Characterizing the optimal operation of photocatalytic degradation of BDE-209 by nano-sized TiO2

Brominated flame retardants have been widely used in industry. There is a rapid growing public concern for their availabilities in the environment. Advanced oxidation process (AOP) is a promising and efficient technology which may be used to remove emerging chemicals such as brominated flame retardants. This project aims at investigating optimal operational conditions for the removal of BDE-209 using nano-scaled titanium(IV) oxide. The residual PBDE congeners after photocatalytical degradation of BDE-209 by TiO₂ were analysed by gas chromatography-mass spectrometry (GC-MS). It was found that the degradability of BDE-209 by TiO₂ was attributed to its photocatalytic activity but not the small size of the particles. The half-life of removing BDE-209 by TiO₂ was 3.05 days under visible light. Tetra- and penta-BDEs were the major degraded products of BDE-209. Optimum conditions for photocatalytical degradation of BDE-209 was found to be at pH 12 (93% ± 1%), 5, 10, 20 mg/L (93.0% ± 1.70%, 91.6% ± 3.21%, 91.9% ± 0.952%, respectively), respectively of humic acid and in the form of anatase/rutile TiO₂ (82% ± 3%). Hence, the efficiency of removing BDE-209 can be maximized while being cost effective at the said operating conditions.     

Fenton法氧化降解聚乙烯醇的机制

为深入了解Fenton法氧化降解聚乙烯醇（PVA）的机制,通过考察反应过程中COD、BOD5、总有机碳及pH等随反应时间的变化,研究了聚乙烯醇Fenton氧化降解过程的特点,结果表明,当PVA被Fenton试剂氧化时,可生成大量CO2,同时生成酸性中间产物。进一步分析认为,当Fenton试剂中H2O2不足景时PVA氧化的中间产物以醛为主,而当H2O2足量时醛会被继续氧化生成有机酸,最终COD去除率达到80％。     

诺氟沙星对芽期玉米的毒性和氧化损伤研究

畜禽养殖废弃物的农田处置,使大量抗生素进入环境,从而对环境生物产生潜在危害.为了研究诺氟沙星(norfloxacin,Nor)对玉米发芽和幼苗生长的影响,采用水培发芽实验,测定了不同浓度下,诺氟沙星对玉米种子的发芽率和玉米幼苗对诺氟沙星的吸收与传输的影响;另外还研究了诺氟沙星对玉米幼苗生物量、自由基水平、丙二醛(MDA)含量、抗氧化酶活性的影响.结果显示,诺氟沙星能被玉米根吸收并传输到地上部分.0.5mg·L-1～50mg·L-1的诺氟沙星暴露均不影响玉米的发芽率.当诺氟沙星浓度大于1mg·L-1时,幼苗的生长受到抑制,其敏感指标依次为根重>根长>芽长>芽重.诺氟沙星暴露使玉米根、芽中MDA含量明显增加,玉米根中谷胱甘肽硫转移酶(GST),过氧化物酶(POD),超氧化物歧化酶(SOD)和过氧化氢酶(CAT)等抗氧化酶的活度有显著改变,这表明诺氟沙星暴露能够引起玉米体内的氧化损伤.用电子自旋共振结合二级自由基自旋捕获技术测定了玉米根中自由基水平,发现诺氟沙星能够引起玉米根中大量羟基自由基的产生,为诺氟沙星引起玉米幼苗的氧化损伤提供了直接的证据.     

