The Binding of Anionic Dyes by Cross-Linked Cationic Starches

Adsorption of anionic dyes on the cross-linked with epichlorohydrin starches containing quaternary ammonium groups (CCS) was investigated and compared with that of modified starches containing only quaternary ammonium groups (CS). The adsorption of anionic dyes on CS and CCS closely follows the Langmuir model of adsorption. The computed Langmuir saturation capacity Q _o increases with increasing degree of substitution (DS) of CS or CCS and has the value from 0.81 mol/kg to 3.22 mol/kg for CCS and from 0.88 mol/kg to 1.87 mol/kg for CS. The effectiveness of the cationic groups in dye binding was about 1 mol/equiv for CSS with DS from 0.47 to 0.62 and all the cationic groups had attached one anionic groups of the dye. Increasing DS of CS decreases the effectiveness of dye binding due to the increase in solubility of CS, and the soluble part of CS binds the dye as a typical soluble polyelectrolyte. CCS are more suitable than CS for the anionic dye adsorption from a textile dyeing solution. DS of CCS should be about 0.5–0.6. They adsorb the anionic dyes in few minutes and acts in the wide range of pH of the solutions. The Langmuir saturation capacity Q _o and the effectiveness of the cationic groups in dye binding increase with an increase of the adsorption temperature. The positive values of the enthalpy and entropy suggest that the adsorption is endothermic and during the adsorption of the anionic dye on CCS the randomness of the system increases.     

Dye removal from colored textile wastewater using chitosan in binary systems

In this paper, the removal of two anionic dyes from textile effluent in single and binary systems was investigated. Direct Red 23 and Acid Green 25 were used as anionic dyes. The surface characteristics of chitosan were investigated using Fourier transform infrared. The effects of operational parameters such as chitosan dosage, initial dye concentration, salt and pH on dye removal were studied. The isotherms of dye adsorption were investigated. It was found that the isotherm data of Direct Red 23 and Acid Green 25 in single and binary systems followed Tempkin isotherm. In addition adsorption kinetics of dyes was studied in single and binary systems and rate sorption was found to conform to pseudo-second order kinetics with a good correlation. Results indicated that chitosan could be used as a biosorbent to remove the anionic dyes from contaminated watercourses in both single and binary systems of pollutants.     

Removal of Acidic and Basic Dyes from Water using Crosslinked Polystyrene Based Quaternary Ethyl Piperazine Resin

In this study, a beaded polymer with quaternary amine functions was prepared in two steps, starting from poly (vinyl benzyl chloride-ethylene glycol dimethacrylate) (PVBC) based beads, according to the synthetic protocol; modification of ethyl piperazine with PVBC (EP-PS), and quaternization of ethylpiperazine modified beads with chloroacetic acid (QEP-PS). The QEP-PS resin was used for the removal of reactive red 120 as an acidic dye and malachite green chloride as a basic dye. Dye extraction experiments were carried out simply by contacting wetted sorbent samples with aqueous dye solutions at room temperature. Capacities were determined by colorimetric analysis of the residual dye contents. The resin showed that reasonable high dye sorption capacity (0.34-0.41 g per gram of dry resin) was achieved. The adsorption conditions (initial dye concentration and pH) were varied to evaluate the mechanism of adsorption of both basic dyes and acidic dyes on the prepared resin. This material is also able to remove both the anionic dye and cationic dyes completely even from highly diluted aqueous dye solutions.     

