臭氧/纳米TiO2催化氧化去除水中微量硝基苯的研究

在悬浮颗粒搅拌混合反应器中,研究了臭氧/纳米TiO2催化氧化去除水中微量硝基苯的性能,结果表明,纳米TiO2催化臭氧化去除硝基苯较单独臭氧氧化有明显的提高,反应20min硝基苯的去除率提高了44%.实验中分别考察了纳米TiO2热处理温度、催化剂投量、臭氧投量、硝基苯初始浓度、pH值对臭氧/纳米TiO2催化氧化去除硝基苯的影响.发现550℃烧结得到的纳米TiO2表现出最好的催化臭氧化活性,在较低的臭氧投量与催化剂用量条件下,硝基苯的去除率可达到56.57%;增大臭氧或者硝基苯的初始浓度,硝基苯的去除率随之提高;但是改变催化剂投量,硝基苯的去除效果几乎不受影响;中性或碱性pH环境利于纳米TiO2催化臭氧化反应的进行.通过研究叔丁醇对纳米TiO2催化臭氧化反应的影响,证明反应遵循羟基自由基(·OH)反应机理.     

臭氧法降解水中对甲基苯磺酸的动力学研究

采用臭氧法降解对甲基苯磺酸废水,研究了对甲基苯磺酸降解的影响因素和动力学.考察了反应液初始浓度、初始pH值、臭氧投量、反应温度、常见无机离子等因素对臭氧氧化降解对甲基苯磺酸反应速率的影响.结果表明,对甲基苯磺酸初始浓度0.29mmol.L-1,pH9.0,臭氧投量3.75×10-6mol.s-1,控制温度25℃,反应6...     

臭氧/纳米TiO2催化氧化去除水中微量硝基苯的研究

在悬浮颗粒搅拌混合反应器中,研究了臭氧/纳米TiO₂催化氧化去除水中微量硝基苯的性能,结果表明,纳米TiO₂催化臭氧化去除硝基苯较单独臭氧氧化有明显的提高,反应20min硝基苯的去除率提高了44%.实验中分别考察了纳米TiO₂热处理温度、催化剂投量、臭氧投量、硝基苯初始浓度、pH值对臭氧/纳米TiO₂催化氧化去除硝基苯的影响.发现550℃烧结得到的纳米TiO₂表现出最好的催化臭氧化活性,在较低的臭氧投量与催化剂用量条件下,硝基苯的去除率可达到56.57%;增大臭氧或者硝基苯的初始浓度,硝基苯的去除率随之提高;但是改变催化剂投量,硝基苯的去除效果几乎不受影响;中性或碱性pH环境利于纳米TiO₂催化臭氧化反应的进行.通过研究叔丁醇对纳米TiO₂催化臭氧化反应的影响,证明反应遵循羟基自由基(·OH)反应机理.     

臭氧/沸石工艺处理水中硝基苯的效能研究

在连续反应器中,考察了臭氧/沸石工艺在不同条件下去除硝基苯的效果.结果表明,臭氧/沸石工艺对硝基苯的去除效率明显高于单纯臭氧氧化,反应7 min后,硝基苯去除率达到100％,并且该反应符合假一级反应动力学.叔丁醇能抑制臭氧/沸石工艺对硝基苯的去除效率,表明在氧化去除硝基苯过程中羟基自由基起主导作用.增加沸石投量和臭氧浓度均能有效地提高臭氧/沸石工艺对硝基苯的去除效率,并且臭氧/沸石工艺对硝基苯的去除速率与沸石投量之间存在1个最优值,与臭氧浓度呈线性关系.臭氧/沸石工艺对硝基苯的去除速率与初始硝基苯浓度无关.离子强度对臭氧/沸石工艺降解硝基苯的效率影响较大,当离子强度从0增加到1×10^-3　mol/L时,臭氧/沸石工艺对硝基苯的去除率从81.2％降低至31.6％.pH值主要影响臭氧的分解能力,随着溶液pH降低,臭氧/沸石工艺对硝基苯的去除效率逐渐下降.沸石具有较长的使用寿命.     

