Low cost removal of reactive dyes using wheat bran

In this study, the adsorption of Reactive Blue 19 (RB 19), Reactive Red 195 (RR 195) and Reactive Yellow 145 (RY 145) onto wheat bran, generated as a by-product material from flour factory, was studied with respect to initial pH, temperature, initial dye concentration, adsorbent concentration and adsorbent size. The adsorption of RB 19, RR 195 and RY 145 onto wheat bran increased with increasing temperature and initial dye concentration while the adsorbed RB 19, RR 195 and RY 145 amounts decreased with increasing initial pH and adsorbent concentration. The Langmuir and Freundlich isotherm models were applied to the experimental equilibrium data depending on temperature and the isotherm constants were determined by using linear regression analysis. The monolayer covarage capacities of wheat bran for RB 19, RR 195 and RY 145 dyes were obtained as 117.6, 119.1 and 196.1 mg/g at 60 degrees C, respectively. It was observed that the reactive dye adsorption capacity of wheat bran decreased in the order of RY 145>RB 19>RR 195. The pseudo-second order kinetic and Weber-Morris models were applied to the experimental data and it was found that both the surface adsorption as well as intraparticle diffusion contributed to the actual adsorption processes of RB 19, RR 195 and RY 145. Regression coefficients (R2) for the pseudo-second order kinetic model were higher than 0.99. Thermodynamic studies showed that the adsorption of RB 19, RR 195 and RY 145 dyes onto wheat bran was endothermic in nature.     

Sorption of reactive dye from aqueous solution on biomass fly ash

This study investigates the adsorption behavior of Reactive Black 5 (RB) and Reactive Yellow 176 (RY) from aqueous solution on coal fly ash (FA-CO), HCl-treated coal fly ash (TFA-HCl), and biomass fly ash (FA-BM). In preliminary study, the FA-BM showed the greatest dye adsorption capacity of both dyes, compared to FA-CO and TFA-HCl. Hence only for the FA-BM, the effects of various experiment parameters (e.g. solution pH, ionic strength, initial dye concentration, contact time) were spectrophotometrically determined. At the final pH of 8.1-8.5, the adsorption capacity of both dyes on the FA-BM was maximum and decreased above or below this pH. A positive effect of salt addition on the dye adsorption capacity was observed. The adsorption capacity of dye on the FA-BM increased with increasing C0. The equilibrium data of both dyes on the FA-BM were fitted to both Langmuir and Freundlich isotherms, but the experimental data of the RB was found to be little better fitted by the Langmuir model. The sorption data was good fit with the pseudo-second-order kinetic model. These results indicate that biomass fly ash is an interesting alternative for dye removal from the wastewater.     

Application of statistical experimental methodology to optimize reactive dye decolourization by commercial laccase

Three-level Box-Behnken factorial design with three factors (pH, temperature and enzyme concentration) combined with response surface methodology (RSM) was applied to optimize the dye degradation of reactive red 239 (RR239), reactive yellow 15 (RY15) and reactive blue 114 (RB114) dyes by commercial laccase. Mathematical models were developed for each dye showing the effect of each factor and their interactions on colour removal. The model predicted for RY15 that a decolourization above 90% (after 24h) could be obtained when the enzyme concentration, temperature and pH were set at 109.8U/L, 39.2 degrees C and 6.6, respectively; whilst for RB114 and RR239 the temperature and enzyme concentration did not affect the decolourization (>90%) in the considered range and optimum pH value was found at 5.5-7.0 and 7.0-7.5, respectively. These predicted values were also experimentally validated. Average final values of responses were in good agreement with calculated values, thus confirming the reliability of the models of RY15, RB114 and RR239 decolourization.     

Adsorption of reactive dyes from aqueous solutions by fly ash: kinetic and equilibrium studies

Adsorption kinetic and equilibrium studies of three reactive dyes namely, Remazol Brillant Blue (RB), Remazol Red 133 (RR) and Rifacion Yellow HED (RY) from aqueous solutions at various initial dye concentration (100–500 mg/l), pH (2–8), particle size (45–112.5 μm) and temperature (293–323 K) on fly ash (FA) were studied in a batch mode operation. The adsorbent was characterized with using several methods such as SEM, XRD and FTIR. Adsorption of RB reactive dye was found to be pH dependent but both RR and RY reactive dyes were not. The result showed that the amount adsorbed of the reactive dyes increased with increasing initial dye concentration and contact time. Batch kinetic data from experimental investigations on the removal of reactive dyes from aqueous solutions using FA have been well described by external mass transfer and intraparticle diffusion models. It was found that external mass transfer and intraparticle diffusion had rate limiting affects on the removal process. This was attributed to the relatively simple macropore structure of FA particles. The adsorption data fitted well with Langmuir and Freundlich isotherm models. The optimum conditions for removal of the reactive dyes were 100 mg/l initial dye concentration, 0.6 g/100 ml adsorbent dose, temperature of 293 K, 45 μm particle size, pH 6 and agitation speed of 250 rpm, respectively. The values of Langmuir and Freundlich constants were found to increase with increasing temperature in the range 135–180 and 15–34 mg/g for RB, 47–86 and 1.9–3.7 mg/g for RR and 37–61 and 3.0–3.6 mg/g for RY reactive dyes, respectively. Different thermodynamic parameters viz., changes in standard free energy, enthalpy and entropy were evaluated and it was found that the reaction was spontaneous and endothermic in nature.     

