Sorption of acid dyes onto GLA and H2SO4 cross-linked chitosan beads

The feasibility of chitosan and cross-linked chitosan beads as efficient adsorbents for the removal of Acid Blue 25 (AB 25) and Acid Red 37 (AR 37) from aqueous solution was studied by using batch adsorption techniques. Glutaraldehyde (GLA) and sulphuric acid were employed as cross-linking reagents. The effect of process parameters like pH, agitation period, agitation rate and concentrations of dyes on the extent of AR 37 and AB 25 adsorption by chitosan and cross-linked chitosan beads was investigated. The best interpretation for the equilibrium data was given by the Langmuir isotherm, while the pseudo-second-order kinetic model could best describe the adsorption of these acid dyes. Thermodynamic parameters such as enthalpy change (ΔH°), free energy change (ΔG°) and entropy change (ΔS°) were estimated and adsorption process was spontaneous and exothermic. The desorbed chitosan, chitosan-GLA and chitosan-H₂SO₄ beads can be reused to adsorb the acid dyes. Results also showed that chitosan, chitosan-GLA and chitosan-H₂SO₄ beads were favourable adsorbers.     

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     

Adsorption of lanthanum by magnetic alginate‐chitosan gel beads

BACKGROUND: The risk of environmental pollution is aggravated by the increasing application of considerable amounts of rare earth elements in advanced materials. This paper reports the preparation of novel magnetic alginate–chitosan gel beads and their application for adsorption of lanthanum ions from aqueous solution. RESULTS: Stable magnetic alginate–chitosan gel beads with average diameter 0.85 ± 0.05 mm were prepared by loading iron oxide nanoparticles onto a combined alginate and chitosan absorbent. The performance of the prepared beads for the adsorption of lanthanum ions from aqueous solution was tested. It was found that various parameters, such as aqueous pH, contact time, metal ion concentration, ion strength and temperature, have an effect on the adsorption. Adsorption equilibrium was reached in 10 h and the maximum uptake capacity was 97.1 mg g^?1. From the analysis of pH, FTIR and XPS data, it is proposed that lanthanum adsorption proceeds through mechanisms of cation exchange, electrostatic interaction and surface complexation, with the oxygen atoms the main binding sites. In addition, lanthanum ions could be selectively separated from coexisting base metal ions such as Pb (II), Cd (II), Co (II), Ni (II) and Cu (II) in the aqueous solution. CONCLUSION: The prepared magnetic alginate–chitosan gel beads exhibit high uptake capacity and selectivity for lanthanum sorption, and thus can be used for adsorptive recovery of lanthanum from aqueous solutions. Copyright © 2010 Society of Chemical Industry     

Adsorptive Removal of Pb(II) and Cu(II) Ions from Aqueous Solutions by Cross-Linked Chitosan-Polyphosphate-Epichlorohydrin Beads

In this study, the cross-linked chitosan-polyphosphate-epichlorohydrin (CCPE) beads were prepared by cross-linking chitosan with both polyphosphate and epichlorohydrin and used as bioadsorbent for the removal of Pb(II) and Cu(II) ions from aqueous solutions. The effects of the dosage of CCPE beads, solution pH, initial metal ion concentration, contact time, and temperature were investigated. Then, three important factors were selected to optimize the removal processes by the orthogonal test. The results show that CCPE beads can effectively remove the Pb(II) and Cu(II) ions from aqueous solutions, and the maximum percentage removals for Pb(II) and Cu(II) ions are 99.7% and 91.2%, respectively. The data show also that the removal processes for both Pb(II) and Cu(II) ions fit best the pseudo-second order kinetic model. Moreover, the decrease of the adsorption ability of CCPE beads is less than 10% after reuse for 9 times, which suggests that CCPE beads have good reusability.     

