Chitosan N-benzyl sulfonate derivatives as sorbents for removal of metal ions in an acidic medium

We synthesized chitosan-based sorbents for the uptake of metal cations in acidic solutions. Chitosan was reacted with 2-formylbenzene sodium sulfonate and 4-formyl-1,3-benzene sodium disulfonate in the presence of NaCNBH₃ to yield N-benzyl mono- and disulfonate derivatives of chitosan. IR and NMR spectra confirmed the presence of benzyl sulfonate groups. The degrees of substitution of the monosulfonate chitosan derivatives were in the range of 80%, while those of disulfonate derivatives were about 50%. These sulfonate derivatives of chitosan were tested on the sorption of heavy metals Cd²⁺, Zn²⁺, Ni²⁺, Pb²⁺, Cu²⁺, Fe³⁺, and Cr³⁺. The sorption capacities for disulfonate compounds were better than for monosulfonate compounds. This phenomenon was attributed to the amphoteric character of the monosulfonate derivatives. To improve the capacity of adsorption of monosulfonate compounds, the amino groups of these compounds were protected by the benzyloxycarbonyl groups. The protection of amino groups of disulfonate derivatives by benzyloxycarbonyl also improved their sorption capacity. The resulting protected polymers were tested for sorption of heavy metals. Both protected polymers were more efficient than are the parent nonprotected polymers. The synthesized sulfonate derivatives of chitosan are especially adapted to the sorption of heavy metals from the acidic industrial effluents. © 1996 John Wiley & Sons, Inc.     

Interaction of metal ions with montmorillonite and vermiculite

The behaviour of montmorillonite and vermiculite toward adsorption of Cd²⁺, Pb²⁺, Zn²⁺, Mn²⁺, Cu²⁺ and Zn²⁺ was compared. In general, the uptake of metal ions on both clay minerals decreased with decreasing of pH and in the presence of ligands forming stable complexes. Metal ion retention on montmorillonite was less affected by the competition of sodium ions at high ionic strengths with respect to vermiculite. On the other hand, the total capacity of vermiculite with respect to the investigated metal ions was found to be much higher than that of montmorillonite, whereas the order of affinity of the metal ions for the two clay minerals was similar, i.e.: Pb²⁺ = Cd²⁺ < Cu²⁺ < Zn²⁺ < Mn²⁺ < Ni²⁺ for montmorillonite and Pb²⁺ < Cu²⁺ < Cd²⁺ < Zn²⁺ < Ni²⁺ < Mn²⁺ for vermiculite.The similarities and differences between the two clay minerals were also investigated by principal component analysis and hierarchical cluster analysis.The results of this study may be used to predict the uptake efficiency of these adsorbents in view of their application for the removal of metal ions from contaminated effluents. The choice of vermiculite or montmorillonite for the uptake of metal ions or other elements will depend on the composition of the effluent to be treated.     

Adsorption behaviors of the aminated chitosan adsorbent

Using inverse suspension technology, a novel aminated chitosan adsorbent with higher adsorption ability for metal cations and metal anions was prepared. Through cross-linking amination reaction, the content of amidocyanogen of aminated chitosan adsorbent was enhanced four times than that of chitosan cross-linked adsorbent. As can be seen from the results, the adsorption ability of the novel aminated chitosan adsorbent for (Nicit)⁻ and Cr(VI) was enhanced remarkably. When the initial concentration of metallic ion was 1,000 mg/L, the adsorption capacity of the novel aminated chitosan adsorbent for nickel citrate and Cr(VI) was up to 30.2 mg/g and 28.7 mg/g, respectively. And the adsorption capacity of the novel aminated chitosan adsorbent for Ni²⁺ was still higher. So the new aminated chitosan adsorbent offers not only a higher uptake for metal cations but also a better adsorption capacity for metal anions.     

