臭氧及催化臭氧化降解2,4-滴丙酸动力学研究

对臭氧及催化臭氧氧化降解2,4-滴丙酸(DCPP)的效率进行了研究,并利用竞争动力学法算得了DCPP与臭氧及羟基自由基的反应速率常数,参比有机物为硝基苯(NB).结果表明,DCPP与臭氧的反应速率常数K-DCPP为(0.733±0.163)L·mol-1·s-1,与羟基自由基的kOH-DCPP为2.367×109L·mol-1·s-1.在单独臭氧和Mn(Ⅱ)催化臭氧化降解DCPP过程中,基于上述结果计算所得的速率常数与实际所测的表观反应速率常数具有较好的吻合度.以上结果对臭氧化处理含DCPP废水具有很好的理论指导意义.     

A~2/O联合臭氧污泥减量技术的改造研究

研究了臭氧化污泥减量技术联合A~2/O、倒置A~2/O与传统A~2/O在出水和污泥产率上的变化。结果表明,臭氧化A~2/O、臭氧化倒置A~2/O的出水与传统A~2/O相比未出现恶化,它们对COD和含氮物质的去除率分别为87.4%,53.7%和93%,66.5%,存在倒置A~2/O对臭氧混合液中有机质及含氮物质的利用率较A~2/O高的可能。试验按每克SS投加0.05 g O_3对A2/O与倒置A~2/O产生的约60%剩余污泥处理时,在短期内未造成出水磷含量的大幅升高,并且出水磷含量受臭氧混合液DO、二沉池底部DO的影响,两系统的污泥产率分别较传统A~2/O降低50%,56%。     

MgO催化臭氧氧化降解苯酚机理研究

对氧化镁(MgO)催化臭氧氧化降解苯酚的机理进行了探讨,并验证其与现有的3种催化臭氧氧化机理的吻合性.同时,研究了羟基自由基(·OH)抑制剂对苯酚去除效果的影响,·OH的产生量,以及臭氧在该体系中的存在位置及苯酚在该体系中的作用.结果表明,O_3和MgO/O_3两种反应体系中都存在·OH,MgO/O_3体系中的·OH是O_3体系中的2.14倍.O_3和MgO/O_3体系中的·OH与臭氧浓度的比值分别为1.47×10~(-9)和3.15×10~(-9).苯酚在MgO催化臭氧氧化体系中起到了促进臭氧吸附在MgO表面的作用,臭氧吸附到MgO表面后,分解产生·OH,一部分释放在溶液中降解苯酚,一部分则留在其表面增加表面羟基密度.     

纳米二氧化锰/还原态氧化石墨烯复合材料催化臭氧降解苯酚的研究

制备以还原态氧化石墨烯为载体的纳米二氧化锰催化剂,并以苯酚为目标降解物,研究了其催化臭氧化性能,对影响催化臭氧化效果因素及降解机理进行了初步探讨。使用SEM、TEM和XPS对材料进行表征;纳米二氧化锰/还原态氧化石墨烯催化臭氧降解苯酚反应为准一级反应;催化剂的最佳使用量为0.2 g/L;当p H=3时,苯酚催化臭氧化去除率相对于单独臭氧提高了119.0%;催化剂连续使用4次性能良好。     

Removal of organic matter and disinfection by-products precursors in a hybrid process combining ozonation with ceramic membrane ultrafiltration

The performance of an integrated process including coagulation, ozonation, ceramic ultrafiltration (UF) and biologic activated carbon (BAC) filtration was investigated for the removal of organic matter and disinfection by-products (DBPs) precursors from micro-polluted surface water. A pilot scale plant with the capacity of 120 m³ per day was set up and operated for the treatment of drinking water. Ceramic membranes were used with the filtration area of 50 m² and a pore size of 60 nm. Dissolved organic matter was divided into five fractions including hydrophobic acid (HoA), base (HoB) and neutral (HoN), weakly hydrophobic acid (WHoA) and hydrophilic matter (HiM) by DAX-8 and XAD-4 resins. The experiment results showed that the removal of organic matter was significantly improved with ozonation in advance. In sum, the integrated process removed 73% of dissolved organic carbon (DOC), 87% of UV₂₅₄, 77% of trihalomethane (THMs) precursors, 76% of haloacetic acid (HAAs) precursors, 83%of trichloracetic aldehyde (CH) precursor, 77% of dichloroacetonitrile (DCAN) precursor, 51% of trichloroacetonitrile (TCAN) precursor, 96% of 1,1,1-trichloroacetone (TCP) precursor and 63% of trichloronitromethane (TCNM) precursor. Hydrophobic organic matter was converted into hydrophilic organic matter during ozonation/UF, while the organic matter with molecular weight of 1000–3000 Da was remarkably decreased and converted into lower molecular weight organic matter ranged from 200–500 Da. DOC had a close linear relationship with the formation potential of DBPs.     