Adsorption equilibria of reactive dye onto highly polyaminated porous chitosan beads

The adsorption of vinyl sulfone type reactive black 5 (RB 5) in aqueous solution onto chitosan beads and cross-linked chitosan beads with glutaraldehyde has been investigated in terms of initial pH and temperature of the solution. The adsorption equilibrium data were correlated with three adsorption models, such as Langmuir, Freundlich and Sips isotherms. Among them, the Freundlich isotherm best fit the data over the entire pH and temperature range of the solution. The adsorption capacity of RB 5 onto chitosan beads and cross-linked chitosan beads increased with decreasing initial pH and with increasing temperature. Equilibrium amount of RB 5 on chitosan beads was greater than that of cross-linked chitosan beads at the same initial pH values. Thermodynamic studies have also been carried out and values of standard free energy (°Gℴ), enthalpy (°Hℴ) and entropy (°Sℴ) were calculated.     

Preparation and characterization of porous chitosan–tripolyphosphate beads for copper(II) ion adsorption

Porous chitosan–tripolyphosphate beads, prepared by the ionotropic crosslinking and freeze‐drying, were used for the adsorption of Cu(II) ion from aqueous solution. Batch studies, investigating bead adsorption capacity and adsorption isotherm for the Cu(II) ion, indicated that the Cu(II) ion adsorption equilibrium correlated well with Langmuir isotherm model. The maximum capacity for the adsorption of Cu(II) ion onto porous chitosan–tripolyphosphate beads, deduced from the use of the Langmuir isotherm equation, was 208.3 mg/g. The kinetics data were analyzed by pseudo‐first, pseudo‐second order kinetic, and intraparticle diffusion models. The experimental data fitted the pseudo‐second order kinetic model well, indicating that chemical sorption is the rate‐limiting step. The negative Gibbs free energy of adsorption indicated a spontaneous adsorption, while the positive enthalpy change indicated an endothermic adsorption process. This study explored the adsorption of Cu(II) ion onto porous chitosan–tripolyphosphate beads, and used SEM/EDS, TGA, and XRD to examine the properties of adsorbent. The use of porous chitosan–tripolyphosphate beads to adsorb Cu(II) ion produced better and faster results than were obtained for nonporous chitosan–tripolyphosphate beads. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Facile preparation of magnetic chitosan modified with thiosemicarbazide for adsorption of copper ions from aqueous solution

In this study, magnetic chitosan modified with thiosemicarbazide (TSC‐Fe₃O₄/CTS) was facilely synthesized with glutaraldehyde as the crosslinker, and its application for removal of Cu(II) ions was investigated. The as‐prepared TSC‐Fe₃O₄/CTS was characterized by Fourier transform infrared spectroscopy (FTIR), X‐ray powder diffraction (XRD), and scanning electron microscopy (SEM). The results showed that TSC‐Fe₃O₄/CTS has high adsorption capacity and selectivity towards Cu(II) ions. Adsorption experiments were carried out with different parameters such as pH, solution temperature, contact time and initial concentration of Cu(II) ions. The adsorption process was better described by the pseudo‐second‐order model. The sorption equilibrium data was fitted well with the Langmuir isotherm model and the maximum adsorption capacity toward Cu(II) ions was 256.62 mg/g. The thermodynamic parameters indicated that the adsorption process of Cu(II) ions was exothermic spontaneous reaction. Moreover, this adsorbent showed excellent reusability and the adsorption property remained stable after five cycles. This adsorbent is believed to be one of the promising and favorable adsorbent for the removal of Cu(II) ions from aqueous solution. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44528.     

Zeolite X/chitosan hybrid microspheres and their adsorption properties for Cu(II) ions in aqueous solutions

The preparation of zeolite X/chitosan (CS) hybrid microspheres for efficient removal of Cu(II) ions by an impregnation-gelation-hydrothermal synthesis technique is reported here. Characterizations by various techniques indicate that the microspheres show porous structures and intimate interaction between zeolite and CS. The adsorption experiments are performed to evaluate the adsorption capacity of zeolite X/CS hybrid microspheres and comparisons are made with binderless zeolite X microspheres, pure CS microspheres and mechanical mixed zeolite X/CS microspheres. The effects of Cu(II) solution concentration and the pH are investigated. The results indicate that zeolite X/CS hybrid microspheres with the zeolite content of 60 wt% show the highest adsorption capacity, which is 90 mg/g at the initial Cu(II) concentration of 10 mg/L and 150.4 mg/g at Cu(II) concentration of 500 mg/L. The adsorption capacity increases with increasing initial pH and reaches a maximum at pH 5.5 in the range of 0–6.0. The equilibrium adsorption data are well described by the Langmuir isotherm model, exhibiting a maximum adsorption capacity of 152.0 mg/g, and the kinetic data are well fitted with the pseudo-second-order equation. Complete removal of Cu(II) ions can be obtained even at very low concentrations. The microspheres show high adsorption capacity and efficiency for Cu(II) ions, exhibiting potential practical application in the treatment of water pollution of heavy metal ions.     

