) and Zn(II) from aqueous solutions by batch and column techniques. Experimental data obtained from batch equilibrium tests have been analyzed by two isotherm models: Freundlich and Langmuir. The overall adsorption tendency of CRs toward Pb(II), Cd(II) and Zn(II), under non-competitive conditions, followed the order: Cd(II) > Pb(II) > Zn(II). Selectivity studies were performed in ternary mixture of Pb(II), Cd(II) and Zn(II) to check if the synthesized CRs can be useful for selective separation of heavy metal cations. The results revealed that the CRs with IDA groups exhibited high selectivity toward Pb(II), both in batch and column techniques. Regeneration of the resins was achieved using 0.1 M HCl solution.     

Analysis of Extraction of Cu(II) by Strip Dispersion Hybrid Liquid Membrane (SDHLM) using PMBP as Carrier

A liquid membrane system, denoted a strip dispersion hybrid liquid membrane (SDHLM) containing 1‐phenyl‐3‐methyl‐4‐benzoyl‐pyrazolone –5 as carrier in xylene, was reported for the transport and separation of Cu(II) from Zn (II) ions. The effects of various factors on the transport of copper(II) ions through SDHLM were systematically investigated by orthogonal tests. The optimum transport conditions of copper ions were summarized. In the overall mass transfer process the mass transfer resistance due to the aqueous boundary layer diffusion and diffusion in the microporous membrane is dominant. The accumulation of the Cu(II)‐carrier coordination compound in the membrane shows that the transfer in SDHLM possesses the characteristic of nonequlibrium mass transfer in this study. The rheologic experiments verified that the organic phase in the SDHLM system was the non‐Newtonian fluid and the organic phase after transport of 6 hr was a system of thixotropy in our experimental conditions. The lag ring experiments proved that the thixotropy of the organic phase in the SDHLM system was relevant to the composition of the membrane. In the experimental comparison of two types of liquid membrane, SDHLM has superiority over SLM in respect of transport flux, permeability coefficient, recovery percentage or concentration of solute in the stripping solution, efficiency of uphill transport, loss of membrane solution, and the separation efficiency of the membrane.     

Distribution Behavior of Nb,Ta, and Pa as Homologues of Db in Cation Exchange and Solid-Liquid and Liquid-Liquid Extractions by Aliquat 336 from Hydrochloric Acid

Detailed chemical studies on transactinide elements will clarify their characteristic properties caused by strong relativistic effect. In this work, to realize chemical study on transactinide element ₁₀₅Db, cation exchange, and solid-liquid and liquid-liquid extractions of micro amounts of Nb, Ta (homologues of Db), and Pa (pseudo homologue) by Aliquat 336 were performed employing hydrochloric acid. Clearly different chloride complex formations and distribution reaction kinetics were observed among these elements, and the present results are useful for studying the chemical properties of Db. Based on these results, we propose suitable experimental conditions for Db.     

Synergistic Solvent Extraction and Transport of Zn(II) and Cu(II) across Polymer Inclusion Membranes with a Mixture of TOPO and Aliquat 336

Separation of zinc(II) and copper(II) ions from aqueous solutions by synergistic extraction and transport through polymer inclusion membranes (PIMs) has been investigated. A mixture of trioctylphosphine oxide (TOPO) and trioctymethylammonium chloride (Aliquat 336) was used as a selective extractant as well as an ion carrier in polymer membranes. The effects of hydrochloric acid concentration in the aqueous phase and extractants concentration in the organic phase on the separation process of zinc(II) and copper(II) ions have been studied. Zn(II) ions were successfully separated from Cu(II) ions in solvent extraction process using 0.025 M TOPO and 0.06 M Aliquat 336 in kerosene. Polymer inclusion membranes (PIMs) containing a mixture of TOPO and Aliquat 336 as the ion carrier have been prepared and the facilitated transport of Zn(II) and Cu(II) ions has been studied. The influence of membrane composition on the transport kinetic of Zn(II) and Cu(II) has been evaluated. Zn(II) ions were preferably transported from the aqueous solutions containing Cu(II) and above 87% of Zn(II) ions were effectively recovered from the 0.5 M HCl solution as the source phase through PIM into 0.5 M H₂SO₄ as the stripping phase.     

