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     

Conversion of soybean oil into ion exchange resins: Removal of copper (II), nickel (II), and cobalt (II) ions from dilute aqueous solution using carboxylate‐containing resin

An ion‐exchange resin containing carboxylic acid groups was prepared by reaction of epoxidized soybean oil with triethylene tetramine, followed by hydrolysis of glycerides by using sodium hydroxide solution. The cation exchange capacity of the resins was determined to be 3.50 mequiv/g. The adsorption capacity for Cu²⁺, Ni²⁺, and Co²⁺ on the obtained resin at pH 5.0 was found to be 192, 96, and 78 mg/g, respectively. Effect of pH on the adsorption capacity for copper (II), nickel (II), and cobalt (II) ions were also studied. Cu²⁺, Ni²⁺, and Co²⁺ were adsorbed at a pH above 3. These metal ions adsorbed on the resin are easily eluted by using 1N HCl solution. The selectivity of the resin for Cu²⁺ from mixtures containing Cu²⁺/Co²⁺/Ni²⁺ ions in the presence of sodium chloride was also investigated © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2386–2396, 2002     

Sorption properties of the iminodiacetate ion exchange resin,amberlite IRC‐718, toward divalent metal ions

The sorption properties of the commercially available cationic exchange resin, Amberlite IRC‐718, that has the iminodiacetic acid functionality, toward the divalent metal‐ions, Fe²⁺, Cu²⁺, Zn²⁺, and Ni²⁺ were investigated by a batch equilibration technique at 25°C as a function of contact time, metal ion concentration, mass of resin used, and pH. Results of the study revealed that the resin exhibited higher capacities and a more pronounced adsorption toward Fe²⁺ and that the metal‐ion uptake follows the order: Fe²⁺ > Cu²⁺> Zn²⁺ >Ni²⁺. The adsorption and binding capacity of the resin toward the various metal ions investigated are discussed. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

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.     

Studies of Retention and Reusable Capacities of Melamine Formaldehyde Based Terpolymer Against Some Toxic Metal Ions by Batch Equilibrium Method

Chelating terpolymer resin was synthesized and characterized by elemental, physico-chemical, spectral, SEM, XRD, and GPC to elucidate the structure and properties of the terpolymer. Ion-exchange analysis involving evaluation of metal ion uptake in different electrolyte concentrations, pH, and time have been studied to assess the retention capacities of the terpolymer for the metal ions viz. Fe³⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, and Pb²⁺. The adsorption isotherm was evaluated using the Langmuir and Freundlich isotherms models and the results were found best fitting with each other. The resin can be successfully used in the field of recovery of metal ions from effluents and contaminated water.     

Preparation and adsorption properties of poly(N‐vinylformamide/acrylonitrile) chelating fiber for heavy metal ions

In this article we report a new chelating fiber that was prepared from a hydrolyzate of poly(N‐vinylformamide/acrylonitrile) by a wet‐spinning method. This fiber contains chelating groups, such as amidine groups, amino groups, cyano groups, and amide groups, with high densities. We examined the chelating abilities for several metal ions with this fiber, and present the morphological merit of the fibrous product compared with the globular resin. Based on the research results, it is shown that the fiber has higher binding capacities and better adsorption properties for heavy metal ions than the resin. The pH value of the metal ion solution shows strong influences on the adsorption of the metal ions. The maximum adsorption capacities of the fiber for Cu²⁺, Cr³⁺, Co²⁺, Ni²⁺, and Mn²⁺ are 112.23, 88.11, 141.04, 108.06, and 73.51 mg/g, respectively. In mixed metal ions solution, the fiber adsorbs Cr³⁺, Cu²⁺ and Co²⁺ efficiently. The adsorbed metal ions can be quantitatively eluted by hydrochloric acid. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1378–1386, 2002     

Preparation of Chelating Resins Containing a Pair of Neighboring Carboxylic Acid Groups and the Adsorption Characteristics for Heavy Metal Ions

