Photochemical degradation and mineralization of 4-chlorophenol

INTENTION, GOAL, SCOPE, BACKGROUND: Since the intermediate products of some compounds can be more toxic and/or refractory than the original compund itself, the development of innovative oxidation technologies which are capable of transforming such compounds into harmless end products, is gaining more importance every day. Advanced oxidation processes are one of these technologies. However, it is necessary to optimize the reaction conditions for these technologies in order to be cost-effective. OBJECTIVE: The main objectives of this study were to see if complete mineralization of 4-chlorophenol with AOPs was possible using low pressure mercury vapour lamps, to make a comparison of different AOPs, to observe the effect of the existence of other ions on degradation efficiency and to optimize reaction conditions. METHODS: In this study, photochemical advanced oxidation processes (AOPs) utilizing the combinations of UV, UV/H2O2 and UV/H2O2/Fe2+ (photo-Fenton process) were investigated in labscale experiments for the degradation and mineralization of 4-chlorophenol. Evaluations were based on the reduction of 4-chlorophenol and total organic carbon. The major parameters investigated were the initial 4-chlorophenol concentration, pH, hydrogen peroxide and iron doses and the effect of the presence of radical scavengers. RESULTS AND DISCUSSION: It was observed that the 4-chlorophenol degradation efficiency decreased with increasing concentration and was independent of the initial solution pH in the UV process. 4-chlorophenol oxidation efficiency for an initial concentration of 100 mgl(-1) was around 89% after 300 min of irradiation in the UV process and no mineralization was achieved. The efficiency increased to > 99% with the UV/H2O2 process in 60 min of irradiation, although mineralization efficiency was still around 75% after 300 min of reaction time. Although the H2O2/4-CP molar ratio was kept constant, increasing initial 4-chlorophenol concentration decreased the treatment efficiency. It was observed that basic pHs were favourable in the UV/H2O2 process. The results showed that the photo-Fenton process was the most effective treatment process under acidic conditions. Complete disappearance of 100 mgl(-1) of 4-chlorophenol was achieved in 2.5 min and almost complete mineralization (96%) was also possible after only 45 min of irradiation. The efficiency was negatively affected from H2O2 in the UV/H2O2 process and Fe2+ in the photo-Fenton process over a certain concentration. The highest negative effect was observed with solutions containing PO4 triple ions. Required reaction times for complete disappearance of 100 mgl(-1) 4-chlorophenol increased from 2.5 min for an ion-free solution to 30 min for solutions containing 100 mgl(-1) PO4 triple ion and from 45 min to more than 240 min for complete mineralization. The photodegradation of 4-chlorophenol was found to follow the first-order law. CONCLUSION: The results of this study showed that UV irradiation alone can degrade 4-CP, although at very slow rates, but cannot mineralize the compound. The addition of hydrogen peroxide to the system, the so-called UV/H2O2 process, significantly enhances the 4-CP degradation rate, but still requires relatively long reaction periods for complete mineralization. The photo-Fenton process, the combination of homogeneous systems of UV/H2O2/Fe2+ compounds, produces the highest photochemical elimination rate of 4-CP and complete mineralization is possible to achieve in quite shorter reaction periods when compared with the UV/H2O2 process. RECOMMENDATIONS AND OUTLOOK: It is more cost effective to use these processes for only purposes such as toxicity reduction, enhancement of biodegradability, decolorization and micropollutant removal. However the most important point is the optimization of the reaction conditions for the process of concern. In such a case, AOPs can be used in combination with a biological treatment systems as a pre- or post treatment unit providing the cheapest treatment option. The AOP applied, for instance, can be used for toxicity reduction and the biological unit for chemical oxygen demand (COD) removal.     