Degradation of azo dyes in water by Electro-Fenton process

The degradation of the azo dyes azobenzene, p-methyl red and methyl orange in aqueous solution at room temperature has been studied by an advanced electrochemical oxidation process (AEOPs) under potential-controlled electrolysis conditions, using a Pt anode and a carbon felt cathode. The electrochemical production of Fenton's reagent (H₂O₂, Fe²⁺) allows a controlled in situ generation of hydroxyl radicals (^·OH) by simultaneous reduction of dioxygen and ferrous ions on the carbon felt electrode. In turn, hydroxyl radicals react with azo dyes, thus leading to their mineralization into CO₂ and H₂O. The chemical composition of the azo dyes and their degradation products during electrolysis were monitored by high performance liquid chromatography (HPLC). The following degradation products were identified: hydroquinone, 1,4-benzoquinone, pyrocatechol, 4-nitrocatechol, 1,3,5-trihydroxynitrobenzene and p-nitrophenol. Degradation of the initial azo dyes was assessed by the measurement of the chemical oxygen demand (COD). Kinetic analysis of these data showed a pseudo-first order degradation reaction for all azo dyes. A pathway of degradation of azo dyes is proposed. Specifically, the degradation of dyes and intermediates proceeds by oxidation of azo bonds and aromatic ring by hydroxyl radicals. The results display the efficiency of the Electro-Fenton process to degrade organic matter. Electronic Publication     

水中羟基氧化铁催化臭氧分解和氧化痕量硝基苯的机理探讨

测定了木质颗粒活性炭(GAC)和负载在GAC上的羟基氧化铁(FeOOH)催化水中臭氧分解的速率常数并探讨了催化臭氧分解的途径.以水中几种氧化物表面羟基密度和表面零电荷pH值(pH_zpc)为表征氧化物表面性质的参数,考察了2个参数对催化臭氧氧化水中硝基苯的影响.GAC和负载在GAC上的FeOOH使水中臭氧一级分解速率常数分别提高了68%和108%,用叔丁醇捕获掉生成的羟基自由基后,前者的分解速率常数降低了9%,后者降低了20%.GAC在催化臭氧分解时主要起到吸附剂和还原剂的作用,FeOOH催化臭氧分解过程中促进了羟基自由基生成.氧化物表面羟基密度和催化臭氧氧化水中硝基苯的效果之间没有直接的关系,由氧化物的pH_zpc决定的表面电荷状态与催化氧化效果有关,表面接近电中性时对催化氧化硝基苯有利.高密度的表面羟基会使表面羟基之间形成较强的氢键,使催化作用减弱.     

氧活性粒子氧化NO生成HNO_3

采用强电离介质阻挡放电方法制取高浓度氧活性粒子(O+2、O3)并注入气体外排烟道中,实现O+2、O3氧化NO转化成资源酸(HNO3)的等离子化学反应。描述强电离放电的氧活性粒子产生器,讨论烟道中O+2、O3氧化NO成HNO3等离子体反应机制,分析回收酸液的NO-2、NO-3离子种类及浓度。考察强电离放电等离子体源的输入功率、水体积百分比、气体温度、气体流速对NOx氧化率的影响。氧化率为97.2%的最佳实验条件是:O+2浓度为1.38×1010个/cm3,O3浓度为210 mg/L,烟气温度为65℃,H2O体积浓度为5.6%,停留时间为0.94 s。     

Aerobic degradation of methyl tert-butyl ether by a Proteobacteria strain in a closed culture system

The contamination of methyl ten-butyl ether （MTBE） in underground waters has become a widely concerned problem all over the world. In this study, a novel dosed culture system with oxygen supplied by H2O2 was introduced for MTBE aerobic biodegradation. After 7 d, almost all MTBE was degraded by a pure culture, a member of β-Proteobacteria named as PMI, in a closed system with oxygen supply, while only 40% MTBE was degraded in one without oxygen supply. Dissolved oxygen （DO） levels of the broth in closed systems respectively with and without H2O2 were about 5-6 and 4 mg/L. Higher DO may improve the activity of monooxygemase, which is the key enzyme of metabolic pathway from MTBE to tert-butyl alcohol and finally to CO2, and may result in the increase of the degrading activity of PM1 cell. The purge and trap GC-MS result of the broth in closed systems showed that tea-butyl alcohol, isopronol and acetone were the main intermediate products.     

