Desorption of dye from activated carbon beds: effects of temperature, pH, and alcohol.

The adsorption isotherms of yellow and red dye solutions onto granular activated carbon at varying solution pHs (2-8). temperatures (15-50 degrees C), and alcohol concentrations (0-20%) were experimentally determined by batch tests and the Tóth model was found to best fit the adsorption isotherm data for varying solution pHs. temperatures, and alcohol concentrations. The maximum adsorption capacity was found to decrease with increasing solution pH and alcohol concentration and could be predicted by the correlation equations obtained in this study. A correlation equation was also obtained to account for the effects of solution temperature on the adsorption equilibrium constant. The 25 degrees C water was found to be a very poor regenerant for the carbon bed presaturated with the yellow dye compared with 20% alcohol solution. A simple equation was derived, based on non-linear wave propagation theory, to predict the desorption curves of activated carbon bed. Given presaturation concentration, bed density and void fraction, and adsorption isotherm, the wave propagation theory predicted the desorption curves quite satisfactorily.     

Adsorption of basic dyes on granular activated carbon and natural zeolite

The adsorption of basic dyes from aqueous solution onto granular activated carbon and natural zeolite has been studied using an agitated batch adsorber. The influence of agitation, initial dye concentration and adsorbent mass has been studied. The parameters of Langmuir and Freundlich adsorption isotherms have been determined using the adsorption data. Homogeneous diffusion model (solid diffusion) combined with external mass transfer resistance is proposed for the kinetic investigation. The dependence of solid diffusion coefficient on initial concentration and mass adsorbent is represented by the simple empirical equations.     

Adsorption of ciprofloxacin on surface-modified carbon materials

The adsorption capacity of ciprofloxacin (CPX) was determined on three types of carbon-based materials: activated carbon (commercial sample), carbon nanotubes (commercial multi-walled carbon nanotubes) and carbon xerogel (prepared by the resorcinol/formaldehyde approach at pH 6.0). These materials were used as received/prepared and functionalised through oxidation with nitric acid. The oxidised materials were then heat treated under inert atmosphere (N₂) at different temperatures (between 350 and 900 °C). The obtained samples were characterised by adsorption of N₂ at −196 °C, determination of the point of zero charge and by temperature programmed desorption. High adsorption capacities ranging from approximately 60 to 300 mg_CPx g_C⁻¹ were obtained (for oxidised carbon xerogel, and oxidised thermally treated activated carbon Norit ROX 8.0, respectively). In general, it was found that the nitric acid treatment of samples has a detrimental effect in adsorption capacity, whereas thermal treatments, especially at 900 °C after oxidation, enhance adsorption performance. This is due to the positive effect of the surface basicity. The kinetic curves obtained were fitted using 1st or 2nd order models, and the Langmuir and Freundlich models were used to describe the equilibrium isotherms obtained. The 2nd order and the Langmuir models, respectively, were shown to present the best fittings.     

Effect of OH and silanol groups in the removal of dyes from aqueous solution using diatomite

The removal of methylene blue, reactive black (C-NN), and reactive yellow (MI-2RN) from aqueous solution by calcined and raw diatomite at 980 degrees C was studied. These studies demonstrated the importance of the various functional groups on the mechanism of adsorption. The role of pore size distribution in the dye adsorption studies was also investigated. The adsorption isotherms were pH dependent. Henry and Freundlich adsorption isotherms were used to model the adsorption behavior and experimental results for all dyes used exhibited heterogeneous surface binding. The removal of the ionisable functional groups increased the pH(ZPC) value from 5.4 to 7.7, while FTIR, SEM and XRD analysis showed a remarkable decrease of the characteristic Si-OH peaks after calcinations at 980 degrees C. The removal of hydroxyl groups from the surface of diatomite lead to a decrease in the adsorption. It was evident from pH and infrared spectra results that mechanisms of methylene blue and reactive yellow adsorption differed from that of reactive black. Accordingly, adsorption on the external surface by n-pi interaction between the pi system of the RB and the electron lone pairs of the oxygen atoms of siloxane group and columbic attraction between the dye and the surface of calcined diatomite was proposed as a possible adsorption mechanism.     

