Adsorption in columns packed with porous adsorbent particles having partially fractal structures

A mathematical model is constructed and solved that could describe the dynamic behavior of the adsorption of a solute of interest in single and stratified columns packed with partially fractal porous adsorbent particles. The results show that a stratified column bed whose length is the same as that of a single column bed, provides larger breakthrough times and a higher dynamic utilization of the adsorptive capacity of the particles than those obtained from the single column bed, and the superior performance of the stratified bed becomes especially more important when the superficial velocity of the flowing fluid stream in the column is increased to accommodate increases in the system throughput. This occurs because the stratified column bed provides larger average external and intraparticle mass transfer and adsorption rates per unit length of packed column. It is also shown that increases in the total number of recursions of the fractal and the ratio of the radii between larger and smaller microspheres that make up the partially fractal particles, increase the intraparticle mass transfer and adsorption rates and lead to larger breakthrough times and dynamic utilization of the adsorptive capacity of the particles. The results of this work indicate that highly efficient adsorption separations could be realized through the use of a stratified column comprised from a practically reasonable number of sections packed with partially fractal porous adsorbent particles having reasonably large (i) total number of recursions of the fractal and (ii) ratio of the radii between larger and smaller microspheres from which the partially fractal particles are made from. It is important to mention here that the physical concepts and modeling approaches presented in this work could be, after a few modifications of the model, applied in studying the dynamic behavior of chemical catalysis and biocatalysis in reactor beds packed with partially fractal porous catalyst particles.     

Kinetic study of the mass transfer of S-Tr?ger's base in the system cellulose triacetate and ethanol.

A recent study of the mass transfer kinetics of (-)- or S-Tr?ger's base (TB) between ethanol and microcrystalline cellulose triacetate (CTA) allows an analysis of the concentration dependence of the mass transfer rate coefficient (k(m)). S-TB elutes before R-TB. The retention time of the both compounds decreases with increasing temperature. In this study, experimental data measured between 30 and 50 degrees C were analyzed to provide information on the kinetics of several mass transfer processes which take place in the chromatographic column, i.e., axial and intraparticle dispersion, the fluid-to-particle mass transfer, and the kinetics of adsorption/desorption at the actual adsorption sites. Intraparticle diffusion has the dominant contribution to band broadening at high flow-rates. Both intraparticle diffusivity and the surface diffusion coefficient exhibit a small concentration dependence. The positive dependence of k(m) on the concentration of S-TB seems to result from the properties of the adsorption/desorption kinetics and can be interpreted by considering the phase equilibrium properties. A quantitative analysis of the activation energy of the mass transfer kinetics of S-TB in the CTA column was also attempted.     

Chromium adsorption in olive stone activated carbon

In this work, Cr(III) adsorption on activated carbon obtained from olive stones in an upflow fixed-bed column at 30^∘C was studied. The flow rate influence on the breakthrough curves at a feed concentration of 0.87 meq/L was investigated in an attempt to minimize the diffusional resistances. Breakthrough curves for a flow range of 2–8 mL/min were obtained at 10.5 cm bed height and inlet diameter of 0.9 cm. The mass transfer parameters indicated that the bed minimal resistance was attained at 2 mL/min. Therefore, the data equilibrium was carried out until the bed was saturated at 2 mL/min. The dynamic system generated a favorable isotherm with a maximum chromium uptake of 0.45 meq/g. A column sorption mathematical model was created considering the axial dispersion in the column and the intraparticle diffusion rate-controlling steps. The isotherm was successfully modeled by the Langmuir equation and the mathematical model described the experimental dynamic data adequately for feed concentrations from 0.26 to 3.29 meq/L.     

Comparison of general rate model with a new model--artificial neural network model in describing chromatographic kinetics of solanesol adsorption in packed column by macroporous resins

Herein, two models, the general rate model taking into account convection, axial dispersion, external and intra-particle mass transfer resistances and particle size distribution (PSD) and the artificial neural network model (ANN) were developed to describe solanesol adsorption process in packed column using macroporous resins. First, Static equilibrium experiments and kinetic experiments in packed column were carried out respectively to obtain experimental data. By fitting static experimental data, Langmuir isotherm and Freundlich isotherm were estimated, and the former one was used in simulation coupled with general rate model considering better correlative coefficients. The simulated results showed that theoretical predictions of general rate model with PSD were well consistent with experimental data. Then, a new model, the ANN model, was developed to describe present adsorption process in packed column. The encouraging simulated results showed that ANN model could describe present system even better than general rate model. At last, by using the predictive ability of ANN model, the influence of each experimental parameter was investigated. Predicted results showed that with the increases of particle porosity and the ratio of bed height to inner column diameter (ROHD), the breakthrough time was delayed. On the contrary, an increase in feed concentration, flow rate, mean particle diameter and bed porosity decreased the breakthrough time.     