ZnCl2–NH4Cl溶液中锌配合离子的阴极还原

采用多种电化学方法探讨了ZnCl2–NH4Cl溶液配制液中精炼锌的阴极过程. 结果表明：Zn(II)离子在ZnCl2–NH4Cl溶液配制液中阴极还原生成金属锌的电极过程，具有两电荷放电一步完成和电荷转移控制的不可逆电极过程动力学规律，Zn(II)离子在此溶液配制液中主要以[Zn(NH3)4]2+配合离子存在，而直接在阴极放电的配合离子物种是[Zn(NH3)2]2+.     

Selective extraction,separation and recovery of Cu(II) in presence of Zn(II) and Ni(II) from leach liquor of waste printed circuit board using microcapsules coated with Cyanex 272

The study was conducted to optimize the selective extraction and recovery of Cu(II) in the presence of Zn(II) and Ni(II) from the leach liquor of waste printed circuit boards (PCBs). The extraction experiments were carried out according to 2⁴ factorial design of experiment to optimize the extraction factors. The design was analyzed using MINITAB to determine the main effects and interactions of the chosen extraction factors. The factors chosen were: extraction pH, amount of Cyanex 272 in dispersed phase during MC-Xs preparation, amount of MC-Xs and temperature. The pH, amount of MC-Xs and temperature were found to be statistically significant. The optimized experimental conditions for the Cu(II) extraction in presence of Zn(II) and Ni(II) were extraction pH 6.0, amount of Cyanex 272 in dispersed phase 3 g, amount of MC-Xs 2.5 g and Temperature 45 °C. Factorial design of experiment was also carried out to determine the Cu(II) stripping factors from the loaded MC-Xs using H₂SO₄ solution. The liquid-liquid extraction Cu(II) was conducted with the prime aim to evaluate the nature of Cu(II) complex extracted by Cyanex 272. Results showed that the extraction species is [Cu(HA₂)(Ac)·2HA]. Finally, a complete process for the separation and recovery of Cu(II), Zn(II) and Ni(II) from the leach liquor of waste PCBs was conducted based on the optimized experimental condition and effect of pH on extraction.     

Removal of Cu(II) and Zn(II) Using Lignocellulosic Fiber Derived from Citrus reticulata (Kinnow) Waste Biomass

Abstract

The biosorption of Cu(II) and Zn(II) using dried untreated and pretreated Citrus reticulata waste biomass were evaluated. The Cu(II) and Zn(II) sorption were found to be dependent on the solution pH, the biosorbent dose, the biosorbent particle size, the shaking speed, the temperature, the initial metal ions (800 mg/L), and the contact time. Twenty-eight physical and chemical pretreatments of Citrus reticulata waste biomass were evaluated for the sorption of Cu(II) and Zn(II) from aqueous solutions. The results indicated that biomass pretreated with sulphuric acid and EDTA had maximum Cu(II) and Zn(II) uptake capacity of 87.14 mg/g and 86.4 mg/g respectively. Moreover, the Langmuir isotherm model fitted well than the Freundlich model with R ² > 0.95 for both metal ions. The sorption of Cu(II) and Zn(II) occurred rapidly in the first 120 min and the equilibrium was reached in 240 min. FTIR and SEM studies were also carried out to investigate functional groups present in the biomass and the surface morphological changes of biomass.     

An automated system for liquid-liquid extraction in monosegmented flow analysis

An automated system to perform liquid-liquid extraction in monosegmented flow analysis is described. The system is controlled by a microcomputer that can track the localization of the aqueous monosegmented sample in the manifold. Optical switches are employed to sense the gas-liquid interface of the air bubbles that define the monosegment. The logical level changes, generated by the switches, are flagged by the computer through a home-made interface that also contains the analogue-to-digital converter for signal acquisition. The sequence of operations, necessary for a single extraction or for concentration of the analyte in the organic phase, is triggered by these logical transitions. The system was evaluated for extraction of Cd(II), Cu(II) and Zn(II) and concentration of Cd(II) from aqueous solutions at pH 9.9 (NH₃/NH₄Cl buffer) into chloroform containing PAN (1-(2-pyridylazo)-2-naphthol) . The results show a mean repeatability of 3% (rsd) for a 2.0 mg l^-1 Cd(II) solution and a linear increase of the concentration factor for a 0.5mg l^-1 Cd(II) solution observed for up to nine extraction cycles.     

