Photocatalytic degradation of cellulose bleaching effluent by supported TiO2 and ZnO

A cellulose bleaching effluent (E1) was degraded in batch conditions by photocatalysis using TiO2 and ZnO supported on glass Raschig rings. The effluent was completely decolourised and the total phenol content was reduced by 85% after 120 min treatment with both catalysts. Partial mineralization of the organic matter was confirmed by total organic carbon (TOC) reduction, approximately 50%. The residual organic matter shows a low acute toxicity as compared to the initial values and AOX values are strongly reduced after the photocatalytic oxidation. Molecular mass distribution showed that high molecular mass compounds were almost completely degraded.     

Post-treatment of bio-treated acrylonitrile wastewater using UV/Fenton process: degradation kinetics of target compounds

In this study, post-treatment of bio-treated acrylonitrile wastewater was performed using the UV/Fenton process. Five target compounds (furmaronitrile, 3-pyridinecarbonitrile, 1,3-dicyanobenzene, 5-methyl-1H-benzotriazole, and 7-azaindole) were selected as target compounds and their degradation kinetics were examined. Under optimal reaction conditions (H₂O₂ dosage 3.0 mM, Fe²⁺ dosage 0.3 mM, and initial pH 3.0), more than 85% of total organic carbon (TOC) was eliminated in 30 min when a 10-W UV lamp was employed, and the electrical energy per order of magnitude for TOC removal was as low as 2.96 kWh m^?3. Furthermore, the target compounds and the toxicity were largely removed from the bio-treated effluent. Size exclusion chromatography with organic carbon detector analysis revealed that organic components with a wide range of molecular weights were greatly reduced after the UV/Fenton process. A simplified pseudo steady-state (SPSS) model was applied to predict the degradation of target compounds during the UV/Fenton process. The concentrations of generated hydroxyl radicals were estimated to be 3.06 × 10^?12 M, 6.37 × 10^?12 M, and 10.9 × 10^?12 M under 5-, 10-, and 15-W UV lamps, respectively. These results demonstrate that the proposed SPSS model fitted well with experimental data on the post-treatment of real wastewater, and consequently indicate that this model can be a useful tool in the prediction of degradation of target compounds during the UV/Fenton process.

     

Mineralization of dinitrotoluenes and trinitrotoluene of spent acid in toluene nitration process by Fenton oxidation

Fenton's reagent, UV/H2O2 and UV/Fenton's reagent were employed to mineralize dinitrotoluene (DNT) isomers and 2,4,6-trinitrotoluene (TNT) of spent acid in toluene nitration process. The bench-scale experiments were conducted to elucidate the influence of various operating variables on the performance of removal of total organic compounds (TOC) from spent acid, including reaction temperature, concentration of ferrous ion and H2O2 dosage. It is remarkable that organic compounds were completely mineralized by Fenton oxidation, of which removal efficiency is superior to that of UV/H2O2. Nevertheless, it makes slight difference between Fenton oxidation and UV/Fenton oxidation. According to the spectra identified by gas chromatograph/mass spectrometer (GC/MS), it is proposed that oxidative degradation of DNT isomers leads to o-, m-, p-mononitrotoluene (MNT) and 1,3-dinitrobenzene respectively. Besides, the oxidation of 2,4,6-TNT gives the 1,3,5-trinitrobenzene intermediate. Apparently, Fenton oxidation is promising for purification of spent acid industrially.     

