Kinetic, equilibrium and thermodynamic studies of ternary system dye removal using a biopolymer

In this paper, dye removal ability of sodium alginate (SA) as a biopolymer from ternary systems was investigated. Physical characteristics of SA were studied using Fourier transform infra-red (FTIR) and scanning electron microscopy (SEM). Three textile basic dyes were used as model compounds. The adsorption kinetics, isotherms and thermodynamics were studied. The effect of SA dosage, initial dye concentration and pH on dye removal was elucidated. It was found that adsorption kinetics of dyes followed with pseudo-second order kinetics. In addition, dyes followed with Langmuir, and extended Langmuir isotherm in single and ternary systems, respectively. The thermodynamic data showed that the dye adsorption onto SA was a spontaneous, endothermic and physisorption reaction. Based on the data of present investigation, one could conclude that the alginate being a biocompatible, eco-friendly and low-cost adsorbent might be a suitable alternative for elimination of dyes from colored aqueous solutions.     

Dye removal using polymeric adsorbent from wastewater containing mixture of two dyes

In this paper, poly(amido primary-secondary amine) (PAPSA) as a high capacity polymeric adsorbent was synthesized. Dye removal ability of PAPSA from single and binary systems was investigated. The functional groups of PAPSA were studied using Fourier transform infrared (FTIR). Acid Blue 92 (AB92), Direct Red 23 (DR23), and Direct Red 81 (DR81) were used as model compounds. The kinetic and isotherm of dye adsorption were studied. The effect of operational parameter such as adsorbent dosage, dye concentration, and pH on dye removal was evaluated. It was found that adsorption of dyes onto PAPSA showed Langmuir isotherm. The maximum dye adsorption capacity (Q ₀) of PAPSA was 10000 mg/g, 12500 mg/g, and 10000 mg/g for AB92, DR23, and DR81, respectively. Adsorption kinetic of dyes followed pseudo-second order kinetics. Dye desorption tests showed that the dye release of 85 % for AB92, 91 % for DR23 and 89 % for DR81 were achieved in aqueous solution at pH 12. The results showed that the PAPSA as a polymeric adsorbent with high dye removal ability might be a suitable alternative to remove dyes from colored wastewater.     

Preparation and acid dye adsorption behavior of polyurethane/chitosan composite foams

We prepared a series of polyurethane(PU)/chitosan composite foams with different chitosan content of 5∼20 wt% and investigated their adsorption performance of acid dye (Acid Violet 48) in aqueous solutions with various dye concentrations and pH values. It was observed that PU/chitosan composite foams exhibited well-developed open cell structures. Dye adsorption capacities of the composite foams increased with the increment of chitosan content in composite foams, because amine groups of chitosan serve as the binding sites for sulfonic ions of acid dyes in aqueous solutions. In addition, dye adsorption capacities of composite foams were found to increase with decreasing the pH value, which stems from the fact that the enhanced chemisorption between protonated amine groups of chitosan and sulfonic ions of acid dye is available in acidic solutions. The dye adsoption kinetics and equilibrium isotherm of the composite foams were well described with the pseudo-second order kinetic model and Langmuir isotherm model, respectively. The maximum adsorption capacity (q _max) for the PU/chitosan composite foams with 20 wt% chitosan content is evaluated to be ca. 30 mg/g.     

Dye Adsorption from Aqueous Solution by Cellulose/Chitosan Composite: Equilibrium,Kinetics, and Thermodynamics