Mineralisation of coloured aqueous solutions by ozonation in the presence of activated carbon

The degradation of organic matter in coloured solutions of different classes of dyes by ozonation in the presence of activated carbon is investigated. The kinetics of the decolourisation and mineralisation of three different dyes solutions (CI Acid Blue 113, CI Reactive Red 241 and CI Basic Red 14) were studied in a laboratory scale reactor by three different processes: adsorption on activated carbon, oxidation with ozone and ozonation in the presence of activated carbon. The mineralisation of the solutions was followed by measuring the total organic carbon (TOC). Under the experimental conditions used in this work, activated carbon was not capable of completely removing the colour of the solutions in reasonable time. On the other hand, ozonation quickly decolourised all the solutions, but satisfactory removal of TOC was never achieved by this process. The combination of activated carbon with ozone enhanced the decolourisation of the solutions and especially the mineralisation of the organic matter. Activated carbon acts both as an adsorbent and as a catalyst in the reaction of ozonation. The surface chemistry of the activated carbon is an important parameter; it was observed that basic samples improve TOC removal. The main conclusions of this work were validated by treating a real textile effluent collected after the conventional biological treatment.     

Adsorption de colorants ioniques sur le dechet lainier de carbonisage

Wool carbonizing waste is not used although large amounts are available in the countries where wool is processed. Wool carbonizing waste is made up of two components: the plant particles can be considered as sulfo lignins; the short-size wool fibres have undergone chemical modifications. Owing to its physical structure and to the polar as well as apolar properties of its macromolecules, this waste is liable to adsorb ionic organic solutes. The adsorption of ionic dyes on wool carbonizing waste was therefore investigated so as to evaluate its possible use for the decolourization of dyeing effluents. The effect of the solution-substrate reaction time on the adsorption at various temperatures was studied first. Temperature had a marked effect on the adsorption of the acid dye (AB 80) (Fig. 1) whereas the basic dye (BR 22) (Fig. 2) was characterized by its faster diffusion within the wool carbonizing waste particles. These differences can be ascribed to the higher steric hindrance of the AB 80 molecules and to their possible aggregation. The L-type adsorption isotherms corroborated the temperature effect already mentioned as well as the high affinity of the wool carbonizing waste with acid (Fig. 3) and basic (Fig. 4) dyes. The shape of the adsorption isotherms suggests that the adsorption proceeds through ionic bonding; as the dye molecules are oriented flatwise on the surface of the waste, the dye-substrate hydrophobic interactions can be maximum. The amounts adsorbed were 0.744 mmol g⁻¹ (i.e. 52.5%) for AB 80 at pH 2 and 0.193 mmol g⁻¹ (i.e. 5.5%) for BR 22 at pH 4. Higher amounts of basic dyes might however be expected to be adsorbed since the adsorption maximum is reached at pH 9 in the case of BR 22 (Fig. 5), as a result of the increasingly electronegative charge of the substrate. The Langmuir and Freundlich equations (Table 1) were used to have a mathematical model for the operation of a waste water processing unit. As shown by the L-type adsorption isotherms, the wool carbonizing waste used is suitable for the processing of low concentration effluents, such as dyeing waste waters: the decolourization of synthetic solutions was therefore considred. The column processing of an AB 80 solution showed the effect of the reaction time on the efficiency of the material used (Table 2). Investigation of the processing of a BR 22 solution in a stirred reactor led to the determination of the optimum carbonizing waste concentration (Fig. 6). as well as of the optimum effluent-substrate reaction time and the number of reactors to be used (Fig. 7). Eventually, the adsorptive power of the wool carbonizing waste used was compared with that of various materials (Table 3): the uptake capacity of wool carbonizing waste is lower than or equal to that of other substrates in the case of basic dyes but it is 6–10-fold higher in the case of acid dyes.     