Fenton法降解垃圾渗滤液中的溶解性有机质

垃圾渗滤液是一种高浓度难降解废水,含有大量有毒物质和溶解性有机质（dissolved organic matter, DOM）,可生化性差。Fenton试剂（Fe2++H2O2）能产生活性极强的羟基自由基（·OH）,能快速氧化渗滤液中DOM和微量有机物质。本研究采用Fenton法处理垃圾渗滤液,结果表明,在优化的处理条件下,渗滤液COD和TOC去除率分别为65%和42%,其中混凝作用去除的COD和TOC分别为20%和21%。进一步通过紫外可见光谱扫描、SUVA254、E3/E4等指标评价,发现Fenton法可以有效降低渗滤液中的DOM含量,大分子有机物的含量明显减少,而分子量小的有机物含量相对增加,反应体系中溶解性有机物分子量随着反应的进行而降低,腐殖化程度降低。利用GC-MS定性出渗滤液原液中47种有机物,该类有机物在Fenton反应后上清液中未再检出,但5种物质（邻苯二甲酸二（2-乙基己）酯、植酮、角鲨烯、麥角甾烷醇和二氢胆固醇）在沉淀的铁泥中检出。研究发现不同pH值、H2O2和Fe2+浓度条件下,残留的COD与DOM、TOC和UV254存在显著的相关关系（R2> 0.9）。本研究结果为改进垃圾渗滤液处理工艺和探索DOM在Fenton过程中的降解行为提供科学依据。     

Effects of operating parameters on advanced oxidation of diuron by the Fenton's reagent: a statistical design approach

Advanced oxidation of diuron in aqueous solution by Fenton's reagent using FeSO(4) as source of Fe(II) was investigated in the absence of light. Effects of operating parameters namely the concentrations of pesticide (diuron), H(2)O(2) and Fe(II) on oxidation of diuron was investigated by using Box-Behnken statistical experiment design and the surface response analysis. Diuron oxidation by the Fenton reagent was evaluated by determining the total organic carbon (TOC), diuron, and adsorbable organic halogen (AOX) removals. Concentration ranges of the reagents resulting in the highest level of diuron oxidation were determined. Diuron removal increased with increasing H(2)O(2) and Fe(II) concentrations up to a certain level. Diuron concentration had a more profound effect than H(2)O(2) and Fe(II) in removal of diuron, TOC and AOX from the aqueous solution. Nearly complete (98.5%) disappearance of diuron was achieved after 15min reaction period. However, only 58% of diuron was mineralized after 240min under optimal operating conditions indicating formation of some intermediate products. Optimal H(2)O(2)/Fe(II)/diuron ratio resulting in the maximum diuron removal (98.5%) was found to be 302/38/20 (mgl(-1)).     

焦化废水泡沫分离液的Fenton催化氧化预处理

以焦化废水处理过程产生的泡沫分离液为研究对象,对其进行Fenton催化氧化处理实验,考察H₂O₂用量、Fe²⁺浓度、pH和反应时间4个因素对处理效果的影响,并结合GC/MS方法比较处理前后泡沫分离液中有机物的种类及其生物降解性的变化。结果表明,采用［H₂O₂］=100 mmol/L、［Fe²⁺］=100 mg/L、pH=3、反应时间为30 min的Fenton催化氧化反应条件,可以使分离液的COD去除率达到68%以上;经Fenton处理后,分离液的B/C值由0.12提高至0.38,生物降解性明显改善;通过GC/MS的分析,基本明确分离液中含有的有机物主要为酚、胺、腈、酯类有机物及喹啉、吡啶等杂环化合物,大多数属于难降解且生物毒性较强的有机物。针对这些复杂组分共存的泡沫分离液,利用Fenton试剂较强的氧化能力能够将其含有的有毒/难降解有机物转化为低毒或无毒的小分子有机物,为其后续的生物处理创造良好的条件。     

Kinetic degradation of the pollutant guaiacol by dark Fenton and solar photo-Fenton processes

