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。     

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.     

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.     

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%.     

Influence of type and dose of coagulants on effectiveness of PAH removal in coagulation water treatment

This study evaluated the influence of the type and dose of coagulants on the removal of 16 polycyclic aromatic hydrocarbons (PAHs) in the coagulation process. The effects of coagulant type and dose in reducing water turbidity, colour, and the total content of organic compounds were also assessed. The surface water samples had the turbidity of 9.3–11.2 NTU and colour of 25–35 mg/L. The content of organic compounds determined with total organic carbon (TOC) was 9.2–12.5 mg/L. For the coagulation process, pre-hydrolyzed polyaluminium chloride (PACl) coagulants with basicity values of 41%, 65%, and 85% were used. This shows that water purification performance increased as the basicity of the coagulant increased. When the coagulant with the highest basicity and a dose of 3 mg Al per litre was used, a removal efficiency of 83% in the concentration of benzo(a)pyrene was achieved, and efficiencies for the remaining 15 PAHs ranged from 80% to 91%. These values were 4%–9% higher than those achieved using other coagulants. The removal efficiencies of turbidity, colour, and TOC were 80%, 60%, and 35%, respectively. The water purification performance, including PAH removal, was improved with the increased coagulant dose. Increasing the coagulant dose had more pronounced effects on PAH removal than on the reduction of turbidity and TOC.     

Effect of Fenton's treatment on the biodegradability of chromium-complex azo dyes.

Pretreatment of an acid dyebath effluent bearing a new generation chromium complex azo dyestuff (C0 = 350 mg/L) with Fenton's reagent was investigated. Preliminary optimisation (baseline) experiments were conducted to determine the Fe2+, H2O2 concentrations and pH required to the highest possible COD and colour removals. Kinetic studies were carried out at varying temperatures (20 degrees C < T < 70 degrees C) to establish a relationship between COD abatement and H2O2 consumption. The activation energy found for catalytic H2O2 decomposition (Ea = 9.8 kJ/mol) appeared to be significantly less than that of fermentative (Ea = 23 kJ/mol) and of thermal (Ea = 76 kJ/mol) H2O2 decomposition, implying that H2O2 decomposition during the Fenton's reaction occurs more spontaneously. The experimental studies indicated that approximately 30% COD and complete colour removal could be achieved under optimised Fenton pretreatment conditions (Fe2+ = 2 mM; H2O2 = 30 mM; pH = 3; at T = 60 degrees C). Long-term activated sludge experiments revealed that although the raw and pretreated acid dyebath effluent contained practically the same amount of "readily biodegradable" COD (inert COD fraction < or = 10%), biodegradation of the chemically pretreated acid dye effluent proceeded appreciably faster than that of the untreated acid dyebath effluent.     

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.     

Optimization of the removal of phenol by soybean seed coats using response surface methodology

Peroxidase from soybean seed coats catalyzes the oxidation and polymerization of aromatic compounds in the presence of H(2)O(2). The present study investigated the optimization of the phenol removal from wastewaters by direct using of soybean seed coats that can be extended to large scale, as a cost-effective option in comparison to pure enzyme. A central composite design was used to evaluate the effect of the following factors on the phenol removal: H(2)O(2) concentration (1-40 mmol/L), polyethylene glycol (PEG) concentration (0-1 g/L) and the amount of soybean seed coats (10-60 g/L). The results showed that PEG concentration had no significant effect on phenol conversion. Additionally, by increasing the amount of soybean seed coats, the extent of phenol conversion was increased and a higher concentration of H(2)O(2) was required to reach the maximum phenol conversion. Under optimum conditions for 1 mmol/L initial phenol, 50 g/L soybean seed coats, 14 mmol/L H(2)O(2) and 0.8 g/L PEG, the phenol conversion after 30 min was 78%. After 2 h, the catalyzed process was capable of achieving 90-92% removal of the total phenol from synthetic wastewater. A cubic model was also developed that was verified by predicting some independent experimental results.     

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%。     

Advanced oxidation of commercial textile biocides in aqueous solution: effects on acute toxicity and biomass inhibition.

In the present study, the decomposition of two biocides used in the textile finishing process with Advanced Oxidation Processes (AOPs) has been studied. Different AOPs, i.e O3/OH-, TiO2/UV-A and Fe2+/H2O2 have been used representing mutually combined components of the chemically and photochemically driven advanced oxidation systems. The course of reaction was examined by changes in chemical oxygen demand (COD), total organic carbon (TOC) and acute toxicity towards the water flea Daphnia magna (assessed in terms of the effective dilution ratio LD50). Particular attention has been paid to determine the inhibitory effect of raw and ozonated biocides on biological activated sludge consortium at concentrations typically encountered in textile finishing effluents. Significant oxidation and mineralization of both biocides could be achieved employing ozonation at pH = 11.5 and heterogeneous photocatalysis (TiO2/UV-A) at pH = 5.0, whereas Fenton's reagent appeared to be less effective in COD and acute toxicity abatement.     