A novel eco-friendly porous adsorbent of cellulose (CE)/chitosan (CS) aerogel was prepared through sol-gel process and freeze-drying to remove Congo Red (CR). A series of aerogels were prepared by adjusting the mass ratios of CE and CS. Composite aerogels were characterized by Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), and X-ray diffraction (XRD). SEM images showed that it was possible to change the structure of the aerogel by adjusting the amount of chitosan. The effects of dosage of chitosan, initial pH, temperature, adsorbent dosage, contact time, and initial dye concentration on adsorption capacities for CR were studied in detail. Batch adsorption studies showed that aerogel exhibited maximum removal efficiency to CR at a composite ratio of 1:3 and dosage of 2.5 g/l. CE/CS aerogel had excellent adsorption capacities for CR at a pH range of 3-11, which indicated stability of the aerogel in both acidic and alkaline conditions. CR adsorption on the composite aerogel fitted pseudo-second-order kinetics and Langmuir isotherm. The Langmuir isotherm model revealed that the maximum theoretical adsorption capacity of this material for CR was 381.7 mg/g at pH 7.0 at 303 K for 24 h. The adsorption mechanism included electrostatic and chemical interactions. The results indicated that the adsorption capacity of CE/CS aerogels was higher than the other chitosan composites adsorbents.     

Surface modification and ternary system dye removal ability of manganese ferrite nanoparticle

In this paper, the surface of magnetic manganese ferrite nanoparticles (MFN) was modified using cetyl trimethylammonium bromide (CTAB). The modified MFN was studied using Fourier transform infrared spectroscopy (FTIR). The adsorption capacity of surface modified MFN (MFN-CTAB) was investigated for dye removal for single and ternary systems. Three anionic dyes, C.I. Direct Red 80 (DR80), C.I. Direct Red 31 (DR31), and C.I. Acid Blue 92 (AB92), were used as model compounds. The effects of operational parameters on dye removal (i.e. adsorbent dosage, dye concentration and salt) and the kinetic and isotherm of dye adsorption were studied. The adsorption kinetic for the dyes was found to be well described by the pseudo-second order model. The maximum dye adsorption capacity (Q ₀) of MFN-CTAB for DR80, DR31 and AB92 was 83 mg/g, 59 mg/g and 70 mg/g, respectively. The adsorption isotherm data were analyzed using the Langmuir, Freundlich, and Temkin equations. The results revealed that the Langmuir model fitted the adsorption data better. The results showed that the MFN-CTAB as a magnetic adsorbent might be a suitable alternative to remove dyes from colored aqueous solutions.     

Copper oxide-carbon nanotube (CuO/CNT) nanocomposite: Synthesis and photocatalytic dye degradation from colored textile wastewater

In this paper, CuO/CNT nanocomposite was synthesized and its photocatalytic dye degradation ability for colored textile wastewater was studied. The characteristics of the nanocomposite were investigated by XRD, SEM and FTIR. The photodegradation of Direct Red 31 (DR31) and Reactive Red 120 (RR120) by CuO/CNT in presence of H₂O₂ was investigated. Photocatalytic dye degradation was determined by UV-vis spectrophotometer. Effects of catalyst dosage, initial dye concentration and salt on photodegradation performance were studied. The photocatalytic dye degradation ability of pure CuO and CuO/CNT nanocomposite is 78 % and 89 % for DR31 and 70 % and 87 % for RR120, respectively. The results showed that CNT increased the photocatalytic activity of CuO. The presence of salt decreases dye degradation efficiency. The dye degradation kinetics by nanocomposite followed first-order kinetic model. The reaction rate at 0.005 g catalyst was 0.0137 and 0.0105 min^-1 for DR31 and RR120, respectively. It was found that the CuO/CNT nanocomposite as a photocatalyst could be used to degrade dyes from colored wastewater.     

Organic-inorganic hybrid of chitosan/poly (vinyl alcohol) containing yttrium(III) membrane for the removal of Cr(VI)

In this present study, an organic-inorganic hybrid membrane was prepared by embedding yttrium(III) into chitosan matrix for the removal of Cr(VI) from aqueous solutions. Several techniques, including fourier infrared spectrum (FTIR), scanning electron microscope (SEM), X-ray diffraction (XRD), and transmission electron microscope (TEM) are employed to characterize the properties of the membrane. The mechanical properties of the membrane were also examined. The chitosan/poly(vinyl alcohol) containing yttrium(III) (CY) membrane was experimentally used for the removal of Cr(VI) ions from aqueous solution under the optimized conditions. The results showed that the adsorption capacity for the removal of Cr(VI) ions was enhanced when yttrium(III) was introduced. The adsorption data from the experiment were fit well by Langmuir isotherm. Based on Langmuir model, q _m was calculated to be 38.48 mg g^?1. Kinetic study results indicated that the adsorption process followed a pseudo-second-order kinetics.     

