Potential of UV/H2O2 oxidation for enhancing the biodegradability of municipal reverse osmosis concentrates

UVC/H2O2 and VUV/H2O2 oxidation processes were evaluated for the degradation of organic pollutants in reverse osmosis concentrate (ROC) produced from a municipal secondary effluent. It was found that the oxidation by UVC/H2O2 and VUV/H2O2 processes could be described as a pseudo first-order reaction. For UVC increased oxidation occurred with increasing H2O2 dosage up to 2 mM above which improvement in oxidation performance decreased. At the same H2O2 dosage, VUV irradiation gave better overall oxidation performance. Compared with UVC/6 mM H2O2, VUV/2 mM H2O2 gave a greater rate of reduction of chemical oxygen demand, but a lower rate for reduction of dissolved organic carbon, suggesting that oxidation of organics by the two methods followed different pathways. The change of absorbance at 254 nm and fluorescence excitation emission matrix spectra of irradiated samples indicated that the large and complex compounds were fragmented rapidly by the *OH, resulting in rapid decolourisation. The biodegradability of the organics in the ROC was increased from 11% to 35% after 1 h treatment by UVC/3 mM H2O2, whereas a greater increase (41%) was obtained with VUV/2 mM H2O2. This increase in biodegradability indicates the potential for employing a subsequent biological treatment process.     

二氧化氯催化氧化降解铬黑T试验研究

在常温常压下,对Fe2O3/γ—A12O3+H2O2和ClO2+TiO2两种催化氧化体系处理铬黑T废水的效果进行了分析。试验结果表明,处理甲基橙废水效果较好的Fe2O3/γ—Al2O3+H2O2组合对铬黑T的降解效果非常有限,而ClO2+TiO2组合的处理效果较好:以500 mg/L的铬黑T溶液为模拟废水,当pH为4,C102投加量为200 mg/L,TiO2投加量为500 mg/L,反应时间为90 min时,脱色率达89.96%,CODCr的去除率可达45.36%。     

Treatment of wastewater from a cotton dyeing process with UV/H2O2 using a photoreactor covered with reflective material

Wastewater containing several dyes, including sulfur black from the dyeing process in a textile mill, was treated using a UV/H2O2 process. The wastewater was characterized by a low BOD/COD ratio, intense color and high acute toxicity to the algae species Pseudokirchneriella subcaptata. The influence of the pH and H2O2 concentration on the treatment process was evaluated by a full factorial design 22 with three replicates of the central experiment. The removal of aromatic compounds and color was improved by an increase in the H2O2 concentration and a decrease in pH. The best results were obtained at pH 5.0 and 6 g L(-1). With these conditions and 120 min of UV irradiation, the removal of the color, aromatic compounds and COD were 74.1, 55.1 and 44.8%, respectively. Under the same conditions, but using a photoreactor covered with aluminum foil, the removal of the color, aromatic compounds and COD were 92.0, 77.6 and 59.4%, respectively. Moreover, the use of aluminum foil reduced the cost of the treatment by 40.8%. These results suggest the potential application of reflective materials as a photoreactor accessory to reduce electric energy consumption during the UV/H2O2 process.     

Comparison of different advanced oxidation process to reduce toxicity and mineralisation of tannery wastewater.

Many organic compounds contained in wastewater are resistant to conventional chemical and/or biological treatment. Because of this reason different degradation techniques are studied as an alternative to biological and classical physico-chemical processes. Advanced Oxidation Processes (AOPs) probably have developed to become the best options in the near future. AOP while making use of different reaction systems, are all characterised by the same chemical feature: production of OH radicals (*OH). The versatility of AOPs is also enhanced by the fact that they offer different possibilities for OH radical production, thus allowing them to conform to specific treatment requirements. The main problem with AOPs is their high cost. The application of solar technologies to these processes could help to diminish that problem by reducing the energy consumption required for generating UV radiation. In this work, different AOPs (O3, TiO2/UV, Fenton and H2O2/UV) were examined to treat tannery wastewater or as a pre-treatment step for improving the biodegradation of tannery wastewater, at different pH and dosage of the chemicals. Under certain circumstances retardation in biodegradation and/or an increase in toxicity may be observed within these treatment steps. Two different bioassays (Daphnia magna and Vibrio fischeri) have been used for testing the progress of toxicity during the treatment. In parallel other objectives were to analyse and identify organic compounds present in the untreated wastewater and arising degradation products in AOP treated wastewater samples. For this purpose substance specific techniques, e.g., gas chromatography-mass spectrometry (GC-MS) in positive electron impact (El(+)) mode and atmospheric pressure ionisation (API) in combination with flow injection analysis (FIA) or liquid chromatography-mass and tandem mass spectrometry (LC-MS or LC-MS-MS) were performed.     

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.     