Kinetics of alkaline hydrolysis of 2-ethylbutylformate

The theory of mass transfer accompanied by chemical reaction has been used for studying the kinetics of alkaline hydrolysis of 2-ethylbutylformate at different temperatures and ionic strengths of aqueous alkaline solution. Experiments have been conducted in a stirred cell having a flat liquid-liquid interface. For aqueous phases containing 1–3 kmol/m³ sodium hydroxide, the alkaline hydrolysis conforms to the fast pseudo-first order reaction regime. The system is of considerable practical importance and can be successfully employed for the measurement of the interfacial area of a mechanically-agitated and flooded packed-bed liquid-liquid contactor.     

Simultaneous Transport and Separation of Cu(II) and Zn(II) in Cu-Zn-Co Sulfate Solution by Double Strip Dispersion Hybrid Liquid Membrane (SDHLM)

A double strip dispersion hybrid liquid membrane (SDHLM) was successfully used in the simultaneous extraction and separation of Cu(II), Zn(II), and Co(II) from Cu-Zn-Co dilute feed phase. In the double SDHLM system, Acorga M5640-loaded membrane was placed between the 1st and the 2nd compartment, whereas the mono(2-ethylhexyl) 2-ethylhexyl phosphonate [HEH(EHP)]-loaded membrane was placed between the 1st and the 3rd compartment of the transport cell. The feed solution was filled in the central feed compartment(1st compartment) of the transport cell. The effect of the different experimental variables on separation was examined. The optimum separation conditions were summarized.

An analysis of mass transfer resistances in the double SDHLM system shows that the mass transfer resistance for the diffusion of Zn(II) ions in the microporous membrane phase is dominant and the mass transfer resistances for the diffusion of copper (II) ions in the aqueous boundary layer and in the microporous membrane phase are dominant in comparison with the overall mass transfer resistance. The experiments verify that the double strip dispersion hybrid liquid membrane (SDHLM) possesses the nonequlibrium mass transfer characteristic.     

Photoredox processes in the Cr(VI)–Cr(III)–oxalate system and their environmental relevance

Irradiation of the [Cr(C₂O₄)₃]³⁻ complex or the chromate(VI)–oxalate mixture, or the ternary system composed of Cr(III), Cr(VI) and oxalate, leads to chromium photoreductions in consequence of the ligand to metal charge transfer (LMCT) excitations induced by artificial solar radiation. In the case of the Cr(III) complex, the photoreduction involves the innersphere electron transfer leading to the formation of the Cr(II) species and the C₂O₄⁻ radicals. On reacting with molecular oxygen, Cr(II) is oxidised to Cr(III) catalysing thereby the oxalate substitution reaction. Moreover, under specific conditions, Cr(II) can be also oxidised to Cr(VI). Chromate(VI) is not photoreducible, but in the presence of oxalate, or other sacrificial electron donor, the outersphere photoinduced electron transfer (PET) produces Cr(V) species and the C₂O₄⁻ radicals. This initiates a series of thermal reactions leading to the formation of Cr(III) and oxidized oxalate (CO₂). In the system composed of [Cr(C₂O₄)₃]³⁻ and chromate(VI), the acidic medium and anoxic conditions favour the Cr(VI) photoreduction, whereas alkaline oxygenated solutions assist the Cr(VI) photoproduction. When an approximately neutral solution equilibrated with the ambient air is irradiated intermittently, Cr(VI) is consumed and/or produced, accordingly to the time sequence of exposure and dark periods. The oscillations of Cr(VI) concentrations are accompanied by continuous oxidation of oxalate, playing the role of the sacrificial electron donor. The effects of solution pH, molecular oxygen, concentrations of reagents and cations on the reaction rates were investigated. The results of this paper revealed that the Cr(III)/Cr(VI) system under environmental conditions behaves as the photocatalytic one catalysing the oxidation of oxalate or other organic matter by molecular oxygen, contributing thereby to the abatement of pollution.     

