Designing Fixed Bed Column and Batch Studies of Chitosan Nanoparticles for Defluoridation of Drinking Water

The aim of present investigation was to prepare nanoparticles of chitosan and perform batch and column studies with them to study their defluoridation capacity. The nanoparticles of chitosan were characterized by techniques like FTIR, SEM, TEM, etc. Effect of initial fluoride concentration, adsorbent dose, pH and temperature were studied in the batch studies. Effect of bed height, flow rate, and inlet concentration on the column performance were studied. Performance of packed columns were described through the concept of breakthrough curves and column parameters were predicted as a function of bed heights. The breakthrough curves were defined by the Adams-Bohart and Wolborska models.     

Use of laterite for the removal of fluoride from contaminated drinking water

The effects of different operational variables on the mechanistic function of laterite in removal of fluoride have been investigated. Thermodynamic parameters such as free energy change, enthalpy, and entropy of the process, as well as the sorption isotherm, were evaluated. The extent of solute removal is determined by initial solute concentration, operational conditions, laterite dose, and solution pH. For a fixed set of experimental conditions, a model equation is developed from which the percent removal corresponding to each load of fluoride is determined. The mechanism of fluoride adsorption is governed by the zero point charge of laterite and follows a first-order rate equation. pH has a vital role influencing the surface characteristics of laterite. To simulate the flow dynamics, fluoride solution was run through a fixed bed column. The pattern of breakthrough curves for different influent fluoride concentration, pH, and column bed height was characterized. The column efficiency was tested from the bed depth-service time model. The elution of the retained fluoride was studied and the effectiveness of column operation was determined by the retention-elution cycles.     

Volcanic Rock Materials for Defluoridation of Water in Fixed-Bed Column Systems

Consumption of drinking water with a high concentration of fluoride (>1.5 mg/L) causes detrimental health problems and is a challenging issue in various regions around the globe. In this study, a continuous fixed-bed column adsorption system was employed for defluoridation of water using volcanic rocks, virgin pumice (VPum) and virgin scoria (VSco), as adsorbents. The XRD, SEM, FTIR, BET, XRF, ICP-OES, and pH Point of Zero Charges (pH_PZC) analysis were performed for both adsorbents to elucidate the adsorption mechanisms and the suitability for fluoride removal. The effects of particle size of adsorbents, solution pH, and flow rate on the adsorption performance of the column were assessed at room temperature, constant initial concentration, and bed depth. The maximum removal capacity of 110 mg/kg for VPum and 22 mg/kg for VSco were achieved at particle sizes of 0.075–0.425 mm and <0.075 mm, respectively, at a low solution pH (2.00) and flow rate (1.25 mL/min). The fluoride breakthrough occurred late and the treated water volume was higher at a low pH and flow rate for both adsorbents. The Thomas and Adams–Bohart models were utilized and fitted well with the experimental kinetic data and the entire breakthrough curves for both adsorbents. Overall, the results revealed that the developed column is effective in handling water containing excess fluoride. Additional testing of the adsorbents including regeneration options is, however, required to confirm that the defluoridation of groundwater employing volcanic rocks is a safe and sustainable method.     

Boron Removal from Aqueous Solutions by Adsorption on Waste Sepiolite and Activated Waste Sepiolite Using Full Factorial Design

In the present paper, boron removal from aqueous solution by adsorption was investigated and 2³ full factorial design was applied. Non activated waste sepiolite (NAWS) and HCl activated waste sepiolite (AWS) were used as adsorbents. Regression equation formulated for boron adsorption was represented as a function of response variables. The results obtained from the study on parameters showed that as pH increased and temperature decreased boron removal by adsorption increased. Adsorbed boron amount on AWS was higher than that of NAWS. Maximum boron removal was obtained at pH 10 and 20°C for both adsorbents. Adsorption data obtained from batch adsorption experiments carried out with NAWS and AWS fitted to the Langmuir equation. The batch adsorption capacities were found in mg/g: 96.15 and 178.57 for NAWS and AWS, respectively. The capacity value for column study was obtained by graphical integration as 219.01 mg/g for AWS. The Thomas and the Yoon-Nelson models were applied to experimental data to predict the breakthrough curves and to determine the characteristic parameters of the column useful for process design.     

