A review on applicability of naturally available adsorbents for the removal of hazardous dyes from aqueous waste

The effluent water of many industries, such as textiles, leather, paper, printing, cosmetics, etc., contains large amount of hazardous dyes. There is huge number of treatment processes as well as adsorbent which are available for the processing of this effluent water-containing dye content. The applicability of naturally available low cast and eco-friendly adsorbents, for the removal of hazardous dyes from aqueous waste by adsorption treatment, has been reviewed. In this review paper, we have provided a compiled list of low-cost, easily available, safe to handle, and easy-to-dispose-off adsorbents. These adsorbents have been classified into five different categories on the basis of their state of availability: (1) waste materials from agriculture and industry, (2) fruit waste, (3) plant waste, (4) natural inorganic materials, and (5) bioadsorbents. Some of the treated adsorbents have shown good adsorption capacities for methylene blue, congo red, crystal violet, rhodamine B, basic red, etc., but this adsorption process is highly pH dependent, and the pH of the medium plays an important role in the treatment process. Thus, in this review paper, we have made some efforts to discuss the role of pH in the treatment of wastewater.     

Fish Bone as a Low-Cost Adsorbent for Dye Removal from Wastewater: Response Surface Methodology and Classical Method

This research studied the application of fish bone as a low-cost adsorbent for the removal of two basic dyes (C.I. Basic Blue 41 and C.I. Basic Yellow 28) from textile wastewaters. The surface morphology and functional groups of the fish bone was studied by scanning electron microscopy and Fourier transform infrared, respectively. The experiments were designed in two methods: classical method and response surface methodology (RSM). The effect of operating parameters including pH, initial dye concentration, adsorbent dosage, and inorganic salts was investigated by both methods. The optimum conditions to satisfy 75 % of dye removal for both dyes were predicted by RSM method and the results were very close to the experimental values. So, it was concluded that the fish bone can be used as a low-cost adsorbent for dye removal from effluents.     

Dye removal using modified copper ferrite nanoparticle and RSM analysis

In this paper, copper ferrite nanoparticle (CFN) was synthesized, modified by cetyl trimethylammonium bromide, and characterized. Dye removal ability of the surface modified copper ferrite nanoparticle (SMCFN) from single system was investigated. The physical characteristics of SMCFN were studied using Fourier transform infrared, scanning electron microscopy, and X-ray diffraction. Acid Blue 92, Direct Green 6, Direct Red 23, and Direct Red 80 were used as model compounds. The effect of operational parameters (surfactant concentration, adsorbent dosage, dye concentration, and pH) on dye removal was evaluated. Response surface methodology (RSM) was used for the analysis of the dye removal data. The experimental checking in these optimal conditions confirms good agreements with RSM results. The results showed that the SMCFN being a magnetic adsorbent might be a suitable alternative to remove dyes from colored aqueous solutions.     

有机改性对凹凸棒黏土吸附四环素类抗生素的影响

采用OECD guideline 106批量平衡吸附法研究四环素类抗生素在十六烷基三甲基溴化铵改性凹凸棒黏土(CTAB-ATP)上的吸附作用,并考察了溶液pH、吸附剂的投加量、离子强度对吸附过程的影响。结果表明,CTAB-ATP对四环素、土霉素、金霉素3种四环素类抗生素的吸附容量随着溶液pH的增加而增加;随着吸附剂投加量的增大而减小;随着离子强度的增加呈现缓慢减小的趋势。CTAB-ATP对四环素、土霉素、金霉素的吸附过程均符合准二级动力学模型(r0.998),吸附等温线较好地符合Langmuir等温式。有机改性凹凸棒黏土的疏水性增强,提高了对有机污染物的吸附能力,其沉降性能良好,这使其作为一种吸附剂用于实际抗生素废水的处理成为可能。     

Adsorption characteristics of a phenoxy acetic acid herbicide on activated carbon

The adsorption of 2,4-dichlorophenoxyacetic acid (2,4-D) by two powdered coal activated carbons was studied in aqueous solution. The modelling of the adsorption equilibrium showed that the adsorption of 2,4-D fitted a Langmuir isotherm. Adsorption was influenced by the activated carbon type, adsorbent concentration and solution characteristics. The adsorption was found to decrease with an increase in pH over the range 1.5-9. Maximum adsorption occurred at pH approximately 2.5, which corresponds to the 2,4-D pKa value. The amount of 2,4-D adsorbed was also found to depend on the NaCl concentration.     