饮用水中内分泌干扰物双酚A的臭氧氧化降解研究

采用臭氧氧化工艺对饮用水中内分泌干扰物双酚A特性进行了研究.研究表明:在原水浓度为1.0mg/L左右,臭氧总投加量为1.0、1.5和2.0mg/L条件下,30min BPA去除率可达70%、82%和90%.通过考察不同臭氧投加量、不同本底条件、不同BPA初始浓度和不同臭氧投加时间对BPA臭氧氧化的影响,分析得出臭氧投加量对BPA的降解占主导地位,而臭氧接触时间对去除效果的影响很小;采用紫外波长扫描确定在臭氧降解BPA的同时生成了在UV₂₅₄上有吸收的产物.通过考察臭氧氧化双酚A过程中UV₂₅₄的变化,提出低臭氧投加量下BPA不能完全被氧化,而采用缩短臭氧投加时间、加大臭氧投加量以及提高水中余臭氧浓度等方法,有利于水中BPA的完全降解.     

臭氧氧化反渗透浓缩垃圾渗滤液动力学

采用臭氧氧化法处理经反渗透膜处理后的浓缩垃圾渗滤液,并建立了氧化降解反应动力学模型.结果表明,氧化降解初始反应速率主要与初始pH、臭氧投量、反应温度和初始COD有关.在pH 8.0,温度30℃,臭氧投量5.02 g/h,反应时间90 min的条件下,反渗透浓缩渗滤液的COD去除率达到67.6%;并且在pH为2.0～8....     

敌敌畏的臭氧氧化处理

在12 L的反应器中,观察了臭氧浓度分别为4.9、6.7和7.6 mg/L,溶液温度10.50℃,pH值为3.1、5.3、7.2、9.4和11.2条件下,臭氧氧化浓度为30 mg/L的有机磷杀虫剂敌敌畏的处理效果,并计算了臭氧氧化敌敌畏的反应动力学.结果表明,臭氧氧化法是处理敌敌畏的高效方法.不同浓度臭氧处理5 min时敌敌畏的去除率均在96%以上,6.7 mg/L的臭氧氧化处理敌敌畏4 min时矿化度(以TOC 计)可达34.8%.臭氧浓度越高,敌敌畏的降解速率越快.随着敌敌畏初始浓度的升高,敌敌畏的氧化去除率下降,但绝对去除量升高.试验范围内的pH值和温度对敌敌畏的臭氧氧化去除效果影响不大.在臭氧浓度6.7 mg/L,pH 7.2和室温20℃的条件下,臭氧氧化敌敌畏的反应级数为0.11,反应速率常数k为7.72 mg·(L·min)-1.     

污泥基活性炭催化臭氧氧化降解水中微量布洛芬的效能研究

以城市污水处理厂脱水污泥和玉米芯为原料,氯化锌为活化剂制备污泥基活性炭(SAC),考察其催化臭氧氧化去除水中稳定性药物布洛芬(IBP)的效能.试验中对比考察了单独臭氧氧化、单独SAC吸附、SAC催化臭氧氧化这3种工艺对水中IBP(初始浓度为500μg.L-1)的去除效果,同时研究了臭氧与SAC投加量对催化效果的影响.结果表明,单独臭氧氧化对IBP的去除率随臭氧浓度的增加而增加,当臭氧浓度由0.75 mg.L-1增加至3.0 mg.L-1时,IBP的去除率由44.4%提高到100%;单独SAC对IBP的吸附去除效果较差,即使SAC投加量增至100 mg.L-1,吸附时间为40 min时,IBP的吸附去除率仅为44.56%;SAC催化臭氧氧化工艺中,IBP去除速率大大加快,在反应的初始阶段(0～5 min)SAC催化臭氧氧化对IBP的去除率要远远高于单独臭氧氧化和单独SAC吸附二者作用之和.臭氧与SAC的投加量对IBP的催化氧化去除效果具有较大影响.SAC催化臭氧氧化IBP分为瞬时需氧阶段反应(0～5 min)和慢速反应(5～40 min)两阶段.快速反应阶段以.OH与IBP反应为主,慢速反应阶段残余臭氧浓度很低,此时主要以SAC吸附去除IBP为主.     