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     

Preparation and characterization of magnetic chelating resin based on chitosan for adsorption of Cu(II), Co(II), and Ni(II) ions

Cross-linked magnetic chitosan–diacetylmonoxime Schiff’s base resin (CSMO) was prepared for adsorption of metal ions. CSMO obtained was investigated by means of scanning electron microscope (SEM), FTIR, ¹H NMR, wide-angle X-ray diffraction (WAXRD), magnetic properties and thermogravimetric analysis (TGA). The adsorption properties of cross-linked magnetic CSMO resin toward Cu²⁺, Co²⁺ and Ni²⁺ ions were evaluated. Various factors affecting the uptake behavior such as contact time, temperature, pH and initial concentration of the metal ions were investigated. The kinetics was evaluated utilizing the pseudo-first-order and pseudo-second-order. The equilibrium data were analyzed using the Langmuir, Freundlich, and Tempkin isotherm models. The adsorption kinetics followed the mechanism of the pseudo-second-order equation for all systems studied, evidencing chemical sorption as the rate-limiting step of adsorption mechanism and not involving a mass transfer in solution. The best interpretation for the equilibrium data was given by Langmuir isotherm, and the maximum adsorption capacities were 95 ± 4, 60 ± 1.5, and 47 ± 1.5 mg/g for Cu²⁺, Co²⁺ and Ni²⁺ ions, respectively. Cross-linked magnetic CSMO displayed higher adsorption capacity for Cu²⁺ in all pH ranges studied. The adsorption capacity of the metal ions decreased with increasing temperature. The metal ion-loaded cross-linked magnetic CSMO were regenerated with an efficiency of greater than 84% using 0.01–0.1 M ethylendiamine tetraacetic acid (EDTA).     

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.     

Uptake of heavy metal ions from aqueous solution using Mg–Al layered double hydroxides intercalated with citrate, malate, and tartrate

Mg–Al layered double hydroxide (Mg–Al LDH) was modified with organic acid anions using a coprecipitation technique, and the uptake of heavy metal ions from aqueous solution by the Mg–Al LDH was studied. Citrate·Mg–Al LDH, malate·Mg–Al LDH, or tartrate·Mg–Al LDH, which had citrate³⁻ (C₆H₅O₇³⁻), malate²⁻ (C₄H₄O₅²⁻), or tartrate²⁻ (C₄H₄O₆²⁻) anions intercalated in the interlayer, was prepared by dropwise addition of a mixed aqueous solution of Mg(NO₃)₂ and Al(NO₃)₃ to a citrate, malate, or tartrate solution at a constant pH of 10.5. These Mg–Al LDHs were found to take up Cu²⁺ and Cd²⁺ rapidly from an aqueous solution at a constant pH of 5.0. This capacity was mainly attributable to the formation of the citrate–metal, malate–metal, and tartrate–metal complexes in the interlayers of the Mg–Al LDHs. The uptake of Cu²⁺ increased in the order malate·Mg–Al LDH < tartrate·Mg–Al LDH < citrate·Mg–Al LDH. The uptake of Cd²⁺ increased in the order malate·Mg–Al LDH < tartrate·Mg–Al LDH = citrate·Mg–Al LDH. These differences in Cu²⁺ and Cd²⁺ uptake were attributable to differences in the stabilities of the citrate–metal, malate–metal, and tartrate–metal complexes. These results indicate that citrate³⁻, malate²⁻, and tartrate²⁻ were adequately active as chelating agents in the interlayers of Mg–Al LDHs.     

Polymer pendant ligand chemistry, 4. Recovery of precious metal ions from strongly acidic solution with a polymer-supported o-phenylenediamine hydrochloride ligand

We report on the synthesis and reactivity of a polymer-supported o-phenylenediamine hydrochloride ligand, PS-PDHC, using macroporous 6% crosslinked polystyrene-divinylbenzene beads. The PS-PDHC ligand was found to be highly selective to AuCl₄⁻ ions in strongly acidic solutions in the presence of other precious metal ions, PdCl₄²⁻, PtCl₄²⁻, RhCl₆³⁻, and RuCl₅²⁻ (selectivity values: 2.5, Au/Pd; 7.5, Au/Pt; 7, Au/Rh; 2.2, Au/Ru) as well as other transition metal ions, Fe ³⁺, Cr³⁺, CU²⁺, Nit+, and Mn²⁺. The sorption capacity, selectivity, kinetics of removal and recovery, and solution isotherms have been determined for AuCl₄⁻ ions in competition with the above-mentioned metal ions. The relative ease of formation of the anionic complex in 0.5 M HCI, AuCl₄⁻ was thought to be the primary reason for its selective ability to bind to the PS-PDHC ligand by an anion-exchange mechanism. Therefore, the effect of the HCI concentration on the kinetics of AuCl₄⁻ ion removal from solution was also investigated to clearly show that raising the pH from 0 to 5 caused a dramatic decrease in rate. The AuCl₄⁻ ion can be recovered quantitatively from the PS-PDHC beads using a 5% thiourea solution in 0.1 M HCl, allowing the polymer-supported ligand to be reused.     

