Application of Nonlinear Regression Analysis for Methyl Violet (MV) Dye Adsorption from Solutions onto Illite Clay

Dyes are toxic chemicals and the main source of color pollution in the textile wastewaters. Therefore, the use of illite clay as an adsorbent to remove methyl violet dye from solutions was investigated in this study. Equilibrium experiments were carried out in batch mode as a function of temperature, ionic strength, and pH. The equilibrium was attained within 24 hours. The capacity of illite clay increased when pH, temperature, and ionic strength were raised. Four adsorption isotherm models, viz, the Langmuir, Freundlich, Khan, and Sips, were used to analyze the equilibrium data. The nonlinear optimization technique was used to fit the data to the isotherm models, and for this purpose five error functions were used. The equilibrium data could be explained by the Sips isotherm model, and among the entire error equations generally the HYBRID error function provided the lowest sum of the normalized error values. Thermodynamic parameters indicated that dye adsorption had endothermic and unspontaneous nature. Also, the positive enthalpy change indicated that dye uptake occurred by physical binding. The maximum dye capacity of illite was found as 159.95 mg g^?1 at 60°C. High dye capacity exposed that illite would be used effectively in cationic dye removal.     

Partially carboxymethylated cotton dust waste for sorption of textile wastewater coloured with the cationic dye Basic Blue 41 as a model: synthesis,regeneration and biodegradability

The removal of residual dyes in coloured textile wastewaters is mandatory, and a significant portion of the dyes used are cationic. Textile factories mainly process cotton yarns, and 8 % of this virgin feedstock is lost as cotton dust waste (CDW). Using factorial experimental design, this dust was derivatised with monochloroacetic acid (MCAA) to produce a partially carboxymethylated cellulose (CM^?-CDW) with NaOH, MCAA and isopropanol for the retention of Basic Blue 41 dye (BB 41) (column and batch), and biodegradability was investigated. The dye retention efficiency was examined with additional experiments varying the initial concentration, contact time and addition of salts. Heteronuclear multiple bonding correlation-nuclear magnetic resonance confirmed the covalent insertion of CM^? groups in the cellulosic fibres. The selected matrix provided a dye sorption of 58.33 (column) and 64.50 mg/g (batch). The Langmuir isotherm was a good fit to the sorption data. The efficiency of uptake of BB 41 was predominantly dictated by the concentration of alkali in the matrix synthesis. Biodegradability by cellulases was similar when using uncharged and dye-charged matrices. The latter were fully regenerated by washing in dilute acid. Retention was proportional to the initial dye concentration and the contact time required to reach equilibrium, which was longer for higher dye concentrations. The addition of 10 mmol/l NaCl decreased BB 41 retention by 50 %. Therefore, CM^?-CDW proved effective for the removal of the cationic dye BB 41 and thus represents an important alternative in the treatment of coloured textile effluents.     

Selective adsorption of the cationic dye rhodamine-6G from aqueous solution by phosphotungstic acid@MOF-199 composites

In this paper, H₃[ P(W₃O₁₀)₄]@MOF-199 composites ([email protected]) were successfully synthesized by a simple one-step reaction under solvothermal conditions and characterized by XRD, SEM, FT-IR and N₂ adsorption–desorption isotherms. Additionally, rhodamine-6G (Rh6G, a cationic dye) and methyl orange (MO, a anionic dye) as model dyes were employed to assess its adsorption performance. The adsorption capacity of MOF-199 towards Rh6G and MO were enhanced and weakened respectively after the introduction of PTA (from 8.6 mg/g to 41 mg/g; 11.4 mg/g to 2.6 mg/g) proving that the selective adsorption capacity for the cationic dye of porous MOF-199 could be improved through the modification of PTA. Moreover, in diverse initial concentrations of single Rh6G and MO aqueous solutions (10 mg/L, 25 mg/L, 50 mg/L and 100 mg/L), [email protected] exhibited much higher adsorbing capacity towards Rh6G (about 25, 30, 11 and 16 times higher than that of MO). In mixed dyes adsorption studies, the adsorption capacity of [email protected] towards Rh6G (2.871 mg) are nearly five times larger than that of MO (0.437 mg) even in a solution with a higher concentration of MO than Rh6G (5 mg/L of Rh6G and 10 mg/L of MO). The kinetic study indicated that the adsorption of the Rh6G and MO onto [email protected] followed the pseudo second-order model well. The isotherm obtained from experimental data fitted the Freundlich model (the linearly dependent coefficient are 0.99839 and 0.94845 for Rh6G and MO respectively) indicating multilayer adsorption mechanism. In summary, all these results implied that the as-prepared [email protected] is of great potential to be used as a cationic pollutants adsorbent with high efficiency and selectivity.     

