Advanced oxidation of bleached eucalypt kraft pulp mill effluent.

In this study a poorly biodegradable (BOD/COD = 0.3) industrial alkaline ECF bleaching filtrate was treated using different advanced oxidation processes to evaluate their use in combined chemical-biological treatment aimed at increasing recalcitrant COD removal and improving final effluent quality. Oxidative treatments included ozonation combined with hydrogen peroxide (2, 5, 10, 20 mmol L(-1) O3/0.7, 2, 5, 10 mmol L(-1) H2O2) and photocatalysis with hydrogen peroxide (UV/2, 4 and 8 mmolL(-1) H2O2) and with TiO2 (UV/TiO2/0.7 and 4 mmol L(-1) H2O2). The O3/H2O2 process increased effluent biodegradability by up to 68% as a result of increasing BOD and decreasing COD. Increasing the O3 dose had a greater effect on biodegradability improvement and lignin and colour removal efficiencies than increasing the H2O2 dose. A combined oxidant dose of 5 mmol L(-1) O3 and 2 mmol L(-1) H2O2 resulted in 75% lignin removal, 40% colour removal and 6% carbohydrate loss without mineralizing the organic carbon. The photocatalytic processes led to a decrease in effluent biodegradability through combined decrease in BOD and increase in COD and did not result in efficient lignin or colour removal. Photocatalytic oxidation was apparently inhibited by the high chloride and COD levels in the alkaline filtrate, and may be more efficient in recalcitrant COD removal if performed after biological.     

O3、O3/H2O体系处理染料废水酸性嫩黄G的试验研究

以配制的酸性嫩黄G染料废水为研究对象,考察O3、O3/H2O2体系对去除染料废水中的COD.和色度,提高可生化性的效果,分析pH值、初始污染物浓度、H2O2投加量等各种因素对O3氧化染料废水的影响.试验结果表明:臭氧氧化对COD.去除率达55.1%,对色度的去除率接近100%,B/C由原水的0.08上升到03;臭氧化酸...     

O_3、O_3/H_2O_2体系处理染料废水酸性嫩黄G的试验研究

以配制的酸性嫩黄G染料废水为研究对象,考察O3、O3/H2O2体系对去除染料废水中的CODcr和色度,提高可生化性的效果,分析pH值、初始污染物浓度、H2O2投加量等各种因素对O3氧化染料废水的影响。试验结果表明：臭氧氧化对CODcr去除率达55.1%,对色度的去除率接近100%,B/C由原水的0.08上升到0.3;臭氧化酸性嫩黄G最适宜的pH值为12;H2O2/O3的最佳摩尔比为0.4。     

Study on the treatment of Acid Red 4 wastewaters by a laminar-falling-film-slurry-type VUV photolytic process.

The purpose of this study is to develop the design equation of a laminar-falling-film-slurry-type (LFFS) photoreactor for the treatment of organic wastewaters (Acid Red 4) by 185 nm vacuum ultra-violet (VUV) related processes. The LFFS photoreactor is one of the most efficient reactor configurations for conducting heterogeneous photocatalytic reactions, particularly for wastewater treatment. The decomposition of Acid Red 4 dye wastewaters by VUV-based photo-oxidation process was studied under various UV light intensities, dosages of H2O2 and TiO2. By the treatment of the LFFS-VUV only process, it was found that the decomposition rates of the dye in aqueous solutions increased with the increasing of VUV light intensity, dosage of TiO2, dosage of H2O2. The apparent potential of OH. generation from the photolysis of used oxidants (i.e. OH. sources, H2O, H2O2, TiO2) to decompose the targeted dye wastewater was investigated and compared.     

Leachate detoxification by combination of biological and TiO2-photocatalytic processes.

