Removal of Dissolved Organic Carbon and Color from Dyeing Wastewater by Pre-ozonation and Subsequent Biological Treatment

The effects of pre-ozonation and subsequent biological treatment on the decrease in dissolved organic carbon (DOC) and color from dyeing wastewater were investigated. Moreover, the compositions of organic compounds in raw wastewater (RW) and the respective treated waters were estimated, and microscopic observations of the mixed liquor were conducted. The amount of ozone required to remove 1 mg of DOC and the DOC removal rate brought about by pre-ozonation ranged from 6.6 to 13.2 mgO₃/mgC and 12 to 15%, respectively. The total amount of DOC removed was increased by the combined use of pre-ozonation and subsequent biological treatment, and pre-ozonation did not necessarily lead to an increase in the amount of DOC removed by biological treatment. However, this combined method was effective in decreasing color and adsorbable organic halide formation potential (AOXFP). The rates of the dyestuff in RW and the respective treated waters were less than 10% of total DOC, and those of the other non-biodegradable compounds were much higher than those of the dyestuff. The morphological difference was observed in the predominant bacteria in RW with and without pre-ozonation.     

Application of Ozonation to Dyeing Wastewater Treatment—Case Study in Nishiwaki Treatment Plant

Three treatment methods, raw wastewater (RW)?→?coagulation?→?biological treatment (RCB), RW→?pre-ozonation?→?biological treatment (ROB) and RW?→?biological treatment?→?post-ozonation (RBO), were investigated to clarify their effectiveness in treating dyeing wastewater from a treatment plant. The decrease in dissolved organic carbon (DOC) was in the following order: RCB?≥?RBO?>?ROB. DOC removal of 200 mg/L by biological treatment of RW was clearly higher than that of 12 mg/L by ozonation. On the other hand, only DOC removal of 108 mg/L was observed by biological treatment in RW after ozonation. The decrease in biological oxygen demand (BOD₅) was in the following order: ROB?≥?RCB?>?RBO. Because of the enhancement of biodegradability brought about by ozonation, BOD₅ after ozonation in RBO was higher than that of RW after biological treatment. Color was effectively removed by ozonation for both RW and RW after biological treatment, and the decrease in color was in the following order: RBO?>?ROB?≥?RCB. Adsorbable organic halide formation potential (AOXFP) and toxicity unit (TU15, exposure time is 15 min) were more effectively decreased by biological treatment than by coagulation or ozonation, although the differences among RCB, ROB and RBO were very small.     

Interaction of ozone and organic matter in coagulation with inorganic polymer flocculant-PACl: Role of organic components

In this study, two model waters were used to evaluate the ozone effect on aquatic organic matter (AOM) removal by coagulation with inorganic polymer flocculant (IPF)-polyaluminum chloride (PACl). Flocs formation during coagulation processes were detected by using PDA (Photometric Dispersion Analyzer). Apparent molecular weight distribution (AMWD) and resin fractionation (RF) were also performed to characterize the change of AOM as a result of pre-ozonation. The experimental results show that the dosage of O₃, characteristics and composition of AOM are the most important factors on the behavior of coagulation. Great differences have been found between the two model waters. Coagulation in model water 1 (MW1) (composed of humic acids) is impaired markedly by pre-ozonation, as more DOC (Dissolved Organic Carbon) is produced with increasing O₃ dosage. Floc formation, as exhibited from decreasing of the slopes of FI (Flocculation Index), is retarded gradually during coagulation process. Although residual turbidity is reduced with 1.15 mg/L O₃, removals of DOC and UV₂₅₄ all decreased. As for model water 2 (MW2) (composed of salicylic acid), FI is retarded also, but turbidity and DOC removals of coagulation after pre-ozonation are improved to a certain extent. Coagulation performance judged from removal of DOC is improved distinctly by pre-ozonation. Fractionation results show that molecular weight of organic matter (OM) of MW1 is converted from higher to lower; and OM becomes from more hydrophobic to more hydrophilic, which might be one of the mechanisms involved in the impairment of ozonation on coagulation effect. OM in MW2 is oxidized and mineralized to a greater extent, thus its impairment on coagulation is released. Finally, according to water properties, some proposed applications were provided for application of ozone in water treatment process.     

