Film‐surface diffusion during the adsorption of acid dyes onto activated carbon

A mass transport model has been developed and applied to the adsorption of three acid dyes onto activated carbon in three single component systems. The mass transfer model is based on two rate controlling mass transfer steps, namely external film mass transfer and homogeneous solid‐phase surface diffusion (HSD). Almost all previous film‐HSD models have been based on numerical solutions to the diffusion equation using orthogonal collocation or Crank–Nicolson finite difference solutions. However, in the present model a semi‐analytical solution to the solid surface diffusion equation is presented, yielding a sophisticated solution of the differential equations. The solutions provide a good correlation between the experimental concentration–time decay curves by incorporating the Langmuir equilibrium isotherm to describe the solid phase surface dye concentrations. However, the surface diffusivities show a dependence on the carbon particle surface coverage and these diffusivities have been correlated using a Darken relationship. Copyright © 2004 Society of Chemical Industry     

Two-resistance mass transfer models for the adsorption of dyestuffs from aqueous solutions using activated carbon

The adsorption of telon blue (acid blue 25) dye and deorlene yellow (basic yellow) dye on to carbon has been studied. A two-resistance mass transfer model has been developed based on film resistance and homogeneous solid phase diffusion. The model may be applied over a wider range of operating conditions than previous models since it has more extensive analytical components. The variables investigated were initial dye concentration and solid: liquid ratio, and the experimental and theoretical results were in good agreement. The adsorption of telon blue on to carbon has been described using an external mass transfer coefficient of 2.0 × 10⁻³ cm s⁻¹ and a homogeneous solid phase diffusion coefficient of 2.0 × 10⁻⁹ cm² s⁻¹. The adsorption of deorlene yellow has been described using an external mass transfer coefficient of 1.0 × 10⁻³ cm s⁻¹ and a homogeneous solid phase diffusion coefficient of 3.0 × 10⁻¹⁰ cm² s⁻¹.     

The Adsorption of basic dye onto silica from aqueous solution-solid diffusion model

The adsorption of Basic Blue 69 dye onto silica in a batch adsorption system has been studied. A two resistance mass transfer model has been developed based on film resistance and homogeneous solid phase diffusion. An analytical solution is presented and experimental results and theoretical data are in good agreement, for a wide range of operating conditions, using a single external mass transfer coefficient and a single effective solid diffusivity. The variables investigated are: initial dye concentration, solid/liquid ratios and adsorbent particle size range. Under constant agitation conditions almost all data can be correlated using a film mass transfer coefficient of 2.0 x 10^?4 cm sec^?1 and a diffusion coefficient of 1.2 x 10^?9 cm² sec^?1.     

Mass transfer model for the adsorption of basic dyes on woodmeal in agitated batch adsorbersStoffübergangsmodell für die Adsorption basischer Farbstoffe an Holzmehl in durchmischten,absatzweise betriebenen Adsorbern

The adsorption of three basic dyes, Basic Blue 3, Basic Blue 69 and Basic Orange 2, onto woodmeal has been studied in batch adsorbers. The effects of initial dye concentration and mass of woodmeal have been studied.A two-resistance mathematical model has been developed based on external mass transfer, pore diffusion and the assumption of an irreversible isotherm for operating conditions lying on the monolayer of observed Langmuir isotherms. The model, which has an analytical solution, predicts theoretical concentration decay curves which show good agreement with observed experimental decay curves.     

A study of adsorption behavior of 2,4-Dichlorophenoxyacetic Acid onto various GACs

Adsorption and desorption of 2,4-dichlorophenoxyacetic acid (2,4-D) onto granular activated carbon (GAC) were studied to get basic information on their removal from aqueous solution. Single species adsorption equilibria of 2,4-D dissolved in water have been measured using F400, SLS103, and WWL. Equilibrium capacity increased with decreasing pH. The magnitude of adsorption capacity of 2,4-D was the order of F400> SLS103>WWL. Kinetic parameters were measured in a batch adsorber to analyze the adsorption rate of 2,4-D. The internal diffusion coefficients were determined by comparing the experimental concentration curve with that predicted from the surface diffusion model (SDM) and Pore diffusion model (PDM). The linear driving force approximation (LDFA) model was used to simulate isothermal adsorption behaviors in a fixed bed adsorber and successfully simulated experimental adsorption breakthrough behavior under various operation conditions. This paper is dedicated to Professor Dong Sup Doh on the occasion of his retirement from Korea University.     