HAN基ECSP凝胶模型的构建与分子动力学模拟

目的 从微观分子的角度对硝酸羟胺(HAN)基电控固体推进剂(Electrically Controlled Solid Propellants,ECSP)的性能参数进行模拟与计算。方法 利用分子表面静电势(ESP)对HAN分子2种可能的构型进行优化和稳定性分析。通过真空非周期性分子动力学模拟得到聚乙烯醇(PVA)分子稳定构型,并以HAN基ECSP的主要成分按一定比例构建凝胶模型。基于RESP(Restrained Electrostatic Potential)电荷生成更准确的凝胶模型拓扑文件,并进行凝胶模型的分子动力学模拟、模型稳定分析以及模型参数计算。结果 凝胶模型总能量相对平均值的周期性波动不超过7%。由于三维PVA链的包裹,H2O分子的扩散系数被大幅削弱。氢键分析和径向分布函数表明氢键键长主要分布在0.282 6 nm附近,PVA与H2O间的氢键较少,H2O与HAN、H2O与H2O之间的氢键较多。模型密度为1.405 g/cm³,与实验值吻合度高。在283、293、303 K下,HAN基ECSP凝胶模型的拉伸模量依次降低,剪切模量先增后减。在15 K/600 ps冷却速率下,HAN基ECSP凝胶模型的拉伸模量和剪切模量均增大。结论 ECSP制备结束后,冷却过程中的环境温度不宜过高,否则容易造成ECSP力学性能的快速下降,快速冷却可以提高ECSP的力学性能。     

Experimental investigation on extinguishing performance of a novel nanocomposite for gaseous fires

A novel nanocomposite was synthesized by incorporating three different types of flame-retardants and its extinguishing performance was tested for gaseous fires. The nanocomposite consists of the inorganic magnesium hydroxide (MH) nanoparticles as the dominant component, the nitrogen-based melamine cyanurate (MCA), and the phosphorus-based ODOPB. The wet mixing, dry mixing, and ultrasonic agitation were employed in the preparation process to enhance the homogeneity of the nanocomposite. The prepared powders were characterized using a series of analytical instruments including X-ray diffraction (XRD), scanning electron microscopy (SEM), thermal gravity analyzer (TGA), and differential scanning calorimeter (DSC). The efficiency of various samples in extinguishing gaseous fires was investigated in a lab-scale extinguishing system. The fire extinguishing tests indicated that the nanocomposite is considerably more effective in fire extinguishing than other powders in terms of extinction time and agent mass consumed. The fire extinction time of nanocomposite was 45.2% shorter than that of commercial ABC-MAP powder. Furthermore, the consumed amount of nanocomposite was 63.2% less than that of commercial powder. In addition, the order of extinguishing mass concentrations was as follows: the novel nanocomposite (103.7 g/m³) < MH/MCA (148.1 g/m³) < MH/ODOPB (155.6 g/m³) < MH (170.4 g/m³) < commercial ABC powder (281.5 g/m³) < MCA/ODOPB (384.1 g/m³). The fire suppression mechanisms of the nanocomposite were also discussed. It was inferred that the extinguishing mechanism of nanocomposite comprised of simultaneous chemical and physical inhibition actions involving chemical inhibition action, cooling action, and asphyxiation action. This study provides a promising attempt to gain benefits from the striking features of nanotechnology and flame-retardants in extinguishing gaseous fires.     

乙醛废水处理的工程实例

溧阳市某化工厂以乙醇氧化法生产乙醛,该厂原有一套污水处理站,但系统出水难以达标.在改造过程中,利用原有污水处理系统,在调节池后新建多级内循环厌氧(MIC)反应器.该废水经过冷却到35～39℃、在调节池加营养和碱调节pH为7左右,MIC反应器进水CODCr约为3200mg/L、HRT为24h时,CODCr去除率为85%以上,MIC出水进入推流式好氧池,采用微孔曝气器曝气,HRT为36h,好氧出水CODCr小于100mg/L.该工艺运行稳定,为乙醛化工企业处理该废水提供一条新途径.