Equilibrium and kinetics studies for adsorption of direct blue 71 from aqueous solution by wheat shells

This paper deals with the application of wheat shells (WS), an agricultural by-product, for the removal of direct blue 71 (DR) from aqueous solution. The characteristics of WS surface, such as surface area, Bohem titration and scanning electron microscopy (SEM) were obtained. The removal of direct blue 71 onto WS from aqueous solution was investigated by using parameters, such as pH, temperature, adsorbent dose, contact time and initial concentration. The adsorption process attains equilibrium within 36 h. The extent of dye removal decreased with increasing adsorbent dosage and also increased with increasing contact time, temperature, in solution concentration. Optimum pH value for dye adsorption was determined between 6 and 8. The experimental data were analysed by the Langmuir and Freundlich models of adsorption. It was found that the Langmuir equation fit better than the Freundlich equation. Maximum adsorption capacity (Q(m)) was calculated as at different temperatures (293, 303 and 313 K) 40.82, 45.66 and 46.30 mgg(-1), respectively. In addition, the adsorption data obtained at different temperatures of DR by WS were applied to pseudo first-order, pseudo second-order and Weber-Morris equations, and the rate constants of first-order adsorption (k(1)), the rate constants of second-order adsorption (k(2)) and intraparticle diffusion rate constants (k(3)) at these temperatures were calculated, respectively. The rates of adsorption were found to conform to pseudo second-order kinetics with good correlation (R(2)>or=0.9904). Also, free energy of adsorption (DeltaG degrees), enthalpy (DeltaH degrees), and entropy (DeltaS degrees) changes were determined to predict the nature of adsorption. Furthermore, the results indicate that WS could be employed as a low-cost alternative to other adsorbents in the removal of direct blue 71 from aqueous solution.     

Sorption of reactive dye from aqueous solution on biomass fly ash

This study investigates the adsorption behavior of Reactive Black 5 (RB) and Reactive Yellow 176 (RY) from aqueous solution on coal fly ash (FA-CO), HCl-treated coal fly ash (TFA-HCl), and biomass fly ash (FA-BM). In preliminary study, the FA-BM showed the greatest dye adsorption capacity of both dyes, compared to FA-CO and TFA-HCl. Hence only for the FA-BM, the effects of various experiment parameters (e.g. solution pH, ionic strength, initial dye concentration, contact time) were spectrophotometrically determined. At the final pH of 8.1-8.5, the adsorption capacity of both dyes on the FA-BM was maximum and decreased above or below this pH. A positive effect of salt addition on the dye adsorption capacity was observed. The adsorption capacity of dye on the FA-BM increased with increasing C0. The equilibrium data of both dyes on the FA-BM were fitted to both Langmuir and Freundlich isotherms, but the experimental data of the RB was found to be little better fitted by the Langmuir model. The sorption data was good fit with the pseudo-second-order kinetic model. These results indicate that biomass fly ash is an interesting alternative for dye removal from the wastewater.     

Removal of Acid Orange 7 and Remazol Black 5 reactive dyes from aqueous solutions using a novel biosorbent

This study utilizes canola stalks (CS), an agro-residue, as a biosorbent to remove two different dyes, namely Acid Orange 7 (AO7) and Remozol Black 5 (RB5) from aqueous solutions. The effects of operational parameters on the efficiency of dye removal including pH, adsorbent mass, initial dye concentration and contact time have been investigated. For both tested dyes, the maximum absorption capacity was reached at initial pH 2.5 and 120 min contact time. The results showed that the absorption of both dyes depended on the pH of milieu, temperature, dye and CS concentrations. Freundlich and Langmuir models were used to analyze the obtained experimental data. The isotherms are found to be linear over the entire concentration range for both dyes. The highest value of linear correlation coefficients for AO7 (0.9926) and RB5 (0.9882) showed that the Langmuir is the best model to fit the experimental data. Kinetic study of absorption was done applying the pseudo first-order and the pseudo second-order equations. Absorption of both dyes could be well predicted by the pseudo second-order equation. The obtained results are very promising since: (i) high levels of dye removal (> 90%) were achieved with low contact times biosorbent/dye (less than 20 min contact); and (ii) the whole CS can be successfully used as biosorbent of AO7 and RB5 dyes in aqueous solution without needing any chemical modifications.     

