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。     

附着式塔式起重机附着间距及悬臂高度的研究

附着式塔式起重机广泛应用于高层建筑施工中,现行塔式起重机设计规范GB 13752—1992并没有对附着式塔式起重机附着间距作出相关规定。运用等效惯性矩法建立了附着式塔式起重机的等效有限元模型,以塔身稳定性和静刚度为约束条件,分析了附着间距对塔式起重机塔身最大悬臂高度及塔身与塔臂连接处水平位移的影响,对施工过程中附着架附着间距及悬臂高度给出合理建议。     

电-多相臭氧催化工艺深度处理焦化废水

本文采用新型电-多相臭氧催化（E-catazone）工艺深度处理焦化废水生化二级出水,开展工艺可行性研究.通过与O₃/TiO₂纳米花（TiO_2-NF）与O₃/TiO_2-NF/H₂O₂及单独电化学氧化工艺相比较,对E-catazone工艺技术优势及氧化机理进行探究.结果表明：在相同条件下（O₃浓度84mg/L）,电-多相臭氧催化获得的COD和TOC的去除率（分别为67.9%,50.0%）显著优于O₃/TiO_2-NF获得的去除率（25.8%,20.9%）,即便在O₃/TiO_2-NF体系中投加5g/L的H₂O₂以促进臭氧均相催化效果,但COD和TOC去除率也仅分别提高到63.6%,43.6%.     

载铁ACF/Ni阴极电化学体系除藻效能与机制

采用化学浸渍法将Fe@Fe₂O₃纳米线负载在活性炭纤维/泡沫镍上组成Fe@Fe₂O₃/ACF/Ni复合阴极,以钛基铂（Pt/Ti）为阳极,考察载铁量、初始pH值和不同电化学体系对除藻效果的影响,探究无供氧条件下Pt/Ti-Fe@Fe₂O₃/ACF/Ni电化学体系除藻的效能;基于·OH间接检测、铁离子浓度、H₂O₂浓度及pH值的分析和·O₂^-的检测研究Pt/Ti-Fe@Fe₂O₃/ACF/Ni中性电化学体系反应机制.结果表明,当制备阴极阶段投加0.03g FeCl₃×6H₂O,初始藻浓度为0.7×10⁹~0.8×10⁹个/L,电流密度为75mA/cm²,初始pH6.2时,电解60min,该体系除藻率可达到92.3%.在Pt/Ti-Fe@Fe₂O₃/ACF/Ni电化学体系中,Fe@Fe₂O₃/ACF/Ni阴极可通过电化学反应产生大量·OH和·O₂^-,使藻细胞破裂死亡;该体系除藻的主要机理是非均相电Fenton反应.     

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.     

The production of formaldehyde and hydroxyacetone in methacrolein photooxidation: New insights into mechanism and effects of water vapor

Methacrolein(MACR) is an abundant multifunctional carbonyl compound with high reactivity in the atmosphere. In this study, we investigated the hydroxyl radical initiated oxidation of MACR at various NO/MACR ratios(0 to 4.04) and relative humidities( 3% to80%) using a flow tube. Meanwhile, a box model based on the Master Chemical Mechanism was performed to test our current understanding of the mechanism. In contrast to the reasonable predictions for hydroxyacetone production, the modeled yields of formaldehyde(HCHO) were twice higher than the experimental results. The discrepancy was ascribed to the existence of unconsidered non-HCHO forming channels in the chemistry of CH_3-UC(=CH_2)OO, which account for approx. 50%. In addition, the production of hydroxyacetone and HCHO were affected by water vapor as well as the initial NO/MACR ratio. The yields of HCHO were higher under humid conditions than that under dry condition. The yields of hydroxyacetone were higher under humid conditions at low-NO_x level, while lower at high-NOxlevel. The reasonable explanation for the lower hydroxyacetone yield under humid conditions at high-NO_x level is that water vapor promotes the production of Umethacrolein nitrate in the reaction of HOCH_2 C(CH_3)(OO)CHO with NO due to the peroxy radical-water complex formation, which was evidenced by calculational results. And the minimum equilibrium constant of this water complex formation was estimated to be 1.89 × 10~(-18) cm~3/molecule. These results provide new insights into the MACR oxidation mechanism and the effects of water vapor.