Ion Sequestration,Solvent Extraction and Antimicrobial Behavior of Quinoline Functionalized Chitosan

Chemically modified chitosan incorporating amino quinoline was prepared by reacting 6-amino-2-chloroquinoline-3-carbaldehyde with chitosan; it was found to have high selective and chelating efficiency towards transition metal ions at pH 1–8. Enhanced adsorption capacity and strong affinity for Cu²⁺ was observed as compared to Cd²⁺, Ni²⁺, and Co²⁺ at 4–6 pH. This selectivity appeared to be independent of the size and the hardness of the ions. Potentiometric methods confirmed the order of selectivity which was independent of physical form of chitosan-amino-quinoline derivative (CAQ). CAQ was chemically synthesized and characterized by ¹HNMR, ¹³CNMR, and FTIR techniques. ¹HNMR results suggested a degree of substitution (DS) ranging from 14.6 to 95.2%. The adsorption capacity, ion selectivity of CAQ and antimicrobial activity against Escherichia coli, Staphylococcus aureus, Pseudomonas aeruginosa, and Candida albicans were investigated. Our results prompted us to further investigate the utility of CAQ as a green depolluting agent. The new chitosan-amino-quinoline derivative showed elevated potential as a good adsorbent, depolluting agent having selective memory for metal ions, and could be utilized especially for ion sequestration and solvent extraction.     

Synthesis of a novolac‐based 3‐aminopropylsiloxane resin and its application for the removal of Cu2+, Cr3+, and Ni2+ from electroplating wastewater

Novolac resin was modified with 3‐aminopropyltrimthoxysilane to obtain phenol‐formaldehyde‐aminopropylsiloxane resin (PF‐APS). Fourier transformation infra‐red spectra, thermogravimetric analysis, elemental analysis, and pH‐metric titration were used to characterize PF‐APS. Its chemical formula was suggested to be C₁₄H_12.49N_0.1O₂Si_0.1. The resin shows high experimental metal ions uptake capacity within short time of equilibration. The metal capacity was determined by atomic absorption spectrometry to be 0.787 mEq Cu/g. Maximum separation efficiencies of Cu²⁺, Cr³⁺, and Ni²⁺ from aqueous solutions on PF‐APS were at pH 8.0 and time of stirring 60 min; 94.0%, 90.8%, 83.2%, respectively. No significant interference from the background ions Na⁺, Cl^?, and was observed on the separation process. The heavy metal ions were eluted using 0.01 mol L^?1 EDTA at 65°C releasing >94% of the separated metal ions. The method of separation was applied successfully to remove the heavy metal ions Cu²⁺, Cr³⁺, and Ni²⁺ from electroplating wastewater from Dekirnis, Dakahlia Governorate, Egypt. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40993.     

Organic arsenic removal from an aqueous solution by iron oxide-coated fungal biomass: An analysis of factors influencing adsorption

A two-level seven-factor (2^7-2) fractional factorial design analysis was conducted to examine the parameters influencing dimethylarsinic acid (DMA) removal from an aqueous solution using iron oxide-coated A. niger biomass. The factors examined were the concentration of DMA in solution, the mass of the adsorbent, the solution temperature, the Ca²⁺ ions in solution, the Fe²⁺ ions in solution, the SO₄²⁻ ions in solution, and the Cl⁻ ions in solution. The magnitude of the influence of the factors considered on DMA removal was observed in the order: presence of Ca²⁺ ions in solution > the DMA concentration > solution temperature > presence of SO₄²⁻ in solution > presence of Fe²⁺ in solution > the mass of adsorbent > the presence of Cl⁻ in solution.     

