Amidoximation of Cyano Group for Chelating Ion Exchange of Some Heavy Metal Ions from Wastewater

Ion exchange behavior of some heavy metal ions, Pb²⁺, Ni²⁺, and Cd²⁺, onto amidoximated polyacrylonitrile based Ce(IV) phosphate was investigated. Polyacrylonitrile based Ce(IV) phosphate was prepared and followed by functionalization of the cyano group to amidoxime group with hydroxylamine. The amidoximated resin was characterized using FT-IR and SEM. Removal of Pb²⁺, Ni²⁺, and Cd²⁺ ions from aqueous solution was examined by studying some factors using the batch technique such as effect of pH, contact time, initial metal ion concentration, and temperature. Some kinetic and isotherm models had been applied. The calculated amount of the sorbed values in case of the pseudo-second-order model are closer to the experimental data than that of the pseudo-first-order model, and with a correlation coefficients R² > 0.99. Therefore, the sorption of the three metal ions can be approximated more favorably by the pseudo-second-order model. The sorption process obeys the Freundlich isotherm model. The sorption has an endothermic nature which is indicated by the positive value of the enthalpy change, ΔH, the high positive values of the entropy change, and ΔS show the increased randomness at the solid/solution interface. The obtained negative values of free energy change, ΔG, indicate the feasibility and the spontaneous nature of the sorption process.     

Absence of Donnan Exclusion at High‐Concentration Ion Exchange for Macroporous Anionic Resin

Abstract

High‐concentration ion exchange has been studied for an anionic macroporous resin. The mechanism of interaction of Lewatit MP‐500 (strong base resin) with several high‐concentration inorganic salts was analyzed in order to determine the effect of the Donnan potential in the process.

The systems under study were Cl^?, SO₄ ^2? as counter‐ions and K⁺, Na⁺ as co‐ions in different combinations as single electrolytes. These salts were chosen because of their interest as raw materials in the fertilizer industry. The study focuses mainly on the behavior of high‐concentration (over 1 M) counter‐ and co‐ions in the anionic resin. The results showed that Donnan exclusion does not take place completely and that electrolyte penetration inside the resin is observed. Furthermore, a certain amount of ion exchange was observed for the co‐ions (K⁺ and Na⁺) when the resin was presaturated with sulphate and chlorides that were present in the solution. Equilibrium and kinetics data were obtained under these special experimental conditions. Equilibrium constants were obtained for counter‐ions and adsorption constants for co‐ions using a constant separation factor isotherm, while diffusion coefficients were obtained using a pore diffusion model.     

Chelation ion‐exchange properties of copolymer resin derived from 4‐hydroxyacetophenone,oxamide, and formaldehyde

A copolymer (4‐HAOF) prepared by condensation of 4‐hydroxyacetophenone and oxamide with formaldehyde in the presence of an acid catalyst proved to be a selective chelating ion‐exchange copolymer for certain metals. Chelating ion‐exchange properties of this copolymer were studied for Fe³⁺, Cu²⁺, Ni²⁺, Co²⁺, Zn²⁺, Cd²⁺, Pb²⁺, and Hg²⁺ ions. A batch equilibrium method was employed in the study of the selectivity of metal‐ion uptake involving the measurements of the distribution of a given metal ion between the copolymer sample and a solution containing the metal ion. The study was carried out over a wide pH range and in media of various ionic strengths. The copolymer showed a higher selectivity for Fe³⁺ ions than for Co²⁺, Zn²⁺, Cd²⁺, Pb²⁺, Cu²⁺, Ni²⁺, and Hg²⁺ ions. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 787–790, 2003     

Equilibrium data of the exchange of Cu2+, Cd2+ and Zn2+ ions for H+ on the cationic exchanger Lewatit TP‐207

