Chemical modification of chitosan and equilibrium study for mercury ion removal

To increase the uptake capacity of mercury ions, several chemical modifications of chitosan beads which are cross-linked with glutaraldehyde were performed. Among them, aminated chitosan bead prepared through chemical reaction with ethylenediamine had a high uptake capacity of about 2.3 mmol g(-1) dry mass at pH 7. The increased number of amine groups was confirmed by IR analysis and measuring the saturation capacities for adsorption of HCl. The surface condition and existence of mercury ions on the beads was confirmed by the environmental scanning electron microscope and energy dispersive X-ray spectroscopy instrumental analyses. The beads showed the characteristic of competitive sorption between mercury and hydrogen ions and it was successfully modelled by an equilibrium model.     

Uptake of mercury by thiol-grafted chitosan gel beads

This study describes the synthesis and characterization of thiol-grafted chitosan beads for use as mercury (Hg) adsorbents. Chitosan flakes were dissolved and formed into spherical beads using a phase inversion technique, then crosslinked to improve their porosity and chemical stability. Cysteine was grafted onto the beads in order to improve the adsorption affinity of Hg to the beads. The beads possessed an average diameter of 3.2 mm, porosity of 0.9, specific surface area of approximately 100 m2/g, average pore size of approximately 120 angstroms, and specific gravity of 2.0. Equilibrium and kinetic uptake experiments were conducted to study the uptake of Hg by the beads. The adsorption capacity was approximately 8.0 mmol-Hg/g-dry beads at pH 7, and decreased with decreasing pH. Hg adsorption kinetics was modeled as radial pore diffusion into a spherical bead with nonlinear adsorption. Use of the nonlinear Freundlich isotherm in the diffusion equation allowed modeling of the uptake kinetics with a single tortuosity factor of 1.5 +/- 0.3 as the fitting parameter for all initial Hg concentrations, chitosan loadings, and agitation rates. At agitation rates of 50 and 75 rpm, where uptake rate was reduced significantly due to the boundary layer effect, the mass transfer coefficient at the outside boundary was also used as a fitting parameter to model the kinetic data. At agitation rates higher than 150 rpm, pore diffusion was the rate-limiting step. The beads exhibited a high initial uptake rate followed by a slower uptake rate suggesting pore diffusion as the rate-determining step especially at high agitation rates. Higher uptake rates observed in this study compared to those in a previous study of chitosan-based crab shells indicate that dissolution and gel formation increase the porosity and pore accessibility of chitosan.     

Optimization of capacity and kinetics for a novel bio-based arsenic sorbent, TiO2-impregnated chitosan bead

The optimization of TiO₂-impregnated chitosan beads (TICB) as an arsenic adsorbent is investigated to maximize the capacity and kinetics of arsenic removal. It has been previously reported that TICB can 1) remove arsenite, 2) remove arsenate, and 3) oxidize arsenite to arsenate in the presence of UV light and oxygen. Herein, it is reported that adsorption capacity for TICB is controlled by solution pH and TiO₂ loading within the bead and enhanced with exposure to UV light. Solution pH is found to be a critical parameter, whereby arsenate is effectively removed below pH 7.25 and arsenite is effectively removed below pH 9.2. A model to predict TICB capacity, based on TiO₂ loading and solution pH, is presented for arsenite, arsenate, and total arsenic in the presence of UV light. The rate of removal is increased with reductions in bead size and with exposure to UV light. Phosphate is found to be a direct competitor with arsenate for adsorption sites on TICB, but other relevant common background groundwater ions do not compete with arsenate for adsorption sites. TICB can be regenerated with weak NaOH and maintain full adsorption capacity for at least three adsorption/desorption cycles.     

漂珠对玻化微珠保温混凝土力学性能影响研究

在C35等级的玻化微珠保温混凝土的基础上,将漂珠取代玻化微珠保温混凝土中的天然砂,研究了5种不同漂珠取代率(0、25%、50%、75%、100%)对玻化微珠保温混凝土的立方体抗压强度、劈裂抗拉强度、轴心抗压强度以及弹性模量的影响规律。试验结果表明,随漂珠取代率的增加玻化微珠保温混凝土的立方体抗压强度、劈裂抗拉强度、轴心抗压强度以及弹性模量均表现出下降的趋势;当漂珠取代率为50%(100%)时,玻化微珠保温混凝土的立方体抗压强度,劈裂抗拉强度、轴心抗压强度及弹性模量分别下降了12.4%(39.0%)、6.74%(33.71%)、15.79%(39.47%)、24.1%(42.5%);漂珠的掺入对玻化微珠保温混凝土的力学性能影响较大,因此漂珠的取代率不宜过高。     

