Synthesis and characterization of PET fibers grafted with binary mixture of 2-methylpropenoic acid and acrylonitrile by free radical: its application in removal of cationic dye

Grafting of binary vinyl monomer mixtures such as 2-methylpropenoic acid (MPA) and acrylonitrile (AN) onto poly (ethylene terephthalate) fibers (PET) was achieved in an aqueous medium with using benzoyl peroxide like free radical initiator. A new reactively fibrous adsorbent was used for removal of dye such as methylene blue (MB) from aqueous media through batch sorption method. Fibers adsorbent was swelled in solution to support the graft and the subsequent polymerization of MPA/AN onto polyester fibers. Optimum conditions for grafting were discovered and reactive fiber were characterized. Variations of graft yield with time, temperature, initiator concentration and monomer mixture ratio were investigated. The optimum initiator concentration was found to be 8 × 10^?3 mol/L. The percentage of grafting rose steadily with the vinyl monomer mixture monomer concentration (50 %). The optimum temperature and polymerization time were found to be 80 °C and 120 min, respectively. The use of AN and MPA monomers together in grafting produce a significant increased in the graft yield. Experimental studies showed that the percentage removal of MB was a great higher on the MPA/AN grafted PET (MPA/AN-g-PET) fibers than on the original PET fibers. The adsorbed quantity of MB improved with pH and basic pH was appropriate for the elimination of MB. MPA/AN-g-PET fibers removed 98 % of cationic dye when initial concentration diverse from 10 to 80 mg L^?1 at pH 9.0. Almost all of the adsorbed cationic dye was eluted by ethanoic acid in methanol. Ten removal–desorption cycles indicated that the reactive fibers were favorable for repetitive use without notable change in removal capacity. Consequently, the MPA/AN-g-PET fibers have demonstrated potential as an effective adsorbent for the extremely effective removal of cationic dyes from aqueous media.     

Adsorption behavior of Congo red from an aqueous solution on 4‐vinyl pyridine grafted poly(ethylene terephthalate) fibers

In this study, a reactive fibrous adsorbent was prepared through the grafting of 4‐vinyl pyridine monomer onto poly(ethylene terephthalate) (PET) fibers for the removal of Congo red (CR) dye from an aqueous solution with the batch adsorption method. Effects of various parameters such as the grafting yield, pH, treatment time, and initial dye concentration on the amount of adsorption of the dye onto the reactive fibers were investigated. The effective pH was 4.0 for adsorption on grafted PET fibers. The sufficient time to attain equilibrium was 150 min. The maximum adsorption capacity of the reactive fibers for CR was 17.3 mg/g of fiber. The rates of adsorption conformed to pseudo‐second‐order kinetics with good correlation. The adsorption isotherm of CR fit a Langmuir‐type isotherm. The reactive fibers were stable and regenerable by acid and base without loss of activity. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

EFFECT OF TEMPERATURE ON THE ADSORPTION OF METHYLENE BLUE DYE ONTO SULFURIC ACID–TREATED ORANGE PEEL

The present study explains the preparation and application of sulfuric acid–treated orange peel (STOP) as a new low-cost adsorbent in the removal of methylene blue (MB) dye from its aqueous solution. The effects of temperature on the operating parameters such as solution pH, adsorbent dose, initial MB dye concentration, and contact time were investigated for the removal of MB dye using STOP. The maximum adsorption of MB dye onto STOP took place in the following experimental conditions: pH of 8.0, adsorbent dose of 0.4 g, contact time of 45 min, and temperature of 30°C. The adsorption equilibrium data were tested by applying both the Langmuir and Freundlich isotherm models. It is observed that the Freundlich isotherm model fitted better than the Langmuir isotherm model, indicating multilayer adsorption, at all studied temperatures. The adsorption kinetic results showed that the pseudo-second-order model was more suitable to explain the adsorption of MB dye onto STOP. The adsorption mechanism results showed that the adsorption process was controlled by both the internal and external diffusion of MB dye molecules. The values of free energy change (ΔG ^o) and enthalpy change (ΔH ^o) indicated the spontaneous, feasible, and exothermic nature of the adsorption process. The maximum monolayer adsorption capacity of STOP was also compared with other low-cost adsorbents, and it was found that STOP was a better adsorbent for MB dye removal.     

