Comparison of Diuron degradation by direct UV photolysis and advanced oxidation processes

The rates of Diuron elimination by some advanced oxidation processes (AOPs) such as Fe(III)/UV, Ferrioxalate/UV, Fe(III)/H(2)O(2)/UV, Ferrioxalate/UV/H(2)O(2) and Fe(III)/H(2)O(2) have been compared. Experiments have been conducted at pH=2.3+/-0.1 with a batch reactor equipped with a low-pressure mercury lamp emitting mainly at 253.7nm. Data obtained under the following experimental conditions ([H(2)O(2)](0)=10(-3)M, [Diuron](0)=5x10(-5)M and [Fe(III)](0)=10(-3)M) have shown that rates of Diuron oxidation were higher with the systems Fe(III)/H(2)O(2)/UV and Ferrioxalate/UV/H(2)O(2) than with Fe(III)/UV and Fe(III)/H(2)O(2). On the other hand, Fe(III)/UV was found to be very efficient in mineralization of Diuron solution in comparison to direct UV photolysis. The experimental results showed that radical ()OH is the major pathway in the process of Diuron degradation.     

Effect of chloride ions on the oxidation of aniline by Fenton's reagent

The objective of this study was to experimentally probe the mechanism of chloride ions specifically affecting aniline oxidation by Fenton's reagent. Batch experiments were carried out to investigate the effects of pH, Fe2+, H2O2 and chloride concentration on the oxidation reaction. Results show that the inhibition caused by chloride ions can be overcome by extending the reaction time if the concentration of chloride ions is low. At a high concentration of chloride ions, however, the oxidation of aniline was inhibited, and actually ceased due to the complexation of Fe-Cl. In this study, the chloride ion concentration was kept at 0.2 M in the experiments when studying the effect of ferrous ion concentration on the Fenton reaction. If the ratio of [Cl-]/[Fe2+] was < or = 200, the inhibition effect was very significant. In other words, adding more ferrous ions rather than hydrogen peroxide can break the inhibition originating from the chloride ions at an initial stage of pH 3. The inhibition effect of chloride ions on the aniline reaction depended on the reaction pH; the extent of inhibition decreased with increasing the initial pH as long as the pH was less than 5. Consequently, the inhibition effect by chloride ions was primarily due to the complexation of iron species and chloride ions. The influence of chloride ions on aniline oxidation due to the competition of hydroxyl radicals was not significant.     

Degradation of a commercial textile biocide with advanced oxidation processes and ozone

The occurrence of significant amounts of biocidal finishing agents in the environment as a consequence of intensive textile finishing activities has become a subject of major public health concern and scientific interest only recently. In the present study, the treatment efficiency of selected, well-known advanced oxidation processes (Fenton, Photo-Fenton, TiO(2)/UV-A, TiO(2)/UV-A/H(2)O(2)) and ozone was compared for the degradation and detoxification of a commercial textile biocide formulation containing a 2,4,4'-trichloro-2'-hydroxydiphenyl ether as the active ingredient. The aqueous biocide solution was prepared to mimic typical effluent originating from the antimicrobial finishing operation (BOD(5,o) < or =5 mg/L; COD(o)=200 mg/L; DOC(o) (dissolved organic carbon)=58 mg/L; AOX(o) (adsorbable organic halogens)=48 mg/L; LC(50,o) (lethal concentration causing 50% death or immobilization in Daphnia magna)=8% v/v). Ozonation experiments were conducted at different ozone doses (500-900 mg/h) and initial pH (7-12) to assess the effect of ozonation on degradation (COD, DOC removal), dearomatization (UV(280) and UV(254) abatement), dechlorination (AOX removal) and detoxification (changes in LC(50)). For the Fenton experiments, the effect of varying ferrous iron catalyst concentrations and UV-A light irradiation (the Photo-Fenton process) was examined. In the heterogenous photocatalytic experiments, Degussa P25-type TiO(2) was used as the catalyst and the effect of reaction pH (3, 7 and 12) and H(2)O(2) addition on the photocatalytic treatment efficiency was examined. Although in the photochemical (i.e. Photo-Fenton, TiO(2)/UV-A and TiO(2)/UV-A/H(2)O(2)) experiments appreciably higher COD and DOC removal efficiencies were obtained, ozonation appeared to be equally effective to achieve dearomatization (UV(280) abatement) at all studied reaction pH. During ozonation of the textile biocide effluent, AOX abatement proceeded significantly faster than dearomatization and was complete after 20 min ozonation (267 mg O(3)). On the other hand, for complete detoxification, ozonation had to be continued for at least 30 min (corresponding to 400mg O(3)). Effective AOX and acute toxicity removal was also obtained after heterogeneous photocatalytic treatment (TiO(2)/UV-A and TiO(2)/UV-A/H(2)O(2)). The Fenton-based treatment experiments and particularly the dark Fenton reaction resulted in relatively poor degradation, dearomatization, AOX and acute toxicity removals.     

