Preparation and characterization of an IPN type chelating resin containing amino and carboxyl groups for removal of Cu(II) from aqueous solutions

A novel IPN type chelating resin, amino-functionalized poly (glycidyl methacrylate)/poly (acrylic acid), (pGMA/pAA), was synthesized by a combination of serial reactions including, conventional radical polymerization, amination and photopolymerization. To assess the efficacy and characteristics of the resin in removal of Cu (II), batch adsorption experiments were carried out, and the effects of different parameters such as contact time, adsorbent dosage, initial metal ion concentration, temperature, and pH on the adsorption process were investigated. The results showed that 0.5 g/L dosage and pH 5 are the optimum values to achieve the maximum adsorption capacity and the adsorption kinetic of Cu (II) was well represented by pseudo-second-order kinetic model. In addition, it was found that the adsorption was mainly controlled by the film diffusion mechanism, along with a considerable contribution of the intra-particle diffusion mechanism, and Langmuir, Freundlich and Dubinin–Radushkevich (D–R) isotherm models can be used for interpreting the adsorption process. Moreover, FT-IR analysis results and the mean free energies of adsorption clearly indicate that the ion exchange and chelation mechanisms took place as dominating mechanisms simultaneously during the adsorption process. It was also found to be that IPN resin could be used at least four times without losing its original activity.     

Study on adsorption of Cu(II)–Cr(VI) binary system by carbonized Eupatorium adenophorum

We first report a mechanism study on the adsorption of Cu(II)-Cr(VI) binary mixture by a novel low-cost adsorbent, carbonized Eupatorium adenophorum. The influences by pH value, dosage, initial concentration, temperature, and adsorption time on its performance to absorb copper and chromium were investigated. The experimental data were fitted according to the Langmuir and Freundlich adsorption isotherm models, the pseudo-first-order kinetics, the pseudo-second-order kinetics, and the intra-particle diffusion model. The results indicated that when the reaction system was with its pH = 5, the dosage of carbonized Eupatorium adenophorum was 0.1 g, the adsorption time was 30 min, and the temperature was 25°C; the adsorption capacities for Cu(II) and Cr(VI) reached 27.62 mg/g and 9.68 mg/g, respectively. The process of carbonized Eupatorium adenophorum to absorb Cr(VI) is also accompanied by redox reactions. The Langmuir model and the pseudo-second-order model can better ?t the experimental data. Observation by fourier transform infrared spectroscopy (FTIR) and scanning electron microscope (SEM) found no significant change of functional groups before and after the adsorption by carbonized Eupatorium adenophorum, and this adsorption process is mainly a physical adsorption.     

Removal of Copper(II) and Zinc(II) from Aqueous Solutions Using a Lignocellulosic-Based Polymeric Adsorbent Containing Amidoxime Chelating Functional Groups

In this study, the adsorption of Cu(II) and Zn(II) ions from aqueous solutions onto amidoximated polymerized banana stem (APBS) has been investigated. Infrared spectroscopy was used to confirm graft copolymer formation and amidoxime functionalization. The different variables affecting the sorption capacity such as pH of the solution, adsorption time, initial metal ion concentration, and temperature have been investigated. The optimum pH for maximum adsorption was 10.5 (99.99%) for Zn²⁺ and 6.0 (99.0%) for Cu²⁺ at an initial concentration of 10 mg L^?1. Equilibrium was achieved approximately within 3 h. The experimental kinetic data were analyzed using pseudo-first-order and pseudo-second-order kinetic models and are well fitted with pseudo- second-order kinetics. The thermodynamic activation parameters such as ΔG^o, ΔH^o, and ΔS^o were determined to predict the nature of adsorption. The temperature dependence indicates an exothermic process. The experimental isotherm data were well fitted to the Langmuir model with maximum adsorption capacities of 42.32 and 85.89 mg g^?1 for Cu(II) and Zn(II), respectively, at 20°C. The adsorption efficiency was tested using industrial effluents. Repeated adsorption/regeneration cycles show the feasibility of the APBS for the removal of Cu(II) and Zn(II) ions from water and industrial effluents.     

