Cu(Ⅱ)螯合壳聚糖磁性微球的制备、表征及性能研究

以(NH4)2Fe(SO4)2.6H2O、NH4Fe(SO4)2.12H2O和壳聚糖为原料,经羟丙基化、Cu(Ⅱ)螯合,采用一步包埋法制备了一种Cu(Ⅱ)螯合壳聚糖磁性微球。通过正交实验法确定了磁性微球的最佳制备条件,即搅拌速度1 200 r/min,壳聚糖用量3.0 g,环氧氯丙烷用量1.0 mL,CuCl2.2H2O为0.010 mol。并用IR、TG、XRD和SEM对其结构及形貌进行了表征,结果表明,Fe3O4磁性粒子已包埋了一层Cu(Ⅱ)螯合壳聚糖,呈较规则的球形,平均粒径为240 nm,且具有顺磁性。     

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     

壳聚糖希夫碱及壳聚糖改性微球的吸附性能研究

以壳聚糖和对二甲氨基苯甲醛为原料合成壳聚糖希夫碱,以壳聚糖希夫碱为底物,采用反相悬浮聚合法,制备壳聚糖希夫碱微球。对二者的吸附性能进行比较研究。结果表明,希夫碱微球的吸附性能优于壳聚糖希夫碱,对四氧化三铁的吸附容量分别为113.179 mg/g和39.279 mg/g,对亚甲基蓝的吸附平衡时间均为150 min,饱和吸附容量随着亚甲基蓝初始质量浓度的增大而增大,且微球的吸附容量大于壳聚糖希夫碱,吸附率不随浓度增大单调递增,而是有一极大值。     

Studies of adsorption properties of crosslinked chitosan for vanadium(V), tungsten(VI)

In this article, the adsorption properties of crosslinked chitosan (CCTS) for V(V) and W(VI) were studied. Experimental results showed the adsorption rates of CCTS for V(V) and W(VI) were closely related to the acidity of solution. The adsorption rates were 97% for V(V) at pH 4.0 and 96% for W(VI) at pH 4.5. The adsorption balance times, adsorption capacities, and adsorption mechanism were explored. This research is of significance for removal of V(V) and W(VI) in industrial wastewater and their preconcentration in trace analysis. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1584–1588, 2004     

Preparation and adsorption properties of metal ions of crosslinked chitosan azacrown ethers

The novel azacrown ether chitosan derivatives (CCAE‐I, CCAE‐II) were prepared by reaction between crosslinked chitosan with epoxy‐activated azacrown ethers. Their structures were confirmed by elemental FTIR spectra analysis and X‐ray diffraction analysis. The adsorption and selectivity properties of the crosslinked chitosan azacrown ethers for Pb²⁺, Cu²⁺, Cr³⁺, Cd²⁺, and Hg²⁺ were also investigated. The experimental results showed that they have high adsorption capacity for Cu²⁺, Cd²⁺, and Hg²⁺. The adsorption capacity of CCAE‐II is higher than CCAE‐I for Cd²⁺ and Hg²⁺. The selectivity properties of CCAE are better than chitosan and crosslinked chitosan. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 3053–3058, 1999     

Preparation and properties of chitosan/poly(vinyl alcohol) blend foams for copper adsorption

A new form of polymer blend, macroporous chitosan/poly(vinyl alcohol) (PVA) foams made by a starch expansion process, exhibits the functionalities of chitosan while avoiding its poor mechanical properties and chemical instabilities. The appropriate conditions for foaming are discussed using both insoluble and water‐soluble chitosan. The chitosan/PVA foams demonstrated interconnected and open‐cell structures with large pore size from tens to hundreds of micrometers and high porosities from 73.6 to 84.3%. Glutaraldehyde was employed to improve the retention of chitosan and copper adsorption of the chitosan/PVA foams. While it increased the retention of chitosan and the adsorption capacities, glutaraldehyde decreased the pore size and porosity. The macroporous structure of the chitosan/PVA foams indicates extensive application prospects in terms of the considerable adsorption of heavy metal ions. Copyright © 2006 Society of Chemical Industry     

Relationship between breakthrough curve and adsorption isotherm of Ca(Ⅱ) imprinted chitosan microspheres for metal adsorption

In this work, an equilibrium-dispersion model was successfully established to describe the breakthrough performance of Ca(II) imprinted chitosan (Ca(II)-CS) microspheres packed column for metal adsorption, and the assumptions of Langmuir isotherms and axial dispersion controlled mass transfer process were confirmed. The axial dispersion coefficient in Ca(II)-CS microspheres packed column was found to be almost proportional to the linear velocity and fit for prediction through single breakthrough test. Sensitivity analysis for breakthrough curve indicated the axial dispersion coefficient as well as Langmuir coefficient was sensitive variable for deep removal requirement. The retrieval of the adsorption isotherms of Ca(II)-CS microspheres from breakthrough curve was fulfilled by model ing calibration. A strategy based on the correlation between adsorption isotherms and breakthrough performance was further proposed to simplify the column adsorption design using absorbents with smal/uniform size and fast adsorption kinetics like Ca(II)-CS microspheres to cut down the gap between lab and industry.     