Sorption Behavior of Dowex PSR-2 and Dowex PSR-3 Resins of Different Structures for Metal(II) Removal

The sorption behavior of palladium(II) (Pd(II)) onto strongly basic anion exchange Dowex resins was studied depending on the concentration of hydrochloric acid (0.1–6.0 M HCl–100 mg Pd(II)/L), concentration of hydrochloric and nitric(V) acids (0.1–0.9 M HCl–0.9–0.1 M HNO₃–100 mg Pd(II)/L), and the time of contact of the solution with the anion exchange resin in the batch mode. Similar research was carried out also for the base metal ions such as cobalt(II) (Co(II)), copper(II) (Cu(II)), nickel(II) (Ni(II)), and zinc(II) (Zn(II)). The sorption process was also examined depending on the initial Pd(II) concentration, agitation rate, bead size distribution, and temperature. Pd(II) sorption was also checked in the column mode. The equilibrium and kinetic characteristics of the sorption of Pd(II) with the Dowex PSR-2 and Dowex PSR-3 anion exchange resins were determined. The possibilities of Pd(II) elution and reuse using the batch method was exploited. Pd(II) and Zn(II) sorption on the Dowex resins is time and concentration of acids dependent. Evaluating the determination coefficients, the kinetic studies showed that the pseudo-second-order equation and the Langmuir model described the data more appropriately than others. The maximum sorption capacity was 165.15 mg Pd(II)/g for Dowex PSR-2 and 184.39 mg Pd(II)/g for Dowex PSR-3. Dowex resins give quantitative Pd(II) removal from diluted acidic solutions.     

Effect of competitive interference on the biosorption of lead(II) by Chlorella vulgaris

Batch experiments were carried out to asses the effect of Cu(II) and Zn(II) on the biosorption of lead(II) ions by non-living Chlorella vulgaris. The uptake of Pb(II) was examined for single, binary and ternary solutions at different initial concentrations and different pH values. The experimental results showed that the uptake increased with increasing pH from 3.0 to an optimum value of 5.0. The biosorption of Pb(II) was found to be adversely affected by the presence of Cu(II) ions, while Zn(II) ions seemed to have negligible effect on the process. The equilibrium data were fitted to four isotherm models: Langmuir, Freundlich, Sips and Dubinin–Radushkevich; the Sips isotherm gave the best fit for the data. Modeling of the controlling mechanisms indicated that both intrinsic kinetics and mass transfer played major roles in controlling the process. A new dimensionless parameter, Ψ, was defined to asses the relative contributions of the two mechanisms to the biosorption of lead(II). Mass transfer seemed to be the dominant mechanism at low initial lead(II) concentrations, while intrinsic kinetics dominates at high concentrations.     

微通道中钒的液-液流型和萃取传质动力学研究

采用伯胺N1923萃取剂在微通道中研究V(V)的液-液流型和萃取传质动力学,以15vol% N1923作为连续相、钒氧酸根水溶液作为分散相,研究不同流速下两不混溶相的流型变化规律及两相停留时间和微通道管径作为流速的函数对传质的影响。随两相流速增大,段塞流长度和比界面面积基本不变,且两相流体由Raydrop微通道流入外接毛细管微通道时由于微通道的扩张会改变两相流动方式,使同一实验条件下在微通道中同时出现多种流型,与此同时两相流速和总体积传质系数(kLa)呈正相关,表明流型在本研究体系中对传质的影响可忽略。在相同管径通道内,停留时间与总体积传质系数呈负相关,表明在两相接触通道入口处发生了显著传质。在相同的两相混合速度和相比下,254 μm的管径传质效果是750 μm的9倍,表明小管径内传质效果更加,循环强度更大。最后将实验总体积传质系数结果与总体积传质系数的经验式进行了关联,有望为实现将微通道放大的绿色冶金技术提供理论基础。     

Sorption of Cu(II) from Ammoniacal Solutions into α-Zirconium(IV) bismonohydrogenphosphate (α-ZrP) Intercalated with Butylamine

Abstract

Studies on the sorption of tetraamminecopper(II) complex from ammoniacal solutions of various compositions into α-ZrP modified with butylamine were performed in the temperature range of 40 to 80°C. The experimental results were discussed in terms of first-order reaction kinetics. The activation energy of sorption of Cu(II) into modified α-ZrP was found to be equal to 46.1 ± 3 kJ/mol. The effects of the concentrations of ammonia and ammonium sulfate were also examined. Pure and modified α-ZrP loaded with tetraamminecopper(II) were characterized by means of elemental analysis, X-ray diffractometry, FTIR, and Raman spectroscopy. Copper was recovered quantitatively from pure and modified α-ZrP at room temperature using 0.5 M HCl solution.     

