Polyacrylate anion exchangers in sorption of heavy metal ions with non-biodegradable complexing agents

The polyacrylate anion exchangers are widely used in purification of heavy metal ions from wastewaters and different accompanying complexing agents. Such effluents containing the chelators (EDTA, NTA, HEDTA, DTPA, and IDA) are discharged from relevant industries such as printed circuits boards, plating on plastics, metal finishing and others. The sorption was studied as a function of phase contact time and pH by the batch technique. It was found that the removal of heavy metal ions in the presence of EDTA, NTA and IDA strictly depends on the phase contact time and pH values. Various kinetic models such as the pseudo first-order and the pseudo second-order as well as the intraparticle one were also tested to estimate the sorption rate. The equilibrium capacities of the studied anion exchangers for Cu(II), Zn(II), Co(II), Ni(II), Pb(II) and Cd(II) in the presence of EDTA were the highest for Pb(II) and Cd(II). The order of sorption for Amberlite IRA 458, Amberlite IRA 958 as well as Amberlite IRA 67 can be as follows: Pb(II) > Cd(II) > Zn(II) > Cu(II) > Ni(II) > Co(II). The stability of forming complexes was also compared. The estimation of the capacities of anion exchangers under investigation by the continuous column studies was also carried out.     

Polyacrylate anion exchangers in sorption of heavy metal ions with the biodegradable complexing agent

The removal of Co(II) and Ni(II) from aqueous solutions in the presence of complexing agent on the polyacrylate anion exchangers with different basicity of functional groups Amberlite IRA 458, Amberlite IRA 958 and Amberlite IRA 67 was described. The complexing agent Baypure CX 100 is a new generation of chelators, undergoing biodegradation. It constitutes an alternative for the reagents of EDTA or NTA type. The studies were carried out by the static (batch) and the dynamic (column) methods. The influence of several parameters such as ratio of M(II)–L, pH, temperature were studied with respect to sorption equilibrium. Sorption isotherms were obtained and fitted using the Langmuir and Freundlich models. Kinetic curves were fitted using the pseudo first-order, the pseudo second-order as well as the intraparticle diffusion model equations to evaluate most effective one. Physicochemical properties of anion exchangers such as their structure, basicity of functional groups were also taken into account. Additionally, the obtained results were compared with those for the weakly acidic cation exchanger Purolite C-104.     

Calixarene-based extractants for heavy metal ions removal from aqueous solutions

The article reviews the literature on the possibility of application of the calixarene-based compounds for selective separation of toxic heavy metals from aqueous solutions by the solvent extraction and transport across liquid membranes. The specific three-dimensional structure of calixarenes and their derivatives, simple and low-cost synthesis, and ease of chemical transformation qualify these compounds for the role of selective chemical extractants of toxic heavy metal ions present in industrial wastewater. This article analyses the influence of various process factors, with the greatest emphasis on the structure of the extractants/carriers, on efficient separation of heavy metal ions, primarily those most commonly found in galvanic wastewater.     

Adsorption of some heavy metal ions from aqueous solutions on Nafion 117 membrane

Nafion 117 membrane was investigated for the removal of Ni(II), Co(II), Pb(II), Cu(II) and Ag(I) metal ions from their synthesized aqueous solutions. The different variables affecting the adsorption capacity of the membrane such as contact time, initial metal ion concentration in the feed solution, pH of the sorption medium and temperature of the solution were investigated on a batch sorption basis. The affinity of Nafion 117 membrane towards heavy metal ions was found to increase in the sequence of Cu(II), Ni(II), Co(II), Pb(II), and Ag(I) with adsorption equilibrium achieved after 30 min for all metal ions. Among all parameters, pH has the most significant effect on the adsorption capacity, particularly in the range of 3.1-5.9. The variation of temperature in the range of 25-65 °C was found to have no significant effect on the adsorption capacity. Nafion 117 membrane was found to have high stability combined with repeated regeneration ability and can be suggested for effective removal of heavy metal ions such as Cu(II), Ni(II) and Co(II) from aqueous solutions.     

