Oualid Hamdaoui

In this work, the extraction of Congo red (CR), an anionic disazo direct dye, from aqueous solutions by emulsion liquid membrane (ELM) was investigated. The important operational parameters governing emulsion stability and extraction behavior of dye were studied. The extraction of CR was influenced by a number of variables such as surfactant concentration, stirring speed, acid concentration in the feed solution and volume ratios of internal phase to organic phase and of emulsion to feed solution. Under most favorable conditions, practically all the CR molecules present in the feed phase were extracted even in the presence of salt (NaCl). At the optimum experimental conditions, total removal of antharaquinonic dye Acid Blue 25 was attained after only 10 min. Influence of sodium carbonate concentration as internal receiving phase on the stripping efficiency of CR was examined. The best sodium carbonate concentration in the internal phase that conducted to excellent stripping efficiency (>99%) and emulsion stability was 0.1N. The membrane recovery was total and the permeation of CR was not decreased up to seven runs. ELM process is a promising alternative to conventional methods and should increase awareness of the potential for recovery of anionic dyes.

In this work, the influence of CCl4 on the sonochemical decolorization of anthraquinonic dye Acid Blue 25 (AB25) in aqueous medium was investigated using high frequency ultrasound (1700 kHz). This frequency, reputed ineffective, was tested in order to introduce the ultrasound waves with high frequency in the field of degradation or removal of dyes from wastewater, due to its limited use in this field, and to increase the application of high frequency ultrasound wave in the field of environmental protection. The effects of various parameters such as the concentration of CCl4, frequency (22.5 and 1700 kHz), solution pH, temperature and tert-butyl alcohol adding on the decolorization rate of AB25 was studied. The obtained results clearly demonstrated the significant intensification of AB25 decolorization in the presence of CCl4. The enhancement effect of CCl4 increased by decreasing temperature and by increasing the CCl4 concentration. The pH has a significant influence on the bleaching of dye both in the absence and presence of CCl4. The three investigated dosimeter methods (KI oxidation, Fricke reaction and H2O2 production) well corroborate the improvement of the sonochemical effects in the presence of CCl4. The best sonochemical decolorization rate of AB25 in aqueous solution both in the absence and presence of CCl4 is observed to occur at 1700 kHz compared to 22.5 kHz. The sonochemical oxidation of CCl4 generates oxidizing species in the liquid phase that are highly beneficial for oxidation of hydrophilic and non-volatile pollutant, such as dyes, because they are less susceptible to free radical attack due to lower stability of the generated free radicals.

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.

The efficiency of eucalyptus bark as a low cost sorbent for removing cadmium ions from aqueous solution has been investigated in batch mode. The equilibrium data could be well described by the Langmuir isotherm but a worse fit was obtained by the Freundlich model. The five linearized forms of the Langmuir equation as well as the non-linear curve fitting analysis method were discussed. Results show that the non-linear method may be a better way to obtain the Langmuir parameters. Maximum cadmium uptake obtained at a temperature of 20 °C was 14.53 mg g−1. The influence of temperature on the sorption isotherms of cadmium has been also studied. The monolayer sorption capacity increased from 14.53 to 16.47 when the temperature was raised from 20 to 50 °C. The ΔG° values were negative, which indicates that the sorption was spontaneous in nature. The effect of experimental parameters such as contact time, cadmium initial concentration, sorbent dose, temperature, solution initial pH, agitation speed, and ionic strength on the sorption kinetics of cadmium was investigated. Pseudo-second-order model was evaluated using the six linear forms as well as the non-linear curve fitting analysis method. Modeling of kinetic results shows that sorption process is best described by the pseudo-second-order model using the non-linear method. The pseudo-second-order model parameters were function of the initial concentration, the sorbent dose, the solution pH, the agitation speed, the temperature, and the ionic strength.