纸载P-TiO_2光催化降解甲醛的影响因素研究

本文以牛皮纸作载体,用浸渍法制备了具有光催化作用的纳米P-TiO2光催化剂,对室内一定浓度的甲醛气体进行了降解实验研究。通过实验探讨了甲醛的初始浓度、催化剂的用量、湿度条件、溶胶pH值和金属离子的掺杂5个影响甲醛降解率的因素,结果采用美国interscan公司生产的4160型甲醛分析仪进行表征。实验结果表明,当甲醛的初始浓度约为1.53mg/m3,P-TiO2用量为11.94g,湿度约为52%,溶胶pH=5.01,掺杂6.00mL 0.20 mol/L Cu2＋离子时,甲醛的降解效果最好,最高可达93.50%,甲醛浓度降至0.0994mg/m3,达到了GB/T 18883—2002标准中规定的0.10 mg/m3。     

Influence of pyrene combination state in soils on its treatment efficiency by Fenton oxidation

Interactions of hydrophobic organic compounds (HOCs) with soil organic matter (SOM) determine their combination state in soils, and therefore strongly influence their mobility, bioavailability, and chemical reactivity. Contact time (aging) of an HOC in soil also strongly influences its combination state and environmental fate. We studied Fenton oxidation of pyrene in three different soils to reveal the influences of SOM, contact time, and combination state on the efficiency of vigorous chemical reactions. Pyrene degradation efficiency depended strongly on the dose of oxidant (H(2)O(2)) and catalyst (Fe(2+)); the greatest degradation was achieved at an oxidant to catalyst molar ratio of 10:1. Pyrene degradation differed among the three soils, ranging from 65.4% to 88.9%. Pyrene degradation efficiency decreased with increasing SOM content, and the aromatic carbon content in SOM was the key parameter. We hypothesize that pyrene molecules that combine with the compact net structure of aromatic SOM are less accessible to Fenton oxidation. Furthermore, pyrene degradation efficiency decreased considerably after aged for 30 days, but further aging to 60 and 180 days did not significantly change degradation efficiency. The Fenton oxidation efficiency of pyrene in both unaged and aged soils was greater than the corresponding desorption rate during the same period, perhaps because Fenton reaction can make pyrene more accessible to the oxidant through the enhancement of HOCs' desorption by generating reductant species or by destroying SOM through oxidation.     

油田含油污水高级氧化技术研究

以气浮—过滤预处理后的污水为处理对象,通过臭氧氧化与Fenton氧化两种方法处理油田含油污水。经实验验证:Fenton在pH为4,H2O2初始浓度为0.08mol/L,Fe2+与H2O2的摩尔比为1:10,H2O2与CODCr的质量比为1:1,反应时间为60min的条件下,去除率达54.3%(CODCr100mg/L),可达到GB8978-1996《污水综合排放标准》二级标准。     

Application of lime and calcium hypochlorite in the dephenolisation and discolouration of olive mill wastewater

