Photochemical degradation of diethyl phthalate with UV/H2O2

The decomposition of diethyl phthalate (DEP) in water using UV-H2O2 process was investigated in this paper. DEP cannot be effectively removed by UV radiation and H2O2 oxidation alone, while UV-H2O2 combination process proved to be effective and could degrade this compound completely. With initial concentration about 1.0mg/L, more than 98.6% of DEP can be removed at time of 60 min under intensity of UV radiation of 133.9 microW/cm2 and H2O2 dosage of 20mg/L. The effects of applied H2O2 dose, UV radiation intensity, water temperature and initial concentration of DEP on the degradation of DEP have been examined in this study. Degradation mechanisms of DEP with hydroxyl radicals oxidation also have been discussed. Removal rate of DEP was sensitive to the operational parameters. A simple kinetic model is proposed which confirms to pseudo-first order reaction. There is a linear relationship between rate constant k and UV intensity and H2O2 concentration.     

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.     

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.     

An integrated technique using zero-valent iron and UV/H2O2 sequential process for complete decolorization and mineralization of C.I. Acid Black 24 wastewater

The zero-valent iron (ZVI) reduction succeeds for decolorization, while UV/H(2)O(2) oxidation process results into mineralization, so that this study proposed an integrated technique by reduction coupling with oxidation process in order to acquire simultaneously complete both decolorization and mineralization of C.I. Acid Black 24. From the experimental data, the zero-valent iron addition alone can decolorize the dye wastewater yet it demanded longer time than ZVI coupled with UV/H(2)O(2) processes (Red-Ox). Moreover, it resulted into only about 30% removal of the total organic carbon (TOC), which was capable to be effectively mineralized by UV/H(2)O(2) process. The proposed sequential ZVI-UV/H(2)O(2) integration system cannot only effectively remove color and TOC in AB 24 wastewater simultaneously but also save irradiation power and time demand. Furthermore, the decolorization rate constants were about 3.77-4.0 times magnitude comparing with that by UV/H(2)O(2) process alone.     

Photooxidative degradation of 4-nitrophenol (4-NP) in UV/H2O2 process: influence of operational parameters and reaction mechanism

The photooxidative degradation of 4-nitrophenol (4-NP) was studied in the UV/H2O2 process. The effects of applied H2O2 dose, initial 4-NP concentration and UV light intensity have been studied. Degradation was complete in 13 min and follows apparent first-order kinetics. The removal efficiency of 4-NP depends on the operational parameters and increases as the initial concentration of H2O2 and light intensity are increased but it decreases when the initial concentration of 4-NP is increased. From HPLC analysis, major intermediate products were hydroxyl derivatives of 4-NP as a result of photooxidative hydroxylation.     

Decolorization of azo dye acid black 1 by the UV/H2O2 process and optimization of operating parameters

An advanced oxidation process, UV/H2O2, was applied for decolorization of a di-azo dye (acid black 1). The effects of operating parameters such as hydrogen peroxide dosage, UV dosage and initial dye concentration, on decolorization have been evaluated. The acid black 1 solution was completely decolorized under optimal hydrogen peroxide dosage of 21.24 mmol/l and UV dosage of 1400 W/l in less than 1.2 min. The decolorization rate followed pseudo-first order kinetics with respect to the dye concentration. The rate increased linearly with volumetric UV dosage and nonlinearly with increasing initial hydrogen peroxide concentration. It has been found that the degradation rate increased until an optimum of hydrogen peroxide dosage, beyond which the reagent exerted an inhibitory effect. For real case application, an operation parameter plot of rate constant was developed. To evaluate the electric power and hydrogen peroxide consumption by UV/H2O2 reactor, 90% color removal was set as criteria to find the balance between both factors.     

