Catalytic bubble-free hydrogenation reduction of azo dye by porous membranes loaded with palladium nanoparticles

Catalytic bubble-free hydrogenation reduction of azo dye by porous membranes loaded with palladium （Pd） nanoparticles was studied for the first time. The effects of Pd loading, dye concentration and reuse repetitions of membranes were investigated. In reduction, the dye concentration decreased whereas the pH rose gradually. An optimal Pd loading was found. The catalytic membranes were able to be reused more than 3 times.     

Reaction mechanism and metal ion transformation in photocatalytic ozonation of phenol and oxalic acid with Ag+/TiO2

Photocatalytic ozonation of phenol and oxalic acid （OA） was conducted with a Ag^＋/TiO2 catalyst and different pathways were found for the degradation of different compounds. Ag^＋ greatly promoted the photocatalytic degradation of contaminants due to its role as an electron scavenger. It also accelerated the removal rate of OA in ozonation and the simultaneous process for its complex reaction with oxalate. Phenol could be degraded both in direct ozonation and photolysis, but the TOC removal rates were much higher in the simultaneous processes due to the oxidation of hydroxyl radicals resulting from synergetic effects. The sequence of photo-illumination and ozone exposure in the combined process showed quite different effects in phenol degradation and TOC removal. The synergetic effects in different combined processes were found to be highly related to the properties of the target pollutants. The color change of the solution and TEM result confirmed that Ag＋ was easily reduced and deposited on the surface of Tit2 under photo-illumination, and dissolved again into solution in the presence of ozone. This simple cycle of enrichment and distribution of Ag^＋ can greatly benefit the design of advanced oxidation processes, in which the sequences of ozone and photo-illumination can be varied according to the needs for catalyst recycling and the different properties of pollutants.     

Effects of metal and acidic sites on the reaction by-products of butyl acetate oxidation over palladium-based catalysts

Catalytic oxidation is widely used in pollution control technology to remove volatile organic compounds. In this study, Pd/ZSM-5 catalysts with different Pd contents and acidic sites were prepared via the impregnation method. All the catalysts were characterized by means of N2 adsorption- desorption, X-ray fluorescence （XRF）, HE temperature programmed reduction （H2-TPR）, and NH3 temperature programmed desorption （NH3-TPD）. Their catalytic performance was investigated in the oxidation of butyl acetate experiments. The by-products of the reaction were collected in thermal desorption tubes and identified by gas chromatography/mass spectrometry. It was found that the increase of Pd content slightly changed the catalytic activity of butyl acetate oxidation according to the yield of CO2 achieved at 90%, but decreased the cracking by-products, whereas the enhancement of strong acidity over Pd-based catalysts enriched the by-product species. The butyl acetate oxidation process involves a series of reaction steps including protolysis, dehydrogenation, dehydration, cracking, and isomerization. Generally, butyl acetate was cracked to acetic acid and 2- methylpropene and the latter was an intermediate of the other by-products, and the oxidation routes of typical by-products were proposed. Trace amounts of 3-methylpentane, hexane, 2-methylpentane, pentane, and 2-methylbutane originated from iso4merization and protolysis reactions.     

Mo-modified Pd/Al2O3 catalysts for benzene catalytic combustion

Mo-modified Pd/Al2O3catalysts were prepared by an impregnation method and tested for the catalytic combustion of benzene. The catalysts were characterized by N2 isothermal adsorption, X-ray diffraction（XRD）, X-ray photoelectron spectroscopy（XPS）, temperatureprogrammed desorption of NH3（NH3-TPD）, H2temperature-programmed reduction（H2-TPR）, and high-angle annular dark-field scanning transmission electron microscopy（HAADF-STEM）. The results showed that the addition of Mo effectively improved the activity and stability of the Pd/Al2O3catalyst by increasing the dispersion of Pd active components, changing the partial oxidation state of palladium and increasing the oxygen species concentration on the surface of catalyst. In the case of the Pd-Mo/Al2O3catalyst,benzene conversion of 90% was obtained at temperatures as low as 190°C, which was 45°C lower than that for similar performance with the Pd/Al2O3catalyst. Moreover, the 1.0% Pd-5% Mo/Al2O3catalyst was more active than the 2.0% Pd/Al2O3catalyst. It was concluded that Pd and Mo have a synergistic effect in benzene catalytic combustion.     

FBC-DPF在柴油机颗粒物控制中的应用研究

目前针对加装FBC-DPF(燃油添加剂-柴油机颗粒捕集器)后的柴油机放特性研究较少,并且缺乏FBC-DPF对颗粒物中PAHs排放量的影响效果研究.为全面评估加装FBC-DPF后柴油机颗粒物排放特性和FBC-DPF对柴油机尾气中的颗粒物排放污染控制效果,在发动机台架上对装有FBC-DPF的重型柴油机进行了颗粒物排放特性试验.利用电子低压撞击仪(ELPI)测量加装FBC-DPF前、后柴油机颗粒物的数浓度与粒径分布,用玻璃纤维滤膜采集加装FBC-DPF前、后尾气中的固相PAHs,利用色谱质谱联用仪对加装FBC-DPF前、后尾气中的固相PAHs进行定量分析.结果表明:①加装FBC-DPF后柴油机排放的颗粒物数浓度大幅降低,FBC-DPF对尾气中颗粒物的捕集效率平均值在95%左右;②加装FBC-DPF后柴油机固相PAHs总比排放量有所降低,在大负荷区域降幅在25.0%～88.0%之间;③加装FBC-DPF前的颗粒物中位直径为30～89 nm,而加装FBC-DPF后的颗粒物中位直径为41～98 nm,平均增幅为38.2%.对于国Ⅳ及未来国Ⅴ柴油机排放法规,FBC-DPF是解决柴油机颗粒物排放的有效手段;此外,FBC-DPF可以大幅降低柴油机尾气中的有毒成分,并且能够适应高含硫量的燃油环境.     