This work is first intended to optimize the experimental conditions for the maximum degradation of guaiacol (2-methoxyphenol) by Fenton’s reagent, and second, to improve the process efficiency through the use of solar radiation. Guaiacol is considered as a model compound of pulp and paper mill effluent. The experiments were carried out in a laboratory-scale reactor subjected or not to solar radiation. Hydrogen peroxide solution was continuously introduced into the reactor at a constant flow rate. The kinetics of organic matter decay was evaluated by means of the chemical oxygen demand (COD) and the absorbance measurements. The experimental results showed that the Fenton and solar photo-Fenton systems lead successfully to 90% elimination of COD and absorbance at 604 nm from a guaiacol solution under particular experimental conditions. The COD removal always obeyed a pseudo-first-order kinetics. The effect of pH, temperature, H₂O₂ dosing rate, initial concentration of Fe²⁺, and initial COD was investigated using the Fenton process. The solar photo-Fenton system needed less time and consequently less quantity of H₂O₂. Under the optimum experimental conditions, the solar photo-Fenton process needs a dose of H₂O₂ 40% lower than that used in the Fenton process to remove 90% of COD.     

Fenton氧化对制浆造纸废水分子量及可生化性变化的影响

以制浆造纸废水的初沉池出水为研究对象,对不同剂量的Fenton氧化试剂处理制浆造纸厂初沉废水的效果进行了研究,初沉废水中的分子量大于10 000的有机污染物含量占到83%,废水可生化性较差;在Fe2+与H2O2的摩尔比为1∶5,废水pH为3.5的条件下,H2O2(30%)投加量小于3.25 mL/L时,Fenton试剂的氧化效率更高;H2O2(30%)投加量为6.50 mL/L时,废水中污染物的去除率更高,其中废水COD的去除率为79.5%,AOX的去除率为75.3%,色度去除率为97.5%,同时处理后废水中分子量在500~3 000之间的有机物含量占到82.98%,废水的BOD5/COD值提高到0.56。Fenton氧化作为前置技术处理制浆造纸废水,可以降低废水中的有机物分子量,减少废水的生物毒性,增加废水生物降解性,有助于后续生物处理的正常运行。     

Solar photodegradation of dichloroacetic acid and 2,4-dichlorophenol using an enhanced photo-Fenton process

The photo-Fenton process using potassium ferrioxalate as a mediator was investigated for the photodegradation of dichloracetic acid (DCA) and 2,4-dichlorophenol (DCP) in aqueous medium using solar light as source of irradiation. The influence of the solution depth, the light intensity and the effect of stirring the solution during irradiation process were evaluated using DCA as a model compound. A negligible influence of stirring the solution was observed when the concentration of ferrioxalate (FeOx) was 0.8 mM and solution depth was 4.5 or 14 cm. The optimum FeOx concentration determined for solution depths between 4.5 and 14 cm was 0.8 mM considering total organic carbon (TOC) removal during DCA irradiation. The high efficiency of the photo-Fenton process was demonstrated on summer days, when only 10 min of exposition (around noon) were sufficient to completely destroy the organic carbon of a 1.0 mM DCA solution in the presence of 0.8 mM FeOx and 6.0 mM H2O2 using a solution depth of 4.5 cm. It was observed that the photodegradation efficiency increases linearly with the solar light intensity up to values around 15 Wm(-2) but this linear relationship does not hold above this value showing a square root dependence. The photodegradation of a solution of DCP/FeOx showed a lower TOC removal rate than that observed for DCA/FeOx, achieving approximately 90% after 35 min irradiation under 19 W m(-2), while under this light intensity, the same TOC removal of DCA/FeOx was achieved in only 10 min irradiation.     

预处理-水解酸化-厌氧-好氧工艺对玉米淀粉废水有机污染物的降解

采用气相色谱/质谱(GC/MS)、三维荧光光谱(EEM)等检测手段分析预处理/水解酸化/厌氧/好氧组合工艺对玉米淀粉废水有机污染物的降解情况。结果表明,竖流沉淀预处理阶段对TOC平均去除率36.7%,废水中主要为芳烃、烷烯烃以及杂环类物质,EEM产生的5个荧光峰均为芳香蛋白类有机物;水解酸化阶段大部分杂环以及芳烃类有机物水解成有机酸和醇类物质,TOC平均去除率22.7%;厌氧阶段TOC平均去除率最高,达到97.8%,废水中以芳烃和烷烯烃为主,荧光峰减少至2个且强度减弱;好氧阶段TOC平均去除率为61.3%,有机物主要为难降解的长链烷烃物质,芳香蛋白类有机物荧光峰全部消失,新生成了与微生物代谢相关的腐殖酸类物质。     