Dynamic and static adsorption and desorption of Hg(II) ions on chitosan membranes and spheres

The adsorption and desorption of Hg(II) ions was studied using static and dynamic methods, employing membranes and spheres of chitosan as the adsorbent. The quantity of adsorption was influenced by chitosan crosslinking and by the adsorbent shape. The Langmuir model was applied to fit the experimental equilibrium data. Glutaraldehyde-crosslinked membranes presented a lower desorption capacity, when compared to natural membranes, but could be regenerated for use in successive cycles. Dynamic adsorption experiments suggested that the adsorption capacity depended mainly on adsorbent geometry, due to differences between surface area to mass ratio and initial concentration of Hg(II) ions. The adsorption capacity determined by the dynamic method was 65% and 77% for membranes and spheres, respectively of the value obtained static method results. A process combining dynamic adsorption and static desorption can be used to concentrate the Hg(II) ions by a factor of nearly seven (7x), when compared to the initially treated volume.     

Removal of chlorophenols from groundwater by chitosan sorption

The equilibrium and kinetics of chlorophenol (CP) sorption by chitosan, poly D-glucosamine, were studied under simulated groundwater conditions. Lower temperature, from 25 degrees C to 15 degrees C and then 5 degrees C, markedly decreased the adsorption rates by a factor of 30-53% and 7-22%. Comparison between two types of chitosan, flakes and highly swollen beads, demonstrated that the maximum pentachlorophenol (PCP) uptake capacities in Langmuir and Freundlich models depend on the specific surface area of the particle. Low temperature (5 degrees C) significantly increased the PCP uptake capacity in comparison to higher temperatures (15 degrees C and 25 degrees C). PCP uptake capacity was halved at pH levels higher than 6.5, and NaCl concentrations greater than 1% blocked PCP sorption almost completely. Of five kinds of chlorophenols, i.e. 2,4,6-trichlorophenol (2,4,6-TCP), 3,4-dichlorophenol (3,4-DCP), 2,3-dichlorophenol (2,3-DCP), 2,6-dichlorophenol (2,6-DCP), 3-monochlorophenol (3-MCP), TCP had the maximum sorption efficiency on flake-type chitosan, followed by DCPs, and finally MCP (the three kinds of DCP, with the same elemental compositions, achieved similar sorption performances).     

Cellulose/chitin beads for adsorption of heavy metals in aqueous solution

We successfully prepared the biodegradable cellulose/chitin beads by coagulating a blend of cellulose and chitin in 6 wt% NaOH/5 wt% thiourea aqueous solution with 5% H2SO4 as coagulant, and investigated the adsorption of heavy metals (Pb2+, Cd2+, Cu2+) from an aqueous solution on the beads by atomic absorption spectrophotometer. Batch adsorption experiments were carried out as a function of ion concentrations, initial pH, ionic strength, temperature, adsorption time and desorption time. The results revealed that the cellulose/chitin beads could adsorb effectively Pb2+, Cd2+ and Cu2+ ions, and the uptakes of Pb2+, Cd2+ and Cu2+ ions on cellulose/chitin beads were 0.33 mmol/g at pH0 4, 0.32 mmol/g at pH0 5 and 0.30 mmol/g at pH0 4, respectively. Experimental results also showed that the adsorption of these heavy metals was selective to be in the order of Pb2+ > Cd2+ > Cu2+ in a low ion concentration solution. The adsorption equilibrium time of these heavy metals on beads was 4-5 h, but the desorption time was 5-15 min. Moreover, these beads could be regenerated up to about 98% by treating with 1 mol/L HCl aqueous solution. The mechanisms for the removal of free heavy metal ions by cellulose/chitin beads was based on mainly complexation adsorption model, as well as a affinity of hydroxyl groups of the materials on metals. Therefore, we developed new environment-friendly beads prepared by a simple produce process for removal and recovery of heavy metals.     