Efficient adsorption of lead (II) and copper (II) from aqueous phase using oxidized multiwalled carbon nanotubes/polypyrrole composite

Polypyrrole coated oxidized multiwalled carbon nanotubes (oMWCNT/Ppy) were applied to determine the adsorption characteristics of Pb(II) and Cu(II) from their aqueous solutions. Structural and morphological characterization studies using scanning electron microscopy, thermogravimetric analysis, Fourier transform infrared and Raman spectroscopy showed successful preparation of the oMWCNT/Ppy composite. The influence of pH, contact time, and initial metal ion concentration on the adsorption of Pb(II) and Cu(II) was studied. The adsorption processes fitted well with Langmuir isotherm and pseudo-second-order kinetic models. The maximum adsorption capacities for Pb(II) and Cu(II) were determined as 26.32 and 24.39 mg/g, respectively. Desorption studies indicated that the oMWCNT/Ppy composite could be reused for five cycles with minimum loss of its initial adsorption capacity.     

Humic acid-immobilized polymer/bentonite composite as an adsorbent for the removal of copper(II) ions from aqueous solutions and electroplating industry wastewater

In this study, humic acid (HA) was immobilized onto amine-modified polyacrylamide/bentonite composite (Am-PAA-B) which was prepared by direct intercalation polymerization technique and the product (HA-Am-PAA-B) was used as an adsorbent for the removal of copper(II) ions from aqueous solutions. The surface characteristics of bentonite, Am-PAA-B and HA-Am-PAA-B were investigated. The adsorbent behaved like a cation exchanger and more than 99.0% Cu(II) ions’ removal was observed at the pH range 5.0–6.0. Kinetic and isotherm experiments showed that amount of Cu(II) ions adsorbed increases with increase of the initial concentration and temperature. The adsorption kinetic data were interpreted by pseudo-first-order and pseudo-second-order rate equations. The suitability of Langmuir, Freundlich and Dubinin–Radushkevich (D-R) adsorption models to the equilibrium data was investigated. The Langmuir isotherm was found to provide the best theoretical correlation of the experimental equilibrium data. The thermodynamic and kinetic activation parameters were derived to predict the nature of adsorption process and discussed in detail. The isosteric heat of adsorption was constant even after increase in surface loading. The removal efficiency of HA-Am-PAA-B was tested using electroplating industry wastewater. The desorption of adsorbed Cu(II) ions was achieved by 0.1 M HCl and four adsorption/desorption cycles were performed without significant decrease in the adsorption capacity.     

Synthesis,characterization and application of a novel nanometer-sized chelating resin for removal of Cu(II), Co(II) and Ni(II) ions from aqueous solutions

A novel nanometer-sized chelating resin (NSCR) was prepared via two steps, First step: copolymerization reaction of N-methacryloxyphtalimide (NMP) with methylenebisacrylamide (MBA) by suspension polymerization method to give ultrafine poly (NMP-co-MBA). Second step: reaction of triethylenetetramine (TETA) with poly (NMP-co-MBA) to give NSCR. The prepared NSCR was characterized by Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), Transmission electron microscopy (TEM), Brunauer-Emmett-Taller (BET) and thermogravimetric analysis (TGA). This study illustrated the capability of NSCR for extraction of Cu(II), Co(II) and Ni(II) from aquatic solutions. The pH effect, metal ions concentration, temperature and contact time were elaborated in batch experiments. The results showed that high capacities were 1.3, 1.0 and 0.95 mmol/g resin for Cu(II), Ni(II) and Co(II) ions, respectively. The experimental data of adsorption isotherms were convenient for Langmuir isotherm, and the kinetic data illustrated that the removal process was described by pseudo-second order kinetic model. The parameters of Thermo dynamic illustrated that the process of adsorption was endothermic and spontaneous reaction. The prepared NSCR was regenerated and used repetitively for five times with small decrease in adsorption capacity.     