Adsorption of cadmium (II) and copper (II) ions from aqueous solution using chitosan composite

The binary chitosan/silk fibroin composite synthesized by reinforcement of silk fibroin fiber into the homogenous solution of chitosan in formic acid was used to investigate the adsorption of two metals of Cu(II) and Cd(II) ions in an aqueous solution. The binary composite was characterized by Fourier transform infrared and scanning electron microscopy. The optimum conditions for adsorption by using a batch method were evaluated by changing various parameters such as contact time, adsorbent dose, and pH of the solution. The experimental isotherm data were analyzed using the Freundlich and Langmuir equations, indicated to be well fitted to the Langmuir isotherm equation under the concentration range studied, by comparing the correlation co‐efficient. Adsorption kinetics data were tested using pseudo‐first‐order and pseudo‐second‐order models. Kinetics studies showed that the adsorption followed a pseudo‐second‐order reaction. Due to good performance and low cost, this binary chitosan/silk fibroin composite can be used as an adsorbent for removal of Cu(II) and Cd(II) from aqueous solutions. POLYM. COMPOS., 2013. © 2013 Society of Plastics Engineers     

交联壳聚糖磁性颗粒吸附去除水溶液中的铜

The performance of cross-linked magnetic chitosan, coated with magnetic fluids and cross-linked with epichlorohydrin, was investigated for the adsorption of copper (II) from aqueous solutions. Infrared spectra of chitosan before and after modification showed that the coating and cross-linking are effective. Experiments were performed at different pH of solution and contact time, and appropriate conditions for the adsorption of Cu(II) were determined. Experimental equilibrium data were correlated with Langmuir and Freundlich isotherms for determination of the adsorption potential. The results showed that the Langmuir isotherm was better compared with the Freundlich isotherm, and the uptake of Cu(II) was 78.13 mg•g－1. The kinetics of adsorption corresponded with the first-order Langergren rate equation, and Langergren rate constants were determined.     

Simultaneous removal of copper and zinc ions by low cost natural snail shell/hydroxyapatite/chitosan composite

In this work, the snail shell/hydroxyapatite/chitosan composite was prepared as adsorbent. The adsorption potential of the composite was studied for simultaneous sorption behavior of Zn(Ⅱ) and Cu(Ⅱ) ions in a batch system. Chitosan and hydroxyapatite(HAP) were extracted from shrimp shell and bone ash,respectively, so this is a low cost natural composite. To prepare the composite, chitosan was dissolved in acetic acid, then HAP and snail shell powders were added to the chitosan solution. The morphology and characterization of the composite was studied by SEM and EDX analysis. Atomic adsorption was used to measure the amount of the ions. Experimental parameters were optimized with Design Expert Software and five parameters such as the concentration of ions, p H, adsorbent amount and contact time were studied at room temperature. Optimized value for the parameters of Zn(Ⅱ) and Cu(Ⅱ) concentrations, p H, adsorbent dose, and contact time were 3.01 mg·L~(-1), 5.5, 0.02 g and 95 min, respectively. The adsorption isotherms for Zn(Ⅱ) and Cu(Ⅱ) showed Langmuir and Tempkin, respectively. Kinetic and equilibrium studies showed the experimental data of Zn(Ⅱ) and Cu(Ⅱ) ions were best described by the pseudo-second-order model. Studies on thermodynamic show the adsorption process were physical and spontaneous.     

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.     

