Synthesis and Characterization of a Novel Hybrid Chelating Ion Exchanger and its Application as an Amphoteric Exchanger

A new and novel, hybrid chelating ion exchanger zirconium tri ethylene tetra amine (ZrT) has been synthesized by a simple sol-gel route using inexpensive and easily available chemicals. ZrT has been characterized for elemental analysis, TGA, FTIR, X-ray diffraction, SEM, and EDX. Physical and ion exchange characteristics as well as chemical stability of the material in various acids, bases, and organic solvent media have also been studied. Anion exchange capacity (AEC) for Cl^?, Br^?, Cr₂O₇^2?, F^?, and AsO₄^3? has been determined and distribution coefficient K_d for Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺ (transition metal ions) and Hg²⁺,Cd²⁺, Pb²⁺ (heavy metal ions) has been evaluated by batch equilibration techniques in aqueous and various electrolyte media/concentrations. Based on α, the separation factor, a few binary separations have been performed on a chromatographic column packed with ZrT. The amphoteric behavior of ZrT has been demonstrated using CuCl₂ and HgCl₂ and amount of cation and anion simultaneously exchanged determined. The practical applicability of ZrT as an amphoteric exchanger has been further highlighted by performing a case study. A study on the regeneration and reuse of ZrT indicates that it is effective up to six cycles without much decline in performance.     

Removal of toxic metal ions by using composite cation-exchange material

Polyanilinezirconium(IV) arsenate composite cation exchange material was synthesized under different experimental conditions by the incorporation of polyaniline into the matrices of inorganic precipitate (zirconium(IV)arsenate). The experimental parameters such as concentration, mixing volume ratio, and pH were established for the synthesis of the material. Ion-exchange material that was synthesized at pH 1.0 showed an ion exchange capacity of 1.33 meq g⁻¹ for Na⁺ ions. The composite material exhibits improved ion-exchange capacity along with chemical and thermal stability. The exchanger was characterized based on FTIR, TGA, XRD, and SEM analysis. The X-ray diffraction study shows semi-crystalline nature of the material. The distribution coefficient studies (K_d) of metal ions on the material were performed in diverse solvent systems. Based on K_d values the material was found to be selective for Pb(II) and Hg(II) ions. Some analytically important binary separations of metal ions in synthetic mixtures viz. Ba²⁺-Pb²⁺, Pb²⁺-Ni²⁺, Cd²⁺-Hg²⁺, Ni²⁺-Hg²⁺, Zn²⁺-Pb²⁺, Ca²⁺-Bi³⁺, Al³⁺-Hg²⁺, and Ca²⁺-Pb²⁺ were achieved on the columns of polyanilinezirconium(IV) arsenate cation exchanger. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

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     

Characterization and adsorption behavior of newly synthesized sodium bis(2-ethylhexyl) sulfosuccinate–cerium (IV) phosphate (AOT–CeP) cation exchanger

A new cationic exchange material, sodium bis(2-ethylhexyl) sulfosuccinate (AOT) with cerium (IV) phosphate (AOT–CeP) has been synthesized. The characterization of the ion exchanger was performed by using infra red spectroscopy (IR), X-ray diffraction (XRD), scanning electron microscopy (SEM), thermo gravimetric analysis/differential thermo gravimetric analysis (TGA/DTA/DTG) and elemental analysis. The ion exchange properties like ion exchange capacity, elution and concentration behavior of AOT–CeP were determined by taking the material into a column and elution of H⁺ was done by NaNO₃. The thermal stability of the ion exchanger was studied by determining ion exchange capacity after heating to different temperatures for one hour. The adsorption studies on AOT–CeP demonstrated that the material is selective for Cu²⁺, Pb²⁺, Cd²⁺, Zn²⁺ and Hg²⁺ ions. AOT–CeP was found to be effective for the separation of Cu²⁺, Pb²⁺, Cd²⁺, Zn²⁺ and Hg²⁺ ions in the presence of alkali metals/alkaline earth metals. This cationic exchanger was also effective for the removal of Cu²⁺, Pb²⁺, Cd²⁺, Zn²⁺ and Hg²⁺ ions in the presence of acid and other transition metal ions. Thus, AOT–CeP can be used for the removal of these ions from the waste water during its treatment.     