Degradation of C.I. Reactive Red 2 (RR2) using ozone-based systems: comparisons of decolorization efficiency and power consumption

This study investigated the decolorization efficiency of C.I. Reactive Red 2 (RR2) in O3, O3/H2O2, O3/Fe3+, O3/H2O2/Fe3+, UV/O3, UV/O3/Fe3+, UV/O3/H2O2 and UV/O3/H2O2/Fe3+ systems at various pHs. The effective energy consumption constants and the electrical energy per order of pollutant removal (EE/O) were also determined. The experimental results indicated that the energy efficiency was highest at [H2O2]0=1000mg/l and [Fe3+]0=25mg/l. Accordingly, the H2O2 and Fe3+ doses in the hybrid ozone- and UV/ozone-based systems were controlled at these values. This work suggests that the dominant reactant in O3, O3/Fe3+ and O3/H2O2 systems was O3 and that in the O3/H2O2/Fe3+ system was H2O2/Fe3+. The experimental results revealed that the combinations of Fe3+ or H2O2/Fe3+ with O3 at pH 4 and of H2O2 or H2O2/Fe3+ with UV/O3 at pH 4 or 7 yielded a higher decolorization rate than O3 and UV/O3, respectively. At pH 4, the EE/O results demonstrated that the UV/O3/H2O2/Fe3+ system reduced 85% of the energy consumption compared with the UV/O3 system. Moreover, the O3/H2O2/Fe3+ system reduced 62% of the energy consumption compared with the O3 system. At pH 7, the EE/O results revealed that the UV/O3/H2O2/Fe3+ system consumed half the energy of the UV/O3 system.     

Oxidative degradation of dimethyl phthalate (DMP) by UV/H(2)O(2) process

The photochemical degradation of dimethyl phthalate (DMP) in UV/H(2)O(2) advanced oxidation process was studied and a kinetic model based on the elementary reactions involved was developed in this paper. Relatively slow DMP degradation was observed during UV radiation, while DMP was not oxidized by H(2)O(2) alone. In contrast, the combined UV/H(2)O(2) process could effectively degraded DMP, which is attributed to the strong oxidation strength of hydroxyl radical produced. Results show that DMP degradation rate was affected by H(2)O(2) concentration, intensity of UV radiation, initial DMP concentration, and solution pH. A kinetic model without the pseudo-steady state assumption was established according to the generally accepted elementary reactions in UV/H(2)O(2) advanced oxidation process. The rate constant for the reaction between DMP and hydroxyl radical was found to be 4.0 x 10(9) M(-1)s(-1) through fitting the experimental data to this model. The kinetic model could adequately describe the influence of key factors on DMP degradation rate in UV/H(2)O(2) advanced oxidation process, and could serve as a guide in designing treatment systems for DMP removal.     

Photocatalytic degradation of C.I. Direct Red 23 in aqueous solutions under UV irradiation using SrTiO3/CeO2 composite as the catalyst

The photocatalytic degradation of C.I. Direct Red 23 (4BS) in aqueous solutions under UV irradiation was investigated with SrTiO3/CeO2 composite as the catalyst. The SrTiO3/CeO2 powders had more photocatalytic activity for decolorization of 4BS than that of pure SrTiO3 powder under UV irradiation. The effects of catalytic dose, pH value, initial concentration of dye, irradiation intensity as well as scavenger KI were ascertained, and the optimum conditions for maximum degradation were determined. Under the irradiation of a 250 W mercury lamp, the best catalytic dose was 1.5 g/L and the best pH was 12.0. Light intensity exhibited a significant positive effect on the efficiency of decolorization, whereas the initial dye concentration showed a significant negative effect. Under the conditions of a catalytic dose of 1.5 g/L, pH of 12.0, initial dye concentration of 100mg/L, light intensity of 250 W, and air flow rate of 0.15 m3/h, complete decolorization, as determined by UV-visible analysis, was achieved in 60 min, corresponding to a reduction in chemical oxygen demand (COD) of 69% after a 240 min reaction. A tentative degradation pathway based on the sensitization mechanism of photocatalysis is proposed.     

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.     

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.     