Preparation and adsorption behavior of macrocyclic tetra‐amine derivatives of chitosan

The new macrocyclic polyamine derivatives of chitosan were synthesized by reacting epoxy‐activated macrocyclic tetra‐amine with the C6 hydroxyl or C2 amino group in chitosan. The obtained copolymers (CTS‐OM, CTS‐NM) contain amino functional groups, the secondary amines, and more polar hydroxyl groups in its skeleton. Elemental analysis, infrared spectra, and solid‐state ¹³C‐NMR analysis confirmed their structures. The adsorption behavior of the macrocyclic polyamine grafted chitosan for Ag⁺, Pb²⁺, Hg²⁺, and Cr³⁺ was investigated. The experimental results showed that the two novel derivatives of chitosan have high adsorption capacity and good selectivity for some metal ions. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 407–412, 2005     

Removal of Hg2+ from aqueous solution using a novel composite carbon adsorbent

A novel composite carbon adsorbent (GCA) has been prepared by immobilizing activated carbon and genipin‐crosslinked chitosan into calcium alginate gel beads via entrapment and applied to the removal of mercury (Hg²⁺) ions from aqueous solution (e.g., drinking water). Two bead sizes and two mixing ratios of components were obtained and characterized. Batch experiments were performed to study the uptake equilibrium and kinetics of Hg²⁺ ions by the GCA. The Hg²⁺ adsorption capacity of GCA was found to be dependent of pH and independent of size of the adsorbent. The Hg²⁺ adsorption rate of GCA increases with decreasing its bead size. However, both adsorption capacity and rate of GCA for Hg²⁺ increase with increasing its chitosan content. Otherwise, it was shown that the GCA has higher Hg²⁺ adsorption capacity and rate than activated carbon, which might be caused by the incorporation of chitosan into the GCA. The maximum Hg²⁺ adsorption capacity of GCA was found to be 576 mg/g, which is over seven times higher than that of activated carbon. Our results reveal the uniform distribution of activated carbon and chitosan within the alginate gel bead and that Hg²⁺ ions can diffuse inside the bead. It also demonstrated the feasibility of using this GCA for Hg²⁺ removal at low pH values. The Hg²⁺ absorbed beads of the GCA can be effectively regenerated and reused using H₂SO₄. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Adsorption characteristics of metal ions by CO2-fixing Chlorella sp. HA-1

Single and binary metal systems were employed to investigate the removal characteristics of Pb²⁺, Cu²⁺, Cd²⁺, and Zn²⁺ by Chlorella sp. HA-1 that were isolated from a CO₂ fixation process. Adsorption test of single metal systems showed that the maximum metal uptakes were 0.767 mmol Pb²⁺, 0.450 mmol Cd²⁺, 0.334 mmol Cu²⁺ and 0.389 mmol Zn²⁺ per gram of dry cell. In the binary metal systems, the metal ions on Chlorella sp. HA-1 were adsorbed selectively according to their adsorption characteristics. Pb²⁺ ions significantly inhibited the adsorption of Cu²⁺, Zn²⁺, and Cd²⁺ ions, while Cu²⁺ ions decreased remarkably the metal uptake of Cd²⁺ and Zn²⁺ ions. The relative adsorption between Cd²⁺ and Zn²⁺ ions was reduced similarly by the presence of the other metal ions.     

Preparation and adsorption behavior for metal ions of cyclic polyamine derivative of chitosan

The new macrocyclic polyamine derivatives of chitosan were synthesized by reacting epoxy‐activated macrocyclic tetra‐amine with C6 hydroxyl or C2 amino group in chitosan. The obtained copolymers contain amino functional groups in its skeleton and secondary amines, and more polar hydroxyl groups. Elemental analysis, infrared spectra, and solid‐state ¹³C NMR analysis confirmed their structures. The adsorption behavior of the macrocyclic polyamine grafted chitosan for Ag⁺, Pb²⁺, Hg²⁺, and Cr³⁺ were investigated. The experimental results showed that the two novel derivatives of chitosan have high adsorption capacity and good selectivity for some metal ions. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3018–3023, 2006     

Uptake of Cu, Cd and Pb on Zn–Al layered double hydroxide intercalated with edta

Hydrotalcite-like compound [Zn₂Al(OH)₆]₂edta·nH₂O(ZnAl-edta) was obtained from the precursor [Zn₂Al(OH)₆]NO₃·nH₂O (ZnAl-NO₃), by the anion exchange method, with the aim of uptake Cu²⁺, Cd²⁺ and Pb²⁺ from the aqueous solutions by chelating process between edta and metal cations. The amount of Cu²⁺, Cd²⁺ and Pb²⁺ adsorbed was monitorized by atomic absorption technique at different contact time, pH and metal concentrations. The results indicate the very fast adsorption of the metal cations by ZnAl-edta reaching the equilibrium of the uptake reaction in two hours for Cu and Pb and 24 h for Cd. The shape of the adsorption isotherms suggests specific interaction and high host–guest affinity. At pH 5.5 and initial concentration C_i = 10 mM, the amount adsorbed was C_s = 1117, 375 and 871 μmol/g for Cu²⁺, Cd²⁺ and Pb²⁺, respectively.     