紫外活化过硫酸盐对甲基橙脱色处理实验研究

采用紫外活化光催化剂过硫酸盐对废水中的甲基橙进行脱色处理,研究反应pH、温度、过硫酸盐投加量、初始甲基橙浓度及投加锐钛矿TiO_2、共存阴离子(HCO_3~-、Cl~-)对甲基橙脱色速率的影响。结果表明:甲基橙氧化去除过程符合准一级动力学,反应最佳pH为9.0。在pH=9.0、过硫酸盐投加量0.5 mmol/L、甲基橙初始浓度100 mg/L、反应温度25℃时,经90 min光催化反应,甲基橙脱色效率可达87.6%,反应速率常数k为0.096 min~(-1)。甲基橙的去除速率随温度升高而增大,随甲基橙初始浓度的增加而减小;投加适量的TiO_2(200 mg/L)将抑制甲基橙氧化分解。废水中共存HCO_3~-离子时,甲基橙的去除速率下降,而Cl~-(0~200 mg/L)对甲基橙的去除速率无影响。     

油田作业废水臭氧化处理技术的实验研究

针对油田作业废水(COD)高、难降解的特点,探讨了废水的pH、COD初始浓度、臭氧投加量和臭氧化时间等因素对油田作业废水的COD去除效果的影响。结果表明,臭氧化对油田作业废水COD去除效果影响的主要因素为废水pH、废水的COD和臭氧投加量;当废水的COD为1064.0mg/L、pH为3.0、臭氧投加量为10g/L时,废水的COD去除率达到69.1%;臭氧化处理对低浓度油田作业废水的COD去除效果低于其对高浓度废水的处理效果。     

Removal of a type of endocrine disruptors-di-n-butyl phthalate from water by ozonation

Ozonation of synthetic water containing a type of endocrine disruptor-di-n-butyl phthalate （DBP） was examined. Key impact factors such as pH, temperature, ionic strength, ozone dosage and initial DBP concentration were investigated. In addition, the activities of radicals on uncatalysed and catalysed ozonation were studied. The degradation intermediate products were followed and the kinetic of the ozonation were assessed as well. Results revealed that ozonation of DBP followed two mechanisms. Firstly, the reaction rate of direct ozonation was slower at lower pH, temperature, and ionic strength. Secondly, when these factors were increased for indirect radical reaction, higher percentage of DBP was removed with the increase of the initial ozone dosage and the decrease of the initial DBP concentration. In addition, tea-butanol, humic substances and Fe（Ⅱ） affected DBP ozonation through the radical pathway. It was determined that ozonation was restrained by adding tea-butanol for its radical inhibition effect. Furthermore, humic substances enhanced the reaction to some extent, but a slight negative effect would be encountered if the optimum dosage was exceeded. As a matter of fact, Mn（Ⅱ） affected the ozonation by ＂active sites＂ mechanism. In the experiment, three different kinds of intermediate products were produced during ozonation, but the amount of products for each one of them decreased as pH, temperature, ionic strength and initial ozone dosage increased. A kinetic equation of the reaction between ozone and DBP was obtained.     

