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.     

Preparation and characterization of a novel nanocomposite of clinoptilolite/maghemite/chitosan/urea for manganese removal from aqueous solution

Synthesis of a new magnetic nanocomposite of Clinoptilolite/Maghemite/Chitosan/Urea has been carried out to introduce an adsorbent to remove manganese as a toxic heavy metal from aqueous solution. Clinoptilolite zeolite became magnetic using the maghemite nanoparticles, then coated using chitosan as a biodegradable and non-toxic polymer, and finally functionalized by urea to increase the adsorption capacity. For characterization of the nanocomposite, the X-Ray diffraction, IR spectroscopy, vibrating sample magnetometery, and scanning electron microscopy were used. The effects of temperature, contact time, initial metal concentration, solution pH and adsorbent dose on the manganese removal capacity were evaluated. The kinetics of adsorption by the pseudo-first-order, pseudo-second-order, and Elovich kinetic models was studied and the results suggested the compliance of pseudo-second-order kinetic model with the kinetic data. The maximum adsorption capacity of manganese under the optimum condition of pH=2.13, the adsorbent amount of 0.02 g, initial solution concentration of 46.00 mg/L with response surface methodology, equaled 16.30 mg/g. The Langmuir, Freundlich, Temkin and Dobinin-Rudoshkovich adsorption isotherm models were investigated and Langmuir best fit the isotherm data. In the study of the thermodynamic results, negative Gibbs free energy represents the spontaneous nature of manganese removal process.     

Microwave preparation and adsorption properties of EDTA‐modified cross‐linked chitosan

A novel chitosan‐based adsorbent (CCTE) was synthesized by the reaction between epichlorohydrin O‐cross‐linked chitosan and EDTA dianhydride under microwave irradiation (MW). The chemical structure of this new polymer was characterized by infrared spectra analysis, thermogravimetric analysis, and X‐ray diffraction analysis. The results were in agreement with the expectations. The static adsorption properties of the polymer for Pb²⁺, Cu²⁺, Cd²⁺, Ni²⁺, and Co²⁺ were investigated. Experimental results demonstrated that the CCTE had higher adsorption capacity for the same metal ion than the parent chitosan and cross‐linked chitosan. In particular, the adsorption capacities for Pb²⁺ and Cd²⁺ were 1.28 mmol/g and 1.29 mmol/g, respectively, in contrast to only 0.372 mmol/g for Pb²⁺ and 0.503 mmol/g for Cd²⁺ on chitosan. Kinetic experiments indicated that the adsorption of CCTE for the above metal ions achieved the equilibrium within 4 h. The desorption efficiencies of the metal ions on CCTE were over 93%. Therefore, CCTE is an effective adsorbent for the removal and recovery of heavy metal ions from industrial waste solutions. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Adsorption of Pb2+ and Cd2+ onto a Novel Activated Carbon‐Chitosan Complex

A novel activated carbon‐chitosan complex adsorbent (ACCA) was prepared via the crosslinking of glutaraldehyde and activated carbon‐(NH₂‐protected) chitosan complex under microwave irradiation. The surface morphology of this adsorbent was characterized. The adsorption of ACCA for Pb²⁺ and Cd²⁺ was investigated. The results demonstrate that ACCA has higher adsorption capacity than chitosan. The adsorption follows pseudo first‐order kinetics. The isotherm adsorption equilibria are better described by Freundlich and Dubinin‐Radushkevich isotherms than by the Langmuir isotherm. The adsorbent can be recycled. These results have important implications for the design of low‐cost and effective adsorbents in the removal of heavy metal ions from wastewaters.     

