Advanced oxidation of raw and biotreated textile industry wastewater with O3, H2O2 /UV‐C and their sequential application

The advanced chemical oxidation of raw and biologically pretreated textile wastewater by (1) ozonation, (2) H₂O₂ /UV − C oxidation and (3) sequential application of ozonation followed by H₂O₂ /UV − C oxidation was investigated at the natural pH values (8 and 11) of the textile effluents for 1 h. Analysis of the reduction in the pollution load was followed by total environmental parameters such as TOC, COD, UV–VIS absorption kinetics and the biodegradability factor, f_B. The successive treatment combination, where a preliminary ozonation step was carried out prior to H₂O₂ /UV − C oxidation without changing the total treatment time, enhanced the COD and TOC removal efficiency of the H₂O₂ /UV − C oxidation by a factor of 13 and 4, respectively, for the raw wastewater. In the case of biotreated textile effluent, a preliminary ozonation step increased COD removal of the H₂O₂ /UV − C treatment system from 15% to 62%, and TOC removal from 0% to 34%. However, the sequential process did not appear to be more effective than applying a single ozonation step in terms of TOC abatement rates. Enhancement of the biodegradability factor (f_B) was more pronounced for the biologically pretreated wastewater with an almost two‐fold increase for the optimized Advanced Oxidation Technologies (AOTs). For H₂O₂ /UV − C oxidation of raw textile wastewater, apparent zero order COD removal rate constants (k_app), and the second order OH· formation rates (r_i) have been calculated. © 2001 Society of Chemical Industry     

Ozone-Based Advanced Oxidation Processes for the Decomposition of N-Methyl-2-Pyrolidone in Aqueous Medium

The present study investigates the decomposition of N-Methyl-2-Pyrolidone (NMP) using conventional ozonation (O₃), ozonation in the presence of UV light (UV/O₃), hydrogen peroxide (O₃/H₂O₂), and UV/H₂O₂ processes under various experimental conditions. The influence of solution pH, ozone gas flow dosage, and H₂O₂ dosage on the degradation of NMP was studied. All ozone-based advanced oxidation processes (AOPs) were efficient in alkaline medium, whereas the UV/H₂O₂ process was efficient in acidic medium. Increasing ozone gas flow dosage would accelerate the degradation of NMP up to certain level beyond which no positive effect was observed in ozonation as well as UV light enhanced ozonation processes. Hydrogen peroxide dosage strongly influenced the degradation of NMP and a hydrogen peroxide dosage of 0.75 g/L and 0.5 g/L was found to be the optimum dosage in UV/H₂O₂ and O₃/H₂O₂ processes, respectively. The UV/O₃ process was most efficient in TOC removal. Overall it can be concluded that ozonation and ozone-based AOPs are promising processes for an efficient removal of NMP in wastewater.     

Ozone-Based Processes Applied to Municipal Secondary Effluents

This study analyzes the performances of 2 methods of oxidation based on ozone, namely ozonation and ozone combined with hydrogen peroxide (O₃/H₂O₂), on two biotreated municipal wastewater effluents. The main parameters monitored to evaluate the effectiveness of the processes were Chemical Oxygen Demand (COD), Dissolved Organic Carbon (DOC) and Biochemical Oxygen Demand (BOD₅). Ozonation and O₃/H₂O₂ treatment removed 44% and 48%, respectively, of the COD, after 90 min, of the secondary effluent of Calafell wastewater treatment plant (Spain). On the secondary effluent from the Grasse wastewater treatment plant (France), these same treatments (O₃; O₃/H₂O₂) achieved, respectively, a degradation of 52% and 100% of the COD after 60 min. The transferred ozone dose (TOD) during Calafell and Grasse effluents' ozonation were 122 mg·L^?1 and 77 mg·L^?1 after 90 min, respectively. A low removal of DOC was monitored during both O₃ or O₃/H₂O₂ treatments applied to Calafell wastewater, respectively 12% and 14%. Better DOC reductions were obtained on the water of Grasse treated with O₃ or O₃/H₂O₂, respectively, 48% and 60%. In addition, ammonia nitrogen was oxidized to nitrate nitrogen thus giving rise to an over ozone consumption. And finally, both processes proceeded with an increase of pH values. These results highlight the strong dependency of O₃ or O₃/H₂O₂ treatment effectiveness in terms of dissolved organic matter (DOM) removal and ozone consumption on wastewater composition (organic and inorganic substances).     

