Decolorization and mineralization of a phthalocyanine dye C.I. Direct Blue 199 using UV/H2O2 process

In this study, the successful decolorization and mineralization of phthalocyanine dye (C.I. Direct Blue 199, DB 199) by an advanced oxidation process (AOP), UV/H2O2, were observed while the experimental variables such as hydrogen peroxide dosage, UV dosage, initial dye concentration and pH were evaluated. The operating conditions for 90% decolorization of C.I. DB 199 and 74% removal of total organic carbon (TOC) were obtained for initial dye concentration of 20 mgl(-1), hydrogen peroxide dosage of 116.32 mM, UV dosage of 560 W and pH of 8.9 in 30 min. The pseudo-first order rate constant is a linear function of reverse of initial dye concentration. They linearly increased by incrementing UV dosage, yet were non-linear enhancement by increasing the hydrogen peroxide concentration. A higher pseudo-first order rate constant about 0.15 min(-1) was observed while hydrogen peroxide concentration within 5.82-116.32 mM. Moreover, the decolorization of C.I. DB 199 was observed to be more difficult than that of an azo dye, C.I. Acid Black 1, under the same operating conditions.     

Effects of gap size and UV dosage on decolorization of C.I. Acid Blue 113 wastewater in the UV/H2O2 process

The wastewater from textile dyeing industry is difficult to be treated successfully according to both high variability of composition and color intensity. To investigate the effects of reactor gap size and UV dosage on the decolorization of dye wastewater, a commercially available azo dye C.I. Acid Blue 113 was chosen as a model compound. UV/H2O2 processes with various gap sizes and setups of plug flow reactor and recirculated batch reactor were proposed to deal with the dye wastewater in this study. The experimental parameters including the design of reactor configurations of annular gap size, and in batch system or plug flow reactors and hydrogen peroxide dosage, UV dosage were investigated. The gap size of reactor was adjusted by different diameter of reactor shells in order to optimize the reactor configuration. The color removal percentage was used to evaluate the treatment efficiency. An optimal hydrogen peroxide concentration of 46.53 mM was observed in this study for highest decolorization rate. Besides, the pseudo-first-order rate constant of 3.14 min(-1) was obtained by plug flow reactor with 0.5 cm gap size, 120.70 W/l of UV dosage and 23.27 mM of H2O2 dosage. The first-order rate constant, which was about 20 times less than that of plug flow reactor, was obtained 0.1422 min(-1) by recirculated batch reactor with 2.0 cm gap size, 7.0 W/l of UV and 23.27 mM of H2O2 dosages. Ultimately, we developed an effective pre-treatment or treatment technology for dye wastewater to provide the dyeing industries and dye manufacturers an alternative to meet the effluent standards.     

Kinetics of decolorization of an azo dye in UV alone and UV/H(2)O(2) processes

The decolorization of C.I. Acid Red 27 (AR27), a monoazo anionic dye, was studied in the ultraviolet radiation (UV) alone and UV plus hydrogen peroxide (UV/H(2)O(2)) processes. The experimental results indicated that the kinetics of both oxidation processes fit well by pseudo-first order kinetics. The reaction rate was sensitive to the operational parameters and increased with increasing H(2)O(2) concentration and light intensity. The reaction orders of H(2)O(2) concentration and light intensity in both processes were obtained with linear regression method. A regression model was developed for pseudo-first order rate constant (k(ap,UV/H(2)O(2))) as a function of the Cconcentration and UV light intensity. (k(ap,UV/H(2)O(2)))=(2 x 10(-4)I(0.75)(0) + k(3)I(1.38)(0)[H(2)O(2)](n)(0))phi(AR27). As a result of two opposing effects of H(2)O(2) concentration at low and high concentrations, n has a value of 0.49 and -0.39 and k(3) has a value of 3 x 10(-4) and 0.1 for the regions of 0 mg l(-1) < [H(2)O(2)](0) < 650 mg l(-1) and 650 mg l(-1) < [H(2)O(2)](0) < 1500 mg l(-1)1, respectively. PhiAR27 is the initial dye concentration correlation index for developing of model for different initial concentrations of AR27. This rate expression can be used for predicting k(ap,UV/H(2)O(2) at different conditions in UV alone and UV/H2O2 processes. The results show that UV alone cannot be an efficient method for decolorization of AR27 in comparison with UV/H(2)O(2) process, therefore the first term of the model can be neglected.     