The application of hypochlorite for the removal of soluble COD, phenolic and polyphenolic like compounds, and other organic compounds responsible for the olive mill wastewater (OOWW) colour has been experimentally studied. After the OOWW filtration on a sand column, the effluent was subjected to a fast liming under optimal conditions. Lime application reduced polyphenols, COD and SS contents to half of their initial values but an important blackening of the treated OOWW was observed, especially when adding high concentrations of lime (10% (W/V) and 15% (W/V)).A second stage of treatment was applied using calcium hypochlorite. In this stage, removal of the studied compounds reached as much as 95% at higher concentrations, and particularly the colouring of OOWW which is generally difficult to eliminate was greatly reduced. The OOWW hypochloration acted through coagulation–flocculation and a rapid oxidation of the organic matter proceeded from the first 5 min. The kinetic study of the degradation of the waste polluting compounds from liming showed that Ca(ClO)₂ reacts similarly in the elimination of organic compounds, polyphenols, SS and colouration. The analysis of the organochloride compounds generated by the reaction between hypochlorite and the organic compounds showed that DDD, DDT and the heptachlor contents exceeded the values recommended by the International and European drinking water standards.     

Degradation of aqueous piperazine in carbon dioxide capture

Concentrated, aqueous piperazine (PZ) is a novel solvent for carbon dioxide (CO₂) capture by absorption/stripping. One of the major advantages of PZ is its resistance to thermal degradation and oxidation.At 135 and 150 °C, 8 m PZ is up to two orders of magnitude more resistant to thermal degradation than 7 m monoethanolamine (MEA). After 18 weeks at 150 °C, only 6.3% of the initial PZ was degraded, yielding an apparent first order rate constant for amine loss of 6.1 × 10^?9 s^?1. PZ was the most resistant amine tested, with the other screened amines shown in order of decreasing resistance: 7 m 2-amino-2-methyl-1-propanol, 7 m Diglycolamine^®, 7 m N-(2-hydroxyethyl)piperazine, 7 m MEA, 8 m ethylenediamine, and 7 m diethylenetriamine. Thermal resistance allows the use of higher temperatures and pressures in the stripper, potentially leading to overall energy savings.Concentrated PZ solutions demonstrate resistance to oxidation compared to 7 m MEA solutions. Experiments investigating metal-catalyzed oxidation found that PZ solutions were 3–5 times more resistant to oxidation than MEA. Catalysts tested were 1.0 mM iron (II), 4.0–5.0 mM copper (II), and a combination of stainless steel metals (iron (II), nickel (II), and chromium (III)). Inhibitor A reduced PZ degradation catalyzed by iron (II) and copper (II).     

常用氧化剂性能研究

用四种常用的氧化剂:高锰酸钾、漂白粉、NaClO和H2O2/Fe2+对大港油田港深11井酸化废水进行了处理。考察了氧化剂的投加量、氧化时间和pH值对酸化废水色度和COD去除率的影响。实验结果表明,在最佳条件下,H2O2/Fe2+对酸化废水的色度和COD的去除率最高;用高锰酸钾处理废水,其COD去除率较高,但脱色效果差;而漂白粉和NaClO的脱色率较高,但其氧化能力有限。建议油田用氧化法处理废水时应采用H2O2/Fe2+催化氧化体系。     

光催化氧化处理低浓度含醇废水实验

室内实验了TiO2紫外光催化氧化处理废水中的低浓度甲醇。通过对TiO2催化剂活性及添加方式、溶液pH、紫外光强与催化剂加量等参数优化,在TiO2加入浓度为300mg/L和120 W紫外灯照射条件下,对6.8L甲醇浓度为2.77%的低浓度含醇废水持续处理70min后,废水中的甲醇去除率可达98.31%。该实验为进一步处理低浓度含醇废水提供了方法依据。     

电化学氧化处理焚烧厂渗滤液膜浓缩液混凝出水的研究

为了降低城市生活垃圾焚烧厂渗滤液膜浓缩液混凝出水中的有机物浓度,采用电化学氧化对渗滤液膜浓缩液混凝出水进行了处理.同时,考察了阳极材料、电流密度、初始pH值和电解时间对有机物的去除影响,使用三维荧光光谱分析了有机物的去除特性,并通过氯离子的转化探讨了有机物的降解机理.结果 表明,钌铱(Ru-Ir/Ti)阳极对有机物的去...     

