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.     

Sorption of heavy metal ions from aqueous solutions in the presence of EDTA on monodisperse anion exchangers

Conventional precipitation methods of industrial sewage and wastewater purification are not very effective and are insufficient in many cases. This implies the necessity of searching new, effective methods exploiting cheap, accessible and ecologically safe ion exchangers and sorbents. The paper presents the studies on removal of heavy metal ions — Cu(II), Zn(II), Co(II), Ni(II) and Fe(III) — from aqueous solutions in the presence of EDTA carried out on commercially available, strongly basic monodisperse anion exchangers with the polystyrene skeleton gel, Lewatit MonoPlus M 500; and the macroporous, Lewatit MonoPlus MP 500, which are more widely applied in water purification processes. The research results indicate a high affinity of the Lewatit MonoPlus M 500 and Lewatit MonoPlus MP 500 anion exchangers in the chloride form for copper(II), nickel(II), cobalt(II) and zinc(II) complexes with EDTA. The affinity series for the heavy metal complexes in the 0.001 M M(II)/(III)–0.001 M EDTA and 0.001 M M(II)/(III)–0.001M EDTA–0.001 M–0.002 M NaOH systems were found for the Lewatit MonoPlus M 500 anion exchanger in the chloride form to be as follows: Cu(II) > Ni(II) > Co(II) > Zn(II) Fe(III). In the case of the Lewatit MonoPlus MP 500 anion exchanger in the chloride form there was found the following affinity series: Cu(II) > Co(II) > Ni(II) > Zn(II) Fe(III). These anion exchangers can be applied in the removal of copper(II) complexes from waters and wastewaters.     

Studies of sorption of Pd(II) microquantities on strongly basic polyacrylate anion exchangers

The sorption of palladium(II) microquantities from a chloride and chloride-nitrate (V) model 0.1-6.0 M HCl, 0.1-0.9 M HCl-0.9-0.1 M HNO₃, 1.0 M ZnCl₂-0.1 M HCl and 1.0 M AlCl₃-0.1 M HCl systems on strongly basic polyacrylate anion exchangers was studied. The research was carried out by means of dynamic and static methods. The recovery factors of Pd(II) were determined from the static studies. The working ion-exchange capacities as well as weight and bed distribution coefficients of Pd(II) were calculated from the breakthrough curves. The commercial strongly basic anion exchangers of the functional quaternary ammonium groups — Purolite A-850 and Amberlite IRA-958 — can be used in recovery technologies of Pd(II) from anodic slime, wastewaters and spent catalysts due to their high selectivity.     

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 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.     

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.     

Unforseen factors influencing Fe(III)‐containing cations sorption on strongly basic anion exchangers

The sorption and partial destruction of the Fe(III)‐containing compounds in the aqueous medium in strongly basic anion exchangers AV‐17 and Varion‐AD phase have been investigated. It is shown that partial destruction of the Fe (III) compounds in acidulated water (pH = 2) and in K₂SO₄, Fe₂(SO₄)₃ solutions takes place. With increasing of temperature up to 50°C, the desorption degree of the iron ions from polymer phase decreases. In dried polymer, the structural and electronic state of iron compounds, according to their magnetic susceptibility, remains stable for a long time. The sorption of the Fe(III)‐containing cations at 50°C during 12 h depends essentially on the sizes of polymer granules. Sorption increases with growing of polymer granules. For comparison of sorptional capacities, the sorption of Fe(III)‐containing cations was determined on different cation and anion exchangers. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Hydrophilic PVA-co-PE nanofiber membrane functionalized with iminodiacetic acid by solid-phase synthesis for heavy metal ions removal

A novel hydrophilic poly(vinyl alcohol-co-ethylene) (PVA-co-PE) nanofiber membrane for heavy metal ions removal was fabricated by the solid phase synthesis of iminodiacetic acid (IDA) on nanofiber membrane surfaces. The hydrophilic PVA-co-PE nanofiber membranes were activated with cyanuric chloride. The IDA was then covalently linked to the activated PVA-co-PE nanofiber membranes. The chemical structures of activated and functionalized PVA-co-PE nanofiber membranes were confirmed with FTIR–ATR. The morphology of PVA-co-PE nanofiber membranes were characterized with SEM. The increase in the amount of IDA on functionalized PVA-co-PE nanofiber membranes significantly improved the adsorption amount of Cu²⁺. The IDA functionalized PVA-co-PE nanofiber membranes demonstrated excellent adsorption capability of Cu²⁺, Co²⁺, Zn²⁺ and Ni²⁺. The adsorption of above heavy metal ions could be repeatedly regenerated by desorbing the ions adsorbed on nanofiber membranes. The novel IDA functionalized PVA-co-PE nanofiber membranes have great potential in the application of industry and drinking water treatment.     

