Contact time optimization of two-stage batch adsorber design using second-order kinetic model for the adsorption of phosphate onto alunite

The adsorption of phosphate onto alunite in a batch adsorber has been studied. Four kinetic models including pseudo first- and second-order equation, intraparticle diffusion equation and the Elovich equation were selected to follow the adsorption process. Kinetic parameters, rate constants, equilibrium adsorption capacities and related correlation coefficients, for each kinetic model were calculated and discussed. It was shown that the adsorption of phosphate onto alunite could be described by the pseudo second-order equation. Adsorption of phosphate onto alunite followed the Langmuir isotherm. A model has been used for the design of a two-stage batch adsorber based on pseudo second-order adsorption kinetics. The model has been optimized with respect to operating time in order to minimize total operating time to achieve a specified amount of phosphate removal using a fixed mass of adsorbent. The results of two-stage batch adsorber design studies showed that the required times for specified amounts of phosphate removal significantly decreased. It is particularly suitable for low-cost adsorbents/adsorption systems when minimising operating time is a major operational and design criterion, such as, for highly congested industrial sites in which significant volume of effluent need to be treated in the minimum amount of time.     

Comparison of the efficiency of palladium and silver nanoparticles loaded on activated carbon and zinc oxide nanorods loaded on activated carbon as new adsorbents for removal of Congo red from aqueous solution: Kinetic and isotherm study

The adsorption of Congo red (CR) into three new adsorbents including Palladium and silver nanoparticles loaded on activated carbon (Pd NPs-AC, Ag NPs-AC) and zinc oxide nanorods loaded on activated carbon (ZnO-NRs-AC) in a batch method has been studied following the optimization of effective variables including pH, amount of adsorbents and time. The experimental data was fitted to conventional kinetic models including the pseudo first-order and second-order Elovich and intraparticle diffusion model and based on calculated respective parameters such as rate constants, equilibrium adsorption capacities and correlation coefficients. It was found that for all adsorbents the removal process follows the pseudo second other kinetic model with involvement of interparticle diffusion model. The experimental isotherm data were analyzed using the Langmuir, Freundlich, Tempkin and Dubinin and Radushkevich equations and it was found for all adsorbents that the removal process followed the Langmuir isotherm.     

Adsorption of phenol by MMT-CTAB and WPT-CTAB: Equilibrium,kinetic, and thermodynamic study

In this study, the phenol adsorption capacity of cetyltrimethylammonium bromide modified clays (MMT-CTAB) and cetyltrimethylammonium bromide modified pulp tea (WPT-CTAB) were studied. In batch adsorption experiments performed with MMT-CTAB, the effects of parameters such contact time, phenol concentration, pH of solution and adsorbent dosage were investigated. The effect of temperature on phenol adsorption onto MMT-CTAB and WPT-CTAB was examined; equilibrium and thermodynamic studies were completed. The highest phenol removal was found at pH 4.0 for MMT-CTAB and WPT-CTAB. To analyze the kinetics of phenol adsorption onto MMT-CTAB, the pseudo first-order and pseudo second-order kinetic models were applied. The kinetic data fitted better to the pseudo second-order model than the pseudo first-order kinetic model for MMT-CTAB. The characterization of adsorbents in phenol adsorption was clarified with the FTIR technique. Thermodynamic parameters such as ΔH°, ΔS° and ΔG° were calculated for each adsorption process. The adsorption process was found to be exothermic and spontaneous for phenol adsorption by MMT-CTAB and WPT-CTAB. The results were analyzed with the Langmuir, Freundlich, Temkin and Harkins–Jura equations using linearized correlation coefficients at different temperatures. The Langmuir equation was found to best represent the equilibrium data for phenol adsorption onto MMT-CTAB and WPT-CTAB.     

Sorption of SPADNS azo dye on polystyrene anion exchangers: Equilibrium and kinetic studies

The sorption of SPANDS from aqueous solution onto the macroporous polystyrene anion exchangers of weakly basic Amberlyst A-21 and strongly basic Amberlyst A-29 in a batch method was studied. The effect of initial dye concentration and phase contact time was considered to evaluate the sorption capacity of anion exchangers. Equilibrium data were attempted by various adsorption isotherms including the Langmuir, Freundlich and Dubinin–Radushkevich (D–R) models. A comparison of kinetic models applied to the adsorption rate constants and equilibrium sorption capacities was made for the Lagergren first-order, pseudo second-order and Morris–Weber intraparticle diffusion kinetic models. The results showed that the adsorption isotherm is in the good agreement with the Langmuir equation and that the adsorption kinetics of SPADNS on both anion exchangers can be best described by the pseudo second-order model.     