Selective adsorption behavior of ion-imprinted magnetic chitosan beads for removal of Cu(II) ions from aqueous solution

Heavy metal ion is one of the major environmental pollutants. In this study, a Cu(II) ions imprinted magnetic chitosan beads are prepared to use chitosan as functional monomer, Cu(II) ions as template, Fe₃O₄ as magnetic core and epichlorohydrin and glutaraldehyde as crosslinker, which can be used for removal Cu(II) ions from wastewater. The kinetic study shows that the adsorption process follows the pseudo-second-order kinetic equations. The adsorption isotherm study shows that the Langmuir isotherm equation best fits for the monolayer adsorption processes. The selective adsorption properties are performed in Cu(II)/Zn(II), Cu(II)/Ni(II), and Cu(II)/Co(II) binary systems. The results shows that the IIMCD has a high selectivity for Cu(II) ions in binary systems. The mechanism of IIMCD recognition Cu(II) ions is also discussed. The results show that the IIMCD adsorption Cu(II) ions is an enthalpy controlled process. The absolute value of ΔH (Cu(II)) and ΔS(Cu(II)) is greater than ΔH (Zn(II), Ni(II), Co(II)) and ΔS (Zn(II), Ni(II), Co(II)), respectively, this indicates that the Cu(II) ions have a good spatial matching with imprinted holes on IIMCD. The FTIR and XPS also demonstrates the strongly combination of function groups on imprinted holes in the suitable space position. Finally, the IIMCD can be regenerated and reused for 10 times without a significantly decreasing in adsorption capacity. This information can be used for further application in the selective removal of Cu(II) ions from industrial wastewater.     

Kinetics and thermodynamics of Cu(II) adsorption on oil shale wastes

The oil shale waste material, retorted shale, was utilized as an adsorbent for Cu(II) removal from aqueous solution. The kinetics and thermodynamic adsorption was investigated during a series of batch adsorption experiments. The removal efficiency was controlled by solution pH, temperature, initial ion concentration and contact time. Two simple kinetic models, pseudo-first-and second-order, were used to investigate the adsorption mechanisms. The pseudo-second-order chemical reaction kinetics provides the best correlation with the experimental data. Langmuir and Freundlich models were used to fit the equilibrium data, which showed that Langmuir best-fitted these data. Thermodynamic parameters such as free energy, enthalpy and entropy were calculated to predict the nature of the adsorption process.     

Artificial neural network (ANN) approach for modeling Zn(II) adsorption in batch process

Artificial neural networks (ANN) were applied to predict adsorption efficiency of peanut shells for the removal of Zn(II) ions from aqueous solutions. Effects of initial pH, Zn(II) concentrations, temperature, contact duration and adsorbent dosage were determined in batch experiments. The sorption capacities of the sorbents were predicted with the aid of equilibrium and kinetic models. The Zn(II) ions adsorption onto peanut shell was better defined by the pseudo-second-order kinetic model, for both initial pH, and temperature. The highest R² value in isotherm studies was obtained from Freundlich isotherm for the inlet concentration and from Temkin isotherm for the sorbent amount. The high R² values prove that modeling the adsorption process with ANN is a satisfactory approach. The experimental results and the predicted results by the model with the ANN were found to be highly compatible with each other.     

Assessment of Cu (II) removal from an aqueous solution by raw Gundelia tournefortii as a new low-cost biosorbent: Experiments and modelling

Lignocellulosic materials can be used as biosorbent for refinement of the wastewaters when they are available in large quantities. Many studies were conducted to uptake Cu (II) ion from aqueous solutions. In this paper, the biosorption efficiency of Cu (II) ions from a synthetic aqueous solution was investigated using Gundelia tournefortii (GT), without any pre-treatment. Fourier transform infrared spectroscopy, scanning electron microscopy and determining the point of zero charge were employed to characterise the biosorbent. Batch experiments were performed to study the influence of pH, biosorbent dosage, contact time, temperature and initial Cu (II) concentration on Cu (II) removal. The biosorption isotherms were investigated using the Langmuir, Freundlich, Temkin and D-R isotherm models. The findings show that the biosorption isotherm was better fitted by the Langmuir equation and the maximum adsorption capacity of GT was found to be 38.7597 mg·g^-1. The kinetics data were analysed by pseudo-first order, pseudo-second order, and intra-particle diffusion equations. The results indicate that the pseudosecond-order model was found to explain the adsorption kinetics most effectively. The values of thermodynamic parameters including Gibbs free energy (△G°), enthalpy (△H°), and entropy (△S°) demonstrate that the biosorption process was exothermic and spontaneous. The multiple nonlinear regression (MnLR) and artificial neural network (ANN) analyses were applied for the prediction of biosorption capacity. A relationship between the predicted and observed data was obtained and the results show that the MnLR and ANN models provided successful predictions.     