Sorption of Zn(II) and Pb(II) ions in the presence of the biodegradable complexing agent of a new generation

The macroporous chelating ion exchangers containing different functional groups i.e. Purolite S-920, Purolite S-930 and Lewatit TP-208 have been used in the sorption process of Zn(II) and Pb(II) ions. The effect of the presence of biodegradable, environmentally friendly aminopolycarboxylate chelating agent, trisodium salt of methylglycinediacetic acid (MGDA) on its sorption capacity was also examined. The investigations were carried out by the static method. Besides the effect of initial concentration of Zn(II) and Pb(II) and the complexing agent the research concerns the influence of solution pH, phase contact time on effectiveness of sorption. The equilibrium and kinetics of Zn(II)–MGDA and Pb(II)–MGDA complexes sorption were obtained and fitted using the Langmuir, Freundlich, Temkin and Dubinin–Radushkevich (D–R) models as well as the pseudo first and pseudo second order kinetic models. The intraparticle diffusion model was also used. The results showed that the sorption processes of Zn(II) and Pb(II) complexes with MGDA on Purolite S-920, Purolite S-930 and Lewatit TP-208 followed well the pseudo second order kinetics.     

Adsorption of heavy metal ions from aqueous solutions by porous polyacrylonitrile beads

The adsorption of Cu(II), Ni(II), Zn(II), and Pb(II) from aqueous solutions on acrylonitrile copolymer sorbents was studied. We prepared five types of sorbents from polyacrylonitrile by varying its concentration in the initial polymer solution and the composition of the coagulation bath, aiming to achieve a different porous structure. The specific area, pore volume, and pore radius of the sorbents were determined on a porosimeter. The porous structure was studied by scanning electron microscopy. Modification of sorbents with sodium hydroxide and hydroxylamine was carried out to form amidooxyme and carboxylic groups with proven complex‐forming properties toward heavy metal ions. The optimal pH of the sorption of metal ions was found. The adsorption kinetics were investigated. The order of polymer sorbents toward the sorption of Pb(II), Cu(II), Ni(II), and Zn(II) ions, and the order of heavy metal uptake were determined for all types of sorbents. The effectiveness of heavy metal desorption and the coefficient of recovery of sorption ability were determined. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 3036–3044, 2002; DOI 10.1002/app.2334     

Synthesis of a carbamide-based dithiocarbamate chelator for the removal of heavy metal ions from aqueous solutions

This study was carried out to develop a carbamide-based dithiocarbamate (CDTC) chelator for the removal of heavy metal ions from wastewater. Its structural properties were characterized by FT-IR, ¹H NMR and ¹³C NMR. Results confirmed the functional groups of HNC(S)S existed. The adsorption isotherms showed CDTC had a high adsorption capability for Zn (119.8 mg/g) and Cu (63.1 mg/g). It exhibited a distinctive selectivity for the removal of metal ions (Cu²⁺ > Zn²⁺ > Cr³⁺ > Pb²⁺ > Cd²⁺) as they coexisted. The influence of initial pH of wastewater for the removal efficiency of metal ions was also investigated and a pH > 7 was preferred.     

Retention of gallium ions from acidic solutions by pyridine strong‐base anion exchangers

Using the batch method, the retention of Ga(III) from HCl solutions by two gel‐type pyridine strong‐base anion exchangers containing 1‐methyl‐ or 1‐butyl‐4‐vinylpyridinium chloride structural units, called S₁ and S₂ resins, respectively, was studied. The influence of the HCl and Ga(III) concentrations as well as of the contact time between the resin and the liquid phase was investigated. The parameters, which characterize the retention process, were estimated using Langmuir and Freundlich isotherms. Both resins exhibited a higher affinity for gallium ions from a 6M HCl solution. According to Langmuir isotherms, maximum retention capacities of 44.44 and 60 mg Ga(III)/g dry resin for the S₁ and S₂ resins, respectively, were obtained. Freundlich isotherms provide additional proof for a higher affinity of the S₂ resin for Ga(III) from HCl solutions. It is clear that the substituent length increase on N⁺ atoms led to an increasing affinity of the pyridine strong base anion exchangers toward Ga(III). © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3440–3444, 2002     

Sorption studies of heavy metal ions on pectin-nano-titanium dioxide composite adsorbent

The Cu(II), Cd(II), Zn(II), and Pb(II) sorption kinetics and equilibrium on hybrid material, composed of pectin and titanium dioxide nanopowder, were examined. Parameters, such as pH and adsorbent dose, were also investigated. The experimental data were better described by the Langmuir model. The maximum adsorption capacities were 1.37, 0.68, 0.51, and 0.83 mmol/g for Cu(II), Cd(II), Zn(II), and Pb(II), respectively. The introduction of nano-TiO₂ improved the kinetics of the metal ion sorption. The titanium dioxide, despite its small content (6%), contributes to the removal of the examined metal ions and eventually to the adsorption capacity of hybrid beads.     