Adsorption of BSA and Hemoglobin on Hydroxyapatite Support: Equilibria and Multicomponent Dynamic Adsorption

Interactions of Bovin Serum Albumin and Hemoglobin with an hydroxyapatite gel (HA-Ultrogel, Sepracor), have been studied separately in batch experiments. The adsorption isotherms are of the Langmuir type and can be used directly to scale column operations.For adsorption of hemoglobin alone, in column at pH 6.8 (equal to its isoelectric point) we notice that a classical intraparticle transfer model, based on a constant effective diffusion coefficient represents perfectly the symmetrical breakthrough curve. For acid pH values (pH 5.8), Langmuir isotherms of BSA and hemoglobin adsorptions showed a strong curvature, sign of a quite irreversible adsorption and breakthrough curves obtained under these conditions, exhibit a high dissymmetrical shape for both proteins. In that case, a model of diffusion based on the adsorption on two types of independent sites, with two intraparticle transfer coefficients, gives a good representation of the breakthrough for adsorption of both proteins separately.Binary mixtures of these components were prepared and injected in columns packed with the same support. Competitive Langmuir equation, based on the results obtained in monocomponent batch experiments, give a very good fit to our system. The intraparticle transfer in that case seems to be facilitated, and one effective coefficient alone is enough to predict the breakthrough curves obtained. This behaviour may be the result of an increase of the solution ionic strength, and of the smaller irreversibility feature of the adsorption when proteins are in competition.     

Adsorption of Cu(II) and Zn(II) ions from aqueous solutions onto fine powder of Typha latifolia L. root: kinetics and isotherm studies

Fine powder of Typha latifolia L. root was used for adsorption of copper and zinc ions from buffered and nonbuffered aqueous solutions. The adsorption reached equilibrium in 60 min. During this time, more than 90 % of the adsorption process was completed. The effect of initial pH, initial concentration of metal ion, and contact time was investigated in a batch system at room temperature. The optimum adsorption performance was observed at pH 5.00 and 4.25 for nonbuffered solutions of Cu(II) and Zn(II), respectively, while for buffered solutions it occurred at pH 6.00. The total metal uptake decreased on application of ammonium acetate buffer, from 37.35 to 17.00 mg g^?1 and 28.80 to 9.90 mg g^?1 for Cu(II) and Zn(II) solutions, respectively, with 100 mg L^?1 initial concentration. The pseudo-first-order, pseudo-second-order, intraparticle diffusion, and Elovich models were used to describe the adsorption kinetics. The experimental data followed the pseudo-second-order kinetic model. The biosorption equilibrium was well described by Langmuir and Freundlich isotherm models.     

A study of mass transfer kinetics of alanyl-alanine on a chiral crown ether stationary phase

The mass transfer kinetics of alanyl-alanine enantiomers in a column packed with a chiral stationary phase (CSP) ChiroSil RCA(+) was studied by means of the moment method. Methanol-water solutions acidified with sulphuric acid were used as the mobile phase. It was shown that the spreading of peaks in the column was strongly affected by abnormal eddy diffusion. This effect was well described within the framework of the Giddings coupling theory. The comprehensive four-term Giddings equation for eddy diffusion was applied, considering simultaneous contribution of the trans-column, trans-channel, short-range inter-channel, and long-range inter-channel dispersion factors. Through these calculations, a predominant importance of the trans-column flow velocity bias was revealed. Besides eddy diffusion, the adsorption kinetic resistance to mass transfer plays a noticeable role in band broadening, all the other contributions (from longitudinal molecular diffusion, external and intraparticle mass transfer) being of minor significance. A relative importance of the mass transfer kinetics increases correlatively with a growth of the retention factor. Both the retention and kinetics of the adsorption of alanyl-alanine on the CSP in study are enantioselective. The influence of the column pressure on retention as well as corrections required because of this influence are also discussed.     