Efficacy of modified distillation sludge of rose (Rosa centifolia) petals for lead(II) and zinc(II) removal from aqueous solutions

Removal of lead(II) and zinc(II) from aqueous solutions was studied using chemically modified distillation sludge of rose (Rosa centifolia) petals by pretreatment with NaOH, Ca(OH)(2), Al(OH)(3), C(6)H(6), C(6)H(5)CHO and HgCl(2). The adsorption capacity of biomass was found to be significantly improved. NaOH pretreated biomass showed remarkable increase in sorption capacity. Maximum adsorption of both metal ions was observed at pH 5. When Freundlich and Langmuir isotherms were tested, the latter had a better fit with the experimental data. The overall adsorption process was best described by pseudo second order kinetics. The thermodynamic assessment of the metal ion-Rosa centifolia biomass system indicated the feasibility and spontaneous nature of the process and DeltaG degrees was evaluated as ranging from -26.9501 to -31.652 KJmol(-1) and -24.1905 to -29.8923KJmol(-1) for lead(II) and zinc(II) sorption, respectively, in the concentration range 10-640mgL(-1). Distribution coefficient (D) showed that the concentration of metal ions at the sorbent-water interface is higher than the concentration in the continuous aqueous phase. Maximum adsorption capacity of biomass tends to be in the order Pb(II) (87.74mgg(-1))>Zn(II) (73.8mgg(-1)) by NaOH pretreated biomass.     

Dye adsorption on unburned carbon: kinetics and equilibrium

Unburned carbon in fly ash is an important by-product from coal combustion. In this investigation, unburned carbon has been separated from fly ash and been employed as a low cost adsorbent for a basic dye adsorption (Rhodamine B) in aqueous solution. Adsorption isotherm and kinetics of adsorption have been investigated using batch experiments. It is found that dye adsorption capacity depends on initial concentration, pH of solution, and temperature. The adsorption isotherm can be described by Langmuir model and the adsorption capacity of Rhodamine B at 30, 40, and 50 degrees C can reach 9.7 x 10(-5), 1.14 x 10(-4), and 1.5 x 10(-4)mol g(-1), respectively. The pseudo first- and second-order kinetic models have been employed to fit the dynamic adsorption. It is found that the dynamic adsorption follows the pseudo second-order model. Thermodynamic calculations indicate that the adsorption is endothermic reaction with DeltaH degrees at 25 kJ mol(-1).     

Removal of direct blue-86 from aqueous solution by new activated carbon developed from orange peel

The use of low-cost, easy obtained, high efficiency and eco-friendly adsorbents has been investigated as an ideal alternative to the current expensive methods of removing dyes from wastewater. This study investigates the potential use of activated carbon prepared from orange peel for the removal of direct blue-86 (DB-86) (Direct Fast Turquoise Blue GL) dye from simulated wastewater. The effects of different system variables, adsorbent dosage, initial dye concentration, pH and contact time were studied. The results showed that as the amount of the adsorbent increased, the percentage of dye removal increased accordingly. Optimum pH value for dye adsorption was determined as approximately 2.0. Maximum dye was sequestered within 30min after the beginning for every experiment. The adsorption of direct blue-86 followed a pseudo-second-order rate equation and fit well Langmuir, Tempkin and Dubinin-Radushkevich (D-R) equations better than Freundlich and Redlich-Peterson equations. The maximum removal of direct blue-86 was obtained at pH 2 as 92% for adsorbent dose of 6gL(-1) and 100mgL(-1) initial dye concentration at room temperature. The maximum adsorption capacity obtained from Langmuir equation was 33.78mgg(-1). Furthermore, adsorption kinetics of DB-86 was studied and the rate of adsorption was found to conform to pseudo-second-order kinetics with a good correlation (R2>0.99) with intraparticle diffusion as one of the rate determining steps. Activated carbon developed from orange peel can be attractive options for dye removal from diluted industrial effluents since test reaction made on simulated dyeing wastewater show better removal percentage of DB-86.     