用酵母菌吸附处理废水中重金属离子研究现状

酵母菌作为一种生物吸附剂,廉价易得,对重金属、低pH及其它外界条件有较强的耐受度.利用酵母菌,特别是固定化酵母菌吸附废水中的重金属离子,不仅成本低、去除率高、再生能力强,而且对吸附的重金属易于回收.随着相关技术的发展,酵母菌吸附剂必将在废水处理中得到更广泛的应用.     

Sorption of Cr(III)‐containing cations on strongly basic anion exchangers

It is shown that strongly basic anion exchangers AV‐17 and Varion‐AD in definite conditions are able to retain Cr(III)‐containing ions from Cr(III) sulfate solution. It is found that the sorption of Cr(III)‐containing ions on the polymers is essentially dependent on the pH, temperature, and Cr(III) sulfate concentration. The maximum temperature dependence of sorption was found to be about 60°C. The sorption isotherms are well described by Langmuir's equations. The sorption kinetics is determined by the diffusion of Cr(III)‐containing ions into polymer's phase. It is assumed that the Cr(III)‐containing ions are retained through formation, in polymer's phase, of the jarosite‐type mineral compounds: R₄N[Cr₃(OH)₆(SO₄)₂], H₃O[Cr₃(OH)₆(SO₄)₂], and K[Cr₃(OH)₆(SO₄)₂]. For comparison of sorptional capacities, the sorption of Cr(III)‐containing ions was determined on different cation and anion exchangers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3978–3985, 2006     

Removal of heavy metal ions by dithiocarbamate-anchored polymer/organosmectite composites

In this study, the dithiocarbamate-anchored polymer/organosmectite composites were prepared for the removal of heavy metal ions (lead, cadmium and chromium) from aqueous media containing different amounts of these ions (50–750 ppm) and at different pH values (2.0–8.0). Initially, the modification of the natural smectite minerals was performed by treatment with quartamin styrene and chloromethylstyrene. Then, modified smectite nanocomposites were reacted with carbondisulfide, in order to incorporate dithiocarbamate functional groups into the nanolayer of organoclay. The dithiocarbamate-anchored nano-composites have been characterized by FTIR and used in the adsorption–desorption process. The maximum adsorptions of heavy metal ions onto the dithiocarbamate-anchored polymer/organosmectite composites from their solution was 170.7 mg g^− 1 for Pb(II); 82.2 mg g^− 1 for Cd(II) and 71.1 mg g^− 1 for Cr(III). Competition between heavy metal ions (in the case of adsorption from mixture) yielded adsorption capacities of 70.4 mg g^− 1 for Pb(II); 31.8 mg g^− 1 for Cd(II) and 20.3 mg g^− 1 for Cr(III). Desorption of the heavy metal ions from composite was studied in 0.5 M NaCl and very high desorption rates, greater than 93%, were achieved in all cases. Adsorption–desorption cycles showed the feasibility of repeated uses of this nanocomposite.     

啤酒酵母对重金属离子的吸附和解吸效果影响的实验研究

以固定化的啤酒酵母作为生物吸附剂,海藻酸钠和聚乙烯醇作为包埋剂,研究了pH值、ρ(初始重金属离子)、ρ(菌体)、吸附时间、吸附温度对吸附Pb2+、Cu2+、Zn2+和Cd2+的影响,并进行了解吸剂及其质量浓度对固定化啤酒酵母解吸影响的研究.研究结果表明,在pH值=5.5,ρ(菌体)=20 g/L,吸附时间2h,吸附温度...     

Determination of heavy metal ions in mixed solution by imprinted SAMs

Specific selectivity toward different heavy metal ions could be introduced into self-assembled monolayers (SAMs) by ion imprinting. In the mixed solution, good response toward mercury ions could be obtained on mercury ions imprinted SAMs, the copper ions imprinted SAMs presented good selectivity toward copper ions, while on lead ions imprinted SAMs, significantly higher insertion of lead ions than mercury and copper ions were observed. Linear calibration plots were obtained for each heavy metal ion and the regression equations were: [Hg(II)]/(10⁻⁶ M), [Cu(II)]/(10⁻⁶ M) and [Pb(II)]/(10⁻⁶ M) for mercury, copper and lead ions, respectively. The detection limits were determined to be: 1.46×10⁻⁸ M for Hg(II), 3.73×10⁻⁸ M for Cu(II) and 4.34×10⁻⁸ M Pb(II). The decreases in current response for mercury, copper and lead ions in the presence of 100-fold interferential ions were: 3.37%, 9.16% and 7.60%, respectively. Acceptable recoveries were obtained in mixed solutions at both high and low concentrations.     

