Application of an effective method in predicting breakthrough curves of fixed-bed adsorption onto resin adsorbent

Removal of many organic pollutants including phenolic compounds from industrial wastewater can always be achieved by fixed-bed adsorption onto the polymeric resin adsorbent, and the relevant breakthrough curves would provide much valuable information to help to design a fixed-bed adsorption process in field application. In the present study, a model developed based on the constant-pattern wave approach theory and the Freundlich model was adopted to describe the breakthrough curves of phenol and p-nitrophenol adsorption onto a macroreticular resin adsorbent NDA-100 from aqueous solution. Column experiments were performed at different conditions to verify the model and the results proved that the model would describe the breakthrough curves well. Effect of the operation parameters on breakthrough curves was also discussed to get helpful information in choosing the adsorption process.     

介孔碳对气相多环芳烃的吸附研究

选取两种典型多环芳烃(Polycyclic Aromatic Hydrocarbons,PAHs)菲、芘为研究对象,对其在CMK-3上的吸附特性进行了研究。通过实验得到各组吸附质—吸附剂的吸附等温线及不同浓度下的穿透曲线,并分别由吸附等温线模型(Langmuir、Freundlich、DR)以及基于恒定浓度波假设的动力学模型拟合,获得相应的吸附平衡及动力学参数。研究结果表明:Langmuir模型能很好的描述低浓度的菲在CMK-3的吸附行为,Freundlich模型能很好的描述低浓度的芘在CMK-3上的吸附行为(R~299%)。基于恒定浓度波假设的穿透曲线模型能较好的预测浓度较低时PAHs的穿透曲线;相同浓度的PAHs在其上吸附的内扩散系数呈现PyrPhe的规律,而总传质系数则呈现出相反的规律,且菲的浓度越大总传质系数越大,芘正好相反。     

Factorial experimental design for recovering heavy metals from sludge with ion-exchange resin

Wastewaters containing heavy metals are usually treated by chemical precipitation method in Taiwan. This method can remove heavy metals form wastewaters efficiently, but the resultant heavy metal sludge is classified as hazardous solid waste and becomes another environmental problem. If we can remove heavy metals from sludge, it becomes non-hazardous waste and the treatment cost can be greatly reduced. This study aims at using ion-exchange resin to remove heavy metals such as copper, zinc, cadmium, and chromium from sludge generated by a PCB manufacturing plant. Factorial experimental design methodology was used to study the heavy metal removal efficiency. The total metal concentrations in the sludge, resin, and solution phases were measured respectively after 30 min reaction with varying leaching agents (citric acid and nitric acid); ion-exchange resins (Amberlite IRC-718 and IR-120), and temperatures (50 and 70 degrees C). The experimental results and statistical analysis show that a stronger leaching acid and a higher temperature both favor lower heavy metal residues in the sludge. Two-factors and even three-factor interaction effects on the heavy metal sorption in the resin phase are not negligible. The ion-exchange resin plays an important role in the sludge extraction or metal recovery. Empirical regression models were also obtained and used to predict the heavy metal profiles with satisfactory results.     

Adsorption dynamics of trichlorofluoromethane in activated carbon fiber beds

Adsorption on carbon fixed-beds is considered as an inexpensive and highly effective way for controlling chlorofluorocarbons (CFCs) emissions. In the present work, a dynamic model under constant-pattern wave conditions has been developed to predict the breakthrough behavior of trichlorofluoromethane (CFC-11) adsorption in a fixed bed packed with activated carbon fibers (ACFs). The adsorption of CFC-11 vapor onto viscose-based ACFs was performed in a fixed bed at different test conditions. The results showed that, in a deep bed (>120 mm), the analytical model based on the external mass transfer with the Langmuir isotherm could describe the adsorption dynamics well. The model parameters, the characteristic breakthrough time and the film mass-transfer coefficients are related to such operating parameters as the superficial gas velocity, feed concentration and bed height. It was found from the breakthrough dynamics that the mass transfer from the fluid phase to the fiber surface dominated the CFC-11 adsorption onto ACFs in fixed beds.     

