模拟环境条件下δ-MnO_2氧化As(Ⅲ)的搅拌流动动力学特征

采用搅拌流动法研究了酸性水钠锰矿及水羟锰矿2种δ-MnO2矿物氧化As(Ⅲ)的动力学过程,构建了可用于多相体系的搅拌-流动氧化还原反应动力学模型.经过As吸附量的校正后,该模型对酸性水钠锰矿及水羟锰矿氧化As(Ⅲ)动力学数据拟合度分别为0.980和0.951,模型拟合得到pH 7时2种矿物单位比表面上氧化As(Ⅲ)的初始反应速率常数k分别为0.131,0.014min-1·m-2.相比而言,该速率常数明显高于批量法得到的表观速率常数kobs,0.021,0.001min-1?m-2更接近真实的化学动力学参数.搅拌流动法与批量法得到的不同矿物的速率常数大小趋势一致,即尽管酸性水钠锰矿对As(Ⅲ)的氧化率低于水羟锰矿,单位比表面上酸性水钠锰矿氧化As(Ⅲ)初始反应速率却远高于水羟锰矿.反应过程分析表明,反应初始阶段,As(Ⅲ)的吸附为主要限速步骤;而随着反应的进行,矿物表面反应位点逐渐钝化或减少,反应位点数量成为限速步骤.     

催化还原法净化处理氮氧化物的工程实例

针对不锈钢产品酸洗处理过程中产生的氮氧化物浓度高、对大气污染的影响大、且难于净化治理等特性,在上海某不锈钢项目中设计了一套酸雾净化系统。该设计解决了酸洗中产生的氮氧化物难以净化的问题,提升了氮氧化物处理技术,它将成为不锈钢酸洗行业中氮氧化物净化处理技术的发展方向。     

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.     

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.     

Fast increasing of surface ozone concentrations in Pearl River Delta characterized by a regional air quality monitoring network during 2006-2011

Based on the observation by a Regional Air Quality Monitoring Network including 16 monitoring stations, temporal and spatial variations of ozone(O3), NO2and total oxidant(Ox) were analyzed by both linear regression and cluster analysis. A fast increase of regional O3concentrations of 0.86 ppbV/yr was found for the annual averaged values from 2006 to 2011 in Guangdong, China. Such fast O3increase is accompanied by a correspondingly fast NOx reduction as indicated by a fast NO2 reduction rate of 0.61 ppbV/yr. Based on a cluster analysis, the monitoring stations were classified into two major categories – rural stations(non-urban) and suburban/urban stations. The O3concentrations at rural stations were relatively conserved while those at suburban/urban stations showed a fast increase rate of 2.0 ppbV/yr accompanied by a NO2 reduction rate of 1.2 ppbV/yr. Moreover, a rapid increase of the averaged O3 concentrations in springtime(13%/yr referred to 2006 level) was observed, which may result from the increase of solar duration, reduction of precipitation in Guangdong and transport from Eastern Central China. Application of smog production algorithm showed that the photochemical O3production is mainly volatile organic compounds(VOC)-controlled. However, the photochemical O3production is sensitive to both NOx and VOC for O3pollution episode. Accordingly, it is expected that a combined NOx and VOC reduction will be helpful for the reduction of the O3 pollution episodes in Pearl River Delta while stringent VOC emission control is in general required for the regional O3 pollution control.     

Arsenic removal from groundwater by acclimated sludge under autohydrogenotrophic conditions

Arsenic in the environment is attracting increasing attention due to its chronic health effects. Although arsenite(As(III)) is generally more mobile and more toxic than arsenate(As(V)), reducing As(V) to As(III) may still be a means for decontamination, because As(III) can be removed from solution by precipitation with sulfide or by adsorption or complexation with other metal sulfides. The performance of As(V) bio-reduction under autohydrogenotrophic conditions was investigated with batch experiments. The results showed that As(V) reduction was a biochemical process while both acclimated sludge and hydrogen were essential. Most of the reduced arsenic remained in a soluble form, although 20% was removed with no addition of sulfate, while 82% was removed when sulfate was reduced to sulfide. The results demonstrated that the reduced arsenic was re-sequestered in the precipitates, probably as arsenic sulfides. Kinetic analysis showed that pseudo first-order kinetics described the bio-reduction process better than pseudo second-order. In particular, the influences of pH and temperature on As(V) reduction by acclimated sludge under autohydrogenotrophic conditions and total soluble As removal were examined. The reduction process was highly sensitive to both pH and temperature, with the optimum ranges of pH 6.5–7.0 and 30–40°C respectively. Furthermore, Arrhenius modeling results for the temperature effect indicated that the As(V) reduction trend was systematic. Total soluble As removal was consistent with the trend of As(V) reduction.     

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。     

污泥浓度对生物海绵铁体系中Fe~0的腐蚀影响研究

通过单因素实验,研究了不同活性污泥浓度对海绵铁体系中铁离子浓度变化的影响。结果表明:随着反应的进行,反应器泥水混合液中Fe(Ⅱ)和TFe浓度在不断升高,与活性污泥浓度成正相关性;pH值也呈现升高趋势,活性污泥浓度越高,pH值变化的越小;试验还发现海绵铁释铁过程包括生物腐蚀和化学腐蚀,生物腐蚀的影响要远远大于化学腐蚀。     

V2O5/TiO2催化剂脱除NO的研究

采用了等体积浸渍法制备二氧化钛负载钒氧化物催化剂（V2O5/TiO2）,研究了V2O5负载量、反应温度、烟气流量、氨氮比以及运行时间各因素对NH3选择性催化还原NO反应（SCR）效率的影响.研究结果表明：经过500℃温度下煅烧,烟气流量为200ml/min,负载量为7wt％的V2O5/TiO2催化剂,在400℃温度下反应,NO脱除率可达70.5％.