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     

海藻酸钠负载聚乙烯亚胺功能球对Cu~(2+)吸附研究

以海藻酸钠-聚乙烯亚胺均相水溶胶为前驱体,用溶胶-凝胶法制备了毫米级(2.8³ mm)海藻酸钠负载聚乙烯亚胺(SA-PEI)功能球,考察了pH、吸附时间、初始浓度、温度对Cu3 mm)海藻酸钠负载聚乙烯亚胺(SA-PEI)功能球,考察了pH、吸附时间、初始浓度、温度对Cu⁽²⁺⁾吸附过程的影响。结果表明,SA-PEI功能球对Cu(2+)吸附过程的影响。结果表明,SA-PEI功能球对Cu⁽²⁺⁾最佳吸附pH为5.5,吸附平衡时间为36 h,吸附Cu(2+)最佳吸附pH为5.5,吸附平衡时间为36 h,吸附Cu⁽²⁺⁾为自发、吸热、熵增过程;吸附动力学过程遵循拟二级动力学模型,吸附符合Freundlich等温模型,且在实验浓度范围内,功能球对Cu(2+)为自发、吸热、熵增过程;吸附动力学过程遵循拟二级动力学模型,吸附符合Freundlich等温模型,且在实验浓度范围内,功能球对Cu⁽²⁺⁾最大吸附量为260.5 mg/g;吸附饱和的SA-PEI功能球可以用EDTA-2Na溶液很好的脱附,6次吸附-脱附后仍保持较好的吸附活性。     

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     

Removal of perchlorate from aqueous solution using protonated cross-linked chitosan

Protonated cross-linked chitosan was used to remove perchlorate from aqueous solution. Adsorption isotherms, the effects of pH and co-existing anions on the adsorption process, proper actual contact time in the adsorption column and the regeneration ability of the adsorbent were investigated. The equilibrium data fitted well with Langmuir and Freundlich isotherm models, and the maximum monolayer adsorption capacity was 45.455 mg g^?1. To balance the protonated degree of the amino groups and the effect of the ion competing on adsorption capacity, the optimal pH value was determined to be about 4.0. Column adsorption results indicated that the proper actual contact time was 8.1 min and the effluent perchlorate could be steadily kept below 24.5 μg L^?1 up to about 95 bed volumes with the influent perchlorate of 10 mg L^?1. The presence of other anions weakened the perchlorate adsorption, especially the high valence anion such as sulfate. The adsorbents could be well regenerated by sodium hydroxide solution with pH 12 and reused at least for 15 cycles. Electrostatic attraction as well as physical force was the main driving force for perchlorate adsorption.     

Removal of boron from aqueous solution by composite chitosan beads

Various metal-oxide nanoparticles and chitosan were blended to form new adsorbents (M-Oxide-CTS) for removing boron from aqueous solutions in a batch system. The maximum boron adsorption capacity (q = 7.8 mg/g) was reached at pH = 4 within 5 min. Calculations based on Langmuir, Freundlich, and Dubinin–Radushkevich models showed the heterogeneous and physical nature of boron adsorption on M-Oxide-CTS. Modeling of the thermodynamic date indicated the nonspontaneous and exothermic process. The pseudo-second-order model adequately described the boron adsorption on M-Oxide-CTS. Desorption by means of alkaline solution at pH = 12 was carried out successfully.     

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.     

Removal of trace boron from aqueous solution using iminobis-(propylene glycol) modified chitosan beads

In this paper, a new boron chelating chitosan based polymer with multi-hydroxyl iminobis (propylene glycol) (IBPG) functions was prepared. A cross-linked chitosan (CCTS) with 2.70 mmol g⁻¹ amine content was modified with excess amount of glycidol at pH 7 and boron chelating resin with IBPG functions (4.60 mmol g⁻¹) was obtained. The boron chelating ability of the resulting resin was investigated under different experimental conditions (pH, foreign ions). This prepared material was evaluated by FT–IR spectra and UV spectra analysis. The IBPG modified CCTS resin was demonstrated to have a boron loading capacity of 2.2 ± 0.05 mmol g⁻¹ within 45 min. Desorption and resin regeneration studies were carried out to determine the effectiveness of the synthesized resin with HCl and NaOH respectively. The adsorption test indicated that the chitosan based chelating resin with IBPG functions exhibited higher selectivity of boron (2.05 mmol g⁻¹) in the presence of foreign ions especially Fe(III).     

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     

Removal of copper ions from aqueous solution by adsorption using LABORATORIES-modified bentonite (organo-bentonite)

Equilibrium, kinetic and thermodynamic aspects of the adsorption of copper ions from an aqueous solution using linear alkylbenzene sulfonate (LABORATORIES) modified bentonite (organo-bentonite) are reported. Modification of bentonite was performed via microwave heating with a concentration of LABORATORIES surfactant equivalent to 1.5 times that of the cation exchange capacity (CEC) of the raw bentonite. Experimental parameters affecting the adsorption process such as pH, contact time and temperature were studied. Several adsorption equations (e.g., Langmuir, Freundlich, Sips and Toth) with temperature dependency were used to correlate the equilibrium data. These models were evaluated based on the theoretical justifications of each isotherm parameter. The Sips model had the best fit for the adsorption of copper ions onto organo-bentonite. For the kinetic data, the pseudo-second order model was superior to the pseudo-first order model. Thermodynamically, the adsorption of copper ions occurs via chemisorption and the process is endothermic (ΔH⁰>0), irreversible (ΔS⁰>0) and nonspontaneous (ΔG⁰>0).     