Equilibrium ion exchange isotherms in aqueous medium of H⁺/Cu²⁺, H⁺/Zn²⁺ and H⁺/Cd²⁺ on a weak acid resin Lewatit TP‐207, at different pH values and at 298 K have been determined in order to assess the possibility of using ion exchange to eliminate heavy metal ions from industrial aqueous liquid streams. The experimental equilibrium data have been satisfactorily correlated using a Langmuir‐type empirical equation. It was found that the operating resin capacity with respect to each metal ion increased with increase in solution pH, in accordance with a second‐degree polynomial equation. Taking into account the variation of operating capacity with pH, each system exhibited a unique separation factor, namely all the experimental points can be described by a unique isotherm in a dimensionless form. Resin Lewatit TP‐207 exhibited the following selectivity order: Cu²⁺ > Zn²⁺ > Cd²⁺ at 298 K. Copyright © 2004 Society of Chemical Industry     

Kinetics and Equilibrium Studies for the Removal of Cobalt,Manganese, and Silver in Ethanol using Dowex 50W-x8 Cation Exchange Resin

Organic solvents such as ethanol, find a wide range of applications in fuel, pharmaceutical industries, food industries, and paint formulations, among others. The removal of Ag(I), Co(II), and Mn(II) ions in ethanol by cation exchange resin, Dowex 50W-x8, was investigated. The adsorption characteristics of metal ions onto Dowex 50W-x8 resin were described by Langmuir isotherms. The maximum sorption exchange capacities at 298 K were obtained as 47.4 mg g^?1, 52.6 mg g^?1, and 58.5 mg g^?1 for Ag(I), Co(II), and Mn(II), respectively. The data was also fitted to Temkin and Dubinin-Radushkevich adsorption isotherm models to evaluate other adsorption properties. The ion exchange of silver, cobalt, and manganese on cation exchange resin followed pseudo-second-order kinetics, and the intraparticle diffusion was rate-determining step. The thermodynamic parameters indicated that the sorption of metal ions onto Dowex 50W-x8 resin was spontaneous (negative ΔG°) and endothermic in nature (positive ΔH°) implying that the adsorption capacity increased with increasing temperature. The resin can be regenerated by eluting metal ions with 3.0 mol L^?1 HNO₃ followed by washing it with 10 mL of Millipore water and 10 mL of 2.0 M NaOH, respectively. The proposed method was applied for metal ion removal in real ethanol samples.     

Preparation and characterization of a phosphonylated polypropylene ion exchanger

Because typical ion exchange resins used for treating wastewater contain sulfur binding sites and suffer from application limitations, a new ion exchange system was developed by phosphonylating nonwoven polypropylene fabric (PP). These fabrics were phosphonylated for 0.5, 1, 2, and 4 h; amount of phosphorus on phosphonylated PP increased with an increase in phosphonylation time. After hydrolysis, the appropriate phosphonylated sample was placed in a glass column where a europium (Eu³⁺), lead (Pb²⁺), or mercury (Hg²⁺) salt solution was passed through the fabrics after an equilibration period of 5 min. Filtrate samples were then analyzed by atomic absorption spectroscopy for metal concentration. Results showed that metal binding efficiency for Eu³⁺ increased with an increase in phosphonylation time; Pb²⁺ binding efficiency increased up to 2 h phosphonylation time and then decreased; Hg²⁺ binding efficiency was practically independent of phosphonylation time. PP fabrics were also sulfonated and tested for binding efficiency to determine if phosphorus was a better binding site than sulfur. By comparing the results from phosphonylated PP and sulfonated PP, data showed that phosphonylated PP bound metal ions at a higher efficiency than sulfonated PP. Also, phosphonylated PP had higher binding efficiencies with Eu³⁺ and Pb²⁺ than a commercial exchange resin. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 93–100, 2000     

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     

Mechanism of the Adsorption of Ammonium Ions from Aqueous Solution by a Chinese Natural Zeolite

Abstract

The adsorption of ammonium ions onto a Chinese natural zeolite in an agitated batch adsorber was studied. A trial‐and‐error non‐linear method was developed to examine two widely used isotherms, the Langmuir and Freundlich. The data gained from the adsorption system fitted the Freundlich isotherm better. An ion exchange model, describing the relationship among the total metal ions in the solution, NH₄ ⁺ removed from the solution, and ions initially released from the zeolite, was developed for the adsorption system. In addition, a parameter of the ion exchange potential was defined to describe the adsorption mechanism. Ion exchange was the main mechanism that accounted for the adsorption of ammonium ions onto the Chinese natural zeolite.     