Ti/MCM-22/MCM-41微介孔复合材料光催化降解酸性红B模拟废水的研究

采用纳米自组装法制备了具有吸附性和光催化性的Ti/MCM-22/MCM-41微介孔复合材料,利用X射线衍射、N2吸附、扫描电镜等方法对其进行表征。将复合材料用于光催化降解酸性红B的实验,考察了催化剂用量、光照时间、pH值和染料初始浓度对光催化降解率的影响,并对光降解产物进行了紫外光谱分析。结果表明:当染料的初始浓度为50 mg/L,废水pH在6左右,催化剂投加量为0.1 g/L,光照时间120 min,酸性红B的去除率可达98%以上,光催化降解反应遵循一级反应动力学方程。降解产物的紫外光谱图表明,降解后酸性红B的两个特征吸收带消失,结构的共轭系被打破,颜色消失,说明该复合材料去除水中的酸性红B主要是通过光催化作用。     

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.     

Photocatalytical polishing of paper-mill effluents.

Photocatalytic oxidation (PCO) is a promising technology for purification of biological pretreated wastewater or destruction of non-biodegradable compounds. For this reason PCO has been investigated as a last step of purification of biologically pre-treated paper-mill effluents. The influence of the parameters pH, TiO2-modification, TiO2-concentration, catalyst re-use, concentration of substances to be oxidised (wastewater quality) has been determined. The TOC of the biologically pretreated wasterwater was up to 55 mg L(-1). This wastewater was treated with a previously presented aerated cascade photoreactor which was modified for batch experiments. A high specific oxidation rate of up to 0.76 g TOC m(-2) h(-1) as well as a complete TOC mineralization has been achieved after the optimisation of the process parameters. The complete destruction of recalcitrant compounds will offer the opportunity to reuse the wastewater in the production process. The increase of the BOD5/TOC ratio after a short irradiation period indicates the transformation of recalcitrant organic compounds to better biodegradable intermediates. The use of PCO as a pre-treatment step for the enhancement of the biodegradability of wastewater, containing recalcitrant or inhibitory compounds is an alternative to a long and energy-intensive total pollutant mineralization.     

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.     

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。     

Fenton试剂对铁锰矿井废水处理的实验研究

使用Fenton试剂对铁锰矿井水进行处理试验,论述了反应温度、H2O2的投加量、pH、反应时间对Fenton试剂处理矿井水的影响,讨论了Fenton试剂处理酸性矿井废水的机理。结果表明:芬顿试剂对铁锰矿井水中锰的去除效率很高,矿井水中的Fe2+能与H2O2形成Fenton试剂后产生的具有强氧化性的.OH能有效处理矿井水中的Mn2+。对于原水Mn2+的初始浓度为2 mg/L,Fe2+的初始浓度为250 mg/L,pH为5,当控制反应温度为25℃,H2O2的投加量为8 mmol/L,调节pH值为4.5,反应时间为10 m in,Mn2+去除效率可以达到78.1%以上。     

UV/H2O2和UV/TiO2/H2O2去除水中微量硝基苯的比较研究

研究比较了UV/H2O2和UV/TiO2/H2O2对水中微量硝基苯的降解效果,并考察了水中常见HCO-3和腐殖酸对硝基苯降解的影响.结果表明,薄膜状TiO2的存在对UV/H2O2降解硝基苯有显著的促进作用,在最佳H2O2投加量2.1 mg/L时,UV/TiO2/H2O2的反应速率常数比UV/H2O2高32.8%;2 min内UV/TiO2/H2O2对硝基苯的去除率达到80%以上.HCO-3和腐殖酸对硝基苯降解有很强的抑制作用,HCO-3和腐殖酸浓度分别为2 mmol/L和3.2 mg/L时,UV/TiO2/H2O2对硝基苯的反应速率常数分别下降84.6%和92.2%.     

H2O2、Fenton试剂与活性炭联用对CODCr去除效果的对比试验研究

为了开发高效低成本、达到回用水质标准的污水处理工艺,本试验采用H2O2、Fenton试剂与活性炭联用对CODCr进行去除的对比试验研究。结果表明：在室温下200 mL水样,当pH为3,震荡强度为150 rpm时,Fenton试剂-活性炭联用与H2O2-活性炭相比,活性炭用量少200 mg,时间缩短10 h,CODCr去除率高17.6%。试验揭示了Fenton试剂-活性炭联用的反应机理：Fe2＋与活性炭共同催化分解H2O2生成大量.OH,能快速氧化降解有机物,使CODCr浓度迅速降低。从工程应用角度和技术经济方面考虑,Fenton试剂-活性炭联用的pH值在5～7适宜;且处理成本更低。Fenton试剂-活性炭联用是处理二级出水CODCr高效、低耗的方法,值得进一步研究和推广应用。     

Physico-chemical treatment for the depuration of wine distillery wastewaters (vinasses).

