Mechanisms and kinetics of trisodium 2-hydroxy-1,1'-azonaphthalene-3,4',6-trisulfonate adsorption onto chitosan

Chitosan, a naturally abundant biopolymer, has widely been studied for metal adsorption from various solutions, but the extension of chitosan as an adsorbent to remove organic substances from water and wastewater has seldom been explored. In this study, the adsorption of an azo dye, trisodium 2-hydroxy-1,1'-azonaphthalene-3,4',6-trisulfonate (1), from aqueous solution onto the various degrees of deacetylated chitosan has been investigated. Equilibrium studies have been carried out to determine the capacity of chitosan for dye. The experimental data were analyzed using two isotherm correlations, namely, Langmuir and Freundlich equations. The linear correlation coefficients were determined for each isotherm and the Langmuir provided the best fit. The experimental adsorption isotherms were perfectly reproduced in the simulated data obtained from numerical analysis on the basis of the Langmuir model and the isotherm constants. Adsorption of (1) onto the chitosan flakes was found to be strongly depending on degrees of deacetylation in chitosan and temperatures. Significant amounts of (1) were adsorbed by chitosan 8B (higher degree of deacetylated chitosan), but the adsorption capacity was reduced remarkably with increasing solution temperatures. Thermodynamic parameters such as change in free energy (DeltaG), enthalpy (DeltaH), and entropy (DeltaS) were also determined. In addition, kinetic study indicated that the adsorption process mechanisms were both transport- and attachment-limited.     

Use of Biopolymers for the Removal of Metal Ion Contaminants from Water

Summary: Naturally abundant biosorbants such as chitin and chitosan are recognized as excellent metal ligands, forming stable complexes with many metal ions, and serving as effective protein coagulating agents. Chitosan is a heteropolymer made of D-glucosamine and a small fraction of N-acetyl-D-glucosamine residues. Therefore, the adsorption ability of chitosan is found to be much higher than that of chitin, which has relatively fewer amino groups. Zeolites are crystalline microporous aluminosilicates with ion exchange properties suitable for a wide range of applications in catalysis and separation of liquid and gaseous mixtures. Incorporation in chitosan membranes is an effective method to control the diffusion outside the zeolite crystals and appropriately designed composite systems can find numerous opportunities for applications in wastewater treatment. In this paper we present the synthesis of zeolite-chitosan and zeolite-ethyl cellulose composites by encapsulation of clinoptilolite using a gelling solution of chitosan or an ethyl cellulose solution in ethyl acetate. The adsorption process of Cu²⁺ and Cd²⁺ on some adsorbents was investigated: clinoptillolite tuff (0.05 mm), chitosan flakes, ethyl cellulose, zeolite-chitosan and zeolite- ethyl cellulose composites. Zeolite-chitosan composites have been prepared by encapsulation of zeolites by a gelling solution of chitosan. Micrometric crystals of clinoptillolite were dispersed in a 3% chitosan solution in 1% aqueous acetic acid. The chitosan gel was formed and the zeolite crystals were encapsulated during the gelling process. The same procedure was used to obtain zeolite – ethyl cellulose composites. Study of the metal ion retention properties of different adsorbent materials was carried out using a steady state regime. The concentration of heavy metal ions in supernatant was determined by the atomic absorption spectrophotometric method. Adsorption isotherms of metal ions on adsorbents were determined and correlated with common isotherm equations such as Langmuir and Freundlich models.     

Coprecipitation Behavior of Some Metals with Chitosan and Their Determination by Graphite Furnace Atomic Absorption Spectrometry

Chitosan is derived from chitin by deacetylation. Chitosan forms a complex with metal ions and is soluble an organic acid. The metal ions were concentrated in the precipitates of chitosan when the sample solution containing metal ions was adjusted to neutral after the chitosan solution was added. These properties are applied to the preconcentration of metal ions in water samples and their determination by graphite furnace atomic absorption spectrometry. Metal ions,such as ruthenium, indium, vanadium, strontium,rhodium were collected in the chitosan precipitates.     

