羧甲基甲壳胺纤维对铜离子的吸附性能

为了提高甲壳胺纤维对重金属离子的吸附性能,用氯乙酸对纤维进行改性处理,在纤维的结构中引入羧甲基团后使纤维同时具有能结合重金属离子的胺基和羧酸基团。研究了改性后纤维在不同的改性程度、添加量、时间、温度、pH值等条件下对铜离子的吸附性能。结果表明:羧甲基化改性后的甲壳胺纤维对铜离子有很好的吸附性能。在同样的条件下,未改性的纤维对铜离子的吸附值为41.3mg/g,而改性后的纤维为79.4mg/g。经过羧甲基化改性的甲壳胺纤维对铜离子的饱和吸附容量可以达到148.1mg/g。     

Removal of copper(II) ions from aqueous solution onto chitosan and cross-linked chitosan beads

The adsorption of Cu(II) ions onto chitosan and cross-linked chitosan beads has been investigated. Chitosan beads were cross-linked with glutaraldehyde (GLA), epichlorohydrin (ECH) and ethylene glycol diglycidyl ether (EGDE) in order to obtain sorbents that are insoluble in aqueous acidic and basic solution. Batch adsorption experiments were carried out as a function of pH, agitation period, agitation rate and concentration of Cu(II) ions. A pH of 6.0 was found to be a optimum for Cu(II) adsorption on chitosan and cross-linked chitosan beads. Isotherm studies indicate Cu(II) can be effectively removed by chitosan and cross-linked chitosan beads. Adsorption isothermal data could be well interpreted by the Langmuir equation. Langmuir constants have been determined for chitosan and cross-linked chitosan beads. The experimental data of the adsorption equilibrium from Cu(II) solution correlated well with the Langmuir isotherm equation. The uptakes of Cu(II) ions on chitosan beads were 80.71 mg Cu(II)/g chitosan, on chitosan-GLA beads were 59.67 mg Cu(II)/g chitosan-GLA, on chitosan-ECH beads were 62.47 mg Cu(II)/g chitosan-ECH and on chitosan-EGDE beads were 45.94 mg Cu(II)/g chitosan-EGDE. The Cu(II) ions can be removed from the chitosan and cross-linked chitosan beads rapidly by treatment with an aqueous EDTA solution and at the same time the chitosan and cross-linked chitosan beads can be regenerated and also can be used again to adsorb heavy metal ions.     

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.     

The effects of picolinic acid and pH on the adsorption of Cu(II) by activated carbon fibers

The adsorption characteristics of Cu(II) on activated carbon fibers (ACFs) from simulated wastewater was investigated in the picolinic acid concentration range from 0.15 to 15 mM by varying pH from 2 to 8. When pH is below 4, the removal fraction of Cu(II) ions decreased with the decrease of pH. The removal fraction of Cu(II) ions is almost constant above pH 4. The removal efficiency of Cu(II) ions increased as the molar ratio of picolinic acid to Cu(II), specific surface area of ACFs and pH of the solution increased. In the case of [Pic]/[Cu(II)]=10, complete adsorption of Cu(II) was performed on ACF, even at pH 2.     

The absorption and release of silver and zinc ions by chitosan fibers

When chitosan fibers were treated with AgNO₃ and ZnCl₂ solutions, the silver and zinc ions were chelated by chitosan through the amine groups in the fibers. These novel metal ions can be released into the solution when the silver‐ and zinc‐containing fibers are placed in contact with normal saline. Results showed that the silver‐containing chitosan fibers have good antimicrobial properties, while the zinc‐containing fibers can be used to deliver zinc ions in wound care applications. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 766–771, 2006     

Separation of some metal ions by high performance centrifugal partition chromatography with di‐2‐methylnonylphosphoric acid

The separation of such metal ions as Cu(II), Mn(II), Co(II), Ni(II), Mg(II) and Ca(II) has been investigated by high performance centrifugal partition chromatography (HPCPC) employing di‐2‐methylnonylphosphoric acid/heptane as a stationary phase. The four transition metal ions have mutually been separated by the two‐step elution method, changing the pH of the chloroacetic acid mobile phase, and the two alkaline earth metal ions have been separated by an isocratic elution. The HPCPC system was operated with 2136 partition channels, at a rotation speed of 800 rpm, and at a flow rate of 2.0 cm³ min^?1. The elution curve was obtained by monitoring the absorbance of each metal complex post‐labeled with chromogenic compounds. Copyright © 2003 Society of Chemical Industry     

