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     

Degradation of Two Persistent Surfactants by UV-Enhanced Ozonation

In this study the treatment efficiency of different ultraviolet (UV)-enhanced ozonation processes for degradation of two surfactants, sodium dodecylbenzene sulfonate [200 mg/L or 0.3 critical micelle concentration (CMC)] and a nonylphenol ethoxylate with 40 oxyethylene units (200 mg/L ~0.5 CMC), were investigated in laboratory-scale experiments at ambient temperature. The absorbance band of the aromatic ring of the surfactants was monitored during the oxidation process. The reduction in chemical oxygen demand (COD) and total organic carbon (TOC) of the surfactant solution was evaluated. The results showed that a combination of UV irradiation and ozonation was considerably more efficient than the individual processes (at least two times more efficient in terms of COD and TOC reductions). The synergistic effect of ozonation and UV irradiation was particularly pronounced when medium-pressure UV irradiation was used. By adding alkali to the solution, the efficiency of the UV-enhanced ozonation increased with respect to COD reduction but decreased with respect to TOC reduction. This indicates partial oxidation with lower degree of mineralization of the surfactants.     

Treatment of Leather Dyeing Wastewater with Associated Process of Coagulation-Flocculation/Adsorption/Ozonation

This study is based on the investigation of performance of associated wastewater treatments of coagulation-flocculation/adsorption (CF-ADS) and coagulation-flocculation/ozonation (CF-OZ) for the removal of pollutants from tannery wastewater. The chemical dosage was optimized and the use of waste from the tannery process was tested as a low-cost alternative adsorbent for wastewater treatment plants. For the CF-ADS the removal of TOC, COD, Na⁺ and color were 50.04%, 53.13%, 17.05% and 61.13%, respectively, and for the CF-OZ the removal were 46.50%, 56.25%, 11.10% and 85.34%. Also, BOD/COD and COD/TOC ratios were studied to verify the oxidation efficiency of the wastewater.     

Impact of ozonation on subsequent treatment of azo dye solutions

BACKGROUND: Aqueous solutions of four azo‐dyes, Acid Red 14 (AR14), Congo Red (CR), Reactive Black 5 (RB5), and Reactive Violet 5 (RV5) were treated with ozone, and the impact of ozonation on their subsequent treatability by aerobic biodegradation processes was investigated. RESULTS: In all cases, ozonation at the highest ozone doses investigated could remove more than 96% of the original dye, and the corresponding residual colour of the azo dye solutions declined to less than 20 on the Pt‐Co scale. Ozonation also resulted in reduction of chemical oxygen demand (COD), total organic carbon (TOC) the COD/TOC ratio and pH, while in all cases electrical conductivity of the dye solutions increased. Activity of the microbial colonies present in domestic wastewater was not inhibited when un‐ozonized solutions of these dyes were mixed in a 1:1 volumetric ratio with domestic wastewater, although the dyes themselves were not degraded. Also, no significant inhibition of microbial activity was observed in 1:1 mixtures of ozonized dye solutions and domestic wastewater, especially when the initial dye concentration was low and the applied ozone dose was high. In almost all cases, progressively enhanced BOD exertion was observed in mixtures containing dye solutions ozonized with progressively higher doses. This indicated that some ozonation by‐products of the above dyes could be degraded by microorganisms present in domestic wastewater. CONCLUSIONS: It was concluded that the above dye solutions, after ozonation for partial or complete colour removal, could be mixed with domestic wastewater for subsequent treatment by aerobic biological processes, with no adverse impact on the activity of the microbial colonies present in domestic wastewater. Copyright © 2007 Society of Chemical Industry     

Energy requirement of ultraviolet and AOPs for the post-treatment of treated combined industrial effluent

Post-treatment was carried out to eliminate the colour and COD of treated combined industrial effluent. Ozonation at a dose of 300 mg/h for 10 min resulted in 100% colour and 96% COD removal at pH 8 and temperature 25 °C. The application of UV/H₂O₂ resulted in 91% colour and 82% COD removal. 79% colour and 60% COD removal was obtained with the Fenton process after 60-min treatment in the presence of 170 mg/l H₂O₂, while the photo-Fenton process showed an almost complete elimination of both parameters. Electrical energy consumption showed that the photo-Fenton resulted in the highest removal efficiency with 95% removal in terms of colour and COD abatement rates. The electrical energy requirements of the tested processes followed the increasing order UV/Fe/H₂O₂ < O₃ < UV/H₂O₂ < UV.     