Photolytic decolorization of Rose Bengal by UV/H(2)O(2) and data optimization using response surface method

Rose Bengal (C.I. name is Acid Red 94) was irradiated with UV light in the presence of hydrogen peroxide. The photoinduced decolorization of the dye was monitored spectrophotometrically. The apparent rate of decolorization was calculated from the observed absorption data and was found to be pseudo first order. A systematic study of the effect of dye concentration and H(2)O(2) concentration on the kinetics of dye decolorization was also carried out. Dye decolorization increased with increasing H(2)O(2) concentration and decreasing dye concentration. The maximum dye decolorization was determined as 90% with 0.005 mM dye at optimum 0.042 M H(2)O(2) and pH 6.6. Additionally, the effect on decolorization of this dye in the presence of some additives (ions) was also investigated. It was seen that sulphite caused a maximum effect on % decolorization of the dye solution. A plausible explanation involving the probable radical initiated mechanism was given to explain the dye decolorization. The experimental data was also optimized using the response surface methodology (RSM). According to ANOVA results, the proposed model can be used to navigate the design space. It was found that the response of Rose Bengal degradation is very sensitive to the independent factors of dye concentration, H(2)O(2) concentration, pH and reaction time. The proposed model for D-optimal design fitted very well with the experimental data with R(2) and R(adj)(2) correlation coefficients of 0.85 and 0.80, respectively.     

Design equation with mathematical kinetic modeling for photooxidative degradation of C.I. Acid Orange 7 in an annular continuous-flow photoreactor

The decolorization of C.I. Acid Orange 7 (AO7), an anionic monoazo dye of acid class was investigated using UV/H(2)O(2) process in an annular continuous-flow photoreactor (ACFP) as a function of oxidant, dye concentrations, reactor length and volumetric flow rate. The removal efficiency of AO7 was a function of operational parameters and increased with increasing initial concentration of H(2)O(2) but it was low at high flow rate and initial concentration of AO7. Results indicated that the decolorization rate was pseudo-first order kinetic with respect to the dye concentration. A rate equation for decolorization of AO7 was obtained by kinetic modeling. Design equation for ACFP reactor was obtained with combination of kinetic model and rearranged tubular reactor design equation. Design equation was used for predicting concentration of AO7 and also electrical energy per order (E(EO)) at different conditions. The calculated results obtained from design equation and kinetic model were in good agreement with experimental data.     

Decolorization of alkaline TNT hydrolysis effluents using UV/H(2)O(2)

Effects of H(2)O(2) dosage (0, 10, 50, 100 and 300 mg/l), reaction pH (11.9, 6.5 and 2.5) and initial color intensity (85, 80 and 60 color unit) on decolorization of alkaline 2,4,6-trinitrotoluene (TNT) hydrolysis effluents were investigated at a fixed UV strength (40 W/m(2)). Results indicated that UV/H(2)O(2) oxidation could efficiently achieve decolorization and further mineralization. Pseudo first-order decolorization rate constants, k, ranged between 2.9 and 5.4 h(-1) with higher values for lower H(2)O(2) dosage (i.e., 10 mg/l H(2)O(2)) when the decolorization occurred at the reaction pH of 11.9, whereas a faster decolorization was achieved with increase in H(2)O(2) dosage at both pH 6.5 and 2.5, resulting in the values of k as fast as 15.4 and 26.6 h(-1) with 300 mg/l H(2)O(2) at pH 6.5 and 2.5, respectively. Difference in decolorization rates was attributed to the reaction pH rather than to the initial color intensity, resulting from the scavenging of hydroxyl radical by carbonate ion. About 40% of spontaneous mineralization was achieved with addition of 10 mg/l H(2)O(2) at pH 6.5. Efficient decolorization and extension of H(2)O(2) longevity were observed at pH 6.5 conditions. It is recommended that the colored effluents from alkaline TNT hydrolysis be neutralized prior to a decolorization step.     

