Adsorption kinetics and mechanism of cationic methyl violet and methylene blue dyes onto sepiolite

The use of low-cost and ecofriendly adsorbents was investigated as an ideal alternative to the current expensive methods of removing dyes from wastewater. Sepiolite was used as an adsorbent for the removal of methyl violet (MV) and methylene blue (MB) from aqueous solutions. The rate of adsorption was investigated under various parameters such as contact time, stirring speed, ionic strength, pH and temperature for the removal of these dyes. Kinetic study showed that the adsorption of dyes on sepiolite was a gradual process. Quasi-equilibrium reached within 3 h. Adsorption rate increased with the increase in ionic strength, pH and temperature. Pseudo-first-order, the Elvoich equation, pseudo-second-order, mass transfer and intra-particle diffusion models were used to fit the experimental data. The sorption kinetics of MV and MB onto sepiolite was described by the pseudo-second-order kinetic equation. Intra-particle diffusion process was identified as the main mechanism controlling the rate of the dye sorption. The diffusion coefficient, D, was found to increase when the ionic strength, pH and temperature were raised. Thermodynamic activation parameters such as ΔG¹, ΔS¹ and ΔH¹ were also calculated.     

Kinetic and equilibrium studies of Pb(II) and Cd(II) removal from aqueous solution onto colemanite ore waste

The adsorption characteristics of Pb(II) and Cd(II) onto colemanite ore waste (CW) from aqueous solution were investigated as a function of pH, adsorbent dosage, contact time, and temperature. Langmuir, Freundlich and Dubinin-Radushkevich (D-R) models were applied to describe the adsorption isotherms. Langmuir model fitted the equilibrium data better than the Freundlich isotherm. The adsorption capacity of CW was found to be 33.6 mg/g and 29.7 mg/g for Pb(II) and Cd(II) ions, respectively. Analyte ions were desorbed from CW using both 1 M HCl and 1 M HNO₃. The recovery for both metal ions was found to be higher than 95%. The mean adsorption energies evaluated using the D-R model indicated that the adsorption of Pb(II) and Cd(II) onto CW were taken place by chemisorption. The thermodynamic parameters (ΔG^o, ΔH^o and ΔS^o) showed that the adsorption of both metal ions was feasible, spontaneous and exothermic at 20-50 °C. Adsorption mechanisms were also investigated using the pseudo-first-order and pseudo-second-order kinetic models. The kinetic results showed that the adsorption of Pb(II) and Cd(II) onto CW followed well pseudo-second order kinetics.     

Adsorption behaviors of mercury from aqueous solution using sulfur-impregnated adsorbent developed from coal

Adsorption of mercury from aqueous solution on sulfur-impregnated adsorbent has been studied. Raw coal was mixed with K₂S powder, and then heated at 800-1000 °C for 30 min in nitrogen to produce sulfur-impregnated adsorbent. The sulfur content and specific surface area of the adsorbent were determined, and the ability of the adsorbent to adsorb mercury in aqueous solution was examined. With increasing temperature of sulfur-impregnation, specific surface area of the adsorbent increases, while sulfur content of the adsorbent is almost constant. The adsorbent obtained at 900 °C shows the highest and fastest adsorption of mercury from aqueous solution at 25 °C, and the elution extents of adsorbed mercury are negligible in distilled water and 10% in 0.1 M HCl solution, respectively. Adsorption kinetics was tested for pseudo-first order and pseudo-second order reactions, and the rate constants of adsorption for these kinetic models were calculated. Adsorption experiments demonstrate that the adsorption process corresponds to pseudo-second-order kinetic model than pseudo-first-order model. With increasing temperature of aqueous solution, the kinetics of adsorption becomes faster and the amount of mercury adsorbed on the adsorbent increases. The thermodynamic values, ΔG⁰, ΔH⁰ and ΔS⁰, indicated that adsorption was an endothermic and spontaneous process.     