Tailoring Chitosan/LTA Zeolite Hybrid Aerogels for Anionic and Cationic Dye Adsorption

Chitosan (CS) is largely employed in environmental applications as an adsorbent of anionic dyes, due to the presence in its chemical structure of amine groups that, if protonated, act as adsorbing sites for negatively charged molecules. Efficient adsorption of both cationic and anionic dyes is thus not achievable with a pristine chitosan adsorbent, but it requires the combination of two or more components. Here, we show that simultaneous adsorption of cationic and anionic dyes can be obtained by embedding Linde Type A (LTA) zeolite particles in a crosslinked CS-based aerogel. In order to optimize dye removal ability of the hybrid aerogel, we target the crosslinker concentration so that crosslinking is mainly activated during the thermal treatment after the fast freezing of the CS/LTA mixture. The adsorption of isotherms is obtained for different CS/LTA weight ratios and for different types of anionic and cationic dyes. Irrespective of the formulation, the Langmuir model was found to accurately describe the adsorption isotherms. The optimal tradeoff in the adsorption behavior was obtained with the CS/LTA aerogel (1:1 weight ratio), for which the maximum uptake of indigo carmine (anionic dye) and rhodamine 6G (cationic dye) is 103 and 43 mg g⁻¹, respectively. The behavior observed for the adsorption capacity and energy cannot be rationalized as a pure superposition of the two components, but suggests that reciprocal steric effects, chemical heterogeneity, and molecular interactions between CS and LTA zeolite particles play an important role.     

多种因素对MIL-101(Cr)选择性吸附水溶液中染料的影响

在多种条件下研究了金属有机框架MIL-101(Cr)对阳离子型染料(亚甲基蓝、罗丹明B)和阴离子型染料(甲基橙、酸性铬蓝K)的吸附性质,主要研究了MIL-101(Cr)对亚甲基蓝和甲基橙的选择性吸附作用。结果表明,中性环境下无论在单组分还是双组分体系中MIL-101(Cr)对阴离子型染料的吸附能力均大于对阳离子型的吸附能力。在pH=3,T=300 K的条件下,选择性系数β可达5.9,但随着pH的增加,选择性系数逐渐降低。相比之下,温度对吸附的选择性影响不大。选择性吸附的机理可以解释为:由于表面带正电荷,MIL-101(Cr)对阴离子型染料产生静电吸引作用;相反,对阳离子型染料的排斥作用而降低了其吸附能力。另外,乙二胺改性提高了MIL-101(Cr)对阴离子型染料的选择吸附性能,而草酸改性降低了选择吸附性。     

Adsorption of anionic dyes on poly(epicholorohydrin dimethylamine) modified bentonite in single and mixed dye solutions

The performance of poly(epicholorohydrin dimethylamine) modified bentonite (EPIDMA/bentonite) as an adsorbent to remove anionic dyes, namely Direct Fast Scarlet, Eosin Y and Reactive Violet K-3R, was investigated in single, binary and ternary dye systems. In adsorption experiments in single dye solutions, the adsorption of the three dyes onto EPIDMA/bentonite was described by the Langmuir isotherm model and the pseudo-second-order kinetic model. At low dosage of EPIDMA/bentonite, preferential adsorption was observed for the dye with higher affinity to the adsorbent in mixed dye systems. The reduction in uptake of the dye with increasing equilibrium dye concentration in the isotherm and desorption in the kinetic curves were observed for the dye with lower affinity. The total amount of dyes adsorbed versus the total equilibrium dye concentrations were fitted well by the Langmuir isotherm model. The kinetics of the total adsorbed amount of dyes followed the pseudo-second-order kinetic model. The effect of the dosage of adsorbent on color removal efficiency, residual color distribution and adsorption kinetics was investigated.     

Chemically modified sunflower stalks as adsorbents for color removal from textile wastewater

Quaternary ammonium groups were chemically grafted onto sunflower stalks in order to improve their adsorption performance to anionic species in wastewater. The chemically modified sunflower stalks were evaluated as adsorbents for two basic dyes (Methylene Blue and Basic Red 9) and two direct dyes (Congo Red and Direct Blue 71) in aqueous solutions by using equilibrium isotherms and kinetic adsorption. Before the modification, sunflower stalks exhibited relatively low adsorption to the direct dyes but very high adsorption to the basic dyes. The modified sunflower stalks showed increased adsorption to the anionic dyes, but slightly reduced adsorption to the cationic dyes, due to the existence of quaternary ammonium ions on the surface of the residues. The maximum adsorption capacities of two direct dyes on the modified sunflower stalks are 191.0 and 216.0 mg g for Congo Red and Direct Blue 71 at 50°C, respectively, which were at least four times higher than that of the unmodified residues. The adsorption rates of two direct dyestuffs are much higher on the modified residues than on the unmodified ones. Within 30 min, about 80% of direct dyes were removed from the solutions by the residues. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1841–1850, 1999     