Dynamic sorption of methylene blue by cedar sawdust and crushed brick in fixed bed columns

The dynamic removal of methylene blue by cedar sawdust and crushed brick was studied in packed bed columns. The values of column parameters were predicted as a function of flow rate and bed height. On evaluating the breakthrough curves, the sorption isotherms of methylene blue onto cedar sawdust and crushed brick in 20 degrees C aqueous solution were experimentally determined in batch conditions. Both the Freundlich and the Langmuir models were found to fit the sorption isotherm data well, but the Langmuir model was better. A series of column tests using cedar sawdust and crushed brick as low-cost sorbents were performed to determine the breakthrough curves with varying bed heights and flow rates. To predict the breakthrough curves and to determine the characteristic parameters of the column useful for process design, five kinetic models; Bohart and Adams, bed depth service time (BDST), Clark, Wolborska, and Yoon and Nelson models were applied to experimental data. All models were found suitable for describing the whole or a definite part of the dynamic behavior of the column with respect to flow rate and bed height, with the exception of Bohart and Adams model. The simulation of the whole breakthrough curve was effective with the Yoon and Nelson and the Clark models, but the breakthrough was best predicted by the Wolborska model.     

Influence of the coexisting contaminants on bisphenol A sorption and desorption in soil

The effects of different heavy metals (Cd, Pb), surfactants (cetyltrimethylammonium bromide (CTAB), cetylpyridine chloride (CPC)) and the ionic strength (Ca2+, NH4+) on breakthrough curves (BTCs) for sorption and desorption of bisphenol A (BPA) were studied using soil column experiment. Results showed that the presence of heavy metals and cationic surfactants caused a significant increase on the BPA sorption. In addition, the volume required when effluent concentration reached half of the influent concentration (VC1/2) increased due to the introduction of heavy metals and surfactants. It was also found that the larger amount of BPA was absorbed with higher ionic strength. The cationic surfactants enhanced the desorption ability of BPA from the soil. The results provided a better understanding of BPA behavior in environment and facilitated more accurate assessment of its ecological risk and identification of appropriate management strategies.     

Equilibria and dynamics of liquid-phase trinitrotoluene adsorption on granular activated carbon: effect of temperature and pH

Environmental regulations for removal of trinitrotoluene (TNT) from wastewater have steadily become more stringent. This study focuses on the adsorption equilibrium, kinetics, and column dynamics of TNT on heterogeneous activated carbon. Adsorption equilibrium data obtained in terms of temperature (298.15, 313.15 and 323.15K) and pH (3, 8 and 10) were correlated by the Langmuir equation. In addition, the adsorption energy distribution functions which describe heterogeneous characteristics of porous solid sorbents were calculated by using the generalized nonlinear regularization method. Adsorption breakthrough curves were studied in activated column under various operating conditions such as temperature, pH, concentration, flow rate, and column length. We found that the effect of pH on adsorption breakthrough curves was considerably higher than other operating conditions. An adsorption model was formulated by employing the surface diffusion model inside the activated carbon particles. The model equation that was solved numerically by an orthogonal collocation method successfully simulated the adsorption breakthrough curves.     

Removal of copper(II) from aqueous phase by Purolite C100-MB cation exchange resin in fixed bed columns: modeling

The dynamic removal of copper by Purolite C100-MB cation exchange resin was studied in packed bed columns. The values of column parameters are predicted as a function of flow rate and bed height. Batch experiments were performed using the Na-form resin to determine equilibrium and kinetics of copper removal. The uptake of Cu(II) by this resin follows first-order kinetics. The effect of stirring speed and temperature on the removal kinetics was studied. The activation energy for the exchange reaction is 13.58kJmol(-1). The equilibrium data obtained in this study have been found to fit both the Langmuir and Freundlich isotherm equations. A series of column tests were performed to determine the breakthrough curves with varying bed heights and flow rates. To predict the breakthrough curves and to determine the characteristic parameters of the column useful for process design, four kinetic models; Bohart-Adams, Bed Depth Service Time (BDST), Clark and Wolborska models are applied to experimental data. All models are found suitable for describing the whole or a definite part of the dynamic behavior of the column with respect to flow rate and bed height. The simulation of the whole breakthrough curve is effective with the Bohart-Adams and the Clark models, but the Bohart-Adams model is better. The breakthrough is best predicted by the Wolborska model. The breakthrough data gave a good fit to the BDST model, resulting in a bed exchange capacity very close to the value determined in the batch process.     

Copper(II) and lead(II) removal from aqueous solution in fixed-bed columns by manganese oxide coated zeolite