Combination of biological and chemical processes for the treatment of textile wastewater containing reactive dyes

The treatment of a segregated textile wastewater containing reactive dyes was investigated in two continuous‐flow process trains using ozonation and biological processes. The degree of decolorization and dissolved organic carbon (DOC) removal achieved by ozonation followed by aerobic treatment (two‐stage) was compared with that found when an anaerobic and aerobic pretreatment was added (four‐stage). Although the biological pretreatment reduced color by ～70%, similar amounts of ozone were required in both trains to achieve high degrees of overall removal of color and DOC. In both trains, ozonation increased biodegradability in the following aerobic reactor, however, in order to reach ～80% overall DOC removal, a specific ozone absorption (A*) of ～6 gO₃ gDOC_o^?1 was required and >50% of the DOC was mineralized in the ozone reactor. A comparison of cost estimates based on investment and operating costs for the process alternatives showed that a four‐stage train would reduce costs only if it enabled a decrease in A* to less than 2 gO₃ gDOC_o^?1. Difficulties in comparing treatment processes for segregated vs full‐stream wastewaters are discussed. Copyright © 2003 Society of Chemical Industry     

Removal of Pesticides by a Combined Ozonation/Attached Biomass Process Sequence

Different combinations of ozonation and biological treatments were tested on an industrial effluent containing high pesticide concentrations. Ozonation was performed in 450 L columns at 1.5 h HRT each. Biological treatment was carried out in a submerged filter (BIOFOR). Ozone was effective in removing herbicides but dosages up to 1000 mg L^?1 were needed. The improved biodegradability of the organic compounds after pre-ozonation was demonstrated by Oxygen Uptake Rates (OUR) tests and by the efficiency of biological treatment towards COD, and pesticides. The Italian discharge limit of 50 ppb total pesticides was achieved by combining pre-ozonation, biological treatment, and post- ozonation.     

Ozonation of C.I. Reactive Yellow 3 and Further Decrease in Dissolved Organic Carbon Concentration by Post-Biodegradation

Using C.I. Reactive Yellow 3 as the target compound, the effect of the combined use of ozonation and post-biodegradation on the decrease in dissolved organic carbon (DOC) concentration was investigated, and the synergistic effect (the difference in the amounts of DOC removed by the biological process between solutions with and without ozonation) was estimated. A decrease in DOC concentration was observed during ozonation and ΔO₃/ΔDOC was decreased from 16.0 to 5.2 with increasing ozonation time. Moreover, an enhancement of biodegradability was shown. A further decrease in DOC concentration was observed during the biodegradation after ozonation. The total amount of DOC removed by the combined method was increased from 73.6 mg at 30 min to 159.9 mg at 4 h. The synergistic effect was in the range of 22.7 to 39.2 mg. BOD₅ was a better indicator of the synergistic effect than BOD₅/DOC.     

Evaluation of Decolorization,Mineralization, and Toxicity Reduction of Tropaeolin O in Water by Ozonation with UV Irradiation

The combination of ozonation with UV irradiation can remove Tropaeolin O (AO6) and its by-products effectively and completely. The ozone dose affects the rate of decolorization, AO6 species removal, and dissolved organic carbon (DOC) reduction significantly. After 240 minutes of ozonation, the average DOC removal efficiency (η_DOC) for O₃ alone was about 0.79, while η_DOC for O₃/UV was 1.0. The average DOC removal rate was low at early stage of ozonation due to decolorization and low DOC. At later stage of ozonation, average DOC removal rate decreases because of the formation of persistent intermediates. The ozone consumption was consistent with η_DOC. The ratio of ozone consumption to ozone applied decreased from 14 to 12% when η_DOC < 40% because the decolorization in the early stage of the ozonation of AO6 may consume a relatively large amount of ozone. It was found that NO₂, NO, CO₂, and small amount of SO₂ was detected in the off-gas. The effective concentration (EC50) increased from 23.48% to 100%, suggesting that the toxic reduction was achieved, and O₃/UV system was superior to O₃ alone system     