In the present study, the aptitudes of cedar (Cedrus atlantica Manatti) sawdust and crushed brick to remove copper(II) ions from aqueous solutions were investigated. Kinetic results and equilibrium removal isotherms were determined. The influence of pH and ionic strength on the sorption of copper was also studied. The removal of copper by both sorbents increased with an increase in contact time and pH (from 1 to 6) and decreased with an increase in ionic strength. Various kinetic models such as the pseudo-first and pseudo-second order rate equations, Boyd model, and external mass-transfer expression were tested. It was concluded that, for both sorbents, copper sorption occurs through a film diffusion mechanism and the kinetic results were best described by the pseudo-second order kinetic model. The equilibrium data has been correlated with both Langmuir and Freundlich isotherms. The results indicate that the Langmuir model fits the data better. The Freundlich model does not lead to a correct determination of the maximum sorption capacity. Thermodynamic parameters such as the changes in free energy, enthalpy, and entropy of sorption of the copper-sorbent systems were also evaluated. The negative values of the change in free energy indicate the feasibility and spontaneous nature of the process, and the negative heats of the change in enthalpy suggest the exothermic nature of the process. Additionally, different types of chemical treatments were applied: alkaline treatments (NaOH, KOH), acidic treatments (H2SO4, H3PO4, CH3COOH), treatments with mineral salts (NaCl, KCl, Na2HPO4, NaHCO3), treatment with urea, and phosphorylation treatment (urea + H3PO4) in order to enhance the sorption aptitudes of the both sorbents. Among the studied chemical treatments applied, treatments with mineral salts (Na2HPO4, KCl, NaCl, and NaHCO3) for crushed brick and alkaline treatments by NaOH and KOH for cedar sawdust were the most effective.

The adsorption equilibrium isotherms of five phenolic compounds from aqueous solutions onto granular activated carbon (GAC) were studied and modeled. Phenol (Ph), 2-chlorophenol (2-CP), 4-chlorophenol (4-CP), 2,4-dichlorophenol (DCP), and 2,4,6-trichlorophenol (TCP) were chosen for the adsorption tests. To predict the adsorption isotherms and to determine the characteristic parameters for process design, seven isotherm models: Langmuir (five linear forms), Freundlich, Elovich, Temkin, Fowler–Guggenheim, Kiselev, and Hill–de Boer models were applied to experimental data. The results reveal that the adsorption isotherm models fitted the data in the order: Fowler–Guggenheim > Hill–de Boer > Temkin > Freundlich > Kiselev > Langmuir isotherms. Adsorption isotherms modeling shows that the interaction of phenolic compounds with activated carbon surface is localized monolayer adsorption, that is adsorbed molecules are adsorbed at definite, localized sites. Each site can accommodate only one molecule. The interaction among adsorbed molecules is repulsive and there is no association between them, adsorption is carried out on energetically different sites and is an exothermic process. Uptake of phenols increases in the order Ph < 2-CP < 4-CP < DCP < TCP, which correlates well with respective increase in molecular weight, cross-sectional area, and hydrophobicity and decrease in solubility and pKa. Additionally, for the four tested chlorophenols, it seems that the magnitude of adsorption is directly proportional to their degree of chlorination.

In this work, the mechanisms underlying ultrasonic desorption of 4-chlorophenol from granular activated carbon have been explored. Desorption experiments are investigated in the absence and presence of 516 kHz ultrasound of different intensities. Using three regenerating solutions and two temperatures, it has been shown that ultrasonic irradiation considerably improves both the amount and the rate of desorption. Desorption increases with increasing temperature and ultrasound intensity. The addition of sodium hydroxide or a mixture of sodium hydroxide and ethanol to the regenerating medium leads to an enhancement of the desorption, especially in the presence of ultrasound. The mechanisms of ultrasonically enhanced desorption is due both to the thermal and non-thermal (hydrodynamical) effects of ultrasound. Hydrodynamical phenomena are principally produced by the acoustic vortex microstreaming within porous solids as well as at the solid-liquid interface and by the high-speed micro-jets and high-pressure shock waves produced by acoustic cavitation. The thermal effects are evaluated as localized hot spots formed when bubbles cavitated as well as by global heating of the medium and piezoelectric transducer heating-up. Additionally, the non-thermal effect of ultrasound is greater than the thermal effect, and it is more noticeable when the ultrasonic irradiation is carried out in a high temperature regenerating medium. © 2007 American Institute of Chemical Engineers AIChE J 2007

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 °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.