Sunflower seed shells: a novel and effective low-cost adsorbent for the removal of the diazo dye Reactive Black 5 from aqueous solutions

In this paper, the potential of two low-cost adsorbents such as sunflower seed shells (SS) and mandarin peelings (MP) in the removal of the synthetic anionic dye Reactive Black 5 (RB5) from aqueous solutions was investigated. SS led to a percentage of dye removal higher than MP (85% and 71% after 210min, respectively, for an initial RB5 concentration of 50mgL(-1) and an initial pH of 2.0). The rate of adsorption followed a pseudo-second-order kinetic model and the intra-particle diffusion was found to be the rate-controlling stage. In addition, the equilibrium data fitted well both the Freundlich and multilayer adsorption isotherm equations indicating the heterogeneity of the adsorbent surface. This was also corroborated by the SEM photographs. On the whole, the results in this study indicated that SS were very attractive materials for removing anionic dyes from dyed effluents.     

Removal of Reactive Red 195 from aqueous solutions by adsorption on the surface of TiO2 nanoparticles

Nanoparticles of TiO₂ were synthesized and characterized by XRD, BET, TG/DTA and TEM measurements. The commercial azo dye Reactive Red 195 (RR195) was selected as a model dye in order to examine the adsorption capacity of TiO₂ at room temperature, under dark conditions. It was demonstrated that RR195 could be efficiently adsorbed in aqueous suspension of TiO₂. A study on the effects of various parameters like initial pH, concentration of dye and concentration of adsorbent has been carried out in order to find optimum adsorption conditions. The optimum pH of sorption was 3. Substantial reduction of COD, besides removal of colour, was also achieved. The experimental data were analyzed by the Langmuir and Freundlich adsorption models. Equilibrium data fitted very well with the Langmuir model signifying the energetic homogeneity of TiO₂ surface adsorption sites. At the temperature of 30 °C, the maximum monolayer adsorption capacity obtained from the Langmuir model is 87 mg/g (pH 3.0). Kinetic studies were carried out and showed a rapid sorption of dye in the first 30 min while equilibrium was reached at 1 h. Three kinetic adsorption models were used to describe the kinetics data, the pseudo-first-order model, the pseudo-second-order model and the intraparticle diffusion model. The sorption kinetics of dye was best described by the pseudo-second-order kinetic model.     

Adsorption of Reactive Red M-2BE dye from water solutions by multi-walled carbon nanotubes and activated carbon

Multi-walled carbon nanotubes and powdered activated carbon were used as adsorbents for the successful removal of Reactive Red M-2BE textile dye from aqueous solutions. The adsorbents were characterised by infrared spectroscopy, N₂ adsorption/desorption isotherms and scanning electron microscopy. The effects of pH, shaking time and temperature on adsorption capacity were studied. In the acidic pH region (pH 2.0), the adsorption of the dye was favourable using both adsorbents. The contact time to obtain equilibrium at 298 K was fixed at 1 h for both adsorbents. The activation energy of the adsorption process was evaluated from 298 to 323 K for both adsorbents. The Avrami fractional-order kinetic model provided the best fit to the experimental data compared with pseudo-first-order or pseudo-second-order kinetic adsorption models. For Reactive Red M-2BE dye, the equilibrium data were best fitted to the Liu isotherm model. Simulated dyehouse effluents were used to check the applicability of the proposed adsorbents for effluent treatment.     

Determination of adsorptive properties of a Turkish Sepiolite for removal of Reactive Blue 15 anionic dye from aqueous solutions

Reactive Blue 15 (RB 15) adsorption on the Turkish Sepiolite was carried out by batch equilibrium technique. IR spectrum and surface area measurement of the composite of dye-sepiolite (Turkish) pointed out that dye species replaced partly the zeolitic water to form hydrogen bond with bound water and adsorbed to the channels sites. The effects of temperature, pH and ionic strength on adsorption of dye molecules were investigated and the nature of adsorption process was determined by calculating DeltaH, DeltaS and DeltaG values. The adsorbed amount increased with increase in temperature, but that for high pH values decreased for the adsorption of reactive dye.     

