臭氧/过氧化氢降解扑草净试验研究

采用O3/H2O2体系降解内分泌干扰物类除草剂扑草净,并对氧化产物进行色谱分析,考察了该体系去除扑草净的效果。结果表明,当扑草净初始浓度为2 mg/L时,在H2O2/O3(物质的量之比)为0.7、O3投量为16.8 mg/L、温度为25℃、pH值为6.2的最佳条件下,O3/H2O2体系对扑草净的去除率接近93%;在自来水本底条件下,对扑草净的去除率较纯水中的高约9%;腐殖酸对扑草净降解的影响表现为低浓度促进、高浓度抑制,碳酸氢根对扑草净降解的抑制作用较小;伴随扑草净的降解,有硝酸根和硫酸根离子产生,这表明O3/H2O2体系能够有效降解扑草净。     

Fe_3O_4/Bi_2O_3复合粒子的制备及其可见光催化性能

首先通过共沉淀法制备Fe3O4磁粒子,然后采用水热法制备Fe3O4/Bi2O3复合粒子,并利用X-射线衍射、X-光电子能谱、扫描电子显微镜等进行表征。结果表明,复合粒子由Fe3O4和Bi2O3组成,形貌呈球形,具有三维多级结构。在可见光照射下,所制备的复合粒子对罗丹明B的降解率达95.2%。降解完成后,在外界磁场的作用下,Fe3O4/Bi2O3很快从体系中分离,可进行重复利用,实现循环催化。实验发现,Fe3O4/Bi2O3经5次循环催化后,对罗丹明B的降解率仍达93%以上。     

O3/H2O2氧化页岩气产出水有机物动力学及机理研究

对O3/H2O2氧化页岩气产出水降解有机物动力学、特征污染物苯胺降解动力学及机理进行实验分析,研究结果表明：页岩气产出水有机物、苯胺降解符合一级反应动力学;臭氧分子的分解符合零级反应动力学。通过液相色谱-质谱（LC-MS）分析O3/H2O2氧化苯胺降解过程中间产物,发现O3/H2O2氧化法不能完全 将页岩气产出水矿化为二氧化碳和水,只是将复杂有机物分子转化为结构简单的直链烷烃或者羧酸类物质,需与其他氧化方式相结合才可将有机物完全去除,并提出了降解返排液中苯胺的两条可能途径,为O3/H2O2氧化工艺实际应用提供理论依据。     

氧化沉淀法制备纳米Fe_3O_4及其类Fenton催化活性

通过化学氧化沉淀法制备出球形和八面体形貌的Fe3O4纳米颗粒,对其进行XRD、Raman和SEM等表征。以合成的纳米Fe3O4催化H2O2氧化降解橙黄Ⅱ,考察了不同形貌Fe3O4的类Fenton催化活性。结果表明:使用化学氧化沉淀法制备Fe3O4,在低pH(8⁹)条件下所得到的产物呈类球形,高pH(13)条件得到的产物为八面体形貌,其粒径均在210nm左右,并且结晶良好。Fe3O4/H2O2体系能有效降解橙黄II,并且催化反应主要发生在Fe3O4表面,最佳催化条件为pH 3.0、温度40℃。类球形Fe3O4纳米颗粒的催化活性高于八面体Fe3O4,并且Fe3O4具有良好的化学稳定性,重复使用4次效果稳定。     

O3/H2O2对水中微量2,4-D的降解效果

研究了O3／H2O2工艺对水中微量农药2，4-D的氧化效果，探讨了H2O2投量和溶液pH值对2，4-D氧化效率的影响规律，利用LC-MS和GC-MS等手段对降解产物进行了定性分析，并在此基础上提出了2，4-D的氧化降解途径。     

蒸汽相水解法制备磁性光催化剂Fe_3O_4/SiO_2/TiO_2及其光催化性能

采用蒸汽相水解法,以Fe3O4纳米磁性颗粒为磁核,在其表面包覆一层SiO2来阻止光腐蚀,然后将锐钛矿相纳米氧化钛沉积在Fe3O4/SiO2颗粒表面,从而制得核壳结构的Fe3O4/SiO2/TiO2磁性复合光催化材料。用X射线粉末衍射仪(XRD)、场发射扫描电镜(FE-SEM)、高分辨率透射电子显微镜(HR-TEM)、探针式震动磁强计等手段对所制备的产物的结构、形貌、磁强度性能进行表征。以300W汞灯为光源,用亚甲基蓝和酸性红模拟污水中的有机染料来评价复合光催化剂的性能。结果表明,磁性纳米微球中TiO2的含量越大,其光催化性能越好,含TiO2质量分数50%的F3O4/SiO2/TiO2磁性纳米微球可在180min内降解亚甲基蓝模拟染料废水,降解率达99%,在80min内降解酸性模拟染料废水,降解率达98%。     