Hierarchically structured β-Ni(OH)2 clusters: a uniquely efficient aqueous phase pollutant adsorbent for multiple anionic dyes and heavy metal ions

Herein, for the first time mesostructured 3D self-assembled β-Ni(OH)₂ clusters with high surface area, large pore size, and uniform flower-like morphology have been synthesized by implementing a novel microwave heating method, using glycine as the cappant. The β-Ni(OH)₂ clusters are subjected to aqueous phase pollutant adsorption for multiple anionic dyes [congo red (CR), acid fuchsin (AF) and acid red 27 (AR-27)], and heavy metal ions [divalent lead ion, Pb(II) and divalent cadmium ion, Cd(II)]. The comprehensive kinetic analyses show that the adsorption of dyes and metal ions on the β-Ni(OH)₂ cluster surface occurs by chemisorption (pseudo-second order kinetics) and intraparticle diffusion (film and pore diffusion) processes. Further, the β-Ni(OH)₂ clusters show excellent equilibrium adsorption capacity for all the anionic dyes and metal ions. The equilibrium isotherm data show homogenous distribution of CR and AF dyes, and heterogeneous distribution of AR-27 dye on the β-Ni(OH)₂ surface. The excellent adsorption efficiency is attributed to the microwave-induced highly hydroxylated rippled 2D surface, open pore architecture, and suitable pore distribution of the β-Ni(OH)₂ clusters, which collectively cause strong hydrogen bonding between the cluster surface and anionic dyes as well as metal ions.     

Simultaneous adsorption of copper ions and humic acid onto an activated carbon

In this study, simultaneous adsorption of copper ions and humic acid (HA) from Aldrich onto an activated carbon is investigated. It is found that the HA adsorption in the absence of copper decreases as the pH is increased. It leads to a reduction of 34.7% in the specific surface area of carbon. There exists a critical concentration (CC) of HA for copper adsorption. At HA concentrations < CC, a decrease in copper adsorption is observed; however, the HA improves the adsorption at HA concentrations > CC. An increase in ionic strength can enhance the copper uptake; however, zinc and/or cobalt ions have an insignificant influence on copper adsorption. The adsorption is significantly increased by citric acid, whereas addition of EDTA slightly decreases the uptake. An intraparticle diffusion model is successfully used to describe the copper adsorption kinetics.     

Sorption characteristics of an economical sorbent material used for removal radioisotopes of cesium and europium

Application study for the evaluation of sorption characteristics of sawdust as an economical sorbent material used for decontamination of radioisotopes cesium and europium from aqueous solution has been carried out in the present work. In this respect, sawdust (untreated and treated by HNO₃) has been prepared from the commercial processing of wood for furniture production. Pore properties of the activated carbon such as BET surface area, pore volume, pore size distribution, and pore diameter were characterized by N₂ adsorption and DFT software. Radiotracer method onto sawdust from aqueous solutions was studied in a batch technique with respect to pH, contact time, temperature. The kinetics of adsorption of Eu³⁺ and Cs⁺ have been discussed using five kinetic models namely, pseudo-first-order model, pseudo-second-order model, Elovich equation, intraparticle diffusion model, and modified Freundlich equation that have been tested in order to analysis the experimental data. Kinetic parameters and correlation coefficients were determined. It was shown that the second-order kinetic equation could describe the sorption kinetics for two metal ions. The metal uptake process was found to be controlled by intraparticle diffusion. Thermodynamic parameters, such as ΔH, ΔG and ΔS, have been calculated by using the thermodynamic equilibrium coefficient obtained at different temperatures. The obtained results indicated that endothermic nature of sorption process for both ^152+154Eu and ¹³⁴Cs onto sawdust.     

Microcolumn test and model analysis of activated carbon adsorption of dissolved organic matter after precoagulation: effects of pH and pore size distribution

Microcolumn adsorption experiments were conducted to generate breakthrough profiles of dissolved organic matter (DOM) remaining after coagulation treatment of a naturally colored surface water for three coal-based activated carbons (ACs) and four water pH levels. A plug-flow homogeneous surface diffusion model was applied to determine the intraparticle surface diffusivities of the DOM at different AC-pH combinations. It was found that, for all three ACs, the removal of DOM increased as pH decreased and the increasing extent changed with the ACs used. The pH dependency of the column performance seemed to be attributed more apparently to pH's capability in changing the zeta potential of AC particles. In addition, at all pH levels, the column performance varied markedly with the ACs used. Correlation analyses of the accumulated amounts of DOM onto all three ACs with corresponding pore volumes in several divided pore size regions clearly indicated that pores with sizes 30-100 A were more effective in adsorbing organic macromolecules. Furthermore, based on model simulations, the sensitivity of bed performance to equilibrium and kinetic parameters was quantified by conducting variance analyses with a four-way classification method.     