Pore diffusion model for dye adsorption onto peat in batch adsorbers

The adsorption of Acid Blue 25, Basic Blue 69, Basic Orange 2, and Disperse Blue 7, on peat has been studied using a series of batch adsorption runs. A model has been developed based on external mass transfer and internal diffusion to explain the concentration decay curves. Two system variables, namely, adsorbate concentration and adsorbent concentration, have been studied. The paper presents a rapid analytical solution for predicting the concentration decay curve in batch adsorbers using peat as a cheap adsorbent to remove various classes of dyestuffs from aqueous solution. The analytical solution depends on the assumption of a psdeudo-irreversible isotherm and that the internal diffusion process occurs via a pore diffusion mechanism. External mass transfer coefficients and internal diffusivities have been estimated for the various systems.     

Kinetic modeling of pentachlorophenol adsorption from aqueous solution on activated carbon fibers

The adsorption equilibrium data of pentachlorophenol (PCP) onto activated carbon fiber (ACF) in felt form were obtained in a batch adsorber at T = 25 °C and pH 12 and the Langmuir isotherm fitted reasonably well with the experimental data. The rate of adsorption of PCP on ACF was investigated in this work and the experimental concentration decay data were obtained in a differential column batch adsorber. The overall rate of adsorption of PCP was interpreted by a diffusional model that takes into account the external mass transport and intrafiber diffusion. The experimental concentration decay can be described quite well with the diffusional model if the overall rate of adsorption is mainly controlled by intrafiber diffusion and the external mass transport is not important to the overall rate of adsorption. Moreover, intrafiber diffusion was significantly affected by restricted diffusion since the molecular diameter of the PCP was closed to 55% of the average pore diameter. The effect of restricted diffusion was estimated using correlations reported in the literature. The molecules of PCP adsorbed on the surface of the pore also hindered the diffusion of PCP molecules inside the pores.     

Acid Black 172 dye adsorption from aqueous solution by hydroxyapatite as low-cost adsorbent

The Acid Black 172 dye adsorption on the uncalcined hydroxyapatite nanopowder was investigated. The hydroxyapatite prepared by wet coprecipitation method has high specific surface area of 325 m²/g and crystal sizes smaller than 70 nm. The batch adsorption experiments revealed that under the optimum adsorption conditions (pH 3, hydroxyapatite dosage 2 g/L, initial dye concentration 400 mg/L and temperature 20 °C) the dye removal efficiency was 95.78% after 1 h of adsorption. The adsorption kinetics was best described by the pseudo-second order kinetic model. The intraparticle diffusion model shows that intraparticle diffusion is not the sole rate-limiting step; the mass transfer also influences the adsorption process in its initial period. The Langmuir isotherm model best represented the equilibrium experimental data, and the maximum adsorption capacity (q _m ) was 312.5 mg/g.     

Adsorption of acid dye onto woodmeal by solid diffusional mass transfer

The adsorption of Telon Blue (Acid Blue 25) dye onto wood has been studied using an agitated batch adsorber. The variables studied include agitation, initial dye concentration, wood mass, wood particle size and dye solution temperature. Isotherms were measured and the isotherm parameters were determined.

A mathematical model has been developed using the basis of the model proposed by Mathews and Weber Jr. This model is based on external mass transfer and solid-phase diffusion, and has been used to generate theoretical concentration—time decay curves. The results of the model were adjusted to the experimental data using a ‘best fit’ approach. The external mass transfer coefficient was found to vary with the degree of agitation, and consequently all other variables were considered at a constant agitation speed of 400 rev min⁻¹. A good agreement between the theoretical generated and the experimental concentration—time decay curves was achieved using a constant external mass transfer coefficient, 0.30 × 10⁻³ cm ⁻¹, and a constant solid-phase diffusivity, 0.200 × 10⁻⁸ cm² s⁻¹, for varying initial dye concentrations as well as wood mass. In experiments where the particle diameter was varied, a constant external mass transfer coefficient was sufficient to describe the system, but a decreasing diffusivity was required with increasing particle size. To simulate the effect of varying temperature, both external mass transfer coefficient and diffusivity were varied.     

Contact time optimization of two-stage batch adsorber systems using the modified film-pore diffusion model

In this paper, a contact time optimization methodology of a two-stage batch adsorber system taking minimum contact time as the objective function has been developed. The initial concentration of the second stage unit and adsorbent weight have been designated as variables and these have been studied under two conditions of the equilibrium solid-phase concentration, q_e, namely, when q_e is a variable and when q_e is a constant. Contact time optimization of a two-stage batch adsorber system has been demonstrated at three different conditions/cases for the adsorption of phenol on activated carbon and the adsorption of Astrazone Blue dye (Basic Blue 69) onto silica. A new concept of “pinch point” for the optimum design of batch adsorber system has been proposed. The optimization solutions show that there is a significant difference for minimum contact time at different process conditions.The diffusion mass transport model used to predict the concentration-time decay curve is a film-pore diffusion model. An analytical solution has been used for simplicity which assumes a constant capacity pseudo-irreversible isotherm.     