Fenton试剂高级氧化法降解甲基橙模拟废水研究

甲基橙是一种较难降解的有机苯环偶氮染料之一,研究其降解性能对其他染料废水体系的降解研究具有普遍参考价值。通过研究Fenton试剂降解甲基橙过程中的H202浓度、Fe2＋浓度、反应时间和反应体系pH值对甲基橙降解的影响,确定其最佳降解工艺条件为：当甲基橙浓度为20mg／L、pH值为3、Fe2＋浓度为1．5mmol／L、H2O2为32mmol/L时,降解率达到最大值（98．95％）。     

树脂纳米零价铁催化过硫酸钠降解甲基橙的研究

采用树脂负载零价纳米铁（NZVI-resin）作为铁源,活化过硫酸钠,产生硫酸根自由基氧化降解偶氮染料甲基橙。考察了温度、NZVI-resin加入量、pH值及过硫酸钠的浓度等因素对甲基橙降解率的影响,并对其降解动力学规律作了初步探讨。结果表明：降解反应遵循准一级反应动力学,在pH=3.0、Fe0=0.2 g.L-1、Na2S2O8=1.33 g.L-1的条件下,30 mg.L-1的甲基橙溶液降解率为99.7%。     

UV-H_2O_2联用工艺去除水中阿特拉津的研究

采用间歇式反应器考察了UV-H2O2高级氧化技术去除水中阿特拉津的效果及其影响因素,并进行了相关的反应动力学研究。结果表明,在pH值6.9,阿特拉津初始浓度500μg/L,紫外辐照强度172μW/cm2时,H2O2投加量50mg/L,反应10min后,阿特拉津的去除率90%。UV-H2O2联用工艺对阿特拉津的降解符合一级反应动力学。H2O2在该联用工艺降解阿特拉津中具有双重作用,一方面,当H2O2投加量较小时,一级反应速率常数随H2O2投加量的增加基本呈现线性增加的趋势;另一方面,当H2O2浓度增加到一定程度(90mg/L)后,阿特拉津的降解速率随H2O2浓度的变化已不明显,而H2O2浓度为102mg/L时,则出现了抑制作用。     

超声辅助电催化氧化降解水杨酸的研究

通过对水杨酸降解的UV扫描吸收光谱的研究表明,在水杨酸的电催化氧化和超声辅助电催化氧化降解过程中,都有吸收紫外光的中间体生成,对吸光度峰值随降解反应时间的变化关系进行非线性最小二乘法拟合(NLSF),发现其衰减均符合表观一级反应动力学规律;而COD值的衰减也都符合表观一级反应动力学规律。GC-MS检测到水杨酸超声辅助电催化氧化降解60 min后,有中间产物甲酸、乙酸、苯酚,认为是水杨酸在.OH的作用下,开环氧化降解生成乙酸和甲酸等小分子有机物,最后降解为二氧化碳和水。     

Intensification of degradation of aqueous solutions of rhodamine B using sonochemical reactors at operating capacity of 7 L

In the present work, degradation of rhodamine B, a typical dye effluent commonly observed in chemical processing wastewaters has been investigated using a sonochemical reactor with capacity of 7 L. The reactor consists of an ultrasonic bath equipped with a single large transducer having longitudinal vibrations with operating frequency of 25 kHz and rated power output of 1 kW. The effect of operational conditions such as the rhodamine B initial concentration, operating pH and use of additives such as H(2)O(2), CCl(4) and TiO(2) has been investigated initially. A mathematical model has also been fitted to estimate the rate constant for rhodamine B removal under different operating conditions. Intensification studies have been carried by combining sonochemical oxidation with photocatalytic oxidation under optimized conditions. In all the investigated systems, complete removal of rhodamine B (10 ppm initial concentration) was obtained using a combination of sonochemical reactor and CCl(4). Sonocatalysis (in the presence of TiO(2)) of rhodamine B showed 92% degradation, while sonophotocatalysis gave degradation of 93%. TOC analysis at various optimum conditions was also performed to quantify the extent of mineralization and it was observed that the extent of mineralization is always lower than the extent of removal of parent compound.     