Applicability of Fenton and H2O2/UV reactions in the treatment of tannery wastewaters

In this paper we evaluated the H2O2/UV and the Fenton's oxidation processes for the treatment of tannery wastewater under different experimental conditions. Efficiencies were judged by the amounts of organic substances degraded or eliminated under these treatment techniques. Daphnia magna and Vibrio fischeri were used to monitor toxicity. Organic compounds contained in the untreated and treated tannery wastewater were determined and identified using substance specific techniques. Gas chromatography-mass spectrometry (GC-MS) in positive electron impact (EI(+)) mode was applied to determine volatile organics. Atmospheric pressure ionization (API) mass (MS) and tandem mass spectrometry (MS-MS) coupled with flow injection analysis (FIA) or liquid chromatography (LC) were used to detect or identify polar organic pollutants. The experimental results indicated that both oxidation processes--H2O2/UV at pH 3 and Fenton at pH 3.5--are able to reduce TOC content by mineralisation of the organic compounds.     

Identification and level estimation of chlorinated neutral aromatic sulfur compounds and their alkylated derivatives in pulp mill effluents and sediments

Seven effluent samples from a modern pulp mill, in which chlorine and chlorine dioxide bleaching is used, and five sediment samples from the recipient watercourse were investigated for polychlorinated dibenzothiophenes (PCDBTs), polychlorinated thianthrenes (PCTAs), polychlorinated diphenylsulfides (PCDPSs) and for alkylated derivatives of these. Mainly di-, tri-, tetra- and pentachlorinated congeners were studied. Particles and filtrates from the effluents were analyzed separately. The concentration levels of the nonalkylated compounds were found to be higher in the filtrates than in the particles. Trichlorinated dibenzothiophenes and thianthrenes were found as the major congeners. Pentachlorinated derivatives were not found. Alkylated di- and trichlorodibenzothiophenes were detected in some samples, while alkylated chlorinated thianthrenes and diphenylsulfides were nondetectable. The estimated concentration levels of the compounds detected were in the range of 40–2700 pg/L in the pulp mill effluents and in the range of 2–40 pg/g dry weight in the sediments. Mixtures of methylated di- and trichlorodibenzothiophenes used as references in analyses were prepared from methylchlorobiphenyls. Some new pure model compounds were obtained by HPLC fractionation of the chlorination mixture of dibenzothiophene. Structures of these were determined by ¹H NMR.     

Comparative toxicity of effluents processed by different treatments in V79 fibroblasts and the algae Selenastrum capricornutum

The efficacy of ozonation and of photocatalysis processing in the treatment of pulp mill ECF (elementary chlorine free) bleaching and textile effluents was evaluated by determining total organic carbon reduction (TOC) and the toxicity. The chronic toxicity of the effluents was evaluated by the ability to inhibit the growth of algae Selenastrum capricornutum. Cultured hamster V79 fibroblasts were used to assess the cytotoxicity of effluents submitted to different detoxification processes. Two endpoints were measured in V79 cells: 3-(4,5-dimethylthiazole-2-yl)-2,5-biphenyl tetrazolium bromide (MTT) reduction and neutral red uptake (NRU). Both treatment processes were able to reduce the TOC, although ozonization was less effective for pulp mill ECF bleaching. The pulp mill ECF bleaching and textile effluents reduced the growth of S. capricornutum by 39% and 27%, respectively. However, at the highest concentration tested, the textile effluents treated by photochemical process for 60 min showed increased cytotoxicity in V79 cells compared to the untreated effluent when assessed by the NRU and MTT reduction assays (increases of 30% and 40%, respectively). Pulp mill ECF bleaching effluent treated by ozonization had a similar cytotoxicity to that of untreated effluent in the NRU assay. In contrast, the MTT reduction assay indicated that effluents treated with ozone were around 20% more cytotoxic than untreated effluents. These results show that cultured fibroblasts may be useful for studying cellular responses to pollutants and may be included in tests to monitor the efficiency of effluent detoxification processes.     