Cationic polyelectrolyte/bentonite prepared by ultrasonic technique and its use as adsorbent for Reactive Blue K-GL dye

In this study, the cationic polyelectrolyte polyepicholorohydrin-dimethylamine (EPI-DMA) was intercalated into bentonite using ultrasonic. The structure of EPI-DMA/bentonite and its adsorption of Reactive Blue K-GL (RB K-GL) dye were investigated. Compared with raw bentonite, the EPI-DMA/bentonite had larger interlayer spacing and was more hydrophobic, providing with better surface properties for adsorption. The adsorption of RB K-GL on EPI-DMA/bentonite was described by the adsorption models of Langmuir, Freundlich and Dubinin-Radushkevic. The adsorption kinetics was analyzed using pseudo-first- and second-order kinetic models and intraparticle diffusion model. Results showed that both the intraparticle diffusion and first-order adsorption occur in the initial period of adsorption, and that pseudo-second-order kinetic model was more suitable for describing the whole adsorption process. The reaction rates were also calculated. The changes of free energy, enthalpy and entropy of adsorption were evaluated for the adsorption of RB K-GL onto EPI-DMA/bentonite, suggesting that the adsorption process was spontaneous and exothermic.     

Biosorption of Reactive Black 5 dye by Penicillium restrictum: the kinetic study

Biosorption of Reactive Black 5 (RB 5) dye onto dried Penicillium restrictum biomass was studied with respect to pH, contact time, biosorbent and dye concentrations. The effect of temperature on the biosorption efficiency was also carried out and the kinetic parameters were determined. Optimum initial pH, equilibrium time and biomass concentration for RB 5 dye were found to be 1.0, 75 min and 0.4 g dm(-3) at 20 degrees C, respectively. The maximum biosorption capacities (q(max)) of RB 5 dye onto dried P. restrictum biomass were 98.33 and 112.50mg (g biomass)(-1) at 175 mg dm(-3) initial dye concentration at 20 and 50 degrees C, respectively, and it was 142.04 mg (g biomass)(-1) at 200 mg dm(-3) initial dye concentration at 35 degrees C. The results indicate that the biosorption process obeys a pseudo-second-order kinetic model.     

Competition of Reactive red 4, Reactive orange 16 and Basic blue 3 during biosorption of Reactive blue 4 by polysulfone-immobilized Corynebacterium glutamicum

Competition of Reactive red 4 (RR4), Reactive orange 16 (RO16) and Basic blue 3 (BB3) during biosorption of Reactive blue 4 (RB4) by polysulfone-immobilized protonated Corynebacterium glutamicum (PIPC) was investigated in batch and column mode of operations. Through potentiometric titrations, and with the aid of proton-binding model, carboxyl, phosphonate and amine were identified as functional groups of PIPC, with apparent pK(a) values of 3.47+/-0.05, 7.08+/-0.07 and 9.90+/-0.05 mmol/g, respectively. Since reactive dyes release dye anions (ROSO(3)(-)) in solutions, the positively charged amine groups were responsible for biosorption. PIPC favored biosorption at pH 3 when RB4 was studied/used as single-solute; while the presence of RR4 and RO16 severely affected the RB4 biosorption. When present as a single-solute, PIPC recorded 184.5mg RB4/g; while PIPC exhibited 126.9, 120.9 and 169.6 mg RB4/g in the presence of RR4, RO16 and BB3, respectively. In general, the accessibility of amine group depends on the molecular size, number of sulfonate groups and reactivity of each reactive dye. Single and multicomponent Freundlich equations successfully described the biosorption isotherms. With 0.1M NaOH, it is possible to reuse PIPC for RB4 biosorption in 10 repeated cycles. Column experiments in an up-flow packed column coincided with batch results, that is PIPC showed strong preference towards highly reactive and relatively small RB4 anions; however, the presence of competing dyes hinder the RB4 column biosorption performance.     

Solar/UV-induced photocatalytic degradation of three commercial textile dyes.