Abstract

For the functional enhancement of chelating resins containing carboxylic acids, copolymer beads were prepared by suspension polymerization of styrene (St), methyl methacrylate (MMA), and divinylbenzene (DVB) in the presence of toluene as diluent. The phenyl rings of the beads were directly chloromethylated, and the carboxylic ester groups of the beads were converted into hydroxymethyl groups by reduction followed by chlorination to give chloromethyl groups, respectively. The chelating resins containing a pair of neighboring carboxylic acid groups (NCAGs) were obtained by the alkylation of chloromethyl groups in copolymer beads with diethyl malonate in the presence of sodium hydride followed by hydrolysis using aqueous alkali solution. Accordingly, the structural effects of the resins on the adsorption of heavy metal ions were investigated. Poly(St‐co‐DVB)‐based chelating resin containing NCAGs showed adsorption abilities toward heavy metal ions like Pb²⁺, Cd²⁺, and Cu²⁺, whereas poly(MMA‐co‐DVB)‐based chelating resin containing NCAGs showed adsorption abilities toward heavy metal ions like Cu²⁺, Cd²⁺, and Co²⁺. On the other hand, poly(St‐co‐MMA‐co‐DVB)‐based chelating resin containing NCAGs showed adsorption abilities toward heavy metal ions like Pb²⁺, Cd²⁺, Hg²⁺, Co²⁺, and Cu²⁺: a synergistic effect on the adsorption of heavy metal ions like Pb²⁺, Cd²⁺, Hg²⁺, and Co²⁺ was observed. The adsorption ability of poly(St‐co‐MMA‐co‐DVB)‐based chelating resin among three kinds of chelating resins was relatively good.     

Synthesis,characterization, and metal adsorption properties of tannin–phenol–formaldehyde resins produced using tannin from dried fruit of Terminalia chebula (Aralu)

In this study, tannin extracted from Terminalia chebula (Aralu) was used to produce tannin–phenol–formaldehyde resins. They were produced to obtain resins with different tannin to phenol ratio in an attempt to optimize the ion exchange capacities of resins produced. The resins made were sulfonated to improve their properties further. Bivalent cations, such as Zn²⁺, Pb²⁺, Ca²⁺, Mg²⁺, and Cu²⁺, were used to estimate the adsorption properties of both unsulfonated and sulfonated resins. The glass transitions of representative resins were estimated using differential scanning calorimeter thermograms. Fourier transform infrared spectroscopic analysis was used to gauge changes on resins by sulfonation and adsorption of cations. The glass transition values of unsulfonated, sulfonated, and metal‐adsorbed sulfonated resins showed a similar increasing trend with the increase of phenol content in the resin. The glass transition temperature values reach a plateau beyond the tannin/phenol ratio of 1 : 0.5, indicating the formation of large molar masses facilitating entanglements beyond that ratio. The phenol ratio of 1 : 0.5 has shown the highest adsorption capacity for all the metal ions used. The highest adsorption capacity was shown for sulfonated tannin–phenol–formaldehyde resin with the tannin/phenol ratio of 1 : 0.5 for Pb²⁺, which is 0.610 meq/g. The adsorption equilibrium data obtained using the column technique were found fitting Freundlich isotherm. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis and adsorption properties of macroporous cross‐linked polystyrene that contains an immobilizing 2,5‐dimercapto‐1,3,4‐thiodiazole with tetraethylene glycol spacers

A novel chelating resin macroporous cross‐linked polystyrene immobilizing 2,5‐dimercapto‐1,3,4‐thiodiazole via a hydrophilic tetraethylene glycol spacer (PS‐TEG‐BMT) is synthesized and the structure is characterized by means of Fourier transform infrared spectroscopy (FTIR), energy dispersive X‐ray microanalysis (EDX), and elementary analysis. Its adsorption capacity for several metal ions such as Hg²⁺, Ag⁺, Ni²⁺, Pb²⁺, Cd²⁺, Fe³⁺, Bi³⁺, Zn²⁺, and Cu²⁺ are investigated. The initial experimental result shows that this resin has higher adsorption selectivity for Hg²⁺ and Ni²⁺ than for the other metal ions and the introduction of hydrophilic TEG spacer is beneficial to increase adsorption capacities. The result also shows that the Langmuir model is better than the Freundlich model to describe the isothermal process of PS‐TEG‐BME resin for Hg²⁺. Five adsorption‐desorption cycles demonstrate that this resin are suitable for reuse without considerable change in adsorption capacity. POLYM. ENG. SCI., 45:1515–1521, 2005. © 2005 Society of Plastics Engineers     

Highly porous,water-swellable,and reusable chelating polymeric gels for heavy metal ion removal from aqueous waste