Physicochemical Parameters of Cu(II) Ions Adsorption from Aqueous Solution by Magnetic-Poly(divinylbenzene-n-vinylimidazole) Microbeads

This study is aimed at the synthesis and characterization of the mesoporous magnetic-poly(divinylbenzene-1-vinylimidazole)[m-poly(DVB-VIM))microbeads(average diameter = 53–212 µm); their application as adsorbent in the removal of Cu(II) ions from aqueous solutions was investigated. The mesoporous m-poly(DVB-VIM) microbeads were prepared by copolymerizing of divinylbenzene (DVB) with 1-vinylimidazole (VIM). The mesoporous m-poly(DVB-VIM) microbeads were characterized by N₂ adsorption/desorption isotherms, ESR, elemental analysis, scanning electron microscope (SEM), and swelling studies. At fixed solid/solution ratio the various factors affecting adsorption of Cu(II) ions from aqueous solutions such as pH, initial concentration, amount of mesoporousm-poly(DVB-VIM)) microbeads, contact time, and temperature were analyzed. Langmuir, Freundlich, and Dubinin-Radushkvich isotherms were used the model adsorption equilibrium data. The Langmuir isotherm model was the most adequate. The pseudo first-order, pseudo-second-order, Ritch-second-order, and intraparticle diffusion models were used to describe the adsorption kinetics. The experimental data fitted to pseudo second-order kinetic. The study of temperature effect was quantified by calculating various thermodynamic parameters such as Gibbs free energy, enthalpy, and entropy changes. Morever, after the use in adsorption, the mesoporous m-poly(DVB-VIM) microbeads with paramagnetic property was separated via the applied magnetic force. These features make the mesoporous m-poly(DVB-VIM) microbeads a potential candidate for support of Cu(II) ions removal under magnetic field.     

Selective separation and concentration of Pd(II) from Fe(III), Co(II), Ni(II), and Cu(II) ions using thiourea‐formaldehyde resin

Thiourea‐formaldehyde (TUF), a well‐known chelating resin, has been synthesized and it was used in the adsorption, selective separation, and concentration of Pd(II) ions from Fe(III), Co(II) Ni(II), and Cu(II) base metal ions. The composition of the synthesized resin was determined by elemental analysis. The effect of initial acidity/pH and the adsorption capacity for Pd(II) ions were studied by batch technique. The adsorption and separation of Pd(II) were then examined by column technique. FTIR spectra and SEM/EDS analysis were also recorded before and after the adsorption of Pd(II). The optimum pH was found to be 4 for the adsorption. The adsorption data fitted well to the Langmuir isotherm. The maximum adsorption capacity of the TUF resin for Pd(II) ions was found to be 31.85 mg g⁻¹ (0.300 mmol g⁻¹). Chelating mechanism was effective in the adsorption. Pd(II) ions could be separated efficiently from Fe(III), Cu(II), Ni(II), and Co(II) ions using TUF resin. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Adsorption of Cu(II) ions from an aqueous solution by crosslinked amphoteric starch

The adsorption process of Cu(II) ions from aqueous solutions by crosslinked amphoteric starch with quaternary ammonium and carboxymethyl groups was investigated. The adsorption capacity was found to be dependent on the solution pH, the dose of the crosslinked amphoteric starch, and the initial concentration of Cu(II) ions. Moreover, the adsorption capacity increased with an increasing degree of substitution (DS) of the carboxymethyl groups. The adsorption followed a Freundlich adsorption isotherm. The adsorption process was endothermic, and the thermodynamic parameters were calculated at different DS values. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 728–732, 2004     

Removal Characteristics of Cd(II), Cu(II), Pb(II), and Zn(II) by Natural Mongolian Zeolite through Batch and Column Experiments

The removal characteristics of Cd(II), Cu(II), Pb(II), and Zn(II) from model aqueous solutions by 5 natural Mongolian zeolites were investigated. The adsorption of metals on zeolites reached a plateau value within 6 h. The adsorption kinetic data were fitted with adsorption kinetic models. The equilibrium adsorption capacity of the zeolites was measured and fitted using Langmuir and Freundlich isotherm models. The order of adsorption capacity of zeolite was Pb(II) > Zn(II) > Cu(II) > Cd(II). The maximum adsorption capacity of natural zeolite depends on its cation exchange capacity and pH. The leaching properties of metals were simulated using four leaching solutions. The results show that natural zeolite can be used as an adsorbent for metal ions from aqueous solutions or as a stabilizer for metal-contaminated soils.     