Lead(II) Adsorption onto Sulphuric Acid Treated Cashew Nut Shell

In this study, sulphuric acid treated cashew nut shell (STCNS) was used as adsorbent for the removal of lead(II) ions from the aqueous solutions. Adsorption studies were performed by varying the solution pH, contact time, and temperature. Experimental data were analyzed by the model equations such as Langmuir, Freundlich, Temkin, and Dubinin-Radushkevich isotherms and it was found that the Freundlich isotherm model fits best with the experimental data at different temperatures studied. The maximum adsorption capacity of lead(II) on STCNS was determined as 408.6, 432, 446.3, and 480.5 mg/g, respectively, at different temperatures (30, 40, 50, and 60°C). The thermodynamic parameters (ΔG^o, ΔH^o, and ΔS^o) were calculated and the thermodynamic properties of lead(II) ions-STCNS system indicate the exothermic process. Adsorption kinetic constants were determined using pseudo-first-order, pseudo-second-order, and the Elovich kinetic models at various temperatures. The adsorption results clearly showed that the adsorption of lead(II) ions onto STCNS followed pseudo-second-order model and the adsorption was both by film diffusion and by intraparticle diffusion. A single-stage batch adsorber was designed using the Freundlich equation.     

STUDIES ON THE ADSORPTION OF FURFURAL FROM AQUEOUS SOLUTION ONTO LOW-COST BAGASSE FLY ASH

The present study deals with the sorptive removal of furfural from aqueous solution by carbon-rich bagasse fly ash (BFA). Batch studies were performed to evaluate the influence of various experimental parameters, namely, initial pH (p H ₀), adsorbent dose, contact time, initial concentration, and temperature on the removal of furfural. Optimum conditions for furfural removal were found to be p H ₀ ≈ 5.5, adsorbent dose ≈4 g/L of solution, and equilibrium time ≈4 h. The adsorption followed pseudo-second-order kinetics. The effective diffusion coefficient of furfural is of the order of 10^?13 m²/s. Equilibrium adsorption data on BFA was analyzed by Freundlich, Langmuir, Dubnin-Radushkevich, Redlich-Peterson, and Temkin isotherm equations using regression and error analysis. The Redlich-Peterson isotherm was found to best represent the data for furfural adsorption onto BFA. Adsorption of furfural on BFA is favorably influenced by a decrease in the temperature of the operation. Values of the change in entropy (ΔS ⁰) and heat of adsorption (ΔH ⁰) for furfural adsorption on BFA were negative. The high negative value of change in Gibbs free energy (ΔG ⁰) indicates the feasible and spontaneous adsorption of furfural on BFA.     

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.     

Removal of Pb(II) from aqueous solutions by adsorption onto clayey soil of Indian origin: Equilibrium, kinetic and thermodynamic profile

The feasibility of applying natural, untreated clayey soil as low-cost alternative adsorbent for Pb(II) removal from aqueous solutions was investigated with a batch experimental set-up. Experiments were carried out as a function of initial solution pH (1?C8), contact time (10?C360 min), initial Pb(II) concentration (20?C100 mg L^?1), adsorbent dose (0.5?C5 g) and temperature (303?C333 K). Adsorption equilibrium data were well described by the Langmuir isotherm with maximum adsorption capacity of 121.86 mg g^?1 at 303 K. Adsorption of Pb(II) followed pseudo-second-order kinetics. Gibbs free energy (??G⁰) was spontaneous for all interactions, and the adsorption process exhibited exothermic enthalpy values. The adsorbent was easily regenerated by using 0.1M HNO₃ solution and was reused for five sorptiondesorption cycles without any considerable loss in adsorption capacity. It could be concluded that clayey soil may be used as an inexpensive and effective adsorbent without any treatment or any other modification for the removal of Pb(II) ions from aqueous solutions.     

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.     

Removal of arsenic from aqueous solution using polyaniline/rice husk nanocomposite

The present study deals with the adsorption of arsenic ions from aqueous solution on polyaniline/rice husk (PAn/RH) nanocomposite. Batch studies were performed to evaluate the influence of various experimental parameters like pH, adsorbent dosage, contact time and the effect of temperature. Optimum conditions for arsenic removal were found to be pH 10, adsorbent dosage of 10 g/L and equilibrium time 30 minutes. Adsorption of arsenic followed pseudo-second-order kinetics. The equilibrium adsorption isotherm was better described by Freundlich adsorption isotherm model. The adsorption capacity (q _max ) of PAn/RH for arsenic ions in terms of monolayer adsorption was 34.48 mg/g. The change of entropy (ΔS⁰) and enthalpy (ΔH⁰) was estimated at −0.066 kJ/(mol K) and −22.49 kJ/mol, respectively. The negative value of the Gibbs free energy (ΔG⁰) indicates feasible and spontaneous adsorption of arsenic on PAn/RH.     