Preparation,characterization, and adsorption properties of chitosan microspheres crosslinked by formaldehyde for copper (II) from aqueous solution

The chitosan microspheres crosslinked by formaldehyde were prepared by spray drying method and used as an adsorbent for copper (II) from aqueous solution. A batch adsorption system was applied to study the adsorption of copper (II) from aqueous solution by chitosan microspheres. The maximum adsorption capacity of the chitosan microspheres for copper (II) was 144.928 mg/g at pH 6.0. Langmuir adsorption model was found to be applicable in interpreting the adsorption process. To elucidate the adsorption mechanism, the chitosan microspheres before and after copper (II) adsorption were further characterized by Fourier transform infrared spectra, zeta potential analysis, and scanning electron microscope. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Adsorption characteristics of Reactive Black 5 onto chitosan beads cross-linked with epichlorohydrin

In this study, epichlorohydrin cross-linked chitosan beads were used for the removal of Reactive Black 5 (RB 5) from aqueous solution. The adsorption of RB 5 onto the cross-linked chitosan beads was strongly pH dependent. The adsorption capacity of RB 5 onto the cross-linked chitosan beads increased with increasing temperature, indicating the endothermic nature of the adsorption process. The thermodynamic parameters, namely the Gibbs free energy, enthalpy and entropy of the RB 5 adsorption process were calculated. The kinetic parameters were measured in a batch adsorber to analyze the rate of adsorption of RB 5 onto the cross-linked chitosan beads.     

Removal of Cd(II), Hg(II), and Pb(II) ions from aqueous solution using p(HEMA/chitosan) membranes

An interpenetration network (IPN) was synthesized from 2‐hydroxyethyl methacrylate (HEMA) and chitosan, p(HEMA/chitosan) via UV‐initiated photo‐polymerization. The selectivity to different heavy metal ions viz Cd(II), Pb(II), and Hg(II) to the IPN membrane has been investigated from aqueous solution using bare pHEMA membrane as a control system. Removal efficiency of metal ions from aqueous solution using the IPN membranes increased with increasing chitosan content and initial metal ions concentrations, and the equilibrium time was reached within 60 min. Adsorption of all the tested heavy metal ions on the IPN membranes was found to be pH dependent and maximum adsorption was obtained at pH 5.0. The maximum adsorption capacities of the IPN membrane for Cd(II), Pb(II), and Hg(II) were 0.063, 0.179, and 0.197 mmol/g membrane, respectively. The adsorption of the Cd(II), Hg(II), and Pb(II) metal ions on the bare pHEMA membrane was not significant. When the heavy metal ions were in competition, the amounts of adsorbed metal ions were found to be 0.035 mmol/g for Cd(II), 0.074 mmol/g for Hg(II), and 0.153 mmol/g for Pb(II), the IPN membrane is significantly selective for Pb(II) ions. The stability constants of IPN membrane–metal ions complexes were calculated by the method of Ruzic. The results obtained from the kinetics and isotherm studies showed that the experimental data for the removal of heavy metal ions were well described with the second‐order kinetic equations and the Langmuir isotherm model. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Microwave preparation and copper ions adsorption properties of crosslinked chitosan/ZSM molecular sieve composites

A novel chitosan‐based composite (CTS/ZSM) made of chitosan and ZSM molecular sieve was prepared under microwave irradiation and was used for the removal of Cu (II) ions from aqueous solution. The composites were characterized by FTIR spectra, XRD spectra, and thermogravimetric analysis. The effects of the ZSM content, amount of glutaraldehyde and pH value on adsorption properties of Cu (II) ions by CTS/ZSM were discussed in detail. Contrast with crosslinked chitosan (CCTS), the CTS/ZSM had higher adsorption capacity for Cu (II). Kinetic studies showed that the adsorption of Cu (II) onto CTS/ZSM composite had low correlation coefficients for the pseudo‐first and ‐second order model and intraparticle diffusion model. The equilibrium process was better described by the Langmuir than Freundlich isotherm model. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Effect of heparin coating on epichlorohydrin cross-linked chitosan microspheres on the adsorption of copper (II) ions