The adsorption of Cu(II) ion from aqueous solution upon acrylic acid grafted poly(ethylene terephthalate) fibers

This study is concerned with the investigation of the adsorption properties of acrylic acid grafted poly(ethylene terephthalate) fibers by the use of Cu(II) ions in aqueous solutions. Influence of pH, graft yield, contact time, concentration of the ion, and reaction temperature on the amount of ion adsorbed upon reactive fiber were investigated. The time in which the adsorption reached to the equilibrium value was determined as 1 h. The adsorption isotherm of Cu(II) ion was found to be a Langmuir type and the heat of adsorption was calculated as ?10.1 kJ mol^?1. It was observed that the adsorbed Cu(II) ion upon acrylic acid grafted poly(ethylene terephthalate) fibers could be recovered in acidic media. The fiber could also readsorb Cu(II) ions without losing its activity. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1216–1220, 2003     

Preparation of amidoximated polyester fiber and competitive adsorption of some heavy metal ions from aqueous solution onto this fiber

In this study, a fibrous adsorbent containing amidoxime groups was prepared by graft copolymerization of acrylonitrile (AN) onto poly(ethylene terephthalate) (PET) fibers using benzoyl peroxide (Bz₂O₂) as initiator in aqueous solution, and subsequent chemical modification of cyano groups by reaction with hydroxylamine hydrochloride in methanol. The grafted and modified fibers were characterized by FTIR, TGA, SEM, and XRD analysis. The crystallinity increased, but thermal stability decreased with grafting and amidoximation. The removal of Cu(II), Ni(II), Co(II), Pb(II), and Cd(II) ions from aqueous solution onto chelating fibers were studied using batch adsorption method. These properties were investigated under competitive conditions. The effects of the pH, contact time, and initial ion concentration on the removal percentage of ions were studied. The results show that the adsorption rate of metal ions followed the given order Co(II) > Pb(II) > Cd(II) > Ni(II) > Cu(II). The percentage removal of ions increased with initial ion concentration, shaking time, and pH of the medium. Total metal ion removal capacity was 49.75 mg/g fiber on amidoximated fiber. It was observed that amidoximated fibers can be regenerated by acid without losing their activity, and it is more selective for Pb(II) ions in the mixed solution of Pb‐Cu‐Ni–Co‐Cd at pH 4. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

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     

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 of cibacron blue F3GA‐attached polyamide hollow fibers for heavy metal removal

Dye‐affinity adsorption has been used increasingly for heavy metal removal. Synthetic hollow fibers have advantages as support matrices in comparison to conventional bead supports because they are not compressible and they eliminate internal diffusion limitations. The goal of this study was to investigate in detail the performance of hollow fibers composed of modified polyamide to which Cibacron Blue F3GA was attached for the removal of heavy metal ions. The Cibacron Blue F3GA loading was 1.2 mmol/g. The internal matrix was characterized by scanning electron microscopy. No significant changes in the hollow fiber cross‐section or outer layer morphology were observed after dye modification. The effect of the initial concentration of heavy metal ions and medium pH on the adsorption efficiency were studied in a batch reactor. The adsorption capacity of the hollow fibers for the selected metal ions [i.e., Cu(II), Zn(II) and Ni(II)] were investigated in aqueous media with different amounts of these ions (10–400 ppm) and at different pH values (3.0–7.0). The maximum adsorptions of metal ions onto the Cibacron Blue F3GA‐attached hollow fibers were 246.2 mg/g for Cu(II), 133.6 mg/g for Zn(II), and 332.7 mg/g for Ni(II). Furthermore, a Langmuir expression was calculated to extend the adsorption equilibrium. Nitric acid (0.1M) was chosen as the desorption solution. High desorption ratios (up to 97%) were observed in all cases. Consecutive adsorption/desorption operations showed the feasibility of repeated use of this novel sorbent system. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 3089–3098, 2002; DOI 10.1002/app.2338     