Calcium and fluoride release from ion exchange polyphasic systems

The present study concerns the kinetics of ion exchange accompanied by CaF₂ precipitation in tri‐phasic and quadri‐phasic systems involving a weak base anionic exchanger and a carboxylic cationic exchanger in the F^? and Ca²⁺ forms, respectively, in contact with a solution of artificial saliva. It was shown that in both systems the rate of Ca²⁺ release from the cationic exchanger is much lower than that of F^? from the anionic one. The rate of release for both ions, controlled by intraparticle diffusion, has been characterized by a Fick's law model. The kinetic parameters of effective rate of release (B) and diffusion coefficient (D) of the respective ion in the resin phase depend on the type of resin and the presence of different numbers of phases. The amount of the precipitate crystallizing on the surface of the resin beads depends on the type of the ion exchange resin, its particle size and on the ratio of resin components. By varying this ratio and the particle size of the ion exchangers it is possible to accomplish the precipitation mostly on the larger surface of the ionic exchanger. Copyright © 2003 Society of Chemical Industry     

Treatment of wastewater containing Pb and Fe using ion‐exchange techniques

Treatment of wastewater containing lead and iron was examined using two different ion‐exchange resins namely Duolite ES 467 (containing amino‐phosphonic functional groups) and a chelating ion‐exchange resin (containing hydroxamic acid functional groups). Initially different sorption parameters such as contact time, pH, concentrations of sorbent, sorbate and chloride ion were studied. The sorption kinetics was observed to be fast and equilibrium could be reached within 30 min. Lead sorption efficiency increased with increase in pH whereas the opposite trend was observed with iron. The presence of chloride ions greatly reduced the Pb sorption efficiency in the case of Duolite ES 467. Column studies were carried out to recover Pb and Fe individually using Duolite ES 467 resin. The maximum uptake of Pb at pH 2 and 3 was observed to be 11.63 and 33.96 g dm^?3 of resin respectively. Similarly, for Fe at pH 2 and 3 the uptake was observed to be 10.07 and 6.96 g dm^?3 of resin respectively. In the presence of chloride ions, column studies were carried out using Duolite ES 467 for iron and chelating ion‐exchange resin containing hydroxamic acid functional groups for lead sorption. Hydroxamic acid resin's loading capacity remains constant for at least up to 20 cycles. Copyright © 2005 Society of Chemical Industry     

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     

Removal and recovery of heavy metal ions in fixed and semi-fluidized beds

Uptakes of heavy metal ions such as Pb²⁺ and Ni²⁺ were studied experimentally in fixed and semifluidized beds packed with a strong cation exchange resin, Amberlite 200. Single and binary aqueous solutions of lead and nickel ions were passed through ion exchange columns, and the exit concentrations were measured to get the breakthrough behavior of the ions. From the exit concentration profiles, the breakthrough time and the ion exchange capacity were evaluated. After removal of heavy metal ions from binary solution of lead and nickel ions until the breakthrough time, two metal ions were recovered by precipitation and resolubilization of lead. In this paper, the recovery yield and separation efficiency are rigorously discussed.     

Ion‐exchange adsorption of calcium ions from water and geothermal water with modified zeolite A

The modified zeolite A was prepared by a two‐step crystallization method to remove scale‐forming cations from water and geothermal water. The adsorption kinetics, mechanism and thermodynamics were studied. The calcium ion adsorption capacity of the modified zeolite A was 129.3 mg/g (1 mg/g = 10^?3 kg/kg) at 298 K. The adsorption rate was fitted well with pseudo‐second‐order rate model. The adsorption process was controlled by film diffusion at the calcium ion concentration less than 250 mg/L (1 mg/L = 10^?3 kg/m³), and it was controlled by intraparticle diffusion at the concentration larger than 250 mg/L. The calculated mass‐transfer coefficient ranged from 2.23 × 10^?5 to 2.80 × 10^?4cm/s (1 cm/s = 10^?2m/s). Dubinin–Astakhov isotherm model could appropriately describe the adsorption thermodynamic properties when combined with Langmuir model. The adsorption process included not only ion exchange but also complexation between calcium and hydroxyl ions. The adsorption was spontaneous and endothermal. The high adsorption capacity indicates that the modified zeolite A is a suitable adsorption material for scale removal from aqueous solution. © 2014 American Institute of Chemical Engineers AIChE J, 61: 640–654, 2015     