可用于去除高盐废水中有机污染物的混凝-Fenton氧化联合工艺

以某环氧树脂生产厂产生的高盐有机废水为对象,对比研究了Fenton、Fenton-混凝、混凝-Fenton等工艺去除废水中有机污染物的效能。考察了Fenton反应中Fe2+、H2O2投加比、初始pH、反应时间以及混凝反应中混凝剂种类、投加量等参数对处理效果的影响。结果表明：Fenton工艺的最佳条件为亚铁和过氧化氢投加比1：20,投加量分别为25 mmol·L-1和500 mmol·L-1,初始pH 3,反应时间120 min,TOC去除率为62.50%;混凝工艺选择FeSO4混凝剂,投加量为300 mg·L-1,TOC去除率为23.78%;废水经过Fenton-无混凝剂混凝、Fenton-混凝剂混凝、混凝-一级Fenton氧化和混凝-二级Fenton氧化工艺处理,TOC去除率分别为68.32%、71.51%、80.69%和89.27%。     

Formation of organochlorine compounds in kraft pulp bleaching processes

The most abundant volatile organochlorine compounds (VOCCs), trichloroacetic and dichloroacetic acids and AOX, were determined in bleaching effluent and waste water from three kraft pulp mills during ClO₂ bleaching. 0.6–7.7 g of VOCCs per ton bleached pulp were formed, the most abundant being chloroform and dichloroacetic acid methyl ester. Most of the VOCCs were removed during treatment, and it was estimated that 2–30 t of VOCCs would be removed annually from activated sludge treatment plants in Finnish kraft pulp mills using elemental chlorine free bleaching, most likely by volatilization. Dichloroacetic acid was formed in considerably higher amounts than trichloroacetic acid, and both compounds were removed effectively during treatment. The formation of all organochlorine compounds decreased considerably when non-chlorinated bleaching was employed.     

Spectroscopic changes on fulvic acids from a kraft pulp mill effluent caused by sun irradiation

Large volumes of wastewater with a high organic load are generated by the pulp and paper industry that negatively affect the quality of receiving waters. The main waste products in the pulp mill effluents are lignin derived macromolecular compounds, which are similar to natural humic substances and very resistant to wastewater treatments. Fulvic acids (FA) represent the higher percentage of these humic substances and it was observed that solar irradiation modify their properties. Several analytic tools, namely, UV–Visible, molecular fluorescence and FTIR spectroscopies, were used to assess the effect of solar exposition on fulvic acids from a kraft pulp mill effluent. It may be concluded that sun irradiation may alter to a high extent the physicochemical properties of macromolecular organic matter, namely fulvic acids, released by kraft pulp mill effluents. After solar exposition, the aromaticity decreases, the aliphatic structures become more oxygenated, and the fulvic acids from the pulp mill effluent remaining in solution are more similar to aquatic fulvic acids from non polluted sites.     

Fenton-接触氧化联合工艺处理铁合金镀件电镀前处理废水

电镀前处理废水中含有大量难降解有机物,成分复杂,用传统生化法难以处理达标.本实验采用Fenton 氧化技术对前处理废水进行预处理,再用生物接触氧化技术后续降解COD,使出水中COD达到《电镀污染物排放标准》(GB21900-2008)表3的水质要求.实验采用实际电镀生产废水,COD=300 mg/L,通过芬顿-生物接触氧化因素实验,优化工艺参数,去除率可达到83%以上,COD降到50 mg/L以下.最佳芬顿反应参数为:pH=3.0,COD/H2O2=1.5,Fe2+/H2O2=2,反应时间t=10 min;生物接触氧化法最佳水力停留时间为7 h,进水pH在6~8之间.     