催化臭氧氧化降解水溶液中亚甲基蓝的动力学研究

以废啤酒酵母为原材料、采用吸附-活化法制备得到负载过渡金属铁的活性炭(Fe/AC),对Fe/AC吸附亚甲基蓝(MB)性能和催化臭氧氧化MB效果进行了评价。Fe/AC对MB的吸附符合Langmuir等温吸附模型;20℃,pH=7的条件下,Fe/AC对MB的最大吸附量达到107.43 mg/g。吸附MB达到平衡的Fe/AC催化臭氧氧化降解水中MB,30 min内MB的转化率达到99%以上,5 h后总有机碳(TOC)的降解率达到70%。结合Fe/AC吸附MB特性和催化臭氧氧化MB行为,将Langmuir等温吸附模型分别与近似一级和二级反应动力学模型进行耦合,构建了Langmuir-Kinetic近似一级和近似二级耦合模型,均能较好地拟合MB转化率的动力学数据,但对体系的TOC去除率动力学数据的拟合度较低。     

MIL-101(Cr~(3+))可见光催化氧化降解甲基橙的研究

以金属有机多孔材料MIL-101(Cr3+)为非均相催化剂,过硫酸钠(Na2S2O8)为类Fenton体系的氧化剂,在可见光(300 W)下对甲基橙进行催化氧化降解研究。结果表明,MIL-101(Cr3+)在反应时间为120 min时对甲基橙降解率高达91.0%,且回收利用3次后仍表现出优异的降解性能(降解率达到81.0%)。同样条件下,把MIL-101(Cr3+)替换为TiO2或者不添加任何催化剂,甲基橙的降解率分别为25.6%和8.8%。采用紫外-可见漫反射光谱考察了常温下MIL-101(Cr3+)的禁带宽度大小,进一步证明其优异的光催化降解性能;同时还探讨了MIL-101(Cr3+)催化降解甲基橙的可能机理。     

活性炭催化过氧化氢去除荧光增白剂

研究了活性炭(activated carbon,AC)吸附、改性活性炭(activated carbon modified,ACM)吸附、过氧化氢(H2O2)氧化、AC催化H2O2等方法对水体中荧光增白剂VBL的处理效果,并通过自由基俘获剂叔丁醇、催化过程气体分析等探讨了AC催化H2O2分解VBL的机制.结果表明,经硝酸铁[Fe(NO3)3]改性过的ACM对VBL的吸附去除率高于未改性的AC.活性炭催化H2O2对VBL的去除效果明显,但未改性AC催化去除率高于ACM.60 min时,AC催化氧化去除率即可达到95%以上,而ACM仅为58%.叔丁醇的加入降低了AC和ACM催化氧化对VBL的去除率,表明AC催化H2O2氧化能促进H2O2形成羟基自由基(·OH)和原子氧参与反应.AC催化H2O2分解及释放气体分析表明,AC能催化H2O2形成氧气并放热,且ACM明显快于AC.结合催化H2O2去除VBL效率的结果分析,ACM催化反应时活性中间物(自由基和原子氧等)产生速率快于AC,活性中间物自身消耗形成氧气,而不是用于分解VBL.催化反应中活性中间产物的形成速率与反应物供给速率的不匹配可能是导致ACM催化效果弱于AC的重要原因.     

杭州灰霾天气超细颗粒浓度分布特征

利用快速迁移率粒径谱仪(FMPS)对杭州2013年12月6～11日连续灰霾天气和灰霾消退过程超细颗粒进行监测,分析颗粒物浓度变化和粒径谱分布特征及其与气象的相关性.结果表明,颗粒物日变化特征为夜晚数浓度较高,凌晨数浓度开始降低,08:00和18:00上下班高峰期出现一个小峰值,体现出明显的交通源峰值,表明交通排放对大气污染影响较大.灰霾天气下颗粒物最高数浓度达到8.0×104cm-3.粒径谱呈双峰分布,峰值粒径分别为15 nm和100 nm,粒径在100 nm附近的粒子占大多数,粒子以爱根核模态和积聚模态为主,平均数量中位径CMD(count medium diameter)为85.89 nm.而在灰霾消退过程,颗粒物数浓度降低,峰值粒径向小粒径演变,粒径在100 nm附近的粒子逐渐减少,核模态粒子增多,大于积聚模态,平均CMD为58.64 nm.气象因素中能见度和风力与数浓度主要呈负相关,相关系数R分别为-0.225和-0.229,相对湿度与数浓度正相关,相关系数R为0.271,冬季大气比较稳定,水平温度与数浓度的相关性较小.研究灰霾天气数浓度分布和气象因素的综合影响对其形成机制及控制有重要意义.     

双组分VOCs的催化氧化及动力学分析

考察了微波加热与管式炉加热下挥发性有机化合物(VOCs)甲苯与氯苯的催化氧化性能,并对双组分VOCs的反应动力学进行了分析.结果表明,VOCs的竞争吸附使得双组分中甲苯和氯苯的转化率比单组分降低3%~12%;微波的"热点效应"与"非热效应"使得VOCs转化效率明显优于管式炉加热,尤其是氯苯的转化率提高了31%~38%;微波加热降低了氧化反应温度和处理能耗.动力学分析表明,微波加热下甲苯和氯苯的反应活化能比管式炉加热下减少了2146 J·mol-1和1450J·mol-1,微波加热下氯苯的化学反应速率常数是管式炉加热的35倍,甲苯的反应速率常数提高了6倍.