Effects of a fulvic acid on the adsorption of mercury and cadmium on goethite

The effects of an aquatic fulvic acid on the pH-dependent adsorption of Hg(II) and Cd(II) to particulate goethite (alpha-FeOOH) were studied in batch systems. The ionic medium consisted of 0.01 M HClO(4) and the total concentrations of mercury and cadmium were maintained at 10(-8) M with 203Hg and 109Cd as tracers. pH In the systems was varied in the range 3-10 by addition of HClO(4) and NaOH. All commercial chemicals were of analytical grade or better. An aquatic fulvic acid (20 ppm), previously isolated and characterised in detail, was used as a model for humic substances and its adsorption to goethite is included in this study. The adsorption of the fulvic acid (20 ppm) onto goethite decreased slowly from 90% at pH 3-7.5 to 10% at pH 10. In systems without fulvic acid the adsorption of mercury increased in a linear fashion from 10% at pH 3 to 70% at pH 10. In the presence of fulvic acid (20 ppm), the adsorption was almost quantitative in the intermediate pH range (pH 5-7), and exceeded 92% over the entire pH range. Thus, association between mercury and the fulvic acid enhanced adsorption in general although the largest impact was found at low pH. Adsorption of cadmium increased from nearly 0 to almost 100% at approximately pH 6. In the presence of fulvic acid, the adsorption increased below pH 7 and decreased above pH 7. The adsorption isotherm for mercury when the concentration was increased from 10(-8) to 1.8 x 10(-4) M showed a corresponding increase of K(d) (l/g) up to a total concentration at 10(-6) M. At higher mercury concentrations K(d) was lowered. In the presence of fulvic acid the corresponding relationship of K(d) was bi-modal, i.e. high values at low and intermediate concentrations of mercury. This behaviour suggests that in the absence of fulvic acid the adsorption follow the expected behaviour, i.e. adsorption sites with similar affinity for mercury. In the presence of fulvic acid, additional adsorption sites are available by the organic molecule (possibly sulfur groups) when it is associated to the goethite. The adsorption isotherm for cadmium indicates a lowering of K(d) at 10(-4) M. Cadmium had no competitive effect on mercury and vice versa. Zinc, however, affected the adsorption of cadmium but not the adsorption of mercury.     

硅藻土对水相中Sr^2＋的吸附性能研究

研究了硅藻土对水相中Sr^2＋的吸附过程,讨论了各种因素对吸附效果的影响。结果表明：硅藻土对水相中的Sr^2＋具有较好的吸附效果。溶液pH值是影响硅藻土吸附Sr^2＋的重要因素,在强酸性环境下,硅藻土对Sr^2＋的吸附效果较佳。硅藻土对Sr^2＋的去除率随着硅藻土用量增加而增大,随着Sr^2＋初始质量浓度增加而降低;吸附量则随着硅藻土用量增加而降低,随着Sr^2＋初始浓度增加而增大。动力学研究表明,硅藻土对Sr^2＋的吸附是快速吸附过程,吸附进行到60min时,去除率和吸附量达到吸附平衡的95%;吸附过程较好地拟合伪二级动力学方程。     

固定化活性污泥球形颗粒的制备及其性能实验

本文以海藻酸钠和聚乙烯醇(PVA)为包埋剂,并适当添加粉末活性炭和硅藻土作为吸附剂探讨了固定化活性污泥球形颗粒的制备过程.继而以餐厅废水为实验用水对所制备的4种固定化小球进行了性能实验,结果表明:含活性炭配方的固定化活性污泥小球兼有包埋法和吸附法的双重特性.是较理想的固定化微生物形式.     

Low energy ballasted flotation

A novel process which involves the replacement or supplementation of bubbles in the dissolved air flotation process with low density beads is presented. The work comprised a series of bench-scale flotation trials treating three commonly encountered algal species (Microcystis, Melosira and Chlorella) that were removed in a flotation cell configured as either: conventional dissolved air flotation (DAF); ballasted flotation using low density 70 μm glass beads with a density of 100 kg m⁻³; or a hybrid process of ballasted flotation combined with conventional DAF. Results indicated that the bead only system was capable of achieving better residual turbidity than standard DAF at bead concentrations of 500 mg L⁻¹. Addition of beads in combination with standard DAF reduced turbidity further to even lower residual turbidity levels. Algae removal was improved when glass beads were dosed, but removal was dependent on algal species. Microcystis was removed by 97% for bead only systems and this removal did not change significantly with the addition of air bubbles. Melosira was the next best removed algae with bead only dosed systems giving similar removals to that achieved by standard DAF using a 10% air recycle ratio (81 and 76% removal respectively). Chlorella was the least well removed algae by bead only systems (63% removal). However, removal was rapidly improved to 86% by the addition of air bubbles using only a 2% recycle ratio. Energy estimations suggested that at least a 50% energy reduction could be achieved using the process offering a potential route for future development of low energy separation processes for algae removal.     