In the present work, an integrated Fenton-coagulation/flocculation process was applied for the depuration of wine distillery wastewaters, commonly known as "vinasses". This study evaluates the Fenton process (H2O2/Fe2+), involving oxidation--in a first stage and coagulation/flocculation (using Ca(OH)2 as base-precipitant)--in a second stage for the removal of chemical oxygen demand (COD). The experimental variables studied were the dosages of hydrogen peroxide and iron salts, the molar ratio [H2O2]o: [Fe2+]o, the effluent dilution and the manner in which the reagents were added (splitting the reagent dose of hydrogen peroxide and ferrous salt into different fractions). The optimal operating conditions of the integrated process were: [H2O2]o = 0.5 mol/L using an optimal concentration ratio [H2O2]o: [Fe2+]o= 15 mol/mol. Under these conditions, the COD removal was 74%.     

Fenton氧化法深度处理制革废水生化出水试验研究

采用Fenton氧化法深度处理以制革废水为主的园区生化处理出水,试验表明:影响Fenton氧化的因素从大到小依次为H2O2投加量、Fe2+浓度、pH、反应时间。当进水CODCr平均为116.6mg/L时,在H2O2投加量50mmol/L、Fe2+投加量10mmol/L、pH为3、反应时间60min的最佳条件下,出水CODCr平均为31.7mg/L;在H2O2投加量25mmol/L、Fe2+投加量7.5mmol/L、pH为5、反应时间40min的经济运行条件下,出水CODCr平均为46.6mg/L。经济条件下的运行成本比最佳条件下的运行成本可节约2.3元/m3。     

Heterogeneous photocatalytic ozonation of 2,4-D in dilute aqueous solution with TiO2 fiber

Photocatalytic ozonation (O(3)/UV/TiO2) is an emerging oxidation method for recalcitrant organic contaminants in water. However, immobilised TiO2 catalysts suffer from reduced photonic efficiency. Therefore, TiO2 catalysts with excellent mechanical and thermal properties and enhanced photonic efficiencies are sought. This paper aimed to elucidate the mineralisation of low concentration 2,4-D (45.0 microM) by O(3)/UV/TiO2 using the world's first high-strength TiO2 fibre in laboratory batch experiments. 2,4-D degradation and TOC removal followed pseudo first-order reaction kinetic. The removal rates for 2,4-D and TOC in O(3)/UV/TiO2 were 1.5 and 2.4-fold larger than the summation of the values for ozonation (O3)) and photocatalysis (UV/TiO2), respectively. O(3)/UV/TiO2 was characterised by few aromatic intermediates with low abundance, fast degradations of aliphatic intermediates and dechlorination as a major step. The significantly enhanced 2,4-D mineralisation in O(3)/UV/TiO2 was attributed to increased ozone dissolution and decomposition, and reduced electron-hole recombination resulting in large number of hydroxyl radical (*OH) formation from more than one parallel path. The discrepancies in the organic carbon mass budget were attributed to few apparently major unidentified intermediates, while chlorine mass balance was reasonably acceptable. The mineralisation efficiency of O(3)/UV/TiO2 with the TiO2 fibre can further be enhanced by optimisation of experimental design parameters. The new TiO2 fibre is very promising to overcome the problem of reduced efficiency of TiO2 catalyst in an immobilised state.     

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.     

Water matrix effect on UV photodegradation of perfluorooctanoic acid

The widespread detection of perfluorinated compounds (PFCs) in the water environment has been a concern for the last several years, while effluents from wastewater treatment facilities are the major sources of these compounds. Even advanced oxidation technologies (AOTs) are not useful for mineralization of the compounds due to their very high stability. Photochemical techniques using particularly vacuum UV (VUV) have been found to be very promising in this regard. But the use of VUV in UV-based AOTs has still not progressed much. Moreover, the impact of water quality on PFCs photomineralization is unknown. This investigation aimed to assess photomineralization potentials of perfluorooctanoic acid (PFOA) in ultrapure water (UPW), tap water (TW), surface water and treated wastewater effluent using a reactor setup enabling maximum utilization of VUV emission of low pressure lamp in laboratory batch experiments. Neya River water (NRW) and the Nakahama Wastewater Treatment Plant Effluent (NWWTPE) represented surface water and treated wastewater effluent respectively. Also, tests were carried out in 50% diluted NRW and NWWTPE. PFOA photomineralization in terms of PFOA removal, defluorination and total organic carbon (TOC) removal are discussed. The usefulness of the method for PFOA mineralization in organic-rich wastewaters, and further research needs are also highlighted.     

Fenton试剂处理港口化学品洗舱废水

根据珠海某港口化学品洗舱废水的组成,配置甲醛、甲苯、苯酚的单独污染物模拟废水,采用Fenton试剂对港口废水和模拟废水进行氧化处理。通过实验探讨了不同的H2O2和Fe2+浓度、pH值、反应时间下各种废水COD的去除情况,确定了各种废水最佳的操作条件。港口废水在最佳的操作条件下COD去除率约为88%,废水的COD质量浓度从2 000~2 200 mg/L降到低于280 mg/L,废水由原来的无法生化变为易生物降解。苯酚、甲醛、甲苯模拟废水在各自最佳的操作条件下,COD去除率也都达到85%以上。