Boosting nitrification by membrane-attached biofilm.

Nitrification is a key step for reliable biological nitrogen removal. In order to enhance nitrification in the activated sludge (AS) process, membrane-attached biofilm (MAB) was incorporated in a conventional activated sludge tank. Simultaneous organic carbon removal and nitrification of the MAB incorporated activated sludge (AS + MAB) process was investigated with continuous wastewater treatment. The effluent TOC concentration of AS and the AS + MAB processes were about 6.3 mg/L and 7.9 mg/L, respectively. The TOC removal efficiency of both AS and AS + MAB were above 95% during the wastewater treatment, indicating excellent organic carbon removal performance in both processes. Little nitrification occurred in the AS process. On the contrary, successful nitrification was obtained with the AS + MAB process with nitrification efficiency of about 90%. The volumetric and surface nitrification rates were about 0.14 g/Ld and 6.5 g/m2d, respectively. The results clearly demonstrated that nitrification in the conventional AS process was boosted by MAB. Furthermore, the microfaunal population in the AS + MAB process was different from that in the AS process. The high concentration of rotifers in the AS + MAB process was expected to decrease the generation of excess sludge in the process.     

掺杂石墨烯气体扩散电极电芬顿氧化降解三氯生废水模拟

为了解决水中个人护理品难以处理的问题,以具有优良氧还原催化活性的掺杂石墨烯气体扩散电极（rGO/C-PTFE GDE）为阴极,构建了均相电芬顿氧化体系,探讨了石墨烯掺杂量、电流密度、电解质浓度等因素对rGO/C-PTFE GDE原位生成H2O2的产率和电流效率的影响,确定了电生成H2O2的最优化条件,即石墨烯与片状石墨的质量比为1∶8,电流强度为2.0 mA/cm2,电解液浓度为0.05mol/L。该条件下经180 min电解H2O2积累浓度可达到187.1mg/L。以rGO/C-PTFE GDE为阴极构建了均相电芬顿氧化体系,并应用于含三氯生模拟废水的氧化降解,研究了电解液pH值和外加Fe2＋浓度对三氯生去除效果的影响。结果表明：对于初始浓度为45 mg/L的三氯生,在pH值为3.0,外加Fe2＋浓度0.75 mmol/L的条件下,经过180 min均相电芬顿氧化的处理,73.9%的三氯生可被氧化降解。     

Combining photo-Fenton process with biological sequencing batch reactor for 2,4-dichlorophenol degradation.

The effect of the photo-Fenton process on biodegradability enhancement of 100 mg x L(-1) aqueous 2,4-dichlorophenol (2,4-DCP) solution has been investigated. An initial concentration of 65 mg x L(-1) H2O2 and 10 mg x L(-1) Fe (II) during 35 minutes of irradiation time was sufficient for total 2,4-DCP removal. At these working conditions, biodegradability, measured as BODS/COD ratio, was increased from 0 for the original solution up to 0.15. Biological oxidation of photo-Fenton pre-treated solutions was performed in a sequencing batch reactor (SBR). After 32 days of start-up, the reactor was fed with different pre-treated solutions and cycle duration was reduced progressively. TOC removal efficiencies in the SBR went from 30 up to 70%.     

Evaluation of the combined solar TiO2/photo-Fenton process using multivariate analysis.

The effect of combining the photocatalytic processes using TiO2 and the photo-Fenton reaction with Fe3+ or ferrioxalate as a source of Fe2+ was investigated in the degradation of 4-chlorophenol (4CP) and dichloroacetic acid (DCA) using solar irradiation. Multivariate analysis was used to evaluate the role of three variables: iron, H2O2 and TiO2 concentrations. The results show that TiO2 plays a minor role when compared to iron and H2O2 in the solar degradation of 4CP and DCA in the studied conditions. However, its presence can improve TOC removal when H2O2 is totally consumed. Iron and peroxide play major roles, especially when Fe(NO3)3 is used in the degradation of 4CP. No significant synergistic effect was observed by the addition of TiO2 in this process. On the other hand, synergistic effects were observed between FeOx and TiO2 and between H2O2 and TiO2 in the degradation of DCA.     

Optimised photocatalytic degradation of a mixture of azo dyes using a TiO(2)/H(2)O(2)/UV process

The aim of the present study was to optimise the photocatalytic degradation of a mixture of six commercial azo dyes, by exposure to UV radiation in an aqueous solution containing TiO(2)-P25. Response surface methodology, based on a 3(2) full factorial experimental design with three replicates was employed for process optimisation with respect to two parameters: TiO(2) (0.1-0.9 g/L) and H(2)O(2) (1-100 mmol/L). The optimum conditions for photocatalytic degradation were achieved at concentrations of 0.5 g TiO(2)/L and 50 mmol H(2)O(2)/L, respectively. Dye mineralisation was confirmed by monitoring TOC, conductivity, sulfate and nitrate ions, with a sulfate ion yield of 96% under optimal reactor conditions. Complete decolorisation was attained after 240 min irradiation time for all tested azo-dyes, in a process which followed a pseudo-first kinetic order model, with a kinetic rate constant of approximately 0.018 min(-1). Based on these results, this photocatalytic process has promise as an alternative for the treatment of textile effluents.     