Equilibrium, kinetics and mechanism modeling and simulation of basic and acid dyes sorption onto jute fiber carbon: Eosin yellow, malachite green and crystal violet single component systems

Batch experiments were carried out for the sorption of eosin yellow, malachite green and crystal violet onto jute fiber carbon (JFC). The operating variables studied are the initial dye concentration, initial solution pH, adsorbent dosage and contact time. Experimental equilibrium data were fitted to Freundlich, Langmuir and Redlich-Peterson isotherm by non-linear regression method. Langmuir isotherm was found to be the optimum isotherm for eosin yellow/JFC system and Freundlich isotherm was found to be the optimum isotherm for malachite green/JFC and crystal violet/JFC system at equilibrium conditions. The sorption capacities of eosin yellow, malachite green and crystal violet onto JFC according to Langmuir isotherm were found to 31.49 mg/g, 136.58 mg/g, 27.99 mg/g, respectively. A single stage batch adsorber was designed for the adsorption of eosin yellow, malachite green and crystal violet onto JFC based on the optimum isotherm. A pseudo second order kinetic model well represented the kinetic uptake of dyes studied onto JFC. The pseudo second order kinetic model successfully simulated the kinetics of dye uptake process. The dye sorption process involves both surface and pore diffusion with predominance of surface diffusion at earlier stages. A Boyd plot confirms the external mass transfer as the rate limiting step in the dye sorption process. The influence of initial dye concentration on the dye sorption process was represented in the form of dimensionless mass transfer numbers (Sh/Sc(0.33)) and was found to be agreeing with the expression:     

Kinetic and isotherm studies of Cu(II) biosorption onto valonia tannin resin

The biosorption of Cu(II) from aqueous solutions by valonia tannin resin was investigated as a function of particle size, initial pH, contact time and initial metal ion concentration. The aim of this study was to understand the mechanisms that govern copper removal and find a suitable equilibrium isotherm and kinetic model for the copper removal in a batch reactor. The experimental isotherm data were analysed using the Langmuir, Freundlich and Temkin equations. The equilibrium data fit well in the Langmuir isotherm. The experimental data were analysed using four sorption kinetic models - the pseudo-first- and second-order equations, the Elovich and the intraparticle diffusion model equation - to determine the best fit equation for the biosorption of copper ions onto valonia tannin resin. Results show that the pseudo-second-order equation provides the best correlation for the biosorption process, whereas the Elovich equation also fits the experimental data well.     

Adsorption of basic dyes from single and binary component systems onto bentonite: simultaneous analysis of Basic Red 46 and Basic Yellow 28 by first order derivative spectrophotometric analysis method

The present study deals with the simultaneous analysis and adsorption of Basic Yellow 28 and Basic Red 46 dyes in binary mixture onto bentonite. First order derivative spectrophotometric method was used for simultaneous analysis of BY28 and BR46 in binary mixtures. The adsorption experiments were carried out in a batch system. The mono- and multi-component Langmuir and Freundlich isotherm models were applied to experimental data and the isotherm constants were calculated for BY28 and BR46 dyes. The monolayer coverage capacities of bentonite for BY28 and BR46 dyes in single solution system were found as 256.4 mg/g and 333.3mg/g, respectively. It was observed that the equilibrium uptake amounts of BY28 and BR46 dyes in binary mixture onto bentonite decreased considerably with increasing concentrations of the other dye resulting in their antagonistic effect. The adsorption equilibrium data fitted more adequately to mono-component Langmuir isotherm model than mono-component Freundlich isotherm model, while the extended Freundlich isotherm model adequately predicted the multi-component adsorption equilibrium data at moderate ranges of concentration. Thermodynamic parameters showed that adsorption of BR46 and BY28 was endothermic and spontaneous in nature.     