Quartzite an efficient adsorbent for the removal of anionic and cationic dyes from aqueous solutions

Quartzite obtained from local source was investigated for the removal of anionic dye congo red (CR) and cationic dye malachite green (MG) as an adsorbent from aqueous solution in batch experiment. The adsorption process was studied as a function of dye concentration, contact time, pH and temperature. Adsorption process was described well by Langmuir and Freundlich isotherms. The adsorption capacity remained 666.7 mg/g for CR dye and 348.125 mg/g for MG dye. Data was analyzed thermodynamically, ΔH⁰ and ΔG⁰ values proved that adsorption of CR and MG is an endothermic and spontaneous process. Adsorption data fitted best in the pseudo-first order kinetic model. The adsorption data proved that quartzite exhibits the best adsorption capacity and can be utilized for the removal of anionic and cationic dyes.     

Removal of some dyes from industrial effluents by polymeric materials and gamma-irradiation

The radiolysis of two basic dyes (Astrazon Red 6B and Astrazon Blue BG-200%), was investigated as a function of dye concentration, pH, irradiation dose and dose rate. It was found that the Astrazon Red 6B dye showed more radiation degradation than the Astrazon Blue BG-200% dye. Combining irradiation with the conventional treatment enhanced the degree of degradation. Addition of oxygen or hydrogen peroxide showed this enhancement, while nitrogen showed no change. A pH drop was observed and may be attributed to the degradation of the dye molecules to lower molecular weight compounds such as organic acids. Experiments on the adsorption or exchange the dyes onto GAC, some polymeric ion exchange resins and polymeric membranes were carried out showing that GAC had the highest adsorption capacity. By combined treatment of irradiation and adsorption, the total removal of these toxic dyes was achieved.     

Modification of microcrystalline cellulose with pyridone derivatives for removal of cationic dyes from aqueous solutions

Microcrystalline cellulose (MCC) was modified with pyridone derivatives such as pyridone diester (PDE) and pyridone diacid (PDA) by using succinic acid anhydride as a linker. The modified MCCs were characterized by the fourier transform infrared spectroscopy, scanning electron microscopy, thermal gravimetric analysis, elemental analysis and solid state ¹³C NMR. The adsorption capacities of the modified MCCs to cationic dyes were examined by using methylene blue (MB) as a model dye. It was found that the kinetic adsorption data followed the pseudo-second-order kinetic model, and the adsorption equilibriums were reached less than 10 min. The isothermal adsorption data were fitted with the Langmuir isotherm model very well, from which the maximum adsorption capacities of the MCCs modified with PDE and PDA were determined to be 101.01 and 142.86 mg/g, respectively. Further investigation showed that the modified MCCs were pH-dependent for adsorption of MB in aqueous solutions. The modified MCCs could be used for removal of MB from an aqueous solution at pH 8, and reused by regeneration in an acidic solution. It was tested that the modified MCCs had a high reusability for removal of MB from aqueous solutions, and still maintained high adsorption capacities even after multiple cycles of desorption–adsorption processes. Hence, the MCCs modified with PDE and PDA could be an effective and efficient approach to removal of cationic dyes from aqueous solutions.     

Adsorption characteristics of malachite green dye onto novel kappa-carrageenan-g-polyacrylic acid/TiO2–NH2 hydrogel nanocomposite

Batch adsorption experiments were carried out for the removal of malachite green (MG) cationic dye from aqueous solution using novel hydrogel nanocomposite that was prepared by graft copolymerization of acrylic acid (AA) onto kappa-carrageenan (κC) biopolymer in the presence of a crosslinking agent, a free radical initiator and aminosilica-functionalized TiO₂ nanoparticles (κC-g-PAA/TiO₂–NH₂). The factors influencing adsorption capacity of the adsorbents such as initial pH value (pH₀) of the dye solutions, TiO₂–NH₂ content (wt%), initial concentration of the dye, amount of adsorbents, and temperature were investigated. The adsorption capacity of hydrogel nanocomposite for MG was compared with hydrogel. The adsorption behaviors of both adsorbents showed that the adsorption kinetics and isotherms were in good agreement with a pseudo-second-order equation and the Langmuir equation. The high adsorption capacity (q _m= 666–833 (mg/g)) and the favorable heterogeneity factor (n = 1.2–1.5) calculated from isotherm equations show the efficiency of the novel adsorbents.     