微量Fe3+对过氧化氢热分解爆炸的影响

采用加速量热仪(ARC)对含微量Fe3+的30%H2O2进行热危险性分析,并与30%H2O2的热分解过程进行对比。结果表明:微量Fe3+的存在对H2O2的分解有一定的催化作用,能降低其低温分解活化能,使其在较低温度下发生缓慢的分解反应,从而导致H2O2浓度逐渐降低,并使随后的绝热自分解反应变慢、完全分解时间变长、分解过程中产生的压升速率和温升速率变低。但是,在相同绝热分解温度下,含微量Fe3+的H2O2分解压力高于纯H2O2的分解压力。     

H2O2强化水力空化降解二甲苯的试验研究

进行了水力空化单独作用和水力空化与H2O2联用降解相同浓度二甲苯废水的对比试验,结果表明：H2O2对水力空化具有强化作用,加入10ml 25mg/l的H2O2,可使含5.0mg/l二甲苯废水溶液的降解率在120min时达到51.42%。     

UV/H2O2/O3工艺降解典型有机防晒剂

有机防晒剂作为一种新兴污染物引发的环境安全风险备受关注。采用紫外/双氧水/臭氧联用工艺(UV/H₂O₂/O₃)降解典型有机防晒剂2,4-二羟基二苯甲酮(UV-0),基于中心组合设计方法进行实验,考察影响因素,并探索降解机理。结果表明,在H₂O₂浓度为340μmol/L、UV-0初始浓度为5 mg/L、UV光强为170μW/cm²、O₃流量为0.38 L/min条件下,20 min内对UV-0的降解率高达99.9%,反应速率常数为0.570 7 min^-1,降解效果良好。响应面模型能较好地模拟和预测实验结果,并探索反应空间,H₂O₂浓度、UV光强、O₃流量等因素会影响降解效果。高分辨率质谱和量子化学结构分析表明,UV-0降解过程中羟基加成反应首先发生在C10位置,形成羟基和二羟基加成产物,随后通过碳碳键断裂和芳香环裂解生成草酸等小分子酸。UV/H     

O3/H2O2联合氧化法预处理制药废水的初步探讨

针对制药废水的特点和目前制药废水预处理技术现状,介绍了O3/H2O2在制药废水处理中的应用,阐述了O3/H2O2氧化工艺机理,分析了O3/H2O2联合氧化法在工程实际中的应用情况,并通过与其他方法对比,得出该工艺是最好的制药废水预处理工艺。     

O3／H2O2艺去除饮用水中2-MIB的效能与机制

以2-甲基异莰醇（MIB）为嗅味物质的代表物,采用过氧化氢／臭氧氧化（O3／H2O2）工艺去除水中嗅味物质,考察了O3／H2O2工艺对水中2一MIB的去除效能与主导作用机制。研究表明,投加H2O2显著提高了单独0,氧化对2-MIB的去除效能,H2O2与O3最佳物质的量比为0．3：1,且2-MIB去除效果随pH值的升高而升高。叔丁醇对2-MIB的去除表现出显著的抑制作用,在O3氧化2-MIB过程中,除O3分子氧化2-MIB外,O3在水中自分解产生的强氧化性的羟基自由基（HO·）也具有协同氧化作用。不同浓度的天然有机物（NOM）对2-MIB去除效果的影响不同,较低浓度的NOM促进了2-MIB的去除,但随着其浓度的升高,2-MIB去除率明显降低。O3／H2O2工艺对水中2-MIB表现出良好的去除效果,是强化去除水中2-MIB等致臭微量有机物的重要工艺。     

