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     

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.     

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.     

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.     

Mass transport processes for the adsorption of dyestuffs onto chitin

The adsorption of four dyestuffs onto chitin has been studied. A model has been developed to explain the mass transport of dyestuffs onto chitin. The two-resistance mass transfer model is based on external film mass transfer and pore diffusion. Two solutions are presented: the first is a rapid analytical model which may be applied to adsorption systems in which the operating lines and tie lines terminate on the monolayer of the isotherm, assumed pseudo-irreversible; the second is a model which can be applied for any operating conditions but necessitates differentiation of the experimental concentration decay curve.     

Two-resistance mass transfer model for the adsorption of various dyestuffs onto chitin

The kinetics of the adsorption of various dyestuffs onto chitin have been studied. The dyestuffs used are Neoland Blue 2G, Eriochrome Flavine A, and Solophenyl Brown 3RL and a number of process variables were considered, such as adsorbent mass and dye concentration. The mass transfer model is based on the assumption of a pseudoirreversible isotherm and two resistances to mass transfer. These are external mass transfer and internal pore diffusion mass transfer. The rate of adsorption of dyestuffs onto chitin can thus be described by an external mass transfer coefficient and a pore diffusion coefficient. The external mass transfer coefficients are 5.0 × 10^?5, 5.0 × 10^?5, and 1.0 × 10^?5 m·s^?1 and the pore diffusivities are 3.0 × 10^?10 and 4.0 × 10^?11 m²·s^?1 for Neolan Blue 2G, Eriochrome Flavine A, and Solophenyl Brown 3RL, respectively.     

An evaluation of single resistance transfer models in the sorption of metal ions by peat

The adsorption of Pb²⁺, Cd²⁺, Cu²⁺, Zn²⁺ and Al³⁺ onto peat has been studied using a system of standardised batch adsorbers under equilibrium and transient rate conditions. Models based on the assumption of a single external mass transfer resistance to adsorption have been developed to attempt to predict the concentration decay curves obtained experimentally, for several variable system parameters, under transient batch conditions. In this instance the single resistance is taken as that of film diffusion of the sorbate through the liquid film surrounding the sorbent particle. Two methods of determining the external mass transfer coefficient have been used, one based on the Weber model and the other on the Furusawa-Smith model. Equilibrium data have been analysed and shown to conform to a linear Langmuir plot. The decay curves predicted by the models represented the experimental data very well, particularly at high sorbent masses. Under these conditions film diffusion appears to be the rate controlling step in the adsorption of metal ions by the peat. At low sorbent loadings, however, the influence of internal mass transfer is evident.     

Pore diffusion and external mass transport during dye adsorption on to Fuller's earth and silica

The adsorption of dyes on to Fuller's earth and silica has been studied. A mass transfer model has been developed to describe the adsorption process based on external mass transfer and internal pore diffusion. Theoretical concentration decay curves have been predicted using the model and compared with experimental decay curves.     

红霉素在大孔树脂上的吸附动力学研究

采用液膜及孔内扩散模型,模拟不同温度和不同红霉素(EM)初始浓度条件下,大孔吸附树脂HZ816及XAD16吸附红霉素的动态吸附曲线,并获得液膜传质及孔内扩散系数;考察了温度及溶质浓度对红霉素在两种树脂中吸附动力学的影响.结果表明,在实验范围内,红霉素在HZ816和XAD16两种树脂上的吸附平衡数据满足Langmuir吸附等温线方程,液膜及孔内扩散模型能较好地描述红霉素在两种树脂上的吸附动力学,同时,模型拟合得到的液膜传质系数随着温度的升高而增大,随着初始浓度的增大而增大,孔内扩散系数随着温度的升高而增大,随着初始浓度的增大而减小.     