Kinetic parameters for the removal of lead and chromium from wastewater using activated carbon developed from fertilizer waste material

The waste slurry generated in fertilizer plants in India has been converted into a cheap carbonaceous adsorbent material. The prepared adsorbent has been characterised and used for the removal of lead and chromium metals. The kinetics of adsorption and the extent of adsorption at equilibrium are dependent on the physical and chemical characteristics of the adsorbate, adsorbent and experimental system. Results of laboratory scale studies conducted to delineate the effect of such parameters on the kinetics of adsorption of metal ions are reported. Parameters evaluated include: hydronium ion concentration, temperature, initial adsorbate concentration, size of adsorbent, and amount of adsorbent. On the basis of these studies the various physical parameters such as effective diffusion coefficient, activation energies and entropy of activation are evaluated, as these provide some information regarding the mechanistic aspects. Mass transfer coefficient values suggest a rapid transport of the adsorbate from bulk to solid phase.     

Optimization of pulp mill effluent treatment with catalytic adsorbent using orthogonal second-order (Box-Behnken) experimental design

Novel catalytic adsorbent (ruthenium on carbon) was employed for the treatment of pulp mill effluent in the presence of hydrogen peroxide. Mathematical model and optimization of the process regarding the most favorable COD (%), TOC (%) and color (%) removal rates was developed and performed with experimental design taking into account catalytic adsorption process kinetics. As the initial experimental design, 3(3-1) half-fractional factorial design (H-FFD) was accomplished at two levels to study the significance of the main effects, such as catalytic adsorbent (g l(-1)) and hydrogen peroxide (ppm) concentrations using the response surface methodology (RSM). Finally, a four factor-three coded level central composite design (CCD) with 28 runs was performed in order to fit a second-order polynomial model. Validation of the model was accomplished by different criteria including coefficient of determination and the corresponding analysis of variance. The achieved removal rates for TOC (up to 75%), COD (up to 73%) and color (up to 68%) were observed for the defined optimal conditions: 1g l(-1) of ruthenium on carbon, 7 ppm of hydrogen peroxide, pH = 4 and ambient temperature. The proposed method benefited significantly improved TOC, COD and color removal efficiency, regenerability and reusability of the catalytic adsorbent and unaltered initial pH of an effluent in comparison to traditional adsorption or oxidation processes.     

硝酸镧改性聚丙烯酸对水中氟离子的吸附试验探讨

以丙烯酸为原料,乙二醇二甲基丙烯酸酯为交联剂制得聚丙烯酸树脂(PAA),用于制备表面粗糙、介孔丰富的镧(Ⅲ)改性聚丙烯酸复合树脂(La-PAA)。试验表明,当500 mg/L氟离子溶液pH值为5、吸附时间为300 min时,La-PAA对氟离子的去除率在90%以上。Langmuir方程能较好地拟合氟离子在La-PAA上的吸附等温线,最大吸附量为159.24 mg/g,吸附动力学过程符合准二级动力学方程。     

The potential of different bio adsorbents for removing phenol from its aqueous solution

The use of natural resources for the removal of phenol and phenolic compounds is being looked upon by researchers in preference to other prevailing methods. In the present study, different biosorbents, brown algae (Padina pavonia), fresh water macrophyta (Ceratophyllum demersum), and black tea residue, were tested as adsorbent for the removal of phenol from aqueous solutions. The optimum conditions for maximum adsorption in terms of concentration of the adsorbate and pH were identified. The results show that the initial concentration increases as the removal of phenol increases in C. demersum; in the case of the other two adsorbents, the initial concentration increases as the removal of phenol decreases, especially for an initial concentration lower than 100 and 1,000 μg/L for P. pavonia and black tea residue, respectively. Maximum percentage removal of phenol by each adsorbent is 77, 50.8, and 29 % for C. demersum, P. pavonia, and black tea residue, respectively. Also, the biosorption capacity was strongly influenced by the pH of the aqueous solution with an observed maximum phenol removal at pH of around 6–10. The first biosorbent (black tea residue) displays the maximum adsorption capacity at a pH of 10 with a percentage sorption capacity of 84 %; P. pavonia revealed a greater adsorption percentage at pH?10, reaching 30 %, while for C. demersum, the removal of phenol increases with the increase in initial pH up to 6.0 and decreases drastically with further increase in initial pH. The Freundlich, Langmuir, and Brauner–Emmet–Teller adsorption models were applied to describe the equilibrium isotherms. The results reveal that the equilibrium data for all phenol adsorbents fitted the Freundlich model which seemed to be the best-fitting model for the experimental results with similar values of coefficient of determination.     