Synthesis and characterization of a new guar gum 4‐hydroxybenzoic acid resin and its use for the separation of heavy metal ions in industrial effluents

Hydroxybenzoic acid group has been incorporated onto guar gum by modified Porath's method of functionalization of polysaccharides. The newly synthesized guar gum 4‐hydroxybenzoic acid (GHBA) resin was characterized by Fourier‐transform infrared spectroscopy, elemental analysis, ion‐exchange capacity, column reusability, and physicochemical properties. The distribution coefficient (K_d) values and effect of pH on chelation of these metal ions using batch method were studied. The separations of mixture of Fe²⁺, Zn²⁺, Cu²⁺, Cd²⁺, and Pb²⁺ metal ions on GHBA resin on the basis of their distribution coefficient at various pH were also achieved using column chromatography. The effect of experimental parameters such as pH, treatment time, agitation speed, temperature, adsorbent dose, initial metal ion concentration, and flow rate on the removal of metal ions has been also studied. GHBA resin is effective adsorbents for the removal of different toxic metal ions from aqueous solutions and follows the order: Fe²⁺ > Zn²⁺ > Cu²⁺ > Cd²⁺ > Pb²⁺. POLYM. ENG. SCI. 2013. © 2012 Society of Plastics Engineers     

Synthesis of resin IV: Salicylic acid,diaminonaphthalein, and formaldehyde terpolymer and its ion exchange

This article reports the synthesis, characterization, and ion exchange properties of a terpolymer. The terpolymer resin salicylic acid‐diaminonaphthalein‐formaldehyde (SDNF) was synthesized by the condensation of salicylic acid and diaminonaphthalein with formaldehyde in the presence of a hydrochloric acid catalyst. Terpolymer resin was characterized by elemental analysis, infrared (IR) spectroscopy, nuclear magnetic resonance spectroscopy, and UV–Visible spectral studies. The number average molecular weight of the resin was determined by nonaqueous conductometric titration. Chelation ion exchange properties have also been studied for Fe³⁺, Cu²⁺, Ni²⁺, Co²⁺, Zn²⁺, Cd²⁺, Pb²⁺ ions employing a batch equilibrium method. It was employed to study the selectivity of metal ion uptake involving the measurements of distribution of a given metal ion between the polymer sample and a solution containing the metal ion. The study was carried out over wide pH range and in a media of various ionic strengths. The terpolymer showed higher selectivity for Fe³⁺, Cu²⁺, and Ni²⁺ions than for Co²⁺, Zn²⁺, Cd²⁺, and Pb²⁺ ions. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Polymer hydrogel cross-linked by inorganic nanoparticles for removing trace metal ions

Hydrogels for absorbing metal ions in wastewater have attracted more attentions in the environmental field especially for recent years. The removal efficiency of hydrogel adsorbents for eliminating metal ions is highly related with the effective contact between adsorbents and adsorbates. However, poor water absorption capacity of the hydrogel adsorbents would restrict on the expose of adsorption sites to the targeted subjects, causing undesirable removal ratio (RR) especially for metal ions at trace level. Thereby, the reported hydrogel adsorbents mainly focus on the removal of high content but not the trace level of metal ions so far. In this work, poly(acrylamide) (PAM)/poly(acrylic acid) (PAA)/Ca(OH)₂ composite hydrogel is applied to adsorb trace metal ions. Swelling ratio of such PAM/PAA/Ca(OH)₂ gel reaches 2,530 g/g, resulting in effective exposure of active sites and further expected RR for trace metal ions. The RRs of such adsorbent for Cu²⁺ (initial concentration C₀ = 0.064 mg/L), Al³⁺ (C₀ = 0.27 mg/L), Co²⁺ (C₀ = 0.59 mg/L), Cr⁶⁺ (C₀ = 0.52 mg/L), Mn²⁺ (C₀ = 0.55 mg/L), Ni²⁺ (C₀ = 0.59 mg/L), Zn²⁺ (C₀ = 0.65 mg/L), Ag⁺ (C₀ = 1.08 mg/L), and La³⁺ (C₀ = 1.39 mg/L) are 56.6, 80.8, 41.3, 29.3, 34.6, 44.6, 55.9, 45.8, and 35.5%, respectively. This work broadens the application of hydrogel adsorbent for eliminating trace metal ions from polluted water.     