Adsorption of Congo Red dye by native amine and carboxyl modified biomass of <Emphasis Type="Italic">Funalia trogii</Emphasis>: Isotherms,kinetics and thermodynamics mechanisms

Native, iminodiacetic acid and triethylenetetraamine modified biomasses of Funalia trogii were used for removal of Congo Red dye (CRD) from aqueous medium. The native and modified fungal biomasses were characterized using ATR-FTIR, Zeta potential, contact angle studies and analytical methods. FTIR studies of the native and chemically modified adsorbent preparations show that amine, carboxyl and hydroxyl groups are involved in the adsorption of the model dye (i.e., Congo Red). The maximum adsorption of the CRD on the native, carboxyl and amine groups modified fungal biomasses was obtained at pH 5.0. The amount of adsorbed dye on the adsorbent samples increased as the initial concentration of CRD in the solution increased to 200mg/L. The adsorption capacities of native, carboxyl groups and amine modified fungal preparations were 90.4, 153.6 and 193.7mg/g dry adsorbents, respectively. The data was fitted well with the Langmuir isotherm model, and followed the pseudo-second-order equations. Thermodynamic parameters (ΔG ^o , ΔH ^o and ΔS ^o ) were also calculated. The results showed that triethylenetetraamine (TETA) modified biomass of F. trogii presented an excellent dye removal performance and can be used in various environmental applications such as various micro-pollutants removal from aqueous medium.     

Adsorption studies on the removal of Malachite Green from aqueous solutions onto halloysite nanotubes

Halloysite nanotubes (HNTs) were used as nano-adsorbents for removal of the cationic dye, Malachite Green (MG), from aqueous solutions. The adsorption of the dye was studied with batch experiments. The natural HNTs used as adsorbent in this work were initially characterized by FT-IR and TEM. The effects of adsorbent dose, initial pH, temperature, initial dye concentration and contact time were investigated. Adsorption increased with increasing adsorbent dose, initial pH, and temperature. Equilibrium was rapidly attained after 30 min of contact time. Pseudofirst-order, pseudo-second-order and intraparticle diffusion models were considered to evaluate the rate parameters. The adsorption followed pseudo-second-order kinetic model with correlation coefficients greater than 0.999. The factors controlling adsorption process were also calculated and discussed. The maximum adsorption capacity of 99.6 mg g⁻¹ of MG was achieved in pH = 9.5. Thermodynamic parameters of ΔG°, ΔH° and ΔS° indicated the adsorption process was spontaneous and endothermic.     

Adsorptive removal of cationic dye from aqueous solutions by ZnO/ZnMn2O4 nanocomposite

The ZnO/ZnMn₂O₄ nanocomposite (ZnMn) was used as adsorbent for the removal of cationic dye Basic Yellow 28 (BY28) from aqueous solutions. The adsorbent was characterized by X-ray diffraction, scanning electron microscope, TEM, Fourier transform infrared ray, BET, particle size distribution and zeta potential measurements. The adsorption parameters, such as temperature, pH and initial dye concentration, were studied. Kinetic adsorption data were analyzed using the pseudo-first-order, pseudo-second-order and intraparticle diffusion kinetic models. The Langmuir and Freundlich isotherm models were applied to fit the equilibrium data. The maximum adsorption capacity of BY28 was 48.8 mg g^?1. Various thermodynamic parameters, such as ΔG°, ΔH° and ΔS°, were calculated.     