Landfill leachates are a problematic wastewater due to their variable concentration, volume changing in time and presence of refractory and hazardous components. In this paper, the results of a new approach to photocatalysis assisted by biological process for the detoxification of stabilised landfill leachate are presented. The biologically pre-treated leachate still contained a significant amount of non-biodegradable COD and TOC amounting to 500 and 200 mg/L, respectively. The 300 min of photocatalytic treatment (UVC/TiO2) brought about a significant decrease in more than 80% refractory organics remaining in leachate. The effect of pH and catalyst loading on mineralisation, colour removal rate and biodegradability (BOD/COD) improvement in the photoreactor were discussed. The bio-accessibility of formed photocatalytic oxidation intermediates was confirmed by oxygen uptake rate (OUR) measurements. Consequently, a part of COD was successfully removed in post-biological treatment.     

Treatment of industrial wastewater using photooxidation and bioaugmentation technology.

The versatile metabolism of microorganisms has an played important role in the biodegradation of recalcitrant toxic compounds entering into the natural environment. The biodegradability of organics can be enhanced using bioaugmentation and advanced oxidation processes (AOP) for aerobic/anaerobic treatment programs. Wastewater from a bulk drug (cresol) plant had high levels of TDS, COD and BOD, whilst the levels from a pigment plant low. Both contained organics difficult to degrade. AOP using hydroxyl radical generated in 1 L glass reactor using UV and H2O2 efficiently oxidised phenol and cresol. COD and sulphite reduction in cresol containing wastewater were 20-60% in 1-6 h. A twenty to thirty percent reduction in copper phthalocyanine pigment effluents was achieved in 6 h using AOP. Strains of Micrococcus, Pseudomonas, and Nocardia degrading phenol, cresol were isolated from soil and sludge. Mixed biomass of these organisms removed phenols (1,000 ppm) and cresols (500 ppm) completely in 24 and 72 h, respectively. The COD and BOD reductions under the optimum nutritional and physiological conditions were in the range of 70 to 90%. When added to the bioreactor, 20% of the developed biomass of mixed strains of Micrococcus, Nocardia and Pseudomonas increased the rate of COD and BOD reduction gradually and stabilised at 80-90%. Added biomass improved the overall efficiency of the aerobic process.     

Degradation of wine industry wastewaters by photocatalytic advanced oxidation.

Wine industry wastewaters contain a high concentration of organic biodegradable compounds as well as a great amount of suspended solids. These waters are difficult to treat by conventional biological processes because they are seasonal and a great flow variation exists. Photocatalytic advanced oxidation is a promising technology for waters containing high amounts of organic matter. In this study we firstly investigated the application of H2O2 as oxidant combined with light (artificial or natural) in order to reduce the organic matter in samples from wine industry effluents. Secondly, we studied its combination with heterogeneous catalysts: titanium dioxide and clays containing iron minerals. The addition of photocatalysts to the system reduces the required H2O2 concentration. Although the H2O2/TiO2 system produces higher efficiencies, the H2O2/clays system requires a H2O2 dosage between three and six times lower.     

Advanced electro-Fenton degradation of biologically-treated coking wastewater using anthraquinone cathode and Fe-Y catalyst

The electrocatalytic activity of bare and 2-ethyl anthraquinone-modified graphite felt (2-EAQ/GF) toward oxygen reduction was investigated using a cyclic voltammetry technique in a neutral solution. The prepared cathodes were tested for electrogeneration of H2O2 and electro-Fenton oxidation (EFO) treatment of neutral coking wastewater (CW) after biological process, using a graphite anode and Fezeolite Y catalyst. The results showed that (i) H2O2 yield and current efficiency greatly depended on cathodic potential and materials; (ii) hydroxyl radicals, generated from Fe-zeolite Y-catalyzed H2O2 decomposition, played a great role in EFO treatment, while anodic direct and indirect oxidation was insignificant; (iii) chemical oxygen demand, total organic carbon (TOC) and acute toxicity of wastewater decreased by 40-50, 30-40 and 50-60%, respectively, and biodegradability increased after 1 h of EFO treatment. Due to the free-pH adjustment, EFO presents a potential engineering application for advanced treatment of CW.     

Effect of photochemical pre-treatment on COD fractionation of a non-ionic textile surfactant.