Acid/Base-treated activated carbons: characterization of functional groups and metal adsorptive properties

Surface modification of activated carbons by various physicochemical methods directs an attractive approach for improvement of heavy metal uptake from aqueous solutions. Activated carbons were modified with HCl and HNO3 optionally followed by NaOH. The effects of surface modifications on the properties of the carbons were studied by the specific surface area, carbon pH, and total acidity capacity as well as by scanning electron microscopy, X-ray photoelectron spectroscopy, and Fourier transform infrared spectroscopy. The modifications bring about substantial variation in the chemical properties whereas the physical properties remain nearly unchanged. NaOH causes an increase in the content of hydroxyl groups, while the HCl treatment results in an increase in the amount of single-bonded oxygen functional groups such as phenols, ethers, and lactones. The HNO3 modification generates a large number of surface functional groups such as carbonyl, carboxyl, and nitrate groups. The HNO3 modification significantly increases the copper adsorption, while the HCl treatment slightly reduces the copper uptake. Most of the copper ions are adsorbed rapidly in the first 2 h; the adsorption equilibrium is established in around 8 h. An intraparticle diffusion model successfully describes the kinetics of copper adsorption onto the carbons.     

Removal of uranium(VI) from aqueous solution using citric acid modified pine sawdust: batch and column studies

This study described adsorption of uranium(VI) by citric acid modified pine sawdust (CAMPS) in batch and fixed-bed column modes at 295 K. The equilibrium adsorption data were analyzed by Langmuir, Freundlich, Koble–Corrigan and Dubinin–Radushkevich isotherm models. The results indicated that the Langmuir and Koble–Corrigan models provided the best correlation of the experimental data. The Elovish model was better to fit the kinetic process, which suggested that ion exchange was one of main mechanism. The effective diffusion parameter D _i values indicated that the intraparticle diffusion was not the rate-controlling step. In fixed-bed column adsorption, the effects of bed height, feed flow rate, and inlet uranium (VI) concentration were studied by assessing breakthrough curve. The Thomas, the Yan and the bed-depth/service time (BDST) models were applied to the column experimental data to determine the characteristic parameters of the column adsorption. The results were implied that CAMPS may be suitable as an adsorbent material for adsorption of uranium (VI) from an aqueous solution.     

Removal of zinc metal ion (Zn) from its aqueous solution by kaolin clay mineral: A kinetic and equilibrium study

A laboratory batch study has been performed to study the effect of various physic-chemical factors such as initial metal ion concentration, solution pH, and amount of adsorbent, contact time and temperature on the adsorption characteristics of zinc (Zn²⁺) metal ions onto kaolin. It has been found that the amount of adsorption of zinc metal ion increases with initial metal ion concentration, contact time, solution pH but decreases with the amount of adsorbent and temperature of the system. Kinetic experiments clearly indicate that adsorption of zinc metal ion (Zn²⁺) on kaolin is a two steps process: a very rapid adsorption of zinc metal ion to the external surface is followed by possible slow decreasing intra-particle diffusion in the interior of the adsorbent which has also been confirmed by intra-particle diffusion model. The equilibrium time is found to be in the order of 60 min. Overall the kinetic studies showed that the zinc adsorption process followed pseudo-second-order kinetics among pseudo-first-order and intra-particle diffusion model. The different kinetic parameters including rate constant are determined at different initial metal ion concentration, solution pH, amount of adsorbent and temperature respectively. The equilibrium adsorption results are analyzed by both Langmuir and Freundlich models to determine the mechanistic parameters associated with the adsorption process. The value of separation factor, R_L from Langmuir equation also gives an indication of favorable adsorption. Finally thermodynamic parameters are determined at three different temperatures and it has been found that the adsorption process is exothermic due to negative ΔH° accompanied by decrease in entropy change and Gibbs free energy change (ΔG°).     

