Competitive effect of glucose–fructose adsorption in a fixed‐bed chromatographic column

A continuous separation system such as a simulated moving‐bed process requires adsorption data with precise equilibrium and kinetic model parameters of a single chromatographic column. The adsorption of glucose and fructose in a fixed‐bed chromatographic column was investigated to determine the competition effect of each component resulting from their initial molar ratios. The model parameters including bed porosity and axial dispersion coefficient were determined using the moment analysis method. The equilibrium isotherm parameters were estimated by conducting experiments at various molar ratios and initial sugar concentrations. The parameters obtained were then used for the simulation of dynamic breakthrough curves of glucose and fructose. The equilibrium isotherms revealed that the linear adsorption pattern provided good prediction for each molar ratio using the Henry equation. In addition, the modified Langmuir model was proposed to account for the competitive adsorption, due to the cooperative competition effect whereby glucose was promoted to the active sites by fructose to a greater degree than vice versa. A good agreement between the experimental and numerical data of the adsorption time profiles was also observed.     

Sorptive elimination of fluoride from contaminated groundwater in a fixed bed column: A kinetic model validation based study

The current investigation involves a continuous adsorption experiment in a packed bed column for the sorptive elucidation of fluoride from contaminated groundwater using an activated soil-clay mixture. Through the combination of naturally accessible laterite soil with silica enriched clay (3:1 ratio), a low-cost Al–Si heterogeneous material has been developed. Following detailed characterization, the developed materials were employed in a long-time column process to achieve a high degree of fluoride separation from real-world groundwater. In a packed bed column investigation, the effect of bed height, initial fluoride concentration, and flow rate on the breakthrough properties of the adsorption system were investigated. By using a non-linear regression equation, three model kinetics, such as the Thomas Model, Adams-Bohart Model, and Yoon-Nelson Model, were fitted to validate the column-based experimental data, by analysing the breakthrough curves profiles, and distinct kinetic parameters. The Bed Depth Service Time Analysis (BDST) model was tested to express the effect of bed height on breakthrough curves, as well as to predict the time for breakthrough, and material depletion under optimal conditions. The Thomas and Yoon-Nelson models were identified to be the most appropriate ones for describing the entire breakthrough curve, whereas the Adams-Bohart model was only utilised to predict the first half of the dynamic process. With correlation coefficients (R²) 0.96, the experimental results were well suited to Thomas, Yoon-Nelson, and Adams-Bohart models. Finally, regeneration assessment was carried out where even after four cycles of operation, regenerated adsorbent showed a rejection efficacy of 78% to fluoride that proves the viability of the material and methodology.     

Influence of particle diameter distribution on protein recovery in the expanded bed adsorption process

The General Rate model has been developed and solved to describe protein adsorption in an expanded bed. The model takes into account axial and local variation of particle size distribution (PSD), external and intra-particle mass transfer resistances, and dispersion in liquid phase. The influence of PSD on breakthrough profiles has been analysed. The simulation results show that for a significantly high expanded bed the lower part of the breakthrough curve profiles, calculated for local particle size distribution (LPSD) and for axial average particle size distribution (APSD) are very similar. However, the upper part of breakthrough profiles calculated for LPSD approaches inlet concentration much more slowly than those calculated for APSD. The retention times of the lower part of uptake curves calculated with average particle diameter are constantly shorter than those obtained from LPSD. For the calculation of the dynamic capacity (DC), the LPSD can be replaced by APSD for large expanded bed heights. Using breakthrough profiles calculated for average particle size, DC values are constantly underestimated.     

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.     

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.     

Influence of the particle porosity on chromatographic band profiles

The mass transfer kinetics of butyl benzoate, eluted on a monolithic RPLC column with methanol-water (65:35, v/v) as the mobile phase was investigated, using the perturbation method to acquire isotherm data and the mobile phase velocity dependence of the height equivalent to a theoretical plate of perturbation peaks to acquire kinetics data. The equilibrium isotherm of butyl benzoate is accounted for by the liquid-solid extended multilayer BET isotherm model. The total porosity of the column varies much with the butyl benzoate concentration, influencing strongly the parameters of its mass transfer kinetics and the profiles of the breakthrough curves. Using all these parameters, the general rate model of chromatography predicts band profiles and Van Deemter curves that are in excellent agreement with experimental results provided the influence of concentration on the porosity is properly taken into account. This agreement confirms the validity of the models selected for the isotherm and for the mass transfer kinetics.     