Modeling separation of proteins by inert core adsorbent in a batch adsorber

Adsorption/desorption kinetics of protein on the binding ligand of inert core adsorbent in a batch adsorber is analyzed theoretically for Langmuir isotherm coupled with the intraparticle diffusion and film mass transfer resistances. For the two limiting cases of Langmuir isotherm, there are analytical solutions. New analytical solutions are derived for Henry isotherm, and the analytical solution of shrinking core model is recommended for rectangular isotherm. The effects of the inert core radius, equilibrium constant, intraparticle diffusion and film mass transfer resistances on the time evolution of bulk concentration and particle radial profiles were investigated. The applicable range of the analytical solution with rectangular isotherm is given. A new method to estimate both film mass transfer coefficient, k_f, and effective pore diffusivity, D_pe, from a single bulk concentration-time curve in batch adsorber is given and tested with literature data for the adsorption of BSA on CB-6AS inert core adsorbent.     

Model simulation and analysis of surface diffusion of liquids in porous solids

A general mathematical model for the rates of adsorption of solutes from a liquid by porous solids in a batch system has been derived. The model includes external mass transfer, pore volume accumulation and diffusion, adsorption using nonlinear isotherms, and surface diffusion. Numerical solutions and parametric plots were obtained.The presence of surface diffusion has a large effect on increasing rates of adsorption for slightly and highly adsorbing solutes. External mass transfer controls the rate for small values of the mass transfer coefficient. Appreciable errors can occur if pore diffusion is neglected for the slightly adsorbing case with little error for the highly adsorbing case. Internal concentration profiles show marked differences for slightly and highly adsorbing solutes.     

The Adsorption of Pollutants by Peat,Lignite and Activated Chars

The ability of peat, lignite and activated chars made from peat and lignite to adsorb dyes and metals from wastewater and NO₂ from air was investigated. Equilibrium isotherms were determined to assess the maximum adsorption capacity of the adsorbents for the pollutants. Kinetic studies for the adsorption of dyes and metal ions onto the adsorbents were undertaken in agitated batch adsorbers. Mass transport models were tested to predict the concentration decay curves in batch adsorbers. The models tested were single resistance models based on the assumption of a single external mass transfer coefficient and two resistance models which included an internal diffusion coefficient and an external mass transfer coefficient. The surface phenomena which influence the extent and the rate of uptake have been studied. The equilibrium capacity data conform to Langmuir plots. A previously proposed model was used to evaluate the external single resistance mass transfer model and was successfully applied to predict the adsorption of metal ions in single component systems under batch conditions. It has been shown that the assumption of negligible intraparticle diffusion is valid and that external film diffusion is the rate limiting step in describing the adsorption processes at high sorbent loadings. The same type of result is not observed for the adsorption of coloured organic matter onto peat where the sorption processes cannot be successfully modelled by use of a single resistance model and a two resistance model incorporating internal diffusion is required. The surface phenomena which influence the extent and the rate of uptake of NO₂ have been studied. The type of chars produced and the activation processes affect the adsorption. As activation increases, micropore volume and surface area increase and the maximum capacity of the adsorbent increases. Surface area alone is not the only parameter which affects equilibrium uptake. © 1997 SCI.     

Analytical solution using a pore diffusion model for a pseudoirreversible isotherm for the adsorption of basic dye on silica

An analytical solution for a two resistance mass transfer model explaining the adsorption of Astrazone Blue dye (Basic Blue 69) onto Sorbsil silica has been developed. The model includes a film mass transfer coefficient, k_f1 = 80 × 10⁻⁶cm·s−1, and an internal effective diffusivity, D_eff = 18×10⁻⁹cm²·s⁻¹ which controls the internal mass transport processes based on a pore diffusion mechanism.     

Competitive adsorption of two dissolved organics onto activated carbon—III: Adsorption kinetics in fixed beds