Sequestration and removal of heavy metal ions from aqueous solutions pose multiple challenges. Ease of synthesis, high adsorption capacity and ease of regeneration are important considerations in the design of polymeric adsorbent materials developed for this purpose. To meet this objective, a new approach was used to design and synthesize a highly porous polystyrene-based resin (IDASR15) bearing iminodiacetate functional groups in every repeat unit by free radical polymerization with N, N'-methylenebisacrylamide as crosslinker followed by base hydrolysis. The physiochemical chemical properties of the resin were characterized by Fourier transform infrared spectroscopy, scanning electron microscope, equilibrium swelling value (ESV) and thermogravimetric analysis. Metal uptake capacity of IDASR15 towards low concentrations of various toxic heavy metal ions such as Cu²⁺, Cd²⁺, Mn²⁺, Zn²⁺, Pb²⁺, Ni²⁺, Co²⁺, Co³⁺, Cr³⁺, Fe²⁺, Fe³⁺, and Al³⁺ were investigated from their aqueous solution by batch method and found to be 0.943–2.802 mmol/g. The maximum capacity was 2.802 mmol/g obtained for Cu²⁺ ion at pH 5. The potential for regeneration and reuse has been demonstrated with Cu²⁺ ion by batch and column methods. The reported results suggest that IDASR15 is a highly efficient and porous complexing agent for commonly found toxic metal ions in aqueous streams with a high ESV of 68.55 g of water/1.0 g of IDASR15. It could also be reused ~99.5% of adsorption efficiency which is very promising and holds significant potential for waste-water treatment applications.     

SPOTLIGHT ON MANUFACTURING TRENDS IN JAPAN

Three reactive and functional polymers were synthesized by reacting formaldehyde with the phenolic Schiff bases derived from 4,4′-diaminodiphenylsulfone and o-, m-, and p-hydroxybenzaldehydes, respectively. The metal ion uptake behavior of these resins towards Cu²⁺, Ni²⁺, Co²⁺, and UO₂ ²⁺ ions in dilute aqueous media was studied. The optimum conditions for the absorption of metal ions were determined by varying the various parameters like contact time, size of the sorbents, concentration of the metal ion solutions, and the pH of the reaction medium. Suitable conditions were ascertained for preferential adsorption of the above metal ions from the salt solutions containing other interfering ions such as Na⁺, K⁺, and Mg²⁺. Presence of these alkali and alkaline earth metal ions in the salt solutions did not affect the adsorption behavior of the resins. It was observed that the structural features of the resins have a profound effect on the uptake characteristics. The position of the OH group present in the meta position with respect to the imine nitrogen atom in the resin, demonstrated a significant influence on the extent of metal ion adsorption by the resin. Out of the three resins reported here, the resin derived from the Schiff base of m-hydroxybenzaldehyde-4,4′-diaminodiphenylsulfone showed higher efficiency in uptake of metal ions from the solutions than the corresponding resins derived from the Schiff bases of o- and p-hydroxybenzaldehyde-4,4′-diaminodiphenylsulfone.     

Ethylenediamine tetraacetic acid modification of crosslinked chitosan designed for a novel metal‐ion adsorbent

Novel chitosan‐based adsorbent materials were synthesized with a higher fatty diacid diglycidyl as a crosslinking agent, and the adsorption ability of the resulting polymers for several metal ions was evaluated. Selective adsorption for Cu²⁺ in comparison with other divalent metal ions, such as Ni²⁺, Pb²⁺, Cd²⁺, and Ca²⁺, was observed with the crosslinked chitosan sorbent at pH 6; however, the adsorption power decreased abruptly as the pH value of the solution decreased. The addition of ethylenediamine tetraacetic acid (EDTA) residues to crosslinked chitosan significantly enhanced the adsorption power for metal ions, especially for Ca²⁺. The adsorptivity of Ca²⁺ was dramatically improved with the introduction of EDTA residues, and the value was greater than that obtained with a commercial chelate resin (CR11). Although the adsorption power of the EDTA‐derivatized sorbent for other metal ions was just comparable to that of the CR11 material, the newly synthesized adsorbent could be used for the recovery of metal ions from industrial waste solutions with a relatively wide range of pHs, from 4.0 to 6.0. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2758–2764, 2004     

Preparation of crosslinked poly(styrene–g–N-carboxyalkylated ethylenimine) as chelating resin

Carboxymethyl and ethyl groups were introduced into crosslinked poly(styrene–g–ethylenimine) (PSt–g–EI), consisting of a crosslinked polystyrene backbone with linear polyethylenimine branches, by the reaction of PSt–g–EI with monochloroacetic acid and β-chloropropionic acid. Carboxyethylation was also performed by reaction of the PSt–g–EI with acrylic acid. The extent of the reaction was determined by the change in the nitrogen content of the resin. The adsorption of metal ions such as Cu²⁺, Cd²⁺, Hg²⁺, Ni²⁺, and Ca²⁺ by carboxyalkylated PSt–g–EI was examined. With the introduction of carboxyalkyl groups, the adsorption capacity for metal ions (per gram of resin) decreased, whereas the affinity of the resin for these ions increased.     