Adsorption de colorants ioniques sur le dechet lainier de carbonisageAdsorption of ionic dyes on wool carbonizing waste

Wool carbonizing waste is not used although large amounts are available in the countries where wool is processed. Wool carbonizing waste is made up of two components: the plant particles can be considered as sulfo lignins; the short-size wool fibres have undergone chemical modifications. Owing to its physical structure and to the polar as well as apolar properties of its macromolecules, this waste is liable to adsorb ionic organic solutes. The adsorption of ionic dyes on wool carbonizing waste was therefore investigated so as to evaluate its possible use for the decolourization of dyeing effluents. The effect of the solution-substrate reaction time on the adsorption at various temperatures was studied first. Temperature had a marked effect on the adsorption of the acid dye (AB 80) (Fig. 1) whereas the basic dye (BR 22) (Fig. 2) was characterized by its faster diffusion within the wool carbonizing waste particles. These differences can be ascribed to the higher steric hindrance of the AB 80 molecules and to their possible aggregation. The L-type adsorption isotherms corroborated the temperature effect already mentioned as well as the high affinity of the wool carbonizing waste with acid (Fig. 3) and basic (Fig. 4) dyes. The shape of the adsorption isotherms suggests that the adsorption proceeds through ionic bonding; as the dye molecules are oriented flatwise on the surface of the waste, the dye-substrate hydrophobic interactions can be maximum. The amounts adsorbed were 0.744 mmol g^?1 (i.e. 52.5%) for AB 80 at pH 2 and 0.193 mmol g^?1 (i.e. 5.5%) for BR 22 at pH 4. Higher amounts of basic dyes might however be expected to be adsorbed since the adsorption maximum is reached at pH 9 in the case of BR 22 (Fig. 5), as a result of the increasingly electronegative charge of the substrate. The Langmuir and Freundlich equations (Table 1) were used to have a mathematical model for the operation of a waste water processing unit. As shown by the L-type adsorption isotherms, the wool carbonizing waste used is suitable for the processing of low concentration effluents, such as dyeing waste waters: the decolourization of synthetic solutions was therefore considred. The column processing of an AB 80 solution showed the effect of the reaction time on the efficiency of the material used (Table 2). Investigation of the processing of a BR 22 solution in a stirred reactor led to the determination of the optimum carbonizing waste concentration (Fig. 6). as well as of the optimum effluent-substrate reaction time and the number of reactors to be used (Fig. 7). Eventually, the adsorptive power of the wool carbonizing waste used was compared with that of various materials (Table 3): the uptake capacity of wool carbonizing waste is lower than or equal to that of other substrates in the case of basic dyes but it is 6–10-fold higher in the case of acid dyes.     

Adsorption-desorption characteristics of phenol and reactive dyes from aqueous solution on mesoporous activated carbon prepared from waste tires

Liquid-phase adsorption-desorption characteristics and ethanol regeneration efficiency of an activated carbon prepared from waste tires and a commercial activated carbon were investigated. Water vapor adsorption experiments reveal that both activated carbons showed hydrophobic surface characteristics. Adsorption experiments reveal that the prepared activated carbon possessed comparable phenol adsorption capacity as the commercial one but clearly larger adsorption capacity of two reactive dyes, Black 5 and Red 31. It was ascertained that the prepared activated carbon exhibited less irreversible adsorption of phenol and the two dyes than its commercial counterpart. Moreover, ethanol regeneration efficiency of the prepared AC saturated with either dye was higher than that of the commercial AC. Because of its superior liquid-phase adsorption-desorption characteristics as well as higher ethanol regeneration efficiency, the prepared activated carbon is more suitable for wastewater treatment, especially for adsorbing similarly bulky adsorbates.     

Adsorption of Cr(III) on ozonised activated carbon. Importance of Cpi-cation interactions

The adsorption of Cr(III) in aqueous solution was investigated on a series of ozonised activated carbons, analysing the effect of oxygenated surface groups on the adsorption process. A study was carried out to determine the adsorption isotherms and the influence of the pH on the adsorption of this metal. The adsorption capacity and affinity of the adsorbent for Cr(III) increased with the increase in oxygenated acid groups on the surface of the activated carbon. These findings imply that electrostatic-type interactions predominate in the adsorption process, although the adsorption of Cr(III) on the original (basic) carbon indicates that other forces also participate in the adsorption process. Thus, the ionic exchange of protons in the -Cpi-H3O(+) interaction for Cr(III) accounts for the adsorption of cationic species in basic carbons with positive charge density. Study of the influence of pH on the adsorption of Cr(III) showed that, in each system, the maximum adsorption occurred when the charge of the carbon surface was opposite that of the species of Cr(III) present at the pH of the experiment. These results confirmed that electrostatic interactions predominate in the adsorption process.     