Adsorption breakthrough curves for bisolute systems of dissolved organics on activated carbon are measured in fixed beds.Results for strongly adsorbable species indicate that at low liquid concentrations (X<0.1 mmol/l.) only external mass transfer resistance is rate determining.However, at higher liquid concentrations internal mass transfer becomes increasingly significant. Breakthrough behaviour is predicted using alternatively three different models with different assumptions about diffusion in the liquid filled pores and diffusion on the surface in series with external film diffusion.Multi-solute adsorption equilibria are predicted from single-solute data using the ideal adsorbed solution theory developed by Myers and Prausnitz, while the single-solute equilibria are represented by Freundlich isotherms. The external mass transfer coefficient for each component is calculated by a general correlation for heat and mass transfer in fixed beds. The internal diffusion coefficient for each component is determined in batch reactor tests with the single-solute system.Systematic deviations between measured breakthrough curves and those calculated from different models using only single-solute data are observed in all experiments with mixed solutes if there is significant internal diffusional resistance and marked displacement of one component inside the carbon particles. The deviations may be due to mutual interference of diffusing molecules. A better agreement between calculated and observed breakthrough curves can be obtained using an extended model in which mixture data are required.     

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.     

The effect of diffusivity on gas-liquid mass transfer in stirred vessels. Experiments at atmospheric and elevated pressures

Mass transfer has been studied in gas-liquid stirred vessels with horizontal interfaces which appeared to the eye to be completely smooth. Special attention has been paid to the influence of the coefficient of molecular diffusion. The results are compared with those published before. The simplifying assumptions of identical hydrodynamical conditions at the same stirrer speed in one particular geometry, which have been made in some previous investigations, is shown to be wrong and may lead to incorrect conclusions on the influence of the diffusion coefficient. For the gas phase the mass transfer can be described by the penetration theory (Higbie, R., 1935, Trans. Am. Inst. Chem. Engrs35, 36–60) or surface renewal model (Danckwerts, P. V., 1951, Ind. Engng Chem.43, 1460–1467). With the use of a dimensionless equation, Sh, Re and Sc numbers, all data, even experiments carried out at elevated pressures, could be well correlated. For the liquid phase the results indicate that the mass transfer cannot be described by a simple model. The King model (King, C.J., 1976, Ind. Engng Chem. Fundam.5, 1–8), a combination of molecular and eddy diffusivity, is able to explain qualitatively the observed phenomena and the literature data.     

Supercritical Fluid Extraction of Pentachlorophenol from Pressure-Treated Wood

Abstract

The extraction of pentachlorophenol (PCP) from pressure-treated wood wafers with supercritical carbon dioxide (SC-CO₂) was studied in a continuous-flow extractor. PCP extraction rates were determined as a function of pressure (17.5–25 MPa), temperature (313–353 K), flow rate (1–3 mL/min at supercritical conditions), and sample size (0.8 × 10 × 50 mm and 2.2 × 10 × 50 mm) by measuring PCP concentrations in the extractor effluent intermittently. The rate of extraction increased with an increase in solvent pressure and a decrease in particle size. A fundamental model was developed which includes rates of intraparticle diffusion, external film mass transfer, linear desorption isotherms, and initial distribution of PCP between pore volume (cell lumen) and pore surfaces (cell wall) of wood wafers. The overall mass transfer coefficient and the rate of extraction increased with an increase in solvent pressure, temperature, and flow rate. The adsorption equilibrium coefficients of PCP with wood substance were very small, and more than 80% of the PCP was found to be in the cell lumen initially.     

大孔吸附树脂HZ816对红霉素的固定床吸附过程研究

在上柱质量浓度为2.31—6.56 mg/mL、流量为14.33—42.80 mL/h的范围内研究了固定床吸附柱中大孔吸附树脂HZ816对红霉素的动态吸附过程,考察了原料液质量浓度和进口流量等操作参数对穿透曲线的影响。并采用基于液膜及孔内扩散模型的动力学模型,同时考虑吸附树脂颗粒内外扩散阻力及轴向扩散的影响,研究了固定床上红霉素在大孔吸附树脂中的吸附动力学,并从穿透曲线回归得到液膜传质系数孔内扩散系数。结果表明,在实验范围内,该模型能较好地描述红霉素在HZ816树脂上的吸附过程,由模型拟合得到的液膜传质系数随着原料液质量浓度减小而增大,随着流量升高而增大;孔内扩散系数随着原料液质量浓度增大而减小,随着流量升高而减小。为采用大孔吸附树脂HZ816吸附技术分离纯化红霉素工艺提供了实验和理论基础。     

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.     

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