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     

羧甲基壳聚糖的制备及膜性能测试

用氯乙酸与壳聚糖反应制备了羧甲基壳聚糖 ,测定了羧甲基壳聚糖取代度。考察了氯乙酸浓度、反应时间、反应温度对羧甲基壳聚糖取代度的影响。将羧甲基壳聚糖制成膜 ,测定了膜的机械强度。结果表明 ,在壳聚糖∶NaOH∶氯乙酸 (质量比 ) =1∶1 3∶1 8和室温条件下反应 2h、升温至 6 5℃再反应 2h时 ,所得的羧甲基壳聚糖取代度较高 (为 0 6 7)。羧甲基壳聚糖膜有较好的韧性度     

Adsorption properties of poly(acrylaminophosphonic-carboxyl-hydrazide)type chelating fiber for heavy metal ions

In this article, the adsorption properties of poly(acrylaminophosphonic-carboxyl-hydrazide) chelating fibers for Cu(II), Cd(II), Co(II), Mn(II), Pb(II), Zn(II), Ni(II), and Cr(III) are investigated by a batch technique. Based on the research results of binding capacity, adsorption isotherm, effect of pH value on sorption, and adsorption kinetics experiments, it is shown that the poly(acrylaminophosphonic-carboxyl-hydrazide) chelating fibers have higher binding capacities and good adsorption kinetic properties for heavy metal ions. The sorption of the metal ions on the chelating fibers is strongly dependent on the equilibrium pH value of the solution. The adsorption isotherms of Cu(II) and Cd(II) on the chelating fiber exhibit a Langmuir-type equation. The adsorbed Cu(II), Cd(II), Zn(II), and Pb(II) could be eluted by diluted nitric acid. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 7–14, 1998     

Metal ion retention properties of water‐insoluble polymers containing carboxylic acid groups

Crosslinked poly(acrylic acid), PAA, and poly(2‐acrylamidoglycolic acid), PAAG, were synthesized by radical polymerization. Both resins contain carboxylic acid groups. PAA at basic pH exists basically as an acrylate anion and PAAG shows three atoms or groups, carboxylic acid, hydroxyl, and amide groups, that can act as ion exchanger or chelating groups. Both resins are studied as adsorbents to trace metal ions from saline aqueous solutions and natural sea water and their properties by Batch equilibrium procedure are compared. The metal ions studied under competitive and noncompetitive conditions were Cu(II), Pb(II), Cd(II), and Ni(II). The effects of pH, time of contact, amount of resin, temperature, and salinity were studied. Resin PAA shows a high affinity (>80%) for Cu(II) and Cd(II) and resin PAAG shows also a high affinity for Ni(II), Pb(II), and Cd(II). By treatment of the metal ion‐loaded resin with 4M HNO₃ it is possible to recover completely the Cu(II) ions from resin PAA and Ni(II) and Pb(II) from resin PAAG. The metal ion retention properties were studied with natural sea water. For those natural sea waters containing Cu(II) and Cd(II), the resins showed a high affinity for Cd(II) ions. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 697–705, 2006     

Sorption isotherms of metal ions onto an N-(2-sulfoethyl)chitosan-based material from single- and multi-component solutions

The scope of work is to study the mutual influence of metal ions during their sorption by sulfoethylated chitosan. The sorption isotherms of metal ions from single- and multi-component solutions are obtained. The sorption capacity of the sorbent towards Ag(I) and Cu(II) is revealed to be 1.63 and 1.41 mmol/g in single-, and 1.40 and 0.85 mmol/g in five-component solution. By comparing the affinity parameter and capacity of sulfoethylated chitosan towards ions in single- and multi-component solutions, it is concluded that Ag(I) and Cu(II) ions suppress the sorption of cobalt(II), nickel(II), zinc(II), cadmium(II), magnesium(II), calcium(II), strontium(II), barium(II), manganese(II) and lead(II).     