Effect of acid and alkali treatments of a forest waste,Pinus brutia cones,on adsorption efficiency of methyl green

The removal of methyl green (MG) dye from aqueous solutions using acid- or alkali-treated Pinus brutia cones (PBH and PBN) waste was investigated in this work. Adsorption removal of MG was conducted at natural pH, namely, 4.5 ± 0.10 for PBH and near 4.8 ± 0.10 for PBN. The pseudo-second-order model appeared to be the most appropriate to describe the adsorption process of MG on both PBN and PBH with a correlation coefficient R² > 0.999. Among the tested isotherm models, the Langmuir isotherm was found to be the most relevant to describe MG sorption onto modified P. brutia cones with a correlation factor R² > 0.999. The ionic strength (presence of other ions: Cl^?, Na⁺, and SO₄^2?) also influences the adsorption due to the change in the surface properties; it had a negative impact on the adsorption of MG on these two supports. A reduction of 68.5% of the adsorption capacity for an equilibrium dye concentration Ce of 30 mg/L was found for the PBH; while with PBN no significant influence of the ionic strength on adsorption was observed, especially in the presence of NaCl for dye concentrations superior to 120 mg L^?1.     

Adsorption study of cationic dyes having a trimethylammonium anchor group on hectorite using electrooptic and spectroscopic methods

Clay minerals are natural or synthetic material of colloidal dimensions. Due to the sheetlike structure clay minerals offer a huge specific surface area and hence optimal properties for modification through adsorption. The current work studies the adsorption of five cationic dyes on the synthetic clay mineral hectorite. All dyes have a trimethylammonium anchoring group in common. The adsorbed dye molecules are characterized by means of pulsed electric linear dichroism and UV-VIS spectroscopy. With increasing dye loading a continuous shift in the absorption spectra is observed. But there is no occurrence of a new absorption band. Therefore we conclude that the dyes preferentially adsorb as amorphous aggregates on the clay surface. At low dye loadings the dye molecules lie flat on the clay mineral surface. Increasing dye concentration leads to a continuous increase in average tilt angle. However the orientation of the dye molecules is very sensitive to functional groups. The introduction of a nitro group to a particular dye increases significantly the tendency to lie flat on the surface whereas the introduction of a methoxy group at the same position has the opposite effect.     

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.     

Modified Calcium Alginate Beads with Sodium Dodecyl Sulfate and Clay as Adsorbent for Removal of Methylene Blue

In present study, we have investigated the effect of an anionic surfactant sodium dodecyl sulfate (SDS) and clay on calcium alginate beads was studied to remove methylene blue (MB) and to improve the adsorption capacity. The effects of various experimental parameters, such as shaking rate, initial dye concentration, temperature, and pH on the adsorption rate, have been studied. Equilibrium studies showed that the sorption of the dye was enhanced in presence of SDS. Scanning electron microscope (SEM) analysis showed that SDS entrapped beads have more pores and cavities which could be responsible for improved adsorption of MB. The kinetics of cationic dye adsorption nicely followed pseudo-second-order process. The evaluated thermodynamic parameters (ΔG ^o, ΔH ^o, ΔS ^o) suggest endothermic adsorption of MB. The results revealed that the surfactant entrapped alginate could be considered as potential adsorbents for MB removal from aqueous solutions.     

Adsorption and kinetic studies of cationic and anionic dyes on pyrophyllite from aqueous solutions

The adsorption of cationic Methylene Blue (MB) and anionic Procion Crimson H-EXL (PC) dyes from aqueous medium on pyrophyllite was studied. Changes in the electrokinetics of pyrophyllite as a function of pH were investigated in the absence and presence of multivalent cations. The results show that pyrophyllite in water exhibits a negative surface charge within the range pH 2-12. Pyrophyllite is found to be a novel adsorbent for versatile removal of cationic and anionic dyes. The negative hydrophilic surface sites of pyrophyllite are responsible for the adsorption of cationic MB molecules. The adsorption of anionic PC dye is possible after a charge reversal by the addition of trivalent cation of Al. Nearly 2 min of contact time are found to be sufficient for the adsorption of both dyes to reach equilibrium. The experimental data follow a Langmuir isotherm with adsorption capacities of 70.42 and 71.43 mg dye per gram of pyrophyllite for MB and PC, respectively. For the adsorption of both MB and PC dyes, the pseudo-second-order chemical reaction kinetics provides the best correlation of the experimental data.     