Heterogeneous Catalytic Ozonation of Refinery Wastewater over Alumina-Supported Mn and Cu Oxides Catalyst

An economical method was proposed to develop an efficient alumina-supported manganese (Mn) and copper (Cu) oxides (Mn-Cu-O/Al₂O₃) catalyst with a high surface area, 184.06 cm² g^?1. The catalyst was utilized for degradation refinery wastewater by heterogeneous catalytic ozonation. The effects of various operating variables including pH, ozone and catalyst dosages, and temperature were systematically investigated in detail to obtain the optimized conditions for accelerated degradation of refinery wastewater. The optimum values were as follows: ozone dose 50.0 mg L^?1, catalyst dose 3.0 g L^?1, initial pH = 6.8, T = 17 °C. Refinery wastewater samples were analyzed by chemical oxygen demand (COD) and the results indicated that kinetics of COD followed a pseudo–first-order degradation. Moreover, hydroxyl radical mechanism rather than absorption was proposed, indicating that the surface hydroxyl groups were the active sites that played a significant role in catalytic ozonation.     

Chemical treatment of cork‐processing wastewaters for potential reuse

The chemical treatment of cork‐processing wastewater by ozonation, alone and in combination with hydrogen peroxide and UV radiation was investigated. A reduction of the chemical oxygen demand (COD) ranging from 42% to 76% was obtained during ozonation after 3 h of reaction, depending on the experimental conditions. The additional presence of hydrogen peroxide and UV radiation enhanced the efficiency of the ozonation treatment due to the contribution of the OH radicals formed in the decomposition of ozone. Thus, final reductions of the COD higher than 90% and a complete elimination of phenolic compounds and absorbance at 254 nm were achieved in both Advanced Oxidation Processes (AOPs), O₃/H₂O₂ and O₃/UV. Therefore the effluent resulting from the ozonation treatments can be reused in the cork‐processing industry. In a second step, the chemical treatment was conducted by means of UV radiation alone and by the action of hydroxyl radicals, which were generated by the following AOPs: UV/H₂O₂, Fenton's reagent, and photo‐Fenton system. The single photochemical process resulted in 9% of the organic matter present being removed, while the AOPs significantly enhanced this reduction with values in the range 20–75%. Kinetic studies for both groups of treatments were performed, and apparent kinetic rate constants were evaluated. In the ozone‐based experiments, the rate constants ranged from 1846 to 10922 dm³ mol^?1 O₃ h^?1, depending on the operating conditions. In the oxidation experiments using oxidants other than ozone, the rate constants varied between 0.06 and 1.19 h^?1. Copyright © 2004 Society of Chemical Industry     

Post-Treatment of Pulp and Paper Industry Wastewater by Advanced Oxidation Processes

The aim of this study was to investigate the effectiveness of chemical oxidation by applying ozonation, combination of ozone and hydrogen peroxide and Fenton's processes for decolorization and residual chemical oxygen demand (COD) removal of biologically pretreated pulp and paper industry effluents. The batch tests were performed to determine the optimum operating conditions including pH, O₃, H₂O_2, and Fe²⁺ dosages. H₂O₂ addition reduced the reaction times for the same ozone dosages; however combinations of ozone/hydrogen peroxide were only faintly more effective than ozone alone for COD and color removals. In the Fenton‘s oxidation studies, the removal efficiencies of COD, color and ultraviolet absorbance at 254 nm (UV₂₅₄) for biologically treated pulp and paper industry effluents were found to be about 83, 95, and 89%, respectively. Experimental studies indicated that Fenton oxidation was a more effective process for the reduction of COD, color, and UV₂₅₄when compared to ozonation and ozone/hydrogen peroxide combination. Fenton oxidation was found to have less operating cost for color removal from wastewater per cubic meter than the cost for ozone and ozone/hydrogen peroxide applications.     