Sorption behavior of ion-exchange terpolymer resin with environmental impact: synthesis,characterization and isotherm models

A novel terpolymer acts as an effective chelating ion exchanger which was synthesized using 2-amino-6-nitro-benzothiazole and semicarbazide with formaldehyde (BSF) by solution condensation technique. Its ion exchange properties was determined against certain metal ions viz. Fe³⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺ and Pb²⁺ using batch equilibrium technique with different electrolyte concentrations, pH ranges and time intervals. The results of batch studies revealed that the separation of the selected metal ions from the aqueous solution by the terpolymer is found to be excellent compared to the available commercial resins and earlier reported resins. The order of metal ion uptake at higher concentrations by the BSF terpolymer at lower pH is Cu²⁺ > Ni²⁺ > Fe³⁺ and at lower concentration at higher pH is Zn²⁺ > Co²⁺ > Pb²⁺. The reusability of the resin was also reported for its effective ion-exchange behaviour for several cycles. The adsorption isotherm model was evaluated and the results are in good agreement with each other. The order of kinetics was also determined and the resin follows pseudo-second-order kinetics. Moreover, the physico-chemical analysis gives strong evidence for the effective metal ion removal compared with the earlier reported and commercial resins. Earlier, the structure and the properties of the synthesized novel chelating resin were clearly elucidated by elemental, FTIR, UV–Vis, ¹H & ¹³C NMR spectra, GPC, SEM and XRD.     

Synthesis,Characterization, and Applications of a New Ion Exchanger Tamarind 4-aminobenzoic Acid (TABA) Resin in Industrial Wastewater Treatment

Chromatographic column separations of toxic metal ions from industrial wastewater were achieved in acid media at optimized (K_d) values with a synthesized cation exchange TABA resin. The prepared TABA resin was characterized by FTIR, elemental, and thermogravimetric analysis. Studies of total ion exchange capacity, resin durability, and swelling were carried out. The distribution coefficient values of metal ions, viz Cu²⁺, Fe²⁺, Zn²⁺, Cd²⁺ and Pb²⁺ at different pH, were also studied using a batch equilibration method. The different factors affecting metal ions adsorption on this substrate, such as treatment time, agitation speed, and temperature, were studied in detail.     

Adsorption of selected toxic metals by modified peanut shells

The objective of this study was to modify peanut shells to enhance their adsorptive properties toward the metal ions cadmium (Cd²⁺), copper (Cu²⁺), nickel (Ni²⁺), lead (Pb²⁺) and zinc (Zn²⁺). Milled peanut shells were initially washed with water or 0.1 N NaOH or left unwashed. Following these treatments or lack of treatment, the shells were either left unmodified or modified by a heat treatment in the presence of either 1.0 M phosphoric acid or 0.6 M citric acid. Modified peanut shells were evaluated either for adsorption efficiency or for adsorption capacity using the five metal ions listed above. Adsorption efficiencies and capacities were compared with efficiencies and/or capacities for the commercial chelating or cation exchange resins Amberlite 200, Amberlite IRC‐718, Duolite GT‐73, and carboxymethylcellulose. For the adsorption efficiencies of individual metal ions, modified peanut shells met or exceeded the adsorption values for cadmium, copper, nickel or zinc ions compared with the commercial resins Duolite GT‐73 and carboxymethylcellulose. In a solution containing all five metal ions, modified peanut shells met or exceeded the adsorption efficiencies for cadmium, copper and lead ions compared with Duolite GT‐73, Amberlite IRC‐718 and carboxymethylcellulose. Adsorption capacities of modified peanut shells met or exceeded the adsorption capacity of Duolite GT‐73 for lead ions only. Citric or phosphoric acid‐modified peanut shells showed a preference for Cu²⁺ and Pb²⁺ and appear promising as potentially inexpensive adsorbents for selected metal ions. © 2001 Society of Chemical Industry     

