In this work, pumpkin seed hull (PSH), an agricultural solid waste, is proposed as a novel material for the removal of methylene blue (MB) from aqueous solutions. The effects of the initial concentration, agitation time and solution pH were studied in batch experiments at 30 degrees C. The equilibrium process was described well by the multilayer adsorption isotherm. The adsorption kinetics can be predicted by the pseudo-first-order and the modified pseudo-first-order models. The mechanism of adsorption was also studied. It was found that for a short time period the rate of adsorption is controlled by film diffusion. However, at longer adsorption times, pore-diffusion controls the rate of adsorption. Pore diffusion takes place in two distinct regimes, corresponding to diffusion in macro- and mesopores. The results demonstrate that the PSH is very effective in the removal of MB from aqueous solutions.
In current research work, chitosan (Chi) was subjected to subsequent physical and chemical modifications by incorporating kaolin clay (KA) into its polymeric structure, and crosslinking process with a covalent cross-linker namely epichlorohydrin (ECH) respectively. The final product of crosslinked chitosan-epichlorohydrin/kaolin (Chi-ECH/KA) composite was successfully applied for color removal and chemical oxygen demand (COD) reduction of textile dye namely reactive blue 19 dye (RB19) from aqueous environment. The influence of pertinent parameters, i.e. A: Chi-ECH/KA dose (0.02-0.1 g), B: pH (4-10), and C: time (5-30 min) on the RB19 color removal and COD reduction were statistically optimized by using response surface methodology with Box-Behnken design (RSM-BBD). The experimental data of the adsorption kinetic and the adsorption isotherm demonstrated a better fitness to pseudo-second order model and Langmuir isotherm model respectively. Excellent absorption ability of 560.9 mg/g was recorded for Chi-ECH/KA composite. The calculated thermodynamic functions clarified that the RB19 adsorption process was endothermic and spontaneous in nature. The mechanism of RB19 adsorption onto the Chi-ECH/KA may include electrostatic interactions, hydrogen bonding, Yoshida H-bonding, and n-π interactions. This study introduces Chi-ECH/KA composite as an eco-friendly, potential and multi-function composite bio adsorbent for removal of textile dye and COD reduction from aqueous environment.
The world water resources are contaminated due to discharge of a large number of pollutants from industrial and domestic sources. A variety of a single and multiple units of physical, chemical, and biological processes are employed for pollutants removal from wastewater. Adsorption is the most widely utilized process due to high efficiency, simple procedure and cost effectiveness. This paper reviews the research work carried out on the use of geopolymer materials for the adsorption of heavy metals and dyes. Geopolymers possess good surface properties, heterogeneous microstructure and amorphous structure. The performance of geopolymers in the removal of heavy metals and dyes is reported comparable to other materials. The pseudo-second order kinetics and Langmuir isotherm models mostly fit to the adsorption data suggesting homogeneous distribution of adsorption sites with the formation of monolayer adsorbate on the surface of geopolymers. Adsorption of heavy metals and dyes onto geopolymers is spontaneous, endothermic and entropy driven process. Future research should focus on the enhancement of geopolymer performance, testing on pollutants other than heavy metals and dyes, and verification on real wastewater in continuous operation.
Hydrothermal carbonization of biomass wastes presents a promising step in the production of cost-effective activated carbon. In the present work, mesoporous activated carbon (HAC) was prepared by the hydrothermal carbonization of rattan furniture wastes followed by NaOH activation. The textural and morphological characteristics, along with adsorption performance of prepared HAC toward methylene blue (MB) dye, were evaluated. The effects of common adsorption variables on performance resulted in a removal efficiency of 96% for the MB sample at initial concentration of 25mg/L, solution pH of 7, 30°C, and 8h. The Langmuir equation showed the best isotherm data correlation, with a maximum uptake of 359mg/g. The adsorbed amount versus time data was well fitted by a pseudo-second order kinetic model. The prepared HAC with a high surface area of 1135m(2)/g and an average pore size distribution of 35.5Å could be an efficient adsorbent for treatment of synthetic dyes in wastewaters.