pH shifting effect on anionic dye removal by surfactant-modified sugar beet pulp: Modeling of column studies

pH shifting effect on the adsorption of anionic RBB dye was tested by using untreated and CTAB-treated SBP as adsorbent in both batch and continuous systems. Characterization of the sorbents revealed the effects of surface modification. Enhanced binding sites and more porous surface structure resulted in improved adsorption capability. Flow rate and initial RBB concentration effects were tested in packed bed column. Optimum pH value of the adsorption, which was determined as 2.0 in the batch studies with untreated SBP, shifted to 8.0 with 20 g/L CTAB treated SBP. Experimental data in column studies showed the decreasing capacity with increasing flow rate and enhanced performance with increasing inlet RBB concentration for both sorbents. Maximum capacities of the columns were found as 36.9 and 2.6 mg/g with dried SBP at pH 2.0 and 8.0, respectively, at a maximum inlet RBB concentration of 500 mg/L and a minimum flow rate of 0.8 mL/min. The highest capacity value at pH 8.0 was found as 140.0 mg/g under the same operating conditions, which reveals positive effect of the treatment on adsorptive performance. Langmuir isotherm was found to be most convenient model for the all equilibrium cases in the column. Moreover, Thomas model accurately predicted the breakthrough curves of each system. This is the first study reporting the modeling data of an anionic dye adsorption in a packed bed column by using modified SBP.     

Kinetic modeling of liquid-phase adsorption of phosphate on dolomite

The adsorption of phosphate from aqueous solution on dolomite was investigated at 20 and 40 degrees C in terms of pseudo-second-order mechanism for chemical adsorption as well as an intraparticle diffusion mechanism process. Adsorption was changed with increased contact time, initial phosphate concentration, temperature, solution pH. A pseudo-second-order model and intraparticle diffusion model have been developed to predict the rate constants of adsorption and equilibrium capacities.The activation energy of adsorption can be evaluated using the pseudo-second-order rate constants. The adsorption of phosphate onto dolomite are an exothermically activated process. A relatively low activation energy and a model highly fitting to intraparticle diffusion suggest that the adsorption of phosphate by dolomite may involve not only physical but also chemisorption. This was likely due to its combined control of chemisorption and intraparticle diffusion. However, for phosphate/dolomite system chemical reaction is important and significant in the rate-controlling step, and for the adsorption of phosphate onto dolomite the pseudo-second-order chemical reaction kinetics provides the best correlation of the experimental data.     

Adsorptive features of polyacrylic acid hydrogel for UO2 2+

Polyacrylic acid hydrogel was synthesized by Free Radical polymerization and characterized by means of FTIR. The FTIR results show that the carboxylic groups in the complexes coordinated to the metal ions in the form of two dentate. The effects of contact time, solid/liquid ratio, pH value, and initial concentration on the adsorption of UO₂ ²⁺ ions onto polyacrylic acid were investigated. The adsorption of UO₂ ²⁺ ions was highly dependent on the initial pH of metal ions solution and initial metal ions concentration. The adsorption kinetic data indicated that the chemical adsorption was the swiftness processes, the adsorption equilibrium could be achieved within 15 min. And there are very good correlation coefficients of linearized equations for Freundlich model, which indicated that the sorption isotherm of the hydrogel for UO₂ ²⁺ can be fitted to the Freundlich model. It was found that the maximum adsorption quantity of UO₂ ²⁺ was 1,179 mg/g. After five times of repeated tests for the hydrogel it still remained its excellent adsorption.     

Fixed bed phosphate adsorption by immobilized nano-magnetite matrix: experimental and a new modeling approach

Nano-sized magnetite impregnated charcoal granular activated carbon (nFe-GAC) was utilized for the removal of phosphate from aqueous solutions using a fixed bed column. The dynamic of the phosphate adsorption was analyzed using a new approach to the Thomas model based on a two-step differential sorption rate process. The initial adsorption was found to be external mass transfer controlled, while intra-particle diffusion was the predominant mechanism in the latter stage. Consequently, two kinetic coefficients were calculated for each breakthrough curve resulting in an excellent model prediction. By implementing this approach a transition point, at which diffusion becomes the predominant adsorption mechanism, can be accurately determined. The effect of varying parameters, such as feed flow rates, feed pH, initial phosphate concentrations and adsorbent bed height were examined and described using the modified Thomas model. Reaction rates increased with augmentation of the flow rates from 1 to 40 mL/min while the adsorption capacity and transition point decreased. Similar transition points were obtained for initial phosphate concentrations between 10 and 100 mg/L. The unique characteristics of the nFe-GAC were evident as it exhibited very high phosphate adsorption capacity, at a wide range of pH values (4–9) with negligible effect of competing ions and short critical bed depth.