Remediation of lead by pretreated red algae: adsorption isotherm,kinetic, column modeling and simulation studies

Batch and column biosorption experiments were carried on for lead uptake using ecofriendly biosorbents (raw and calcium chloride [CaCl₂] or formaldehyde pretreated form of red marine algae Jania ruben [Linnaeus]). The best-fit (linear and nonlinear) isotherms, kinetics, and column adsorption models were identified using statistical analysis. Freundlich, Langmuir, Temkin, Redlich–Peterson, and Elovich adsorption isotherm models were tested. Highest adsorption capacity (774 mg/g) has been observed with Jania algae pretreated with formaldehyde. Pseudo-first- and second-order adsorption kinetics were applicable. The column capacity for lead removal with Jania pretreated with CaCl₂ was found to be 1089.6 (mg/g) from the breakthrough curve area method. Thomas, Yoon-Nelson, Yan, and Clark column models were tested with regression analysis. Thomas model is the best column model with capacity q_Th = 1092.4 mg/g. Overall, 98.5% regeneration of column was achieved, indicating the suitability of using algae materials in multioperational cycles. Adsorbed lead present in algae material was confirmed by thermal analysis.     

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.     

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 U (VI) ions from aqueous solution using silicon dioxide nanopowder

The adsorption kinetics for removal of uranium (V1) from aqueous solution using silicon dioxide nanopowder (nano-SiO₂) was investigated in batch and continuous techniques. Pseudo-first order and pseudo-second order were used to analyze the kinetics of batch experiments. In continuous technique the important parameters (initial concentration, flow rate and bed height) on the breakthrough curves were studied and the adsorption kinetics was analyzed using Thomas and Yoon and Nelson kinetic models. The comparison between the kinetic models was evaluated by the correlation coefficients (r²). The results indicated that the batch experiments fitted well with pseudo second-order kinetic model. The comparison of the experimental breakthrough curve to the breakthrough profile obtained from Thomas and Yoon and Nelson methods showed a satisfactory fit for silicon dioxide nanopowder.     

Mathematical modeling and simulation of inulinase adsorption in expanded bed column

A mathematical model for an expanded bed column was developed to predict breakthrough curves for inulinase adsorption on Streamline SP ion-exchange adsorbent, using a crude fermentative broth with cells as the feedstock. The kinetics and mass transfer parameters were estimated using the PSO (particle swarm optimization) heuristic algorithm. The parameters were estimated for each expansion degree (ED) using three breakthrough curves at initial inulinase concentrations of 65.6 U mL⁻¹. In sequence, the model parameters for an ED of 2.5 were validated using the breakthrough curve at an initial concentration of 114.4 U mL⁻¹. The applicability of the validated model in process optimization was investigated, using the model as a process simulator and experimental design methodology to optimize the column and process efficiencies. The results demonstrated the usefulness of this methodology for expanded bed adsorption processes.     

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.     

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.     

Binary biosorption of uranium(VI) and nickel(II) from aqueous solution by Ca-pretreated Cystoseira indica in a fixed-bed column

Simultaneous biosorption of uranium(VI) and nickel(II) ions onto Ca-pretreated Cystoseira indica biomass was studied and compared with single uranium or nickel biosorption in a fixed-bed column. Results of single biosorption showed the breakthrough and exhaustion time increase with the increase of the flow rate and inlet metal concentration for both metal ions. Also, it was observed that there was an optimum flow rate of 1.4 mL min⁻¹ (surface loading of 0.792 cm min⁻¹) for both metal ions in the column. Results from both single and binary systems showed the adsorption capacity of C. indica for both metal ions increases with the increasing inlet concentration of each component and C. indica had a stronger affinity for uranium than nickel ions. The binary system results showed that the presence of the second component affected the adsorption of the first one by C. indica so the antagonistic action was observed. Also, the inhibitory effect of uranium ions on the nickel adsorption was greater than nickel ions on the uranium adsorption. The uranium and nickel breakthrough curves under different conditions were described by the Thomas, Yoon-Nelson and Yan models. Among these models, the Yan model appeared to describe the experimental results better.     

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 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.     