Ametryn degradation in the ultraviolet (UV) irradiation/hydrogen peroxide (H2O2) treatment

Ultraviolet (UV) irradiation (253.7nm) in the presence of hydrogen peroxide (H(2)O(2)) was used to decompose aqueous ametryn. The concentrations of ametryn were measured with time under various experiment conditions. The investigated factors included H(2)O(2) dosages, initial pH, initial ametryn concentrations, and a variety of inorganic anions. Results showed that ametryn degradation in UV/H(2)O(2) process was a pseudo-first-order reaction. Removal rates of ametryn were greatly affected by H(2)O(2) dosage and initial concentrations of ametryn, but appeared to be slightly influenced by initial pH. Furthermore, we investigated the effects of four anions (SO(4)(2-), Cl(-), HCO(3)(-), and CO(3)(2-)) on ametryn degradation by UV/H(2)O(2). The impact of SO(4)(2-) seemed to be insignificant; however, Cl(-), HCO(3)(-), and CO(3)(2-) considerably slowed down the degradation rate because they could strongly scavenge hydroxyl radicals (OH) produced during the UV/H(2)O(2) process. Finally, a preliminary cost analysis revealed that UV/H(2)O(2) process was more cost-effective than the UV alone in removal of ametryn from water.     

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.     

Photodegradation of Reactive Black 5, Direct Red 28 and Direct Yellow 12 using UV, UV/H(2)O(2) and UV/H(2)O(2)/Fe(2+): a comparative study

The photodegradation of three commercially available dyestuffs (C.I. Reactive Black 5, C.I. RB5, C.I. Direct Yellow 12, C.I. DY12, and C.I. Direct Red 28, C.I. DR28) by UV, UV/H(2)O(2) and UV/H(2)O(2)/Fe(II) processes was investigated in a laboratory-scale batch photoreactor equipped with an 16W immersed-type low-pressure mercury vapour lamp. The experimental results were assessed in terms of absorbance and total organic carbon (TOC) reduction. The initial concentration was kept constant at 100 mg l(-1) for all dyes. Initial results showed that, color removal efficiencies by UV or H(2)O(2) alone were negligible for all dyes. Almost complete disappearance of C.I. RB5 (99%) and DY12 (98%) in UV/H(2)O(2) process was possible to achieve after 60 min of irradiation. The maximum color removal efficiency of C.I. DR28 after 60 min of irradiation, however, was only 40% and reached a maximum value of 70% after 120 min of irradiation. Corresponding mineralization efficiencies were 50, 55 and 7-12%, respectively. The addition of Fe(II) to the system, so-called the photo-Fenton process, greatly enhanced the color removal, the efficiencies being 98, 88 and 85% for C.I. RB5, C.I. DY12 and C.I. DR28 only after 5 min of irradiation. Corresponding mineralization efficiencies were 98% for 45 min irradiation, 100% for 60 min irradiation and 98% for 90 min irradiation, respectively. However, marginal benefit was less significant in the higher range of both H(2)O(2) and Fe(II). Furthermore, decreases in both decolorization and mineralization were observed at higher concentrations of oxidant and catalyst due to the scavenging effect of excess H(2)O(2) and OH radicals. The degradation of all dyes was found to follow first-order reaction kinetics.     

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.     

Degradation and by-product formation of diazinon in water during UV and UV/H(2)O(2) treatment

Kinetics and degradation products resulting from the application of UV and UV/H(2)O(2) to the US EPA Contaminant Candidate List pesticide diazinon were studied. Batch experiments were conducted with both monochromatic (low pressure [LP] UV 253.7 nm) and polychromatic (medium pressure [MP] UV 200-300 nm) UV sources alone or in the presence of up to 50 mg l(-1) H(2)O(2), in a quasi-collimated beam apparatus. Degradation of diazinon by both UV and UV/H(2)O(2) exhibited pseudo first order reaction kinetics, and quantum yield of 8.6 x 10(-2) and 5.8 x 10(-2) mol E(-1) for LP and MP lamps respectively. Photolysis studies under MP UV lamp showed 2-isopropyl-6-methyl-pyrimidin-4-ol (IMP) to be the main degradation product of diazinon at aqueous solution pH values of 4, 7 and 10. Trace levels up to 1.8 x 10(-3) microM of diazinon oxygen analogue diethyl 2-isopropyl-6-methylpyrimidin-4-yl phosphate (diazoxon) were detected only during the UV/H(2)O(2) reaction. Decay of both products was observed, as the UV/H(2)O(2) reaction prolonged, yet no mineralization was achieved over the UV fluence levels examined. Photolysis kinetics, quantum yield and UV/H(2)O(2) degradation of the reaction product IMP was determined using MP UV lamp at pH values of 4, 7 and 10.     