Remedy of dye manufacturing process effluent by UV/H2O2 process

The effluent from dye manufacturing industry is more difficult to be treated than laboratory synthesized wastewater according to high variability of composition and color intensity. Thus, this study aimed to propose the method for remedying industrial effluent by UV/H2O2 process in a recirculated batch reactor system while considering the effects on hydrogen peroxide dosage, UV power and wastewater intensity for the removal of color and COD. From the experimental results, it was feasibly treated that the distinguished removal of color and COD by increasing the hydrogen peroxide dosage and UV power, but not by the strong intensity of industrial effluent. Therefore, UV/H2O2 process of the developed reactor was a positively superior treatment or pre-treatment for dye manufacturing plant effluent to comply the regulated requirements.     

Photodegradation of direct yellow-12 using UV/H2O2/Fe2+

A detailed investigation of photodegradation of direct yellow-12 (DY12) using UV/H(2)O(2)/Fe(2+) has been carried out in a photochemical reactor. Experiments studied degradation as a function of concentration, decolorization and reduction in chemical oxygen demand (COD). The effect of operating parameters, such as UV, pH, amount of Fenton's reagent (H(2)O(2) and FeSO(4)), and amount of DY12 dye has also been determined. It has been observed that simultaneous utilization of UV irradiation with Fenton's reagent increases the degradation rate of DY12 dye. The dye quickly losses its color and there is an appreciable decrease in COD value, indicating that the dissolved organic have been oxidized. The kinetics of degradation of the dye in dilute aqueous solutions follows pseudo-first order kinetics. Final products detected at the end of the reaction include NO(3)(-), NO(2)(-), N(2)O, NO(2), SO(2), CO(2) and CO. Results indicate that dye degradation is dependent upon pH, UV-intensity, concentration of Fenton's reagent and dye. Acidic pH has been found to be more suitable in comparison to neutral and alkaline. The optimum concentration of Fenton's reagent (H(2)O(2)/Fe(2+)) was found as 1500/500 mg l(-1) for 50 mg l(-1) DY12 dye in water at pH 4. The results indicate that the treatment of DY12 dye wastewater with UV/Fe(2+)/H(2)O(2) system is efficient.     

Pilot scale annular plug flow photoreactor by UV/H2O2 for the decolorization of azo dye wastewater

A pilot scale annular plug flow photoreactor with thin gap size, which combines with UV irradiation and hydrogen peroxide, was employed to deal with colored dyeing wastewater treatment. In the experiment, a mono-azo dye acid orange 10 was the target compound. The experimental parameters such as flow rate, hydrogen peroxide dosage, UV input power, pH and dye initial concentrations in a pilot scale photoreactor with flow rate of 9.32 m3day(-1) were investigated. Ultimately, the degradation rates were calculated and compared with a 100-l batch reactor. In our plug flow photoreactor design, the degradation rate of acid orange 10 was 233 times higher than that of 100-l annular batch reactor with same UV light source. The residence time needed for 99% decolorizing of 100 l of 20 mgl(-1) acid orange 10 wastewater was 26.9 min for the thin gap plug flow reactor and was far shorter than that of batch reactor needed.     