Catalytic ozonation with non-polar bonded alumina phases for treatment of aqueous dye solutions in a semi-batch reactor

Semi-batch experiments were conducted to investigate the effects of catalyst type, pH, initial dye concentration and production rate of ozone on the catalytic ozonation of the dyes, namely Acid Red-151 (AR-151) and Remazol Brilliant Blue R (RBBR). The used catalysts were alumina, 25% (w/w) perfluorooctyl alumina (PFOA), 50% (w/w) PFOA and 100% (w/w) PFOA. The results showed that the overall percent dye removal after 30 min of the reaction was not affected significantly by the catalyst type. However, highest COD reduction was achieved by ozonation with alumina for AR-151, and 100% PFOA for RBBR at pH 13. The behavior of COD reduction with the increasing amount of perfluorooctanoic (PFO) acid amount can be explained by the enhancement of catalytic activity of PFOA with alkyl chains. For both of the dyes, the highest dye and COD removals were reached at pH 13. The overall dye reduction after 30 min of ozonation was almost independent of the initial dye concentration at relatively low values while at the higher concentrations, it changed with the initial dye concentration for both of the dyes. Similarly, COD reduction changed on a limited scale with the increasing initial dye concentration from 100 mg/L to 200 mg/L; however, an increase of initial dye concentration to 400 mg/L decreased the COD reduction significantly. All the studied production rates of ozone were sufficient to provide almost 100% dye removal in 30 min, whereas the COD removal percentage was increased gradually by the increasing ozone input to the reactor. The reaction kinetics for the ozonation of each dye with and without catalyst was investigated and discussed in the paper.     

Impact of Ozonation on Decolorization and Mineralization of Azo Dyes: Biodegradability Enhancement,By-Products Formation,Required Energy and Cost

In the present study ozonation process was implemented to analyze the effect of ozonation time on the rate of chemical oxygen demand (COD) removal, mineralization and rate of decolorization of azo dyes. Three types of azo dyes i.e. Acid Red 14, Direct Red 28 and Reactive Black 5 were selected. Decolorization and mineralization of samples were conducted in batch scale. The COD and color removal efficiency were found to be increasing at a certain time of ozonation. The results with Acid Red 14, Congo Red and Reactive Black 5 dyes solutions lead to maximum COD reduction of 75%, 67% & 50% respectively. 93%, 92% and 94% color removal were achieved after 25 min of ozonation time of the same dyes which highlighted that ozonation process was found to be more efficient for reactive dye decolorization. Ozonation by-products analyzed by ion chromatography resulted that it partially mineralized with the formation of chloride, fluoride, sulphate, nitrate and oxalate ions. During ozonation process a rapid decrease in pH value indicated the acidic nature of by-products. The effect of buffered dye solutions on the ozonoation process highlighted that the decolorization efficiency decreases in comparison to unbuffered dye solutions. Ozonation led to enhancement of biodegradability ratio (BOD₅/COD) and increased electrical conductivity of the dye solutions. Optimum ozonation time required for degradation of dye solutions reflected the evaluation of energy consumption and cost of the treatment after ozonation.     

Enhancement in mineralization of some natural refractory organic compounds by ozonation–aerobic biodegradation

Two schemes, the first involving ozonation followed by final aerobic biodegradation (phase I experiments), and the second involving initial aerobic biodegradation, followed by ozonation and subsequent final aerobic biodegradation (phase II experiments), were examined for enhanced mineralization of refractory model compounds, viz. gallic acid, tannin and lignin. In all cases, and irrespective of the applied scheme, chemical oxygen demand (COD), total organic carbon (TOC), COD/TOC ratio, and specific UV absorbance at 280 nm attributed to the model compounds decreased with application of increasing ozone dose. The residual organic matter remaining after ozonation exhibited enhanced aerobic biodegradability in all cases. Further, in all cases and irrespective of the applied scheme, the overall amount of COD and TOC removed through the combination of ozonation and biodegradation processes increased with increase in ozone dose for all three model compounds, and more than 90% COD removal could be achieved with an ozone dose of 3 mg ozone absorbed per mg initial TOC, as compared with approximately 40% COD removal when no ozone was applied. Treatment by the first scheme resulted in the fraction of starting COD removed through biodegradation decreasing with increase in ozone dose in all cases, while this fraction increased or remained constant during treatment using the second scheme. In the case of tannin and lignin, similar overall COD removal could be achieved at lower ozone doses using scheme II. Due to incorporation of the initial aerobic biodegradation step in scheme II, the ozone requirement for additional mineralization, ie mineralization over and above that achieved by aerobic biodegradation, was also lower than that in scheme I. Copyright © 2005 Society of Chemical Industry     