Effect of effluent organic matter on ozonation of bezafibrate

The influence of three effluent organic matter (EfOM) model compounds, humic acid (HA), bovine serum albumin (BSA), and sodium alginate (AGS), on the ozonation of bezafibrate (BF), a typical pharmaceutical and personal care product (PPCP), was investigated. The results show that ozonation efficiently removed BF from aqueous solution with removal efficiencies>95% within 8 min for all conditions. The reaction rate of BF decreased with increasing model compounds concentrations and the influence was more pronounced for HA and BSA, while less pronounced for AGS. Although BF concentration was significantly reduced, the degree of mineralization achieved was only approximately 11%. The addition of HA and BSA improved the mineralization of the solution, while the influence of AGS was minor. The acute toxicity of BF solution during ozonation was determined using the Luminescent bacteria test, and the toxicity exhibited an initial increase and a successive reduction. An overall decreased acute toxicity was observed with an increase of HA. The presence of BSA increased the formation rate of toxicity intermediates and resulted in inhibition peak forward.     

臭氧-曝气生物滤池深度处理垃圾焚烧渗滤液可行性研究

研究了臭氧-曝气生物滤池(BAF)代替纳滤和反渗透深度处理垃圾焚烧渗滤液达标排放的技术可行性.半间歇臭氧氧化试验表明,实验用水的可生化性随着氧化时间的增加而增加,色度及UV254, 15min内去除率分别达91%和64%;氧化时间为45min时COD去除率59%, 45min后COD去除较慢, 120min时去除率77%.确定臭氧氧化时间为1h,在同样臭氧浓度与流量下进行了臭氧-BAF处理垃圾焚烧渗滤液的连续实验.结果发现,此工艺对COD、色度和UV254的去除率分别可达75%,95%和90%,其中2/3运行时间里COD低于排放标准100 mg/L.其中出水色度可稳定保持在40度以下达标排放.经过进一步优化,臭氧-BAF有望用于垃圾焚烧渗滤液的达标处理.GC-MS检测表明烷烃,芳香族化合物及含氮杂环化合物是试验用水的主要污染物,臭氧-BAF能够有效去除后两类化合物,但难以去除烷烃.     

羟基化锌催化臭氧氧化去除水中痕量磺胺嘧啶

以实验室制备的羟基化锌(ZnOOH)为催化剂,研究了其催化臭氧化去除水中痕量磺胺嘧啶(SD)的效能,通过研究叔丁醇对催化效果的影响,推断了催化反应机理,探讨了臭氧投加量、水质因素、催化剂投加量和使用次数对催化性能的影响因素.结果表明,ZnOOH对臭氧氧化水中的SD有较强的催化活性.催化剂表面结合的羟基基团有利于催化反应.在优化的实验条件下,蒸馏水中反应30min时,催化臭氧化比单独臭氧化对SD的去除率提高了47.7%.催化过程遵循自由基反应机理,SD的去除效果随催化剂投加量的增加而提高,催化剂在重复使用后催化效果基本不变,水中的氯离子可以明显降低催化剂的活性,偏碱性条件下,催化效果更佳.     

臭氧催化氧化控制溴酸盐生成效能与机理

比较了单独臭氧氧化和金属氧化物存在下臭氧催化氧化过程中溴酸盐的生成规律,探讨了催化剂投量、溴离子浓度、水的pH值、反应温度等对臭氧催化氧化控制溴酸盐生成的影响规律及在催化剂存在下控制溴酸盐生成的机理.结果表明,催化剂投量从0 mg/L增加到250 mg/L,能减少溴酸盐生成量85.1%;当溴离子浓度为0.5、1.0、2.0 mg/L时,臭氧催化氧化分别能减少溴酸盐生成量69.2%、83.5%和15.2%,溴离子浓度变化对催化作用的影响无明显规律;pH值升高会降低催化作用的效果;反应温度在5～25℃之间时,臭氧催化氧化能降低43%～59%的溴酸根生成量(溴离子浓度1.5 mg/L),反应温度变化不影响催化效果.催化剂通过抑制臭氧对次溴酸的氧化减少了溴酸根的生成量.催化剂表面的某些基团与硫酸根络合会削弱臭氧催化氧化控制溴酸根生成的能力,因此,利用催化剂控制溴酸盐的机理与催化剂表面性质密切相关.     

催化臭氧化降解技术中的两个问题

探讨了有机物特性及中间产物H2O2在催化臭氧化中的作用。结果表明,有机物在自由基链反应过程中的特性直接影响催化臭氧化的降解效率。当目标有机物是对链反应具有促进作用的甲酸时,自由基引发反应可以明显提高甲酸的臭氧化效率。当目标有机物是对自由基链反应具有抑制剂作用的乙酸时,O3和Fe^2＋/O3对乙酸有着相似的降解效率。以上结果表明,自由基引发反应并不是臭氧化降解效率提高的充分条件。另外,当臭氧化过程有H2O2产生时,必须考虑类Fenton反应对臭氧化效率的影响。