Citric acid modified waste cigarette filters for adsorptive removal of methylene blue dye from aqueous solution

Waste cigarette filters (CFs) were recycled and modified with a nontoxic and low-cost citric acid (CA). The modified CFs were employed in the adsorptive removal of methylene blue (MB) dye from aqueous medium. The influence of pH, contact time, initial dye concentration, and adsorbent dose on adsorption of MB dye was evaluated. The adsorption studies were conducted by employing linear and nonlinear Langmuir and Freundlich isotherm models. The adsorption capacity of CF obtained through linear and nonlinear Langmuir model were 88.02 and 94 mg g⁻¹, which improved up to 163.93 and 168.81 mg g⁻¹, respectively, after the introduction of functional groups in CF-CA. The adsorption kinetics data were well fitted by pseudo-second order kinetics with coefficient of regression (R²) closed to unity. The removal efficiency of CF-CA was 97% at equilibrium time of 4 h. Desorption studies indicated that CF-CA could be regenerated by using HCl (0.1 M) and desorption efficiency was up to 82% upon second cycle of reusability experiment. This study proposed a green and economical use of recycled CFs in dyes wastewater treatment, simultaneously reducing the negative environmental impact due to their improper disposal.     

Application of graphene-based adsorbents in the treatment of dye-contaminated wastewater; kinetic and isotherm studies

The adsorption of methylene blue (MB) on graphene-based adsorbents was tested through the batch experimental method. Two types of graphene-based adsorbents as graphene oxide (GO) and reduced graphene oxide (RGO) were compared to investigate the best adsorbent for MB removal. So that optimizing the MB removal for the selected type of graphene-based adsorbent, the diverse experimental factors, as pH (2–10), contact time (0–1440 min), adsorbent dosage (0.5–2 g/L), and initial MB concentration (25–400 mg/L) were analyzed. The conclusions indicated that the MB removal rised with an increase in the initial concentration of the MB and so rises in the amount of adsorbent used and initial pH. Maximum dye removal was calculated as 99.11% at optimal conditions after 240 min. Adsorption data were compiled by the Langmuir isotherm (R²: 0.999) and pseudo-second-order kinetic models (R²: 0.999). The Langmuir isotherm model accepted that the homogeneous surface of the GO adsorbent covering with a single layer. And the adsorption energy was calculated as 9.38 kJ mol⁻¹ according to the D-R model indicating the chemical adsorption occurred. The results show that GO could be utilized for the treatment of dye-contaminated aqueous solutions effectively.     

Pyromellitic dianhydride‐modified β‐cyclodextrin microspheres for Pb(II) and Cd(II) adsorption

In this work, the pyromellitic dianhydride (PMDA)‐grafted β‐cyclodextrin (β‐CD) microspheres have been prepared for the removal of lead and cadmium metal ions in aqueous solution by a batch‐equilibration technique. The effects of the pH of the solution, contact time, and initial metal concentration were studied. The adsorption capacities for the two metal ions increase significantly as a large number of carboxyl groups are present on the microspheres surface. The equilibrium process is better described by the Langmuir isotherm than the Freundlich isotherm. The maximum adsorption capacities are 135.69 and 92.85 mg g^?1 for Pb(II) and Cd(II), respectively. Kinetic studies show good correlation coefficients for a pseudosecond‐order kinetic model, confirming that the sorption rate is controlled by chemical adsorption. The regeneration of the adsorbent can be carried out by treating the loaded microspheres with 0.2 (mol L^?1) HCl obtaining high desorption rate for the two metal ions. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Adsorption characteristics of methylene blue on poplar leaf in batch mode: Equilibrium,kinetics and thermodynamics