Importance of H(2)O(2)/Fe(2+) ratio in Fenton's treatment of a carpet dyeing wastewater

The effectiveness of the Fenton's reagent (H(2)O(2)/Fe(2+)) in the treatment of carpet dyeing wastewater was investigated under different operational conditions, namely, H(2)O(2) and FeSO(4) concentrations, initial pH and temperature. Up to 95% COD removal efficiency was attained using 5.5 g/l FeSO(4) and 385 g/l H(2)O(2) at a pH of 3, temperature of 50 degrees C. The H(2)O(2)/Fe(2+) ratio (g/g) was found to be between 95 and 290 for maximum COD removal. It was noteworthy that, keeping H(2)O(2)/Fe(2+) ratio constant within the range of 95-290, it became possible to decrease FeSO(4) concentration to 1.1 g/l and H(2)O(2) concentration to 96.3 g/l, still achieving nearly the same COD removal efficiency. The relative efficiencies of Fenton's oxidation and coagulation stages revealed that Fenton's coagulation removed organic compounds which were not removed by Fenton's oxidation, indicating that the Fenton's coagulation acted as a polishing step.     

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.     

Photo-catalytic degradation of toxic dye amaranth on TiO2/UV in aqueous suspensions

The photo-catalytic degradation of an azo dye − Amaranth (AM) - has been investigated in TiO₂/UV aqueous suspensions. The results obtained from the experiments during H₂O₂/TiO₂ addition show that the highest decolorization rate is provided by the combination of (UV + TiO₂ + H₂O₂). The decolorization efficiencies were 17%, 26%, 38% and 64% in the runs UV, UV + H₂O₂, UV + TiO₂ and (UV + TiO₂ + H₂O₂) after approximately 100 min illumination periods, respectively. The observed dye degradation rates followed pseudo-first order kinetics with respect to the substrate concentration under the experimental conditions used. Different experimental conditions, such as temperature, pH and presence of electron acceptor were investigated. The temperature effect was investigated at the range of 293-313 K and it was observed that decolorization rate increased by the increase in temperature. Chemical oxygen demand and dye absorbance of the photodegraded dye solution substantially decreased. Effect of pH was also investigated and it was observed that the lower the pH the higher the degradation. In addition, an enhancement in the photodegradation rate was observed by the addition of hydrogen peroxide as an electron acceptor. The adsorption trends of Amaranth at various initial concentrations followed the Langmuir isotherm trend. This work adds to the global discussion on the role of the advanced oxidation processes in water treatment.     

Decolourization of Methyl Orange using Fenton-like mesoporous Fe(2)O(3)-SiO(2) composite

Rapid decolourization of Methyl Orange by Fenton-like mesoporous Fe(2)O(3)-SiO(2) catalyst has been reported. The effect of various parameters such as initial pH, initial H(2)O(2) concentration, Fe content in the catalyst and initial dye concentration on decolourization process were studied. The results show that 20mg of mesoporous Fe(2)O(3)/SiO(2) composite (with Si/Fe=10) was sufficient to decolourize 0.6 mg/ml of Methyl Orange in presence of 2 ml of H(2)O(2) at an initial pH of 2.93 within 20 min. The pH range for effective decolourization (≥90%) was found to be 1-3. Leaching tests indicated that the activity of the catalyst was almost unaffected up to three consecutive cycles although ≤0.2 ppm of Fe ion was leached into treated water in each run.