Graphene oxide/chitosan aerogel (GOCA) was prepared by a facile ice-templating technique without using any cross-linking reagent for metanil yellow dye sequestration. The adsorption performance of GOCA was investigated by varying the adsorbent mass, shaking speed, initial pH, contact time, concentration and temperature. The combined effects of adsorption parameters and the optimum conditions for dye removal were determined by response surface methodology. GOCA exhibited large removal efficiencies (91.5-96.4%) over a wide pH range (3-8) and a high adsorption capacity of 430.99 mg/g at 8 mg adsorbent mass, 400 mg/L concentration, 35.19 min contact time and 175 rpm shaking speed. The adsorption equilibrium was best represented by the Langmuir model. GOCA could be easily separated after adsorption and regenerated for re-use in 5 adsorption-desorption cycles thereby maintaining 80% of its adsorption capability. The relatively high adsorption and regeneration capabilities of GOCA render it an attractive adsorbent for treatment of azo dye-polluted water.
The remediation of wastewater requires treatment technologies which are robust, efficient, simple to operate and affordable such as adsorption. Lately, three-dimensional (3D) graphene based materials have attracted significant attention as effective adsorbents for wastewater treatment. The intrinsic properties of 3D graphene structure such as large surface area and interconnected porous structure can facilitate the transport of pollutants into the 3D network and provide abundant active sites for trapping the pollutants. For the synthesis of 3D graphene structure, ice-templating is commonly practiced due to its facile steps, cost effectiveness and high scalability potential. This review covers the ice-templating fabrication technique for 3D graphene based materials and their application as adsorbents in eliminating dyes and heavy metals from aqueous media. The assembly mechanisms of the ice-templating fsynthesis are comprehensively discussed. Further discussion on the fundamental principles, critical process parameters and characteristics of ice-templated 3D graphene structures is also included. A thorough review on the mechanisms for batch adsorption of dyes and heavy metals is presented based on the structures and properties of the 3D graphene materials. The review further evaluates the dynamic adsorption in packed columns and the regeneration of 3D graphene based materials.
In the current study, we have synthesized an imidazolium based cross-linked polymer, namely, 1-vinyl-3-ethylimidazolium bis(trifluoromethylsulfonyl)imide (poly[veim][Tf2N]-TRIM) using trimethylolpropane trimethacrylate as cross linker, and demonstrated its efficiency for the removal of two extensively used ionic dyes—methylene blue and orange-II—from aqueous systems. The detailed characterization of the synthesized poly[veim][Tf2N]-TRIM was performed with the help of 1H NMR, TGA, FT-IR and FE-SEM analysis. The concentration of dyes in aqueous samples before and after the adsorption process was measured using an UV-vis spectrophotometer. The process parameters were optimised, and highest adsorption was obtained at a solution pH of 7.0, adsorbent dosage of 0.75 g/L, contact time of 7 h and dye concentrations of 100 mg/L and 5.0 mg/L for methylene blue and orange-II, respectively. The adsorption kinetics for orange-II and methylene blue were well described by pseudo-first-order and pseudo−second-order models, respectively. Meanwhile, the process of adsorption was best depicted by Langmuir isotherms for both the dyes. The highest monolayer adsorption capacities for methylene blue and orange-II were found to be 1212 mg/g and 126 mg/g, respectively. Overall, the synthesized cross-linked poly[veim][Tf2N]-TRIM effectively removed the selected ionic dyes from aqueous samples and provided >90% of adsorption efficiency after four cycles of adsorption. A possible adsorption mechanism between the synthesised polymeric adsorbent and proposed dyes is presented. It is further suggested that the proposed ionic liquid polymer adsorbent could effectively remove other ionic dyes and pollutants from contaminated aqueous systems.
This work aims to apply the use of food-grade algae (FGA) composited with chitosan-benzaldehyde Schiff base biopolymer (CHA-BD) as a new adsorbent (CHA-BA/FGA) for methyl violet 2B (MV 2B) dye removal from aqueous solutions. The effect of three processing variables, including CHA-BA/FGA dosage (0.02-0.1 g/100 mL), pH solution (4-10), and contact duration (10-120 min) on the removal of MV 2B was investigated using the Box-Behnken design (BBD) model. Kinetic and equilibrium dye adsorption profiles reveal that the uptake of MV 2B dye by CHA-BA/FGA is described by the pseudo-second kinetics and the Langmuir models. The thermodynamics of the adsorption process (ΔG°, ΔH°, and ΔS°) reveal spontaneous and favorable adsorption parameters of MV 2B dye onto the CHA-BA/FGA biocomposite at ambient conditions. The CHA-BA/FGA exhibited the maximum ability to absorb MV 2B of 126.51 mg/g (operating conditions: CHA-BA/FGA dose = 0.09 g/100 mL, solution pH = 8.68, and temperature = 25 °C). Various interactions, including H-bonding, electrostatic forces, π-π stacking, and n-π stacking provide an account of the hypothesized mechanism of MV 2B adsorption onto the surface of CHA-BA/FGA. This research reveals that CHA-BA/FGA with its unique biocomposite structure and favorable adsorption properties can be used to remove harmful cationic dyes from wastewater.