Using catalytic ozonation and biofiltration to decrease the formation of disinfection by-products

The effect of catalytic ozonation in a fluidized bed reactor (FBR) on the formation of individual disinfection by-products (DBPs) was investigated. A biofiltration column was used to evaluate the removal efficiency of biotreatment on DBP precursors. Dissolved organic carbon (DOC), simulated distribution system trihalomethanes (SDS THMs), and six simulated distribution system haloacetic acids (SDS HAA6) were monitored. The source water was polluted by domestic and agricultural effluents. Catalytic ozonation removed the concentration of DOC by 8.2-51.4% depending on the dosage of the catalyst. The decreases of SDS THMs and SDS HAA6 were 41.3-51.2% and 31.7-48.3%, respectively, under the same operating conditions. Biotreatment greatly improved the removal efficiency of DOC and decreased the formation of DBPs. Up to 81.7%, 76.1%, and 81.3% of DOC, SDS THMs precursors, and SDS HAA6 precursors were removed after the catalytic ozonation followed by biofiltration, respectively. The treatment processes also influenced the proportions of individual DBP species. The proportion of bromine-containing species from the SDS THMs and SDS HAA6 increased in water samples after being treated by biofiltration alone, ozonation alone, catalytic ozonation, and catalytic ozonation followed by biofiltration.     

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 %.     

Post-Treatment of Composting Leachate by Ozonation

The post-treatment of composting leachate via an ozonation process in laboratory scale was studied in batch mode. According to the experiments, the COD removal was 47% after 30 min of ozonation via 0.4 g/h ozone (equivalent to 2.8 mg O₃/mg COD removed) at pH 9. In this circumstance, the removal of color and turbidity was also 86% and 89%, respectively. Increasing the ozone mass flow rate higher than 0.4 g/h had no considerable effect on the process variables. However, increasing the reaction time had a significant effect on both the removal of color and on COD of the leachate. Experimental data indicated that complete removal of color and 51% removal of COD were achieved after about 40 min of ozonation via 0.4 g/h ozone (equivalent to 3.3 mg O₃/mg COD removed). The ozone consumption rate increased as the reaction progressed and reached 4.1 mg O₃/mg COD removed after 60 min.     

Application of Ozonation and Biotreatment for Forest Industry Wastewater

This research is focused on the integrated process for the treatment of bleached Kraft pulp mill effluents. Pre-ozonation of softwood and hardwood combined bleaching effluents at alkaline pH resulted in 50 and 44% COD abatement, respectively. Segregation of highly polluted streams of bleaching process can be recommended to reduce the cost of treatment since the COD removal yield of CEH effluents was higher than combined bleaching effluents. Moreover, biodegradability of CEH effluents in terms of BOD₅/COD ratio was increased from 0.16 to 0.32. Noticeable color removal was achieved by pre-ozonation of the CEH stage and combined bleaching effluents. Pre-ozonation enhanced the performance of subsequent algal treatment in the sequential batch reactor (SBR) and activated sludge treatment. Algae have a higher ability to degrade AOX producing compounds together with a high COD removal rate. Although pre-ozonation increased the abatement rate of COD of SBR, the AOX removal rate remained constant as 87%.     