基于静电作用选择性吸附染料的超分子凝胶剂

设计并合成了一系列季铵盐型凝胶剂，仅通过调控季铵盐烷基侧链的长度，可得到两种自组装模式不同的凝胶剂。通过FTIR、XRD研究了甲苯干凝胶的自组装模式。这两种干凝胶具有相反的表面Zeta电位，通过静电作用实现了对阴阳离子染料的选择性吸附。在二元阴阳离子混合染料水溶液中，表面带有负电荷的干凝胶可优先捕获阳离子染料，而表面带有正电荷的干凝胶可捕获阴离子染料。特别是表面带有负电荷的干凝胶对龙胆紫表现出优异的吸附性能，在60 min左右的平衡吸附量高达1313.16 mg/g。将凝胶剂负载于三聚氰胺海绵骨架表面，得到的改性海绵吸附染料种类与对其改性的干凝胶保持一致，且对染料的吸附量均明显高于干凝胶的吸附量，尤其是对龙胆紫的吸附量提升至2488.22 mg/g。     

Anionic dye adsorption characteristics of surfactant‐modified coir pith,a ‘waste’ lignocellulosic polymer

The surface of coir pith, an agricultural solid waste, was modified using a cationic surfactant hexadecyltrimethylammonium bromide. Adsorption of anionic dyes on surfactant‐modified coir pith was investigated in a series of batch adsorption experiments. Two anionic dyes, acid brilliant blue (acid dye) and procion orange (reactive dye), were used in the adsorption studies. The effect of process variables such as contact time, concentration of the dyes, adsorbent dose, temperature, and pH were studied in order to understand the kinetic and thermodynamic parameters of the process. The kinetics of adsorption obeyed the second‐order rate equation. The equilibrium adsorption data were fitted into the Langmuir and Freundlich isotherms. It was found that modified coir pith yielded adsorption capacities of 159 and 89 mg/g for acid brilliant blue and procion orange, respectively. Mechanisms involving ion exchange and chemisorption might be responsible for the uptake of dyes. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1538–1546, 2006     

Chitosan intercalated montmorillonite: Preparation, characterization and cationic dye adsorption

Chitosan intercalated montmorillonite (Chi-MMT) was prepared by dispersing sodium montmorillonite (Na⁺-MMT) into chitosan solution at 60 °C for 24 h. The Chi-MMT was characterized by XRD, XRF and FT-IR. The intercalation was accomplished via the ion-exchange of Na⁺ ions with –NH₃⁺ of chitosan, resulting in the expansion of d₀₀₁ from 1.42 nm of Na⁺-MMT to 2.21 nm of Chi-MMT. The chitosan content in the Chi-MMT measured by TGA was about 17 mass%. The adsorption capacity of Chi-MMT was investigated in comparison with the starting Na⁺-MMT and chitosan using three different cationic dyes, i.e. basic blue 9 (BB9), basic blue 66 (BB66) and basic yellow 1 (BY1). The Chi-MMT showed the highest adsorption capacity in the range of 46–49 mg/g when the initial dye concentration was 500 mg/L, being equivalent to 92–99 wt.% of dye removal. The adsorption capacities of Chi-MMT for all basic dyes increased with an increase of initial dye concentration. An increase of adsorption capability of Chi-MMT was attributed to the existence of intercalate-chitosan. It could enlarge the pore structure of Chi-MMT, facilitating the penetration of macromolecular dyes, and also electrostatically interact with the applied dyes. These results indicated the competency of Chi-MMT adsorbent for basic dye adsorption.     