This present work targets the production of an eco-friendly adsorbent (hereinafter KA/CEL) from kaolin clay functionalized with cellulose extract obtained from peanut shells. The adsorbents were used for decolorization of two different types of organic dyes (cationic: methylene blue, MB; anionic: Congo red, CR) from an aqueous environment. Several analytical methods, including Brunauer-Emmett-Teller (surface properties), Fourier Transforms infrared (functionality), scanning electron microscope, Energy dispersive X-Ray (morphology), and pHpzc test (surface charge), were used to attain the physicochemical characteristics of KA/CEL. The Box-Behnken Design (BBD) was applied to determine the crucial factors affecting adsorption performance. These included cellulose loading at 25 %, an adsorbent dose of 0.06 g, solution pH set at 10 for MB and 7 for CR, a temperature of 45 °C, and contact times of 12.5 min for MB and 20 min for CR dye. The adsorption data exhibited better agreement with the pseudo-second-order kinetic and Freundlich models. The Langmuir model estimated the monolayer capacity to be 291.5 mg/g for MB and 130.7 mg/g for CR at a temperature of 45 °C. This study's pivotal finding underscores the promising potential of KA/CEL as an effective adsorbent for treating wastewater contaminated with organic dyes.
The hazardous dyes on mixing with water resources are affecting many life forms. Granite stone is popular worldwide for decorating floors, making other forms of decorative materials and items. Granite stone powder waste can be obtained free of cost from marble factories as factories spend on the disposal of this waste. In the present study, novel granite stone powder waste composite has been prepared and utilized for the effective removal of Terasil dye. Two types of granite including gray granite and white granite were used in pure, calcinized, and chemically modified forms. Freundlich adsorption isotherm model best explained the adsorption mechanism of dye removal using granite composites as compared to other adsorption isothermal models. Characterization techniques like scanning electron microscopy (SEM) and Fourier transform infrared (FTIR) spectroscopy were used for the determination of morphological features and functional groups of granite composites. The obtained results were statistically analyzed using analysis of variance (ANOVA) along with the post hoc Tukey test. An extraordinarily high Terasil dye uptake capacity (more than 400 mg/g) was exhibited by granite composites prepared using sodium metasilicate. The synthesized novel nano-constructed composites provided a viable strategy as compared to the pure granite stone for dye removal from wastewater water.
A secure aquatic environment is essential for both aquatic and terrestrial life. However, rising populations and the industrial revolution have had a significant impact on the quality of the water environment. Despite the implementation of strong and adapted environmental policies for water treatment worldwide, the issue of organic dyes in wastewater remains challenging. Thus, this study aimed to develop an efficient, cost-effective, and sustainable material to treat methylene blue (MB) in an aqueous environment. In this research, maize extract solution (MES) was utilized as a green cross-linker to induce precipitation, conjugation, and enhance the adsorption performance of graphene oxide (GO) cross-linked with durian shell activated carbon (DSAC), resulting in the formation of a GO@DSAC composite. The composite was investigated for its adsorptive performance toward MB in aqueous media. The physicochemical characterization demonstrated that the cross-linking method significantly influenced the porous structure and surface chemistry of GO@DSAC. BET analysis revealed that the GO@DSAC exhibited dominant mesopores with a surface area of 803.67 m2/g. EDX and XPS measurements confirmed the successful cross-linking of GO with DSAC. The adsorption experiments were well described by the Harkin-Jura model and they followed pseudo-second order kinetics. The maximum adsorption capacity reached 666.67 mg/g at 318 K. Thermodynamic evaluation indicated a spontaneous, feasible, and endothermic in nature. Regenerability and reusability investigations demonstrated that the GO@DSAC composite could be reused for up to 10 desorption-adsorption cycles with a removal efficiency of 81.78%. The selective adsorptive performance of GO@DSAC was examined in a binary system containing Rhodamine B (RhB) and methylene orange (MO). The results showed a separation efficiency (α) of 98.89% for MB/MO and 93.66% for MB/RhB mixtures, underscoring outstanding separation capabilities of the GO@DSAC composite. Overall, the GO@DSAC composite displayed promising potential for the effective removal of cationic dyes from wastewater.