The photocatalytic degradation of three commercial textile dyes with different structure has been investigated using TiO(2) (Degussa P25) photocatalyst in aqueous solution under solar irradiation. Experiments were conducted to optimise various parameters viz. amount of catalyst, concentration of dye, pH and solar light intensity. Degradation of all the dyes were examined by using chemical oxygen demand (COD) method. The degradation efficiency of the three dyes is as follows: Reactive Yellow 17(RY17) > Reactive Red 2(RR2) > Reactive Blue 4 (RB4), respectively. The experimental results indicate that TiO(2) (Degussa P25) is the best catalyst in comparison with other commercial photocatalysts such as, TiO(2) (Merck), ZnO, ZrO(2), WO(3) and CdS. Though the UV irradiation can efficiently degrade the dyes, naturally abundant solar irradiation is also very effective in the mineralisation of dyes. The comparison between thin-film coating and aqueous slurry method reveals that slurry method is more efficient than coating but the problems of leaching and the requirement of separation can be avoided by using coating technique. These observations indicate that all the three dyes could be degraded completely at different time intervals. Hence, it may be a viable technique for the safe disposal of textile wastewater into the water streams.     

Removal of boron from aqueous solutions by batch adsorption on calcined alunite using experimental design

In the present paper, boron removal from aqueous solutions by batch adsorption was investigated and 2(3) full factorial design was applied. Calcined alunite was used as adsorbent. In the study, three parameters affected the performance and two levels of these parameters were investigated. The chosen parameters were temperature (25 and 45 degrees C, respectively), pH (3 and 10) and mass of adsorbent (0.5 g adsorbent per 25 mL solution and 1g adsorbent per 25 mL solution). The significance of the effects was checked by analysis of variance (statistical software, MINITAB-Version 15). The model-function equation for boron adsorption on calcined alunite was obtained. The results showed that temperature, pH and mass of adsorbent affected boron removal by adsorption. Boron removal increased with increasing pH and adsorbent dosage, but decreased with increasing temperature. The optimum conditions were found as pH 10, adsorbent dosage=1g of calcined alunite per 25 mL solution and temperature=25 degrees C by using factorial design. In addition, the effects of parameters such as calcination temperature, pH, temperature, adsorbent dosage and initial boron concentration on boron removal were investigated. The adsorption isotherm studies were also performed. Maximum adsorbent capacity (q(0)) was calculated as 3.39 mg/g. Thermodynamic parameters such as change in free energy (DeltaG degrees), enthalpy (DeltaH degrees) and entropy (DeltaS degrees) were also determined.     

Microcolumn studies of dye adsorption onto manganese oxides modified diatomite

The method described here cannot fully replace the analysis of large columns by small test columns (microcolumns). The procedure, however, is suitable for speeding up the determination of adsorption parameters of dye onto the adsorbent and for speeding up the initial screening of a large adsorbent collection that can be tedious if a several adsorbents and adsorption conditions must be tested. The performance of methylene blue (MB), a basic dye, Cibacron reactive black (RB) and Cibacron reactive yellow (RY) was predicted in this way and the influence of initial dye concentration and other adsorption conditions on the adsorption behaviour were demonstrated. On the basis of the experimental results, it can be concluded that the adsorption of RY onto manganese oxides modified diatomite (MOMD) exhibited a characteristic "S" shape and can be simulated effectively by the Thomas model. It is shown that the adsorption capacity increased as the initial dye concentration increased. The increase in the dye uptake capacity with the increase of the adsorbent mass in the column was due to the increase in the surface area of adsorbent, which provided more binding sites for the adsorption. It is shown that the use of high flow rates reduced the time that RY in the solution is in contact with the MOMD, thus allowing less time for adsorption to occur, leading to an early breakthrough of RY. A rapid decrease in the column adsorption capacity with an increase in particle size with an average 56% reduction in capacity resulting from an increase in the particle size from 106-250 microm to 250-500 microm. The experimental data correlated well with calculated data using the Thomas equation and the bed depth-service time (BDST) equation. Therefore, it might be concluded that the Thomas equation and the BDST equations can produce accurate predication for variation of dye concentration, mass of the adsorbent, flow rate and particle size. In general, the values of adsorption isotherm capacity obtained in a batch system show the maximum values and are considerably higher than those obtained in a fixed-bed.     

Photocatalytic reduction of Cr(VI) on the new hetero-system CuAl2O4/TiO2

A magnetic adsorbent, amine-functionalized silica magnetite (NH(2)/SiO(2)/Fe(3)O(4)), has been synthesized to behave as an anionic or cationic adsorbent by adjusting the pH value of the aqueous solution to make amino groups protonic or neutral. NH(2)/SiO(2)/Fe(3)O(4) were used to adsorb copper ions (metal cation) and Reactive Black 5 (RB5, anionic dye) in an aqueous solution in a batch system, and the maximum adsorption were found to occur at pH 5.5 and 3.0, respectively. The adsorption equilibrium data were all fitted the Langmuir isotherm equation reasonably well, with a maximum adsorption capacity of 10.41 mg g(-1) for copper ions and of 217 m g g(-1) for RB5. A pseudo-second-order model also could best describe the adsorption kinetics, and the derived activation energy for copper ions and RB5 were 26.92 kJ mol(-1) and 12.06 kJ mol(-1), respectively. The optimum conditions to desorb cationic and anionic adsorbates from NH(2)/SiO(2)/Fe(3)O(4) were provided by a solution with 0.1M HNO(3) for copper ions and with 0.05 M NaOH for RB5.     