The work presented in this paper is focused on the effect of photochemical (H2O2/UV-C) pretreatment on COD fractionation and degradation kinetics of a non-ionic textile surfactant. In the first part of the study, the COD of non-ionic surfactant was adjusted to 1000 mg/L in order to simulate real effluent originating from the textile preparation stage featuring desizing, scouring, washing and rinsing operations. The surfactant was subjected to H2O2/UV-C pretreatment for up to 120 min at a dose of 30 mM (980 mg/L) H2O2. The biodegradability studies for untreated and photochemically treated samples were evaluated on the basis of modeling of oxygen uptake rate (OUR) profiles. Modelling of OUR profiles conducted for untreated sample showed that single complex substrate was subjected to enzymatic breakdown and disintegrated into one readily and two types of slowly biodegradable substrates. After modelling the biodegradation of photochemically pretreated sample, the readily biodegradable COD fraction was reduced, on the other hand, more slowly biodegradable organics were generated. A higher disintegration rate was obtained for chemically pretreated samples. However, other kinetic constants of growth and hydrolysis processes were not affected considerably.     

Advanced H2O2 oxidation for diethyl phthalate degradation in treated effluents: effect of nitrate on oxidation and a pilot-scale AOP operation

One of the objectives of this study was to delineate the effect of nitrate on diethyl phthalate (DEP) oxidation by conducting a bench-scale ultraviolet (UV)/H2O2 and O3/H2O2 operations as suggested in a previous study. We also aim to investigate DEP oxidation at various UV doses and H2O2 concentrations by performing a pilot-scale advanced oxidation processes (AOP) system, into which a portion of the effluent from a pilot-scale membrane bioreactor (MBR) plant was pumped. In the bench-scale AOP operation, the O3 oxidation alone as well as the UV irradiation without H2O2 addition could be among the desirable alternatives for the efficient removal of DEP dissolved in aqueous solutions at a low DEP concentration range of 85+/-15 microg/L. The adverse effect in the UV/H2O2 process was significantly greater than that in the UV oxidation alone, and its oxidation was almost halved by the nitrate. However, the nitrate clearly enhanced the DEP oxidation in the O3 oxidation and O3/H2O2 process. Especially, the addition of nitrate almost doubled the DEP oxidation efficiency in the O3/H2O2 process. The series of pilot-scale AOP operations confirmed that about 30-50% of DEP dissolved in the treated MBR effluent streams was, at least, oxidized by the O3 oxidation alone as well as the UV irradiation without H2O2 addition. The UV photolysis of H2O2 was most effective for DEP degradation with an H2O2 concentration of 40 mg/L at a UV dose of 500 mJ/cm2.     

Comparison between ozone and ferrate in oxidising geosmin and 2-MIB in water.

Among the chemicals causing taste and odour (T&O) in drinking water, the most commonly identified and problematic ones are geosmin and 2-MIB (2-methylisoborneol). Since the reported odour thresholds of geosmin and 2-MIB are as low as 4 and 8.5 ng/L, respectively, they are not readily removed by conventional water treatment processes. In this study, ozone (O3) and ferrate (Fe(VI)) were applied to oxidise geosmin and 2-MIB. Their performances were compared in terms of removal efficiency of geosmin and 2-MIB. In the case of O3, removal efficiency of geosmin and 2-MIB ozonation at different initial O3 doses, H2O2/O3 ratios and water temperatures were evaluated. The oxidation rates of geosmin and 2-MIB by Fe(VI) were measured within pH 6-8. The effect of H2O2 addition was also evaluated. In summary, O3, especially with H2O2, could almost completely oxidise geosmin and 2-MIB, while Fe(VI) could not oxidise them more than 25% at any pH that was considered in this study. This was attributed to the structure of the organics and high reaction selectivity of Fe(VI). Further study should be conducted to find the reason of inhibition of oxidation by Fe(VI).     

酸析—微电解—Fenton氧化预处理亚麻脱胶废水的研究

高浓度亚麻脱胶废水CODCr、色度都很高,不宜直接进行生物处理.试验采用酸析-微电解-Fenton氧化的预处理工艺,并对反应的影响因素进行了研究,试验结果表明,在pH=3,微电解90 min,H2O2投量1 500 mg/L,Fenton氧化120 min的条件下,CODCr去除率可以达到71.4%,色度去除率超过90%.同时该方法提高了废水的可生化性,有利于后续的生化处理.     