Degradation of estrone in aqueous solution by photo-Fenton system

Photodegradation of estrone (E1) in aqueous solutions by UV-VIS/Fe(III)/H2O2 system (photo-Fenton system) was preliminarily investigated under a 250-W metal halide lamp (lambda > or = 313 nm). The influences such as initial pH value, initial concentration of Fe(III), H2O2 and E1 on degradation efficiency of E1 were discussed in detail. The results indicated that E1 could be decomposed efficiently in UV-VIS/Fe(III)/H2O2 system. After 160-min irradiation, the photodegradation efficiency of 18.5 micromol L(-1) E1 reached 98.4% in the solution containing 20.8 micromol L(-1) Fe(III), and 1664 micromol L(-1) H2O2 at initial pH value 3.0. The degradation efficiencies of E1 were dependent on initial pH value, Fe (III) concentration and H2O2 concentration. The degradation of four estrogens estrone (E1), estradiol (E2), 17alpha-ethynylestradiol (EE2) and diethylstibestrol (DES) in UV-VIS/Fe(III)/H2O2 system were also conducted. Under the conditions of pH 3.0, the E1 apparent kinetics equation -dC(E1)/dt=0.00093[H2O2]0.47[Fe(III)]0.63[E1]0.24 (r=0.9935, n=11) was obtained. The E1 mineralization efficiency was lower than degradation efficiency under the same conditions, which implied the mineralization occurred probably only at aromatic ring. There are several intermediate products produced during the course of E1 degradation. The comparison of the degradation efficiencies of E1, E2, EE2 and DES degradation in UV-VIS/Fe(III)/H2O2 system were also conducted, and the relative degradability among different estrogens were followed the sequence: DES>E2>EE2>E1.     

Dual roles of CO2*- for degrading synthetic organic chemicals in the photo/ferrioxalate system

In this study, the relative importance of the dual reaction pathways of CO2*- in the photo/ferrioxalate system, where it acts both as a reductant for reducing the ferric ion and as an agent for the formation of H(2)O(2), was investigated as a function of the concentrations of ferrioxalate and oxygen. We studied the two competitive reactions of CO2*- in the photo/ferrioxalate system, which depend on the relative concentrations of ferrioxalate to oxygen, with the degradation of 2,4-dichlorophenoxyacetic acid (2,4-D), which was used as a target pollutant. At high concentrations of ferrioxalate, almost all of the CO2*- reacted with ferrioxalate to reduce Fe(III) to Fe(II), whereas at low concentrations of ferrioxalate, a majority of the CO2*- contributed to the formation of H(2)O(2), as a result of its reaction with oxygen, which allows the Fenton reaction to occur without any external supply of H(2)O(2).     

微波/Fe-Zr联用技术处理正丁酸模拟废水的研究

采用自制的Fe—Zr为催化剂、H2O2为氧化剂、正丁酸为模拟污染物,以TOC去除率为指标,对微波／Fe—Zr联用技术进行了研究。分别考察了Fe—Zr用量、H2O2用量、微波炉的功率、微波的作用时间及Fe—Zr重复使用的次数对TOC去除率的影响;并利用一次回归正交试验确定了微波／Fe—Zr联用技术处理正丁酸模拟废水的优化条件,即处理TOC约为490mg／L的150mL正丁酸模拟废水,Fe—Zr的用量为4g、H2O2的用量为7mL、微波炉的功率为640W、微波的作用时间为10min,此时对TOC的去除率高达95％;最后在优化条件的基础上,对6种不同的处理工艺进行了比较,结果表明微彬Fe—Zr联用技术对TOC的去除率最高。     

Ti/SnO2,Ti/SnO2-Sb2O3阳极电催化氧化酸性品红的试验研究

采用热氧化法制备了Ti/SnO2和Ti/SnO2-Sb2 O3电极,以酸性品红为研究对象,对两种电极材料进行了性能比较,考察槽电压、电流密度、电解质浓度对电催化氧化处理系统的影响.结果表明:热氧化法制备出的Ti/SnO2-Sb2 O3电极,其电催化性能明显优于Ti/SnO2电极;以Ti/SnO2-Sb2 O3为阳极,在酸性品红初始浓度为100 mg/L、电极间距为2.5 cm、电流密度为75mA/cm2、电解质浓度取12 g Na2SO4/L时,60 min后酸性品红的去除率达到了95.41％.     

Kinetic model of 4-CP degradation by Fenton/O2 system

A kinetic model of the degradation of 4-CP by Fenton/O(2) system was established, in which particular attention was paid to the role of oxygen in the process because many former researches suggested that the presence of oxygen could decrease the input of H(2)O(2). The proposed model well predicted 4-CP degradation and H(2)O(2) consumption by Fenton/O(2) and Fenton/N(2) systems at varying levels of Fe(2+), H(2)O(2), and 4-CP input. Most correlation coefficients between experimental and predicted data of 4-CP and H(2)O(2) concentration were above 0.95. The model could predict the enhancement of 4-CP degradation by oxygen and the difference in the evolution of aromatic intermediates between Fenton/O(2) and Fenton/N(2) system. The predicted and experimental data both showed the degree of benzene ring cleavage in Fenton/O(2) system was higher than that in Fenton/N(2) system. Understanding the role of oxygen is very important to improve the decomposition performance.     