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     

Preparation and adsorption behavior for metal of chitosan crosslinked by dihydroxy azacrown ether

A new type of crosslinked chitosan was prepared using Dihydroxy azacrown ether as the crosslinking agent. Its structure was confirmed by elemental analysis, Fourier transform infrared (FTIR) spectra analysis, solid‐state ¹³C nuclear magnetic resonance (NMR) analysis, and X‐ray diffraction analysis. Its static adsorption properties for Ag⁺, Cd²⁺, Hg²⁺, and Co²⁺ were studied. The experimental results showed that the Dihydroxy azacrown ether crosslinked chitosan has good adsorption capacities and high selectivity for adsorption of Ag⁺ with the coexistence of Hg²⁺ and Co²⁺. The selectivity coefficients of crosslinked chitosan are k/ = 5.47, k/ = 4.64, respectively. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 530–535, 2002     

Removal of Copper (II) and Nickel (II) Ions from Aqueous Solutions by a Composite Chitosan Biosorbent

Abstract

A composite chitosan biosorbent (CCB) was prepared by coating chitosan on to ceramic alumina. The adsorption characteristics of the sorbent for copper and nickel ions were studied under batch equilibrium and dynamic flow conditions at pH 4.0. The equilibrium adsorption data were correlated with Langmuir, Freundlich, and Redlich‐Peterson models. The ultimate monolayer capacities, obtained from Langmuir isotherm, were 86.2 and 78.1 mg/g of chitosan for Cu(II) and Ni(II), respectively. In addition, dynamic column adsorption studies were conducted to obtain breakthrough curves. After the column was saturated with metal ions, it was regenerated with 0.1 M sodium hydroxide. The regenerated column was used for a second adsorption cycle.     

改性磁性壳聚糖微球的制备、表征及性能研究

以(NH4)2Fe(SO4)2.6H2O、NH4Fe(SO4)2.12H2O和壳聚糖为原料,经羟丙基化、胺基化,采用一步包埋法制备了一种新型的多胺基化磁性壳聚糖微球。通过正交实验法确定了磁性微球的最佳制备条件,即搅拌速度1200r/min,壳聚糖用量3.0g,环氧氯丙烷用量2.5mL,乙二胺用量2.5mL。并用IR、TG、XRD和SEM对其结构及形貌进行了表征。结果表明,Fe3O4磁性粒子已包埋了一层胺基化壳聚糖。磁性微球胺基含量为2.302mmol/g;呈较规则的球形,平均粒径为209nm,且具有顺磁性和良好的耐酸性。     

L-胱氨酸交联球形壳聚糖凝胶的制备与Cu2+吸附性能

以L-胱氨酸(L-CYS)作为交联剂,利用滴液成球法制备交联球形壳聚糖凝胶,用傅里叶红外光谱、¹³C NMR、扫描电镜对产物进行了表征,结果表明L-CYS与壳聚糖发生了酰胺化及酯化反应,并且制得的凝胶内部存在着疏松的网络状大孔。交联剂L-CYS中的二硫键有助于二价铜离子的吸附。以L-CYS交联得到的球形壳聚糖凝胶对Cu²⁺的吸附量达到了72.96 mg·g^-1,接近于未交联的球形壳聚糖凝胶的吸附量,而耐溶胀性优于未交联的壳聚糖凝胶。     

Kinetic analysis of the sorption of copper(II) ions on chitosan

The removal of copper ions from aqueous effluents by chitosan was studied in equilibrium and agitated batch contacting systems. The sorption capacities of chitosan for copper ions are 1.26 and 1.12 mmol g^?1 at pH 3.5 and 4.5, respectively. The equilibrium experimental data were best correlated by the Langmuir equation. The kinetics of sorption were studied at an initial solution pH of 4.5 and a chitosan particle size of 355–500 µm. The kinetics were analyzed using four models: the pseudo‐first‐order, pseudo‐second‐order, modified second‐order and Elovich equations. The rate parameters for the four models were determined and the Elovich equation provided the best correlation of the experimental kinetic data. Copyright © 2003 Society of Chemical Industry     

Adsorption of lead(II) from aqueous solution by activated carbon prepared from Eichhornia

Activated carbon prepared from Eichhornia was used for the adsorptive removal of Pb(II) from aqueous solution. As the raw material for the preparation of the activated carbon is an aquatic weed, the production of this carbon is expected to be economically feasible. Parameters such as agitation time, metal ion concentration, adsorbent dose and pH were studied. Adsorption equilibrium was reached in 100 min for a solution containing 15 mgdm^?3 and 125 min for solutions containing 20 and 25 mgdm^?3 Pb(II), respectively. Adsorption parameters were determined using both Langmuir and Freundlich isotherm models. The adsorption capacity was 16.61 mgg^?1 at pH 3.0 for particle sizes of 125–180 µm. Pb(II) removal increased as the pH increased from 2 to 4 and remained constant up to pH 10.0. Desorption studies were also carried out with dilute hydrochloric acid to recover both carbon and Pb(II). Quantitative desorption of Pb(II) from carbon indicates that adsorption of metal ion is by ion exchange. © 2002 Society of Chemical Industry     

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.     