The ability of manganese oxide coated zeolite (MOCZ) to adsorb copper and lead ions in single- (non-competitive) and binary- (competitive) component sorption systems was studied in fixed-bed column. The experiments were applied to quantify particle size, bed length, influent flow rate and influent metal concentration on breakthrough time during the removal of copper and lead ions from aqueous solutions using MOCZ column. Results of fixed-bed adsorption showed that the breakthrough time appeared to increase with increase of the bed length and decrease of influent metal concentration, but decreased with increase of the flow rate. The Thomas model was applied to adsorption of copper and lead ions at bed length, MOCZ particle size, different flow rate and different initial concentration to predict the breakthrough curves and to determine the characteristic parameters of the column useful for process design. The model was found suitable for describing the adsorption process of the dynamic behavior of the MOCZ column. The total adsorbed quantities, equilibrium uptakes and total removal percents of Cu(II) and Pb(II) related to the effluent volumes were determined by evaluating the breakthrough curves obtained at different conditions. The results suggested that MOCZ could be used as an adsorbent for an efficient removal of copper and lead ions from aqueous solution. The removal of metal ion was decreased when other additional heavy metal ion was added, but the total saturation capacity of MOCZ for copper and lead ions was not significantly decreased. This competitive adsorption also showed that adsorption of lead ions was decreased insignificantly when copper ions was added to the influent, whereas a dramatic decrease was observed on the adsorption of copper ions by the presence of lead ions. The removal of copper and lead ion by MOCZ columns followed the descending order: Pb(II) > Cu(II). The adsorbed copper and lead ions were easily desorbed from MOCZ with 0.5 mol l(-1) HNO3 solution.     

Boron removal from aqueous solutions by ion-exchange resin: column sorption-elution studies

A column sorption-elution study was carried out by using a strong base anion-exchange resin (Dowex 2 x 8) for the removal of boron from aqueous solutions. The breakthrough curve was obtained as a function of feed flow rate and the total and breakthrough capacity values of the resin were calculated. The boron on the resin was quantitatively eluted with 0.5M HCl solution at different flow rates. Three consecutive sorption-elution-washing-regeneration-washing cycles were applied to the resin in order to investigate the reusability of the ion-exchange resin. Total capacity values remained almost the same after three sorption-elution-regeneration cycles. The Thomas and the Yoon-Nelson models were applied to experimental data to predict the breakthrough curves and to determine the characteristic column parameters required for process design. The results proved that the models would describe the breakthrough curves well.     

Artificial neural network (ANN) modeling of dynamic adsorption of crystal violet from aqueous solution using citric-acid-modified rice (Oryza sativa) straw as adsorbent

Rice straw, an abundant, lignocellulosic agricultural residue worldwide, was thermochemically modified with citric acid to develop a biodegradable cationic adsorbent. The morphological and chemical characteristics of rice straw and acid-modified rice straw were investigated by scanning electron microscopy, surface area, and porosity analysis by the BET (Brunauer, Emmett, and Teller) nitrogen adsorption method and Fourier transform infrared spectroscopy. The modification process leads to the increase in the specific surface area and pore size of rice straw. In order to investigate the application potential of the prepared adsorbent to remove a cationic dye (Crystal violet) from its aqueous solution, a continuous adsorption study was carried out in a laboratory scale fixed-bed column packed with acid-modified rice straw. Effect of different flow rates and bed heights on the column breakthrough performance was investigated. Results show that with increasing bed height and decreasing flow rate, the breakthrough time was delayed. In order to determine the most suitable model for describing the adsorption kinetics of Crystal violet in the fixed-bed column system, the Bed Depth Service Time model as well as the Thomas model was fitted to the experimental data. An artificial neural network (ANN) based model for determining the dye concentration in the column effluent was also developed. An extensive error analysis was carried out between experimental data and data predicted by the models using the following error functions: correlation coefficient (R ²), average relative error (ARE), sum of the absolute error (SAE), and χ² statistic test. Based on the values of the error functions, the ANN model was most appropriate for describing the dynamic dye adsorption process.     

The use of protonated Sargassum muticum as biosorbent for cadmium removal in a fixed-bed column

The protonated Sargassum muticum seaweed was studied as a possible biosorbent for cadmium removal in a fixed-bed column. The experiments were conducted in order to determine the effect of flow rate (0.42, 5, 10 and 20 mL min(-1)) and bed height (0.6 and 15.3 cm for the lowest flow rate or 7.4, 13 and 16.6 cm for the others) on breakthrough curves behaviour. The determined breakthrough and exhaustion times increased with the diminution in flow rate and with the increase in bed height. The maximum cadmium uptake capacity, obtained from the area below adsorbed cadmium concentration versus time curves, was found to remain practically constant with bed depth and flow rate. The bed depth service time (BDST) model was applied to analyse experimental data, determining the characteristic process parameters. The optimal lowest sorbent usage rate was evaluated at 2 min contact time and the minimum bed height values necessary to prevent the effluent solution concentration from exceeding 0.02 mg L(-1) at zero time were 5.3, 6.9 and 7.5 cm for flow rates of 5, 10 and 20 mL min(-1), respectively. Several empirical models proposed in the literature (Bohart-Adams, Yan, Belter and Chu models) were investigated in order to obtain the best fit of column data, describing in a simple manner the breakthrough curves. A correlation between model parameters and the variables implied in the process was attempted.     