Colour and COD removal from textile effluent by coagulation and advanced oxidation processes

The aim of this study was to compare the performance of coagulation, Fenton's oxidation (Fe²⁺/H₂O₂) and ozonation for the removal of chemical oxygen demand (COD) and colour from biologically pretreated textile wastewater. FeSO₄ and FeCl₃ were used as coagulants at varying doses and varying colour removal efficiency was measured. For the Fenton process, COD and colour removal efficiencies were found to be 78% and 95% for the Fenton process, and to be 64% and 71% for the Fenton-like process (Fe³⁺/H₂O₂), respectively. Ozonation experiments were conducted at different initial pH values and fixed ozone doses. Ozonation resulted in 43% COD and 97% colour removal whereas these rates increased to 54% and 99% when 5 mg/l hydrogen peroxide was added to the wastewater before ozonation at the same dose. The operating costs of all proposed treatment systems were also evaluated in this study.     

Ozone-Induced Biodegradability Enhancement and Color Reduction of a Complex Pharmaceutical Effluent

The treatment of a complex pharmaceutical effluent using a combination of ozonation and biological treatment is reported with the use of ozonation as a pre- and posttreatment. Pretreatment facilitated biodegradability index (BI = BOD/COD) enhancement of up to 0.44 along with COD and color reduction of up to 42% and 33%, respectively. Subsequent anaerobic biodegradation of effluent indicated negligible biogas generation; however, aerobic biodegradation of pretreated effluent resulted in COD reduction (73%) and color reduction (62%), which was also indicated by the biokinetic parameters. Further, ozonation as a posttreatment led to higher overall COD (87%) and color (93%) removal.     

Treatment of Industrial Landfill Leachates By Chemical And Biological Methods: Ozonation,Ozonation + Hydrogen Peroxide,Hydrogen Peroxide And Biological Post-Treatment For Ozonated Water

The objective of this study was to determine a suitable treatment method for variable waters from a forest industry landfill site. The main target was to find out the impact of different chemical treatments on the composition and biodegradability of those waters. Earlier studies have shown that biological treatment alone is not a suitable treatment method for these waters. That is why ozonation, ozonation+hydrogen peroxide and hydrogen peroxide treatment were studied in a laboratory scale. The ozonated waters were also biologically post-treated.

All the methods studied were able to degrade a part of the organic compounds and convert them into a more biodegradable form. Also the BOD/COD -ratio increased significantly. The removal of organic compounds by ozonation was 30 - 50 %. Hydrogen peroxide addition did not improve the degradation. The combination of pre-ozonation and biological post-treatment gave a total TOC removal between 50 - 95 %.     

Incidence of an Ozonation Stage on the Treatment of Cherry Stillage by Activated Sludge

This article presents a laboratory study of the ozonation of diluted cherry stillage, a high-strength wastewater. Influence of variables, kinetics, and the effects of an ozonation stage coupled with the biological treatment by activated sludge are addressed. Single activated sludge processing was shown effective to remove biological oxygen demand (BOD) and chemical oxygen demand (COD) but polyphenols were reduced to a lesser extent. On the other hand, direct wastewater ozonation did not reduce COD and total organic carbon (TOC) appreciably, and foaming problems were experienced when a high gas flow rate was applied. However, polyphenols and UV₂₅₄ absorbance decreased substantially by means of ozonation. To best achieve complete cherry stillage purification, two ways of coupling ozonation with activated sludge are proposed. Ozonation prior to activated sludge is advised for high-concentration wastewater to reduce polyphenol concentration, thus removing inhibiting effects. For wastewater with low polyphenol concentration the sequence activated sludge–ozonation–activated sludge is preferred to enhance the overall process performance in terms of oxidation efficiency and sludge settling.     