UV／H2O2用于中水回用预处理工艺试验研究

本试验采用UV／H2O2光氧化法处理含有较高浓度阴离子表面活性剂（LAS）的洗浴废水,研究了H2O2投加量、pH值、光照时间、紫外灯光强对LAS降解率的影响,并得出了一些有益的结论。     

pH effect on OH radical production in photo/ferrioxalate system

In wastewater treatment using the Fenton and photofenton processes, pH is one of the critical operating parameters, due to the fact that the Fenton reaction can work only under acidic pH conditions. It is hoped that Ferric iron complexed with oxalate (Fe(III)-oxalate; ferrioxalate) will provide an alternative to the traditional Fenton process with its limited range of pH conditions, since its high solubility in aqueous media can broaden the available pH range of the Fenton reaction up to the near neutral pH regime. In this study, we investigated the pH dependency of OH production in the photo/ferrioxalate system, in the presence and absence of externally supplied H(2)O(2), where 2,4--D was used as the probe compound for OH production at a wide range of pH values (1.2--7.4). In the absence of externally supplied H(2)O(2), the 2,4--D degradation was considerably enhanced with increasing pH, whereas it was reduced with increasing pH in the presence of an excess amount of H(2)O(2). These variations in the degradation of 2,4--D were thus found to be precisely related to the formation of H(2)O(2), a factor to which little attention was paid in previous studies. In the absence of H(2)O(2) addition, the in situ formation of H(2)O(2) is facilitated with increasing pH by the reaction of Fe(II) with O(2)(-), which increases with pH, augmenting the production of OH and thereby leading to the faster degradation of 2,4--D. This same reaction can also provide an explanation for the opposite pH dependence of 2,4--D degradation in the presence of H(2)O(2).     

Degradation of 2,4-dichlorophenol by immobilized iron catalysts

The degradation of 2,4-Dichlorophenol (from now on 2,4-DCP) has been carried out on Nafion-Fe (1.78%) in the presence of H2O2 under visible light irradiation. A solution containing 2,4-DCP (TOC 72 mg C/L)) is seen to be mineralized in approximately 1 h in the presence of H2O2 (10 mM) under solar simulated visible light (80 mW cm-2) at pH values between 2.8 and 11. Homogeneous photo-assisted Fenton reactions were capable of mediating 2,4-DCP degradation only up to pH 5.4. The degradation kinetics of 2,4-DCP on Nafion-Fe membranes was more favorable than the one observed during Fenton photo-assisted processes at pH 2.8. The degradation of 2,4-DCP was investigated as a function of the substrate, oxidant concentration and applied light intensity. The Nafion-Fe was seen to be effective over many cycles during the photo-catalytic degradation of 2,4-DCP showing an efficient and stable performance during 2,4-DCP degradation without leaching out Fe(3+)-ions into the solution. Evidence is presented that the degradation at the surface of the Nafion-Fe membrane seems to be controlled by mass transfer and not by chemical reaction of the species in solution. The approach used to degrade 2,4-DCP is shown to be valid for other chloro-carbons like 4-chlorophenol, 2,3-chlorophenol and 2,4,5-trichlorophenol.     

Photodegradation of 2,4-dichlorophenoxyacetic acid in various iron-mediated oxidation systems

The oxidation of herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) by different iron-mediated processes, with or without the presence of ultraviolet (at 253.7 nm) and oxalate, was investigated and compared. The initial decay rate and the overall removal percentage were used as the performance indexes. To extensively explore the associated processes, the following combinations or blank systems were investigated: UV radiation only, Fe(2+)/H(2)O(2), Fe(2+)/H(2)O(2)/UV, ferrous oxalate/H(2)O(2), ferrous oxalate/H(2)O(2)/UV, Fe(3+)/H(2)O(2), Fe(3+)/H(2)O(2)/UV, ferrioxalate/H(2)O(2), and ferrioxalate/H(2)O(2)/UV. This study showed that the degradation of 2,4-D by sole UV or dark processes (without UV) is generally slow, except by the conventional Fenton's process (Fe(2+)/H(2)O(2)). However, these slow reactions can be accelerated by exposure to UV irradiation, which can increase the initial 2,4-D decay rate from ten to more than one hundred times. Furthermore, if the reaction is initiated by ferrous oxalate or ferrioxalate instead of Fe(2+) or Fe(3+) ions, the rates can be further improved, because of the higher light sensitivity of the organometallic complexes. These reactions were also found sensitive to the initial hydrogen peroxide concentration. The competition of hydroxyl free radicals by the primary intermediate, 2,4-dichlorophenol, was also observed.