Degradation of cationic dye methylene blue by ozonation assisted with kaolin

An enhanced ozonation process, methylene blue (MB) wastewater treated by MnO₂/O₃ assisted with kaolin in a slurry reactor, at room temperature and atmospheric pressure, MB wastewater can be effectively purified, a chemical oxygen demand (COD) of 88.3% and a decoloration rate of 98.9% were obtained in 10 min at pH 11. Compared with MnO₂/O₃ catalytic ozonation (16.0% of decoloration and 33.3% of COD reduction), decoloration and COD reduction were markedly increased, indicating that kaolin can significantly improve the catalytic ozonation process. According to the experimental results, the hypothetical mechanism of degradation and the reaction kinetics were also proposed. COD reduction can be described by a second-order model and the reaction rate constant in the presence of kaolin was higher than that of absence of kaolin.     

Remediation of phenolic wastewaters by advanced oxidation processes (AOPs) at ambient conditions: Comparative studies

The efficiency of two AOPs operating at room conditions of pressure and temperature, ozonation (single and catalytic over the laboratorial Mn–Ce–O and the commercial N-150—Fe₂O₃/MnO_x) and Fenton's process (homogeneous and over Fe–Ce–O), was simultaneously checked for the remediation of a phenolic mixture. Gathering up former individual results pointing out as most suitable treatments those involving solid catalysts, either for ozonation or Fenton's, a global conclusion elects this last process as the more interesting for industrial applications. In fact, the lower retention time required by H₂O₂+Fe–Ce–O 70/30 to attain an easily biodegradable effluent makes this technology truly attractive for in-situ remediation of this specific wastewater. These findings were mostly driven by the comparative ability to transform the non-biodegradable raw effluent into streams more amenable to further bio-processing. In this regard, biological parameters superposed chemical COD degradation within the ultimate selection reasons. Indeed, in all cases COD limits were not reached and a subsequent biological treatment is required. Despite COD removal for catalytic ozonation showed to be higher than for heterogeneous Fenton's (63% and 50%), BOD₅/COD was contrarily favorable to Fenton's, which immediately conducted to a biodegradable mixture in the first minutes (0.78 in 10 min) while ozonation took more than 1 h to impart a biodegradable character.     

Improving Dewaterability and Other Properties of Citric Acid Wastewater Treatment Sludge by Ozone and Peroxone

ABSTRACT

The efficacies of ozonation and peroxone (O₃/H₂O₂) pretreatments were compared for citric acid wastewater sludge conditioning with the objective of improving dewatering characteristics of the sludge. Treatment with 84 mg O₃/g dry solid (DS) and 12.5 mg/g DS H₂O₂ greatly enhanced the effectiveness of ozonation, providing sludge dewaterability similar to that obtained by ozonation at 250 mg O₃/g DS. Most importantly, treatment of citric acid wastewater sludge with 84 mg O₃/g DS and 12.5 mg/g DS H₂O₂ led to the preservation of the nutrient elements nitrogen, phosphorus, and potassium in the sludge with a minimal volatile suspended solids/total suspended solids reduction of 5.5%, which is much lower than that with ozonation at 250 mg O₃/g DS.     

Ozone/H2O2 Performance on the Degradation of Sulfamethoxazole

This work aims to analyze the contribution of H₂O₂ on ozonation of Sulfamethoxazole (SMX). A single ozonation was able to totally remove SMX. TOC and COD depletion rates after a transferred ozone dose of 60 mg/L was related to the formation and decomposition of H₂O₂. An increase on O₃ gas inlet concentration from 10 g/m³ to 20 g/m³ improved COD abatement from 11% to 36%. When the presence of H₂O₂ at the beginning of ozonation was tested, it was verified that COD and TOC degradation were enhanced, attaining maximum values of 76% and 32%, respectively, when compared with 35% and 15% reached in a single ozonation.     

An Effective Heterogeneous Ozone-Based Advanced Oxidation Process in Acidic Solution— Ti-MCM-41/H2O2/O3

A useful ozone-based advanced oxidation process in acidic solution- Ti-MCM-41/H₂O₂/O₃ was studied, and acetic acid (HAc) was selected to be degraded because it is a hydroxyl radical-probe compound in ozonation. The results showed that only Ti-MCM-41/H₂O₂/O₃ could effectively degrade HAc at initial pH 3.0, and that other oxidative processes such as O₃, H₂O₂/O₃ Ti-MCM-41/O₃ and MCM-41/H₂O₂/O₃, all could not, indicating the coexistence of Ti-MCM-41 and H₂O₂ was necessary for the generation of hydroxyl radicals under the experimental conditions. The optimization of parameters indicated that the rate of generation of hydroxyl radicals could be regulated by the amount of Ti-MCM-41, and that the amount of hydroxyl radicals could be controlled by the concentration of H₂O₂. The preceding results are of significance for effective treatment of acidic refractory wastewater.     