Preparation and BSA Adsorption Behavior of Chitosan-arginine Based Nanofiber Membranes

In this work, an affinity nanofiber membrane was successfully prepared by solution blowing of arginine-modified chitosan (CS-Arg) for bovine serum albumin (BSA) adsorption. CS-Arg was firstly synthesized by coupling L-arginine onto chitosan backbone. Then, CS-Arg nanofiber membranes (CANFs) were fabricated using solution blowing process with Polylactide (PLA) as assistant polymer. The results showed that CANFs effectively adsorbed BSA, and the adsorption capacities were influenced by the degrees of substitution (DS) of arginine in CS, pH value, contact time, and initial protein concentration. The highest adsorption capacity of 445.19 mg/g was achieved uvnder the following conditions: DS of 43.7 %, pH of 7.14, and initial concentration of 3.0 mg/ml. BSA adsorbed on the CANFs membrane conformed to Langmuir model, and the adsorption rate was consistent with the second-order kinetics model. This work implies that an arginine-modified chitosan nanofiber-based novel biomaterial has a potential application in adsorption of BSA.     

Novel high flux nanofibrous composite membrane based on polyphenylsulfone thin barrier layer on nanofibrous support

A novel thin film nanofibrous composite (TFNC) polyphenylsulfone (PPSU) membrane was fabricated by casting a thin PPSU barrier layer on the surface of the electrospun nanofibrous PPSU support. Polyethylene glycol (PEG) 400 was applied in the electrospinning solution to prevent the penetration of coating solution into the support. The membrane morphology and filtration performance were investigated via scanning electron microscopy (SEM), and filtration of canned beans production wastewater, respectively. Atomic force microscopy (AFM) was utilized to evaluate the surface roughness of the membranes. Furthermore, the mechanical strength and thermal stability of the membranes were determined via tensile test and thermogravimetric analysis (TGA). Comparison of the TFNC membrane and the unsupported membrane prepared through the wet phase inversion method with almost equal rejection values indicated a 2.3 fold higher PWF using the former.     

Water-resistant Lignin/Poly(vinyl alcohol) Blend Fibers for Removal of Hexavalent Chromium

Lignin is the second most abundant renewable biomass-derived natural resource that has been used to replace traditional petrochemical-based materials. However, fabricating the lignin component into the various forms required for practical application is still challenging. In this work, we fabricated water-resistant lignin/poly(vinyl alcohol) (PVA) blend fibers by wet spinning and glutaraldehyde crosslinking methods. The effect of the lignin/PVA blend ratio and glutaraldehyde crosslinking process on the physicochemical properties of wet-spun lignin/PVA blend fibers were studied using maximum draw ratios, hydrolytic degradation profiles, and mechanical properties. Furthermore, the hexavalent chromium [Cr(VI)] removal behavior of lignin/PVA blend fibers was investigated according to the effect of pH, initial Cr(VI) concentration, and contact time. The wet-spun lignin/PVA blend fiber achieved excellent water stability through glutaraldehyde crosslinking and exhibited notable Cr(VI) adsorption capacity (350.87 mg/g) and good regeneration ability. These findings demonstrate that glutaraldehyde-crosslinked lignin/PVA blend fibers could be promising adsorbents for the remediation of heavy metal species containing textile wastewater.     