Removal of contaminants from recirculated white water by ultrafiltration and/or biological treatment

This study investigated the potential of ultrafiltration technology and/or biological treatment to remove contaminants such as total dissolved solids (TDS), chemical oxygen demand (COD), total organic carbon (TOC), and resin and fatty acids (RFAs) from recirculated white water. Batch ultrafiltration experiments indicated that TDS, soluble COD, and TOC removal efficiencies were affected by membrane molecular weight (molar mass) cut-off, but were independent of the operating temperature, in the 20 to 60°C range. Except for fatty acids, where average removals exceeded 90%, the separation efficiency of the process for all other parameters (TDS, soluble COD, TOC, and resin acids) was moderate, ranging from 10 to 41%. Biological treatment using a sequencing batch reactor (SBR) unit was very effective in removing RFAs, TOC, total and soluble COD. Furthermore, ultrafiltration of the biologically treated process water resulted in significant additional TDS, soluble COD, and TOC removal.     

Decolorisation of H-acid manufacturing process wastewater by anion exchange resin

Anion exchange resin was employed to examine the feasibility to treat the H-acid manufacturing wastewater by column experiment. Besides the acidity recovery, the decoloring efficiency and chemical oxygen demand (COD) removal efficiency of the anion exchange resin was investigated in the experiments. The results revealed that the anion exchange resin was able to remove colourful pollutants and degrade a part of COD effectively, and at the same time reserve acidity in the wastewater solution. The resin regenerated by a 10% NaCl aqueous solution had the same ability to discolour and remove the COD from the wastewater as the new resin had. The resin regenerated by 3% w/w NaCl aqueous solution, which was the same concentration as seawater, also had, to some extent, the same effect on decolorisation and the removal of COD; however, its colour and COD removal performance was not as efficient as the resin regenerated by 10% w/w NaCl and the new resin. H-acid (0.25%) was also successfully recovered from the regenerating solutions.     

Degradation and Transformation of Organic Compounds in Songhua River Water by Catalytic Ozonation in the Presence of TiO2/Zeolite

This paper presents experimental results of the catalytic ozonation of Songhua River water in the presence of nano-TiO₂ supported on Zeolite. The removal efficiency of TOC and UV₂₅₄, the variation of AOC and molecular weight distribution of organics was studied. Results showed that TOC and UV₂₅₄ removal efficiency by ozone was improved in the presence of TiO₂/Zeolite, and increased by 20% and 25%, respectively. The part of organic compounds less than 1000 Da increased in ozonation, but decreased in catalytic ozonation. The AOC of water increased in catalytic ozonation, and the increase of AOC was particularly obvious when ozone dose increased from 28.8 mg·L^?1 to 46.6 mg·L^?1. The degradation and transformation of organic compounds was analyzed by means of GC-MS. The total number of organic compounds was reduced from 50 in the untreated water to 36 and 20, respectively, in ozonation and catalytic ozonation. The removal efficiency of the total organic compounds peak area in ozonation and catalytic ozonation were 23.5% and 62.5%, respectively. Most of the hydrocarbons could be removed easily in ozonation and catalytic ozonation. The organic compounds having hydroxyl, carboxyl or carbonyl groups were hard to be removed in ozonation, but could be removed efficiently in the presence of TiO₂/Zeolite.     

多相催化臭氧化处理采油废水试验研究

采用多相催化臭氧化技术在实验室条件下去除采油废水中的COD。考察了催化剂的种类、吸附作用和投加量以及pH、反应时间、HCO3-和CO32-对多相催化臭氧化去除采油废水COD的影响。试验最佳工艺条件为:臭氧质量浓度为80 mg.L-1、催化剂为A3、催化剂投加量为1 000 mg.L-1、pH为10.8和反应时间为50 min。结果表明,在最佳工艺条件下,采用A3/O3氧化工艺处理采油废水,COD去除率可达到79.40%,比O3、A1/O3和A2/O33种氧化工艺对COD的去除率分别提高了33.00%、14.00%和18.10%,出水COD为118.450 mg.L-1,达到了国家污水综合排放标准的二级排放标准;催化剂对采油废水中的有机物具有一定的吸附作用;pH对反应影响显著,pH越大越有利于COD的去除;COD去除率随反应时间的延长其增幅逐渐减小,最终趋于平衡;HCO3-和CO32-对多相催化臭氧化去除COD的效果具有很大的抑制作用,在HCO3-和CO32-质量浓度为200 mg.L-1时,COD去除率分别为39.89%和27.59%,比HCO3-和CO32-质量浓度为0 mg.L-1时的COD去除率分别降低了39.51%和51.81%,试验还发现,CO32-对自由基的抑制作用强于HCO3-。这在某种程度上证明了多相催化臭氧化对有机物的降解遵循羟基自由基氧化机理。     

