Fluoride removal using lanthanum incorporated chitosan beads

Highly selective material based on naturally occurring biomaterial namely chitosan has been designed for the defluoridation of water. Lanthanum incorporated chitosan beads (LCB) were prepared using precipitation method. The synthesis was optimized by varying different synthesis parameters namely lanthanum loading, complexation and precipitation time, strength of ammonia solution used for precipitation, drying time, etc. Lanthanum incorporated chitosan beads were characterized using SEM, FTIR, XRD and EDX. Surface area of LCB was observed to be 2.76 m² g⁻¹. The equilibrium adsorption data fitted well to Langmuir adsorption isotherm and showing maximum fluoride adsorption capacity of 4.7 mg g⁻¹ with negligible lanthanum release. Kinetic study reveals that adsorption of fluoride is fast and follows pseudo-first-order kinetics. The effect of pH was also studied and the best efficiency was observed at pH 5. Presence of sulphate, nitrate and chloride marginally affected the removal efficiency, however drastic reduction in fluoride uptake was observed in the presence of carbonate and bicarbonate. Negative value of change in free energy (ΔG°) and positive value of change in entropy (ΔS°) suggest the adsorption of fluoride by LCB is feasible and spontaneous process. Positive value of change in enthalpy (ΔH°) suggests the process of fluoride adsorption is endothermic in nature. Regeneration study reveals that 1 M ammonium chloride solution appears to be the promising regeneration media showing 81.22% regeneration. The adsorption capacity of LCB was similar in fluoride-contaminated ground water collected from Dhar district of Madhya Pradesh, India, as compared to simulated water.     

Fluoride removal from water by chitosan derivatives and composites: A review

Fluoride is an essential element, indispensable for maintenance of dental health. Nevertheless, fluoride concentrations in drinking water above 1.5 mg L⁻¹ may be detrimental to human health. Many methods have been developed for removing excessive fluoride from drinking water, adsorption seems to be an effective, environmentally friendly and economical one. Since the sorption capacity of fluoride below 2 mg L⁻¹ on most conventional adsorbents is not satisfactory, much effort has been devoted to develop new and cost-effective fluoride adsorbents. This review reports the recent developments in the F⁻ removal in water treatment, using chitosan derivatives and composites in order to provide useful information about the different technologies. When possibly the adsorption capacity of chitosan derivatives and composites under different experimental conditions is reported to help to compare the efficacy of the fluoride removal process. A comparison with the adsorption capacity of other low cost adsorbents is also tabled.     

Synthesis of a chitin-based biocomposite for water treatment: Optimization for fluoride removal

The optimum composition of a chitin-based biocomposite was determined based on both its fluoride adsorption capacity and its chemical resistance in acid aqueous solution. Parameters such as the chitin content, additive content, catalyst content, chitin particle size, degree of acetylation of chitin and effect of pH on adsorption were evaluated. It was possible to chemically reinforce chitin while keeping an acceptable fluoride adsorption capacity onto the chitin-based biocomposites. Optimum chitin content (60%) was limited by the polymer-biopolymer anchoring capacity. An amine-based additive was used to improve the biocomposite adsorption capacity; however, its inclusion was not suitable in terms of biocomposite chemical resistance. The chitin particle size had no effect on adsorption capacity, and the degree of acetylation of chitin notably modified biocomposite adsorption capacity. On the other hand, the biocomposite chemical resistance was notably improved compared to pure chitin. The physicochemical properties of the optimum chitin-based biocomposite showed its potential for being used in continuous adsorption processes.     

Synthesis and performance evaluation of chitosan/zinc oxide nanocomposite as a highly efficient adsorbent in the removal of reactive red 198 from water

In this study, Chitosan and Chitosan-zinc oxide (ZnO) nanocomposite were prepared and applied as a low-cost adsorbent with high adsorption capacity for removing reactive red 198 (RR 198) dye from contaminated water. After preparation, it was characterized using FT-IR, XRD, and SEM. The effect of pH, temperature, time, adsorbent amount, and initial dye concentration were investigated in the removal efficiency of RR 198. The maximum adsorption capacity (q_m) obtained from the Langmuir equation was 172.41 mg/g in adsorbent dose of 0.1 g/L, pH: 4, temperature of 25°C, adsorption time of 40 min. The thermodynamic parameters demonstrated the spontaneous and endothermic nature of the adsorption process. Due to the high efficiency of chitosan/ZnO nanocomposite in removal of RR 198 from water and advantages such as high adsorption capacity, simple synthesis, and easy application, it can be used as an effective method in the removal of RR 198 from water.     