Cellulose-based porous adsorbents with high capacity for methylene blue adsorption from aqueous solutions

A novel cellulose-based porous adsorbent with high adsorption capacity for methylene blue (MB) was prepared by free radical polymerization methods. The obtained polymer grafting rate and dye removal efficiency are as high as 338.64 % and 97.74 %, respectively, when the dosage of monomer is 4.5 g, the polymerization condition is 3 h at 70 °C. The cellulose-based adsorbent showed high mechanical properties and good flexibility. The Langmuir isotherm model revealed that the maximum theoretical adsorption capacity of this material for methylene blue was 1734.816 mg g-1 at pH 9.0 at 313 K, which is higher than the values observed for other adsorbents. Scanning electron microscopy (SEM) showed that the cellulose-based adsorbent exhibits a typical well-defined porous and interconnected three-dimensional framework structure, which is benefits to dye adsorption. The adsorption kinetics (pseudo first-order, pseudo-second-order, and intraparticle diffusion models) was also studied, and the pseudo-second-order model fitted MB adsorption better than the pseudo-first-order and intraparticle diffusion models at different initial dye concentrations (500-3000 mg l ^-1). The novel polyacrylic acid-grafted quaternized cellulose (PAA-g-QC) adsorbent is thus potentially useful for the treatment of dye-contaminated wastewater.     

Thermodynamics of adsorption of laccaic acid onto chitosan and associated dye toxicity studies

The thermodynamics of adsorption of laccaic acid (lac dye) onto chitosan were investigated under acidic condition over various concentrations (20–293 mg/l). Langmuir, Freundlich, and Temkin isotherms were used to analyze the equilibrium data at different temperatures, with the Freundlich isotherm fitting the experimental data significantly better than the other isotherms. The effect of temperature on the adsorption isotherm was studied by carrying out a series of isotherms at 10, 20, 40, and 60 °C. It was found that more dye was strongly adsorbed by chitosan when the temperature of the dye solution increased. Thermodynamic parameters such as free energy change (ΔG°), enthalpy change (ΔH°), and entropy change (ΔS°) were also evaluated. The negative value of ΔG° and positive value of ΔH° indicated that the laccaic acid adsorption process is a spontaneous and an endothermic one. Attenuated total reflectance Fourier transform infrared spectroscopy confirmed the functional groups of chitosan that affected the laccaic acid adsorption. Therefore, laccaic acid molecules could interact with the chitosan via electrostatic forces, hydrogen bonding, and ion-dipole interactions under acidic condition. From the toxicity study, the dye solution with the initial dye concentrations of 40 and 120 mg/l before dye removal showed significant mortality to earthworm Diplocardia communis (P<0.01).     

Sorption properties of iron impregnated activated carbon web for removal of methylene blue from aqueous media

In this study, impregnation of iron chloride was carried out on needle punched web of waste acrylic fibers, which was subsequently carbonized under layer of charcoal by physical activation in high temperature furnace to produce iron impregnated activated carbon (FeAC). For comparison purpose, one more sample of activated carbon (AC) was prepared without impregnation of iron chloride. Both the webs were carbonized at 1200 °C with no holding time, and characterization of BET surface area, SEM morphology, EDX elemental analysis, XRD crystalline structure was performed. The FeAC web was used as adsorbent for the removal of methylene blue from aqueous solution. The dye removal percentage was investigated at different experimental parameters like different dye concentrations, adsorbent dosage, stirring speed and different pH. The obtained results were analyzed using linear and non-linear forms of Langmuir and Freundlich isotherms and adsorption kinetics (i.e. pseudo first order and pseudo second order model).     

Use of 1,6-diaminohexane-functionalized glycidyl methacrylate-g-poly(ethylene terephthalate) fiber for removal of acidic dye from aqueous solution

In this study, removal of Congo red (CR) from aqueous solution by 1,6-diaminohexane-functionalized glycidyl methacrylate-g-poly(ethylene terephthalate) (HMDA-GMA-g-PET) fiber was investigated. A new aminated fibrous adsorbent was prepared by a reaction between amine and epoxy group in GMA-g-PET fiber prepared by grafting GMA monomer onto poly (ethylene terephthalate) (PET) fiber. Effects of various parameters such as pH, treatment time, initial, dye concentration, and reaction temperature on the adsorption amount of dye onto reactive fiber were investigated. The adsorption rates of CR were much higher on the HMDA-GMA-g-PET fiber than on GMA-g-PET and ungrafted PET fiber. The effective pH was 2.0 for adsorption on grafted PET fiber. It was found that the sufficient time to attain equilibrium was 60 min. The maximum adsorption capacity of the reactive fiber for CR is 16.6 mg/g fiber. The rates of adsorption were found to conform to the pseudo-second order kinetics with good correlation. It was found that the adsorption isotherm of CR fitted Freundlich type isotherm.     