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.     

Metal ion binding properties of novel wool powders

Wool fibres have shown potential for the removal and recovery of toxic chemical and metal ions; however, their slow kinetics of binding has limited their widespread application. In this study three wool powders have been prepared from chopped wool fibre using various milling operations. Brunauer, Emmett, Teller analysis (BET) showed negligible change in surface area and Positron annihilation lifetime spectroscopy indicated no change in nanoporosity of the powders on processing. Binding of the transition metal ions, Co²⁺, Cu²⁺, and Cd²⁺ was investigated over the pH range 3–9 at ambient temperature (23°C) using their respective radioisotopes (i.e. ⁵⁷Co, ⁶⁴Cu, or ¹⁰⁹Cd). The optimum pH for binding of Cu²⁺ and Cd²⁺ was in the range 6–8, while Co²⁺ absorption peak was sharp at pH 8. The rate of uptake of Cu²⁺ for each of the wool powder was dramatically faster (～ 42 fold) than that of the wool fibre. In comparison with commercial cation exchange resins, the wool powders showed significantly higher (two to nine fold) metal ion loading capacity. Selective binding of the metal ions could be enhanced by varying pH and/or incubation times. The use of radioisotopes to monitor the metal ion binding allowed the development of a highly sensitive and rapid high‐throughput analysis method for assessing wool powder binding properties. The ability to produce large quantities of wool powders and their ease of handling indicate that they have potential for application in separation and recovery of metal ions from industrial effluents and environmental waterways. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

ION EXCHANGE PROPERTIES OF THE SULFUR-MODIFIED BIOTITE

ABSTRACT

The ion exchange behavior of a sulfur-modified biotite towards Pb²⁺, Hg²⁺, Co²⁺, Cu²⁺, Cd²⁺ and Zn²⁺ ions has been studied. The ion exchange isotherms of divalent cations were determined and concentration equilibrium constants as a function of metal loading were analyzed. Sulfur modified biotite exhibits high affinity for Hg²⁺, Pb²⁺, Cu²⁺ and Cd²⁺ ions in individual solutions and in the presence of electrolytes. About 200 mg Hg/g uptake in 1·10^?3 M Hg²⁺ solution and ～ 35 mg Hg/g in groundwater simulant or an alkaline simulant 2 M in NaN0₃ + 1 M in NaOH was found. The possibility of a complex ion exchange and precipitation mechanism of the sulfur modified biotite towards the soft cations is proposed.     

ION EXCHANGE BEHAVIOUR OF CHELATING RESIN DOWEX A-1WITH ACTINIDES AND LANTHANIDES

Adsorption studies of several actinides and lanthanides have been carried out by chelating ion exchange resin Dowex A-1. The metal ions studied were Pu⁴⁺, Zr⁴⁺, UO₂ ⁺⁺, Am³⁺, Cm³⁺, Bk³⁺, Cf³⁺, Eu³⁺, and Tm³⁺. The separation factors between consecutive trivalent actinides and between Am(III) and Eu(III) have been evaluated. Mechanism of adsorption of actinides and lanthanides from different aqueous media has been discussed. An ion exchange procedure for the separation of Pu⁴⁺ and UO₂ ⁺⁺ has been developed using this resin.     