激光光散射技术用于Fenton反应中Fe(Ⅲ)水解过程的研究

利用激光光散射技术，研究了不同条件下Ferton反应中Fe(Ⅲ)水解过程的粒径变化，并和一般铁盐体系中Fe(Ⅲ)水解过程进行了比较，结果表明，Fe(Ⅲ)的水解过程中，粒径变化受水解度B^*和铁盐浓度的影响，即B^*值愈大，浓度愈高，体系粒径愈大．并且在相同浓度和水解度B^*的条件下，Fenton反应生成的Fe(Ⅲ)比一般铁盐的水解聚合迅速，形成的粒径大，对采油废水进行处理的实验结果表明，Fenton体系对有机物的吸附去除效果明显优于常规铁盐体系，这可能与Fenton体系的高水解速率有关。     

Fenton oxidation of 2, 4-and 2, 6-dinitrotoluene and acetone inhibition

The performances and kinetic parameters of Fenton oxidation of 2,4- and 2,6-dinitrotoluene (DNT) in water-acetone mixtures and explosive contaminated soil washing-out solutions were investigated at a laboratory scale. The experimental results show that acetone can be a significant hydroxyl radical scavenger and result in serious inhibition of Fenton oxidation of 2,4- and 2,6-DNT. Although no serious inhibition was found in contaminated soil washing-out solutions, longer reaction time was needed to remove 2,4- and 2,6-DNT completely, mainly due to the competition of hydroxyl radicals. Fenton oxidation of 2,4- and 2,6-DNT fit well with the first-order kinetics and the presence of acetone also reduced DNT’s degradation kinetics. Based on the comparison and matching of retention time and ultraviolet (UV) spectra between high performance liquid chromatography (HPLC) and standards, the following reaction pathway for 2,4-DNT primary degradation was proposed: 2,4-DNT → 2,4-dinitro-benzaldehyde → 2,4-dinitrobenzoic acid → 1,3-dinitrobenzene → 3-nitrophenol.     

光催化氧化法处理化工废水的测试

本研究通过将UV、O3催化剂等主要条件单独或协同降解化工废水,对比了各反应的降解率,探讨了O3与催化剂在光催化反应中的重要作用。并通过简单的反应动力学分析,证明在各反应初期,溶液中有机物的降解基本符合一级反应。UV／O3共同作用表现了有机物降解的巨大潜力,使反应速率和降解率较其他体系有明显的提高。催化剂／UV／O3三者组合也加快了反应速率,不过对于废水中COD的去除催化剂并未体现出明显优势,但催化剂与UV／O3的组合明显提高了废水中总氮的去除率。     

长隧道韵律型视觉环境设计研究

采用心理物理试验分析公路隧道内部视觉环境对驾驶员行车安全的影响,将E-prime 2.0软件与仿真驾驶模拟器相结合,对驾驶员在隧道内长时间行车中的速度判断准确率及反应时间两个指标进行分析,提出了利用标志标线构建公路隧道内韵律型标线系统的改善措施,以改善隧道内视觉环境,并利用数理统计方法及Logistics拟合分析对设计方案进行评价。结果表明:1)公路隧道内韵律型标线系统能提升隧道内驾驶员的速度判断准确率3.33%~11.66%;2)普通公路隧道场景中,被试者反应时间与隧道内行车时间存在显著关系,公路隧道内韵律型标线系统的场景中,反应时间与隧道内的行车时间没有显著关系,能有效缓解视觉疲劳现象;3)被试者反应时间的增加同时受隧道内视觉环境与行车时间的影响。公路隧道内韵律型标线系统能有效提高驾驶员的反应时间,适用于行驶速度为80 km/h、大于1 333 m的隧道。     

间苯二胺改性磁性壳聚糖对六价铬的还原-吸附协同作用机制研究

通过改进后的方法制备出具有良好颗粒形态的磁性壳聚糖颗粒,并使用间苯二胺(mPD)对其进行改性,在颗粒表面形成了一层含有大量含氮官能团的有机壳层,有效改善了颗粒的比表面积和活性官能团数量.通过序批实验法探究mPD改性磁性壳聚糖颗粒对六价铬Cr(Ⅵ)的吸附行为,实验结果显示初始pH为酸性有利于其对Cr(Ⅵ)的去除;吸附行为复合拟二级动力学模型,以化学吸附为主;在25℃、pH3条件下,由Langmuir等温线计算得吸附量可以达到212.21 mg·g~(-1),优于此前报道过的很多非纳米级新型磁性吸附剂;通过Redlich-Peterson模型的拟合和吸附反应前后的X射线光电子能谱分析,可知mPD改性磁性壳聚糖颗粒对六价铬Cr(Ⅵ)的去除是通过氧化还原反应和吸附作用协同进行的;经过6次吸附-解吸再生过程,mPD改性磁性壳聚糖颗粒仍具有100 mg·g~(-1)以上的吸附能力.综上,mPD改性磁性壳聚糖颗粒体现出其对Cr(Ⅵ)突出的去除性能,同时具有便于分离和再生能力强等特点,对于应用于含铬废水的处理具有良好的前景.     