Treatment of wastewater containing arsenic using Rhazya stricta as a new adsorbent

The effective removal of heavy metals from aqueous wastes is among the most important issues for many industrialized countries. Removal of arsenic (As) from aqueous solutions was studied using Rhazia stricta biomass. The batch experiments are carried out to investigate the effect of the significant process parameters such as pH, contact time, solute concentration and adsorbent dose. The optimum pH required for maximum adsorption was found to be 5. The equilibrium data for the adsorption of As(V) on R. stricta are tested with various adsorption isotherm models such as Langmuir, Freundlich, Tempkin and Generalized equation. Results indicate the following order to fit the isotherm: Langmuir (1 and 2)?>?Tempkin?>?Generalized form?>?Freundlich. A comparison of two kinetic models showed that our data fitted well to the Elovich model.     

Adsorption and removal of oxo-anions of arsenic and selenium on the zirconium(IV) loaded polymer resin functionalized with diethylenetriamine-N,N,N',N'-polyacetic acid

A polymer adsorbent in which a Zr(IV)-edta complex analogue is immobilized has been prepared and applied to the removal of oxo-anions of As(III), As(V) and Se(IV). Effective retention of these anions has been demonstrated with the proposed polymer complex system. The adsorption mechanism of oxo-anions onto the Zr(IV)-chelated polymer complex has been investigated using Zr(IV)-edta as the model compound. The formation of mixed complexes with oxo-anions has been exemplified by the isolation of the carbonato complex K2[Zr(CO3)edta].3H2O, the structure of which has been confirmed by X-ray crystallography. NMR study suggests that oxo-anions that form weak or moderate conjugate acids, including those of As(III), As(V) and Se(IV), can form mixed complexes with Zr(IV)-edta using the unsaturated coordination site. However, oxo-anions of strong conjugate acids did not show any appreciable interaction with this complex. According to these observations, retention of oxo-anions on the Zr(IV)-chelated polymer complex has been interpreted by a ligand substitution reaction. The adsorption characteristics of As(III), As(V) and Se(IV) on the Zr(IV)-loaded resin have been examined with respect to the equilibrium adsorption, percentage extraction and the effect of co-existing ions. The adsorption and desorption cycles of the oxo-anions have been demonstrated using a column packed with the proposed resin without any loss of column performance, which indicates the possibility for repeated use.     

Fruit Stones from Industrial Waste for the Removal of Lead Ions from Polluted Water

Lead, one of the earliest metals recognized and used by humans, has a long history of beneficial use. However, it is now recognized as toxic and as posing a widespread threat to humans and wildlife. Treatment of lead from polluted water and wastewater has received a great deal of attention. Adsorption is one of the most common technologies for the treatment of lead-polluted water. This technique was evaluated here, with the goal of identifying innovative, low-cost adsorbent. This study presents experiments undertaken to determine the suitable conditions for the use of peach and apricot stones, produced from food industries as solid waste, as adsorbents for the removal of lead from aqueous solution. Chemical stability of adsorbents, effect of pH, adsorbents dose, adsorption time and equilibrium concentration were studied. The results reveal that adsorption of lead ions onto peach stone was stronger than onto apricot stone up to 3.36% at 3 h adsorption time. Suitable equilibrium time for the adsorption was 3–5 h (% Pb adsorption 93% for apricot and 97.64% for peach). The effective adsorption range for pH in the range was 7–8. Application of Langmuir and Freundlich isotherm models show high adsorption maximum and binding energies for using these adsorbents for the removal of lead ions from contaminated water and wastewater.     

Preparation of 2-mercaptobenzothiazole-derivatized mesoporous silica and removal of Hg(ii) from aqueous solution

Mesoporous silicas (SBA-15 and MCM-41) have been functionalized by two different methods. Using the heterogeneous route the silylating agent, 3-chloropropyltriethoxysilane, was initially immobilized onto the mesoporous silica surface to give the chlorinated mesoporous silica Cl-SBA-15 or Cl-MCM-41. In a second reaction a multifunctionalized N,S donor compound (2-mercaptobenzothiazol) was incorporated to obtain the functionalized silicas denoted as MBT-SBA-15-Het and MBT-MCM-41-Het. Using the homogeneous route, the functionalization was achieved via the one step reaction of the mesoporous silica with an organic ligand containing the chelating functions, to give the modified mesoporous silicas denoted as MBT-SBA-15-Hom or MBT-MCM-41-Hom. The functionalized mesoporous silicas were employed as adsorbents for the regeneration of aqueous solutions at pH 6 contaminated with Hg(ii) at room temperature. Results obtained indicate that mercury adsorption was higher in the mesoporus silicas prepared by the homogeneous method, and the maximum adsorption value (0.24 +/- 0.02 mmol Hg(ii) g(-1)) was obtained for MBT-SBA-15-Hom. The chemically stability in acid medium of the functionalized silicas, possibility its regeneration washing with concentrate HCl, resulting in the reuse of the adsorbent material for several cycles.     