NaCl-MnO2联合改性沸石对水中Zn2+的动态吸附

研究了NaCl-MnO₂改性沸石填料柱对水中Zn²⁺的动态吸附性能。探讨了填料厚度、Zn²⁺的初始质量浓度和流速对穿透曲线的影响。结果表明,NaCl-MnO₂改性沸石能有效去除水中的Zn²,填料层增厚,穿透曲线上的穿透点向右移动,穿透时间延长;而流速、Zn²⁺的初始浓度增大,穿透曲线上的穿透点向左移动,穿透时间缩短;用Thomas模型描述Zn²⁺初始质量浓度为50mg/L、滤速为4mL/min时改性沸石对Zn²⁺的吸附动力学,相关系数为0.9994,平衡吸附容量为12.04mg/g。     

Removal of Ni(II) ions from aqueous solutions using waste of tea factory: adsorption on a fixed-bed column

The removal efficiency of waste tea from nickel containing aqueous solutions was investigated. All experiments were conducted fixed-bed columns. Experiments were carried out as a function of liquid flow rate (5-20 mL/min), initial Ni(II) concentration (50-200 mg/L), bed height (10-30 cm), pH of feed solution (2.0-5.0) and particle size (0.15-0.25 to 1.0-3.0 mm) of adsorbent. The total adsorbed quantities, equilibrium uptakes and total removal percents of Ni(II) related to the effluent volumes were determined by evaluating the breakthrough curves obtained at different flow rates, different inlet Ni(II) concentrations, different pH value, different bed height and different particle size for waste tea. The longest breakthrough time and maximum of Ni(II) adsorption is obtained at pH 4.0. Decrease in the particle size from 1.0-3.0 to 0.15-0.25 mm resulted in significant increase in the treated volume, breakthrough time and bed capacity. The results show that the column performed well at lowest flow rate. Also, column bed capacity and exhaustion time increased with increasing bed height. When the initial Ni(II) concentration is increased from 50 to 200 mg/L, the corresponding adsorption bed capacity appears to increase from 7.31 to 11.17 mg/g. The bed depth service time (BDST) model and the Thomas model were used to analyze the experimental data and the model parameters were evaluated. Good agreement of the experimental breakthrough curves with the model predictions was observed.     

A comparative study for the ion exchange of Fe(III) and Zn(II) on zeolite NaY

The uptake capacity of Fe(III) and Zn(II) ions in NaY zeolite was investigated. Experiments were carried out in a fixed bed column at 30 degrees C, pH 3.5 and 4.5 for Fe(III) and Zn(II), respectively, and an average particle size of 0.180 mm. In order to minimize the diffusional resistances the influence of flow rate on the breakthrough curves at feed concentrations of 1.56 meq/L for Fe(III) and 0.844 meq/L for Zn(II) was investigated. Flow rate of the minimal resistance in the bed according to mass transfer parameter were 2.0 mL/min for iron and 8.0 mL/min for zinc ions. Freundlich and Langmuir isotherm models have been used to represent the column equilibrium data. The iron dynamic isotherm was successfully modeled by the Langmuir equation and this mathematical model described well the experimental breakthrough curves for feed concentrations from 0.1 up to 3.5 meq/L. The zinc dynamic isotherm was successfully modeled by the Freundlich equation. This equilibrium model was applied to mathematical model. Experimental breakthrough curves could be predicted. Experiments were also carried out in a batch reactor to investigate the kinetics adsorption of the ions Fe(III) and Zn(II). Langmuir kinetic model fit well both experimental data.     

Biosorption of methylene blue from aqueous solution by rice husk in a fixed-bed column

In this study, the ability of rice husk to adsorb methylene blue (MB) from aqueous solution was investigated in a fixed-bed column. The effects of important parameters, such as the value of initial pH, existed salt, the flow rate, the influent concentration of MB and bed depth, were studied. The Thomas model was applied to adsorption of MB at different flow rate, influent concentration and bed depth to predict the breakthrough curves and to determine the characteristic parameters of the column useful for process design using non-linear regression. The bed-depth/service time analysis (BDST) model was also applied at different bed depth to predict the breakthrough curves. The two models were found suitable for describing the biosorption process of the dynamic behavior of the rice husk column. All the results suggested that rice husk as adsorbent to removal MB from solution be efficient, and the rate of biosorption process be rapid. When the flow rate was 8.2ml min(-1) and the influent concentration of MB was 50mgl(-1), the equilibrium adsorption biomass reached 4.41mgg(-1) according to Thomas model.     