Metal recovery from jarosite waste – A resin screening study

Work has been carried out screening hydrometallurgical resins for application in the valorization of industrially produced jarosite. Of the seven resins tested, anion exchange resins performed poorly for valuable metal recovery. Purolite S950+ and S957, along with a strong acid resin, show good extraction properties, but are selective for Fe³⁺ over the other (divalent) metals. Purolite S930+ (iminodiacetic acid-functionalized resin) demonstrates selectivity for Cu²⁺ over Fe³⁺, but poor selectivity for Ni²⁺, Zn²⁺, and Co²⁺. Dowex M4195 (bispicolylamine-functionalized resin) demonstrates promise for extracting metals of value away from a mixed metal pregnant liquor solution (PLS). A three-stage column-based recovery process is proposed for jarosite leachate treatment.     

Evaluation of ion exchange resins for recovery of metals from electroplating sludge

In the present study, the recovery of metal ions from industrial solid residues from a galvanoplasty industry (Rio de Janeiro, Brazil) was investigated by cationic and anionic ion exchange resins. The electroplating residues were composed of the metals Cu²⁺, Fe³⁺, Al³⁺, Ni²⁺, and Cr³⁺. The studies of sorption were conducted under batch and column conditions. Based on these studies, the sorption parameters and the breakthrough curves for both resins were determined. Studies of the sorption equilibrium and kinetics were also performed. The maximum sorption capacities q _e (mg g^?1) of the cationic resin were: Cu²⁺: 1.9, Fe³⁺: 0.6 and Al³⁺: 0.4. For the anionic resin, the maxim values of q _e were Cu²⁺: 0.4 and Fe³⁺: 0.1. The Freundlich model was more adequate to describe the ion exchange equilibrium and the sorption mechanism fit the pseudo second-order kinetic model for both resins. The breakpoint of Cu²⁺ (100 ppm) occurred after passing 1,860 and 2,220 cm³ of residue solution through 20.0 g of the resins (column with h:6.0 cm and d:4.3 cm, flow rate: 60 cm³ min^?1). The column regeneration was carried out for five sorption–desorption cycles using H₂SO₄ 2.4 mol L^?1 (cationic) and HCl 2.0 mol L^?1 (anionic).     

Preparation of gel resins and removal of copper and lead from water

A series of gel resins were prepared by polymerizing glycidyl methacrylate (GMA) and 2‐acrylamido‐2‐methylpropane sulfonic acid (AMPS) and functionalizing with ammonia (NH₃) and tetraethylenepentamine (TEPA). The aminated gel resins were then used as an adsorbent for the removal of heavy metal ions (Cu²⁺ and Pb²⁺). These gel resins containing amino groups and chelating amino groups had excellent adsorptive properties for Cu²⁺ and Pb²⁺. The adsorption process reached equilibrium in 40 min, and the adsorption capacities of Cu²⁺ and Pb²⁺ were 75.0 mg g^?1 and 266.6 mg g^?1 for the NH₃‐aminated gel resins and 57.5 mg g^?1 and 330.6 mg g^?1 for the TEPA‐aminated gel resins, respectively. After five adsorption–desorption processes, the adsorption capacities only decreased slightly. Thus, these aminated gel resins can be used as effective adsorbents for aqueous heavy metal ions (Cu²⁺ and Pb²⁺). © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44466.     

Chelating polymer bearing triazolylazophenol moiety as the functional group

The chelating polymer-bearing triazolylazophenol moiety as the functional group was synthesized, its metal adsorption properties for 6 divalent heavy metal ions; Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Cd²⁺, and Pb²⁺ were investigated. The capacity of the polymer for Cu²⁺ achieved 8.7 mEq/g in pH 5.3 solution. The polymer showed remarkable color changes from orange to red violet or blue violet with its chelations to the heavy metal ions. The metal adsorption rates of the polymer were rapid in performing complete capacity saturation of heavy metal ions in about 30 min. The capacities varied little the presence of alkali or alkaline earth metal ions in solutions. The perfect elimination of metals from the polymer–M²⁺ chelates were performed with mineral acid solutions. The metal ions; Cu²⁺ and Ni²⁺ in plating-process solutions were effectively removed by the chelating polymer, and the polymer can be practically used for the removal of these ions from waste water.