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).     

[Dye molecules/copper(II)/macroporous glutaraldehyde‐chitosan] microspheres complex: Surface characterization,kinetic, and thermodynamic investigations

Chitosan microspheres loaded Cu(II) were prepared using a precipitation method and heterogeneously crosslinked with glutaraldehyde. The abilities of the binary [Cu(II)/Glut‐chitosan] system for binding two acid dyes, that is, Acid blue 25 (AB25) and Calmagite (Calma) were investigated. Sorption experiments were performed using a batch process at 25°C and indicate pH dependence. Evidence for the modification of the raw chitosan polymer was provided by Fourier transform infra red spectral study, thermogravimetry, differential thermogravimetry, differential scanning calorimetry, and scanning electron microscopy analysis. Data gleaned from the thermal analyses, showed that the modification of the polymer decreases the thermal stability of the prepared materials with respect to that of the native one. The effecting factors during dye adsorption have been also studied. Thermodynamic and kinetic experiments were undertaken to assess the capacity and the rate of dyes removal on the surface of [Cu(II)/Glut‐chitosan]. Experimental data were mathematically described using various kinetic models. The pseudo second‐order equation was shown to fit the adsorption kinetics. The interpretation of the equilibrium sorption data complies well with the Freundlich adsorption model. Thermodynamic results indicate that the adsorption follows an exothermic process. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Highly efficient and fast adsorption of Au(III) and Pd(II) by crosslinked polyethyleneimine-glutaraldehyde

An adsorbent (PEI-GA) is prepared by crosslinking polyethyleneimine with glutaraldehyde. PEI-GA shows outstanding adsorption performance towards Au(III) and Pd(II). PEI-GA presents large adsorption capacity towards Au(III) in a wide application pH range from 1 to 9. The adsorption capacities of PEI-GA for Au(III) and Pd(II) at 25°C reach 2575 and 497 mg/g, respectively. Au(III) and Pd(II) can be adsorbed completely within 10 min for 8.3 mg/L Au(III) and 20 min for 9.7 mg/L Pd(II). The adsorption equilibrium time required for 523.9 mg/L Au(III) and for 565.6 mg/L Pd(II) is 2 and 9 h, respectively. The Sips model is the most suitable to describe the adsorption isotherms which leads to more realistic adsorption capacities for both metals. PEI-GA also exhibits high selectivity and repeatability towards Au(III) and Pd(II). The adsorption mechanism involves redox, chelation coordination, and electrostatic interactions for Au(III), and coordination and electrostatic interactions for Pd(II).     

Preparation and characterization of magnetic polymethylmethacrylate microbeads carrying ethylene diamine for removal of Cu(II), Cd(II), Pb(II), and Hg(II) from aqueous solutions

Magnetic polymethylmethacrylate (mPMMA) microbeads carrying ethylene diamine (EDA) were prepared for the removal of heavy metal ions (i.e., copper, lead, cadmium, and mercury) from aqueous solutions containing different amount of these ions (5–700 mg/L) and at different pH values (2.0–8.0). Adsorption of heavy metal ions on the unmodified mPMMA microbeads was very low (3.6 μmol/g for Cu(II), 4.2 μmol/g for Pb(II), 4.6 μmol/g for Cd(II), and 2.9 μmol/g for Hg(II)). EDA‐incorporation significantly increased the heavy metal adsorption (201 μmol/g for Cu(II), 186 μmol/g for Pb(II), 162 μmol/g for Cd(II), and 150 μmol/g for Hg(II)). Competitive adsorption capacities (in the case of adsorption from mixture) were determined to be 79.8 μmol/g for Cu(II), 58.7 μmol/g for Pb(II), 52.4 μmol/g for Cd(II), and 45.3 μmol/g for Hg(II). The observed affinity order in adsorption was found to be Cu(II) > Pb(II) > Cd(II) > Hg(II) for both under noncompetitive and competitive conditions. The adsorption of heavy metal ions increased with increasing pH and reached a plateau value at around pH 5.0. The optimal pH range for heavy‐metal removal was shown to be from 5.0 to 8.0. Desorption of heavy‐metal ions was achieved using 0.1 M HNO₃. The maximum elution value was as high as 98%. These microbeads are suitable for repeated use for more than five adsorption‐desorption cycles without considerable loss of adsorption capacity. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 81–89, 2000