Aluminum-type superparamagnetic adsorbents: Synthesis and application on fluoride removal

Two effective types of superparamagnetic nano-scale adsorbents of bayerite/SiO₂/Fe₃O₄ have been synthesized via three sequential steps: chemical precipitation of Fe₃O₄, coating of SiO₂ on Fe₃O₄ using acidifying method, and further coating of bayerite (Al(OH)₃) on SiO₂/Fe₃O₄ adopting sol–gel (MASG) or homogeneous precipitation (MAHP) methods. The characteristics of MASG and MAHP were identified using the transmission electron microscopy (TEM) micrograph, scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM/EDX), X-ray powder diffractometer (XRD), and superconducing quantum interference device (SQUID). Removal of fluoride from aqueous solution was examined to evaluate the adsorptive capacity of MASG, MAHP, and commercial activated alumina (CA), and the effects of enclosure of Fe₃O₄ with SiO₂ for SiO₂/Fe₃O₄, MASG, and MAHP particles. Among the adsorbents tested under the same experimental condition, MASG is the most effective adsorbent, of which the adsorption capacities are 38 g/kg (based on adsorbent mass of adsorption in terms of equilibrium constant q_L of Langmuir isotherm), and can compete with CA even at a high pH value. The innovative superparamagnetic adsorbents synthesized in this study possess physicochemical stability at pH range of 6–8 and great potential in the adsorption processes due to not only their high adsorption capacity but also the conveniently magnetic separation which can overcome the difficulty in solid–liquid separation for nano-particles in solutions.     

Removal of fluoride from water by electrocoagulation using Mild Steel electrode

Electrocoagulation process was used for defluoridation of synthetic fluoride containing water. In the process Mild Steel (MS) was used as sacrificial electrode and experiments were performed with different varying parameters such as pH and current density (CD). The fluoride removal efficiency was found to be maximum at pH 6 and CD 75.44 A/m² (2 A). At these conditions fluoride concentration reduces from initial concentration of 50 ​mg/dm³ to 5.2 ​mg/dm³. Kinetic study of electrocoagulation process revealed that the order of the reaction was in the range 1.61–1.64 with respect to fluoride concentration. It was observed that fluoride removal efficiency of the present MS electrode is comparable to the other electrodes used in electrocoagulation process available in the literature.     

Selective sorption of fluoride using Fe(III) loaded carboxylated chitosan beads

Chitosan beads (CB) as such have very low defluoridation capacity (DC) of 52 mgF⁻/kg have been suitably modified by carboxylation followed by chelation with Fe³⁺ ion (Fe-CCB), in order to effectively utilize both hydroxyl and amine groups for defluoridation. The modified beads showed enhanced DC to a very significant level of 4230 mgF⁻/kg. The fluoride removal process is governed by both adsorption and complexation mechanism. The sorbent was characterized using Fourier transform infrared spectrometer (FTIR) and scanning electron microscope (SEM) analysis. The experimental data have been analysed using isotherm and kinetic models. Thermodynamic parameters such as ΔG°, ΔH° and ΔS° were calculated to predict the nature of sorption. A field trial was carried out with fluoride water collected from a nearby fluoride-endemic village.     

Synthesis of silver nanoflakes on chitosan hydrogel beads and their antimicrobial potential

Abstract

The present study involves the fabrication of CH and CH-Ag hydrogel beads and the investigation of the antimicrobial properties. The beads were fabricated using a simple coacervation method. The successfully synthesized beads were characterized by UV-Vis and FTIR. The surface morphology, shape and diameter of the samples were determined by optical microscopy and SEM. The antimicrobial activities were determined against potential human pathogens including bacterial and fungal species. Our results demonstrated that beads can be utilized as potential materials for use in biomedical approaches including delivery systems and tissue engineering applications to prevent microbial contamination and to inhibit the growth of microorganisms.     

Adsorption of chromium from aqueous solution using chitosan beads

A basic investigation on the removal of Cr(III) and Cr(VI) ions from aqueous solution by chitosan beads was conducted in a batch adsorption system. The chitosan beads were prepared by casting an acidic chitosan solution into an alkaline solution. The influence of different experimental parameters; pH, agitation period and different concentration of Cr(III) and Cr(VI) ions was evaluated. A pH 5.0 was found to be an optimum pH for Cr(III) adsorption, and meanwhile pH 3.0 was the optimum pH for the adsorption of Cr(VI) onto chitosan beads. The Langmuir and Freundlich adsorption isotherm models were applied to describe the isotherms and isotherm constants for the adsorption of Cr(III) and Cr(VI) onto chitosan beads. Results indicated that Cr(III) and Cr(VI) uptake could be described by the Langmuir adsorption model. The maximum adsorption capacities of Cr(III) and Cr(VI) ions onto chitosan beads were 30.03 and 76.92 mg g⁻¹, respectively. Results showed that chitosan beads are favourable adsorbents. The Cr(III) and Cr(VI) ions can be removed from the chitosan beads by treatment with an aqueous EDTA solution.     