A novel nonchemical approach to the expansion of halloysite nanotubes and their uses in chitosan composite hydrogels for broad‐spectrum dye adsorption capacity

A novel method based on cryoscopic expansion of halloysite nanotubes via frozen water molecules entrapped in their lumens and subsequent lyophilization was described. Detailed analyses confirmed that the inner and outer diameters as well as the surface area of the nanotubes could be efficiently increased without disturbing the inherent tubular structure. The benefits of cryo‐expanded nanotubes for the enhancement of chitosan hydrogel performances were discussed. The composite hydrogels, depending on their compositions and morphologies, exhibited significantly enhanced swelling and mechanical properties compared with neat chitosan hydrogel. This effect was even more pronounced in the hydrogels containing cryo‐expanded halloysite nanotubes. Although neat chitosan is a selectively good adsorbent for anionic dyes, in the presence of a small amount of cryo‐expanded halloysite, the resultant composite hydrogel can establish a relatively high adsorption capacity for anionic and cationic dyes as a broad‐spectrum dye adsorbent. POLYM. COMPOS., 37:2770–2781, 2016. © 2015 Society of Plastics Engineers     

Photostabilization of Beauveria bassiana conidia using anionic dyes

Microbial biocontrol agents, which are selective and non-polluting measures for controlling insect pests, are sensitive to environmental factors, notably solar UV radiation. To overcome the constraint of photoinstability and provide adequate field performance, the photostabilizing potential of organo-clay matrices was studied. The clay mineral surfaces were modified by adsorption of chitosan, a polycationic biopolymer. The positively charged clay–chitosan complexes served for adsorption of potent photoprotective anionic dyes. A variety of clay–chitosan–dye matrices were prepared and examined as to their potential to photostabilize UV-irradiated fungal conidia of the entomopathogen Beauveria bassiana. The matrices were composed of palygorskite, montmorillonite, bentonite and kaolinite and of 6 anionic dyes: Acid Yellow 25 (AY), Chrysophenine G (Chrys.), Direct Yellow 50 (DY), Mordant Blue (MB), Fast Green (FG) and Naphthol Yellow S (NYS). The adsorption isotherms of dyes and their level of adsorption to the organo-clays were established. Clay–chitosan complexes per se were able to bestow significant measures of photoprotection, apparently due to their UV light scattering property. High and relatively consistent levels of photostabilization were observed with clay–chitosan matrices containing Chrys., AY, NYS and DY following prolonged irradiation. Depending on the clay-based matrix, MB and FG provided less persistent photostabilization levels. In contrast to the other clay–chitosan complexes, the high photoprotection bestowed by kaolinite–chitosan per se obscured to a great extent any contribution of the anionic dyes. Apparently, the photostabilization of the clay-based matrices is a combination of UV light scattering capacity of clay minerals and the UV screening effect due to the adsorbed dyes.     

阳离子淀粉染料吸附材料的制备及表征

以玉米淀粉为原料,以3-氯-2-羟丙基三甲基氯化铵（CHPTMAC）为阳离子醚化剂,以NaOH为催化剂,制备了天然高分子多糖基染料吸附剂阳离子淀粉（CS）,用于对活性染料的吸附。对醚化反应机理进行了系统研究,并考察了反应条件对CS取代度（DS）及反应效率（RE）的影响。采用RAM、XRD、SEM对产物进行表征。吸附实验表明,当DS为0.12,染料溶液pH为8时,CS对活性红195、活性金黄K-2RA的吸附量分别为21.0和20.4 mg·g^-1,去除率可达84.1%和81.6%,好于无机吸附材料活性炭。还进行了CS染料吸附材料的再生实验,4次再生后仍有较高的吸附量,表明CS染料吸附材料具有较强的可再生性能,可循环使用。该天然基染料吸附剂CS有望成为无机吸附剂及合成树脂吸附剂的理想替代品,用于工业染料废水的处理中。     