Adsorption characteristics of methylene blue (MB) from aqueous solution on natural poplar leaf were investigated. Batch experiments were carried out to study the effects of initial pH, contact time, adsorbent dosage, and initial MB concentration, salt concentration (Ca²⁺ and Na⁺) as well as temperature on MB adsorption. The optimum condition for adsorption was found at pH 6–9 and adsorbent dosage of 2 g L⁻¹. The equilibration time was 240 min. The salt concentration had a negative effect on MB removal. The equilibrium data were analyzed with Langmuir, Freundlich and Koble-Corrigan isotherm models using nonlinear regression method. The adsorption process was more effectively described by Langmuir isotherm based on the values of the correlation coefficient R² and chi-square statistic x². The maximum monolayer adsorption capacity of poplar leaf from the Langmuir model was 135.35 mg g⁻¹ at 293 K. The pseudo second order equation provided a better fit to experimental data in the kinetic studies. Intraparticle diffusion was involved in adsorption process, but it was not the only rate-controlling step. Thermodynamic quantities such as ΔG, ΔH and ΔS were calculated, indicating that the adsorption process was spontaneous and endothermic. Dye-adsorbent interactions were examined by FTIR and SEM analysis. The FTIR results suggested that there were hydroxyl and carboxyl groups on the surface of poplar leaf, which would make MB adsorption possible. The SEM images showed effective adsorption of MB molecules on the adsorbent surface.     

Sodic and Acidic Crystalline Lamellar Magadiite Adsorbents for the Removal of Methylene Blue from Aqueous Solutions: Kinetic and Equilibrium Studies

The present study reports the feasibility of two synthetic crystalline lamellar nano-silicates, sodic magadiite (Na-mag) and its converted acidic form (H-mag), as alternative adsorbents for the removal of the dye methylene blue (MB) from aqueous solutions. The ability of these adsorbents for removing the dye was explored through the batch adsorption procedure. Effects such as the pH and the adsorbent dosage on the adsorption capacities were explored. Four kinetic models were applied, the adsorption being best fitted to a fractionary-order kinetic model. The kinetic data were also adjusted to an intra-particle diffusion model to give two linear regions, indicating that the kinetics of adsorption follows multiple sorption rates. The equilibrium data were fitted to Langmuir, Freundlich, Sips, and Redlich-Peterson isotherm models. The maxima adsorption capacities for MB of Na-mag and H-mag were 331 and 173 mg g^?1, respectively.     

Equilibrium modeling for the adsorption of methylene blue from aqueous solutions on activated clay minerals

This work reports the application of an activated clay mineral as adsorbent for the removal of a basic dye, methylene blue (MB), from aqueous solutions. The thermal treatment at 300 °C for 2 h and the acid activation with nitric acid of 0.5 mol/dm³ under reflux conditions improve the adsorption capacity of the raw clay mineral. A maximum of 500 mg/g of MB at equilibrium is achieved. Equilibrium data are mathematically modelled using the Freundlich, Langmuir and Toth isotherm adsorption models.     

Assembly of gelatin biopolymer to fibrous sepiolite clay for efficient dye removal from wastewater

This work aimed to fabricate nanocomposites using low-cost and natural materials for fast and efficient dye adsorption from wastewater. To achieve this, fibrous sepiolite clay was incorporated into the gelatin (GE) biopolymer. The obtained nanocomposites were characterized by Fourier transform infrared spectroscopy and scanning electron microscope techniques. The effects of sepiolite/GE ratio, adsorbent dosage, solution pH, contact time, and initial dye concentration on the adsorption capacity of nanocomposites were well studied and optimized through batch adsorption study. Kinetics, isotherms, and thermodynamics analysis were also performed for methylene blue adsorption. The adsorption data were better fitted with the pseudo-second-order and Langmuir isotherm models. The prepared nanocomposites demonstrated a fast and efficient adsorption performance toward the MB dye with the maximum adsorption capacity as high as 684.8 mg g⁻¹ within only an equilibrium time of 30 min, which revealed their promising potential in wastewater treatment. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48266.     