Using ozone to reduce recalcitrant compounds and to enhance biodegradability of pulp and paper effluents.

The effect of ozone based oxidation on removing recalcitrant organic matter (ROM) and enhancing the biodegradability of alkaline bleach plant effluent was investigated. A bubble column ozonation tower was used in the study. The experiments were carried out at different temperatures (20 degrees C and 60 degrees C) and pH (9 and 11), with a number of biological and chemical parameters being monitored including BOD5, COD, TC, pH, color, and molecular weight distribution of organics (nominal cut off of 1,000 Da). Biodegradability of the effluent was determined based on BOD5/COD of the wastewater throughout the process. For all the experiments, ozonation enhanced the biodegradability of the effluent by 30-40%, which was associated with noticeable removal of ROM including high molecular weight (HMW) and color-causing organics by about 30% and 60%, respectively. While the biodegradability of HMW fraction increased by about 50%, there was no biodegradability improvement for low molecular weight (LMW) portion, which was originally readily biodegradable (with BOD5/COD of about 0.5). Statistical analysis of variance (ANOVA) revealed neither pH nor temperature played significant role on the ozonation process at 95% confidence level.     

Effective degradation of para-chloronitrobenzene through a sequential treatment using zero-valent iron reduction and Fenton oxidation

In this study, zero-valent iron (ZVI) was used to pretreat para-chloronitrobenzene (p-CNB), and the major product was para-chloroaniline (p-CAN). By adding H(2)O(2) directly, further p-CAN degradation can be attributed to Fenton oxidation because ferrous ions (Fe(2+)) released during the ZVI corrosion could be used as an activator for H(2)O(2) decomposition. In the reduction process, the reduction efficiency of p-CNB as well as Fe(2+) concentration increased with increasing iron dosage and decreasing solution pH. Under the optimal conditions, 25 mg L(-1) of p-CNB could be transformed in 3 h when initial solution pH was 3.0 and ZVI dosage was 2.0 g L(-1). A sufficient amount of Fe(2+) (50.4 mg L(-1)) was obtained after the above reaction to activate H(2)O(2). In the Fenton process, the oxidization of p-CAN was also more effective in acidic conditions and it increased with increasing H(2)O(2) concentration. The control experiments showed that the sequential treatment was more effective than Fenton oxidation alone in treating p-CNB wastewater since the removal rate of total organic carbon (TOC) was improved by about 34%. It suggested that the amino function group is more susceptible to oxidative radical attack than the nitro function group. Therefore, sequential treatment using zero-valent iron reduction followed by Fenton oxidation is a promising method for p-CNB degradation.     

Preliminary studies using hybrid mediated electrochemical oxidation (HMEO) for the removal of persistent organic pollutants (POPs).

This study investigates the hybrid mediated electrochemical oxidation (HMEO) technology, which is a newly developed non thermal electrochemical oxidation process for organic destruction. A combination of ozone and ultrasonication processes to the mediated electrochemical oxidation (MEO) process is termed as hybrid mediated electrochemical oxidation. The electrochemical cell was developed in this laboratory. In the present study, several organic compounds, such as phenol, benzoquinone and ethylenediaminetetraacetic acid (EDTA), were chosen as the model organic pollutants to be destructed by the hybrid process. The organic destruction was monitored based on the CO2 generation and total organic carbon (TOC) reduction. The HMEO process was found to be extremely effective in the destruction of all the target organics chosen in this study. The information obtained from this study will provide an insight in adopting this technique for dealing with more recalcitrant organics (POPs).     