Batch study of liquid-phase adsorption of methylene blue using cedar sawdust and crushed brick

This paper presents a study on the batch adsorption of basic dye, methylene blue, from aqueous solution (40 mg L(-1)) onto cedar sawdust and crushed brick in order to explore their potential use as low-cost adsorbents for wastewater dye removal. Adsorption isotherms were determined at 20 degrees C and the experimental data obtained were modelled with the Langmuir, Freundlich, Elovich and Temkin isotherm equations. Adsorption kinetic data determined at a temperature of 20 degrees C were modelled using the pseudo-first and pseudo-second-order kinetic equations, liquid-film mass transfer and intra-particle diffusion models. By considering the experimental results and adsorption models applied in this study, it can be concluded that equilibrium data were represented well by a Langmuir isotherm equation with maximum adsorption capacities of 142.36 and 96.61 mg g(-1) for cedar sawdust and crushed brick, respectively. The second-order model best describes adsorption kinetic data. Analysis of adsorption kinetic results indicated that both film- and particle-diffusion are effective adsorption mechanisms. The Influence of temperature and pH of the solution on adsorption process were also studied. The extent of the dye removal decreased with increasing the solution temperature and optimum pH value for dye adsorption was observed at pH 7 for both adsorbents. The results indicate that cedar sawdust and crushed brick can be attractive options for dye removal from dilute industrial effluents.     

Equilibrium and kinetic mechanism for Reactive Black 5 sorption onto high lime Soma fly ash

Batch adsorption studies were carried out for the sorption of C.I. Reactive Black 5, a reactive dye, onto high lime fly ash, obtained from Soma Thermal Power Plant (Turkey), to be low cost adsorbent. The effect of various experimental parameters such as contact time, adsorbent dose and initial dye concentration were investigated. Determination of the adsorption equilibrium concentrations was determined by UV-vis spectrophotometry analytical method. Equilibrium data were fitted to the Freundlich and Langmuir isotherm equations and the equilibrium data were found to be well represented by the Freundlich isotherm equation. The adsorption kinetics of C.I. Reactive Black 5 onto high lime fly ash were also studied to characterize of the surface complexation reaction. A pseudo-second-order mechanism has been developed to predict the rate constant of the adsorption, the equilibrium capacity and initial adsorption rate with the effect of initial concentration. A single-stage batch adsorber design of the adsorption of C.I. Reactive Black 5 onto high lime fly ash has been studied based on the Freundlich isotherm equation.     

Kinetics and equilibrium studies for the adsorption of Acid Red 57 from aqueous solutions onto calcined-alunite

The adsorption of Acid Red 57 (AR57) onto calcined-alunite was examined in aqueous solution in a batch system with respect to contact time, pH and temperature. The first-order, pseudo-second-order kinetic and the intraparticle diffusion models were used to describe the kinetic data and the rate constants were evaluated. The experimental data fitted very well the pseudo-second-order kinetic model and also followed the intraparticle diffusion model up to 90 min. The Langmuir and Freundlich adsorption models were applied to describe the equilibrium isotherms and the isotherm constants were also determined. The equilibrium data are successfully fitted to the Langmuir adsorption isotherm. The Langmuir isotherm constant, K(L), was used to evaluate the changes of free energy, enthalpy and entropy of adsorption for the adsorption of AR57 onto calcined-alunite. The results indicate that calcined-alunite could be employed as low-cost material for the removal of acid dyes from textile effluents.     

An adsorption study of Al(III) ions onto chitosan

The adsorption of Al(III) from aqueous solutions onto chitosan was studied in a batch system. The isotherms and the kinetics of adsorption with respect to the initial Al(III) concentration and temperature were investigated. Langmuir and Freundlich adsorption models were applied to describe the experimental isotherms. Equilibrium data fitted very well to the Langmuir model in the entire concentration range (5-40 mg/L). The negative values of free energy (DeltaG degrees ) and enthalpy (DeltaH degrees ) for the adsorption of Al(III) onto chitosan indicated that the adsorption process is a spontaneous and exothermic one. Two simplified kinetic models, based on pseudo first-order and pseudo second-order equations, were tested to describe the adsorption mechanism. The pseudo second-order kinetic model resulted in an activation energy of 56.4 kJ/mol. It is suggested that the overall rate of Al(III) ion adsorption is likely to be controlled by the chemical process. The values of the enthalpy (DeltaH(#)) and entropy (DeltaS(#)) of activation were 53.7 kJ/mol and -164.4 J/molK, respectively. The free energy of activation (DeltaG(#)) at 30 degrees C was 103.5 kJ/mol.     