Preparation of an Anti-Aggregation Silica/Zinc/Graphene Oxide Nanocomposite with Enhanced Adsorption Capacity

Nanomaterials play a significant role in adsorption treatment of dye wastewater, but irreversible aggregation of nanoparticles poses a significant problem. In this work, nanomesoporous zinc-doped silicate (NMSZ) was prepared by an in situ method. To prevent agglomeration, NMSZ was covalently bonded to graphene oxide (GO) sheets to form a nano-silica/zinc/graphene oxide composite (GO-NMSZ), aimed at removal of cationic dye methylene blue (MB). For comparison, undoped mesoporous silica (MS) was also synthesized and modified to obtain a silica/graphene oxide composite (GO-MS). The materials were characterized by powder XRD, SEM, FTIR spectroscopy, TEM, nitrogen sorption, and X-ray photoelectron spectroscopy (XPS). Preservation of the oxygen-containing groups of GO in the composites led to higher adsorption capacities. The best GO-NMSZ composite exhibited an enhanced adsorption capacity of 100.4 mg g⁻¹ for MB compared to those of undoped GO-MS (80.1 mg g⁻¹) and nongrafted NMSZ (55.7 mg g⁻¹). The nonselective character of GO-NMSZ is demonstrated by effective adsorption of anionic dye Congo red (127.4 mg g⁻¹) and neutral dye isatin (289.0 mg g⁻¹). The adsorption kinetics, adsorption isotherms, and a thermodynamic study suggested that MB adsorption occurs by chemisorption and is endothermic in nature.     

Removal of Rhodamine B,a Cationic Dye From Aqueous Solution Using Poly(cyclotriphosphazene-co-4,4′-sulfonyldiphenol) Nanotubes

Poly(cyclotriphosphazene-co-4,4′-sulfonyldiphenol) (PZS) nanotubes were evaluated as an efficient adsorbent for the removal of Rhodamine B (RhB), a cationic dye from aqueous solution. The as-synthesized adsorbent (PZS nanotubes) were characterized by scanning electron microscopy (SEM), transmission electron microscope (TEM), Fourier transform infrared spectroscopy (FTIR) and N₂ adsorption/desorption isotherms. The factors influencing the adsorption efficiency and capacity had been systematically studied. Results showed that the adsorption was highly dependent on temperature, initial RhB concentration and adsorbent dose. Effects of initial solution pH indicate that the adsorption can proceed in both basic and acidic environment. The equilibrium absorption capacity at 25°C can reach up to 35.58 mg/g within 60 min implying the adsorption procedure was highly rapid. The kinetic data was better described by the pseudo-second-order model with the correlation coefficient (R² = 0.9981), and the adsorption process followed Weber's intraparticle model, indicating the adsorption process could be divided into two stages. Results also showed that the adsorption equilibrium obeyed the Langmuir isotherm, and the value of equilibrium parameter R_L suggested that the PZS nanotubes were an efficient adsorbent for the removal of RhB from aqueous solution.     

Study of variables for optimization of the dye indosol adsorption process using red mud and clay as adsorbents

The effluents from the textile industry, which not properly treated or discharged directly into water bodies, are a serious environmental problem. In order to find options to solve this problem, in this study, it was evaluate two alternative adsorbents: red mud and smectite clay, to remove the dye Indosol dark-blue SF-BL SGR 240. Assays were performed in batch using the experimental design to optimize the process and evaluate the influence of pH, mass and agitation speed on the adsorption capacity of dye by each material. The results showed that the adsorption process was influenced by the amount of mass of the adsorbent, by the pH and the by interaction between pH and mass, thereby obtaining a removal of approximately 0.110 and 0.119 mg g^?1 with red mud and smectite clay respectively.     