Improvement of Biodegradability of Oil Field Drilling Wastewater Using Ozone

The possibility of improving the biodegradability of drilling wastewater using ozone was investigated following coagulation pretreatment. The biodegradability of wastewater was improved significantly following the start of ozonation, and the molecular weight of organic compounds decreased continuously with the progress of oxidation. It is interesting that minimum biochemical oxygen demand, total organic carbon (BOD/TOC) ratio (0.4 g/g) was observed when wastewater was treated with ozone continuously for 15 min. The combination of ozonation for 5 min (ozone consumption ratio of 2.6 g ozone/g TOC) followed by biological degradation produced a total TOC removal rate of 54.3%, which was comparable to direct ozonation for 30 min under the same conditions (TOC removal rate of 54.9%; ozone consumption ratio of 8.7 g ozone/g TOC). It is clear that biological treatment following short-term ozonation was very efficient in TOC removal. A process of successive coagulation-precipitation, ozone oxidation, and biodegradation seemed to be a good option for drilling wastewater treatment.     

Ozone treatment of textile effluents and dyes: effect of applied ozone dose,pH and dye concentration

The ozonation of wastewater supplied from a treatment plant (Samples A and B) and dye‐bath effluent (Sample C) from a dyeing and finishing mill and acid dye solutions in a semi‐batch reactor has been examined to explore the impact of ozone dose, pH, and initial dye concentration. Results revealed that the apparent rate constants were raised with increases in applied ozone dose and pH, and decreases in initial dye concentration. While the color removal efficiencies of both wastewater Samples A and C for 15 min ozonation at high ozone dosage were 95 and 97%, respectively, these were 81 and 87%, respectively at low ozone dosage. The chemical oxygen demand (COD) and dissolved organic carbon (DOC) removal efficiencies at several ozone dose applications for a 15 min ozonation time were in the ranges of 15–46% and 10–20%, respectively for Sample A and 15–33% and 9–19% respectively for Sample C. Ozone consumption per unit color, COD and DOC removal at any time was found to be almost the same while the applied ozone dose was different. Ozonation could improve the BOD₅ (biological oxygen demand) COD ratio of Sample A by 1.6 times with 300 mg dm^?3 ozone consumption. Ozonation of acid dyes was a pseudo‐first order reaction with respect to dye. Increases in dye concentration increased specific ozone consumption. Specific ozone consumption for Acid Red 183 (AR‐183) dye solution with a concentration of 50 mg dm^?3 rose from 0.32 to 0.72 mg‐O₃ per mg dye decomposed as the dye concentration was increased to 500 mg dm^?3. © 2002 Society of Chemical Industry     

Remediation of Kraft Effluent by Ozonation: Effect of Applied Ozone Concentration and Initial pH

In this study, the impact of ozone concentration (14 and 7mg/L^?1 applied for 120min) and pH (10 and 12) on color removal, and reduction of dissolved organic matter (DOC) and total phenol of Kraft E₁ effluent was investigated. The degradation kinetics for the all parameters at pH 12 were slower than of those at pH 10. The degradation at pH 10 ceased after approximately 120min, while for the ozonation at pH 12, ozone was still being consumed even after 5h of treatment. When the ozone dose was increased, the removal efficiency increased; however, the DOC removal efficiency continued limited.     

Pilot Study on Pre-Ozonation Enhanced Drinking Water Treatment Process

The enhancement of TOC, COD_Mn, and UV₂₅₄ reduction in the conventional drinking water treatment process by pre-ozonation was investigated in South China on treating dam source water with a pilot plant consisting of pre-ozonation, coagulation-sedimentation, and filtration units. Pre-ozonation enhanced the reduction of NOM in the conventional coagulation-sedimentation and filtration process, and the total removals of UV₂₅₄, COD_Mn and TOC were improved for 34.6%, 18.1% and 15.3%, respectively by the adoption of pre-ozonation under an ozone dose (in ozone consumption base) of 0.85 mg/L. The enhancement of UV₂₅₄ and COD_Mn removals was mainly achieved through direct ozonation on humic substances, and that for TOC removal was achieved through biodegradation in sand filtration. In comparison with the TOC removal of 38%, a removal of 49% was acquired for SDS-THM under a pre-ozonation dose of 0.80 mg/L, indicating the selective removal of THMFP. The reduction of SDS-THM paralleled the reduction of COD_Mn to a significant degree, suggesting that the COD_Mn might be an effective surrogate parameter for SDS-THM if the raw water does not contain the reductive inorganic matters. Although the source water contains 13.2–27.0μg/L bromide, the formation of bromate was negligible when the ozone dose was below 1.0 mg/L.     