Removal of phosphate ions with a chemically modified chitosan/metal‐ion complex

The adsorption of metal ions (Mo⁶⁺, Cu²⁺, Fe²⁺, and Fe³⁺) was examined on chemically modified chitosans with a higher fatty acid glycidyl (CGCs), and the adsorption of Cu²⁺ was examined on ethylenediamine tetraacetic acid dianhydride modified CGCs (EDTA‐CGCs) synthesized by the reaction of the CGCs with ethylenediamine tetraacetic acid dianhydride. The adsorption of phosphate ions onto the resulting substrate/metal‐ion complex was measured. Mo⁶⁺ depicted remarkable adsorption toward the CGCs, although all the Mo⁶⁺ was desorbed under the adsorption conditions of the phosphate ions. The other metal ions were adsorbed to some extent on CGCs by chelating to the amino group in the substrate, except for CGC‐1, which had the highest degree of substitution (83.9%). Considerable amounts of Fe²⁺ were adsorbed onto CGCs; however, only a limited number of phosphate ions was adsorbed onto the substrate/metal‐ion complex. As a result, the following adsorbent/metal‐ion complexes gave higher adsorption ability toward phosphate ions: CGC‐4/Cu²⁺, CGC‐4/Fe³⁺, and EDTA‐CGC‐3/Fe³⁺. Where, CGC‐3 is a chemically modified chitosan with the degree of substitution of 26.5 percentage, and CGC‐4 is one with the degree of substitution of 16.0 percentage. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Chitosan for wastewater treatment

Chitosan (an amino‐polysaccharide obtained from deacetylation of chitin, the major constituent of crustaceous shells and insect cuticles) presents a cationic character in acidic media allowing its dissolution, its shaping and possible ion‐exchange interactions with anionic compounds (a property applied in adsorption and coagulation–flocculation processes). In neutral media, non‐protonated amino groups allow complexation of metal cations or organic chemicals. These different properties explain the interest taken by the scientific community in using this biopolymer. In solution it contributes to complex metals and their recovery by complexation‐assisted ultrafiltration. It can also be used to coagulate–flocculate organic compounds (as anionic dyes). In the solid state, it can be used for metal ion adsorption, as well as adsorption of organic compounds (dyes, pesticides, drugs, endocrine disruptors, etc.). The adsorption and coagulation–flocculation processes will be compared and examples considered. Moreover, it is noteworthy that the thermal degradation of this type of material is also more environmentally friendly than that of conventional synthetic resins (production of hazardous by‐products, etc.), a supplementary advantage of these biopolymer‐based sorbents. Combined with its ability to be chemically or physically modified improving the potential and phase separation of chitosan‐based materials, all these properties mean it is an excellent candidate for wastewater treatment. © 2017 Society of Chemical Industry     

Removal of Cationic Dyes from Aqueous Solution by Hydrophobically Modified Poly(acrylic Acid) Hydrogels

Hydrophobically modified poly(acrylic acid) hydrogels were synthesized using acrylic acid (AA), methyl methacrylate (MMA), ethyl methacrylate (EMA) and butyl methacrylate (BMA) as copolymer monomers. These hydrogels were carried out for removal cationic dyes from aqueous solution. It was found that the adsorption of cationic dye depended on the length of the side chain, hydrophobic monomer (MMA, EMA and BMA) content and pH of the solution. Increasing the hydrophobic monomer content led to an increase in the adsorption of cationic dyes on the hydrogels. The adsorption kinetics and isotherms of hydrogels were in good agreement with pseudo–second-order equation and the Langmuir equation, respectively. The cationic dyes adsorption of hydrogels involved a mechanism that combined swelling and electrostatic and hydrophobic interaction.     