壳聚糖及其衍生物对金属离子的吸附研究(上)

壳聚糖是一种天然高分子,在其分子结构的重复单元中有-NH2和-OH,因而对金属离子有较好地吸附和配位能力.本文较全面地综述了壳聚糖及其衍生物对金属离子的吸附性能,简述了它们与金属离子形成配合物的结构及吸附机理,并对其发展前景作了展望.其中上篇主要讲述了壳聚糖及其衍生物对金属离子吸附性能的研究进展.     

Adsorption of tannic acid, humic acid, and dyes from water using the composite of chitosan and activated clay

Chitosan is a well-known excellent adsorbent for a number of organics and metal ions, but its mechanical properties and specific gravity should be enhanced for practical operation. In this study, activated clay was added in chitosan slurry to prepare composite beads. The adsorption isotherms and kinetics of two organic acids (tannic acid, humic acid) and two dyes (methylene blue, reactive dye RR222) using composite beads, activated clay, and chitosan beads were compared. With composite beads as an adsorbent, all the isotherms were better fitted by the Freundlich equation. The adsorption capacities with composite beads were generally comparable to those with chitosan beads but much larger than those with activated clay. The pseudo-first-order and pseudo-second-order equations were then screened to describe the adsorption processes. It was shown that the adsorption of larger molecules such as tannic acid (MW, 1700 g mol(-1)), humic acid, and RR222 from water onto composite beads was better described by the pseudo-first-order kinetic model. The rate parameters of the intraparticle diffusion model for adsorption onto such adsorbents were also evaluated and compared to identify the adsorption mechanisms.     

Removal of Cobalt Ions from Aqueous Solution by Adsorption onto Cross-Linked Calcium Alginate Beads

The removal of cobalt ions from dilute aqueous solutions using cross linked calcium alginate beads as the adsorbent is reported in this article. The influence of various experimental parameters such as pH, initial metal ion concentration, contact time and solid to liquid ratio were studied. The adsorption data were applied to Langmuir and Freundlich isotherm equations and various static parameters were calculated. It was observed that the uptake of cobalt ions was found to increase with time and that maximum adsorption was obtained within the first 60 minutes of the process. These results indicate that the cross linked calcium alginate beads have potential for removing cobalt ions from industrial waste water.     

壳聚糖及其衍生物对金属离子的吸附研究(下)

壳聚糖是一种天然高分子,在其分子结构的重复单元中有-NH2和-OH,因而对金属离子有较好地吸附和配位能力。本文较全面的综述了壳聚糖及其衍生物对金属离子的吸附性能,简述了它们与金属离子形成配合物的结构及吸附机理。其中下篇主要讲述了壳聚糖及其衍生物与金属离子形成配合物后的结构以及吸附机理,并对其发展前景作了展望。     

Hydrolysis of mixed monomolecular films of tricaprylin/dilauroylphosphatidylcholine by lipase and phospholipase A₂

The potential of chitosan, a fishery waste-based material, as a soil amendment to clean-up metal contaminated soil was investigated. Chitosan was treated using glutaraldehyde (GLA), epichlorohydrin (ECH) and ethylene glycol diglycidyl ether (EGDE) as cross-linking reagents to enhance its chemical stability in acidic media and to improve its physical properties. Cross-linking treatment had significant effects on chitosan surface area, pore diameter, surface morphology and crystallinity. Interaction with Ag(I), Pb(II) and Cu(II) decreased the crystallinity of the materials and changed their surface morphology significantly. FTIR analysis confirmed that N and O atoms served as binding sites for the metal ions. Chitosan and treated chitosans were able to bind metal ions, even in the presence of K⁺, Cl^? and NO₃^?, which are dominant ions in soil. Therefore, remediation of metal contaminated soil using chitosan and cross-linked treated chitosans as soil amendments is feasible.     