Adsorption of methylene blue from aqueous solution by kaolin and zeolite

In the present study, kaolin and zeolite have been utilized as adsorbents for the removal of a cationic dye, methylene blue (MB), from aqueous solution within a batch process. Characterization of the two adsorbents was carried out by nitrogen adsorption–desorption experiments (specific surface area measurements by the BET method). The effects of various parameters such as initial MB concentration, contact time, adsorbent concentration, stirring speed, solution pH and salt concentration were examined and optimal experimental conditions were determined. The kinetic data were analyzed using pseudo-first-order and pseudo-second-order models. The mass transfer model in terms of interlayer diffusion was applied to the experimental data to examine the mechanisms of the rate controlling step. In order to determine the best-fit-isotherm, the experimental data were analyzed by the Freundlich, Temkin, and Dubinin–Radushkevich equation which are found to best represent the equilibrium data for kaolin and zeolite. The values of activation parameters such as free energy (ΔG), enthalpy (ΔH) and entropy (ΔS) were also determined. The results indicate that kaolin and zeolite could be interesting alternative materials with respect to more costly adsorbents used for dye removal.     

Modelling of heavy metal adsorption into activated carbon from apricot stones in fluidized bed

The purpose of the present study is to investigate the behaviour of activated carbon from apricot stones (ACAS) in a closed circuit fluidized bed (CCFB) for removal of Pb, Cu, Cd and Zn ions from aqueous solution. The expansion characteristics of the bed are studied. A homogeneous solid phase diffusion model was used to describe the mass transfer inside the adsorbent particles. A piston-dispersion model was applied for the liquid phase in the bed and compared to the calculations, assuming perfect mixing conditions in the whole CCFB adsorber. The close correspondence between the experimentally determined adsorption in batch and fluidized bed operation modes support the observation that the CCFB can be described by a stirred batch adsorption model. The concentration profile at the bed exit is satisfactorily predicted by the model, thus confirming the equilibrium and kinetic parameters, determined from the laboratory batch adsorption runs.     

Adsorption of pollutants on to activated carbon in fixed beds

The adsorption of certain pollutants, namely phenol, p-chlorophenol, sodium dodecyl sulphate and mercuric ions, on to activated carbon has been studied using fixed bed systems. There are three main methods of contacting in solid/liquid adsorption systems, namely batch, fixed bed and fluidized bed systems. In fixed bed adsorption the adsorption rate is determined on the basis of adsorption equilibrium (unfavourable, linear, favourable or completely irreversible) and the controlling mechanism (external film mass transport, internal pore diffusion, internal solid phase diffusion or longitudinal diffusion). One or more of the previous transport mechanisms may be rate controlling depending on the solute-adsorbent system. For an adsorbent like activated carbon which is highly porous both external transport and pore diffusion will be very important. An adsorption model, based on external mass transport and internal pore diffusion, has been applied to the systems to predict theoretical breakthrough curves. These curves have then been compared with experimental data and using a ‘best fit’ technique, an effective pore diffusion coefficient can be determined for each sorbate–carbon system.     

Least squares estimation of kinetic parameters in batch adsorption of phenol with confidence interval analysis

Adsorption kinetics of phenol on granular coconut shell activated carbon and granular coal based activated carbon was investigated by the model of homogeneous surface diffusion plus external film mass transfer with the stirred batch adsorber. The model was solved numerically by finite element and the parameter estimation was performed with the nonlinear least squares method. Through the confidence interval analysis and evaluation of the error sum of squares, higher precision of the parameter estimates can be obtained by combining more decay curves; the decay curves with the different initial solution concentrations and adsorbent dosages can be well represented with identical film mass transfer coefficient and surface diffusivity, and the effect of surface adsorption coverage on the surface diffusivity is negligible in the adsorption systems. The values of the film mass transfer coefficient and surface diffusivity are in the order of magnitude 10^?5 and 10^?12, respectively.     

