La-Co-Fe-Cu/HZSM-5在尾气碳颗粒燃烧中的催化性能

采用柠檬酸络合低温浸渍法制备分子筛负载钙钛矿型复合氧化物催化剂。采用XRD、SEM和H2-TPR等手段对催化剂性能进行表征,并在微型固定床反应器中对催化剂进行活性评价。结果表明,在钙钛矿型复合氧化物中进行B位离子掺杂,可以改善催化活性,碳颗粒燃烧温度降低。在20%LaCoO3/HZSM-5催化剂中用铁离子部分取代钴离子可以改善碳颗粒的燃烧性能,取代量增加碳颗粒燃烧温度降低,但是生成CO2的选择性也降低,以20%LaCo0.2Fe0.8O3/HZSM-5为催化剂,Tig、Tm和Tf分别为256℃、399℃和403℃,但生成CO2的选择性只有72.5%。在20%LaCo1-xFexO3/HZSM-5中的钙钛矿型复合氧化物B位离子中加入铜离子后,在碳颗粒燃烧反应中生成CO2的选择性得到明显改善,Sco2提高10个单位以上。以20%LaCo0.2Fe0.6Cu0.2O3/HZSM-5为催化剂,在碳颗粒燃烧反应中生成CO2的选择性可以达到94.7%,Tig、Tm和Tf分别为242℃、427℃和445℃。     

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.     

Genotoxicity removal of reclaimed water during ozonation

Genotoxicity in wastewater and reclaimed water now is gaining increased attention because of genotoxins' potential damage to the ecosystem and human health. The effect of ozonation on genotoxicity in reclaimed water was investigated. It was found that ozonation decreased the genotoxicy dramatically in three tertiary treatment plants. In the further batch ozonation experiment in laboratory,secondary effluent sample used exhibited the genotoxicity of(41.1 ± 4.1) μg 4NQO/L. Ozonation with a dose of 10 mg O3/L completely removed the genotoxicity in secondary effluent. However,after ozonation, the dissolved organic carbonvalue of the sample didn't change much but the specific ultraviolet absorbance(SUVA) value dropped sharply. With the help of Fourier transform infrared spectroscopy, ozonation was found to change chemical aliphatic carbon and C–O of the dissolved arganic matter, which might be the reason of the significant decreases of SUVA and genotoxicity.     

锂电池正极材料Li2FeS2的充放电机理与热稳定性

随着移动电子设备的飞速发展,锂电池作为新型的能源载体也取得了巨大的进步。与嵌入式氧化物正极材料相比,Li2FeS2不仅具有理想的循环性能,而且其理论容量达到400mAh／g,约为嵌入式氧化物正极材料的2倍。因此,本文从晶体结构、电化学性能、充放电机制、充放电过程中的离子电导率变化以及热稳定性等方面对Li2FeS2正极材料进行了详细的阐述。     

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.     

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.     

Bi-PbO2电极电化学氧化去除模拟废水中氨氮的研究

本实验采用钛网作为基体,利用电沉积方法制备了纯PbO2电极和Bi-PbO2电极,通过SEM、XRD、XPS对电极的表面形态进行了表征,利用循环伏安法对Bi-PbO2电极电化学特性进行了研究.同时,以氨氮模拟废水作为研究对象,考察了Bi-PbO2电极的电催化活性,探讨了氨氮电化学氧化降解机理.结果表明,Bi-PbO2电极的形态表征、电催化活性明显高于纯PbO2电极,氨氮的去除效率随电流密度的增加而提高,碱性条件下氨氮的去除效果明显好于酸性条件,适量浓度的Cl-的引入在碱性条件下提高了氨氮的去除效果.当氨氮初始浓度为50 mg·L-1、电流密度为40 mA·cm-2、pH=12、Cl-浓度为600 mg·L-1时,电解120 min后,氨氮100%去除.氨氮的降解机理为:体系中无添加氯离子,酸性条件下氨氮主要是通过间接氧化去除,碱性条件下通过直接电氧化和间接氧化共同完成;体系中添加氯离子,氨氮的去除主要是通过溶液中生成的有效氯间接氧化去除.     

粉煤灰负载Fe2O3脱除气态单质汞的试验研究

在固定床反应器中研究了利用燃煤电厂固废粉煤灰(FA)负载Fe2O3所制备的Fe2O3/FA催化剂对气态Hg0的脱除情况,发现Fe2O3/FA具有较高的脱除Hg0的能力.同时,考察了Fe2O3负载量、温度、空速、Hg0浓度、烟气成分等对Fe2O3/FA脱除Hg0的影响.结果表明,Fe2O3/FA对Hg0的脱除能力随Fe2O3负载量(1%~10%)的增加和温度(120~200℃)的升高而增强;Fe2O3/FA在较低的空速和Hg0浓度条件下表现出了更高的脱除Hg0的活性;HCl和O2促进了Fe2O3/FA对Hg0的脱除,而SO2和H2O抑制了Fe2O3/FA对Hg0的脱除.逐级化学提取实验结果证实,Fe2O3将Hg0氧化为Hg2+的化合物并吸附在FA上,这是Fe2O3/FA具有较高的脱除Hg0能力的原因.     

电化学法处理工业废水的现状与发展研究

随着工业的快速发展,如何对工业废水进行高效处理是我们需要解决的问题。电化学方法反应装置简单,反应效率高,不会产生二次污染。对中国工业废水目前常用的电化学处理技术的进展和应用进行了综述,包括电化学氧化、电化学还原、电絮凝、电渗析等内容,对国内外的研究成果的总结可知,电化学法对工业废水的处理效率较高,有一定的应用前景。同时对电化学法将来的重点研究方向提出了展望。