Selective Competitive Biosorption of Au(III) and Cu(II) in Binary Systems by Magnetospirillum gryphiswaldense

The biosorption of Au(III) and Cu(II) ions in both single and binary systems by Magnetospirillum gryphiswaldense (MSR-1) was investigated. For comparison with the selective reinforced competitive biosorption process in a binary system, the experimental research first explored the biosorption of Au(III) and Cu(II) in a single system under various conditions. The biomass exhibited the highest single Au(III) and Cu(II) ion adsorption yields at room temperature (25°C), pH values of 2.5 and 5.0, respectively, and a biomass concentration of 10 g · L^?1 (3.83 g · L^?1, dry basis). The experimental data from the single component system for the two metallic ions fitted well to a Langmuir isotherm and a pseudo second-order kinetic models. In the Au(III)-Cu(II) binary system, the coexistence of Cu(II) cations promoted the adsorption of Au(III) within a certain range of ratios. A new sigmoidal Cu(II) biosorption isotherm was determined specifically to reveal the Cu(II) adsorption behavior in this case.     

The adsorption behavior of Cu(II), Pb(II), and Co(II) of ethylene vinyl acetate‐clinoptilolite nanocomposites

In this study, ethylene vinyl acetate (EVA) was mixed with clinoptilolite (C), a natural zeolite, to prepare EVA‐C nanocomposites. The films were characterized by SEM‐EDS, XRD, and FT‐IR, and heavy metal removal was studied using the batch technique. The effects of the initial pH value and concentration of solutions, contact time, and filler dosage on the adsorption capacity of the composites were investigated. To study the influence of pretreatment on the filler, clinoptilolite was activated using KCl, NaCl, and HCl. Adsorption results show that equilibrium was reached after 24 h, and that sorption reached its maximum at pH values between 5 and 7. The selectivity trend was observed to be Pb > Cu > Co, which was consistent for both single and mixed metal‐ion solutions. Pretreatment significantly increased adsorption capacity of the composite, but was dependent on the conditioning reagent. Nanocomposites filled with HCl‐activated particles demonstrated a high adsorption capacity of between 70 and 80% for all three metals, while KCl‐activated particles were the least efficient with a maximum adsorption capacity of 69% for Pb(II), 54% for Cu(II) and 48% for Co(II). The adsorption data were then fitted to both Langmuir and Freundlich isotherms over the entire concentration range, and the Langmuir isotherm showed a better fit of the experimental sorption data than the Freundlich isotherm. The results obtained show that this simple methodology which can be up‐scaled has great potential for the preparation of a wide variety of similar particle‐filled adsorbent nanocomposites in other environmental remediation applications. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Adsorption performance of Al-pillared bentonite clay for the removal of cobalt(II) from aqueous phase

In this research, the natural bentonite clay collected from Ashapura Clay Mines, Gujarat State, India, was utilized as a precursor to produce aluminium-pillared bentonite clay (Al-PILC) for the removal of cobalt(II) [Co(II)] ions from aqueous solutions. The original bentonite clay and Al-PILC were characterized with the help of chemical analyses, methylene blue (MB) adsorption isotherm, powder X-ray diffraction (XRD), scanning electron microscopy (SEM) and infrared spectroscopy (IR), while the thermal stability of the samples were studied using thermogravimetry (TG). Surface charge density of the samples as a function of pH was investigated using potentiometric titrations. Adsorption experiments were conducted under various conditions, i.e., pH, contact time, initial concentration, ionic strength, adsorbent dose and temperature. The most effective pH range for the removal of Co(II) ions was found to be 6.0–8.0. The maximum adsorption of 99.8% and 87.0% took place at pH 6.0 from an initial concentration of 10.0 and 25.0 mg l⁻¹, respectively. Kinetic studies showed that an equilibrium time of 24 h was needed for the adsorption of Co(II) ions on Al-PILC and the experimental data were correlated by either the external mass transfer diffusion model for the first stage of adsorption and the intraparticle mass transfer diffusion model for the second stage of adsorption. The intraparticle mass transfer diffusion model gave a better fit to the experimental data. The Arrhenius and Eyring equations were applied to the data to determine the kinetic and thermodynamic parameters for explaining the theoretical behaviour of the adsorption process. The equilibrium isotherm data were analyzed using the Langmuir, Freundlich and Scatchard isotherm equations and the adsorption process was reflected by Freundlich isotherm. The efficiency of the Al-PILC was assessed by comparing the results with those on a commercial ion exchanger, Ceralite IRC-50. The suitability of the Al-PILC for treating Co(II) solutions was tested using simulated nuclear power plant coolant samples. Acid regeneration was tried for several cycles with a view to recover the adsorbed Co(II) and also to restore the adsorbent to its original state.     