Polyethylenimine‐grafted and HSA‐immobilized poly(GMA–MMA) affinity adsorbents for bilirubin removal

The epoxy‐group‐containing microspheres from cross‐linked glycidyl methacrylate and methyl methacrylate, poly(GMA–MMA), were prepared by suspension polymerisation. The epoxy groups of the poly(GMA–MMA) microspheres were used for grafting with an anionic polymer polyethylenimine (PEI) to prepare non‐specific affinity adsorbents (poly(GMA–MMA)–PEI) for bilirubin removal. The specificity of the poly(GMA–MMA)–PEI adsorbent to bilirubin was further increased by immobilization of human serum albumin (HSA) via adsorption onto PEI‐grafted poly(GMA–MMA) adsorbent. Various amounts of HSA were immobilized on the poly(GMA–MMA)–PEI adsorbent by changing the medium pH and initial HSA concentration. The maximum HSA content was obtained at 68.3 mg g^?1 microspheres. The effects of pH, ionic strength, temperature and initial bilirubin concentration on the adsorption capacity of both adsorbents were investigated in a batch system. Separation of bilirubin from human serum was also investigated in a continuous‐flow system. The bilirubin adsorption on the poly(GMA–MMA)–PEI and poly(GMA–MMA)–PEI–HSA was not well described by the Langmuir model, but obeyed the Freundlich isotherm model. The poly(GMA–MMA)–PEI affinity microspheres are stable when subjected to sanitization with sodium hydroxide after repeated adsorption–desorption cycles. Copyright © 2004 Society of Chemical Industry     

Preparation of poly(acrylic acid)/starch hydrogel and its application for cadmium ion removal from aqueous solutions

In this paper, potassium bromate/thiourea dioxide redox system was used to initiate the graft copolymerization reaction of acrylic acid onto maize starch. The so obtained polyacrylic acid/starch graft copolymer was crosslinked by further treatment with alkaline epichlorohydrin to get three dimensional hydrogel. This crosslinked hydrogel was used for the removal of the heavy element, Cd²⁺ from its aqueous solution by adsorption. All factors which are expected to affect the adsorption process, like adsorbent concentration, immersion time, graft yield of the adsorbent, Cd²⁺ concentration and adsorption temperature were extensively studied and reported in the text. The study and investigations demonstrated that the adsorption efficiency is affected by the adsorbent graft yield and the adsorption medium temperature. In addition, on fitting the data obtained from the adsorption process, it was found that the adsorption obeys both Langmuir and Freundlich adsorption isotherms but the Langmuir isotherm shows better mathematical fitting for the equilibrium data than does Freundlich model, based on the higher R² value for the Langmuir isotherm.     

Equilibrium and kinetics of adsorption of methylene blue on Ti‐modified volcanic ashes

Volcanic ashes (VAs) and Ti‐modified volcanic ashes (TVA) were investigated as inexpensive adsorbents to remove methylene blue (MB) from aqueous solutions. TVA displayed higher and faster MB adsorption than VA. Adsorption studies were carried out in a batch system at room temperature. In this work, several variables were studied: contact time, pH, initial MB concentration, and adsorbent dosage. The equilibrium data of MB adsorption were analyzed according to the Langmuir and Freundlich adsorption isotherm models. Optimum adsorption performance for TVAs particles, prepared using a hydrothermal method, was obtained at pH = 10 and 3 g/l adsorbent dose. MB adsorption isotherm data can be described satisfactorily by the Langmuir equation, whereas adsorption kinetic data fit a pseudo second‐order kinetics model. © 2010 American Institute of Chemical Engineers AIChE J, 2011     

Removal of Methylene Blue from Aqueous Solutions by using Cold Plasma,Microwave Radiation and Formaldehyde Treated Acorn Shell

In this paper, cold plasma (CPTAS), formaldehyde (FTAS), and microwave radiation treated (MTAS) acorn shell obtained from Quercus petraea tree as biosorbent was characterized and its dye removal ability at different dye concentrations was studied. The isoelectric point, functional groups and morphology of acorn shell was investigated as adsorbent surface characteristics. Fourier transform infrared (FTIR), scanning electron microscopy (SEM), and UV–Vis spectrophotometry were used. Methylene blue (MB) was used as model cationic dye. The Langmuir and Freundlich adsorption isotherm models were applied to describe the equilibrium isotherms. The results indicated that the data for adsorption of MB onto treated acorn shell fitted well with the Langmuir isotherm model. Comparison of adsorption capacities of CPTAS with FTAS has shown a significant increase by as much as about 30 mg/g (33.32%) in MB adsorption.The pseudo-first order, pseudo-second order kinetic models were examined to evaluate the kinetic data, and the rate constants were calculated. Adsorption kinetic of dyes followed pseudo-first order kinetics. Thermodynamic parameters such as free energy, enthalpy, and entropy of dye adsorption were obtained. The results indicated that acorn shell could be used as a natural biosorbent for the removal of cationic dyes.     