Copolymer resin. VII. 8‐hydroxyquinoline‐5‐sulfonic acid–thiourea–formaldehyde copolymer resins and their ion‐exchange properties

8‐Hydroxyquinoline‐5‐sulfonic acid–thiourea–formaldehyde copolymer resins were synthesized through the condensation of 8‐hydroxyquinoline‐5‐sulfonic acid and thiourea with formaldehyde in the presence of hydrochloric acid as a catalyst and with various molar ratios of the reacting monomers. The resulting copolymers were characterized with UV‐visible, IR and 1H‐NMR spectral data, employed to determine the reactivity of monomers. The average molecular weights of these resins were determined with vapor pressure osmometry and conductometric titration in a nonaqueous medium. The chelation ion‐exchange properties were also studied with the batch equilibrium method. The resins were proved to be selective chelating ion‐exchange copolymers for certain metals. The chelation ion‐exchange properties of these copolymers were studied for Cu²⁺, Ni²⁺, Co²⁺, Pb²⁺, and Fe³⁺ ions. The study was carried out over a wide pH range and in media of various ionic strengths. The copolymers showed a higher selectivity for Fe³⁺ ions than for Cu²⁺, Ni²⁺, Co²⁺, and Pb²⁺ ions. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis of azo‐functionalized ion‐imprinted polymeric resin for selective extraction of nickel(II) ions

The work presented involved the fabrication and evaluation of an ion‐imprinted azo‐functionalized phenolic resin for selective extraction of Ni²⁺ ions from aqueous media. The azo‐containing ligand was first synthesized by coupling of a p‐aminophenol diazonium salt with resorcinol. The ligand was coordinated with Ni²⁺ ion template before condensation polymerization with formaldehyde and resorcinol was performed. The Ni²⁺ ions were extracted from the crosslinked resin matrix to finally afford the Ni²⁺ ion‐imprinted Ni‐PARF adsorbent. The synthetic steps were extensively investigated using elemental analysis and Fourier transform infrared, NMR and energy‐dispersive X‐ray spectroscopies. Also, the surface morphologies along with the surface areas of the adsorbent resin were evaluated using scanning electron microscopy and Brunauer–Emmett–Teller techniques, respectively. Batch experiments indicated that the pseudo‐second‐order kinetic equation provided the best fit with the experimentally obtained kinetic data and equilibrium was reached after 40 min. The isotherm studies were also in a good fit with the Langmuir model and the maximum adsorption capacities of Ni²⁺ ions with respect to both Ni‐PARF and control non‐imprinted C‐PARF adsorbents were around 260 and 100 mg g^?1, respectively. In the presence of Co²⁺, Cu²⁺, Zn²⁺ and Pb²⁺ as competing coexisting ions, the relative selectivity coefficients of Ni‐PARF for Ni²⁺ were, respectively, 84.91, 44.97, 30.41 and 32.20. Regeneration experiments indicated that after eight adsorption/desorption cycles, the Ni‐PARF adsorbent still maintained around 97% of its initial efficiency. © 2018 Society of Chemical Industry     

Separation of metal ions by the influence of a cation‐exchange terpolymer involving 2‐amino‐6‐nitrobenzothiazole–ethylenediamine–formaldehyde

A novel terpolymer involving 2‐amino‐6‐nitrobenzothiazole and ethylenediamine with formaldehyde was synthesized by a polycondensation technique using glacial acetic acid as a reaction medium. The resulting chelating terpolymer resin was characterized using elemental analysis, physicochemical parameters, and UV‐visible, Fourier transform infrared, ¹H NMR and ¹³C NMR spectral studies. Average molecular weights of the terpolymer were determined using gel permeation chromatography. The surface morphology and the nature of the terpolymer were investigated using scanning electron microscopy and X‐ray diffraction. The chelation ion‐exchange property of the terpolymer was determined against some common metal ions such as Fe³⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺ and Pb²⁺ using the batch equilibrium method. Effects of parameters such as the pH, contact time and various electrolyte concentrations were studied. The reusability of the terpolymer was checked in terms of its effective repeated usage. The results of the Langmuir and Freundlich adsorption isotherm models were best fitted with each other and the reaction kinetics followed pseudo second‐order kinetics. The terpolymer showed good results against Fe³⁺, Cu²⁺ and Ni²⁺ ions compared to those against the other metal ions. © 2014 Society of Chemical Industry     