The buckling characteristics of some integrally formed bead stiffened composite panels

Composite panel stability can easily be improved by using vertical male beads. In this paper, new methods of stabilizing techniques used for the panels, webs and ribs of composite structures are studied. A parametric study is performed to assess the effects of important design considerations such as, bead length, number of beads, bead radius, bead depth and bead spacing on the initial buckling load of the panels. The results show that, there is an optimum bead spacing for each panel containing more than one bead which can be estimated using a simple equation. Integration of vertical beads with a length of less than 0.5 times the panel's length has no significant effect on the buckling load. There are no significant changes on the buckling loads of the beaded panels with bead depths greater than 0.6 times the bead radius. In this investigation, the instability of the nose and main ribs of a light airplane wing structure made of woven E-glass material and stiffened by P.V.C foam core and vertical male beads are also studied using experimental methods. The experimental results show that we can easily improve the buckling capability of the panels and webs by using vertical male beads instead of sandwiched construction. It is estimated that this would cause a weight reduction of about 50% and a manufacturing time reduction of about 50%.     

Adsorption of residue oil from palm oil mill effluent using powder and flake chitosan: equilibrium and kinetic studies

The adsorption of residue oil from palm oil mill effluent (POME) using chitosan powder and flake has been investigated. POME contains about 2g/l of residue oil, which has to be treated efficiently before it can be discharged. Experiments were carried out as a function of different initial concentrations of residue oil, weight dosage, contact time and pH of chitosan in powder and flake form to obtain the optimum conditions for the adsorption of residue oil from POME. The powder form of chitosan exhibited a greater rate compared to the flake type. The results obtained showed that chitosan powder, at a dosage of 0.5g/l, 15min of contact time and a pH value of 5.0, presented the most suitable conditions for the adsorption of residue oil from POME. The adsorption process performed almost 99% of residue oil removal from POME. Equilibrium studies have been carried out to determine the capacity of chitosan for the adsorption of residue oil from POME using the optimum conditions from the flocculation at different initial concentrations of residue oil. Langmuir and Freundlich adsorption models were applied to describe the experimental isotherms and isotherm constants. Equilibrium data fitted very well with the Freundlich model. The pseudo first- and second-order kinetic models and intraparticle diffusion model were used to describe the kinetic data and the rate constants were evaluated. The experimental data fitted well with the second-order kinetic model, which indicates that the chemical sorption is the rate-limiting step, i.e. chemisorption between residue oil and chitosan. The significant uptake of residue oil on chitosan was further proved by BET surface area analysis and SEM micrographs.     

Enhanced chitosan beads-supported Fe-nanoparticles for removal of heavy metals from electroplating wastewater in permeable reactive barriers

The removal of heavy metals from electroplating wastewater is a matter of paramount importance due to their high toxicity causing major environmental pollution problems. Nanoscale zero-valent iron (NZVI) became more effective to remove heavy metals from electroplating wastewater when enhanced chitosan (CS) beads were introduced as a support material in permeable reactive barriers (PRBs). The removal rate of Cr (VI) decreased with an increase of pH and initial Cr (VI) concentration. However, the removal rates of Cu (II), Cd (II) and Pb (II) increased with an increase of pH while decreased with an increase of their initial concentrations. The initial concentrations of heavy metals showed an effect on their removal sequence. Scanning electron microscope images showed that CS-NZVI beads enhanced by ethylene glycol diglycidyl ether (EGDE) had a loose and porous surface with a nucleus-shell structure. The pore size of the nucleus ranged from 19.2 to 138.6 μm with an average aperture size of around 58.6 μm. The shell showed a tube structure and electroplating wastewaters may reach NZVI through these tubes. X-ray photoelectron spectroscope (XPS) demonstrated that the reduction of Cr (VI) to Cr (III) was complete in less than 2 h. Cu (II) and Pb (II) were removed via predominant reduction and auxiliary adsorption. However, main adsorption and auxiliary reduction worked for the removal of Cd (II). The removal rate of total Cr, Cu (II), Cd (II) and Pb (II) from actual electroplating wastewater was 89.4%, 98.9%, 94.9% and 99.4%, respectively. The findings revealed that EGDE-CS-NZVI-beads PRBs had the capacity to remediate actual electroplating wastewater and may become an effective and promising technology for in situ remediation of heavy metals.     

天然气液化厂站脱汞的探讨

分析了吸附脱汞和氧化型吸收剂的脱汞效果,吸附脱汞的吸附剂包括煤基活性炭、活性炭纤维、活性焦、钙基吸附剂、壳聚糖类吸附剂.介绍了天然气脱汞的国内外工程实例.     