Adsorption and desorption of binary mixtures of copper and mercury ions on natural and crosslinked chitosan membranes

Copper and mercury ion adsorption on chitosan membranes was investigated in batch systems (with both single and binary solutions). The Langmuir model and its extensions (extended Langmuir, Jain-Snoeyink, and Langmuir-Freundlich models) were tested for the modeling of experimental data. Chitosan membranes presented more affinity for Hg ions than for Cu ions. The decrease of the amount of metal adsorbed on natural chitosan in binary systems (compared to single-metal solutions) showed the competition effects between the two metal ions. For glutaraldehyde-crosslinked chitosan and epichlorohydrin-crosslinked chitosan, the mixture effect was present, producing unexpected result such as higher adsorption capacities, when compared to the monocomponent solution of each metal. The desorption of the metals was also investigated, and copper and mercury ions could be selectively recovered using a combined process by using NaCl and H₂SO₄ as eluant.     

Adsorption isotherm models for basic dye adsorption by peat in single and binary component systems

Colored effluents from textile industries are a problem in many rivers and waterways. Prediction of dye adsorption capacities is important in design considerations. The sorption of three basic dyes, namely Basic blue 3, Basic yellow 21, and Basic red 22, onto peat is reported. Equilibrium sorption isotherms have been measured for the three single-component systems. Equilibrium was achieved after 21 days. The experimental isotherm data were analyzed using Langmuir, Freundlich, Redlich-Peterson, Tempkin, and Toth isotherm equations. A detailed error analysis has been undertaken to investigate the effect of using different error criteria for the determination of the single-component isotherm parameters and hence obtain the best isotherm and isotherm parameters which describe the adsorption process. The linear transform model provided the highest R(2) regression coefficient with the Redlich-Peterson model. The Redlich-Peterson model also yielded the best fit to experimental data for all three dyes using the nonlinear error functions. An extended Langmuir model has been used to predict the isotherm data for the binary systems using the single component data. The correlation between theoretical and experimental data had only limited success due to competitive and interactive effects between the dyes and the dye-surface interactions.     

壳聚糖与尿素的相互作用及其应用研究进展

尿素能够显著破坏甲壳素/壳聚糖分子氢键结构和疏水相互作用,增加其临界胶束浓度,促进多糖大分子的溶解,并能减少其在溶液中的自聚集现象.碱-尿素水溶液可以作为一种新型的甲壳素/壳聚糖绿色溶剂,有望用于对刺激性要求较为苛刻的食品、生物医学等领域.壳聚糖衍生物特别是其与过渡金属离子的配合物具有良好的尿素吸附功能,可用于尿毒症患者血液中小分子毒物的吸附,对机体刺激性小且不吸附血清蛋白等生物大分子.有望成为血液灌流治疗法中清除尿素等小分子毒性物质的良好吸附剂.壳聚糖还可以作为包膜材料,制备壳聚糖包膜尿素,与普通的包膜尿素相比性能更为优越.     

Surface and biological activity of sophorolipid molecules produced by Wickerhamiella domercqiae var. sophorolipid CGMCC 1576

The ion-imprinted magnetic chitosan resins (IMCR) prepared using U(VI) as a template and glutaraldehyde as a cross-linker showed higher adsorption capacity and selectivity for the U(VI) ions compared with the non-imprinted magnetic chitosan resins (NIMCR) without a template. The results showed that the adsorption of U(VI) on the magnetic chitosan resins was affected by the initial pH value, the initial U(VI) concentration, as well as the temperature. Both kinetics and thermodynamic parameters of the adsorption process were estimated. These data indicated an exothermic spontaneous adsorption process that kinetically followed the second-order adsorption process. Equilibrium experiments were fitted in Langmuir, Freundlich, and Dubinin-Radushkevich adsorption isotherm models to show very good fits with the Langmuir isotherm equation for the monolayer adsorption process. The monolayer adsorption capacity values of 187.26 mg/g for IMCR and 160.77 mg/g for NIMCR were very close to the maximum capacity values obtained at pH 5.0, temperature 298 K, adsorbent dose 50 mg, and contact time 3 h. The selectivity coefficient of uranyl ions and other metal ions on IMCR indicated an overall preference for uranyl ions. Furthermore, the IMCR could be regenerated through the desorption of the U(VI) ions using 0.5 M HNO(3) solution and could be reused to adsorb again.     