Degradation of soil fumigants as affected by initial concentration and temperature

Soil fumigation using shank injection creates high fumigant concentration gradients in soil from the injection point to the soil surface. A temperature gradient also exists along the soil profile. We studied the degradation of methyl isothiocyanate (MITC) and 1,3-dichloropropene (1,3-D) in an Arlington sandy loam (coarse-loamy, mixed, thermic Haplic Durixeralf) at four temperatures and four initial concentrations. We then tested the applicability of first-order, half-order, and second-order kinetics, and the Michaelis-Menten model for describing fumigant degradation as affected by temperature and initial concentration. Overall, none of the models adequately described the degradation of MITC and 1,3-D isomers over the range of the initial concentrations. First-order and half-order kinetics adequately described the degradation of MITC and 1,3-D isomers at each initial concentration, with the correlation coefficients greater than 0.78 (r2> 0.78). However, the derived rate constant was dependent on the initial concentration. The first-order rate constants varied between 6 and 10x for MITC for the concentration range of 3 to 140 mg kg(-1), and between 1.5 and 4x for 1,3-D isomers for the concentration range of 0.6 to 60 mg kg(-1), depending on temperature. For the same initial concentration range, the variation in the half-order rate constants was between 1.4 and 1.7x for MITC and between 3.1 and 6.1x for 1,3-D isomers, depending on temperature. Second-order kinetics and the Michaelis-Menten model did not satisfactorily describe the degradation at all initial concentrations. The degradation of MITC and 1,3-D was primarily biodegradation, which was affected by temperature between 20 and 40 degrees C, following the Arrhenius equation (r2 > 0.74).     

大气中SO2的液相氧化研究

大气中ＳＯ２液相氧化是形成酸雨的重要途径，降雨中含有各种无机离子和有机物质，它们可能催化或抑制液相氧化反应的进行。本文根据四川酸雨样品组成，进行了ＳＯ２在模拟雨水及实际雨水中的氧化实验，考查了Ｖ，Ｆｅ，Ｍｎ等离子对ＳＯ２氧化的催化作用，Ｈ２Ｏ２对ＳＯ２的氧化以及降水中有机物质甲醛对各反应的影响。实验结果为了解酸雨的成固，研究酸雨控制对策提供了科学依据。     

Effect of organic matter oxidation on the fractionation of copper, zinc, lead, and arsenic in sewage sludge and amended soils

Long-term land application of sewage sludge (SS) has caused concern over the potential release of trace metals into the environment following the degradation of organic matter (OM). This study was performed to assess the impact of OM degradation on the relative distribution of Cu, Zn, Pb, and As in SS and SS-amended soils. Three SSs of different ages and two soils treated with SS were subjected to incubation and direct chemical oxidation using diluted HO, followed by a sequential extraction. The majority of Cu, Pb, and As were bound to OM, whereas the majority of Zn was bound with Fe/Mn oxides for all three SSs. Incubation of SS for 6 mo did not result in a substantial decrease in OM content or a change in the relative distribution of Cu, Zn, Pb, and As. Direct OM oxidation to 30 and 70% by diluted HO resulted in a significant decrease in organically bound Cu but increased its exchangeable, carbonate-bound, and Fe/Mn-bound fractions. Oxidation of OM slightly decreased organically bound Zn but significantly increased exchangeable Zn in all SSs. Oxide- and carbonate-bound Zn also decreased following OM oxidation. Exchangeable fractions of As and Pb were minute before and after OM degradation, indicating that release into the environment would be unlikely. The relative distribution of Cu, Zn, Pb, and As in SS-treated soils was similar to that of SS, suggesting a dominant role of SS properties in controlling metal distribution following OM oxidation. Overall, OM oxidation increased the mobility and bioavailability of Zn and Cu, whereas it had less impact on Pb and As.     

Fenton试剂对亚甲基蓝氧化褪色的反应动力学实验研究

为了提高Fenton试剂处理有机污染物的效率,探索最佳处理条件,以亚甲基蓝溶液为模型污水,进行了Fenton试剂氧化亚甲基蓝褪色反应的影响因素实验。对不同条件下的时间过程进行了在线动力学跟踪、拟合和比较。研究发现:Fenton试剂高级氧化的反应动力学过程可分为三阶段。反应前期符合一级动力学,后期符合二级动力学,两者之间存在一个过渡性阶段。一级动力学期的反应速度快,氧化能力高,对于污染物的化学处理是比较合理的,实验还确认了反应前期的Fe(II)浓度对过程的支配作用。