Sorption equilibrium of Cr(VI) ions by strong base anion exchangers with pyridine structures

Chromate sorption on pyridine strong base anion exchangers with different functional groups (methyl, ethyl, and butyl groups), at the quaternary nitrogen atoms, was studied as a function of various initial concentrations (100–1500 mg Cr/L) and counterion type. The studied resins in the Cl^?[ form have higher Cr(VI)‐retention capacities than those in the SO form. The pyridine strong base anion exchangers showed a selectivity reversal for the sulfate and chromate anions compared to that of the commercial resins. The alkyl substituent length of the quaternary nitrogen atoms exerted a substantial influence on the Cr(VI)‐retention capacity values for the resins in the Cl^? form; the chromate anions preferred resins with methyl functional groups, that is, resins with a greater hydrophilic structure. For the resins in the SO form the length of the substituent at the quaternary nitrogen atom had only a negligible influence on their Cr(VI)‐retention values. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1957–1963, 2004     

PVA cryogel membranes as a promising tool for the retention and separation of metal ions from aqueous solutions

The sorption and transport of metal ions by poly(vinyl alcohol) hydrogel membranes (PVA HG), obtained by physical crosslinking through the freezing/thawing method, was analyzed using aqueous nitrate solutions of copper, lead, and nickel, at concentrations ranging from 1 to 100 mM, at 25°C. The sorption of heavy metal by PVA HG has been characterized by swelling and loading degrees. The effect of the heavy metals incorporation on the chemical properties of PVA HG matrices has been studied using SEM, to observe changes in the surface morphology of PVA HG membranes, and FTIR–ATR, aiming to monitor the heavy metals ions sorption into PVA hydrogel membranes. The analysis of permeation and diffusion coefficients of 100 mM aqueous solutions of Cu²⁺, Ni²⁺, and Pb²⁺ show that the diffusion process may be mainly described by hydrodynamic models; however, the transport process shows that the distribution coefficient for the different heavy metals are always higher than one, in agreement, with the sorption studies. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation of DNA-encapsulated polyethersulfone hollow microspheres for organic compounds and heavy metal ions removal

DNA-encapsulated polyethersulfone (PES) hollow microspheres are fabricated by means of a liquid-liquid phase separation technique; the hollow microspheres are then used to remove environmental pollutant organic compounds and heavy metal ions. The amounts of DNA encapsulated in the microspheres are dependent on the PES concentration, the DNA concentration used to prepare the particles, and the diameter of the syringe needle. The hollow microspheres can be used to remove harmful organic compounds including ethidium bromide (EB), acridine orange (AO) and endocrine disruptors. With the increase of the DNA amount encapsulated into the hollow microspheres, the removal ratios of these compounds increased. Additionally, the DNA-encapsulated PES hollow microspheres can selectively accumulate and remove heavy metal ions such as Ag⁺, Cu²⁺ and Zn²⁺ These results suggested that the DNA-encapsulated PES hollow microspheres have a potential to be used in environmental applications.     

重金属离子脱除技术进展

综述了脱除水中重金属离子的各类主要方法 ,侧重介绍了近年来开发的若干新技术。     

Sorption of Cd(II)-MGDA Complexes on Polyacrylate Anion Exchangers

The possibility of polyacrylic anion exchangers application in the removal of Cd(II) complexes with MGDA (methylglycinediacetic acid) from aqueous solutions was presented. Batch sorption experiments were performed using Amberlite IRA 458 and Amberlite IRA 958. The initial solution pH, the initial concentration of sorbed complexes in the molar ratio M(II)-MGDA = 1:1, the temperature, as well as the contact time were varied. The kinetics of Cd(II) sorption in the presence of MGDA was analyzed. The Langmuir, Freundlich, Temkin, and Dubinin-Radushkevich models were also applied to describe the adsorption isotherm. The values of the thermodynamic parameters (ΔG°, ΔH°, and ΔS°) indicated that in the majority of cases the sorption process was spontaneous and endothermic. From the determined breakthrough curves, the distribution coefficients and the ion exchange capacities were calculated.