Removal of cationic dyes from aqueous solutions by kaolin: Kinetic and equilibrium studies

Experimental investigations were carried out using commercially available kaolin to adsorb two different toxic cationic dyes namely crystal violet and brilliant green from aqueous medium. Kaolin was characterized by performing particle size distribution, BET surface area measurement and XRD analysis. The effects of initial dye concentration, contact time, adsorbent dose, stirring speed, pH, salt concentration and temperature were studied in batch mode. The extent of adsorption was strongly dependent on pH of solution. Free energy of adsorption (ΔG⁰), enthalpy (ΔH⁰) and entropy (ΔS⁰) changes were calculated. Adsorption kinetic was verified by pseudo-first-order, pseudo-second-order and intra-particle-diffusion models. The rate of adsorption of both crystal violet and brilliant green followed the pseudo-second-order model for the dye concentrations studied in the present case. The dye adsorption process was found to be external mass transfer controlled at earlier stage and intra-particle diffusion controlled at later stage. Calculated external mass transfer coefficient showed that crystal violet dye adsorbed faster than brilliant green on kaolin. Adsorption of crystal violet and brilliant green on kaolin followed the Langmuir adsorption isotherm.     

Use of CaCl2 modified bentonite for removal of Congo red dye from aqueous solutions

CaCl₂ modified bentonite (BCa²⁺), a clean and cost-effective adsorbent with a basal spacing of 15.43 Å, was prepared for the removal of Congo red dye from water. It was effective for the removal of Congo red with a high adsorption capacity, and the adsorption was favored over a broad pH range (5-10). The pseudo-second-order kinetic model provided the best correlation of the experimental data. Adsorption isotherms indicated that sorption took place at specific homogeneous sites within the adsorbent. Furthermore, BCa²⁺ showed higher sorption capacity compared with other common materials used as adsorbents for Congo red dye. The results showed that BCa²⁺ could be employed as a low-cost material for the removal of Congo red from aqueous solutions.     

Ability of iron(III)‐loaded carboxylated polyacrylamide‐grafted sawdust to remove phosphate ions from aqueous solution and fertilizer industry wastewater: Adsorption kinetics and isotherm studies

Iron(III)‐loaded carboxylated polyacrylamide‐grafted sawdust was investigated as an adsorbent for the removal of phosphate from water and wastewater. The carboxylated polyacrylamide‐grafted sawdust was prepared by graft copolymerization of acrylamide and N,N′‐methylenebisacrylamide onto sawdust in the presence of an initiator, potassium peroxydisulfate. Iron(III) was strongly attached to the carboxylic acid moiety of the adsorbent. The adsorbent material exhibits a very high adsorption potential for phosphate ions. The coordinated unsaturated sites of the iron(III) complex of polymerized sawdust were considered to be the adsorption sites for phosphate ions, the predominating species being H₂PO ions. Maximum removal of 97.6 and 90.3% with 2 g L^?1 of the adsorbent was observed at pH 2.5 for an initial phosphate concentration of 100 and 250 μmol L^?1, respectively. The adsorption process follows second‐order kinetics. Adsorption rate constants as a function of concentration and temperature and kinetic parameters, such as ΔG^±, ΔH^±, and ΔS^±, were calculated to predict the nature of adsorption. The L‐type adsorption isotherm obtained in the sorbent indicated a favorable process and fitted the Langmuir equation model well. The adsorption capacity calculated by the Langmuir adsorption isotherm gave 3.03 × 10^?4 mol g^?1 of phosphate removal at 30°C and pH 2.5. The isosteric heat of adsorption was also determined at various surface loadings of the adsorbent. The adsorption efficiency toward phosphate removal was tested using industrial wastewater. Different reagents were tested for extracting phosphate ions from the spent adsorbent. About 98.2% of phosphate can be recovered from the adsorbent using 0.1M NaOH. Alkali regeneration was tried for several cycles with a view to recover the adsorbed phosphate and also to restore the adsorbent to its original state. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2541–2553, 2002     

Phosphate Removal from Aqueous Solution Using Coir-Pith Activated Carbon

The present study deals with the removal of phosphates from aqueous solution using activated carbon developed from coir pith. Batch adsorption experiments were performed to delineate the effect of initial pH, contact time, adsorbent dose and temperature on the removal of phosphates by coir-pith activated carbon (CAC) (activated by H₂SO₄). The removal was found to be maximum in the pH range of 6–10. The kinetics of adsorption showed that the phosphate adsorption onto CAC was a gradual process with a quasi-equilibrium being attained in 3 h. The adsorption equilibrium data followed the Temkin isotherm. Thermodynamic parameters such as ΔG ^o , ΔH ^o , and ΔS ^o were evaluated by applying the Arrhenius and van't Hoff equations, and it was found that the adsorption of phosphate on CAC was spontaneous and endothermic.     