Removal of cationic dyes from aqueous solution using an anionic poly-gamma-glutamic acid-based adsorbent

Natural polymeric materials are gaining interest for application as adsorbents in wastewater treatment due to their biodegradable and non-toxic nature. In this study, a biopolymer, poly-gamma-glutamic acid (gamma-PGA) derived from bacterial sources (Bacillus species) was evaluated for its efficiency in removing basic dyes from aqueous solution. Sorption studies under batch mode were conducted using C.I. Basic blue 9 (BB9) and C.I. Basic green 4 (BG4) as test dyes. Equilibrium process conformed well with the Redlich-Peterson isotherm equation and the monolayer sorption capacity obtained from the Langmuir model was 352.76 and 293.32mg/g for BB9 and BG4 dyes, respectively. The kinetic studies of dye sorption on gamma-PGA gave high coefficients of determination (>0.98) for a pseudo second-order equation. An ion-exchange model, which assumes adsorption as a chemical phenomenon, was also found to fit the kinetic data precisely. The dye sorption largely depended on the initial pH of the solution with maximum uptake occurring at pH above 5. About 98% of the dye adsorbed on gamma-PGA could be recovered at pH 1, which facilitates the reuse of spent gamma-PGA.     

Treatment of wastewater containing toxic chromium using new activated carbon developed from date palm seed

The use of a new activated carbon developed from date palm seed wastes, generated in the jam industry, for removing toxic chromium from aqueous solution has been investigated. The activated carbon has been achieved from date palm seed by dehydrating methods using concentrated sulfuric acid. The batch experiments were conducted to determine the adsorption capacity of the biomass. The effect of initial metal concentration (25-125mgl(-1)), pH, contact time, and concentration of date palm seed carbon have been studied at room temperature. A strong dependence of the adsorption capacity on pH was observed, the capacity increase as pH value decrease and the optimum pH value is pH 1.0. Kinetics and adsorption equilibrium were studied at different sorbent doses. The adsorption process was fast and the equilibrium was reached within 180min. The maximum removal was 100% for 75mgl(-1) of Cr(+ concentration on 4gl(-1) carbon concentration and the maximum adsorption capacity was 120.48mgg(-1). The kinetic data were analyzed using various kinetic models - pseudo-first order equation, pseudo-second order equation, Elovich equation and intraparticle diffusion equation - and the equilibrium data were tested using several isotherm models, Langmuir, Freundlich, Koble-Corrigan, Redlich-Peterson, Tempkin, Dubinin-Radushkevich and Generalized isotherm equations. The Elovich equation and pseudo-second order equation provide the greatest accuracy for the kinetic data and Koble-Corrigan and Langmuir models the closest fit for the equilibrium data. Activation energy of sorption has also been evaluated as 0.115 and 0.229kJmol(-1).     

Equilibrium and kinetic modeling of adsorption of reactive dye on cross-linked chitosan beads

The adsorption of reactive dye (Reactive Red 189) from aqueous solutions on cross-linked chitosan beads was studied in a batch system. The equilibrium isotherms at different particle sizes (2.3-2.5, 2.5-2.7 and 3.5-3.8mm) and the kinetics of adsorption with respect to the initial dye concentration (4320, 5760 and 7286 g/m(3)), temperature (30, 40 and 50 degrees C), pH (1.0, 3.0, 6.0 and 9.0), and cross-linking ratio (cross-linking agent/chitosan weight ratio: 0.2, 0.5, 0.7 and 1.0) were investigated. Langmuir and Freundlich adsorption models were applied to describe the experimental isotherms and isotherm constants. Equilibrium data fitted very well to the Langmuir model in the entire saturation concentration range (0-1800 g/m(3)). The maximum monolayer adsorption capacities obtained from the Langmuir model are very large, which are 1936, 1686 and 1642 g/kg for small, mediumand large particle sizes, respectively, at pH 3.0, 30 degrees C, and the cross-linking ratio of 0.2. The pseudo first- and second-order kinetic models were used to describe the kinetic data, and the rate constants were evaluated. The experimental data fitted well to the second-order kinetic model, which indicates that the chemical sorption is the rate-limiting step, instead of mass transfer. The initial dye concentration and the solution pH both significantly affect the adsorption capacity, but the temperature and the cross-linking ratio are relatively minor factors. An increase in initial dye concentration results in the increase of adsorption capacity, which also increases with decreasing pH. The activation energy is 43.0 kJ/mol for the adsorption of the dye on the cross-linked chitosan beads at pH 3.0 and initial dye concentration 3768 g/m(3).     