Interaction of microcrystalline chitosan with Ni(II) and Mn(II) ions in aqueous solution

The protonation constant of the NH₂ function was determined by the method of Katchalsky and Spitnik and by the SUPERQUAD fitting procedure. Samples with higher concentrations of chitosan indicated aggregations of polymer chains, which led to a loss in the effective concentration of the ligand (L). It followed, as a result of potentiometric titrations, that an excess of L of microcrystalline chitosan (MCCh) with a deacetylation degree of 0.90 was a complexing agent toward the metal (M), which was Ni(II) or Mn(II). Species ML and ML₂ were accepted by SUPERQUAD for both of the M's, where coordination occurred via the amino nitrogen. For Ni(II), however, the hydroxyl oxygen may also have been an electron‐pair donor at lower excesses of MCCh and, by that, made possible the formation of five‐membered chelate rings in the hydroxyl deprotonated MLH_‐1 species. The evaluated formation constants were compared with the values known until now for monomeric D ‐glucosamine. Additional confirmation of the M–L interaction was determined by the spectrophotometric titration of a Ni(II)–MCCh solution. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2572–2577, 2005     

Adsorption of Cd(II) from aqueous solution onto pyrite

The physicochemical factors such as equilibrium time, solution pH, initial concentration of Cd(II), particle size and temperature that control the adsorption of Cd(II) from aqueous solutions onto pyrite has been investigated through batch experiments. Prior to this study, pyrite was characterized through chemical and XRD-analysis. The point of zero charge, pH_pzc was determined using the batch equilibrium technique and was found to be 6.4. The equilibrium time was 30 min at the solution pH of 6.0. The pH influence of Cd(II) adsorption was remarkable and maximum metal uptake was observed at 6.0 which is closer to pH_pzc. Under this weakly acidic condition Cd(II) ions are responsible for adsorption. Concentration dependence of metal uptake indicates that saturation of pyrite surface by adsorbate occurs at an initial Cd(II) concentration of 350 mg/L and the corresponding metal uptake was 576.5 mg/L of −150 mesh size pyrite at pH 6.0 and 30 °C. Particle size affects the adsorption capacity to a great extent and a decrease in particle diameter enhances metal uptake. The effect of temperature on adsorption performance reveals that the effective temperature for Cd(II) adsorption is 30 °C. The empirical Freundlich isotherm was applied to represent the adsorption process, which fits the experimental data quite well. The work reveals that natural pyrite is a very good choice as an adsorbent for the removal of toxic metals from industrial wastewater and bears significant industrial implications.     

Removal of copper (II) and phenol from aqueous solution using porous carbons derived from hydrothermal chars

The feasibility of hydrothermal char (HTC), a byproduct from biomass hydrothermal liquefaction for bio-oil production, as raw material for preparation of porous carbons was investigated in the present study. The resultant HTC-derived porous carbons were characterized and utilized as adsorbents for copper (II) and phenol removal from aqueous solution. Compared with porous carbons using pyrolytic char as precursor, the HTC-derived porous carbons exhibited unique textural features, e.g., narrow pore size distribution, high surface area and large pore size. In addition, FT-IR analysis confirmed that substantial amount of ketene groups existed on the surface of the HTC-derived porous carbons. As the adsorbents, the copper (II) adsorption onto HTC-derived carbons was strongly affected by the pH value of the solution in comparison with phenol adsorption. The carbons derived from pinewood and rice husk HTC exhibited high adsorption capacity of 83.88 and 39.30 mg/g for phenol and 25.18 and 22.62 mg/g for copper (II), respectively. The adsorption data for copper (II) and phenol onto the carbon adsorbents could be well described by Langmuir and Freundlich models. In comparison with pinewood sawdust HTC-derived carbon, the adsorption onto rice husk HTC-derived carbon preferentially followed Freundlich model due to the presence of silica on the surface.     

Removal of cadmium(II) cations from an aqueous solution with aminothiourea chitosan strengthened magnetic biochar

An aminothiourea chitosan modified magnetic biochar composite (TMBC) was prepared for the efficient removal of Cd(II) from wastewater. The synthesized materials were characterized, and the detailed adsorption mechanisms and thermodynamics were studied. The adsorption experiments revealed that TMBC had a higher affinity for Cd(II) than the magnetic biochar composite, raw biochar, and other carbon‐based adsorbents did. The Cd(II) adsorption process fit the pseudo‐second‐order kinetic model, and the maximum adsorption capacities on the basis of the Langmuir model were 93.72, 121.9, and 137.3 mg/g at 298, 308, and 318 K, respectively. The practical efficacy of the adsorbent was also tested with a real mine water. The metal‐ion‐loaded TMBC could be conveniently collected by a magnet and could be easily regenerated with adsorption efficiencies up to 84% after five adsorption–desorption cycles. The as‐prepared TMBC might be a promising adsorbent for the treatment of heavy‐metal‐ion‐contaminated water or highly mineralized mine water. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46239.     