Development of Azo Dye Immobilized Sulfonated Poly (Glycidyl Methacrylate) Polymer Composite as Novel Adsorbents for Water Treatment Applications: Methylene Blue Immobilization Isotherm,Kinetic, Thermodynamic,and Simulations Studies

Methylene blue (MB) immobilized onto a sulfonated poly(glycidyl methacrylate) (SPGMA) polymer composite has been developed as a novel adsorbent for water treatment applications. The MB adsorptions onto sulfonated poly(glycidyl methacrylate) polymer characters have been studied. The adsorption isotherms, namely Langmuir and Freundlich, have been investigated. Other isotherm models. As a compromise between the Freundlich and Langmuir isotherm models, such as the D–R isotherm and the Temkin isotherm, have been compared. The results indicated that the adsorption process followed the Freundlich isotherm model, indicating heterogeneous surface site energies and multi-layer levels of sorption. This study selected three linear kinetic models, namely pseudo-first order, pseudo-second order, and Elovich, to describe the MB sorption process using SPGMA negatively charged nanoparticles (430 nm). The obtained data revealed that the adsorption process obeyed the pseudo-second-order kinetic model, suggesting that the rate-limiting step in these sorption processes may be chemisorption. Furthermore, the thermodynamic parameters have been evaluated. Moreover, the interaction of the MB molecules with SPGMA nanoparticles has been simulated using the governing equation that describes ion exchange resin derived from Nernst—Plank equations between two ion species. Finally, the developed MB-SPGMA composite adsorbent (27 mg/g) wastested for the first time for the removal of Cr⁶⁺ ions and Mn⁷⁺ metal ions from dichromate and permanganate-contaminated waters under mild adsorption conditions, opening a new field of multiuse of the same adsorbent in the removal of more than one contaminant.     

Carrier-mediated blends of Chitosan with polyvinyl chloride for different applications

The current work aims at blending of PVC with Chitosan through simultaneous casting of their separate solutions in different proportions of PVC and Chitosan in suitable solvents. After dissolution, both solutions were added to each other while stirring at room temperature. The obtained mixture was left at room temperature to form the blend after evaporation of the solvent. Similar blends have been prepared similarly in presence of the organic ligand, dithizone, as a carrier-mediating material for different metal ions. PVC/Chitosan blends were characterized by thermal (TGA) and FT-IR Spectroscopic analyses as well as scanning electron microscopy (SEM). The obtained blends were found to have reasonable extent of compatibility between their components. Such compatibility depends mainly on the way with which the components have been blended with each other. The polymer-supported dithizone was investigated toward its ability to be used for removal of some metal ions from their aqueous solutions. Concentration of metal ions was determined by ICP-AES analysis.     

Adsorption of 1-tetradecene/dodecane mixtures on different types of zeolites

The influence of heterogeneity parameters on the shape of excess adsorption isotherms has been discussed. These isotherms have been calculated according to the equations corresponding to different energy distributions. Next, the isotherm equations have been applied to examine the experimental excess isotherms for 1-tetradecene/dodecane mixture adsorption on different types ofX-zeolites at 293 K, 313 K and 333 K. The zeolite samples have been prepared from NaX-zeolite by exchanging the sodium ions for ions of alkalines and calcium group. Analysis of the above adsorption data by means of different isotherm equations showed that the parameters of aDubinin-Radushkevich-type equation change correctly with temperature and the contents of alkalines in the zeolite samples.     