Adsorption of Reactive Red 141 from wastewater onto modified chitin

This research involved the adsorption of synthetic reactive dye wastewater (SRDW) by chitin modified by sodium hypochlorite and original chitin in batch experiments. The comparison of maximum adsorption capacity used the Langmuir model to describe SRDW adsorption onto chitin and modified chitin under a system pH of 11.0. Maximum dye adsorption by chitin increased from 133mgg(-1) to 167mgg(-1) at temperatures of 30-60 degrees C, respectively. For modified chitin, the capacity decreased from 124mgg(-1) to 59mgg(-1) when the temperature increased from 30 degrees C to 60 degrees C, respectively. Both Na(2)SO(4) and Na(2)CO(3) increased in dye adsorption. The spectra of attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectrometry confirmed the hydroxyl groups as functional groups of modified chitin, which affected the modification and the SRDW adsorption. The adsorbed dyes were eluted by distilled water and 1M NaOH to confirm the dye adsorption mechanism. Total elution of modified chitin and chitin were 92.76% and 55.29%, respectively. Although modified chitin had a maximum adsorption capacity less than chitin, elution of the dye from modified chitin was easier than chitin. Therefore, modified chitin could be suitable in a column system for dye pre-concentration as well as wastewater minimisation. In addition, the column study showed that modified chitin could be used for more than four cycles of adsorption and elution by distilled water.     

Chromium(VI) adsorption from aqueous solution by Hevea Brasilinesis sawdust activated carbon

Adsorption capacity of Cr(VI) onto Hevea Brasilinesis (Rubber wood) sawdust activated carbon was investigated in a batch system by considering the effects of various parameters like contact time, initial concentration, pH and temperature. Cr(VI) removal is pH dependent and found to be maximum at pH 2.0. Increases in adsorption capacity with increase in temperature indicate that the adsorption reaction is endothermic. Based on this study, the thermodynamic parameters like standard Gibb's free energy (DeltaG degrees ), standard enthalpy (DeltaH degrees ) and standard entropy (DeltaS degrees ) were evaluated. Adsorption kinetics of Cr(VI) ions onto rubber wood sawdust activated carbon were analyzed by pseudo first-order and pseudo second-order models. Pseudo second-order model was found to explain the kinetics of Cr(VI) adsorption most effectively. Intraparticle diffusion studies at different temperatures show that the mechanism of adsorption is mainly dependent on diffusion. The rate of intraparticle diffusion, film diffusion coefficient and pore diffusion coefficient at various temperatures were evaluated. The Langmuir, Freundlich and Temkin isotherm were used to describe the adsorption equilibrium studies of rubber wood sawdust activated carbon at different temperatures. Langmuir isotherm shows better fit than Freundlich and Temkin isotherm in the temperature range studied. The result shows that the rubber wood sawdust activated carbon can be efficiently used for the treatment of wastewaters containing chromium as a low cost alternative compared to commercial activated carbon and other adsorbents reported.     

Waste metal hydroxide sludge as adsorbent for a reactive dye

An industrial waste sludge mainly composed by metal hydroxides was used as a low-cost adsorbent for removing a reactive textile dye (Remazol Brilliant Blue) in solution. Characterization of this waste material included chemical composition, pH(ZPC) determination, particle size distribution, physical textural properties and metals mobility under different pH conditions. Dye adsorption equilibrium isotherms were determined at 25 and 35 degrees C and pH of 4, 7 and 10 revealing reasonably fits to Langmuir and Freundlich models. At 25 degrees C and pH 7, Langmuir fit indicates a maximum adsorption capacity of 91.0mg/g. An adsorptive ion-exchange mechanism was identified from desorption studies. Batch kinetic experiments were also conducted at different initial dye concentration, temperature, adsorbent dosage and pH. A pseudo-second-order model showed good agreement with experimental data. LDF approximation model was used to estimate homogeneous solid diffusion coefficients and the effective pore diffusivities. Additionally, a simulated real effluent containing the selected dye, salts and dyeing auxiliary chemicals, was also used in equilibrium and kinetic experiments and the adsorption performance was compared with aqueous dye solutions.     