Sonochemical degradation of Basic Blue 41 dye assisted by nanoTiO2 and H2O2

The sonolysis of Basic Blue 41 dye in aqueous solution was performed at 35 kHz using ultrasonic power of 160 W and aqueous temperature of 25+1 degrees C within 180 min. The TiO2 nanoparticles were used as a catalyst to assist the sonication process. The effect of experimental parameters such as pH, H2O2 concentration and initial dye concentration on the reaction were investigated. It was recognized that in lower pH values the dye removal rate decreased. However, dye removal increased via increase in H2O2 concentration and lowering the initial dye concentration. All intermediate compounds were detected by integrated gas chromatography-mass spectrometry (GC/MS) and also ion chromatograph (IC). During the decolorization, all nitrogen atoms and aromatic groups of Basic Blue 41 were converted to urea, nitrate, formic acid, acetic acid and oxalic acid, etc. Kinetic studies revealed that the degradation process followed pseudo-first order mechanism with the correlation coefficient (R2) of 0.9918 under experimental conditions. The results showed that power ultrasound can be regarded as an appropriate tool for degradation of azo dyes to non-toxic end products.     

Decolorization kinetics of Procion H-exl dyes from textile dyeing using Fenton-like reactions

The decolorization kinetics of three commercially used Procion H-exl dyes was studied using a Fenton-like reagent. The effect of the major system parameters (pH, concentration of H(2)O(2) and Fe(3+) and initial dye concentration) on the kinetics was determined. For comparison, the effect of the use of UV irradiated Fenton-like reagent and of Fenton reagent on the kinetics was also examined. In addition, mineralization rates and the biodegradability improvement as well as the effect of the addition of Cl(-), CO(3)(2-) or HCO(3)(-) on the decolorization rates was studied. The reactions were carried out in a 300 ml stirred cylindrical reactor with the capability of UV irradiation. The dye half-life time goes through a minimum with respect to the solution pH between 3 and 4. It also exhibits a broad minimum with respect to Fe(3+) and H(2)O(2) at molar ratios of H(2)O(2)/Fe(3+) from about 100 to 10. The addition of CO(3)(2-) and HCO(3)(-) substantially reduces the decolorization rates, while this effect is significantly less pronounced with Cl(-). At an optimum range of parameters, the mineralization rate (TOC reduction) is very slow for the Fenton-like process (TOC decrease from an initial 49.5 to 41.1 mg/l after 30 min and to only 35.2 mg/l after 600 min), but it increases significantly for the photo-Fenton-like process (to TOC values of 39.7 and 11.4 mg/l, respectively). The biodegradability, as expressed by the BOD/COD ratio, increases significantly from an initial value of 0.11-0.55 for the Fenton-like and to 0.72 for the photo-Fenton-like processes.     

Application of Box-Wilson experimental design method for the photodegradation of bakery's yeast industry with UV/H2O2 and UV/H2O2/Fe(II) process

Decolorization and mineralization of bakery's yeast industry effluent by photochemical advanced oxidation processes (AOPs) utilizing UV with hydrogen peroxide and Photo-Fenton, were investigated in a laboratory scale photo-reactor equipped with a 16 W low-pressure mercury vapor lamp. The Box-Wilson experimental design method was employed to evaluate the effects of major process variables (e.g. pH, oxidant dose, and irradiation time) on the decolorization efficiency. Response function coefficients were determined by regression analysis of the experimental data and prediction results agreed with the experimental results. The optimum hydrogen peroxide concentration and irradiation time were found to be 5 mM and 50 min at pH 3, respectively, for UV/H2O2 process. In the Photo-Fenton process application, maximum decolorization efficiency (96.4%) was obtained at the optimum reaction conditions that were 100 mM H2O2 and 1 mM Fe(II) doses at pH 3, and 10 min of irradiation time.     

A kinetic model for the decolorization of C.I. Acid Yellow 23 by Fenton process

The decolorization of azo dye C.I. Acid Yellow 23 (AY23) by Fenton process was investigated. The decolorization rate is strongly dependent on the initial concentrations of the Fe(2+) and H(2)O(2). The optimum operational conditions were obtained at pH 3. A kinetic model has been developed to predict the decolorization of AY23 at different operational conditions by Fenton process. The model allows to simulate the system behavior involving the influence of hydrogen peroxide, Fe(II) and dye concentrations.     