Adsorption studies of a water soluble dye, Reactive Red MF-3B, using sonication-surfactant-modified attapulgite clay

The removal of water-soluble Reactive Red MF-3B from aqueous media by sonication-surfactant-modified attapulgite clay was studied in a batch system. The surfactant used was octodecyl trimethyl ammonium chloride (OTMAC). Adsorbent characterizations were investigated using X-ray diffraction, infrared spectroscopy, and surface area analysis. The effects of pH, contact time, initial solute concentration, adsorbent dose, and temperature on the adsorption of Reactive Red MF-3B onto modified clay were investigated. On the basis of kinetic studies, specific rate constants involved in the processes were calculated and second-order adsorption kinetics was observed in the case. Film diffusion was found to be the rate-limiting step. Reactive Red MF-3B adsorption was found to increase with increase temperature. The Reactive Red MF-3B equilibrium adsorption data were fitted to Freundlich and Langmuir isotherm models, the former being found to provide the better fit of the experimental data. Thermodynamic parameters were calculated. From the results it can be concluded that the surfactant-modified clay could be a good adsorbent for treating Reactive Red MF-3B-contaminated waters.     

Characteristics of equilibrium, kinetics studies for adsorption of fluoride on magnetic-chitosan particle

The magnetic-chitosan particle was prepared and characterized by the SEM, XRD, FT-IR and employed as an adsorbent for removal fluoride from the water solution in the batch system. The Langmuir isotherms, Bradley's isotherm, Freundlich isotherm and Dubinin-Kaganer-Radushkevich (DKR) isotherm were used to describe adsorption equilibrium. The kinetic process was investigated using the pseudo-first-order model, pseudo-second-order model and intra-particle diffusion model, respectively. The results show that the magnetic-chitosan particle is amorphous of irregular clumps in the surface with groups of RNH(2), RNH(3), Fe-O, etc. Bradley's equation and two-sites Langmuir isotherms were fitted well with the adsorption equilibrium data; the maximal amount of adsorption of 20.96-23.98 mg/l and free energy of 2.48 kJ/mol were obtained from the Bradley's equation, two-sites Langmuir isotherm and DKR modeling, respectively. The pseudo-second-order with the initial adsorption rate 2.08 mg/g min was suitable to describe the kinetic process of fluoride adsorption onto the adsorbent. In overall, the major mechanism of fluoride adsorption onto the heterogeneous surface of magnetic-chitosan particle was proposed in the study.     

Adsorption of reactive dye onto carbon nanotubes: equilibrium, kinetics and thermodynamics

The adsorption efficiency of carbon nanotubes for Procion Red MX-5B at various pHs and temperatures was examined. The amount adsorbed increased with the CNTs dosage; however, the adsorption capacity initially increased with the CNTs dosage (<0.25 g/l) and then declined as the CNTs dosage increased further (>0.25 g/l). The linear correlation coefficients and standard deviations of Langmuir and Freundlich isotherms were determined and the results revealed that Langmuir isotherm fitted the experimental results well. Kinetic analyses were conducted using pseudo first- and second-order models and the intraparticle diffusion model. The regression results showed that the adsorption kinetics were more accurately represented by a pseudo second-order model. Changes in the free energy of adsorption (DeltaG degrees ), enthalpy (DeltaH degrees ) and entropy (DeltaS degrees), as well as the activation energy (E(a)) were determined. DeltaH degrees and DeltaS degrees were 31.55 kJ/mol and 216.99J/molK, respectively, at pH 6.5 and 41.47 kJ/mol and 244.64 J/molK at pH 10. The activation energy was 33.35 kJ/mol at pH 6.5. DeltaH degrees, DeltaG degrees and E(a) all suggested that the adsorption of Procion Red MX-5B onto CNTs was by physisorption.     

