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.     

高效去除水溶液中重金属离子的氧化石墨烯基材料的综述

综述了氧化石墨烯(graphene oxide,GO)基纳米材料对水溶液中各种重金属离子的优异去除能力的最新研究成果。重点论述了吸附剂的合成,吸附过程特征及相互作用机理,概述了各种环境条件的影响。综述旨在为设计和制造GO基纳米材料提供有用的信息,以消除环境污染管理中废水中的重金属离子。此外,简要概述,并提出了这一鼓舞人心的领域所面临的挑战和前景。     

Adsorption of heavy metal ions from aqueous solution by fly ash

The removal characteristics of lead and copper ions from aqueous solution by fly ash were investigated under various conditions of contact time, pH and temperature. The influence of pH of the metal ion solutions on the uptake levels of the metal ions by fly ash were carried out between pH 4 and 12. The level of uptake of Pb²⁺ and Cu²⁺ ions by the fly ash generally increased, but not in a progressive manner, at higher pH values. The effect of temperature on the uptake of Pb²⁺ and Cu²⁺ ions was investigated between 30 °C and 60 °C, the adsorption of being enhanced at the lowest temperature. Rate constants were evaluated in terms of a first-order kinetics. The rate constant, k for uptake of Pb²⁺ and Cu²⁺ ions were 1.77 × 10⁻² s⁻¹ and 2.11 × 10⁻² s⁻¹, respectively. The experimental results underline the potential of coal fly ash for the recovery of metal ions from waste water. The main mechanisms involved in the removal of heavy metal ions from solution were adsorption at the surface of the fly ash and precipitation.     

Simultaneous removal of humic acid and heavy metal from aqueous solutions using charged ultrafiltration membranes

Lab-made negatively charged ultrafiltration (UF) membranes were used for simultaneous removal of humic acid (HA) and heavy metals from water. Effects of the HA/metal ratio, solution pH and ionic strength on rejection coefficients of HA and metals were investigated. The results showed that the rejection coefficients of both HA and metals increase with the increase of pH and the HA/metal ratio, and the decrease of ionic strength. This study indicated that charged UF could be an effective method for the simultaneous removal of HA and heavy metal harnessing the principle of complexation UF and electrostatic repulsion between the membrane and the HA–M complex of the same charges.     

Application of a carbon sorbent for the removal of cadmium and other heavy metal ions from aqueous solution

Treatment of flax shive with sulfuric acid produces a carbonaceous material that has been used to remove metal ions from aqueous solution. Metal ions including Cd(II), Cu(II), Cr(III), Co(II), Ni(II), Zn(II) and Pb(II) have been investigated for kinetic behaviour and sorption capacities. These metal ions show fast sorption kinetics following a first order rate equation. Cadmium was chosen as representative of these metal ions and a detailed study was carried out. The effect of pH on sorption was studied and it was found that maximum uptake occurred above pH 3–7, sorption was accompanied by release of protons into the solution and a ratio of [H⁺] released to [Cd²⁺] sorbed of approximately 2 was found. The sorption capacity showed no significant increase with increase of temperature. The presence of other metal ions such as K⁺, Na⁺, Mg²⁺ and Ca²⁺ decreases the Cd(II) capacity, indicating competition for the ion exchange sites. Successive sorption of Cd(II) shows that the capacity exceeds the monolayer capacity calculated from the Langmuir equation. Column studies showed good performance over a total of seven cycles of loading/stripping. These studies indicate that the sorption mechanism for these metal ions is related to a reversible ion exchange process on the carbon surface. © 2002 Society of Chemical Industry     