Facile preparation of EDTA‐functionalized chitosan magnetic adsorbent for removal of Pb(II)

A novel magnetic adsorbent (EDTA /chitosan/ PMMS) was facilely prepared by reacting chitosan with EDTA anhydride in presence of PEI ‐ coated magnetic microspheres. The as‐synthesized EDTA/ chitosan /PMMS was characterized by XRD, SEM, TGA, FT‐IR , and VSM, and then employed in removal of heavy metals of Pb(II) from aqueous solution. The results of the batch adsorption experiments revealed that the adsorbents had extremely high uptake capacities for Pb(II) in the pH range of 2 to 5.5, and the adsorption kinetics for EDTA/ chitosan /PMMS was consistent with the pseudo – second ‐ order kinetic model. Moreover, its equilibrium data were fitted with the Langmuir isothermal model well, which indicated that the adsorption mechanism was a homogeneous monolayer chemisorptions process. The maximum adsorption capacity of EDTA/ chitosan /PMMS for Pb(II) was found to be 210 mg g ^{? 1} at pH 4 (30 ° C), and further reuse experiments results suggested that EDTA /chitosan/ PMMS could be a potential recyclable magnetic adsorbent in the practical wastewater treatment. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42384.     

Effects of Acylation and Crosslinking on the Material Properties and Cadmium Ion Adsorption Capacity of Porous Chitosan Beads

Abstract

Chitosan is a novel glucosamine biopolymer derived from the shells of marine organisms. This biopolymer is very attractive for heavy metal ion separations from wastewater because it is selective for toxic transition metal ions over less toxic alkali or alkane earth metal ions. Highly porous, 3-mm chitosan beads were prepared by an aqueous phase-inversion technique for casting gel beads followed by freeze drying. In the attempt to simultaneously improve material properties and adsorption capacity, chitosan was chemically modified by 1) homogeneous acylation of amine groups with nonanoyl chloride before bead casting, and 2) heterogeneous crosslinking of linear chitosan chains with the bifunctional reagent glutaric dialdehyde (GA) after bead casting but before freeze drying. The random addition of C₈ hydrocarbon side chains to about 7% of the amine groups on uncrosslinked chitosan beads via N-acylation improved the saturation adsorption capacity from 169 to 216 mg Cd²⁺/g-bead at saturation (pH 6.5, 25°C) but only slightly reduced solubility in acid solution. Crosslinking of the N-acylated chitosan beads with 0.125 to 2.5 wt% GA in the crosslinking bath increased the internal surface area from 40 to 224 m²/g and rendered the beads insoluble in 1 M acetic acid (pH 2.36). However, crosslinking of the N-acylated chitosan beads reduced the saturation adsorption capacity to 136 mg Cd²⁺/g-bead at 0.75 wt% GA and 86 mg Cd²⁺/g-bead at 2.5 wt% GA. Crosslinking also significantly reduced the compression strength. There was no clear relationship between internal surface area and adsorption capacity, suggesting that the adsorbed cadmium was not uniformly loaded into the bead.     

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     

Removal of Cd2+ ions from aqueous solution using cassava starch–based superabsorbent polymers

A comprehensive feasibility study on the adsorption of Cd²⁺ ions by cassava starch–based superabsorbent polymers (CST‐SAPs) as the biosorbent was investigated as a function of adsorbent dosage, pH, initial concentration, contact time, and temperature. An orthogonal experiment and range analysis were applied to optimize the adsorption conditions. Adsorbent dosage and initial concentration were the most sensitive variables for adsorption capacity. The maximum adsorption value of Cd²⁺ ions was determined as 347.46 mg/g at pH 6.0, initial concentration of 200 mg/L, and contact temperature and time of 323 K and 6 h, respectively, with 0.1 g adsorbent dosage. The equilibrium data were well described by a Langmuir model, and the adsorption process was well fitted by pseudo‐second‐order kinetics. The Fourier transform infrared spectroscopy (FTIR) data confirmed that acrylic acid and acrylic amide grafted onto the cassava starch. The X‐ray diffraction and FTIR results for the Cd²⁺‐absorbed CST‐SAP (CST‐SAP‐Cd²⁺) samples showed that the CST‐SAP could effectively adsorb Cd²⁺ ions and that the characteristic groups were translocated by chelation. The scanning electron microscopy results for the CST‐SAP revealed that the surface of the polymer was rough, and the layered structure that was full of folds caused an enhanced specific surface; such conditions were beneficial to Cd²⁺ ion adsorption. It was concluded that the CST‐SAP was an excellent adsorbent for Cd²⁺ ion removal from aqueous solution. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44758.     