Photodegradation of methyl tert-butyl ether (MTBE) by UV/H2O2 and UV/TiO2

Two UV-based advanced oxidation processes (AOPs), UV/H2O2 and UV/TiO2, were tested in batch reactor systems to evaluate the removal efficiencies and optimal conditions for the photodegradation of methyl tert-butyl ether (MTBE). The optimal conditions at an initial MTBE concentration of 1 mM ([MTBE]0=1 mM) were acidic and 15 mM H2O2 in UV/H2O2 system, and pH 3.0 and 2.0 g/l TiO2 in UV/TiO2 suspended slurries system under 254-nm UV irradiation. Under the optimal conditions, MTBE photodegradation during the initial period of 60 min in UV/H2O2 and UV/TiO2 systems reached 98 and 80%, respectively. In both systems, MTBE photodegradation decreased with increasing [MTBE]0. While MTBE photodegradation rates increased with increasing dosage of H2O2 (5-15 mM) and TiO2 (0.5-3 g/l), further increase in the dosage of H2O2 (20 mM) or TiO2 (4 g/l) adversely reduced the MTBE photodegradation. Pseudo first-order kinetics with regard to [MTBE] can be used to describe the MTBE photodegradation in both systems. The pseudo first-order rate constants linearly increased with the increase in the molar ratio of [H2O2]0 to [MTBE]0 in UV/H2O2 system and linearly increased with the decrease in [MTBE]0 in UV/TiO2 system.     

Photooxidative degradation of Acid Red 27 in a tubular continuous-flow photoreactor: influence of operational parameters and mineralization products

The decolorization and mineralization of Acid Red 27 (AR27), an anionic monoazo dye of acid class, was investigated using UV radiation in the presence of H2O2 in a tubular continuous-flow photoreactor as a function of oxidant concentration, reactor length, flow rate and light intensity. The removal efficiency of AR27 depends on the operational parameters and increases as the initial concentration of H2O2 and light intensity are increased but it decreases when the flow rate is increased. The AR27 degradation was followed through HPLC, UV-vis and COD analyses. The results of these analyses showed that the final outlet stream from the photoreactor was completely mineralized. The UV/H2O2 process was also able to mineralize nitrogen and sulfur heteroatoms into NH4+, NO3-, NO2- and SO4(2-) ions, respectively. The nitrogen of azo group was transformed predominantly to NH4+ ions. Decreasing the flow rate results in the reduction of COD and promotion of SO4(2-) at the final outlet stream of the photoreactor.     

Effects of gap size and UV dosage on decolorization of C.I. Acid Orange 7 by UV/H2O2 process

Wastewater from textile processing plants can be highly colored and difficult to decolorize. During the past few years attention has been drawn to chemical techniques that could be used to textile wastewater decolorization. A crucial feature in designing such systems is the optimization of operating conditions. In the present study, advanced oxidation treatment, the UV/H(2)O(2) process has been applied to decolorization of the azo dye C.I. Acid Orange 7 (AO7) in aqueous solution in a batch photo reactor. The effects of the reactor gap size and UV dosage on decolorization of dye have been investigated. The method of study involved monitoring the rate of dye solution decolorization during irradiation by a low-pressure mercury lamp and varying gap size and volume of the reactor. The rate of color removal was studied by measuring of the absorbance at characteristic wavelength. The gap size of the reactor was adjusted by different depths of the reactor. The results of this study showed that the removal efficiency of AO7 is optimal with 0.3 cm gap size and 83.33 Wl(-1) of UV dosage.     