Utilization of some starch derivatives in heavy metal ions removal

Three types of starch derivatives containing amide groups were used in removal of heavy metal ions from their solutions. These starch derivatives were poly(acrylamide)–starch graft copolymer, carbamoylethylated starch, and starch carbamate. The different factors affecting metal ion adsorption on these substrates, such as pH, metal ion concentration, type of starch derivatives, treatment time, and temperature, were studied. Results obtained indicate that the poly(acrylamide)–starch graft copolymer was a selective adsorbant for Hg²⁺ at pH 0.5–1. The adsorption values ofdifferent metal ions on these starch derivatives follow the order of Hg²⁺ > Cu²⁺ > Zn²⁺ > Ni²⁺ > Co²⁺ > Cd²⁺ > Pb²⁺. The adsorption values depend upon pH, type of starch derivative, treatment duration, and temperature. The adsorption efficiency percentage of metal ions on the three substrates follows the order of carbamoylethylated starch > poly(acrylamide) − starch graft copolymer > starch carbamate. © 1998 John Wiley & Sons, Inc. J Appl Polm Sci 69: 45–50, 1998     

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.     

Selective biosorption of mixed heavy metal ions using polysaccharides

Although much research has been conducted on the separation of single species of heavy metal, the selective adsorption of two or more heavy metals in mixture is relatively little known. In this study, polysaccharide beads were prepared to selectively remove the targeted heavy metal ion from mixture. Among the biomasses, polysaccharide was examined due to its low cost and easy accessibility. In a single metal ion system, chitosan, λ-carrageenan, and alginic acid showed high affinity to mercury, copper, and lead, respectively. In the ion mixture, the same trend shown in the single metal ion solution was observed. The optimum electrolyte concentraion was investigated to adsorb the metal ion selectively, and it was possible to remove the targeted metal ion selectively with chitosan, alginic acid and λ-carrageenan at 1 mmol concentration of electrolyte. In order to demonstrate the feasibility of selective biosorption, two packed-bed reactors in series containing chitosan and alginic acid beads in each were studied and selective adsorption to Hg²⁺ and Pb²⁺, respectively, was observed.     

Influence of operating parameters on chromic ions removal from aqueous solution by liquid membranes

This paper presents the possibility of using liquid membranes as a separation and concentration technique to facilitate the recovery of Cr(VI) from water. Chromium(VI) being highly carcinogenic and mutagenic, it is necessary for risk assessment to remove and concentrate it in order to re-use it instead of reducing Cr(VI) to Cr(III). A separation scheme has been designed, using liquid membranes and rotating disk modules as contactors. Separation and enrichment can be simultaneously achieved in the same apparatus. Four operation parameters are considered : rotating disks speed, flow rate of chromium solution, initial chromium concentration and membrane volume. Experiments are performed in continuous mode. Estimation of the mass transfer coefficients is performed using macroscopic mass balances.     

Preparation of amidoximated polyester fiber and competitive adsorption of some heavy metal ions from aqueous solution onto this fiber

In this study, a fibrous adsorbent containing amidoxime groups was prepared by graft copolymerization of acrylonitrile (AN) onto poly(ethylene terephthalate) (PET) fibers using benzoyl peroxide (Bz₂O₂) as initiator in aqueous solution, and subsequent chemical modification of cyano groups by reaction with hydroxylamine hydrochloride in methanol. The grafted and modified fibers were characterized by FTIR, TGA, SEM, and XRD analysis. The crystallinity increased, but thermal stability decreased with grafting and amidoximation. The removal of Cu(II), Ni(II), Co(II), Pb(II), and Cd(II) ions from aqueous solution onto chelating fibers were studied using batch adsorption method. These properties were investigated under competitive conditions. The effects of the pH, contact time, and initial ion concentration on the removal percentage of ions were studied. The results show that the adsorption rate of metal ions followed the given order Co(II) > Pb(II) > Cd(II) > Ni(II) > Cu(II). The percentage removal of ions increased with initial ion concentration, shaking time, and pH of the medium. Total metal ion removal capacity was 49.75 mg/g fiber on amidoximated fiber. It was observed that amidoximated fibers can be regenerated by acid without losing their activity, and it is more selective for Pb(II) ions in the mixed solution of Pb‐Cu‐Ni–Co‐Cd at pH 4. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Boron removal from aqueous solution by using plasma-modified and unmodified anion-exchange membranes