Fabrication of PANI@Fe–Mn–Zr hybrid material and assessments in sono-assisted adsorption of methyl red dye: Uptake performance and response surface optimization

In recent decades, industrial wastewater discharge containing toxic or hazardous manufactured dyes has risen tremendously, creating a serious environmental threat. A new hybrid adsorbent, [email protected]–Mn–Zr synthesized by mixing Fe–Mn–Zr metal oxide composite with polyaniline (PANI), was used to study methyl red (MR) dye removal from aqueous solution. The adsorption process was observed to be influenced by the sonication time, dose of [email protected]–Mn–Zr, and initial concentration of MR dye. At an initial MR dye concentration of 25 mg/L, 0.25 g/L of [email protected]–Mn–Zr dose, 15 min of sonication, and pH 7.0, the maximum MR dye adsorption efficiency of 90.34% was achieved. Kinetic analysis was performed using five different kinetic models, which shows that the pseudo-second-order kinetic model had the best fit among the five models. The Langmuir isotherm best fits the adsorption experiments at pH 7.0, yielding a significant MR dye uptake capacity of 434.78 mgg^?1. The most significant adsorption mechanisms that have been observed in uptake of MR dye onto [email protected]–Mn–Zr were electrostatic attraction, π-π bond interactions and hydrogen bonding. Response surface optimization study was performed for optimizing the experimental conditions from which maximum dye removal of 98.19% was obtained at contact time of 12 min, initial MR dye concentration of 15 mg/L and [email protected]–Mn–Zr dose of 0.4 g/L. Use of real wastewater and water samples suggest that there is only 6–19% reduction in the dye removal efficiency as compared to the blank or controlled experiments conducted with deionized water.     

Interactions between C.I. Basic Blue 41 and aluminosilicate sorbents

Four aluminosilicate sorbents (montmorillonite, bentonite, raw perlite, and expanded perlite) were employed for retention of the cationic dye C.I. Basic Blue 41. Interactions between the clay and the dyestuff were investigated at several temperatures and clay:dye ratios. The mechanism behind the adsorption involves the formation of H-aggregates of the dye on both clays, followed by dye migration into the interlayer in the case of montmorillonite. Time-dependent absorbance spectra revealed the presence of various dye species in montmorillonite. Introduction of the dye molecules into the interlamellar space occurs more rapidly in bentonite than in montmorillonite. The dye molecules inserted between the clay leaves adopt different orientations and, eventually, stack in layers at increased dye loadings for both montmorillonite and bentonite. Higher dye aggregates are then present as suggested by diffuse reflectance spectroscopy. Dye sorption on both raw and expanded perlite proceeds via H-aggregate formation as well.     

Bio-adsorption of dyes from aqueous solution by powdered excess sludge (PES): Kinetic,isotherm, and thermodynamic study

Over 30 million tons of excess sludge is discharged from rural municipal sewage plants annually in China and it is predicted that this figure will keep increasing. However, most of the excess sludge is dumped in landfills except for minor applications. In this study, based on low-cost and recycling waste, the excess sludge was used to adsorb organic dyes from aqueous solution after being directly dewatered. The powdered excess sludge (PES) presents selective adsorption property to cationic dyes. Statics batch adsorption experiments of malachite green (MG) on PES were performed to evaluate the effects of pH, adsorbent dosage, and initial MG concentration. Results revealed that the bio-adsorption equilibrium of MG on the PES can be quickly achieved at 30 min with maximum percentage adsorption of 84% at pH 7, initial dye concentration of 20 mg L^?1, and adsorbent dosage of 1.5 g L^?1. Moreover, the adsorption kinetics follows a pseudo-second-order pathway, and the equilibrium adsorption data could be described well by the Langmuir isotherm equation. Intra-particle diffusion is not the only rate-controlling step in the entire adsorption process. The adsorption process is endothermic, spontaneous, and random. PES can be used as a low-cost adsorbent for refractory cationic organic dye in effluent.     

Polypyrrole-coated cotton textile as adsorbent of methylene blue dye

Pollution caused by organic dyes is of serious environmental and health concern to the population. Dyes are widely used in textile coloring applications. In the present work, cotton textile was coated with a conducting polymer, polypyrrole (PPy), in situ during the oxidative polymerization of pyrrole. The resulting materials were utilized as easily separated and recyclable adsorbent for the removal of methylene blue (MB) as a model of cationic dyes in alkaline solutions. It showed also some affinity to remove Acid Green 25 as an anionic dye in acidic medium. The adsorption was assessed by monitoring the decrease in dye concentration by UV–Visible absorption spectroscopy. The influence of various parameters such as initial dye concentration, contact time, pH, temperature, and adsorbent dose on the adsorption process was studied. The pseudo-second-order kinetic model and Freundlich isotherm model were found to describe the adsorption process. The thermodynamic study revealed that the adsorption of MB by PPy was feasible, spontaneous, and exothermic process. Investigation of the substrate regeneration revealed that PPy deposited on cotton textile can be reused for dye adsorption several times with good efficiency and it allows for the recovery of MB for recycling purposes.