Heavy metals removal from solution by polyaniline/palygorskite composite

Batch adsorption experiments were carried out to remove heavy metal ions such as Cu (II), Ni (II), Cd (II), and Cr (VI) from single‐metal solutions using a polyaniline/palygorskite (PP) composite. Different parameters affecting the adsorption capacity such as contact time and pH of the solution have been investigated. The structural characteristics of the PP composite were studied in this work. Atomic absorption spectroscopy was used for the measurement of heavy metal contents, and the adsorption capacity (q_e) calculated were 114 mg Cu (II) g^?1, 84 mg Ni (II) g^?1, 56 mg Cd (II) g^?1, and 198 mg Cr (VI) g^?1 under optimal conditions. The removal of the metal ions from solutions was assigned to chelation, ionic exchange, and electrostatic attraction. Data from this study proved that the novel organic/inorganic composite presents great potential in the recovery and elimination of noble or heavy metal ions from industrial wastewater. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

New Organic-Inorganic Type Acrylamide Aluminumtungstate: Preparation,Characterization and Analytical Applications as a Cation Exchange Material

Abstract

A crystalline sample of organic-inorganic cation exchanger acrylamide aluminumtungstate has been synthesized. The material behaves as a mono-functional cation-exchanger with an ion–exchange capacity 1.25 meq/g for Na⁺ ions. The material has been characterized on the basis of thermal stability, chemical stability, FTIR, TGA-DTA, X-ray, and SEM studies. The effect of time and temperature on the distribution coefficient of metal ion was studied. It was concluded that 30°C appeared to be the most favorable temperature. Sorption behavior of the metal ions was studied in different solvent systems. On the basis of distribution studies, the material was found to be selective for Pb²⁺ ions. Its selectivity was examined by achieving some important binary separations like Mg²⁺-Pb²⁺, Hg²⁺-Pb²⁺, Ca²⁺-Pb²⁺ Zn²⁺-Pb²⁺, Ni²⁺-Pb²⁺, and Al³⁺-Pb²⁺. The practical applicability of the cation-exchanger was demonstrated in the separation of Pb²⁺ ions from a synthetic mixture.     

Formation of thermosensitive copolymer beads having phosphinic acid groups and adsorption ability for metal ions

Hydrophilic thermosensitive copolymer beads having phosphinic acid groups were prepared by suspension copolymerization of acryloyloxypropyl n‐octylphosphinic acid (APPO), N‐isopropyl acrylamide (NIPAAm), and tetraethyleneglycol dimethacrylate (4G). The thermosensitivity and the adsorption ability of the copolymer beads for metal ions beads were studied. The APPO‐NIPAAm‐4G copolymer beads were obtained in a good yield by suspension copolymerization of monomers (APPO, NIPAAm, and 4G) dissolved in chloroform, in a saturated Na₂SO₄ aqueous solution in the presence of surfactant and MgCO₃. The APPO‐NIPAAm‐4G copolymer beads had higher adsorption ability for lanthanide metal ions (Eu³⁺, Sm³⁺, Nd³⁺, or La³⁺) than for main transition metal ions (Cu²⁺, Ni²⁺, or Co²⁺). Furthermore, it was also found that the APPO‐NIPAAm‐4G copolymer beads had selective adsorption ability between lanthanide metal ions, and the order of adsorption ability for lanthanide metal ions was as follows: Eu³⁺ > Sm³⁺ > Nd³⁺ > La³⁺. The selective adsorption for these metal ions from their mixed solutions was performed by both a batch method and a column method. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 449–460, 2006     

Synthesis and study of the chelating properties of 3-carboxy-4-hydroxyacetophenone-formaldehyde resins

3-Carboxy-4-hydroxyacetophenone (CHAP) was polycondensed with various proportions of formaldehyde using alcoholic alkali as catalyst. The resin samples, designated as CHAP-F, have been characterized by elemental analyses and IR spectroscopy, by estimation of their number average molecular weights (M?_n), by measurement of intrinsic viscosity, and by TGA. Polymeric metal chelates of one CHAP-F sample with Cu²⁺, Fe³⁺, Co²⁺, Ni²⁺, and UO₂²⁺ ions have been prepared and characterized. Ion-exchanging properties of one CHAP-F resin sample for Fe³⁺, Cu²⁺, and Ni²⁺ metal ions are studied by the application of the batch-equilibration method.     