Removal of benzidine-based azo dye from aqueous solution using amide and amine-functionalized poly(ethylene terephthalate) fibers

In this study, amide and amine groups bound to poly(ethylene terephthalate) fibers are used to remove the colored toxic Congo red dye from aqueous solution. The effects of process variables like pH, contact time, graft yield, and initial dye concentration on the adsorption were investigated. The maximum adsorption of Congo red to amide and amine groups was observed at pH 3 and 5 respectively. Equilibrium was attained at approximately 60 min for the amine group. The adsorption capacity of amine group on the poly(ethylene terephthalate) fiber was 46.5 mg g⁻¹ at 25 °C, which was higher than that of the amide group on the poly(ethylene terephthalate) fiber. Desorption was done using 0.1 M NH₃, and recovery was measured at 58.2 %. The used adsorbent was regenerated and recycled six times. The results showed that the amine-functionalized fiber could be considered as potential adsorbents for removal of Congo red from aqueous solution.     

Modified polyamide 66 fibers for the removal of reactive dyes from aqueous suspension

In this paper, we report the modification of polyamide sample (PA) with different contents of chitosan (CS) using citric acid (CA) as a cross-linker [PA-CA-CS]. New materials were confirmed to be formed in PA using FT-IR spectrum. It is also checked in terms of the change in thermal stability event and decomposition behavior in thermogravimetry through TG-DTA instruments. Then, the ability of unmodified and modified supports was tested for the adsorption of two reactive dyes i.e. Cibacron Brilliant Yellow 3G-P and Cibacron Blue P-3R. Sorption experiments were performed under varying several experimental conditions such as pH, contact time, initial dye concentration, and temperature. The isotherm and kinetic models were undertaken to assess the dye removal mechanism. The applicability of Langmuir, Freundlich, Dubinin-Radushkevich, and Temkin equations was checked and data were fitted using Langmuir model. The second-order equation was shown to fit the adsorption kinetics. Data gleaned from both thermodynamic results and modeling data indicate that the adsorption follows a chemical and exothermic process.     

Chitinolytic Bacteria-Assisted Conversion of Squid Pen and Its Effect on Dyes and Pigments Adsorption

The aim of this work was to produce chitosanase by fermenting from squid pen, and recover the fermented squid pen for dye removal by adsorption. One chitosanase induced from squid pen powder (SPP)-containing medium by Bacillus cereus TKU034 was purified in high purification fold (441) and high yield of activity recovery (51%) by ammonium sulfate precipitation and combined column chromatography. The SDS-PAGE results showed its molecular mass to be around 43 kDa. The TKU034 chitosanase used for the chitooligomers preparation was studied. The enzyme products revealed that the chitosanase could degrade chitosan with various degrees of polymerization, ranging from 3 to 9, as well as the chitosanase in an endolytic manner. Besides, the fermented SPP was recovered and displayed a better adsorption rate (up to 99.5%) for the disperse dyes (red, yellow, blue, and black) than the water-soluble food colorants, Allura Red AC (R40) and Tartrazine (Y4). The adsorbed R40 on the unfermented SPP and the fermented SPP was eluted by distilled water and 1 M NaOH to confirm the dye adsorption mechanism. The fermented SPP had a slightly higher adsorption capacity than the unfermented, and elution of the dye from the fermented SPP was easier than from the unfermented. The main dye adsorption mechanism of fermented SPP was physical adsorption, while the adsorption mechanism of unfermented SPP was chemical adsorption.     