活性炭催化臭氧氧化扑热息痛的机制研究

采用活性炭催化臭氧处理典型解热镇痛药扑热息痛,研究了活性炭/臭氧体系的协同效应,优化了工艺参数,分析了降解产物并探讨了降解机制.结果表明:在臭氧活性炭体系下,反应60 min后,TOC的去除率为55.11%,效果明显优于臭氧体系的20.22%和活性炭体系的27.39%之和,具有明显的协同作用,并且BOD5/COD比值从反应前的0.086提高到反应后的0.543,可生化性显著提高.研究了pH、臭氧投加量、污染物初始浓度和活性炭投加量等操作参数的作用规律.在此基础上,探讨了臭氧活性炭体系在不同pH下的催化反应机制,发现在酸性条件下是吸附和臭氧直接氧化共同作用,在碱性条件下以活性炭催化臭氧氧化为主.     

Impact of Fenton and ozone on oxidation of wastewater containing nitroaromatic compounds

Fenton and ozone treatment was investigated at laboratory scale for the degradation of aqueous solutions of nitrobenzene (NB).Effects of reactants concentration (O3,H2O2,and Fe(II)),temperature,and pH on NB degradation were monitored.Reaction kinetic of these processes was also assessed.A rapid reaction took place for Fenton process at higher initial concentration of H2O2,higher temperatures,and more acidic conditions(pH 3).Similarly, ozonation reaction exhibited rapid rates for higher ozone dose,higher temperatures,and more basic conditions(pH 11).Complete NB degradation in 65 min Was achieved using Fenton process.The conditions of complete elimination of 100 mg/L of initial NB concentration,were 250 mg/L of H2O2 concentration,pH 3,and 10 mg/L of Fe(Ⅱ) concentration.Under these conditions,55% organic carbon elimination Was achieved.Total organic carbon mineralization Was attained in 240 min reaction time by Fenton process with 900 mg/L of H2O2 concentration,and 30 mg/L of Fe(II) concentration.Fenton reaction showed a pseudo-first order kinetic;the reaction rate constant Was ranged from 0.0226 to 0.0658 min-1.Complete NB degradation wag also achieyed for an ozone dose of the order of 2.5 g/L.The ozonation Was studied at different ozone doses.different initial pH(7-11)and at difierent temperatures(15-35℃).NB ozonation kinetic Was represented by a bi-molecular kinetic model which was reduced to pseudo-first order kinetic.The pseudo-first order reaction rate constant was determined to increase at 20℃ from 0.004 to 0.020 min-1 as the used ozone increased from 0.4 to 1.9g/L.     

Enhanced ozonation of dichloroacetic acid in aqueous solution using nanometer ZnO powders

Nanometer zinc oxide (ZnO) powders were used as a catalyst to enhance the ozonation for the degradation of dichloroacetic acid (DCAA) in aqueous solution. The batch experiments were carried out to investigate the e ects of key factors such as catalyst dosage, ozone dosage, solution pH and tert-butyl alcohol (t-BuOH) on the degradation e ciency of DCAA. Density functional theory (DFT) was adopted to explore the mechanism of generating hydroxyl radical (.OH) on the ZnO surface. The results showed that adsorption and ozonation processes were not e ective for DCAA removal, and the addition of ZnO catalyst improved the degradation e ciency of DCAA during ozonation, which caused an increase of 22.8% for DCAA decomposition compared to the case of ozonation alone after 25 min. Under the same experimental conditions, the DCAA decomposition was enhanced by increasing catalyst dosage from 100 to 500 mg/L and ozone dosage from 0.83 to 3.2 mg/L. The catalytic ozonation process is more pronounced than the ozonation process alone at pH 3.93, 6.88, and 10. With increasing the concentration of t-BuOH from 10 to 200 mg/L, the degradation of DCAA was significantly inhibited in the process of catalytic ozonation, indicating that ZnO catalytic ozonation followed .OH reaction mechanism. Based on the experimental results and DFT analysis, it is deduced that the generation of .OH on the ZnO surface is ascribed to the adsorption of molecule ozone followed by the interaction of adsorbed ozone with active sites of the catalyst surface. It is also concluded that ZnO may be an e ective catalyst for DCAA removal, which could promote the formation of .OH derived from the catalytic decomposition of ozone.     