Regulatory effects of Zn(II) on the recognition properties of metal coordination imprinted polymers

Using a Zn(II)–quercetin complex as a template (quercetin is a kind of flavonoid; flavonoids are important active ingredients of Chinese herbs), we prepared a new kind of metal coordination imprinted polymer (MCIP) in methanol by a molecular imprinting technique. The coordination mode and coordination ratio between quercetin and Zn(II) were studied in differential ultraviolet absorption spectrometry, and the ternary coordination of quercetin, Zn(II), and 4‐vinylpyridine was verified by similar methods. The effect of the crosslinking agent dosage on the morphology and network structure of MCIP and its binding capacity were studied by transmission electron microscopy and equilibrium binding experiments. The regulation of different anions and cations on the identification system of MCIP was studied in detail. In addition, the binding characteristics of MCIP were evaluated by Scatchard analysis. The experimental results show that the Zn(II)–quercetin imprinted polymer had selective binding to its template complex, including selectivities to the anions and cations, and a class of homogeneous recognition sites was formed in the polymer within the range of studied concentration. The dissociation constant and most apparent specific adsorption amount of the Zn(II)–quercetin imprinted polymer was calculated to be 0.6983 mmol/L and 78.72 μmol/g, respectively. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

微通道内液-液两相流研究进展

从流型、传质和应用3个方面,介绍了近年来微通道内液-液两相流的研究进展。液-液两相流型研究内容主要有两部分,即流型的观察、流型谱图的绘制以及考察多种因素对流型的影响,但是具有普适性的流型谱图和流型转变线仍未提出。液-液两相传质研究方法包括实验研究和数值模拟两种,主要研究在液滴流、弹状流和平行流3种稳定流型下的传质过程;且相对于定性研究,定量的传质研究较少。对于微通道内液-液两相流应用研究,主要体现在萃取、材料合成、生物结晶等方面。此外,对今后微通道内液-液两相的流型、传质和应用研究进行了展望,指出需从实验与模拟计算相结合以及拓展微通道内液-液两相流的应用研究两个方面进行深入研究,推进其工业化进程。     

Mass transfer and chemical test reactions in the continuous flow rotor-stator mixer

This work is on mass transfer in liquid-liquid two-phase systems. To study mass transfer in the continuous flow in-line rotor-stator mixer, a method based on experimental determination of the product distribution of a set of complex chemical reactions has been applied together with drop breakage experiments. Experiments were carried out using the high-shear rotor-stator Silverson mixer for both drop dispersion and intensification of mass transfer. Volume fraction of organic phase was in the range between 0.01 and 0.015. The product distribution of complex reactions was determined based on high-performance liquid chromatography measurements. The drop size distribution was measured with the Malvern MasterSizer just after the process. Results of modeling of mass transfer with chemical reaction were used to characterise energetic efficiency of mass transfer.     

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.     

KINETICS AND MECHANISM OF THE INTERFACIAL MASS TRANSFER OF Zn2+, Co2+, Ni2+ IN THE SYSTEM: BIS(2-ETHYLHEXYL)PHOSPHORIC ACID,n-DODECANE - KNO3, WATER

ABSTRACT

The mass transfer rate of Zn(II), Co(II) and Ni(II) between aqueous nitrate solutions and n-dodecane solutions of the organic soluble ligand HDEHP has been investigated using a forced convection, constant interfacial area stirred cell. The distribution ratios necessary to evaluate the kinetic experiments have been determined and the equilibrium constants which describe the heterogeneous complex formation reaction between Zn²⁺, Co²⁺, Ni²⁺ and HDEHP have been evaluated. The results have been interpreted according to two limiting models: 1) the mass transfer rate is controlled by slow reversible interfacial reactions, 2) the mass transfer is controlled by interfacial film diffusion. Both models are adequate to Interpret the experimental data. The conclusion Is reached that, if interfacial chemical reactions are rate controlling, rate constants of interfacial complex formation reactions independent of the nature of the cation are obtained. This result supports a reaction mechanism which is rate controlled by the microscopic diffusion of the cation through a viscous and structured layer of interfacial water adjacent to the liquid interface