微波场下微珠对碱激发粉煤灰早期力学性能的影响

基于多级微波养护制度,在经浮选、磁选后的焙烧粉煤灰中掺入炭粒、漂珠和磁珠等微珠,研究微珠在微波场下的水化行为及其对碱激发粉煤灰基胶凝材料早期力学性能的影响,并采用X射线衍射(XRD)、傅里叶红外光谱(FTIR)、场发射扫描电子显微镜(FESEM)分析其微观结构.结果表明:掺加5%炭粒对微波养护碱激发粉煤灰基胶凝材料的早期抗压强度没有影响,5%漂珠和磁珠能够显著提升其早期抗压强度;微波养护试样中都生成了羟基方钠石和钠系菱沸石,炭粒、漂珠和磁珠均不会改变水化产物的类型;碱激发反应能够在结构中空的漂珠内外同时进行,因此可以适当缩短富含漂珠的碱激发粉煤灰试样的微波养护时间.     

Removal of arsenic (III) and arsenic (V) from aqueous medium using chitosan-coated biosorbent

A biosorbent was prepared by coating ceramic alumina with the natural biopolymer, chitosan, using a dip-coating process. Removal of arsenic (III) (As(III)) and arsenic (V) (As(V)) was studied through adsorption on the biosorbent at pH 4.0 under equilibrium and dynamic conditions. The equilibrium adsorption data were fitted to Langmuir, Freundlich, and Redlich-Peterson adsorption models, and the model parameters were evaluated. All three models represented the experimental data well. The monolayer adsorption capacity of the sorbent, as obtained from the Langmuir isotherm, is 56.50 and 96.46 mg/g of chitosan for As(III) and As(V), respectively. The difference in adsorption capacity for As(III) and As(V) was explained on the basis of speciation of arsenic at pH 4.0. Column adsorption results indicated that no arsenic was found in the effluent solution up to about 40 and 120 bed volumes of As(III) and As(V), respectively. Sodium hydroxide solution (0.1M) was found to be capable of regenerating the column bed.     

水中重金属离子吸附材料的研究现状与发展趋势

系统介绍了无机吸附材料（碳质类、矿物类、金属氧化物类）、有机高分子吸附材料（纤维素、壳聚糖、农林废弃物、离子交换树脂等）和复合型吸附材料（有机/有机型、无机/无机型、有机/无机型）等重金属离子吸附材料的物化特性和结构特点,对上述材料去除水体典型重金属离子的吸附容量、吸附机理、工程应用进展等进行了综述。阐述了纳米材料、离子选择性材料和可降解生物质材料等新型重金属离子吸附材料的研究现状及发展趋势。结果表明:开发价格低廉、吸附容量高、选择性高、可再生且环境友好的吸附材料是重金属离子吸附研究的重要方向;结合现代化检测技术和分析手段,探索吸附过程中吸附剂与重金属离子间相互作用的本质,对于拓展吸附机理和开发性能优良的吸附材料具有重要的理论和实际意义。     

Mechanisms of lead biosorption on cellulose/chitin beads

Environment-friendly cellulose/chitin beads being prepared by coagulating a blend of cellulose and chitin in 6 wt% NaOH/5 wt% thiourea aqueous solution with 5% H2SO4 possessed higher heavy metals uptake capacity than pure chitin flakes. The mechanisms of Pb2+ adsorption on cellulose/chitin beads at pH0=5 were investigated at the molecular levels by scanning electron micrographs (SEM), transmission electron micrographs (TEM), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR) and powder X-ray diffraction (XRD). The result revealed that mechanisms for the adsorption of Pb2+ on the cellulose/chitin beads could be described as complexation between Pb2+ and N atom in the chitin, and further adsorption of Pb2+ nearby the complexed Pb2+ and precipitation of the hydrolysis product of the Pb2+ complex on the beads as the crystalline state. Furthermore, structural factors such as larger surface area of the beads resulted from microporous-network structure, low crystallinity of cellulose/chitin beads and high hydrophilicity induced by hydrophilic skeleton of cellulose played an important role in increasing adsorption ability.     

Removal of azo and anthraquinone dyes from aqueous solutions by Eichhornia Crassipes

The rate of adsorption of two azo and four anthraquinone anionic dyes on Eichhornia Crassipes (E.C.) has been studied. Raw E.C. and three aminated derivatives of E.C. with different nitrogen percent were used as dye adsorbents. The parameters studied include the amount of substrate, shaking time, chemical structure, concentration of dyestuff and pH of dyeing bath. Simple kinetic adsorption models of dynamics and adsorption parameters for the Langmuir and Freundlich isotherms were determined. A higher nitrogen percent of aminated E.C. showed a higher adsorption capacity than other derivatives. The kinetic adsorption models indicate that the decolourization was complete in a relatively short time (10 min) and the reaction taking place is of the first order. The equilibrium data fit well with the Freundlich model of adsorption for the six dyes. Only dye IV (C.I.A Acid Blue 25) conform both Freundlich and Langmuir adsorption isotherms.