Decolorization of C.I. Reactive Red 2 by catalytic ozonation processes

This study adopted O3, UV/TiO2/O3, O3/Mn(II) and O3/MnO2 systems to assess the decolorization efficiency of C.I. Reactive Red 2 (RR2). The decolorization rate increased with concentrations of Mn(II) and MnO2 in the ranges 0.05-0.1 and 0.05-0.8 g/l, respectively. However, when 0.5-3g/l TiO2 was added, the effect of TiO2 dosage for RR2 decolorization was insignificant in the UV/TiO2/O3 system. At pH 2, the decolorization rate constants of O3, O3/Mn(II) (0.05 g/l), O3/Mn(II) (0.1g/l), O3/Mn(II) (0.15 g/l), O3/MnO2 (0.05 g/l) and O3/MnO2 (0.8 g/l) were 0.816, 2.001, 3.173, 3.087, 1.040 and 1.648 min(-1), respectively. After 5 min of reaction, the decolorization rates followed the order O3/Mn(II)>O3/MnO2>O3>UV/TiO2/O3; however, the TOC removal did not vary among these systems. Adding ethanol reduced the decolorization rate of the UV/TiO2/O3 and O3/MnO2 systems and did not affect the decolorization rate of O3/Mn(II). Decolorization in UV/TiO2/O3, O3/Mn(II) and O3/MnO2 systems is suggested to proceed by mainly radical-, surface- and radical-type mechanisms, respectively. Additionally, direct ozonation cannot be ignored in O3/Mn(II) and O3/MnO2 systems.     

A comparative study of quantum yield and electrical energy per order (E(Eo)) for advanced oxidative decolourisation of reactive azo dyes by UV light

This paper evaluates the quantum yield and electrical energy per order (E(Eo)) efficiency of Reactive Orange 4 (RO4) and Reactive Yellow 14 (RY14) azo dyes by three advanced oxidation processes (AOPs). Both dyes were completely decolourised by all these processes. The relative decolourisation efficiencies of these processes were in the following order: Fe(2+)/H(2)O(2)/UV>UV/TiO(2)>UV/H(2)O(2). The low efficiency of UV/H(2)O(2) process is mainly due to low UV absorption by hydrogen peroxide at the 365nm. The figure of merit E(Eo) values showed that UV/H(2)O(2) process consumes more electrical energy than the other two processes. The electrical energy consumption is in the following order: UV/H(2)O(2)>UV/TiO(2)>Fe(2+)/H(2)O(2)/UV. At low initial dye concentration higher quantum yield was observed in UV/TiO(2) process, whereas in photo-Fenton process higher quantum yield was observed at high initial dye concentration. The structure of dye molecule also influences the quantum yield and E(Eo) value.     

Heterogeneous photo-Fenton decolorization of methylene blue over LiFe(WO4)2 catalyst

Heterogeneous photo-Fenton process using LiFe(WO(4))(2) as catalyst was studied to degrade Methylene blue (MB) dye in aqueous solution. The results indicated that LiFe(WO(4))(2) could effectively catalyze the decolorization of MB in the presence of UV light and H(2)O(2). The effects of different parameters such as amounts of catalyst, H(2)O(2) concentration, initial pH of the dye solution, initial dye concentration and UV light intensity on the decolorization efficiency of the process were investigated. It was found that LiFe(WO(4))(2) possessed a wide applicable pH range. X-ray photoelectron spectroscopy (XPS) was applied to investigate the transformation between Fe(III) and Fe(II). It was also observed that catalytic behavior could be reproduced in consecutive experiments without a considerable drop in the process efficiency.     

Treatment of MSW landfill leachate by a thin gap annular UV/H2O2 photoreactor with multi-UV lamps

The treatment of leachate from landfills is a major disposal problem for municipal solid waste. The leachate is generally recalcitrant to be treated according to complicated characteristics and high color intensity resulting further threat for environment and human health. In this work, the designed thin gap annular photoreactor with 4-UV lamps in UV/H2O2 process was proposed to decolor and remove chemical oxygen demand (COD) from the landfill leachate for solving this environmental problem. Meanwhile, the operating parameters such as UV dosage, hydrogen peroxide concentration and leachate strength were evaluated. The landfill leachate treated with the maximum dosage of 4-UV lamps and 232.7 mM of hydrogen peroxide concentration achieved 72 and 65% of color and COD removal efficiencies in 300 min. As for less concentrated leachate of 20% strength, 91% of color and 87% of COD were removed within only 120 min. From the experimental results, the UV/H2O2 process in this work was an effective pre-treatment or treatment technology for landfill leachate.