二甲胺修饰戊二醛交联壳聚糖树脂的制备及性能

研究了在均匀水相介质条件下，采用戊二醛稀溶液制备交联壳聚糖树脂的方法，并以三聚氯氰为活化剂，合成了二甲胺修饰戊二醛交联壳聚糖树脂．研究了该树脂的红外光谱及吸附性能．该树脂对铜(Ⅱ)和牛血清白蛋白(BSA)的吸附容量分别为42mg／g(干)和940mg／g(干)，其吸附行为均符合Freundlich等温吸附模型．该树脂制备工艺简单，机械强度较好，可作为金属离子或蛋白质分离纯化的吸附剂和色谱填料．     

THE THEORETICAL STUDY OF ADSORPTION OF METAL IONS ON CHITOSAN

1. INTRODUCTION Chitin, the most abundant natural amino polysaccharide and estimated to be produced annually almost as much as cellulose, is well known to consist of 2-acetamido-2-deoxy-β-D- glucose through α, β(1→4) linkage. Chitin is the major source of surface pollution in coastalareas. Chitosan is the N-deacetylated derivative of chitin and their structures are shown in Fig. 1. Fig. 1 Structures of Chitin and Chitosan Because of the excellent properties such as biocompatibility…     

Preconcentration of trace nickel lons from aqueous solutions by using a new and low cost chelating polystyrene adsorbent

A simple and reliable method has been developed using chelating polymeric adsorbent (PSAHSB) to preconcentration of trace amount of Ni(II) ions from aqueous solutions under static loading conditions, and their determination by Ultraviolet and visible (UV–Vis) absorption spectroscopy. The influences of some analytical adsorption parameters, such as pH, temperature and contact time, the ionization constants of chelating groups in the adsorbent and desorption process were investigated. Maximum adsorption ≥98% was achieved at pH 3–7 after 20 min of contact time and the relative standard-deviation values were ≤5%. Adsorbed metal ions have been desorbed with 10 mL of 2 M HCl acid with the detection limit of 0.0157 μg m⁻¹. The Langmuir and Freundlich isotherm equations were used to describe adsorption behavior of the system at different temperatures. Kinetic and thermodynamic behavior of the adsorbent for Ni(II) ion preconcentration was also studied. The possible adsorption mechanism of Ni (II) ions onto modified adsorbent is also discussed. This method was applied efficiently to remove Ni (II) ions from environmental water samples.     

Adsorption of Zinc and Lead Ions from Aqueous Solutions Using Chitosan/Polyvinyl Alcohol Membrane Incorporated via Acid-Functionalized Carbon Nanotubes

Carbon nanotubes were synthesized via the chemical vapor deposition method using cyclohexanol and ferrocene as carbon precursor and catalyst, respectively, and then they are functionalized with acid treatment. Chitosan/polyvinyl alcohol adsorptive membrane incorporated with carbon nanotubes (CS/PVA-CNTs membrane) was prepared via the solution casting method. The CS/PVA-CNTs membrane was employed for adsorption of lead and zinc ions from aqueous solutions. Various isotherms and kinetic models were applied to fit the experimental data. It was found out that adsorption behavior of the heavy metal ions using CS/PVA-CNTs membrane match well with the Freundlich isotherm and the pseudo-first-order kinetic models.     

THE THEORETICAL STUDY OF ADSORPTION OF METAL IONS ON CHITOSAN

The interactions between metal ions such as Zn2+, Pb2+, Mn2+, Hg2+, Cd2+, Ni2+ and chitosan have been investigated using the model cluster model method and density functional method. Full optimization and frequency analysis of all cluster models have been performed employing B3LYP hybrid method at 3-21G basis set level except metal ions which were invoked to use effective core potential (ECP) method. The energy changes, and the main structural parameters have been obtained during the theoretical study of the adsorption of metal ions on the chitosan. The calculations showed that the coordination modes of metal ions with chitosan models were different, the geometries of Mn2+, Zn2+, Cd2+, Hg2+, Pb2+ ions coordinated with two nitrogen atoms and two oxygen atoms were distorted tetrahedral, while the square planar structure of Ni2+ coordinated two nitrogen atoms and two oxygen atoms was observed. The heat of reaction between six metal ions and chitosan models showed the order: Mn2+ ＞Ni2+ ＞Zn2+ ＞Pb2+ ＞Hg2+ ＞Cd2+, this suggested that the coordination strength of Mn2+ ＞Ni2+ ＞Zn2+ ＞Pb2+ ＞Hg2+ ＞Cd2+.