Synthesis and characterization of magnetic beads containing aminated fibrous surfaces for removal of Reactive Green 19 dye: kinetics and thermodynamic parameters

BACKGROUND: Poly(HEMA‐co‐MMA) beads were prepared from 2‐hydroxyethyl‐methacrylate (HEMA) and methylmethacrylate (MMA) in the presence of FeCl₃. Thermal co‐precipitation of Fe(III) ions containing beads with Fe(II) ions was carried out under alkaline conditions. The magnetic beads were grafted with poly(glycidylmethacrylate; p(GMA)), and the epoxy groups of the grafted p(GMA) brushes were converted into amino groups by reaction with ammonia. RESULTS: The magnetic beads were characterized by surface area measurement, electron spin resonance (ESR), Mössbauer spectroscopy and scanning electron microscopy (SEM). The maximum adsorption of Reactive Green‐19 (RG‐19) dye on the p(GMA) grafted and amine modified magnetic beads was around pH 3.0. The adsorption capacity of magnetic beads was 84.6 mg dye g^?1. The effects of adsorbent dosage, ionic strength and temperature have also been reported. Batch kinetic sorption experiments showed that a pseudo‐second‐order rate kinetic model was applicable. CONCLUSION: The p(GMA) grafted and amine modified magnetic beads (adsorbent) were expected to have the advantage of mobility of the grafted chains in the removal of acidic dyes from aqueous solutions. The magnetic beads have potential as an adsorbent for removal of pollutants under various experimental conditions without significant reduction in their initial adsorption capacity. Copyright © 2011 Society of Chemical Industry     

Nano-TiO2 modified with 2-mercaptobenzimidazole as an efficient adsorbent for removal of Ag(I) from aqueous solutions

Nano-TiO₂ was modified with 2-mercaptobenzimidazole via surfactant activation and used as an adsorbent for the removal of Ag(I) under optimum conditions. The adsorbent was characterized using powder X-ray diffraction and FT-IR spectroscopy. The equilibrium data were fitted to the Langmuir, Freundlich and Temkin isotherm models. Langmuir isotherm describes the adsorption data better than Freundlich isotherm and Temkin. Kinetic studies showed that the pseudo second order kinetic model fits the adsorption kinetic processes well. Maximum adsorption capacity for Ag(I) was 128.2 mg g⁻¹ of nano-TiO₂. The method was successfully applied to the removal of silver from radiology film processing wastewater samples.     

Removal of methylene blue from aqueous solution by adsorption onto zeolite synthesized from coal fly ash and its thermal regeneration

BACKGROUND: The removal of cationic dyes from wastewater is of great importance. Three zeolites synthesized from coal fly ashes (ZFAs) were investigated as adsorbents to remove methylene blue (MB), a cationic dye, from aqueous solutions. Experiments were conducted using the batch adsorption technique under different conditions of initial dye concentration, adsorbent dose, solution pH, and salt concentration. RESULTS: The adsorption isotherm data of MB on ZFAs were fitted well to the Langmuir model. The maximum adsorption capacities of MB by the three ZFAs, calculated using the Langmuir equation, ranged from 23.70 to 50.51 mg g^?1. The adsorption of MB by ZFA was essentially due to electrostatic forces. The measurement of zeta potential indicated that ZFA had a lower surface charge at alkaline pH, resulting in enhanced removal of MB with increasing pH. MB was highly competitive compared with Na⁺, leading to only a < 6% reduction in adsorption in the presence of NaCl up to 1.0 mol L^?1. Regeneration of used ZFA was achieved by thermal treatment. In this study, 90–105% adsorption capacity of fresh ZFA was recovered by heating at 450 °C for 2 h. CONCLUSION: The experimental results suggest that ZFA could be employed as an adsorbent in the removal of cationic dyes from wastewater, and the adsorptive ability of used ZFA can be recovered by thermal treatment. Copyright © 2010 Society of Chemical Industry     