Chemical oxidation of C. I. Reactive Red 2 using Fenton-like reactions

A detailed investigation on the kinetics of the oxidative degradation of a reactive dye, C. I. Reactive Red 2 by hydroxyl radicals generated by H202 and Fe2+ has been carried out in aqueous acidic media. Effects of different parameters like initial concentration of dye, H2O2, Fe2+, pH of the solution, reaction temperature and added electrolytes on the oxidation process have been studied. The results indicate that 1.63 x 10(-4) mol dm(-3) dye can be most effectively degraded at a dye: Fe2+: H2O2 molar ratio of 1:0.22: 8.13 at pH approximately 2.7 and at 299 K. The addition of excess 2-propanol or t-butyl alcohol, well known scavengers of hydroxyl radicals, almost stopped the degradation of the dye indicating the absence of any possible reductive pathways in the degradation. The results may be useful for designing the treatment systems of wastewater containing various reactive dyes.     

Color removal from paper mill effluent through adsorption technology

The bagasse fly ash, obtained from the local sugar industry, has been used as an inexpensive and effective adsorbent for the removal of color from pulp and paper industry. Effect of various operating variables, viz., contact time, initial concentration, adsorbent dose and particle size on the removal of color has been studied and discussed. It is found that for optimum removal of color, contact time for adsorption equilibrium equals to 60 min., at dosage of 2 g/l of baggase fly ash. The material exhibits good removal capacity (86%) and follows both the Langmuir and the Freundlich models.     

Almond shell activated carbon: adsorbent and catalytic support in the phenol degradation

In this work, two technologies are studied for the removal of phenol from aqueous solution: dynamic adsorption onto activated carbon and photocatalysis. Almond shell activated carbon (ASAC) was used as adsorbent and catalytic support in the phenol degradation process. The prepared catalyst by deposition of anatase TiO₂ on the surface of activated carbon was characterized by scanning electron microscopy, sorption of nitrogen, X-ray diffraction, Fourier transform infrared (FT-IR) spectroscopy, and pH_ZPC point of zero charge. In the continuous adsorption experiments, the effects of flow rate, bed height, and solution temperature on the breakthrough curves have been studied. The breakthrough curves were favorably described by the Yoon–Nelson model. The photocatalytic degradation of phenol has been investigated at room temperature using TiO₂-coated activated carbon as photocatalyst (TiO₂/ASAC). The degradation reaction was optimized with respect to the phenol concentration and catalyst amount. The kinetics of disappearance of the organic pollutant followed an apparent first-order rate. The findings demonstrated the applicability of ASAC for the adsorptive and catalytic treatment of phenol.     

Adsorption and detection of some phenolic compounds by rice husk ash of Kenyan origin

Rice husk ash (RHA) obtained from a rice mill in Kenya has been used as an inexpensive and effective adsorbent (and reagent) for the removal (and detection) of some phenolic compounds in water. The abundantly available rice mill waste was used in dual laboratory-scale batch experiments to evaluate its potential in: (i) the removal of phenol, 1,3-dihydroxybenzene (resorcinol) and 2-chlorophenol from water; and (ii) the detection of 1,2-dihydroxybenzene (pyrocatechol) and 1,2,3-trihydroxybenzene (pyrogallol) present in an aqueous medium. The studies were conducted using synthetic water with different initial concentrations of the phenolic compounds. The effects of different operating conditions (such as contact time, concentration of the phenolic compounds, adsorbent quantity, temperature, and pH) were assessed by evaluating the phenolic compound removal efficiency as well as the extent of their color formation reactions (where applicable). RHA exhibits reasonable adsorption capacity for the phenolic compounds and follows both Langmuir and Freundlich isotherm models. Adsorption capacities of 1.53 x 10(-4), 8.07 x 10(-5), and 1.63 x 10(-6) mol g(-1) were determined for phenol, resorcinol and 2-chlorophenol, respectively. Nearly 100% adsorption of the phenolic compounds was possible and this depended on the weight of RHA employed. For the detection experiments, pyrocatechol and pyrogallol present in water formed coloured complexes with RHA, with the rate of colour formation increasing with temperature, weight of RHA, concentration of the phenolic compounds and sonication. This study has proven that RHA is a useful agricultural waste product for the removal and detection of some phenolic compounds.     