Fabrication and characterization of dense Chitosan/polyvinyl-alcohol/poly-lactic-acid blend membranes

Dense membranes of Chitosan (CS)/Poly(vinyl alcohol) (PVA)/Poly(lactic acid) (PLA) blend were successfully fabricated using casting technique. The mechanical properties, moisture regain and water vapor permeability of polymer blend membranes were estimated by tensile test, moisture regain rate and dish method test respectively. The microstructures, morphology, chemical composition and thermal properties were also characterized by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), and differential scanning calorimetry (DSC) respectively. Results indicated that there were interactions and good compatibility among CS, PLA and PVA. And the blend membranes have good breaking elongation and slightly decreased breaking strength, and show best moisture regain at the case of CS60 (the content of CS in the blends is 60 %). They also have excellent porous structure, which is beneficial to their air permeability and may also contribute to cell regeneration. With the adding of PVA content, the melting peaks of blend membranes reduce and gradually close to that of PVA, demonstrating that the regularity of CS molecular chain may be destroyed and hydrogen bonds of macromolecules in polymers were newly formed. As a result, solution blending of the three polymers could complement their disadvantages and significantly improve the membrane performance of a single polymer, thus promote the mechanical and biological properties of blend membrane.     

Macroporous cellulose-based cryogels with tunable porous structure and surface functional groups

In this work, cellulose-based macroporous cryogels were fabricated by grafting with acrylic acid and acrylamide, which provided the carboxyl and amino functional groups, respectively. The effects of crosslinker, extra water, acrylic acid/ (acrylic acid+acrylamide) feeding ratio on the structure and swelling performance of the resultant cryogels were experimentally investigated. Cellulose-based cryogels with different pore size were prepared by adjusting the reaction parameters. The pore size and functional group contents influenced the swelling behavior of the cryogels. The fabricated cryogels were also investigated as an adsorbent for the removal of toxic methyl blue (MB) from aqueous solution. The interconnected macroporous structure as well as large number of functional groups of the cryogels led to the high adsorption capacity of MB. The maximum adsorption capacity was around 990.1 mg per 1 g dye gel within 60 min. The investigation of the adsorption kinetics revealed that the adsorption process of MB from aqueous solution was well described by pseudosecond order kinetic model. Large-scale preparation of cryogel adsorbents with tunable porous structure and surface functional groups are possible. Therefore, the macroporous cellulose-based cryogels can be used as an adsorbent for the removal of chemical toxic products from aqueous solution.     

Preparation of electrospun silk fibroin/Cellulose Acetate blend nanofibers and their applications to heavy metal ions adsorption

Silk fibroin (SF)/Cellulose Acetate (CA) blend nanofibrous membranes were prepared by electrospinning and their heavy metal absorbabilities were examined in an aqueous solution after ethanol treatment. The electrospun nanofibrous membranes were comprised of randomly oriented ultrafine fibers of 100–600 nm diameters. As a result of field emission electron microscope (FEEM), the anti-felting properties of the blend nanofibrous membranes were markedly improved after treatment with 100 % ethanol when SF was blended with CA. Metal ion adsorption test was performed with Cu²⁺ as a model heavy metal ion in a stock solution. The SF/CA blend nanofiber membranes showed higher affinity for Cu²⁺ in an aqueous solution than pure SF and pure CA nanofiber membranes. Especially, the blend nanofibrous membranes with 20 % content of CA had an exceptional performance for the adsorption of Cu²⁺, and the maximum milligrams per gram of Cu²⁺ adsorbed reached 22.8 mg/g. This indicated that SF and CA had synergetic effect. Furthermore, the parameters affecting the metal ions adsorption, such as running time and initial concentration of Cu²⁺, had been investigated. The results showed that the adsorption of the Cu²⁺ sharply increased during the first 60 min, the amount of metal ions adsorbed increased rapidly as the initial concentration increased and then slope of the increase decreased as the concentration further increased. This study provides the relatively comprehensive data for the SF/CA blend nanofibrous membranes application to the removal of heavy metal ion in wastewater.