Fixed-bed adsorption of carbon dioxide/methane mixtures on silicalite pellets

The adsorption of carbon dioxide and methane on silicalite pellets packed on a fixed bed has been studied. Equilibrium and kinetic measurements of the adsorption of carbon dioxide and methane have been performed, and a binary adsorption isotherm for carbon dioxide/methane mixtures has been obtained. A model based on the LDF approximation for the mass transfer has been used to describe the breakthrough curves obtained experimentally. A PSA cycle has been proposed for obtaining methane with purity higher than 98% from carbon dioxide/methane mixtures containing 38% and 50% methane, and its performance has been simulated using the proposed model. The simulation results show that silicalite can be a suitable adsorbent for employment in a PSA separation process for carbon dioxide removal from coalseam and landfill gases.     

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.

     

基于BP神经网络研究儿茶素在ADS-8树脂固定床的吸附过程

以信阳毛尖茶叶浸提液为原料,研究儿茶素在ADS-8树脂固定床的吸附过程及优化吸附条件。试验基于BP神经网络建立吸附模型,通过仿真分析上样浓度、柱径比和流速对穿透时间、穿透体积的影响。模型的模拟值与试验值的相关系数为0.992,模拟值与试验值没有显著差异。最佳工艺条件为上样浓度1.5mg/mL,柱径比17:1,流速3.0mL/min。建立的模型可用于模拟儿茶素在ADS-8树脂固定床的吸附过程,结果为吸附树脂法制备儿茶素提供一定的参考。     

Determination of competitive isotherms of enantiomers by a hybrid inverse method using overloaded band profiles and the periodic state of the simulated moving-bed process

A procedure for determination of adsorption isotherms in simulated moving-bed (SMB) chromatography is presented. The parameters of a prescribed adsorption isotherm model and rate constants are derived using a hybrid inverse method, which incorporates overloaded band profiles of the racemic mixture and breakthrough data from a single frontal experiment. The latter are included to reduce the uncertainty on the estimated saturation capacity, due to the dilution of the chromatograms with respect to the injected concentrations. The adsorption isotherm model is coupled with an axially dispersed flow model with finite mass-transfer rate to describe the experimental band profiles. The numerical constants of the isotherm model are tuned so that the calculated and measured band profiles match as much as possible. The accuracy of the isotherm model is then checked against the cyclic steady state (CSS) of the target SMB process, which is readily and cheaply obtained experimentally on a single-column set-up. This experiment is as expensive and time consuming as just a few breakthrough experiments. If necessary, the isotherm parameters are adjusted by applying the inverse method to the experimental CSS concentration profile. The method is successfully applied to determine the adsorption isotherms of Tr?gers base enantiomers on Chiralpak AD/methanol system. The results indicate that the proposed inverse method offers a reliable and quick approach to determine the competitive adsorption isotherms for a specific SMB separation.     

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.     

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.     

Monte carlo simulation and pore-size distribution analysis of the isosteric heat of adsorption of methane in activated carbon

The isosteric heat of adsorption of methane in an activated carbon adsorbent has been modeled by Monte Carlo simulation, using a pore-size distribution (PSD) to relate simulation results for pores of different sizes to the experimental adsorbent. Excellent fits were obtained between experimental and simulated isosteric heats of adsorption of methane in BPL activated carbon. The PSD was then used to predict the adsorption of methane and ethane in the same carbon adsorbent, with good results. The PSD derived from isosteric heat data was shown to be richer in information than PSDs obtained by the more conventional method of fitting to isotherm data.     

Analysis and modeling of fixed bed column operations on As(V) removal by adsorption onto iron oxide-coated cement (IOCC)

Fixed-bed column studies were undertaken to evaluate the performance of iron oxide-coated cement (IOCC) in removing As(V), from aqueous environment, under varying operating conditions. Investigations revealed IOCC to be a very efficient media for the removal of As(V) from water. The Bohart and Adams sorption model was employed to determine characteristic parameters such as depth of exchange zone, time required for exchange zone to move its own height, adsorption rate, and adsorption capacity, useful for process design. The IOCC media effectively removed As(V) from a 2 mg/L solution with a maximum adsorption capacity of 505.3 mg/L. Predicted data points obtained using a Freundlich isotherm model were compared against experimental data points determined in the dynamic process. The effects of important design parameters such as flow rate and influent concentration on the As(V) breakthrough curves were also investigated. The bed depth service time (BDST) model was extended to the prediction of service times of columns operated at different flow rates and influent concentrations and these predicted values were compared with the experimental values. The columns were regenerated by eluting the bound As(V) with 10% NaOH after the adsorption studies.     

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.     

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.