Biosorption of 2,4-dichlorophenol from aqueous solution by Phanerochaete chrysosporium biomass: isotherms, kinetics and thermodynamics

The biosorption of 2,4-dichlorophenol (2,4-DCP) from aqueous solution on non-living mycelial pellets of Phanerochaete chrysosporium was studied with respect to pH, initial concentration of 2,4-DCP, temperature and pellet size. The fungal biomass exhibited the highest sorption capacity of 4.09 mg/g at an initial pH of 5.0, initial 2,4-DCP concentration of 50.48 mg/l, 25 degrees C and a pellet size of 1.0-1.5 mm in the investigated pH 2.0-11.0, initial concentrations of 5-50 mg/l, temperature 25-50 degrees C, and pellet size of 1.0-2.5 mm. The Freundlich model exhibited a slightly better fit to the biosorption data of 2,4-DCP than the Langmuir model. The biosorption of 2,4-DCP to biomass followed pseudo second-order adsorption kinetics. The second-order kinetic constants decreased with increasing temperature, and the apparent activation energy of biosorption was estimated to be -16.95 kJ/mol. The thermodynamic analysis indicates that the biosorption process was exothermic and that the adsorption of 2,4-DCP on P. chrysosporium might be physical in nature. Both intraparticle diffusion and kinetic resistances might affect the adsorption rate and that their relative effects varied with operation temperature in the biosorption of 2,4-DCP by mycelial pellets.     

Study of Cu(II) biosorption by dried activated sludge: effect of physico-chemical environment and kinetics study

Biosorption is a recent technology used to remove heavy metal ions from aqueous solutions. The biosorption of copper ions from aqueous solution by dried activated sludge was investigated in batch systems. Effect of solution pH, initial metal concentration and particle size range were determined. The suitable pH and temperature for studied conditions were determined as 4.0 and 20 °C, respectively. The theoretical max biosorption capacity of activated sludge was 294 mg g⁻¹ at 20 °C for <0.063 mm particle size. The equilibrium data fitted very well to both Langmuir and Freundlich isotherm models. The pseudo first and second-order kinetic models were used to describe the kinetic data. The experimental data fitted to second-order kinetic model. The particle size and initial metal concentration were effected the biosorption capacity of dried activated sludge. An increase in the initial metal concentration increases of biosorption capacity, which also increases with decreasing particle size. Dried activated sludge has different functional groups according to the FT-IR results.     

Adsorption of lead(II) ions onto 8-hydroxy quinoline-immobilized bentonite

In this study, the immobilization of 8-hydroxy quinoline onto bentonite was carried out and it was then used to investigate the adsorption behavior of lead(II) ions from aqueous solutions. The changes of the parameters of pH, contact time, initial lead(II) ions concentration and temperature were tested in the adsorption experiments. The XRD, FTIR, elemental and thermal analyses were done to observe the immobilization of 8-hydroxy quinoline onto natural bentonite. The adsorption was well described by the Langmuir adsorption isotherm model at all studied temperatures. The maximum adsorption capacity was 142.94mgg(-1) from the Langmuir isotherm model at 50 degrees C. The thermodynamic parameters implied that the adsorption process is spontaneous and endothermic. The kinetic data indicate that the adsorption fits well with the pseudo-second-order kinetic model. 8-Hydroxy quinoline-immobilized bentonite can be used as well respective adsorbent for the removal of the heavy metal pollutants according to the results.     

Adsorption of reactive dye from an aqueous solution by chitosan: isotherm, kinetic and thermodynamic analysis

The adsorption of Remazol black 13 (Reactive) dye onto chitosan in aqueous solutions was investigated. Experiments were carried out as function of contact time, initial dye concentration (100-300mg/L), particle size (0.177, 0.384, 1.651mm), pH (6.7-9.0), and temperature (30-60 degrees C). The equilibrium adsorption data of reactive dye on chitosan were analyzed by Langmuir and Freundlich models. The maximum adsorption capacity (qm) has been found to be 91.47-130.0mg/g. The amino group nature of the chitosan provided reasonable dye removal capability. The kinetics of reactive dye adsorption nicely followed the pseudo-first and second-order rate expression which demonstrates that intraparticle diffusion plays a significant role in the adsorption mechanism. Isotherms have also been used to obtain the thermodynamic parameters such as free energy, enthalpy and entropy of adsorption. The positive value of the enthalpy change (0.212kJ/mol) indicated that the adsorption is endothermic process. The results indicate that chitosan is suitable as adsorbent material for adsorption of reactive dye form aqueous solutions.     