A novel green biosorbent from chitosan modified by sodium phytate for copper (II) ion removal

A novel kind of adsorbent bead was prepared from chitosan (CS) by ionic‐linked with sodium phytate (SP) and then covalent cross‐linked with epichlorohydrin (ECH) by nonsolvent‐induced phase separation. The structure of the beads was characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, and X‐ray photoelectron spectroscopy. The adsorption properties of the beads for Cu(II) ions under different adsorption conditions were investigated. The maximum adsorption capacity of Cu(II) ions was 177.1 mg g⁻¹ at the conditions of pH of 5.2, temperature of 50°C, and initial Cu(II) ion concentration of 728.3 mg L⁻¹. The adsorption isotherm of Cu(II) ions on the CS/SP/ECH beads was well correlated with the Langmuir isotherm model, and the whole adsorption process could be better followed the pseudo‐second‐order kinetic model. Moreover, the CS/SP/ECH beads still exhibited good adsorption capacity even after the 15th regeneration cycles.     

Antibacterial activity of methylated chitosan and chitooligomer derivatives: Synthesis and structure activity relationships

The purpose of this study was to synthesize series of methylated chitosaccharide derivatives, possessing various degree of methylation, and to determine their structure activity relationship (SAR) with regard to their antibacterial effect against Staphylococcus aureus. Chitosan polymer and chitooligomers were used as starting materials and were methylated by reaction with methyl iodide. Depending on the reaction conditions the degree of N-quaternization ranged from 0% to 74%, with varying degree of N,N-dimethylation, N-monomethylation and O-methylation. More selective N-quaternization could be obtained with protection group strategy. At pH 5.5 the chitosaccharide polymers and their methylated derivatives were active against S. aureus with minimal inhibitory concentration (MIC) ranging from 16 to 512 μg/mL. At pH 7.2 the non-quaternized derivatives were inactive but their highly N-quaternized derivatives showed MIC as low as 8 μg/mL. The chitooligomers, as well as their derivatives, were inactive at both pH’s. The SAR studies revealed that N-quaternization was mainly responsible for the antibacterial effects at pH 7.2, whereas it did not contribute to the antibacterial activity under acidic conditions.     

Beta-cyclodextrin-linked chitosan beads: preparation and application to removal of bisphenol A from water

Water-insoluble and highly porous chitosan beads having an ability to form inclusion complexes have been synthesized by treatment of a solution of chitosan in aqueous acetic acid with aqueous NaOH followed by crosslinking and reductive alkylation with 2-O-formylmethyl-beta-cyclodextrin. Preliminary experiments for its application to removal of endocrine disrupting chemicals were carried out using a column of the resulting beads and bisphenol A as the model substrate.     

Diethylmethyl chitosan as an antimicrobial agent: Synthesis, characterization and antibacterial effects

Chitosan with excellent biodegradable and biocompatible characteristics has received attention as an oral drug delivery vehicle. A quaternized chitosan (i.e., N-diethylmethyl chitosan, DEMC) was prepared based on a modified two-step process via a 2² factorial design to optimize the preparative conditions. DEMC was fully characterized using FTIR and ¹H-NMR spectroscopies. As calculated using NMR-based data, high degree of quaternization was achieved through the optimized two-step process. The highly quaternized biopolymeric derivative was subjected to microbial experiments. The antimicrobial activities of chitosan and DEMC against Escherchia coli were compared by calculation of minimum inhibitory concentration (MIC) and minimum bactericidal concentration (MBC). Our data indicates that although the antimicrobial activity of DEMC is higher than that of chitosan in acetic acid medium, the both compounds are pH dependent and an increase in concentration of acetic acid results in a significant decrease in both MIC and MBC.     

Synthesis of new chitosan derivatives and combination with biodegradable polymer

New chitosan derivatives are synthesized by the reductive N‐alkylation reaction of chitosan with various aldehydes, such as 2,4‐dihydroxybenzaldehyde, cholesteryl 4‐formylbenzoate, and N‐dehydroabietyl‐4‐formylbenzamide. The palladium‐adsorption ability of the newly synthesized derivatives is found to be as good as that of chitosan. A blend of chitosan and other biodegradable polymers is also found to exhibit palladium‐adsorption ability. In comparison to the starting chitosan, the chitosan derivative having dehydroabietyl‐type side chains exhibited an improved solubility in methanol. The chitosan derivatives are successfully applied as plastic coating materials for electroless plating. Copyright © 2003 John Wiley & Sons, Ltd.     