Synthesis and characterization of poly(acrylaminophosphonic-carboxyl-hydrazide) chelating fibre

The poly(acrylaminophosphonic-carboxyl-hydrazide) chelating ion exchange fibre was prepared by the amination and phosphorization reaction of the hydrazine-modified polyacrylonitrile fibre. The structure of the chelating fibre and the same fibre saturated by Cu(II) and Ag(I) ions was investigated by IR spectrometer in detail. In addition, the crystalline and surface characteristics of the chelating fibre were determined by X-ray diffraction and SEM. The higher binding capacities of the fibrous sorbent for Cu(II), Pb(II), Zn(II), Co(II), Ni(II), Hg(II), Cd(II), Mn(II), Cr(III) and Ag(I) and the effect of pH value on adsorption of the chelating fibre for Cu(II) and Hg(II) ions were examined.     

Removal of copper(II) from an aqueous solution with copper(II)‐imprinted chitosan microspheres

Ion‐imprinted chitosan (CS) microspheres (MIPs) were prepared with Cu(II) as a template and epichlorohydrin as a crosslinker for the selective separation of Cu(II) from aqueous solution. The microspheres showed a higher adsorption capacity and selectivity for the Cu(II) ions than nonimprinted chitosan microspheres (NMIPs) without a template. The results show that the adsorption of Cu(II) on the CS microspheres was affected by the initial pH value, initial Cu(II) concentration, and temperature. The kinetic parameters of the adsorption process indicated that the adsorption followed a second‐order adsorption process. Equilibrium experiments showed very good fits with the Langmuir isotherm equation for the monolayer adsorption process. The maximum sorption capacity calculated from the Langmuir isotherm was 201.66 mg/g for the Cu–MIPs and 189.51 mg/g for the NMIPs; these values were close to the experimental ones. The selectivity coefficients of Cu(II) and other metal ions on the NMIPs indicated a preference for Cu(II). © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Batch and continuous (fixed-bed column) biosorption of Cu(II) by Tamarindus indica fruit shell

The feasibility of employing Tamarindus indica (tamarind) fruit shell (TFS) as low-cost biosorbent for removal of Cu(II) from aqueous solutions was investigated. Batch experiments were carried out as function of initial solution pH (2–7), contact time (10–240 min), initial Cu(II) concentration (20–100 mg L^?1), biosorbent dose (0.5–5 g) and temperature (293–313 K). Biosorption equilibrium data were well described by the Langmuir isotherm model with maximum biosorption capacity of 80.01 mg g^?1 at 313 K. Biosorption of Cu(II) followed pseudo-second-order kinetics. Gibbs free energy (ΔG⁰) was spontaneous for all interactions, and the biosorption process exhibited endothermic enthalpy values. To ascertain the practical applicability of the biosorbent, fixed-bed column studies were also performed. The breakthrough time increased with increasing bed height and decreased with increasing flow rate. The Thomas model as well as the Bed Depth Service Time (BDST) model was fitted to the dynamic flow experimental data to determine the column kinetic parameters useful for designing large-scale column studies. The Thomas model showed good agreement with the experimental results at all the process parameters studied. It could be concluded that TFS may be used as an inexpensive and effective biosorbent without any treatment or any other modification for the removal of Cu(II) ions from aqueous solutions.