Decolourization and mineralization of commercial reactive dyes by using homogeneous and heterogeneous Fenton and UV/Fenton processes

The oxidative decolourization and mineralization of three reactive dyes in separately prepared aqueous solutions C.I. Reactive Yellow 3 (RY3), C.I. Reactive Blue 2 (RB2) and C.I. Reactive Violet 2 (RV2) by using homogeneous and heterogeneous Fenton and UV/Fenton processes have been investigated. The effects of H(2)O(2), Fe(2+) and Fe(0) concentrations, Fe(2+)/H(2)O(2) and Fe(0)/H(2)O(2) molar ratios at pH 3 and T=23+/-1 degrees C have been studied. Optimal operational conditions for the efficient degradation of all three dye solutions (100 mg L(-1)) were found to be Fe(2+)/H(2)O(2)=0.5mM/20mM and Fe(0)/H(2)O(2)=2mM/1mM. The experimental results showed that the homogeneous Fenton process employing UV irradiation was the most effective. By using this process, the high levels of mineralization (78-84%) and decolourization (95-100%) were achieved. Pseudo-first-order degradation rate constants were obtained from the batch experimental data.     

Equilibrium and kinetic modeling of adsorption of reactive dye on cross-linked chitosan beads

The adsorption of reactive dye (Reactive Red 189) from aqueous solutions on cross-linked chitosan beads was studied in a batch system. The equilibrium isotherms at different particle sizes (2.3-2.5, 2.5-2.7 and 3.5-3.8mm) and the kinetics of adsorption with respect to the initial dye concentration (4320, 5760 and 7286 g/m(3)), temperature (30, 40 and 50 degrees C), pH (1.0, 3.0, 6.0 and 9.0), and cross-linking ratio (cross-linking agent/chitosan weight ratio: 0.2, 0.5, 0.7 and 1.0) were investigated. Langmuir and Freundlich adsorption models were applied to describe the experimental isotherms and isotherm constants. Equilibrium data fitted very well to the Langmuir model in the entire saturation concentration range (0-1800 g/m(3)). The maximum monolayer adsorption capacities obtained from the Langmuir model are very large, which are 1936, 1686 and 1642 g/kg for small, mediumand large particle sizes, respectively, at pH 3.0, 30 degrees C, and the cross-linking ratio of 0.2. The pseudo first- and second-order kinetic models were used to describe the kinetic data, and the rate constants were evaluated. The experimental data fitted well to the second-order kinetic model, which indicates that the chemical sorption is the rate-limiting step, instead of mass transfer. The initial dye concentration and the solution pH both significantly affect the adsorption capacity, but the temperature and the cross-linking ratio are relatively minor factors. An increase in initial dye concentration results in the increase of adsorption capacity, which also increases with decreasing pH. The activation energy is 43.0 kJ/mol for the adsorption of the dye on the cross-linked chitosan beads at pH 3.0 and initial dye concentration 3768 g/m(3).     

Synthesis of a novel water-soluble chitosan derivative for flocculated decolorization

To increase the water solubility and cationic charges at pH 7, cationic moieties were introduced onto both the C(6)-OH and C(2)-NH(2) groups in the chitosan (CTS) matrix by graft modification. The chemical structure of the obtained copolymer was demonstrated by characterizations of FT-IR, (13)C NMR, WXRD, SEM. Its excellent decolorization properties as a novel flocculant were evaluated with the C.I. Reactive Orange 5 (RO 5) and C.I. Reactive Blue 19 (RB 19) solutions using a jar test method. Both the nature of the anionic dyes and the pH of the initial dye solutions had effects on the decolorization properties. Charge neutralization played a dominant role for the color removal at pH 4, while polymer bridging contributed mainly to the color removal at pH 7. For the given flocculant/dye solutions, added salt was not in favor of the flocculated decolorization. At 25 °C, the flocculant needed for the highest color removal at pH 4 was 60 wt% of the dye (RO 5 or RB 19), but that at pH 7 were 100 wt% of RB 19 and 120 wt% of RO 5, respectively.