Preparation of an ecofriendly chitosan–ZnO composite for chromium complex dye adsorption

Three chitosan‐ZnO composites were prepared by the chitin deacetylation process using zinc chloride as source material and sodium hydroxide as precipitant. The physical characteristics of chitosan‐ZnO composites were studied using Fourier Transform infrared spectroscopy and scanning electron microscopy. The adsorption of a chromium complex dye onto commercial chitosan, prepared chitosan and chitosan‐ZnO composites was investigated in aqueous dye solution. Dye calibration was carried out by UV‐vis spectroscopy. The calculated dye adsorption values for commercial chitosan, prepared chitosan, and chitosan‐ZnO composite samples are 0.0086, 0.0137, and 0.0214 mg/g respectively, indicating that the chitosan‐ZnO composites have better dye adsorption capacity than commercial chitosan and prepared chitosan. The experimental isotherm data for the composites fitted the Langmuir isotherm model well. Thus, the chitosan‐ZnO composites can be used as an effective biosorbent for the removal of anionic dyes.     

Adsorption behavior of cationic dyes on citric acid esterifying wheat straw: kinetic and thermodynamic profile

The kinetic and thermodynamic behaviors of cationic dye adsorption onto citric acid esterifying wheat straw (EWS) from aqueous solution were investigated. Two cationic dyes, methylene blue (MB) and crystal violet (CV) were selected as adsorbates. The kinetic and thermodynamic parameters of dye adsorption were examined with a batch system by changing various experimental factors (e.g. initial pH, EWS dosage, dye concentration, contact time, temperature). The MB and CV removal ratios came up to the maximum value beyond pH 4. The 2.0 g/L or up of EWS could almost completely remove MB and CV from 250 mg/L of dye solution. The adsorption percentages of MB and CV kept above 95% over a range from 50 to 350 mg/L of dye concentration when 2.0 g/L of EWS was used. The isothermal data followed the Langmuir model. The adsorption processes could be described by the pseudosecond-order kinetic model. The dual linear plots of intraparticle diffusion indicated that two intraparticle diffusion steps occurred in the dye adsorption processes. The thermodynamic study indicated that the adsorptions of dyes were spontaneous and endothermic. High temperatures favored the adsorption processes.     

Synthesis of novel amino(alkylamino)deoxychitins and the adsorption behavior of acid dye onto the resulting polymers

Novel chitin‐based materials were synthesized and the adsorption behavior of typical acid dyes to the resulting polymers has been evaluated. The successful synthetic reaction was confirmed by the infrared spectroscopic measurements. By the reaction of alkalichitin with tosyl chloride, the corresponding tosylchitin was synthesized as a soluble and reactive precursor. Next, aminodeoxychitin was synthesized by the reaction of the tosylchitin with ammonia. Similarly, 2′‐aminoethylamino‐ and 6′‐aminohexylaminodeoxychitins were synthesized by reacting the tosylchitin with ethylenediamine and hexamethylenediamine, respectively. It has been confirmed that the adsorption abilities of these polymers for acid dyes were significantly high, and also that one of the aminodeoxychitins showed a high adsorption ability for Cu²⁺ ion. On the basis of the adsorption data of acid dye on the aminodeoxychitin, the tosylchitin and the original chitin, the amino group contents at C₆ and C₂ positions were estimated. The aminodeoxychitin and aminoalkylaminodeoxychitins could be applicable to the adsorbent for anionic dyes and Cu²⁺ ion along with a precursor for further novel derivatives. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Poly(methacrylic acid)‐modified chitosan for enhancement adsorption of water‐soluble cationic dyes

The preparation of poly(methacrylic acid)‐modified chitosan microspheres and its application for the removal of cationic dyes, methylene blue (MB) and malachite green (MG), in aqueous solution in a batch system were described. The modified chitosan was characterized using SEM, FTIR, and XPS analyses. The effects of the pH of the solution, contact time, and initial dye concentration were studied. The adsorption capacities of the microspheres for the two cationic dyes increased significantly after the modification because a large number of carboxyl groups were introduced. The equilibrium process was better described by the Langmuir than the Freundlich isotherm. According to the Langmuir equation, the maximum adsorption capacities were 1000.0 and 523.6 mg g^?1 for MB and MG, respectively. Kinetic studies showed better correlation coefficients for a pseudo‐second‐order kinetic model, confirming that the sorption rate was controlled by a chemisorption process. POLYM. ENG. SCI., 2009. © 2008 Society of Plastics Engineers