Regeneration of acid orange 7-exhausted granular activated carbons with microwave irradiation

An investigation was performed for the regeneration of three granular activated carbons (GACs) exhausted with acid orange 7 (AO7). The three GACs were made from different materials, i.e. coconut shells, almond nucleus and coal. The AO7 adsorption process was carried out in a continuous-flow adsorption column. After adsorption, the AO7-saturated GAC was dried at 120 °C, then regenerated in a quartz reactor by 2450 MHz microwave (MW) irradiation at 850 W for 5 min. The efficacy of this procedure was analyzed by determining the rates and amounts of AO7 adsorbed in successive adsorption–MW regeneration cycles. Effects of this regeneration on the structural properties, surface chemistry and the AO7 adsorption capacities of GAC samples were examined. It was found that after several adsorption–MW regeneration cycles, the adsorption rates and capacities of GACs could maintain relatively high levels, even higher than those of virgin GACs, as indicated by AO7 breakthrough curves and adsorption isotherms. The improvement of GAC adsorption properties resulted from the modification of pore size distribution and surface chemistry by MW irradiation.     

Application of 'waste' metal hydroxide sludge for adsorption of azo reactive dyes

The capacity and mechanism of metal hydroxide sludge in removing azo reactive dyes from aqueous solution was investigated with different parameters, such as charge amount of dyes, system pH, adsorbent particle size, and adsorbent dosage. The three anionic dyes used were CI Reactive Red 2, CI Reactive Red 120, and CI Reactive Red 141, increasing in number of sulfonic groups, respectively. Only 0.2% (w/v) of powdered sludge (<75microm) achieved color removal from 30 mg l(-1) reactive dye solutions within 5 min without pH adjustment. The larger the charge amount of the dyes, the greater the adsorption (>90%) on the metal hydroxide sludge. The system pH played a significant role in the adsorption on metal hydroxides and formation of dye-metal complexes. The optimum system pH for dye adsorption was 8-9 which was close to the pH(zpc) of the sludge while the precipitation of dye-metal complexes occurred at system pH 2. The maximum adsorption capacity (Q degrees ) of the sludge for the reactive dyes was 48-62 mg dye g(-1) adsorbent. The Langmuir and Freundlich models showed that the higher charged dyes had a higher affinity of adsorption. The smaller particle size and the greater amount of adsorbent showed the faster process, due to an increase in surface area of adsorbent. Desorption studies elucidated that metal hydroxide sludge had a tendency for ion exchange adsorption of sulfonated azo reactive dyes. Leaching data showed that the treated water was nontoxic at a system pH above 5 or a solution pH above 2.     

Removal of azo and anthraquinone dyes from aqueous solutions by Eichhornia Crassipes

The rate of adsorption of two azo and four anthraquinone anionic dyes on Eichhornia Crassipes (E.C.) has been studied. Raw E.C. and three aminated derivatives of E.C. with different nitrogen percent were used as dye adsorbents. The parameters studied include the amount of substrate, shaking time, chemical structure, concentration of dyestuff and pH of dyeing bath. Simple kinetic adsorption models of dynamics and adsorption parameters for the Langmuir and Freundlich isotherms were determined. A higher nitrogen percent of aminated E.C. showed a higher adsorption capacity than other derivatives. The kinetic adsorption models indicate that the decolourization was complete in a relatively short time (10 min) and the reaction taking place is of the first order. The equilibrium data fit well with the Freundlich model of adsorption for the six dyes. Only dye IV (C.I.A Acid Blue 25) conform both Freundlich and Langmuir adsorption isotherms.     