Treatment of biodiesel wastewater by indirect electrooxidation: Effect of additives and process kinetics

Due to the presence of growth inhibitor and high impurity concentration in biodiesel wastewater, both biologicaln and chemical processes are ineffective for treating such wastewater. In this work, biodiesel wastewater was treated by electrooxidation via Ti/RuO2 electrodes in batch and continuous modes. Effects of the additive type, hydrogen peroxide (H₂O₂) and sodium chloride (NaCl), and concentration on the treatment efficiency, monitored in terms of the reduction in the biological oxygen demand (BOD), chemical oxygen demand (COD) and oil and grease level, were explored. The addition of NaCl gave higher treatment efficiency than H₂O₂, and both were higher than no addition, due to the continuous generation of the oxidizing chloride species. The removal of almost all the COD and oil and grease and ~95% BOD was obtained in the presence of 0.061 M NaCl at an applied current density of 4.28 mA/cm² for 7h. In continuous operation mode, the steady state condition was reached within 11 h and the treatment efficiency decreased as the wastewater feed rate increased. By using wastewater feed rate of 2mL/min, approximately 83.56, 61.43 and 91.72% of BOD, COD and oil and grease levels were respectively removed. The rate of pollutant removal fitted a first order reaction for both the batch and continuous operation modes.     

The Fenton Chemistry and Its Combination with Coagulation for Treatment of Dye Solutions

Abstract

Aqueous solutions of Acid Blue 74, Acid Orange 10, and Acid Violet 19 were subjected to Fenton/Fenton‐like oxidation and its combination with lime coagulation. The analysis indicated no dependence of chemical oxidation efficacy on dye concentration in the range of 0.1–1 g L^?1. Complete or nearly complete (higher than 95%) color removal of all treated samples was observed. Dye:H₂O₂ weight ratio of 1∶2 proved optimal for treatment of all dye solutions by means of Fenton/Fenton‐like oxidation. Moderate doses of hydrogen peroxide led to the improvement of biodegradability of dye solutions. No formation of any toxic intermediates during the oxidation of Acid Orange 10 and Acid Violet 19 was detected. Only a slight toxicity increase was observed after Acid Blue 74 degradation by Fenton chemistry. H₂O₂/Fe³⁺ system with pH adjusted to 3 proved the most effective oxidation process. The combination of Fenton chemistry and subsequent lime coagulation was the most feasible treatment method of removing COD and UV₂₅₄ and UV_max absorbance of dye solutions. Combined oxidation and coagulation was more effective for Acid Blue 74 and Acid Orange 10 elimination than for Acid Violet 19.     

A comparative study on the performance of different advanced oxidation processes (UV/O3/H2O2) treating linear alkyl benzene (LAB) production plant's wastewater

A detailed investigation on photooxidation of linear alkyl benzene (LAB) industrial wastewater is presented in this study. The process analysis was performed by varying four significant independent variables including two numerical factors (initial pH (3–11) and initial H₂O₂ concentration (0–20 mM)) and two categorical factors (UV irradiation and ozonation). The experiments were conducted based on a central composite design (CCD) and analyzed using response surface methodology (RSM). To assess the process performance, two parameters viz. TCOD removal efficiency and BOD₅/COD were measured throughout the experiments. A maximum reduction in TCOD was 58, 53, 51, and 49%, respectively for UV/H₂O₂/O₃, H₂O₂/O₃, UV/O₃ and UV/H₂O₂ processes at the optimum conditions (initial pH of 7, initial H₂O₂ concentration of 100 mM, and reaction time of 180 min). A considerable increase in BOD₅/COD ratio was obtained in the combined processes (0.46, 0.51, 0.53, and 0.55 for UV/H₂O₂, UV/O₃, H₂O₂/O₃ and UV/H₂O₂/O₃, respectively) compared to the single oxidant process (0.35). The results showed that mineralization of the LAB industrial wastewater in neutral pH is more favored than in acidic and basic pH. Gas chromatography–mass spectrometry (GC–MS) was applied to show the fate of organic compounds. In conclusion, the photooxidation process (UV/H₂O₂/O₃, H₂O₂/O₃, UV/O₃ and UV/H₂O₂) could be an appropriate pretreatment method prior to a biological treatment process.     