Comparison of AC/O3-BAC and O3-BAC processes for removing organic pollutants in secondary effluent

AC (activated carbon)/O3-BAC (biological activated carbon) process was employed to treat secondary effluent and compared to O3-BAC process. The effects of ozone dosages and empty bed contact time (EBCT) in BAC on dissolved organic carbon (DOC) removal were investigated. The results showed that the presence of AC improved ozone utilization and biodegradability of the effluent. DOC removal increased with ozone dosage and EBCT in BAC, however, 3 mg l(-1) ozone dosage with 15 min oxidation time and 15 min EBCT in BAC were more economical and efficient. For DOC removal, AC/O3-BAC was more efficient than O3-BAC and its synergetic effect was more than that in O3-BAC process. The biomass of the subsequent BAC unit in AC/O3-BAC process was more than that in O3-BAC process and much more than that in BAC alone. Except for organic pollutants with molecular weight (MW) >10 kDa, those of other MW range were decomposed much more by AC/O3 process than by O3 process. GC/MS analysis showed that dibutyl phthalate, bis(2-ethylhexyl) phthalate, 4-bromo-3-chloroaniline, 2-propanone-ethylhydrazone and phenol derivatives were prevalent organic compounds in the secondary effluent. Some aromatic compounds, such as 4-bromo-3-chloroaniline and 2,4-dichloro-benzenamine disappeared after AC/O3 treatment. However, some small molecules were generated, after further biological treatment by BAC, the kinds and concentration of organic compounds were greatly reduced.     

强化3级Fenton氧化结合石灰乳中和混凝处理苯系染料中间体废水

采用多级Fenton氧化结合石灰乳中和混凝对苯系染料中间体废水进行强化处理,考察了Fenton试剂投加级数和投加比例对废水处理效果的影响,以及多级Fenton氧化之间石灰乳中和混凝作用效果,并分析了废水中有机成分的变化趋势。结果表明：Fenton氧化过程中,COD去除率随着Fenton试剂投加级数的增加逐渐增大,3级时效果最佳。3级Fenton处理过程中,Fenton试剂的投加比例为1：2：3时,COD去除率最高。在Fenton试剂投加比例为1：2：3的3级Fenton氧化过程中,石灰乳可有效调节pH由2.5至4.0,同时其混凝作用也可进一步提高COD去除率,最终COD去除率可达97.20%。经GC-MS对各个过程中有机物的分析鉴定,可发现原废水中的苯系有机物逐渐变化为苯酚、对苯醌以及短链小分子脂肪酸等物质。     

Synthetic olive mill wastewater treatment by Fenton’s process in batch and continuous reactors operation

Degradation of total phenol (TPh) and organic matter, (expressed as total organic carbon TOC), of a simulated olive mill wastewater was evaluated by the Fenton oxidation process under batch and continuous mode conditions. A mixture of six phenolic acids usually found in these agro-industrial wastewaters was used for this purpose. The study focused on the optimization of key operational parameters of the Fenton process in a batch reactor, namely Fe²⁺ dosage, hydrogen peroxide concentration, pH, and reaction temperature. On the assessment of the process efficiency, > 99% of TPh and > 56% of TOC removal were attained when [Fe²⁺] = 100 ppm, [H₂O₂] = 2.0 g/L, T = 30 °C, and initial pH = 5.0, after 300 min of reaction. Under those operational conditions, experiments on a continuous stirred-tank reactor (CSTR) were performed for different space-time values (τ). TOC and TPh removals of 47.5 and 96.9%, respectively, were reached at steady-state (for τ = 120 min). High removal of COD (> 75%) and BOD₅ (> 70%) was achieved for both batch and CSTR optimum conditions; analysis of the BOD₅/COD ratio also revealed an increase in the effluent’s biodegradability. Despite the high removal of lumped parameters, the treated effluent did not met the Portuguese legal limits for direct discharge of wastewaters into water bodies, which indicates that coupled chemical-biological process may be the best solution for real olive mill wastewater treatment.