BAF-O_3组合工艺深度处理炼化含盐污水工业应用

臭氧催化氧化与曝气生物滤池的联合工艺可用于炼油厂含盐污水的深度处理。惠州炼化分公司采用BAF-O3组合工艺对含盐二级生化出水进行深度处理改造。运行结果表明,在进水COD浓度平均值97.9mg/L,臭氧催化氧化池和臭氧接触氧化塔的臭氧投加量分别为80~90 mg/L、30~20 mg/L的条件下,装置总出水COD浓度均值为43.5 mg/L,满足污水COD≤50 mg/L的限值要求,COD总去除率达到55.57%。BAF单元前置后,其COD去除率提高,COD去除量由2.71 mg/L提高至9.5 mg/L,经分析主要系生物絮凝作用;由于活性炭罐和BAF单元对悬浮物的有效过滤,有利于保护后续的臭氧催化氧化单元。     

Ozonation of Dyestuffs and Intermediates and Further Decrease in Dissolved Organic Carbon by Post-Biodegradation

Four each of water-soluble dyestuffs, intermediates and reference compounds were examined to determine the effect of the combined use of ozonation and post-biodegradation on the decrease in the amount of dissolved organic carbon (DOC) and the synergistic effect induced by ozonation. The amount of DOC removed by ozonation was increased initially with increasing ozonation time, and showed a plateau thereafter. The amount of ozone required to remove 1 mg of DOC (ΔO₃/ΔDOC) ranged from 5.2 to 18.6 mgO₃/mgC for the dyestuffs and the intermediates. The DOC concentrations of all the ozonized solutions were decreased with incubation time. In the case of the dyestuffs and the intermediates, the total amounts of DOC removed were increased with increasing ozonation time and showed a plateau thereafter. The synergistic effect (the ozonation-induced increase in the amount of DOC removed by the biological process) was dependent on the initial biodegradability, and was observed in all the dyestuffs and the intermediates in the range of 0.2 to 42.7 mgDOC. On the other hand, no synergistic effect was observed in the reference compounds of high biodegradability.     

Effect of Ozonation on Degradation of Organochlorine Compounds in Biosludge of Pulp and Paper Industry

The waste-activated sludge in the pulp and paper industry has been classified as hazardous waste due to the presence of organochlorine compounds. The fate of organochlorine compounds during ozonation of biosludge as well as subsequent treatment in activated sludge process has been studied. Ozonation of biosludge at 45.3 ± 2.1 mg O₃/g dry solid dosage resulted in 23 ± 2 and 26 ± 4% removal of adsorbable organic halides and extractable organic halides compounds, respectively. Out of 12 chlorophenolic compounds identified by USEPA for regulation, 10 compounds were detected in the biosludge and 19–68% removal of the individual compounds was observed during ozonation. High molecular weight chlorinated compounds were decomposed to low molecular weight ones with partial dechlorination. The ozonation followed by biological treatment can remove more than 80% of organochlorine compounds.     

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.     

原水深度处理过程中的生物稳定性和分子量分布

研究了水源水在"预臭氧+常规+主臭氧/生物活性炭"深度处理工艺流程净化中的各工艺段出水有机物及分子量的变化特征,建立了生物稳定性与有机物分子量的关系,实现了对深度处理后供水水质生物稳定性的评估。研究结果表明:预臭氧可将大分子的天然有机物分解为相对分子质量小于1000的有机物,并提高水的可生化性;导致常规处理工艺去除水中有机物的效率降低;主臭氧可将有机物进一步氧化,并将部分氧化成相对分子质量小于500的有机物;生物活性炭可提高出水的生物稳定性,但对相对分子质量小于1000的有机物去除有限;分子量越小生物稳定性越差,越不容易被去除。此研究结果为评估水源水质深度处理的生物稳定性提供了理论依据。