Integration of continuous biological and chemical (ozone) treatment of domestic wastewater: 1. Biodegradation and post‐ozonation

The continuous treatment of domestic wastewater by an activated sludge process and by an integrated biological–chemical (ozone) oxidation process were studied in this work. Chemical oxygen demand (COD), biochemical oxygen demand (BOD), absorbance at 254 nm (UV₂₅₄) and nitrogenous compound content were the parameters followed in order to evaluate the performance of the two processes. Experimental data showed that both UV₂₅₄ and COD reductions are improved in the combined biological–chemical oxidation procedure. Thus, reductions of 59.1% and 37.2% corresponding to COD and UV₂₅₄, respectively were observed after the biological process (hydraulic retention time = 5 h; mixed liquor volatile suspended solids concentration = 3142 g m⁻³) compared with 71.0% and 78.4% obtained when a post‐ozonation step ( D _O3 = 41.7 g m⁻³) was included. During conventional activated sludge treatment, appropriate nitrification levels are only achieved with high hydraulic retention time and/or biomass concentration. Ozonation after the secondary treatment, however, allows improved nitrogen content reduction with total nitrite elimination. Post‐ozonation also leads to a higher biodegradability of the treated wastewater. Thus, the ultimate BOD/COD ratio goes from 0.16 after biological oxidation to 0.34 after post‐ozonation with 41.7 g O₃ m⁻³. © 1999 Society of Chemical Industry     

Advanced Oxidation of Textile Wastewaters

Model dyeing and laundering wastewaters produced during two basic technological operations of the textile industry were subjected to treatment by advanced oxidation processes (AOPs). The following agents were used: ozone (O₃), hydrogen peroxide (H₂O₂) and UV radiation. They were applied separately and in all possible combinations: O₃ + UV, O₃ + H₂O₂, UV + H₂O₂, as well as all three at the same time: O₃ + UV + H₂O₂. Effluents before and after the treatment were analyzed according to requirements of the Polish Standards that included pH, color threshold, COD and concentration of anionic and non-ionic surfactants. Ozonation was carried out in a lab-scale bubble column reactor with a centrally located UV burner. The most effective version of AOPs proved to be the simultaneous use of all three agents. In the case of such treatment of dyeing wastewaters nearly complete discoloration and full decomposition of surface-active substances were obtained at 80% reduction of COD. A similar tendency was observed in the case of laundering wastewater, though in that case the results were slightly worse, which may be explained by much higher initial concentrations of the pollutants. Good treatment effects have also been obtained in combined treatment by simultaneous use of hydrogen peroxide and ozone.     

Treatment of Jewelry Manufacturing Effluent Containing Cyanide Using Ozone-Based Photochemical Advanced Oxidation Processes

This article considers Advanced Oxidation Processes involving O₃, O₃/UV, O₃/H₂O₂/UV, and H₂O₂/UV to destroy cyanide in jewelry manufacturing wastewaters. All experiments were performed in a semibatch reactor. The results showed that total cyanide can be reduced with different reaction rates, and the decrease of total cyanide can be described by pseudo–first-order kinetics. The reaction was performed under different pH values and H₂O₂ dosages to find the optimal conditions for the oxidation processes. The ozonation process destroyed total cyanide faster at a pH = 12, whereas ozonation combined with H₂O₂ and/or UV destroyed cyanide faster at a pH =10. The total cyanide destruction rate in the UV/H₂O₂ (700 mg/L) treatment was the highest among all studied processes, with removal efficiencies of 99% for CN^?, 99% for COD and 99% for TOC.     