Epichlorohydrin cross-linked chitosan microspheres (CS) and chitosan–heparin polyelectrolyte complex microspheres (CSH) were used in the adsorption of copper (II) ions in aqueous solution. The chitosan microspheres were prepared by the phase inversion method. The use of a cross-linking agent improved the resistance to acidic medium. Polyelectrolyte complex microspheres were prepared by impregnating heparin in cross-linked chitosan microspheres. The microspheres were characterized by IR, TGA and DSC. A study on the effect of the pH on the adsorption of copper (II) ions showed that the optimum pH for both CS and CSH microspheres was 6.0. From a kinetic evaluation, it could be established that the adsorption equilibrium was achieved after 8 h for CS and 25 h for CSH microspheres. The adsorption isotherms were interpreted using Langmuir and Freundlich mathematical models. The results revealed that experimental data of CS was best adjusted by Langmuir model, with maximum capacity of surface saturation equal to 39.31 mg g⁻¹. On the other hand, Langmuir and Freundlich models provided a good fit for adsorption by CSH and the adsorption capacity was 81.04 mg g⁻¹. The interactions between copper (II) ions and both CS and CSH were confirmed by electron paramagnetic resonance spectroscopy, which revealed the formation of a square-planar complex with tetrahedral distortion on the surface of the adsorbents.     

Competitive adsorption of Ag (I) and Cu (II) by tripolyphosphate crosslinked chitosan beads

Alkalization of chitosan before crosslinking was applied in this study to enhance the adsorption capacity of the modified chitosan. Competitive adsorption of Ag (I) and Cu (II) from bimetallic solutions was studied using the newly synthesized tripolyphosphate crosslinked alkalized chitosan beads. Results indicated that alkalization before crosslinking helps to protect amine group from crosslinking and hence increases the uptake capacity and selectively of the synthesized beads toward Ag (I). The maximum uptakes of Ag (I) and Cu (II) were 82.9 and 15.5 mg g^?1, respectively, at room temperature with an initial concentration of each metal being 2.0 mM and the sorbent dosage of 1.0 g L^?1. The uptake of Ag (I) and Cu (II) by the beads can be better described by Langmuir isotherm and pseudo‐second rate equation. Analyses from FTIR and XPS confirmed that free amine, hydroxyl, and groups are involved in metal binding with amine and hydroxyl groups more selective to Ag (I). © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42717.     

Adsorption of Cd(II), Pb(II), and Ag(I) in aqueous solution on hollow chitosan microspheres

Cross‐linked chitosans synthesized by the inverse emulsion cross‐link method were used to investigate adsorption of three metal ions [Cd(II), Pb(II), and Ag(I)] in an aqueous solution. The chitosan microsphere, was characterized by FTIR and SEM, and adsorption of Cd(II), Pb(II), and Ag(I) ions onto a cross‐linked chitosan was examined through analysis of pH, agitation time, temperature, and initial concentration of the metal. The order of adsorption capacity for the three metal ions was Cd²⁺ > Pb²⁺ > Ag⁺. This method showed that adsorption of the three metal ions in an aqueous solution followed the monolayer coverage of the adsorbents through physical adsorption phenomena and coordination because the amino (? NH₂) and/or hydroxy (? OH) groups on chitosan chains serve as coordination sites. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Adsorption of Divalent Cobalt from Aqueous Solution onto Chitosan–Coated Perlite Beads as Biosorbent

Abstract

Chitosan coated perlite beads are prepared by drop‐wise addition of a liquid slurry containing chitosan and perlite to an alkaline bath. The resulting beads are characterized using FTIR, SEM, EDXRF, and Surface area analysis and the chitosan content of the beads is 23% as determined by a pyrolysis method. Adsorption of Co (II) metal ions from aqueous solution on chitosan coated perlite beads is studied under both equilibrium and dynamic conditions. In the present investigation, a first order reversible rate equation is used to understand the kinetics of metal removal and to calculate the rate constants at different initial concentrations. The equilibrium characteristics of metal ion on newly developed biosorbent are studied and the experimental adsorption data are well fitted to Freundlich and Langmuir adsorption isotherm models and the model parameters are evaluated. The effect of pH, agitation time, concentration of adsorbate, and amount of adsorbent on the extent of the adsorption are investigated. The sorbent loaded with metal is regenerated with 0.10 mol dm^?3 sodium hydroxide solution. The adsorption desorption cycles indicated that the chitosan coated perlite could be regenerated and reused to remove Co (II) from waste water.