苯为前驱物形成二噁英的反应机理

苯作为垃圾中普遍存在的成分是形成多氯二苯并对二噁英/呋喃（PCDD/Fs）的重要前驱物之一.应用密度泛函理论（DFT）在B3LYP/6-311+G （d,p）水平上研究了苯生成PCDD/Fs的两阶段气相反应机理,获得相关基元反应的势垒与反应热.采用隧道效应校正的变分过渡态理论（VTST）对300~1300K的各基元反应进行速率常数计算.结果表明：苯的氯化过程在合成PCDD/Fs各基元反应中势垒最高,是整个过程的控速步骤;氯酚更有可能被HO·进攻氯苯发生亲核反应后经分子内脱氢形成;邻位Cl能提高芳香烃H的抽取势垒,降低分子反应活性;苯氧自由基经碳碳或碳氧耦合二聚化过程形成不同PCDD/Fs存在竞争机制.相关计算结果可以用于在总二噁英产量基础上评估由苯产生的PCDD/Fs贡献率.     

Fe（Ⅲ）水解过程中无机阴离子的影响作用

本文通过ＰＯ＾３－ ４，Ｆ＾－，ＳＯ＾２－ ４，Ｃｌ＾－，ＮＯ＾－ ３和ＣｌＯ＾－ ４存在时，０．１ｍｏｌ／１ ＦｅＣｌ３溶液的碱中和曲线的分析对比，说明了用曲线斜率区分滴定曲线为三个区域：（Ａ）自发水解反应；（Ｂ）聚合反应；（Ｃ）沉淀反应，以及阴离子对中和曲线的影响及其规律，指出阴子子对Ｆｅ（Ⅲ）浓度中和反应影响为不同程度的竞争配位，参与聚合及电中和脱稳，使沉淀反应提前等。并与ＯＨ＾－共同形成Ｆ     

高氨氮废水处理系统中功能微生物的检测

利用16S rDNA分子检测技术对高氨氮废水处理系统中的氨氧化细菌、亚硝酸盐氧化细菌等难分离培养微生物进行了分析检测.从实验室处理高氨氮废水的生物流化床硝化系统生物膜中提取细菌总DNA,以其为模板,利用氨氧化细菌(AOB)和亚硝酸盐氧化细菌(NOB)的16S rDNA特异性引物进行多聚酶链式反应(PCR)扩增,获得AOB和NOB的特异片段.将特异片段与pGEM-T载体连接并转化到E.coli DH5α中获得重组子,对阳性重组子进行酶切分型,AOB可分为8种不同类型.选取AOB的8种类型代表以及随即选取8个NOB克隆进行测序.经GenBank搜索以及同源性分析,发现所获得的8个AOB类型来自不同的菌株,处理系统中以Nitrosomonas sp.和Nitrosococcus sp.为氨氧化细菌的优势菌属;8株NOB重组子中有7株来自不同的菌株,系统中Nitrobacter sp.和Afipia sp.为亚硝酸盐氧化细菌的优势菌属.图6表1参14     

三维电极体系中苯酚降解效率的影响因素研究

三维电极法用于处理含酚废水的影响因素研究报道较多,但并未充分在理论上阐述其影响方式及机理。采用自制的实验室小试电化学反应器对含酚自配废水进行了处理。试验结果表明:体系中苯酚降解遵循一级反应模式;通过电流效率的核算确定60min作为最佳反应时间,得到的苯酚去除率为64.3%,吨水处理能耗为14.29kW·h·t-1,实际电流效率与理论电流效率相等为0.68。对体系进水控制不同的苯酚起始质量浓度,当反应时间不变时,实际试验结果与法拉第定律一致,即电流密度与去除的污染物的量以及COD去除率与电量和进水质量浓度的比值均呈线性关系;体系中羟基自由基的产生量能够采用式[?OH]=0.1218×EC0进行计算。采用最佳反应时间t=60min、电流密度I=20A,在苯酚质量浓度为500mg·L-1时改变极板间距进行的试验结果表明电压随极板间距的增大而降低,最佳极板间距为0.21m时可获得最大去除率为78.5%,体系的启动电压为0.25V。