Removal of anionic dyes from aqueous solutions by adsorption of chitosan-based semi-IPN hydrogel composites

Semi-IPN hydrogel composites for dye adsorption studies were prepared via photopolymerization of poly(ethylene glycol) (PEG) macromer and acrylamide (AAm) monomer in the presence of chitosan (CS). Swelling properties and kinetics of the hydrogel composites were investigated in aqueous solution and Acid Red 18 (AR 18) solution. The adsorption studies showed that the adsorption capacity for AR 18 increased with the increase of initial dye concentration and chitosan content in the hydrogels, but decreased with the increase of pH and ionic strength of dye solutions. Absorption kinetics of AR 18 followed pseudo second-order kinetic model at pH 2.0. The adsorption capacities for Acid Orange 7 (AO 7), Methyl Orange (MO) and Basic Violet 14 (BV 14) were also examined at pH 2.0, and the equilibrium adsorption data of AR 18, AO 7 and MO well fitted the Langmuir isotherm. The hydrogel composites could be potentially used as absorbents for anionic dye removal in wastewater treatment process.     

Removal of direct blue-106 dye from aqueous solution using new activated carbons developed from pomegranate peel: adsorption equilibrium and kinetics

The use of cheap, high efficiency and ecofriendly adsorbent has been studied as an alternative source of activated carbon for the removal of dyes from wastewater. This study investigates the use of activated carbons prepared from pomegranate peel for the removal of direct blue dye from aqueous solution. A series of experiments were conducted in a batch system to assess the effect of the system variables, i.e. initial pH, temperature, initial dye concentration adsorbent dosage and contact time. The results showed that the adsorption of direct blue dye was maximal at pH 2, as the amount of adsorbent increased, the percentage of dye removal increased accordingly but it decreased with the increase in initial dye concentration and solution temperature. The adsorption kinetics was found to follow pseudo-second-order rate kinetic model, with a good correlation (R(2)>0.99) and intra-particle diffusion as one of the rate determining steps. Langmuir, Freundlich, Temkin, Dubinin-RadushKevich (D-R) and Harkins-Jura isotherms were used to analyze the equilibrium data at different temperatures. In addition, various thermodynamic parameters, such as standard Gibbs free energy (DeltaG degrees ), standard enthalpy (DeltaH degrees ), standard entropy (DeltaS degrees ), and the activation energy (E(a)) have been calculated. The adsorption process of direct blue dye onto different activated carbons prepared from pomegranate peel was found to be spontaneous and exothermic process. The findings of this investigation suggest that the physical sorption plays a role in controlling the sorption rate.     

Adsorption of Congo red from aqueous solutions onto Ca-bentonite

The ability of Ca-bentonite to remove Congo red dye from aqueous solutions has been carried out as a function of contact time, temperature (20-50 degrees C), pH (5-10) and concentration (50-200mgL(-1)). An amount of 0.2g of Ca-bentonite could remove more than 90.0% of the dye from 100mgL(-1) Congo red dye solution for the temperature range studied here. The amount of dye adsorbed per unit weight of Ca-bentonite increased from 23.25 to 85.29mgg(-1) with increasing concentration from 50 to 200mgL(-1), but it had a little change with temperature and decreased slightly with increasing pH. The kinetics of adsorption in view of three kinetic models, i.e., the pseudo-first-order Lagergren model, the pseudo-second-order model and the intraparticle diffusion model, was discussed. The pseudo-second-order kinetic model described the adsorption of Congo red on Ca-bentonite very well. Analysis of adsorption results obtained at 20 degrees C showed that the adsorption pattern on Ca-bentonite followed the Freundlich isotherms. It was indicative of the heterogeneity of the adsorption sites on the clay particles. From thermodynamic studies, it was seen that the adsorption was spontaneous and endothermic.