Aerobic granulation in a mechanical stirred SBR: treatment of low organic loads

Aerobic granular sludge was produced in a sequencing batch reactor (SBR) characterized by a height to diameter ratio of 2.5 and the use of mechanical stirring. Compact and regular aerobic granules of up to 1.75 mm of average diameter were formed in the reactor with an organic loading rate of 1.75 kg COD/(m3 d). Settling properties of the obtained aggregates were: sludge volumetric index of 30-40 mL/g VSS and settling velocity higher than 8 m/h. The effects of different carbon to nitrogen ratios (TOC/N) in the feeding on the organic matter oxidation and nitrification process were studied. The concentration of organic matter in the feeding was stepwise reduced (from 190.0 to 37.5 mg TOC/L) and ammonium increased (from 25 to 50 mg NH4+ -N/L). TOC/N ratios of 7.50, 3.00, 1.50 and 0.75 g/g in the feeding were tested. The TOC removal percentage was around 80-95% during the whole operational period and the N removal percentages obtained in the reactor were up to 40%, however, physical properties of the granules were not maintained.     

Advanced oxidation process-biological system for wastewater containing a recalcitrant pollutant.

Two advanced oxidation processes (AOPs), ozonation and photo-Fenton, combined with a pilot aerobic biological reactor at field scale were employed for the treatment of industrial non-biodegradable saline wastewater (TOC around 200 mgL(-1)) containing a biorecalcitrant compound, alpha-methylphenylglycine (MPG), at a concentration of 500 mgL(-1). Ozonation experiments were performed in a 50-L reactor with constant inlet ozone of 21.9 g m(-3). Solar photo-Fenton tests were carried out in a 75-L pilot plant made up of four compound parabolic collector (CPC) units. The catalyst concentration employed in this system was 20 mgL(-1) of Fe2+ and the H2O2 concentration was kept in the range of 200-500mgL(-1). Complete degradation of MPG was attained after 1,020 min of ozone treatment, while only 195 min were required for photo-Fenton. Samples from different stages of both AOPs were taken for Zahn-Wellens biocompatibility tests. Biodegradability enhancement of the industrial saline wastewater was confirmed (>70% biodegradability). Biodegradable compounds generated during the preliminary oxidative processes were biologically mineralised in a 170-L aerobic immobilised biomass reactor (IBR). The global efficiency of both AOP/biological combined systems was 90% removal of an initial TOC of over 500 mgL(-1).     

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。     

Fenton高级氧化技术去除水中有机污染物2-MIB的影响因素研究

针对目前比较关注的致嗅物质污染问题,选用Fenton高级氧化技术研究了其对水中致嗅物质2-甲基异莰醇（2-MIB）的去除,探讨了Fenton反应对水中致嗅物质的去除效能及H2O2/Fenton摩尔比、Fe2＋浓度、反应时间和溶液pH值各因素对氧化反应的影响。提出了Fenton氧化反应去除2-MIB的最佳反应条件。实验结果表明：Fenton高级氧化能有效去除水中的2-MIB。在H2O2/Fenton摩尔比为3.0、Fe2＋浓度10 mg/L、反应时间10 min和溶液pH值为3.0时,去除效率达到97.9%。Fenton氧化反应的操作条件（浓度、pH值等）比较容易实现,因此Fenton氧化技术在实际污染处理中有很大的应用前景。     

Comparison of Fenton's oxidation and ozonation for removal of estrogens

This study compares efficiency of Fenton's oxidation and ozonation of 17beta-estradiol (E2) and 17alpha-ethinylestradiol (EE2) as two possible processes for removal of estrogens from aqueous solutions. The effectiveness of Fenton's oxidative removal was studied at different ratios of reagents Fe2+:H2O2 (1:0.5; 1:10; 1:20; 1:33), where with some molar ratios up to 100% removal of E2 and EE2 was achieved in the first few minutes of reaction. The best molar ratio for E2 (17beta-estradiol) removal was 1:33, while in the case of EE2 the most efficient one was 1:20 ratio. Ozonation was much faster, because complete removal of estrogens was achieved in 30 seconds (pH approximately eaqual 6), but the time of ozonation was extended up to 60 minutes trying to decompose formed by-products, expressing estrogenic activity, detected by YES (Yeast Estrogen Screening) assay. The obtained results showed that the removal efficiency of estrogens from waters should be assessed by a combination of chemical analyses and bioassay.