A Computational Fluid Dynamic Model for Prediction of Organic Dyes Adsorption from Aqueous Solutions

Modelling of the removal of synthetic dyes from aqueous solutions by adsorbents is important to develop an appropriate treatment plan using adsorption process. This paper presents a computational fluid dynamic model incorporating the Langmuir isotherm scheme and second-order kinetic expression to describe the adsorption process. The governing equation of the model was numerically solved using PHOENICS software to simulate synthetic dyes adsorption from the aqueous system. The experimental results presented in this study and taken from the literature for the removal of synthetic dyes were compared with those results predicted by the numerical model. The predicted outputs of the model match the experimental measurements satisfactory. A sensitivity analysis of the major parameters that influence the percent of dye removal from solution phase has been carried out. Three of the main parameters taken into account were the kinetic rate constant, amount of dye adsorbed at equilibrium and the Langmuir isotherm constant. It was found that the model is most sensitive to the amount of dye adsorbed at equilibrium. This effect is most obvious at the early stages of the adsorption process when the rate of dye removal is very fast. Quantification of the reaction mechanism allows developing an appropriate remediation strategy based on the adsorption process.     

Removal of atrazine and four organophosphorus pesticides from environmental waters by diatomaceous earth-remediation method

A new viable remediation technique based on the use of diatomaceous earth is proposed to improve the ecological system. Its ability to remove atrazine and the four organophosphorus pesticides parathion-methyl, chlorpyriphos, fenamiphos and methidathion from river and waste waters has been proven. A series of experiments including variable conditions, such as temperature, pH, contact time, pesticide concentration and adsorbent quantity, were performed to demonstrate the efficiency of pesticide removal from three different water samples. The batch experiments showed that diatomaceous earth was able to remove 95% of chlorpyriphos, 75% of methidathion and parathion-methyl and 55% of atrazine and fenamiphos from all types of waters tested. The individual adsorption of each pesticide on diatomaceous earth could be described by the Freundlich isotherm and a tentative adsorption mechanism was proposed. The Freundlich coefficient (Kf) and Freundlich constant (1/n) appeared to be closely related to the physicochemical properties (Kow, solubility) of the compounds. The actual results support the conclusion that diatomaceous earth has the potential to serve as an extractant in remediation techniques.     

Removal of mercury(II) ions in aqueous solution using the peel biomass of <Emphasis Type="Italic">Pachira aquatica</Emphasis> Aubl: kinetics and adsorption equilibrium studies

Mercury is a highly toxic substance that is a health hazard to humans. This study aims to investigate powders obtained from the peel of the fruit of Pachira aquatica Aubl, in its in natura and/or acidified form, as an adsorbent for the removal of mercury ions in aqueous solution. The materials were characterized by Fourier transform infrared spectroscopy and thermogravimetric analysis. The infrared spectra showed bands corresponding to the axial deformation of carbonyls from carboxylic acids, the most important functional group responsible for fixing the metal species to the adsorbent material. The thermograms displayed mass losses related to the decomposition of three major components, i.e., hemicellulose, cellulose, and lignin. The adsorption process was evaluated using cold-vapor atomic fluorescence spectrometry (CV AFS) and cold-vapor atomic absorption spectrometry (CV AAS). Three isotherm models were employed. The adsorption isotherm model, Langmuir-Freundlich, best represented the adsorption process, and the maximum adsorption capacity was predicted to be 0.71 and 0.58 mg g^?1 at 25 °C in nature and acidified, respectively. Adsorption efficiencies were further tested on real aqueous wastewater samples, and removal of Hg(II) was recorded as 69.6 % for biomass acidified and 76.3 % for biomass in nature. Results obtained from sorption experiments on real aqueous wastewater samples revealed that recovery of the target metal ions was very satisfactory. The pseudo-second-order model showed the best correlation to the experimental data. The current findings showed that the investigated materials are potential adsorbents for mercury(II) ion removal in aqueous solution, with acidified P. aquatica Aubl being the most efficient adsorbent.