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 isotherms,kinetic, and desorption studies on removal of toxic metal ions from aqueous solutions by polymeric adsorbent

Adsorption of Cd(II), Co(II), and Ni(II) on aminopyridine modified poly(styrene‐alt‐maleic anhydride) crosslinked by 1,2‐diaminoethane as an ion exchange resin has been investigated in aqueous solution. Adsorption behavior of these metal ions on the resin was studied by varying the parameters such as pH (2–6), adsorbent dose (0–4.0 g/L), contact time (0–240 min), and metal ions concentration (20–300 mg/L). Adsorption percentage was increased by increasing each of these parameters. The isotherm models such as: Langmuir, Freundlich, Temkin, and Dubinin–Radushkevich were used to describe adsorption equilibrium. The results showed that the best fit was achieved with the Langmuir isotherm equation, yielding maximum adsorption capacities of 81.30, 49.02, and 76.92 mg/g for Cd(II), Co(II), and Ni(II), respectively. The pseudo‐first‐order, pseudo‐second‐order, and intra‐particle diffusion kinetics equations were used for modeling of adsorption data and it was shown that pseudo‐second‐order kinetic equation could best describe the adsorption kinetics. The intra‐particle diffusion study revealed that external diffusion might be involved in this case. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41642.     

Chelation ion‐exchange study of copolymer resin derived from 8‐hydroxyquinoline 5‐sulphonic acid,oxamide, and formaldehyde

Copolymers (8‐HQ5‐SAOF) were synthesized by the condensation of 8‐hydroxyquinoline 5‐sulphonic acid (8‐HQ5‐SA) and oxamide (O) with formaldehyde (F) in the presence of acid catalyst. Four different copolymers were synthesized by using varied molar proportion of the reacting monomers. Copolymer resin composition has been determined on the basis of their elemental analysis and average molecular weights of these resins were determined by conductometric titration in nonaqueous medium. Viscometric measurement in dimethyl sulphoxide (DMSO) has been carried out with a view to ascertain the characteristic functions and constants. Electronic spectra, FTIR, and proton nuclear magnetic resonance spectra were studied to elucidate the structures. The newly synthesized copolymer proved to be a selective chelating ion‐exchange copolymer for certain metals. The chelating ion‐exchange properties of this synthesized copolymer was studied for different metal ions such as Fe³⁺, Cu²⁺, Ni²⁺, Co²⁺, Zn²⁺, Cd²⁺, and Pb²⁺. A batch equilibrium method was used in the study of the selectivity of metal ion uptake involving the measurements of the distribution of a given metal ion between the copolymer sample and a solution containing the metal ion only for representative copolymer 8‐HQ5‐SAOF‐I due to economy of space. The study was carried out over a wide pH range, shaking time, and in media of various ionic strengths. The copolymer showed a 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     

Synthesis and adsorption properties,toward some heavy metal ions,of a new polystyrene‐based terpyridine polymer

A novel polymeric ligand having 2,2′:6′,2″‐terpyridine as pendant group was prepared through a Williamson type etherification approach for the reaction between 4′‐hydroxy‐2,2′: 6′,2″‐terpyridine and the commercially available 4‐chloromethyl polystyrene. The chelating properties of the new polymer toward the divalent metal ions (Cu²⁺, Zn²⁺, Ni²⁺, and Pb²⁺) in aqueous solutions was studied by a batch equilibration technique as a function of contact time, pH, mass of resin, and concentration of metal ions. The amount of metal‐ion uptake of the polymer was determined by using atomic absorption spectrometry. Results of the study revealed that the resin exhibited higher capacities and a more pronounced adsorption toward Pb²⁺ and that the metal‐ion uptake follows the order: Pb²⁺ > Cu²⁺ > Zn²⁺ > Ni²⁺. The adsorption and binding capacity of the resin toward the various metal ions investigated are discussed. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012