Preparation and characterization of higher degree‐deacetylated chitosan‐coated magnetic adsorbent for the removal of chromium(VI) from its aqueous mixture

Chitosan (90% deacetylated) coated magnetic adsorbent prepared by coprecipitation method to remove Cr(VI) from its aqueous solution. The experimental studies depicts that the predominant option for removal of Chromium by adsorption from its aqueous phase using Magnetic‐Chitosan (MC). The subsequent physical, chemical, and magnetic properties of MC were characterized by X‐ray powder diffraction, scanning electron microscopy, Fourier transform infrared spectrometer, vibrating sample magnetometer. The influence of batch process parameters such as contact time, initial concentration, pH, and coexisting anions were investigated. The Box‐Behnken experimental design in response surface methodology was performed to design the experiment optimal operating conditions. The maximum percentage reduction of Cr(VI) is 96.3 that was obtained by magnetic chitosan with the optimal operating conditions of 149.53 mg/L at pH of 5.32 at the contact time of 80 min and at the temperature of 303 K. The average diameter of the magnetic chitosan was calculated from X‐ray diffractometer analysis as 24.5 nm. The equilibrium adsorption isotherm models such as Langmuir and Freundlich and the adsorption kinetics such as pseudo first order, pseudo second order and intra‐particle diffusion kinetic model were analyzed. The experimental data's suited for the best fit with the Langmuir isotherm model and pseudo first order kinetic model. It also revealed that Cr(VI) adsorption on MC is intrinsically exothermic and spontaneous. The magnetic chitosan was also used to investigate for the removal of Cr(VI) from the real water sources such as surface, underground, and tannery wastewater. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45878.     

Single and Binary Adsorption of Food Dyes on Chitosan/Activated Carbon Hydrogels

The removal of dye contaminants from water is an important issue and different adsorbents have been developed for this purpose. Here, chitosan hydrogel, scaffold‐chitosan hydrogel, and scaffold‐chitosan hydrogel with activated carbon were developed and used in the adsorption of food blue 2 and food red 17, from single and binary aqueous systems. The adsorbents presented good mechanical properties, high efficiency, high adsorption capacity, and fast kinetics for single and binary systems. Chitosan hydrogel presented excellent reusability capacity and can be reused for five cycles. The use of these hydrogels enables the application of adsorbent materials with three‐dimensional frameworks for dye adsorption in single or binary systems.     

Removal of Pb(II) from Aqueous Solutions by using Chitosan Coated Zero Valent Iron Nanoparticles

This study reports the synthesis, characterization, and application of chitosan coated zero valent iron nanoparticles (CTS-Fe⁰) in the removal of Pb(II) from aqueous medium. This nano adsorbent showed a high adsorption capacity and efficient adsorption towards Pb(II) in aqueous medium. Adsorption of Pb(II) on CTS-Fe⁰ obeyed pseudo-second order kinetics and was controlled by a film diffusion process. Among the various isotherm models the experimental data followed the Langmuir isotherm and the maximum adsorption capacity was found to be 666.6 mg/g at pH 5.0 and 318 K. The sorption mean free energy from D-R isotherm was found to be 72, 131, and 177 J/mol at 298, 308, and 318 K, respectively, indicating a physical sorption. The percentage of Pb(II) removal by CTS-Fe⁰ particles is more than 90% at 318 K. The calculated thermodynamic parameters showed that the adsorption of Pb(II) is feasible, spontaneous, and endothermic in nature. Experimental results indicated that the CTS-Fe⁰ appears to be a promising adsorbent for the removal of Pb(II) from aqueous media.     

Adsorption of lead and copper on bentonite and grapeseed activated carbon in single- and binary-ion systems

In this study, bentonite originating from Turkey (Eski?ehir province) and activated carbon obtained from grapeseed were used as adsorbents for the removal of lead (Pb²⁺) and copper (Cu²⁺) ions from aqueous solutions. Experiments were performed in single- and binary-ion systems at constant temperature of 298 K and pH value of 5. In order to describe the adsorption mechanism Langmuir, Freundlich and Temkin isotherms were used. The total adsorption capacity values of adsorbents were compared. It was observed that the total adsorption capacity values were changed depending on the type of adsorbent used, type of metal ion and interaction between metal ions.     