Effect of magnesium carbonate on the uptake of aqueous zinc and lead ions by natural kaolinite and clinoptilolite

Adsorption behavior of Zn²⁺ and Pb²⁺ ions on kaolinite and clinoptilolite, originating from natural resources, was studied as a function of contact time and concentration. Zn²⁺ and Pb²⁺ ions are quickly adsorbed on both minerals and the uptake of the latter is more favored. The uptake of both ions was then examined on kaolinite–MgCO₃ and clinoptilolite–MgCO₃ mixtures over a metal ions range from 1 to 10 000 mg/L. The sorption behavior of Zn²⁺ and Pb²⁺ on pure MgCO₃ was also studied. MgCO₃ is much more effective in the retention of Zn²⁺ and Pb²⁺ ions, in particular at higher concentrations. The large increase in the retarded amounts of both ions was associated with formation of the hydroxy-carbonate phases; namely hydrozincite for Zn²⁺, and cerussite and hydrocerussite in the case of Pb²⁺.     

The Opposite Effect of Metal Ions on Short-/Long-Range Water Structure: A Multiple Characterization Study

Inorganic electrolyte solutions are very important in our society as they dominate many biochemical and geochemical processes. Herein, an in-depth study was performed to illustrate the ion-induced effect on water structure by coupling NMR, viscometer, Raman and Molecular Dynamic (MD) simulations. The NMR coefficient (B_NMR) and diffusion coefficient (D) from NMR, and viscosity coefficient (B_vis) from a viscometer all proved that dissolved metal ions are capable of enhancing the association degree of adjacent water molecules, and the impact on water structure decreased in the order of Cr³⁺ > Fe³⁺ > Cu²⁺ > Zn²⁺. This regularity was further evidenced by Raman analysis; however, the deconvoluted Raman spectrum indicated the decrease in high association water with salt concentration and the increase in low association water before 200 mmol·L⁻¹. By virtue of MD simulations, the opposite changing manner proved to be the result of the opposite effect on short-/long-range water structure induced by metal ions. Our results may help to explain specific protein denaturation induced by metal ions.     

Water‐sorption and metal‐uptake behavior of pH‐responsive poly (N‐acryloyl‐N′‐methylpiperazine) gels

Hydrogels based on N‐acryloyl‐N′‐methylpiperazine (AcrNMP) swelled extensively in solutions of low pH due to the protonation of the tertiary amine. The water transport in the gels under an acidic condition was non‐Fickian and nearly Fickian in neutral pH with the collective diffusion coefficients determined as 2.08 × 10⁻⁷ and 5.00 × 10⁻⁷ cm⁻² s⁻¹, respectively. These gels demonstrated good metal‐uptake behavior with various divalent metal ions, in particular, copper and nickel, with the uptake capacity increased with increasing pH. The swelling ratio of the gel in the presence of metal ions decreased with increasing metal ion uptake. The results suggest that high metal ion uptake can lead to physical crosslinking arising from the interchain metal complex formation. The metal‐loaded gels could be stripped easily with 1M H₂SO₄ without any loss in their uptake capacity. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 268–273, 2001     

Interaction of heavy metal ions with an ion exchange resin obtained from a natural polyelectrolyte

An ion exchange resin was synthesized by using a natural polyelectrolyte, sodium alginate, and barium ion as a cross-linker reagent. Resin was characterized by TGA and SEM. Equilibrium and kinetic experiments of Pb²⁺, Hg²⁺, Ni²⁺, Co²⁺, Fe²⁺, and Fe³⁺ ions uptake by barium alginate beads were carried out in batch-type experiments under different values of pH. The removal efficiency increases with increasing pH. The uptake of metal ions occurs rapidly in the first hour. Maximum retention capacity was also determined being Fe(II) > Fe(III) > Co(II) > Ni(II) > Pb(II) > Hg(II) in mmol/g dry beads basis. Elution from the loaded resins at maximum capacity was studied by using HCl and HNO₃ as eluents at different concentrations.