Modeling of fixed-bed column studies for removal of cobalt ions from aqueous solution using <Emphasis Type="Italic">Chrysanthemum indicum</Emphasis>

The present study investigates the adsorption capability of raw and biochar forms of Chrysanthemum indicum flowers biomass to remove cobalt ions from aqueous solution in a fixed-bed column. Column adsorption experiments were conducted by varying the bed height (1.0, 2.0, 3.0 cm), flow rate (1.0, 2.5, 5.0 mL min^?1) and initial cobalt ion concentration (25, 50, 75 mg L^?1) to obtain the experimental breakthrough curves. The adsorption capacity of the raw and biochar forms of C. indicum flowers were found to be 14.84 and 28.34 mg g^?1, respectively, for an initial ion concentration of 50 mg L^?1 at 1.0 cm bed height and 1.0 mL min^?1 flow rate for Co (II) ion adsorption. Adam–Bohart, Thomas and Yoon–Nelson models were applied to the experimental column data to analyze the column performance. The Thomas model was found to best represent the column data with the predicted and experimental uptake capacity values correlating well and with higher R ² values for all the varying process parameters. Desorption studies revealed the suitability of the adsorbents for repeated use up to four adsorption–desorption cycles without significant loss in its efficiency. It can thus be inferred from the fixed-bed column studies that C. indicum flowers can suitably be used as an effective adsorbent for Co (II) ion removal from aqueous solution on a higher scale.     

Use of expanded bed adsorption to purify flavonoids from Ginkgo biloba L.

Three techniques (liquid–liquid extraction, packed bed adsorption and expanded bed adsorption) have been compared for the purification of flavonoids from the leaves of Ginkgo biloba L. A crude Ginkgo extract was obtained by refluxing with ethanol for 3 h. The yield of flavonoids achieved by this crude extraction was about 19% (w/w) and the purity of flavonoids in the concentrated extract was between 1.9 and 2.3% (w/w). The crude extract was then dissolved in deionized water and centrifuged where necessary to prepare clarified feedstock for further purification. For the method using liquid–liquid extraction with ethyl acetate, the purity, concentration ratio and yield of flavonoids were 25.4–31.0%, 16–18 and >98%, respectively. For the method using packed bed adsorption, Amberlite XAD7HP was selected as the adsorbent and clarified extract was used as the feedstock. The dynamic adsorption breakthrough curves and elution profiles were measured. For a feedstock containing flavonoids at a concentration of 0.25 mg/mL, the appropriate loading volume to reach a 5% breakthrough point during the adsorption stage was estimated to be 550–600 mL for a packed bed of volume 53 mL and a flow rate of 183 cm/h. The results from the elution stage indicated that the majority of impurities were eluted by ethanol concentrations of 40% (v/v) or below and efficient separation of flavonoids from the impurities could be achieved by elution of the flavonoids with 50–80% ethanol reaching an average purity of ∼25%. The recovery yield of flavonoids using the packed bed purification method was about 60% of the flavonoids present in the clarified feedstock (corresponding to around 30% for the total flavonoids in the unclarified crude extract). For the method using expanded bed adsorption also conducted with Amberlite XAD7HP as the adsorbent, the optimal operation conditions scouted during the packed bed experiments were used but unclarified crude extract could be loaded directly into the column. For an expanded bed with a settled bed height of 30 cm, the loss of flavonoids in the column flow-through was about 30%. The two-step elution protocol again proved to be effective in separating the adsorbed impurities and flavonoids. More than 96% of the bound impurities were completely removed by 40% ethanol in the first elution stage and less than 4% remained in the final product eluted by 90% ethanol in the second elution stage. Also, ∼74% of the adsorbed flavonoids on column (corresponding to 51% of the total flavonoids in the unclarified feedstock) were recovered in the product. In addition to higher recovery yield, the average process time to obtain the same amount of product was decreased in the expanded bed adsorption (EBA) process. The results suggest that the adoption of EBA procedures can greatly simplify the process flow sheet and in addition reduce the cost and time to purify flavonoids from Ginkgo biloba. These results clearly demonstrate the potential for the use of EBA to purify pharmaceuticals from plant sources.     

Chemical modification of activated carbon surface with iron functional groups for efficient separation of vanadium: batch and column study

In this study, iron functional groups-impregnated activated carbon (IIAC) composite was prepared as a novel adsorbent for vanadium separation. Adsorption experiments were performed in batch and column systems, and the effects of various operating parameters, such as solution pH, initial concentration, contact time, and temperature, were evaluated. The kinetic data confirmed the validity of the pseudo-second-order kinetic model for vanadium adsorption on IIAC. The sorption equilibrium data were analyzed using Langmuir, Freundlich, and Dubinin–Radushkevich isotherm models. The results showed that IIAC has a vanadium ions adsorption capacity of 313 mg g^?1. The activation and thermodynamic parameters were determined using kinetics and equilibrium data. The experimental data of the column adsorption process were fitted by Thomas and BDST models. The results showed that Thomas model can well describe the breakthrough curves. The column experiments showed that IIAC composite has good adsorption performance for vanadium ions adsorption.