Triphenylmethane dyes (TPM) are recalcitrant colorants brought into the environment. In this study, a lesser-known white rot fungus Coriolopsis sp. (1c3), isolated from compost of Empty Fruit Bunch (EFB) of oil palm, was explored for its decolorization potential of TPM dyes. The isolate 1c3 demonstrated good decolorization efficiencies in the treatment of Crystal Violet (CV; 100 mg l(-1)), Methyl Violet (MV; 100 mg l(-1)) and Cotton Blue (CB; 50 mg(-1)), with 94%, 97% and 91%, within 7, 7 and 1 day(s), respectively. Malachite Green (MG; 100 mg l(-1)) was the most recalcitrant dye, with 52% decolorization after 9 days. Dye removal by 1c3 was presumably via biosorption, whereby the process was determined to be influenced by fungal biomass, initial dye concentrations and oxygen requirements. Biodegradation was also a likely mechanism responsible for dye removal by 1c3, occurred as indicated by the reduction of dye spectra peaks. Detection of laccase, lignin peroxidase and NADH-DCIP reductase activities further substantiate the possible occurrence of biodegradation of TPM dyes by 1c3.
A bio-composite material was developed that contains chitosan, food-grade algae, and zeolite for the removal of brilliant green (BG) dye. The synthesized bio-composite was dried via two different methods (air-drying; AD, and freeze-drying; FD). The physicochemical characterization of air-dried chitosan-algae-zeolite (Cs-Alg-Zl-AD) and freeze-dried chitosan-algae-zeolite (Cs-Alg-Zl-FD) were investigated by spectroscopy (FTIR, SEM-EDX, and XPS), diffraction (XRD), surface charge via pHpzc, specific surface area (SSA) and elemental analyses. The utilization of Box-Behnken Design (BBD) was intended to optimize the three input variables, which are adsorbent dosage, pH of medium, and contact time. The adsorption optimization process yielded optimal conditions, which were verified through a desirability test and implemented in batch-mode equilibrium experiments. The Cs-Alg-Zl-FD has a higher specific surface area (SSA = 3.29 m2/g) compared to Cs-Alg-Zl-AD (SSA = 1.79 m2/g). The Cs-Alg-Zl-FD shows greater adsorptive removal of BG (98.6 %) over Cs-Alg-Zl-AD (88.6 %), in parallel agreement with differences in the SSA. Moreover, the maximum BG dye adsorption capacities of Cs-Alg-Zl-FD (119.5 mg/g) and Cs-Alg-Zl-AD (108 mg/g) at pH = 8.1 and 25 °C. The Freundlich model fits best with Cs-Alg-Zl-AD while Langmuir and Temkin models account for the Cs-Alg-Zl-FD dye adsorption. The Cs-Alg-Zl-FD shows greater dye adsorption over four adsorption cycles, as compared with the Cs-Alg-Zl-AD.
Chitosan/PVA/Na-titanate/TiO2 composite was synthesized by solution casting method. The composite was analyzed via Fourier Transform Infrared Spectroscopy, X-ray diffraction, Field Emission Scanning Electron Microscopy, Thermal gravimetric analysis and water stability test. Incorporation of Na-titanate shown decrease of crystallinity for chitosan but increase water stability. However, the composite structure was deteriorated with considerable weight loss in acidic medium. Two anionic dyes, methyl orange and congo red were used for the adsorption test. The adsorption behavior of the composites were described by pseudo-second-order kinetic model and Lagergren-first-order model for methyl orange and congo red, respectively. For methyl orange, adsorption was started with a promising decolorization rate. 99.9% of methyl orange dye was removed by the composite having higher weightage of chitosan and crystalline TiO2 phase. On the other hand, for the congo red the composite having higher chitosan and Na-titanate showed an efficient removal capacity of 95.76%. UV-vis results showed that the molecular backbone of methyl orange and congo red was almost destroyed when equilibrium was obtained, and the decolorization rate was reaching 100%. Kinetic study results showed that the photocatalytic degradation of methyl orange and congo red could be explained by Langmuir-Hinshelwood model. Thus, chitosan/PVA/Na-titanate/TiO2 possesses efficient adsorptivity and photocatalytic property for dye degradation.
Free laccase and fungal biomass from white-rot fungi were compared in the thermokinetics study of the laccase-catalyzed decolorization of an azo dye, i.e., Trypan Blue. The decolorization in both systems followed a first-order kinetics. The apparent first-order rate constant, k1', value increases with temperature. Apparent activation energy of decolorization was similar for both systems at ∼ 22 kJ mol(-1), while energy for laccase inactivation was 18 kJ mol(-1). Although both systems were endothermic, fungal biomass showed higher enthalpy, entropy, and Gibbs free energy changes for the decolorization compared to free laccase. On the other hand, free laccase showed reaction spontaneity over a wider range of temperature (ΔT = 40 K) as opposed to fungal biomass (ΔT = 15 K). Comparison of entropy change (ΔS) values indicated metabolism of the dye by the biomass.