Magnetic nanocomposite of multi-walled carbon nanotube as effective adsorbent for methyl violet removal from aqueous solutions: Response surface modeling and kinetic study

Magnetic nanocomposite of multi-walled carbon nanotube (m-MWCNT) was synthesized for adsorptive removal of methyl violet (MV) from aqueous solutions. The experiments were conducted using a central composite design (CCD) with the variables of adsorbent dosage (0.4-1.2 g/L), solution pH (3-9), contact time (10-42 min) and ionic strength (0.02-0.1mol L^?1). Regression analysis showed good fit of the experimental data to a quadratic response surface model whose statistical significance was verified by analysis of variance. By applying the desirability functions, optimum conditions of the process were predicted as adsorbent dosage of 0.99g/L, pH=4.92, contact time of 40.98 minutes and ionic strength of 0.04 mol L^?1 to achieve MV removal percentage of 101.19. Experimental removal efficiency of 99.51% indicated that CCD along with the desirability functions can be effectively applied for optimizing MV removal by m-MWCNT. Based on the study, the adsorption process followed Langmuir isotherm model and pseudo-second-order kinetic model could realistically describe the dye adsorption onto m-MWCNT.     

Adsorption Characteristics of Congo Red from Aqueous Solution onto Tea Waste

The feasibility of using tea waste (TW) as a low-cost adsorbent for the adsorption of an anionic dye (Congo red) from aqueous solution has been investigated. Adsorption in a batch process was conducted to study the effect of adsorbent dosage, initial dye concentration, contact time, pH, and temperature. The experimental data were analyzed by the Langmuir, Freundlich, and Temkin models. The adsorption system was best described by the Langmuir isotherm (R ² > 0.99). Adsorption kinetics followed a pseudo-second-order model (R ² > 0.99). The effect of mechanical treatment (vibratory mill) was also studied. The experimental results showed that using this physical treatment leads to an increase in the adsorption capacity of TW from 32.26 to 43.48 mg/g. Thermodynamic analyses revealed that the adsorption of Congo red on TW was endothermic and spontaneous in nature. The results indicated that TW can be employed as a potential low-cost adsorbent for the removal of Congo red from aqueous solution.     

Artificial neural network (ANN) approach for modeling Zn(II) adsorption in batch process

Artificial neural networks (ANN) were applied to predict adsorption efficiency of peanut shells for the removal of Zn(II) ions from aqueous solutions. Effects of initial pH, Zn(II) concentrations, temperature, contact duration and adsorbent dosage were determined in batch experiments. The sorption capacities of the sorbents were predicted with the aid of equilibrium and kinetic models. The Zn(II) ions adsorption onto peanut shell was better defined by the pseudo-second-order kinetic model, for both initial pH, and temperature. The highest R² value in isotherm studies was obtained from Freundlich isotherm for the inlet concentration and from Temkin isotherm for the sorbent amount. The high R² values prove that modeling the adsorption process with ANN is a satisfactory approach. The experimental results and the predicted results by the model with the ANN were found to be highly compatible with each other.     

The adsorption behavior of cesium on poly(N-isopropylacrylamide/itaconic acid) copolymeric hydrogels

In this study, N-isopropylacrylamide/itaconic acid (NIPAAm/IA) hydrogels prepared by irradiating with γ radiation were used in experiments on cesium ion adsorption. The cesium ion adsorption capacity of the hydrogels was investigated as a function of Cs⁺ concentration, pH and temperature. The adsorption behavior of cesium was evaluated by using the radiotracer method. The adsorption isotherm models were applied to the experimental data, and it was seen that Freundlich isotherm explained the adsorption better than Langmuir isotherm. Two simplified kinetic models including pseudo-first-order and pseudo-second-order equation were selected to follow the adsorption processes. The Cs⁺ adsorption could be best described by the pseudo-first-order equation. The thermodynamic parameters including ΔG°, ΔH° and ΔS° for adsorption processes of Cs⁺ on the hydrogel were also calculated, and the negative ΔH° and ΔG° confirmed that the adsorption process was exothermic and spontaneous.