Biosorption of Cu(II) from aqueous solutions by mimosa tannin gel

The biosorption of Cu(II) from aqueous solutions by mimosa tannin resin (MTR) was investigated as a function of particle size, initial pH, contact time and initial metal ion concentration. The aim of this study was to understand the mechanisms that govern copper removal and find a suitable equilibrium isotherm and kinetic model for the copper removal in a batch reactor. The experimental isotherm data were analysed using the Langmuir, Freundlich and Temkin equations. The equilibrium data fit well in the Langmiur isotherm. The experimental data were analysed using four sorption kinetic models -- the pseudo-first- and second-order equations, and the Elovich and the intraparticle diffusion equation -- to determine the best fit equation for the biosorption of copper ions onto mimosa tannin resin. Results show that the pseudo-second-order equation provides the best correlation for the biosorption process, whereas the Elovich equation also fits the experimental data well. Thermodynamic parameters such as the entropy change, enthalpy change and Gibb's free energy change were found out to be 153.0 J mol(-1)K(-1), 42.09 kJ mol(-1) and -2.47 kJ mol(-1), respectively.     

Immobilization of 2,2'-dipyridyl onto bentonite and its adsorption behavior of copper(II) ions

In this study, the immobilization of 2,2'-dipyridyl onto bentonite was firstly carried out and it was then used for the adsorption of copper(II) ions from aqueous solutions. The variation of the parameters of pH, contact time, initial copper(II) concentration and temperature were investigated in the adsorption experiments. The XRD, FTIR, elemental and thermal analyses were performed to observe the immobilization of 2,2'-dipyridyl onto natural bentonite. The adsorption data obtained were well described by the Langmuir adsorption isotherm model at all studied temperatures. The results indicated that the maximum adsorption capacity was 54.07 mg g(-1) from the Langmuir isotherm model at 50 degrees C. The thermodynamic parameters indicated that the adsorption process is spontaneous, endothermic and chemical in nature. The kinetic parameters of the adsorption were calculated from the experimental data. According to these parameters, the best-fit was obtained by the pseudo-second-order kinetic model. The results showed that 2,2'-dipyridyl-immobilized bentonite can be used as the effective adsorbent for the removal of heavy metal contaminants.     

Removal of malachite green by using an invasive marine alga Caulerpa racemosa var. cylindracea

The biosorption of a cationic dye, malachite green oxalate (MG) from aqueous solution onto an invasive marine alga Caulerpa racemosa var. cylindracea (CRC) was investigated at different temperatures (298, 308 and 318 K). The dye adsorption onto CRC was confirmed by FTIR analysis. Equilibrium data were analyzed using Freundlich, Langmuir and Dubinin-Radushkevich (DR) equations. All of the isotherm parameters were calculated. The Freundlich model gave a better conformity than Langmuir equation. The mean free energy values (E) from DR isotherm were also estimated. In order to clarify the sorption kinetic, the fit of pseudo-first-order kinetic model, second-order kinetic model and intraparticle diffusion model were investigated. It was obtained that the biosorption process followed the pseudo-second-order rate kinetics. From thermodynamic studies the free energy changes were found to be -7.078, -9.848 and -10.864 kJ mol(-1) for 298, 308 and 318 K, respectively. This implied the spontaneous nature of biosorption and the type of adsorption as physisorption. Activation energy value for MG sorption (E(a)) was found to be 37.14 kJ mol(-1). It could be also derived that this result supported physisorption as a type of adsorption.     

Optimization,Kinetics, and Equilibrium Studies on the Removal of Lead(II) from an Aqueous Solution Using Banana Pseudostem as an Adsorbent

Natural adsorbents such as banana pseudostem can play a vital role in the removal of heavy metal elements from wastewater. Major water resources and chemical industries have been encountering difficulties in removing heavy metal elements using available conventional methods. This work demonstrates the potential to treat various effluents utilizing natural materials. A characterization of banana pseudostem powder was performed using environmental scanning electron microscopy (ESEM) and Fourier-transform infrared (FTIR) spectroscopy before and after the adsorption of lead(II). Experiments were carried out using a batch process for the removal of lead(II) from an aqueous solution. The effects of the adsorption kinetics were studied by altering various parameters such as initial pH, adsorbent dosage, initial lead ion concentration, and contact time. The results show that the point of zero charge (PZC) for the banana pseudostem powder was achieved at a pH of 5.5. The experimental data were analyzed using isotherm and kinetic models. The adsorption of lead(II) onto banana pseudostem powder was fitted using the Langmuir adsorption isotherm. The adsorption capacity was found to be 34.21 mg·g^–1, and the pseudo second-order kinetic model showed the best fit. The optimum conditions were found using response surface methodology. The maximum removal was found to be 89%.     

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).