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.     

Experimental study on filtration and continuous regeneration of a particulate filter system for heavy-duty diesel engines

This study investigated the filtration and continuous regeneration of a particulate filter system on an engine test bench, consisting of a diesel oxidation catalyst（DOC） and a catalyzed diesel particulate filter（CDPF）. Both the DOC and the CDPF led to a high conversion of NO to NO2 for continuous regeneration. The filtration efficiency on solid particle number（SPN） was close to100%. The post-CDPF particles were mainly in accumulation mode. The downstream SPN was sensitively influenced by the variation of the soot loading. This phenomenon provides a method for determining the balance point temperature by measuring the trend of SPN concentration.     

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.     

Pd/activated carbon sorbents for mid-temperature capture of mercury from coal-derived fuel gas

Higher concentrations of Hg can be emitted from coal pyrolysis or gasification than from coal combustion, especially elemental Hg. Highly efficient Hg removal technology from coal-derived fuel gas is thus of great importance. Based on the very excellent Hg removal ability of Pd and the high adsorption abilities of activated carbon（AC） for H2 S and Hg, a series of Pd/AC sorbents was prepared by using pore volume impregnation, and their performance in capturing Hg and H2 S from coal-derived fuel gas was investigated using a laboratory-scale fixed-bed reactor. The effects of loading amount, reaction temperature and reaction atmosphere on Hg removal from coal-derived fuel gas were studied. The sorbents were characterized by N2 adsorption, X-ray diffraction（XRD） and X-ray photoelectron spectroscopy（XPS）. The results indicated that the efficiency of Hg removal increased with the increasing of Pd loading amount, but the effective utilization rate of the active component Pd decreased significantly at the same time. High temperature had a negative influence on the Hg removal. The efficiency of Hg removal in the N2-H2S-H2-CO-Hg atmosphere（simulated coal gas） was higher than that in N2-H2S-Hg and N2-Hg atmospheres, which showed that H2 and CO, with their reducing capacity, could benefit promote the removal of Hg. The XPS results suggested that there were two different ways of capturing Hg over sorbents in N2-H2S-Hg and N2-Hg atmospheres.     

氧化沟工艺提标过程中总磷的技改分析

昆明第一污水处理厂氧化沟工艺至今已运行25 a,随着滇池水环境的恶化,昆明市于2010年将污水处理厂排放标准由原来的一级B标提升至一级A标,总磷的提标是整个提标过程中的重中之重。作者通过对除磷工艺的摸索,研究了除磷加药工艺优化运行的方式,确定了加药量的计算公式,为国内外其他水厂的提标技改,提供技术参考。     

上海市夏冬两季PM_(2.5)中碳组分污染特征及来源解析

2009年7月和2010年1月在上海市华东理工大学采样点采集PM2.5样品,应用热/光碳分析仪对样品中的有机碳(OC)和元素碳(EC)进行了测定,并计算得到了二次有机碳(SOC)、char-EC和soot-EC的质量浓度。结果显示:采样期间PM2.5、OC、EC、SOC、char-EC、soot-EC夏季平均浓度分别为(58.87±20.04)、(11.37±4.12)、(3.68±1.27)、(4.37±2.86)、(3.00±1.24)和(0.68±0.30)μg/m3;冬季平均浓度分别为(142.31±45.47)、(16.01±4.43)、(5.53±2.36)、(5.67±2.92)、(5.11±2.35)和(0.42±0.17)μg/m3,除soot-EC外,均呈现夏季低、冬季高的特点。在不同空气质量下,OC、EC和char-EC的质量浓度具有明显差异,且三者均与能见度、平均风速呈显著负相关。夏冬两季soot-EC、char-EC、SOC和POC占TC的百分含量相差不大,其中POC/TC值最高,soot-EC/TC值最低。夏季SOC/TC的比值高于冬季,可能由于气温高有利于发生光化学反应。对8个碳组分进行主成分分析,结果显示,燃煤、生物质燃烧、汽油和柴油车排放对PM2.5中碳组分的贡献显著,并且可能受燃煤和汽油车排放的影响最大。     

铁碳微电解法预处理聚氯乙烯(PVC)离心母液废水

采用铁碳微电解法对聚氯乙烯(PVC)离心母液废水进行预处理。分别考察反应时间、铁粉投加量、Fe/C(质量比)、pH值及曝气速率对母液废水中的COD和聚乙烯醇(PVA)去除率的影响,并在此基础上通过正交实验确定了废水COD的最佳处理条件。结果表明,最佳处理条件为:反应时间为4 h、铁粉投加量为30 g/L、Fe/C为1:2、pH值为2、曝气速率为0.8 L/min。在该条件下,废水中COD、PVA和TOC的平均去除率分别为(67%±2)%、(98%±1)%和(55%±3)%,废水的BOD/COD值从0.3提高到0.5,可生化性得到了显著提高。同时,废水中的NH3-N、浊度也在很大程度上得到了去除,出水中总铁含量也很低。     

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。     

维生素B_(12)催化降解三氯乙烯的碳氯同位素分馏机理

挥发性氯代烃(volatile chlorinated hydrocarbons,VCHs)是地下水中一类重要的有机污染物,维生素B12是催化VCHs还原脱氯的高效催化剂。该文选取VCHs中典型的污染物三氯乙烯(TCE)作为研究对象,以Ti(Ⅲ)为电子供体,探索不同pH条件下,维生素B12催化TCE还原脱氯过程中碳、氯同位素分馏机理。反应溶液初始pH为7.5~9.0时,其表观一级动力学反应速率系数k值为0.06~0.15 h-1;碳同位素富集系数εC为-1.8‰~-2.4‰,氯同位素富集系数εCl均值为-1.5‰。这说明,pH增大,Ti(Ⅲ)还原势能增大,反应的速率提高;还原脱氯不同反应途径所占份额改变,碳、氯同位素分馏程度变化。碳、氯的单体同位素分析(CSIA)技术可以用来评价地下水氯代烃污染降解程度和效率,结合分析2种元素能够提高污染物修复评价的准确性,同位素富集系数的稳定性研究可为其不同环境条件下的精确评价提供理论依据。