Modeling high adsorption capacity and kinetics of organic macromolecules on super-powdered activated carbon

The capacity to adsorb natural organic matter (NOM) and polystyrene sulfonates (PSSs) on small particle-size activated carbon (super-powdered activated carbon, SPAC) is higher than that on larger particle-size activated carbon (powdered-activated carbon, PAC). Increased adsorption capacity is likely attributable to the larger external surface area because the NOM and PSS molecules do not completely penetrate the adsorbent particle; they preferentially adsorb near the outer surface of the particle. In this study, we propose a new isotherm equation, the Shell Adsorption Model (SAM), to explain the higher adsorption capacity on smaller adsorbent particles and to describe quantitatively adsorption isotherms of activated carbons of different particle sizes: PAC and SPAC. The SAM was verified with the experimental data of PSS adsorption kinetics as well as equilibrium. SAM successfully characterized PSS adsorption isotherm data for SPACs and PAC simultaneously with the same model parameters. When SAM was incorporated into an adsorption kinetic model, kinetic decay curves for PSSs adsorbing onto activated carbons of different particle sizes could be simultaneously described with a single kinetics parameter value. On the other hand, when SAM was not incorporated into such an adsorption kinetic model and instead isotherms were described by the Freundlich model, the kinetic decay curves were not well described. The success of the SAM further supports the adsorption mechanism of PSSs preferentially adsorbing near the outer surface of activated carbon particles.     

An approach to textile dye removal using sawdust from Aspidosperma polyneuron

The textile industry is responsible for discarding wastewater contaminated with dyes. The timber industry generates waste in the form of sawdust. The aim of the present study was to evaluate the adsorptive potential of sawdust obtained from the Aspidosperma polyneuron tree for the removal of the textile dye from wastewater. Sawdust was subjected to different pre-treatments (acid, alkaline and polyethyleneimine) in order to increase its adsorption capacity. Based on the results from the isotherms, treatment with polyethyleneimine (PEI) led to the greatest adsorption capacity and fits the Freundlich model, indicating cooperative adsorption. Other treatments with sawdust best fit the Langmuir model, but the untreated sawdust presented better results than the treated sawdust. These results were only surpassed by sawdust treated with PEI. A. polyneuron revealed good potential for use as an adsorbent to remove dyes, which is a novel result, since to date there is no study on its use as a sorbent material.     

Ultrasound-assisted Acid red dye removal using leather fibre wastes as matrix: ‘intra wastes interaction’ approach

It is desirable to make effective use of solid wastes, as well as waste liquors, of the dye house generated from leather processing. The present study deals with the adsorption of Acid red 26 (Xylidine ponceau) dye using leather fibre waste (buffing dust) as substrate matrix by the means of ultrasound, magnetic stirring and conventional heating. The research examined the effect of various process parameters: ultrasonic power, concentration of dye, temperature and time. The dye uptake data have been fitted with Freundlich and Langmuir isotherms, indicating a useful dye adsorption process. A mechanism for dye adsorption in leather fibres has also been proposed. This study shows that it is possible to remove dyes from dye house effluent streams using leather waste fibres of buffing dust by means of ultrasound. Two different toxic wastes produced by the same industry can be effectively contained. This ‘Intra wastes interaction’ approach could reduce the burden of discarding wastes of other materials in the leather industry.     

Adsorption of dissolved natural organic matter by modified activated carbons

Adsorption of dissolved natural organic matter (DOM) by virgin and modified granular activated carbons (GACs) was studied. DOM samples were obtained from two water treatment plants before (i.e., raw water) and after coagulation/flocculation/sedimentation processes (i.e., treated water). A granular activated carbon (GAC) was modified by high temperature helium or ammonia treatment, or iron impregnation followed by high temperature ammonia treatment. Two activated carbon fibers (ACFs) were also used, with no modification, to examine the effect of carbon porosity on DOM adsorption. Size exclusion chromatography (SEC) and specific ultraviolet absorbance (SUVA(254)) were employed to characterize the DOMs before and after adsorption. Iron-impregnated (HDFe) and ammonia-treated (HDN) activated carbons showed significantly higher DOM uptakes than the virgin GAC. The enhanced DOM uptake by HDFe was due to the presence of iron species on the carbon surface. The higher uptake of HDN was attributed to the enlarged carbon pores and basic surface created during ammonia treatment. The SEC and SUVA(254) results showed no specific selectivity in the removal of different DOM components as a result of carbon modification. The removal of DOM from both raw and treated waters was negligible by ACF10, having 96% of its surface area in pores smaller than 1 nm. Small molecular weight (MW) DOM components were preferentially removed by ACF20H, having 33% of its surface area in 1--3 nm pores. DOM components with MWs larger than 1600, 2000, and 2700 Da of Charleston raw, Charleston-treated, and Spartanburg-treated waters, respectively, were excluded from the pores of ACF20H. In contrast to carbon fibers, DOM components from entire MW range were removed from waters by virgin and modified GACs.     