Biosorption of copper(II) and lead(II) from aqueous solution by chaff in a fixed-bed column

In this article, the ability of chaff to adsorb heavy metal ions from aqueous solution was investigated in a fixed-bed column. The effect of important parameters, such as the value of pH, the flow rate, the influent concentration of solution and the effect of coexistence ions, was studied. Also the adsorption/desorption recycles of chaff were shown, and the results indicated that chaff could be recycled to remove heavy metal ions. The Thomas model was applied to adsorption of copper and lead at different flow rate and different influent concentration to predict the breakthrough curves and to determine the characteristic parameters of the column useful for process design. The model was found suitable for describing the biosorption process of the dynamic behavior of the chaff column. All the results suggested that chaff as adsorbent to removal heavy metal ions from solution prove efficient, and the rate of biosorption process is speedy. Furthermore, the efficiency of adsorption is high. When the flow rate was 3.6 ml min(-1) and the influent concentration of copper and lead was 14.82 mg l(-1) and 50.12 mg l(-1) respectively, the equilibrium adsorption biomass reached 1.98 mg g(-1) and 6.72 mg g(-1), respectively. The competitive adsorption for lead and copper was studied. Moreover the total adsorbing capability of chaff did not decrease when there were both copper(II) and lead(II) in solution.     

Adsorption of BTEX from aqueous solution by macroreticular resins

Theoretical and experimental investigations were conducted on the adsorption of benzene, toluene, ethylbenzene and xylene (BTEX) by macroreticular resins. A mass transfer model based on the squared-driving force principle is presented for describing the BTEX transfer between the aqueous and solid phases. Also proposed is a theoretical model for describing the BTEX breakthrough curves of the adsorption column. While the mass transfer model involves only an overall mass transfer coefficient, the column adsorption model has two model parameters. Those parameters are conveniently estimated using the observed mass transfer and breakthrough data. The predictions using the proposed models were found to compare well with the experimental data of batch and column BTEX adsorption tests.     

Modeling and analysis of a packed-bed column for the effective removal of zinc from aqueous solution using dual surface-modified biomass

In this research, ultrasonic-assisted fishtail palm Caryota urens seeds (UACUS) have been prepared for the effective removal of Zn(II) ions from aqueous solution in packed-bed column studies. The effect of various operating parameters such as bed depth, initial Zn(II) ions concentration and flow rate on breakthrough curves has been investigated. The dynamic response for the adsorption of Zn(II) ions onto UACUS was described in terms of the breakthrough curves. The results demonstrated that the maximum removal of Zn(II) ions was attained at a low flow rate, influent concentration and high bed depth. The results showed that breakthrough time and exhaustion time were increased with increase of bed height and decreased with increase of flow rate and initial Zn(II) ion concentration. The experimental column data were fitted with different mathematical models, namely Adams–Bohart, Yoon–Nelson and bed depth service time (BDST) models. Amongst the models, the BDST model agreed well with the experimental data. The adsorbent was characterized by Fourier Transform Infrared Spectroscopy (FTIR), Environmental Scanning Electron Microscopy (ESEM), Energy Dispersive X-Ray Spectroscopy (EDX), and Thermogravimetric Analysis (TGA). The experimental results concluded that the prepared UACUS can be utilized as a potential and low-cost adsorbent for the removal of Zn(II) ions from the contaminated liquid.     

Removal of aniline from aqueous solution by PVC-CDAE ligand-exchanger

The adsorption of aniline from aqueous solutions onto cobalt(II)-poly(vinyl chloride)-carboxylated diaminoethane (PVC-CDAE) resin has been studied using a mini-column apparatus at 25 ± 0.1 °C. First of all, experimental data obtained from the breakthrough curves were tested by using the Scatchard plot analysis, to have a preliminary prediction about the types of interaction of the resin with aniline. Our aim was to determine the model which best describes the experimental data. The aspect of the Scatchard plot indicated that the aniline adsorption did not follow the Langmuir model and the presence of two types of binding sites for aniline on the resin. However, the dynamics of aniline uptake were represented by the Freundlich model reasonably well. The kinetics of aniline adsorption from aqueous solution on the cobalt(II)-PVC-CDAE have also been tested using continuous column runs and rate-controlling step of the process was determined. In this study, homogeneous diffusion model was adapted to a column system to describe the change in the aniline concentration at the column exit beginning from breakthrough point as a function of time. Kinetic studies revealed that the rate-controlling step of the aniline adsorption was predominately film diffusion controlled rather particle diffusion.