Adsorption characteristics of 2,4-dichlorophenoxyacetic acid and 2,4-dinitrophenol in a fixed bed adsorber

The influence of temperature and initial pH of aqueous solution on adsorption has been discussed in detail using the Sips equation. Single-component adsorption equilibria of 2,4-D and 2,4-DNP dissolved in water have been measured for three kinds of GACs (F400, SLS103, and WWL). For 2,4-D, the magnitude of adsorption capacity was in the order of F400>SLS103>WWL, and that for 2,4-DNP was SLS103>F400>WWL. These results may come from the effects of the pore size distribution, surface area, surface properties, and difference in adsorption affinity. Kinetic parameters were measured in a batch adsorber to analyze the adsorption rates of 2,4-D and 2,4-DNP. The internal diffusion coefficients were determined by comparing the experimental concentration curves with those predicted from surface diffusion model (SDM) and pore diffusion model (PDM). The linear driving force approximation (LDFA) model was used to simulate isothermal adsorption behavior in a fixed bed adsorber and successfully simulated experimental adsorption breakthrough behavior under various operation conditions. Efficiency of desorption for 2,4-D and 2,4-DNP was about 80% using distilled water at pH of 6.     

Fixed bed modelling for acid dye adsorption onto activated carbon

The adsorption of three separate acid dyes onto activated carbon has been studied using fixed bed adsorption. A film‐pore diffusion model was developed and applied to the experimental breakthrough curve data. A sensitivity analysis showed that pore diffusion was the dominant mass transport mechanism. Pore diffusion coefficients were determined by an optimization routine with a minimization of the sum of errors squared. The external mass transfer coefficients were sensitive to the external fluid dynamic parameters, such as liquid flow rate and mean particle size. These fluid dynamic parameters did not affect the effective diffusion coefficient. The effective diffusion coefficient was not affected by changes in the fluid dynamic parameters but did change with differing initial dye concentrations. This may be due to a contribution from surface diffusion to the effective diffusion coefficient. Copyright © 2003 Society of Chemical Industry     

Removal of methylene blue dye from aqueous solution by activated carbon prepared from cashew nut shell as a new low-cost adsorbent

Methylene blue dye was adsorbed on an adsorbent prepared from cashew nut shell. A batch adsorption study was carried out with variable adsorbent amount, initial dye concentration, contact time and pH. Studies showed that the pH of aqueous solutions affected dye removal as a result of removal efficiency increased with increasing solution pH. The experimental data were analyzed by the Langmuir, Freundlich, Redlich-Peterson, Koble-Corrigan, Toth, Temkin, Sips and Dubinin-Radushkevich models of adsorption using MATLAB 7.1. The experimental data yielded excellent fits within the following isotherm order: Redlich-Peterson>Toth>Sips>Koble-Corrigan>Langmuir>Temkin>Dubinin-Radushkevich>Freundlich, based on its correlation coefficient values. Three simplified kinetic models including a pseudofirst-order, pseudo-second-order and intraparticle diffusion equations were selected to follow the adsorption process. It was shown that the adsorption of methylene blue could be described by the pseudo-second-order equation. The results indicate that cashew nut shell activated carbon could be employed as a low cost alternative to commercial activated carbon in the removal of dyes from wastewater.     

Adsorption and mass transfer characteristics of metsulfuron-methyl on activated carbon

Removal of a synthetic organic herbicide, metsulfuron-methyl (MSM), from aqueous solutions has been studied in batch and stirred tank adsorbers charged with granular activated carbon particles. Two kinetic parameters, film mass transfer and intraparticle diffusion coefficients, were estimated from concentration decay curves obtained in the batch adsorber. Based on these kinetic parameters, the concentration profiles measured in the stirred tank adsorber were simulated. From experimental and simulated results, it was proven that the film mass transfer at external surfaces of carbon particles controls the overall mass transfer, particularly at low mixing (rotation of blades), during the adsorption of MSM by granular activated carbon particles.     

Removal of basic yellow cationic dye by an aqueous dispersion of Moroccan stevensite

The aim of this study was to investigate the adsorption of basic yellow, a cationic dye, from aqueous solution by natural stevensite, with 104 m²/g of specific surface area. The kinetics and the effects of several experimental parameters such as the pH of the solution, adsorbent dose and initial dye concentration were researched using a batch adsorption technique. The results showed that an alkaline pH favoured basic yellow adsorption and the adsorption reached equilibrium in about 20 min. It was concluded that the adsorption process was governed by the electrostatic interaction. The isothermal data were fitted by means of Langmuir and Freundlich equations, and a monolayer adsorption capacity of 454.54 mg/g was calculated. Finally, a good agreement was found between the pseudo-second order model and the experimental data. A high maximum adsorption capacity was obtained (526 mg/g) and a maximum surface density of ~ 9 dye molecules/nm² was estimated, involving a columnar arrangement of the adsorbed molecules.