Ozone applications for after‐clearing of disperse‐dyed poly(lactic acid) fibres

In this study, the effectiveness of the ozonation process, in neutral distilled water at room temperature, as a clearing process for disperse‐dyed poly(lactic acid) fibre fabrics is investigated. The efficiency of simultaneous decolorisation of dyebath effluent and clearing of dyed poly(lactic acid) in the cooled dyebath after completion of the poly(lactic acid) dyeing cycle is also explored. Conventional alkaline reduction clearing with sodium dithionite was chosen as a control clearing process for comparison. Wash fastness, colour difference, colour removal (in Hazen) and chemical oxygen demand values were determined and compared. Long ozone treatment times at high ozone dose resulted in unacceptable colour differences. The colour difference problem was solved by use of lower ozone dose; however, a warm soaping step had to be added to the after‐clearing sequence in order to achieve the desired fastness properties. A 33% reduction on the chemical oxygen demand load of the total process (dyeing + after‐clearing) could be achieved by ozone after‐clearing instead of using a conventional reduction clearing treatment. The addition of the warm soaping step to improve the fastness properties of the ozonated samples increased the total chemical oxygen demand of the process (dyeing + ozonation in water + warm soaping), but a 12–18% reduction on the chemical oxygen demand load of the total process was observed when compared with the conventional treatment sequence (dyeing + reduction clearing).     

臭氧强化电絮凝处理直接耐晒大红4BS模拟染料废水

采用臭氧强化电絮凝法处理直接耐晒大红4BS模拟染料废水,研究了染料脱色的影响因素及其COD_Cr去除动力学。考察了电流密度、溶液初始pH 值、染料初始浓度、支持电解质浓度、反应温度和臭氧流量对臭氧强化电絮凝法处理4BS染料脱色效率的影响。结果表明,电流密度15 mA·cm^-2,pH值10.0,4BS染料初始浓度100 mg·L^-1,支持电解质浓度3000 mg·L^-1,臭氧流量06 L·h^-1,20 ℃下反应50 min后4BS脱色率达94％以上。COD_Cr去除符合拟二级动力学。     

Effect of Calcination Temperature over the Performance of Mn-Ce-O on the Catalytic Ozonation of Olive Mill Wastewater

The effect of calcination temperature on Mn-Ce-O 70/30 characteristics, activity and stability was investigated when this catalyst was applied on the catalytic ozonation of a phenolic mixture. Two crystalline phases (cubic CeO₂ and tetragonal Mn₃O₄) were observed by X-ray diffraction analysis, which also showed an increase of crystallinity with temperature. The material prepared at 300 ºC was the most efficient regarding TPh (100%), TOC (80%) and COD (62%) removal, as well as revealed to be the one leading to the lowest amount of Mn leached. The generalized kinetic model (GKM) was able to describe mineralization during this catalytic process with relative errors of ±10%.     

Perovskite Catalytic Ozonation of Some Pharmaceutical Compounds in Water

The ozonation of two pharmaceutical compounds: the drug diclofenac (DCF) and the synthetic hormone 17α-ethynylstradiol (EST), has been studied in laboratory prepared water and domestic wastewater in the presence of perovskite catalysts. In ultrapure water, catalysts do not lead to any improvement on the ozonation rates of DCF and EST which supports the fact that both compounds are removed by direct ozonation. TOC removal, on the other hand, is significantly increased in the presence of perovskite catalysts, especially when copper perovskite is used, with TOC removals in the order of 90% after 120 minutes of reaction. In domestic wastewater the results are similar regarding the mechanism of initial pharmaceutical compounds removal, which are due to direct reactions with ozone that, in this case, develop during longer reaction times likely due to the presence of other contaminants. Then, regarding TOC removal in domestic wastewater, negligible differences between non-catalytic and catalytic ozonation are observed during the first approximately 25 minutes of reaction. For higher reaction time, TOC removal is improved only in the case copper perovskite catalyst is used although percentages of TOC removal are comparatively lower than those reached in ultrapure water (they hardly reach 50% TOC removal). Finally, a kinetic study has been carried out and apparent rate constants of the heterogeneous reaction between ozone and TOC on the catalyst surface have been determined.