Stability constants of amidoximated chitosan‐g‐poly(acrylonitrile) copolymer for heavy metal ions

Amidoximated chitosan‐g‐poly(acrylonitrile) (PAN) copolymer was prepared by a reaction between hydroxylamine and cyano group in chitosan‐g‐PAN copolymer prepared by grafting PAN onto crosslinked chitosan with epychlorohydrine. The adsorption and desorption capacities for heavy metal ions were measured under various conditions. The adsorption capacity of amidoximated chitosan‐g‐PAN copolymer increased with increasing pH values, and was increased for Cu²⁺ and Pb²⁺ but a little decreased for Zn²⁺ and Cd²⁺ with increasing PAN grafting percentage in amidoximated chitosan‐g‐PAN copolymer. In addition, desorption capacity for all metal ions was increased with increasing pH values in contrast to the adsorption results. Stability constants of amidoximated chitosan‐g‐PAN copolymer were higher for Cu²⁺ and Pb²⁺ but lower for Zn²⁺ and Cd²⁺ than those of crosslinked chitosan. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 73: 469–476, 1999     

交联氧化铝-壳聚糖新杂化吸附剂的制备及去除废水中Cu(Ⅱ)(英文)

A novel biosorbent was developed by coating chitosan,a naturally and abundantly available biopolymer,on to activated alumina based on oil shale ash via crosslinking.The adsorbent was characterized by various techniques,such as Fourier transform infrared spectroscopy,scanning electron microscopy,thermogravimetric-differential thermal analysis,and X-ray photoelectron spectroscope.Batch isothermal equilibrium adsorption experiments were condcted to evaluate the adsorbent for the removal of Cu(Ⅱ) from wastewater.The effect of pH and agitation time on the adsorption capacity was also investigated,indicating that the optimum pH was 6.0.The equilibrium adsorp-tion data were correlated with Langmuir and Freundlich models.The maximum monolayer adsorption capacity of chitosan coated alumina sorbent as obtained from Langmuir adsorption isotherm was found to be 315.46 mg·g-1 for Cu(Ⅱ).The adsorbent loaded with Cu(Ⅱ) was readily regenerated using 0.1 mol?L?1 sodium hydroxide solution.All these indicated that chitosan coated alumina adsorbent not only have high adsorption activity,but also had good stability in the wastewater treatment process.     

Electron Beam Grafted Polymer Adsorbent for Removal of Heavy Metal Ion from Aqueous Solution

Abstract

An electron beam grafted adsorbent was synthesized by post irradiation grafting of acrylonitrile (AN) on to a non‐woven thermally bonded polypropylene (PP) sheet using 2 MeV electron beam accelerator. The grafted poly(acrylonitrile) chains were chemically modified to convert a nitrile group to an amidoxime (AMO) group, a chelating group responsible for metal ion uptake from an aqueous solution. The effect of various experimental variables viz. dose, dose rate, temperature, and solvent composition on the grafting extent was investigated. PP grafted with the amidoxime group (AMO‐g‐PP) was tested for its suitability as an adsorbent for removal of heavy metal ions such as Co²⁺, Ni²⁺, Mn²⁺, and Cd²⁺ from aqueous solution. Langmuir and Freundlich adsorption models were used to investigate the type of adsorption of these ions. The adsorption capacities of the adsorbent for the metal ions were found to follow the order Cd²⁺>Co²⁺>Ni²⁺>Mn²⁺. The kinetics of adsorption of these ions indicated that the rate of adsorption of Cd²⁺ was faster than that of other ions studied.     