A new heterogeneous catalyst for sonocatalytic degradation of amaranth dye in water was synthesized by introducing titania into the pores of zeolite (NaY) through ion exchange method while Fe (III) was immobilized on the encapsulated titanium via impregnation method. XRD results could not detect any peaks for titanium oxide or Fe(2)O(3) due to its low loading. The UV-vis analysis proved a blue shift toward shorter wavelength after the loading of Ti into NaY while a red shift was detected after the loading of Fe into the encapsulated titanium. Different reaction variables such as TiO(2) content, amount of Fe, pH values, amount of hydrogen peroxide, catalyst loading and the initial dye concentration were studied to estimate their effect on the decolorization efficiency of amaranth. The maximum decolorization efficiency achieved was 97.5% at a solution pH of 2.5, catalyst dosage of 2 g/L, 20 mmol/100 mL of H(2)O(2) and initial dye concentration of 10 mg/L. The new heterogeneous catalyst Fe/Ti-NaY was a promising catalyst for this reaction and showed minimum Fe leaching at the end of the reaction.
A modified hydrophilic penta-bismuth hepta-oxide nitrate (Bi5O7NO3) surface was synthesized via a precipitation method using TiO2 and Ag as modified agents. The synthesized product was characterized by different analytical techniques. The removal efficiency was evaluated using mono- and di-sulphonated azo dyes as model pollutants. Different kinetic, isotherm and diffusion models were chosen to describe the adsorption process. X-ray photoelectron spectroscopy (XPS) results revealed no noticeable differences in the chemical states of modified adsorbent when compared to pure Bi5O7NO3; however, the presence of hydrophilic centres such as TiO2 and Ag developed positively charged surface groups and improved its adsorption performance to a wide range of azo dyes. Dyes removal was found to be a function of adsorbent dosage, initial dye concentration, solution pH and temperature. The reduction of Langmuir 1,2-mixed order kinetics to the second or first-order kinetics could be successfully used to describe the adsorption of dyes onto the modified adsorbent. Mass transfer can be described by intra-particle diffusion at a certain stage, but it was not the rate limiting step that controlled the adsorption process. Homogenous behavior of adsorbent surface can be explored by applying Langmuir isotherm to fit the adsorption data.
The removal of Reactive Black 5 dye in an aqueous solution by electrocoagulation (EC) as well as addition of flocculant was investigated. The effect of operational parameters, i.e. current density, treatment time, solution conductivity and polymer dosage, was investigated. Two models, namely the artificial neural network (ANN) and the response surface method (RSM), were used to model the effect of independent variables on percentage of dye removal. The findings of this work showed that current density, treatment time and dosage of polymer had the most significant effect on percentage of dye removal (p<0.001). In addition, interaction between time and current density, time and dosage of polymer, current density and dosage of polymer also significantly affected the percentage of dye removal (p=0.034, 0.003 and 0.024, respectively). It was shown that both the ANN and RSM models were able to predict well the experimental results (R(2)>0.8).
The capabilities of chitosan and chitosan-EGDE (ethylene glycol diglycidyl ether) beads for removing Acid Red 37 (AR 37) and Acid Blue 25 (AB 25) from aqueous solution were examined. Chitosan beads were cross-linked with EGDE to enhance its chemical resistance and mechanical strength. Experiments were performed as a function of pH, agitation period and concentration of AR 37 and AB 25. It was shown that the adsorption capacities of chitosan for both acid dyes were comparatively higher than those of chitosan-EGDE. This is mainly because cross-linking using EGDE reduces the major adsorption sites -NH3+ on chitosan. Langmuir isotherm model showed the best conformity compared to Freundlich and BET. The kinetic experimental data agreed very well to the pseudo second-order kinetic model. The desorption study revealed that after three cycles of adsorption and desorption by NaOH and HCl, both adsorbents retained their promising adsorption abilities. FT-IR analysis proved that the adsorption of acid dyes onto chitosan-based adsorbents was a physical adsorption. Results also showed that chitosan and chitosan-EGDE beads were favourable adsorbers and could be employed as low-cost alternatives for the removal of acid dyes in wastewater treatment.