O_3和O_3/H_2O_2氧化对饮用水中痕量臭味物质的处理效果研究

研究了O3、O3/H2O2深度氧化法对饮用水中的Geosmin、MIB、IBMP、IPMP及TCA等痕量异味物质的去除效能。当O3投加量为4.66mg/L时,对痕量异味物质的去除率按IBMP、TCA、Geosmin、IPMP和MIB的排列,其中对Geosmin的绝对去除量最大,达到了140ng/L。投加O30.43mg/L和H2O210mg/L氧化去除5种痕量异味物质,对IBMP和TCA去除率分别达到75%和67.2%,去除效率较高;但在O3及O3/H2O2这样的投加量下,痕量异味物质尚不能达到标准中对嗅阈值的要求,还需配合后续处理工艺。     

Enhanced degradation of paracetamol by UV-C supported photo-Fenton process over Fenton oxidation

For the treatment of paracetamol in water, the UV-C Fenton oxidation process and classic Fenton oxidation have been found to be the most effective. Paracetamol reduction and chemical oxygen demand (COD) removal are measured as the objective functions to be maximized. The experimental conditions of the degradation of paracetamol are optimized by the Fenton process. Influent pH 3, initial H(2)O(2) dosage 60 mg/L, [H(2)O(2)]/[Fe(2+)] ratio 60 : 1 are the optimum conditions observed for 20 mg/L initial paracetamol concentration. At the optimum conditions, for 20 mg/L of initial paracetamol concentration, 82% paracetamol reduction and 68% COD removal by Fenton oxidation, and 91% paracetamol reduction and 82% COD removal by UV-C Fenton process are observed in a 120 min reaction time. By HPLC analysis, 100% removal of paracetamol is observed at the above optimum conditions for the Fenton process in 240 min and for the UV-C photo-Fenton process in 120 min. The methods are effective and they may be used in the paracetamol industry.     

Dual-electrode oxidation used for aniline degradation in aqueous electrolyte

The electrochemical degradation of aniline in aqueous electrolyte has been studied by dual-electrode oxidation process using Ti/SnO2-Sb2O5 for anodic oxidation and graphite cathode to produce H2O2 in situ. The linear voltammograms were employed to obtain reasonable anodic and cathodic potential values for the purpose of restraining side reactions. The influence of Fe2+ on aniline degradation was investigated under potentiostatic condition with a three-electrode system. It was found that an anodic potential range of 2.0 +/- 0.1 V and a cathodic potential of -0.65 V could favor anodic oxidation and H2O2 generation. Anodic oxidation was accounted for aniline degradation in the absence of Fe2+, while in the presence of Fe2+ both electro-Fenton oxidation and anodic oxidation (dual-electrode oxidation) could degradate aniline effectively. When cathodic potential values were -0.65 and -0.80 V, the optimum Fe2+ concentration were 0.50 and 0.30 mM, respectively. 77.5% COD removal and 70.4% TOC removal with a current efficiency (CE) of 96-100% were achieved under the optimum conditions. This work indicates that dual-electrode oxidation process characterized by a high CE is feasible for the degradation of organic compounds.     

臭氧在饮用水处理中的应用

阐述臭氧在水处理中的氧化消毒机理,其强氧化性能破坏了有机物的分子结构,将一部分有机物彻底分解,同时将大分子有机物生成小分子有机物,改变了有机物性质,提高了其可生化性。介绍臭氧在水处理中的应用,如预氧化对微污染水中有机物、无机物、藻类及颗粒物的去除,以及对饮用水消毒杀菌。     

Phenol wastewater remediation: advanced oxidation processes coupled to a biological treatment.

Nowadays, there are increasingly stringent regulations requiring more and more treatment of industrial effluents to generate product waters which could be easily reused or disposed of to the environment without any harmful effects. Therefore, different advanced oxidation processes were investigated as suitable precursors for the biological treatment of industrial effluents containing phenol. Wet air oxidation and Fenton process were tested batch wise, while catalytic wet air oxidation and H2O2-promoted catalytic wet air oxidation processes were studied in a trickle bed reactor, the last two using over activated carbon as catalyst. Effluent characterisation was made by means of substrate conversion (using high liquid performance chromatography), chemical oxygen demand and total organic carbon. Biodegradation parameters (i.e. maximum oxygen uptake rate and oxygen consumption) were obtained from respirometric tests using activated sludge from an urban biological wastewater treatment plant (WWTP). The main goal was to find the proper conditions in terms of biodegradability enhancement, so that these phenolic effluents could be successfully treated in an urban biological WWTP. Results show promising research ways for the development of efficient coupled processes for the treatment of wastewater containing toxic or biologically non-degradable compounds.