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

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

Removal of Cd2+, Cu2+, Ni2+, and Pb2+ ions from aqueous solutions using tururi fibers as an adsorbent

This work investigates the removal of Cd²⁺, Cu²⁺, Ni²⁺, and Pb²⁺ ions from aqueous solutions using tururi fibers as an adsorbent under both batchwise and fixed‐bed conditions. It was found that modification of the tururi fibers with sodium hydroxide increased the adsorption efficiencies of all metal ions studied. The fractional factorial design showed that pH, adsorbent mass, agitation rate, and initial metal concentration influenced each metal adsorption differently. The kinetics showed that multi‐element adsorption equilibria were reached after 15 min following pseudo‐second‐order kinetics. The Langmuir, Freundlich, and Redlich–Peterson models were used to evaluate the adsorption capacities by tururi fibers. The Langmuir model was found to be suitable for all metal ions. Breakthrough curves revealed that saturation of the bed was reached in 160.0 mL with Cd²⁺ and Cu²⁺, and 52.0 mL with Ni²⁺ and Pb²⁺. The Thomas model was applied to the experimental data of breakthrough curves and represented the data well. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40883.     

Cu2+ removal from aqueous solution by modified chitosan hydrogels

BACKGROUND: The adsorption of Cu²⁺ from aqueous solution using crosslinked chitosan hydrogels impregnated with Congo Red (CR) by ion‐imprint technology was systematically investigated with particular reference to the effects of contact time, pH, and initial concentration on adsorption. RESULTS: The adsorption capacity of the crosslinked chitosan without impregnation was only 68.68 mg g^?1 for Cu²⁺. However, the adsorption capacity increased from 77.42 (without imprint ion) to 84.54 mg g^?1 (imprint ion content 0.5 mmol) after the chitosan was impregnated with a ratio of 1/12 of CR to chitosan. The as‐prepared adsorbents were found to be pH‐dependent and the process of adsorption agreed well with the Freundlich isotherm. The loaded adsorbents could be regenerated and reused without the appreciable loss of capacity. CONCLUSION: Chitosan hydrogels impregnated with CR showed higher Cu²⁺ adsorption capacities compared with those prepared conventionally without imprint ion, and thus developed a good approach to increase Cu²⁺ adsorption efficiency in the treatment of waste‐water. Copyright © 2012 Society of Chemical Industry     

Adsorption of humic acid onto pillared bentonite

Pillared bentonite, a clean and cost-effective adsorbent with high specific areas of 111.3 m²/g and high basalspacing of 1.98 nm, was prepared for the removal of humic acid from water. It is effective for the removal of humic acid with a high adsorption capacity of 537 mg/g, and adsorption is favored under acid conditions. Adsorption is dependent on ionic strength and dissolved NaCl enhanced adsorption. Over 97% removal was observed under natural pH conditions from humic acid solutions containing 10 mg/L Ca²⁺ or Mg²⁺, which suggests that pillared bentonite can be an effective adsorbent for the removal of humic acid for drinking water purification. Pillared bentonite can be regenerated with NaOH, and the regeneration efficiency reaches 83% and 85% when the concentration of NaOH reaches 0.025 and 0.05 mol/L. The mechanism for adsorption of humic acid to pillared bentonite is discussed.     

Chitosan/polyaniline hybrid for the removal of cationic and anionic dyes from aqueous solutions

Nanostructured chitosan/polyaniline (CH/PANI) hybrid was synthesized via in situ polymerization of aniline in the presence of chitosan. The CH/PANI hybrid was characterized by FTIR spectroscopy, X-ray diffraction, thermogravimetric analysis, and scanning electron microscopy. The CH/PANI hybrid had a nanofibrous structure with an average diameter of 70 nm. This hybrid was employed as an ecofriendly and efficient adsorbent with high adsorption capacity for the removal of Acid Green 25 (AG) and methylene blue (MB) from aqueous solutions. AG and MB were used as anionic and cationic model dyes, respectively. The CH/PANI adsorbent showed high dependence on the pH of the medium with an excellent adsorption performance and regeneration manner. The kinetics and adsorption isotherms were studied. The CH/PANI hybrid follows the pseudo second-order adsorption kinetics and Temkin isotherm model for the adsorption of both AG and MB dyes. This assumes that the enthalpy of dyes molecules decreases with the adsorption on heterogeneous surface with various kinds of adsorption sites and as well as the ability to form multilayers of the dye. Also, intraparticle diffusion was found to play an important role in the adsorption mechanism. The maximum adsorption capacity was found to be 240.4 mg g⁻¹ of AG at pH 4 and 81.3 mg g⁻¹ of MB at pH 11. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47056.