Adsorption characteristics of metal ions by CO2-fixing Chlorella sp. HA-1

Single and binary metal systems were employed to investigate the removal characteristics of Pb²⁺, Cu²⁺, Cd²⁺, and Zn²⁺ by Chlorella sp. HA-1 that were isolated from a CO₂ fixation process. Adsorption test of single metal systems showed that the maximum metal uptakes were 0.767 mmol Pb²⁺, 0.450 mmol Cd²⁺, 0.334 mmol Cu²⁺ and 0.389 mmol Zn²⁺ per gram of dry cell. In the binary metal systems, the metal ions on Chlorella sp. HA-1 were adsorbed selectively according to their adsorption characteristics. Pb²⁺ ions significantly inhibited the adsorption of Cu²⁺, Zn²⁺, and Cd²⁺ ions, while Cu²⁺ ions decreased remarkably the metal uptake of Cd²⁺ and Zn²⁺ ions. The relative adsorption between Cd²⁺ and Zn²⁺ ions was reduced similarly by the presence of the other metal ions.     

Competitive Metal Ion Binding to a Silicate-Immobilized Datura innoxia Biomaterial

Abstract

Metal ion binding with a flowing system to a biosorbent comprised of cultured cell-wall fragment within a polysilicate matrix has been investigated. Solutions containing 0.10 mM Pb²⁺, Cu²⁺, Ni²⁺, Cd²⁺, and Zn²⁺ were exposed to the material in combinations of two, three, and five metals while simultaneously monitoring the concentration of all metals in the effluent stream. A relative affinity order of Pb²⁺ > Cu²⁺ >> Zn²⁺ ≈ Cd²⁺ > Ni²⁺ was determined when all five metal ions were exposed to the material. Lower-affinity metal ions were exposed to the material sequentially. Both metal-specific and common binding sites were observed for each metal ion. The presence of both binding sites that are common to all metal ions investigated and sites that appear to be unique for each metal ion could significantly impact the utility of single-metal ion studies on the application of such biosorbents for the selective removal of metal ions from natural water.     

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.     

Poly(2‐acrylamido glycolic acid‐co‐2‐acrylamido‐2‐methyl‐1‐propane sulfonic acid): Synthesis,characterization, and retention properties for environmentally impacting metal ions

Poly(2‐acrylamido glycolic acid‐co‐2‐acrylamido‐2‐methyl‐1‐propane sulfonic acid) [P(AGA‐co‐APSA)] was synthesized by radical polymerization in an aqueous solution. The water‐soluble polymer, containing secondary amide, hydroxyl, carboxylic, and sulfonic acid groups, was investigated, in view of their metal‐ion‐binding properties, as a polychelatogen with the liquid‐phase polymer‐based retention technique under different experimental conditions. The investigated metal ions were Ag⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Cd²⁺, Pb²⁺, and Cr³⁺, and these were studied at pHs 3, 5, and 7. P(AGA‐co‐APSA) showed efficient retention of all metal ions at the pHs studied, with a minimum of 60% for Co(II) at pH 3 and a maximum close to 100% at pH 7 for all metal ions. The maximum retention capacity (n metal ion/n polymer) ranged from 0.22 for Cd²⁺ to 0.34 for Ag⁺. The antibacterial activity of Ag⁺, Cu²⁺, Zn²⁺, and Cd²⁺ polymer–metal complexes was studied, and P(AGA‐co‐APSA)–Cd²⁺ presented selective antibacterial activity for Staphylococcus aureus with a minimum inhibitory concentration of 2 μg/mL. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009