Facile synthesis of hydrous zirconia-impregnated chitosan beads as a filter medium for efficient removal of phosphate from water

The removal and recovery of phosphate from water using adsorption technology require that the adsorbent material is easily separable from treated water. Continuous efforts are still awaited to develop additional efficient phosphate adsorbents that are economical to fabricate. In this study, hydrous zirconia-impregnated chitosan beads (HZCB) containing different Zr/chitosan ratios were synthesized using a facile scheme. We found that HZCB with a Zr/amine molar ratio of?~?1 (HZCB-1) possessed excellent stability and phosphate removal performance. This optimized material was characterized with XRD, SEM, FTIR, XPS, specific surface area and point of zero charge measurements. The maximum adsorption capacity was 42.02 mg/g (at pH?~?6.7). The adsorption kinetics were best described by a pseudosecond-order model, and the rate constant of HZCB-1 was much lower than that of its powder but was similar to the commercial bead product Ferrolox. The removal of phosphate depended substantially upon pH and was enhanced by lowering the pH. Good selectivity of HZCB-1 for phosphate was observed, although the coexistence of sulfate produced a significant negative effect. Direct coordination of phosphate to Zr atoms by replacing hydroxyls was the dominant adsorption mechanism (~?85%), while chitosan also contributed to phosphate removal (~?15%). Adsorbed phosphate was successfully eluted by an NaOH solution, and the material obtained after desorption and regeneration was able to be repeatedly used. The results of column studies indicated that this material could be implemented in long-term application.

     

Automatic microdistillation flow-injection system for the spectrophotometric determination of fluoride

An automatic flow-injection (FI) system including on-line separation by microdistillation and spectrophotometric detection has been developed for the determination of trace amounts of fluoride. This ion was separated from sample matrix by distillation in the presence of sulfuric and phosphoric acids, and was subsequently determined with spectrophotometry based on the mixed-ligand complex of lanthanum(III)-fluoride-alizarin complexone. The proposed FI system has high sampling frequency (20 samples h⁻¹), small sample size (600 μl) and the dynamic range of 0.05-15 mg l⁻¹ with relative standard deviations of below 1.2%. Interfering ions such as aluminum(III) and iron(III) was effectively eliminated. The method was successfully applied to the determination of fluoride in industrial drainage after water treatment.     

Ionic liquid modification of zeolite and its removal of chromate from water

This study focused on using imidazolium of different chain lengths to modify the negatively charged zeolite. The modification involves a cation exchange process of the organic cations of ionic liquids (ILs) for the alkali and alkaline earth elements on zeolite surfaces. X-ray diffraction analyses revealed that the uptake of ILs was on the external surfaces. Fourier transform infrared analyses showed that different mechanisms were attributed to IL uptake on zeolite at below and above the external cation exchange capacity. After modification, the zeolite reversed its surface charge to positive, thus enhancing adsorptive removal of anionic contaminants such as chromate from water. At the same time, the modified zeolite increased their total organic carbon content, and thus could promote better adsorptive removal of hydrophobic organic contaminants from water, too. These features enable IL-modified zeolite to be used as inexpensive sorbents for the removal of multi-types of contaminants from water simultaneously.     

Radiation synthesis of chitosan beads grafted with acrylic acid for metal ions sorption

Radiation-induced grafting of acrylic acid onto chitosan beads was performed in solution at a dose rate of 20.6 Gy/min of cobalt-60 gamma rays. The effect of absorbed dose on grafting yield was investigated. The characterization of the grafted material was performed by FTIR spectroscopy and the swelling measurements at different pHs. The grafting yield increased with the increase in dose, it reached 80% at 40 kGy irradiation dose.The removal of Pb and Cd ions from aqueous solutions was investigated with both ungrafted and grafted chitosan beads. The sorption behavior of the sorbents was examined through pH, kinetics and equilibrium measurements. Grafted chitosan beads presented higher sorption capacity for both metal ions than unmodified chitosan beads.     

水溶性N-马来酰化壳聚糖的合成

马来酸酐;水溶性N-马来酰化壳聚糖的合成     

季铵功能化的金属有机骨架对水中双氯芬酸钠的高效吸附与去除

通过两步合成法制备了季铵功能化的金属有机骨架MIL-101（Cr）即MIL-101（Cr）-NMe₃,并考察了该材料对双氯芬酸钠（DCF）的吸附行为。通过不同浓度的DCF在MIL-101（Cr）-NMe₃吸附剂上的动力学数据,以及在不同温度下的吸附平衡等温线和MIL-101（Cr）-NMe₃吸附剂的重复使用性能考察,发现该材料对DCF的吸附过程符合准二级动力学方程,吸附平衡等温线符合Langmuir等温吸附模型,在20℃下的最大吸附量为310.6 mg/g,5次循环使用后吸附量未明显减少。MIL-101（Cr）-NMe₃对DCF的吸附作用机理可归结为静电相互作用和π-π相互作用,吸附效果远大于未修饰氨基的MIL-101（Cr）。可以预见该材料对水中DCF的去除具有良好的应用前景。