Removal of dyes from a synthetic textile dye effluent by biosorption on apple pomace and wheat straw

This paper deals with two low-cost, locally available, renewable biosorbents; apple pomace and wheat straw for textile dye removal. Experiments at total dye concentrations of 10, 20, 30, 40, 50, 100, 150, and 200 mg/l were carried out with a synthetic effluent consisting of an equal mixture of five textile dyes. The effect of initial dye concentration, biosorbent particle size, quantity of biosorbent, effective adsorbance, dye removal and the applicability of the Langmuir and Freundlich isotherms were examined. One gram apple pomace was found to be a better biosorbent, removing 81% of dyes from the synthetic effluent at a particle size of 2 mm x 4 mm and 91% at 600 microm. Adsorption of dyes by apple pomace occurred at a faster rate in comparison to wheat straw. Both the isotherms were found to be applicable in the case of dye adsorption using apple pomace.     

Removal of water pollutants with activated carbons prepared from H3PO4 activation of lignin from kraft black liquors

Activated carbons with a high BET surface area and a well-developed porosity have been prepared from pyrolysis of H3PO4-impregnated lignin precipitated from kraft black liquors. Impregnation ratios within the range of 1-3 and activation temperatures of 623-873 K have been used, giving rise to carbons with different porous and surface chemical structure. Increasing the activation temperature and the impregnation ratio leads to a widening of the porous structure with a higher relative contribution of mesoporosity. The potential application of these carbons for the removal of water pollutants has been investigated by measuring their adsorption capacities for phenol, 2,4,5-trichlorophenol and Cr (VI) as representative of toxic contaminants found in industrial wastewaters. The results obtained compare well and even favorably with those reported in the literature for other activated carbons. An impregnation ratio and an activation temperature around 2 g H3PO4/g lignin and 700 K, respectively, are recommended as the best combination of operating conditions to prepare activated carbons for aqueous phase applications although at lower values of these two variables carbons with good adsorption capacities are also obtained.     

Color removal via adsorption on wood shaving

Factors affecting the adsorption capacity of dyes on wood shavings, such as the mesh size of the adsorbent, wood dosages, contact time, and the structure of the adsorbant, were studied. Adsorption of dye on wood follows the classical Freundlich's isotherm. Available results indicated that wood shaving is a good adsorbent. Its capacity varies according to the structure of the dye and mesh size. Powdered activated carbon was used as a reference adsorbent for the same dyes under investigation.     

The adsorption of nicotine from aqueous solutions on different zeolite structures

The present work is focused on the adsorption of nicotine from aqueous solutions. Based on the data available in the literature, serious concern is claimed regarding the appearance of nicotine in ground, surface and municipal wastewaters. In order to investigate the possibility of abatement by adsorption, three different types of zeolites (BEA, MFI and HEU) have been applied as adsorbents. In addition, the adsorption was performed on activated carbon, a solid customarily used for removal of pollutants from water. The adsorption of nicotine was studied by isothermal microcalorimetry, which provided the heats evolved as a result of adsorption. The values of these heats revealed that the investigated solids are energetically heterogeneous for the adsorption of nicotine from aqueous solution. Additionally, the amounts of adsorbed pollutant were determined and presented in the form of adsorption isotherms. The obtained adsorption isotherms were interpreted using Langmuir, Freundlich, and Sips equations; the latter was found to express high level of agreement with experimental data of nicotine adsorption on the investigated solids. The possibilities to regenerate the adsorbents were examined by means of thermogravimetry coupled with mass spectrometry. From all obtained results, it was possible to distinguish zeolite BEA as a material which possesses the capacity for adsorption of nicotine comparable to that of activated carbon.