Postconsumer high‐density polyethylene/agave fiber foamed composites coated with chitosan for the removal of heavy metals

Composites of postconsumer high‐density polyethylene with agave fiber were prepared by single‐screw extrusion with azodicarbonamide as a foaming agent to increase the surface area; the composite pellets were coated with chitosan afterward. A chemical pretreatment was applied to the pellets to enhance the chitosan gel compatibility. The adsorption capacities of the composites coated with chitosan were evaluated for Cd(II) and Cu(II) removal from aqueous solutions. The coated composites were characterized by scanning electron microscopy, attenuated total reflectance infrared spectroscopy, and X‐ray photoelectron spectroscopy. Atomic absorption spectroscopy was used to measure metal uptake in batch adsorption studies. The results of this study demonstrated the composites' ability to immobilize chitosan on their surfaces and their capacity to adsorb metal ions. The equilibrium isotherms for Cd(II) and Cu(II) adsorption on the chitosan‐coated composites were described by the Langmuir model. This material represents an attractive low‐cost recycled material for adsorbing metal ions from polluted waters. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effects of Chitosan Concentration and Precipitation Bath Concentration on the Material Properties of Porous Crosslinked Chitosan Beads

Abstract

Flaked chitosan obtained by deacetylating 80% of chitin extracted from crab shell was dissolved in acetic acid aqueous solution, and highly porous chitosan beads were formed by dropping the chitosan solution into aqueous NaOH solution, followed by crosslinking with ethylene glycol diglycidyl ether. Fifteen different crosslinked chitosan beads (CRCS) were fabricated by controlling the concentration C _chitosan of chitosan in the chitosan/acetic acid solution and the concentration C _NaOH of NaOH in the precipitation bath. We presented the way in which the values of C _chitosan and C_NoOH were controlled to fabricate chitosan beads with any desired values of the apparent density, the solid phase concentration of amino group, the pore radius, the total porosity, and the specific surface area. In order to assess the possibility of using CRCS as a matrix of an adsorbent for the separation of metal ions, poly(ethylene imine) was introduced onto the CRCS which had a relatively high concentration of amino group. The polyaminated CRCS had a high capacity, and it had a high selectivity for the adsorption of Hg(II), Cu(II), Ni(II), Cd(II), and Zn(II). The results suggest that CRCS is a good matrix for introducing functional groups.     

Chitosan functionalized with 2[-bis-(pyridylmethyl) aminomethyl]4-methyl-6-formyl-phenol: equilibrium and kinetics of copper (II) adsorption

The complexation agent 2[-bis-(pyridylmethyl) aminomethyl]-4-methyl-6-formyl-phenol (HL) was immobilized in chitosan in order to obtain a new adsorbent material to be employed in studies on adsorption and pre-concentration of Cu(II). The chitosan modified by the complexation agent was characterized by infrared spectroscopy, DSC and TGA. The studies were conducted as a function of the pH of the medium and the mechanism of Cu(II) adsorption in the solid phase was analyzed utilizing several kinetic models. The parameters for the adsorption of Cu(II) ions by chitosan-HL were determined with a Langmuir isotherm, the maximum saturation capacity of the monolayer being 109.4 mg of Cu(II) per gram of polymer. Electron paramagnetic resonance spectroscopy revealed that Cu^II ions coordinate to the donor atoms of the HL ligand anchored to the surface of the polymer forming a stable chelate complex in the solid state.     

Effect of complexing agents on liquid‐phase adsorption and desorption of copper(II) using chitosan

The effect of complexing agents on adsorption and desorption of Cu(II) from aqueous solutions using chitosan was investigated. Three complexing agents were used including EDTA (ethylenediaminetetraacetic acid), citric acid, and tartaric acid. It was shown that the isotherm data could be fitted by the Langmuir equation under a limited concentration range. Furthermore, the adsorption processes were analyzed by an intraparticle diffusion model and the rate parameters of intraparticle diffusion for Cu(II) adsorption could be correlated with the initial Cu(II) concentrations. Finally, the desorption of Cu(II) and its complexes from the loaded chitosan was tested using complexing agent solutions. Under comparable conditions, tartaric acid solution gave the best desorption efficiency. © 1999 Society of Chemical Industry