The removal of boron from aqueous solution through plasma-modified and unmodified AFX anion-exchange membrane was investigated by the Donnan dialysis (DD) method. The surface of anion-exchange membrane was treated by electron cyclotron resonance plasma (ECR) to enhance the performance. The effects of plasma-modified anion-exchange membrane and initial boron concentration on the boron removal were investigated at 25 °C. The optimum pH was chosen as 9.5 from the literature data. The flux values (J) and recovery factor (RF) of boron were obtained before and after the plasma modification. Under Donnan dialysis conditions, flux values and recovery factors of boron were calculated and the highest values were obtained for plasma-modified AFX membrane as compared with the unmodified one. This situation can be explained by change of morphology of pores in the plasma-modified membrane. In addition, the different valence anions also influence the flux of boron and the order of flux was found as Cl⁻ > SO₄²⁻.     

Hydrophilic polystyrene/maleic anhydride ultrafine fibrous membranes

Polystyrene/maleic anhydride (PSMA) was synthesized to reach a viscosity‐average molecular weight of 700 kDa and fabricated into ultrafine fibrous membranes consisting of fibers with an average diameter of 300 nm. These ultrafine PSMA fibers were rendered insoluble in organic solvents by reactions with hydrazine and ethylenediamine (ED). The highly efficient incorporation of diamines into the fibrous membranes was easily achieved by brief immersions in either dilute (0.5 wt %) hydrazine for 1 min or ED ether solution for 2 min. Heating at 150°C for 5 min produced crosslinked PSMA with very little or no solubility in acetone with the retention of the fibrous membrane structure. The ED‐crosslinked membranes were particularly stable to both bases and acids as well as hydrophilic solvents, had a 46° water contact angle, and absorbed 22 times the amount of water as the as‐spun fibrous membrane. This post‐fiber‐formation crosslinking approach was robust, highly efficient, and fast and required very little crosslinking reagent. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

A study of removal of Pb heavy metal ions from aqueous solution using lignite and a new cheap adsorbent (lignite washing plant tailings)

The present study determines the efficiency with which lignite and lignite washing plant tailings can adsorb Pb heavy metal ions. In the first experiment, the effect of size distribution on the absorbance capacity was investigated for the samples. Therefore, lignite sample was ground to five sizes (d₈₀ = 0.600, 0.355, 0.250, 0.106 and 0.063 mm) under nitrogen (N₂), and the tailings sample was classified into seven fractions, along with the original state (original state: d₆₀ = 0.063, −1 + 0.600, −0.600 + 0.355, −0.355 + 0.250, −0.250 + 0.106, −0.106 + 0.063 and −0.063 mm). The test results showed that the optimum size distributions for lignite and tailings were d₈₀ = 0.063 mm and the original state (d₆₀ = 0.063 mm), respectively. Simultaneously, the adsorption capacity results of the two optimum sizes were compared with each other, and the tailings sample (d₆₀ = 0.063 mm) gave the best results, with 9.30 mg/g Pb ions adsorbed value. Therefore, in the second study, a series of laboratory experiments using 2³ full factorial designs was conducted to determine the optimum pH, contact time and initial metal concentration using the original tailings sample. The experimental studies showed that pH 9, a 120 min contact time and 300 ppm initial metal concentration gave the best results, namely an adsorption of 29.92 mg Pb ions/g.     

Removal of heavy‐metal ions from aqueous solution with nanochelating resins based on poly(styrene‐alt‐maleic anhydride)

Chelating resins have been considered to be suitable materials for the recovery of heavy metals in water treatments. A chelating resin based on modified poly(styrene‐alt‐maleic anhydride) with 2‐aminopyridine was synthesized. This modified resin was further reacted with 1,2‐diaminoethan or 1,3‐diaminopropane in the presence of ultrasonic irradiation for the preparation of a tridimensional chelating resin on the nanoscale for the recovery of heavy metals from aqueous solutions. The adsorption behavior of Fe²⁺, Cu²⁺, Zn²⁺, and Pb²⁺ ions were investigated by the synthesis of chelating resins at various pH's. The prepared resins showed a good tendency for removing the selected metal ions from aqueous solution, even at acidic pH. Also, the prepared resins were examined for the removal of metal ions from industrial wastewater and were shown to be very efficient at adsorption in the cases of Cu²⁺, Fe²⁺, and Pb²⁺. However; the adsorption of Zn²⁺ was lower than those of the others. The resin was characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, X‐ray diffraction analysis, and differential scanning calorimetry analysis. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

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.     