Advanced oxidation process and biotreatment: Their roles in combined industrial wastewater treatment

The use of Fenton's reagents in destruction of waste material present in Tambla Tributory (Durgapur,India) industrial wastewater has been investigated. Significant drop in COD removal has been observed. Optimisation of process parameters like pH, temperature, H₂O₂ and FeSO₄ has been done. Temperature and pH played a key role in this treatment process, in addition the process initially liberated heat due to reaction between FeSO₄ and H₂O₂. From the experimental results it has been observed that with increasing FeSO₄ and H₂O₂ concentration the degradation of waste increases. At an optimum concentration of FeSO₄ (6 gm/l) and H₂O₂ 44.40 gm/l reduced 60% COD, whereas 220gm/l H₂O₂ was required for 95% COD removal. To reduce cost and the H₂O₂ concentration for maximum waste degradation, Fenton's oxidation process followed by biochemical treatment was tried at same experimental condition. The treatment enhanced the overall removal efficiency of COD, BOD, salinity and colour significantly. The microbial treatment by Thiobacillus ferrooxidans, following Fenton's reagents treatment, showed that the COD reduction has reached to about 97% compared to 60% with Fenton's reagents and 17% with T. ferrooxidans alone in 24 h, showing the synergistic effect. Thus the combined treatment results indicate the possibility to minimize the Fenton's reagents without compromising the efficiency of the process but ultimately reducing the overall treatment cost. This study seems to be very much important and economical by reducing the required H₂O₂ amount to about five times using a suitable micro-organism. This hybrid treatment system showed 97% COD reduction can be achieved within two days.     

Decolorization and COD reduction of disperse and reactive dyes wastewater using chemical-coagulation followed by sequential batch reactor (SBR) process

This paper summarizes the results of disperse and reactive dyes wastewater treatment processes aiming at the destruction of the wastewater's color and chemical oxygen demand (COD) reduction by means of coagulation/flocculation (CF) followed by sequential batch reactor (SBR) process. The color removal efficiency of magnesium chloride aided with lime [MgCl₂/CaO] was compared with that of alum [Al₂ (SO₄)₃] and lime [Cao]. The experimental results showed that treatment with lime alone (600 mg/l) at pH value of 11.7 proved to be very effective. Color removal reached 100% and COD was reduced by 50%. Treatment with magnesium chloride aided with lime at pH value of 11 removed color completely and reduced the COD value by 40%. However, lime or lime in combination with magnesium chloride produced high amounts of sludge (1.84 kg/m³ for lime & 1.71 kg/m³ for MgCl₂ aided with lime). Also, the pH of the treated effluent was around 11 and needs correction prior to discharge into sewer network. The use of 200 mg/l alum without pH adjustment removed 78.9% of the color. To improve the effectiveness of alum, the cationic polymer namely cytec was used as a coagulant aid. This significantly increased color removal from 78.9 up to 94% and COD reduction was around 44%. Moreover, sludge production was only 0.36 kg/m³. Chemically pre-treated effluent was subjected to SBR process at an HRT of 5.0 h. Residual COD_total, total biochemical oxygen demand (BOD_{5 total}) and total suspended solids (TSS) in the final effluent were 78 ± 7.7; 28 ± 4.2 and 17 ± 4.2 mg/l, corresponding to the removal efficiency of 68.2; 76.3 and 61.4% respectively. Furthermore, almost complete removal of COD_particulate and BOD_5particulate has been achieved.     

Optimization of Fenton process for refinery wastewater biodegradability augmentation

The Fenton process was used to increase the biodegradability of refinery wastewater. Initially, effects of reaction time, H₂O₂/COD and H₂O₂/Fe²⁺ molar ratios were investigated and biodegradability of wastewater was determined in terms of the BOD₅/COD ratio. Preliminary results showed that the Fenton process was able to improve wastewater biodegradability from 0.27 to 0.43. Subsequently, the process was optimized by using response surface methodology based on a five-level central composite design. Adequacy and significance of results were analyzed in analysis of variance. The quadratic model was found to be significant to give less than 0.05 probability of error. The model was fit with data based on insignificant of lack-of-fit test at values of 0.93. The high R² and Adj.R² (0.95 and 0.91) indicates satisfactory adjustment of quadratic model to experimental data. Based on optimized conditions, wastewater biodegradability improved to 0.44 via H₂O₂/COD and H₂O₂/Fe²⁺ molar ratios of 2.8 and 4 within 71 minutes reaction time.