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 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.     

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。     

层状复合氢氧化物的结构调控及其吸附重金属离子的研究进展

层状复合氢氧化物（LDHs）是具有特殊层状结构的阴离子黏土,具有化学组成可调、比表面积大及结构记忆效应独特等性质,在废水处理方面备受关注。调控LDHs自身结构,是进一步扩大其应用范围、提高其吸附性能的有效途径。该文介绍了LDHs特殊的层状结构和其自身性质;总结了LDHs最常用的制备方法,即共沉淀法、离子交换法、尿素水解法、煅烧复原法和溶胶-凝胶法等,分别介绍了各种制备方法的原理和特点;综述了LDHs的结构调控对其吸附重金属离子性能的影响,并总结了LDHs对重金属离子的吸附机理;最后,指出了目前LDHs在处理含有重金属离子废水研究中面临的挑战,并对该材料未来的研究方向和发展趋势进行了展望。     

吸附重金属离子活性炭再生工艺研究

为评价吸附后活性炭再生效果,对吸附重金属离子活性炭的再生工艺进行了研究。考察了各因素对再生活性炭性能的影响。结果表明:升高再生温度及延长再生时间,活性炭质量损耗率随之上升,活性炭性能恢复率随之增加。增加再生次数,活性炭质量损耗率随之上升,活性炭性能恢复率随之降低。     

New chelating polymers for heavy metal ion sorption

Twenty‐six new chelating polymers containing pyridyl (Py) or bipyridyl (Bipy) units as ligating centers were synthesized by free‐radical reactions of 2‐vinylpyridine, 4‐vinylpyridine, or 4‐methyl‐4′‐vinyl‐2,2′‐bipyridine with different dimethacrylate crosslinkers and evaluated for heavy metal ion sorption from aqueous solutions. Both the Py‐ and Bipy‐containing polymers are highly selective for Cu(II) over Co(II) and Ni(II) and for Hg(II) over Cd(II). The polymeric materials with Bipy binding sites generally exhibit more efficient metal ion sorption than do the corresponding Py‐containing copolymers. The metal ion sorption capacity of the copolymer also depends on the structure of the dimethacrylate crosslinker. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 849–856, 1999     

Acrylic weak‐base anion exchangers and their behaviors in the retention process of some heavy‐metal cations

Two macroporous acrylonitrile/10% vinyl acetate/10% divinylbenzene copolymers as beads were obtained by the aqueous suspension copolymerization of the three comonomers in the presence of toluene as a diluent, which was used in two different amounts. These copolymers were chemically modified by their reactions with ethylenediamine, diethylenetriamine, and triethylenetetramine in the presence of water when the aminolysis–hydrolysis reaction of the nitrile groups and the hydrolysis reaction of the acetate groups occurred. From these reactions, weak‐base anion exchangers with high ion‐exchange capacities, between 1.6 and 2.2 mequiv/mL and 6.5 and 10.5 mequiv/g, were obtained. For these anion exchangers, the behaviors in the retention processes of the Ni(II), Cd(II), and Pb(II) cations were evaluated with the bath method. All the resins exhibited retention properties, but the retained amounts of the metal cations differed as a function of the resin and cation nature. Thus, the resin from the reaction with triethylenetetramine of the copolymer obtained in the presence of a larger amount of toluene could be considered the most suitable sorbent for the three metal cations, especially for Ni(II). Its maximum retention capacity for this cation was 2.67 mequiv/g of dried resin. From the noncompetitive and competitive retentions was observed the following selectivity order: Ni(II) > Cd(II) > Pb(II). The retention took place by the chelating processes between the functional groups with the ligand role, especially free amine groups, and metal cations. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 930–938, 2005     

细菌纤维素对重金属离子的吸附机理研究

以细菌纤维素(BC)为吸附剂,对重金属离子Cu2+,Pb2+和Cd2+的吸附等温线和吸附动力学特性进行了研究,并采用红外光谱分析法探讨了吸附作用机理。结果表明:BC对Cu2+,Pb2+和Cd2+吸附更好地符合Langmuir吸附等温方程和准二级反应动力学模型,说明吸附过程为单分子层吸附,化学吸附作用为主。粒子内扩散拟合曲线均不经过原点,证明粒子内扩散并不是唯一速率控制步骤。FT-IR分析表明吸附金属离子后的BC中—OH最大吸收位发生不同程度的蓝移,说明BC中部分—OH参与吸附,即与重金属离子之间发生反应,从而使—OH的数量减少。