Competitive adsorption of Direct Yellow 12 and Reactive Orange 12 on ZnS:Mn nanoparticles loaded on activated carbon as novel adsorbent

A novel adsorbent (ZnS:Mn nanoparticles loaded on activated carbon) was made. The competitive adsorption of Direct Yellow 12 (DY12) and Reactive Orange 12 (RO12) dyes in binary mixture onto this adsorbent was studied. DY12 and RO12 with severe spectra overlapping were chosen and analyzed simultaneously with high accuracy by first order derivative spectrophotometric method in binary solutions. The effect of multi-solute systems on the adsorption capacity was investigated. Because of the specific characteristics of ZnS:Mn-NP-AC was found to be efficient for the removal of the dyes studied. The adsorption capacities were investigated and described by the mono- and multi-component Langmuir and Freundlich isotherm models for both single and binary dye solutions. The isotherm constants for DY12 and RO12 were calculated. For single solution of DY12 and RO12 dyes, the adsorption capacities of the applied adsorbent were found to be 90.05 mg/g and 94.52 mg/g, respectively. Equilibrium uptake amounts of DY12 and RO12 in binary solution onto the applied adsorbent were found to be considerably decreasing with increasing the concentrations of the other dye. A better agreement between the adsorption equilibrium data and mono-component Langmuir isotherm model was found. However, at concentrations within moderate ranges, the extended Freundlich isotherm model satisfactorily predicted multi-component adsorption equilibrium data. An endothermic and a spontaneous nature for the adsorption of the dyes studied were shown from thermodynamic parameters.     

Saccharomyces cerevisiae for the biosorption of basic dyes from binary component systems and the high order derivative spectrophotometric method for simultaneous analysis of Brilliant green and Methylene blue

In this work, biosorption of Brilliant green (BG) and Methylene blue (MB) dyes in binary mixture onto Saccharomyces cerevisiae were studied. pH at which the biosorption capacity of biomass is maximum was found to be 6 which is close to the pH of natural aqueous solutions. This is a big advantage of S. cerevisiae which makes it applicable for the technology of dye removal from natural aqueous dye solutions. Note that the time for the applied biosorption process for the dye removal is considerably short (about 5 min) which is a big improvement for the adsorption processes. This proves that the S. cerevisiae is a promising adsorbent. The BG and MB dyes were simultaneously analyzed using the fifth and fourth order derivative spectrophotometric method, respectively. Several isotherm models were applied to experimental data and the isotherm constants were calculated for BG and MB dyes. Among the applied models, Freundlich isotherm model showed best fit to the biosorption equilibrium data.     

Preparation of methacrylamide grafted and dye-ligand immobilized PET fibers: Studies of adsorption and purification of lysozyme

In this study, novel affinity chromatographic fibers was prepared from methacrylamide grafted poly(ethylene terephthalate), PET-g-pMAA, using benzoylperoxide as an initiator. A dye ligand (i.e., Procion Brown) as a ligand was then covalently immobilized on the different amount of pMAAm grafted PET fibers, (PET-g-pMAAm-PB). The fibers were characterized by surface area measurement, infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), and scanning electron microscopy (SEM). Adsorptive properties of the composite fibers were tested using a model protein (i.e., lysozyme). To achieve these purposes, the influence of pH, ionic strength, initial lysozyme concentration, and temperature on adsorption system has been investigated and evaluated. A maximum lysozyme adsorption PET-g-pMAAm-PB fiber was obtained as 43.9 mg g⁻¹ at pH 7.5. The experimental equilibrium data obtained for lysozyme adsorption onto PET-g-pMAAm-PB fibers fitted well to the Langmuir isotherm model. The result of kinetic analyzed for lysozyme adsorption onto affinity fibers showed that the second-order rate equation was favorable. The purity of the eluted lysozyme, as determined by HPLC, was 84% with recovery 73% for PET-g-pMAAm-PB fiber. Experiments on regeneration and dynamic adsorption were also performed. It appears that PET-g-pMAAm-PB fibers can be applied for lysozyme separation without causing any denaturation. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008