海藻酸钠改性铝污泥功能球吸附Cu(Ⅱ)的研究

以铝污泥(AlS)和海藻酸钠(SA)为主要原材料,经过溶胶-凝胶法制备海藻酸钠改性铝污泥(SA-AlS)功能球,研究了温度、pH、初始浓度、吸附时间对Cu(Ⅱ)吸附过程所产生的影响。结果表明,SA-AlS功能球在Cu(Ⅱ)的吸附过程中最佳pH为5.5,吸附平衡时间为24 h,吸附过程为自发、吸热、熵增的过程,吸附等温线拟合结果表明,SA-AlS功能球对Cu(Ⅱ)的吸附行为更符合Langmuir模型,表明该吸附过程主要涉及单层吸附;拟一级和拟二级动力学模型研究表明,该吸附过程与拟二级动力学模型更符合,故SA-AlS功能球对Cu(Ⅱ)的吸附过程主要由化学吸附控制。吸附饱和的SA-AlS功能球可以用EDTA-2Na溶液很好地脱附,5次吸附-脱附后仍保持较好的吸附活性。     

Removal of Cd(II) ions from aqueous solution using a cation exchanger derived from banana stem

BACKGROUND: Environmental pollution and its abatement have attracted much attention for some time. The problem of removing pollutants from water and wastewater has grown along with rapid industrialization. Formaldehyde polymerized banana stem (FPBS) having sulphonic acid groups was investigated as an adsorbent for cadmium(II) removal from aqueous solutions. RESULTS: The outstanding function of the adsorbent was demonstrated at pH 9.0. The adsorption efficiency of FPBS was compared with BS and results showed that FPBS was two times more effective than BS for cadmium(II) removal. Maximum recoveries of 97.3 and 90.3% for 10 and 25 mg L^?1 initial concentrations were obtained at pH 9.0. Kinetic studies revealed that adsorption occurred in two stages: external mass transport in the first stage and intra‐particular diffusion in the second stage. Adsorption was found to be rapid and equilibrium was attained in 60 min. Among the various desorbing agents tested, 99.2% cadmium recovery was achieved with 0.1 mol L^?1 HCl. CONCLUSIONS: The uptake efficiency of cadmium(II) by FPBS was determined. Repeated adsorption‐desorption study showed that FPBS can be used as an adsorbent for the removal and recovery of Cd(II) from aqueous solutions. Copyright © 2012 Society of Chemical Industry     

Cationic conjugated polyelectrolyte-based fluorometric detection of copper(II) ions in aqueous solution

A series of water-soluble cationic polyfluorene copolymer containing 2,2′-bipyridine moieties (PFP-P_1-3) in the backbone were designed and synthesized as the fluorescent probes for Cu²⁺ ions. In the absence of the Cu²⁺ ion, the PFP-P₂ exhibits strong fluorescence emission in aqueous solution. Upon adding the Cu²⁺ ion, the PFP-P₂ coordinates to Cu²⁺ ions through weak N?Cu interactions, and its fluorescence is efficiently quenched by the Cu²⁺ ion with a Stern-Volmer constant (K_sv) of 1.44 × 10⁷ M⁻¹. The new method has high sensitivity with a detection limit of 20 nM. The minor interference from other heavy metal ions clearly shows that the PFP-P₂ can be used as the Cu²⁺ ion probe with good selectivity.     

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.     

Removal of nickel(II) from aqueous solution by carbon nanotubes

Single‐walled carbon nanotubes (SWCNTs) and multiwalled carbon nanotubes (MWCNTs) were oxidized by NaClO solutions and were employed as sorbents to study sorption characteristics of nickel(II) from aqueous solution. The surface properties of CNTs such as functional groups, total acidic sites and negatively charged carbons were greatly improved after oxidation, which made CNTs become more hydrophilic and resulted in sorption of more Ni²⁺. The amount of Ni²⁺ sorbed onto oxidized CNTs increased with a rise in agitation speed, initial Ni²⁺ concentration and solution pH in the range 1–8, but decreased with a rise in CNT mass and solution ionic strength. The sorption mechanisms are complicated and appear attributable to electrostatic forces and chemical interactions between the Ni²⁺ and the surface functional groups of the CNTs. The oxidized SWCNTs and MWCNTs have shorter equilibrium time and better Ni²⁺ sorption performance than the oxidized granular activated carbon, suggesting that both NaClO oxidized CNTs are efficient Ni²⁺ sorbents and that they possess good potential applications in water treatment. Copyright © 2006 Society of Chemical Industry