Hydrazinodeoxycellulose for collection of metal ions from aqueous solution

We measured ellipsometrically the adsorption of polystyrene and polymethylmethacrylate on high-vacuum-vapoured chromium-, platinum- and gold-mirrors from various solvents under variation of the molecular weight of polymers. For both polymers we find an increase in thickness and adsorbed amount with an increase in polymer-concentration of solution. The concentration of the adsorbed polystyrene-film decreases, the concentration of the adsorbed polymethylmethacrylate-film increase with the polymer concentration of solution. Molecules of high molecular weight produce bigger thicknesses and adsorbed amounts than molecules of low molecular weight. With increasing polarity of the adsorbent we find an increase of thickness and amount of the adsorbed layer and a decrease of concentration. An increasing polarity of the solvent results in a decrease of thickness and amount and in an increase of concentration of the adsorbed layer. In saturation the polystyrene-molecules adsorb in the conformation of statistical coils. For the polar PMMA-molecules we find a divergent behaviour of the adsorption as a result of the strong interactions between the polar polymer-segments.     

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。     

Thiourea modified hyper‐crosslinked polystyrene resin for heavy metal ions removal from aqueous solutions

A hyper‐crosslinked resin chemically modified with thiourea (TM‐HPS) was synthesized, characterized, and evaluated for the removal of heavy metal ions (Pb²⁺, Cd²⁺, and Cu²⁺) from aqueous solutions. The structural characterization results showed that a few thiourea groups were grafted on the surface of the resin with a big BET surface area and a large number of narrow micropores. Various experimental conditions such as pH, contact time, temperature, and initial metal concentration of the three heavy metal ions onto TM‐HPS were investigated systematically. The results indicated that the prepared resin was effective for the removal of the heavy metal ions from aqueous solutions. The isotherm data could be better fitted by Langmuir model, yielding maximum adsorption capacities of 689.65, 432.90, and 290.69 mg/g for Pd²⁺, Cd²⁺, and Cu²⁺, respectively. And the adsorption kinetics of the three metal ions followed the pseudo‐second‐order equation. FTIR and XPS analysis of TM‐HPS before and after adsorption further revealed that the adsorption mechanism could be a synergistic effect between functional groups and metal ions and electrostatic attraction, which may provide a new insight into the design of highly effective adsorbents and their potential technological applications for the removal of heavy metal ions from aqueous solutions. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45568.     

Removal of strontium ions from aqueous solution using hybrid membranes: Kinetics and thermodynamics

The removal of radionuclide from radioactive wastewater has captured much attention. Strontium-90 is one of the major radionuclides. To develop a new type of adsorbents to remove strontium ions from the radioactive wastewater, in this study, novel hybrid membranes were prepared and characterized. The adsorption kinetics, thermodynamic parameters of ΔG, ΔH and ΔS, as well as surface SEM and EDS images were used to investigate the removal of strontium ions from stimulated radioactive wastewater using the previously prepared hybrid membranes as efficient adsorbents. The study of kinetic model confirmed that the adsorption of strontium ions on these hybrid membranes followed the Lagergren pseudo-second order model. Moreover, it was proved that the adsorption of strontium ions on these samples was solely controlled by intraparticle diffusion. The negative values of ΔG and the positive values of ΔH indicated that the adsorption of strontium ions on samples A-D is a spontaneous and endothermic process in nature. Furthermore, surface SEM and DES images give significant evidence to confirm the existence of strontiumions on the surface of the adsorbed samples. These findings demonstrate that these hybrid membranes are promising adsorbents for the removal of strontium ions from aqueous solution and can be potentially applied in the adsorptive separation of radionuclides from the radioactive wastewater.