水中天然有机物的臭氧强化光催化降解研究

研究了饮用水源中大分子天然有机物（NOM）的臭氧强化光催化降解,考察了臭氧投加量、反应时间和HCO3^-浓度对NOM降解速率的影响;分析了臭氧强化光催化过程中NOM相对分子质量的变化,并比较不同相对分子质量大小NOM的降解速率.研究结果表明,臭氧强化光催化比单独臭氧氧化、光催化能更有效地降解NOM,同时增加臭氧投加量和反应时间才能有效提高臭氧强化光催化对TOC的去除率,而单独增加臭氧投加量可显著提高生物可降解性;HCO3^-显著降低光催化的降解效果,臭氧强化光催化能有效地减弱HCO3^-的不利影响;臭氧强化光催化过程中大分子NOM分解为小分子,SUVA值迅速下降,且相对分子质量越大矿化速度越快.     

氯咪巴唑在臭氧降解过程中的影响因素及其降解产物

唑类抗真菌剂广泛应用于药物和个人护理品(pharmaceutical and personal care products,PPCPs)中,常规污水处理工艺难以将其有效去除. 大量唑类抗真菌剂排入受纳环境后会对生态系统造成一系列负面影响. 为了解唑类抗真菌剂的臭氧氧化降解过程和机理,以氯咪巴唑(climbazole,CZ)为例,通过设置不同条件的对比试验,系统研究CZ在臭氧氧化过程中的影响因素及其去除规律,同时采用超高效液相色谱-飞行时间质谱联用仪UPLC-Q/TOF对其降解产物进行鉴定. 影响因素试验结果表明:①CZ起始浓度由1.0 mg/L增至4.0 mg/L时,臭氧氧化20 min下CZ的降解率从99.1%降至69.3%;②反应体系起始pH由5.0升至9.0时,CZ臭氧降解半衰期由1.38 min延长至7.18 min;③臭氧流速由0.1 L/min增至0.4 L/min时,臭氧氧化20 min时CZ的降解率从66.5%提至99.4%,但臭氧流速超过0.3 L/min以后,CZ降解率的增幅较小;④自然水体及其高浓度共存组分(碳酸氢根和腐殖酸)均会明显抑制CZ的臭氧氧化反应速率,CZ降解半衰期大多数超过6 min (空白对照组为1.99 min). 因此,在臭氧氧化降解新兴有机污染物或对臭氧氧化工艺进行优化时,应充分考虑起始污染负荷、pH、臭氧流速、水体水质状况等对处理效果的影响. 产物鉴定结果表明:臭氧氧化反应可将CZ碎裂重组形成两个主要降解产物——TP269和TP297,二者的产率分别为11.45%和8.90%. 研究显示,起始污染负荷、pH、臭氧流速、水体水质状况均会明显影响CZ的臭氧降解效果;两个CZ臭氧降解产物的产率虽不高,但其毒性有待进一步研究.      

饮用水中甲羟孕酮的臭氧氧化降解研究

以饮用水中内分泌干扰物孕激素类甲羟孕酮(MPA)为目标物,采用臭氧氧化工艺对其进行降解,对臭氧降解过程动力学进行了研究,并考察液相臭氧浓度、pH、羟基自由基(.OH)清除剂(HCO3-)对降解过程的影响.结果表明,臭氧在合适条件下能够有效降解水溶液中的MPA,MPA初始浓度为3、5、10 mg.L-1,采用连续臭氧曝气方式降解时,降解过程遵守一级反应动力学模型;采用序批式臭氧投加方式进行降解时,降解过程符合二级反应动力学模型.pH的升高和HCO3-的添加都会对降解效果产生负面影响.在反应温度为20℃,采用序批式臭氧投加方式,MPA的去除率从pH=3.10时的89.8%下降到pH=9.02时的74.6%.相同反应条件下,添加羟基自由基清除剂HCO3-后,降解反应速率常数由0.146 3 L.(mg.min)-1下降到0.049 5 L.(mg.min)-1,去除率下降了22.2个百分点.