柴油车排气净化技术探讨

柴油车的排气污染受到了越来越多的关注。文章分别介绍了柴油机排气中氮氧化物的还原、碳烟颗粒物的氧化以及同时去除氮氧化物和颗粒物的各种催化净化技术及其最新研究进展,并对该研究方向存在的主要问题和应用前景进行了探讨。     

中低温NH3-SCR催化剂抗中毒研究进展

目前,中低温氨选择性催化氮氧化物还原(NH_3-SCR)技术瓶颈在于确保催化剂高活性、高选择性前提下兼有抗硫耐水和抗碱土金属中毒等能力。该文综述了近年来适于中低温环境下SCR催化剂的研究进展,包括催化活性提高和抗中毒能力改进,阐述了影响中低温SCR反应的4大影响因素:表面酸性、活性位点、形貌结构、氧化还原性。并提出从源头设计出发,利用对影响催化剂性能的4大因素,设计出高效的目标催化剂。     

铁矿石催化剂净化汽车排气的研究

以催化转化法控制和净化汽车排气的方法已在很多发达国家广泛采用,在我国也得到重视,现处于试验阶段.此法的关键是催化转化汽车排气中主要有害成分:一氧化碳(CO),碳氢化合物(HC),氮氧化物(NO_x)的催化剂的研制.对此人们进行了大量的研究,从催化剂的组成来看,发达国家目前普遍使用的是以铂、钯、铑、铼,钌等贵金属为活性组分的催化剂.这种催化剂活性高,稳定性好,寿命长,具有良好的净化效果,但由于贵金属价格昂贵,回收又很麻烦,且有些贵金属目前尚无法回收,因此使这些催化剂的广泛应用受到极大限制.由此人们开始了降低催化剂成本的研究,首先提     

氮氧化物与挥发性有机物协同催化净化进展

将垃圾焚烧、钢铁冶炼等典型行业烟气处理中的NH₃-SCR脱硝与VOCs净化模块耦合，发展多污染物协同控制理论和技术，协同催化净化NO_x与VOCs,不仅具有重要的科学意义，还具有重大的生态环境和经济效益。目前，NO_x与VOCs协同催化净化技术已在环境催化领域引起广泛关注，已报道相关研究主要聚焦于协同催化剂性能的考察，但该项研究仍处于初步探索阶段，尚未获得满足实际应用需求的高效协同催化剂，且相关反应机制有待深入考察。未来NO_x与VOCs协同净化催化剂技术的发展需解决3个关键难题：协同净化催化剂酸/氧化还原双核活性位的构建及调控、协同净化催化剂上酸/氧化还原双循环反应路径的理解、协同净化过程中催化剂的抗中毒能力提升。解决这些关键科学问题的第一步仍是设计并制备高活性、高稳定性、抗中毒的协同净化催化剂；然后探究催化剂的化学组成、结构特点和理化性质，解析催化剂双核活性位的微化学环境；进一步利用原位测试手段、表面反应技术以及理论模拟计算，解析催化剂结构与性能的构效关系，阐释催化净化过程高效协同机制和催化剂抗中毒机...     

新型汽车尾气净化催化剂的适应性能

研制了一种新的汽车尾气净化催化剂。其贵金属以Ｐｔ，Ｐｄ为主活性组分，载体以堇青石陶瓷蜂窝体涂复天然沸石粉，经测定，催化剂净化汽车尾气的活性，热稳定性，及抗铅，中毒等性能均较好，台架试验表明，催化箱对ＨＣ和ＣＯ均有很高的净化效果，ＨＣ转化率≥８５％，ＣＯ转化率≥９１％，并且该催化剂具有良好的冷起动性能。     

柴油车尾气排放污染控制技术综述

从柴油机机内净化技术和柴油车尾气后处理技术2方面综述了国际、国内柴油车尾气排放污染控制技术研究现状,重点论述了柴油车颗粒物捕集技术和氮氧化物选择性催化还原技术的研究思路和进展,并展望了相关技术今后发展的方向.     

改性贵金属催化剂催化还原脱除NO

含有NO的工业废气直接排放会严重污染空气,须对含有NO的工业废气进行净化处理.采用NH3为还原剂贵金属铂催化剂进行了低温还原NO脱除烟气中氮氧化物性能的研究.结果表明:实验室制备的贵金属铂催化剂具有高的低温活性和选择性催化还原脱除NO的性能,但该催化剂易被原料气中少量的硫化物(SO₂)中毒而影响其稳定性;用稀土元素La和Ce对贵金属铂催化剂进行改性,改性后贵金属铂催化剂的稳定性得到了大幅度提高,出口气体中氮氧化物浓度大幅度降低.本实验Pt∶La∶Ce最佳摩尔比为1∶3.78∶3.56.     

贵金属催化剂氧化去除炭黑颗粒研究现状

本文介绍了Pt、Ru、Au和Ag为活性元素的贵金属催化剂的研究现状,说明贵金属催化剂在柴油车尾气中颗粒物净化中具有一定的抗硫抗水性能,可在柴油车尾气的实际中应用而不存在催化剂中毒现象。     

复合氧化物催化剂用于汽车尾气净化的研究

研制了一系列非贵金属复合氧化物催化剂,测定这些催化剂净化汽车尾气的活性和抗硫、磷、铅及析碳中毒等性能,排出了它们的活性和抗硫中毒的顺序。实验表明,ASC(Re-Mn-Pb-Cu-Cr-A-O_x/Al_2O_3,A助剂)催化剂具有较高的活性及较好的抗硫磷、铅及析碳中毒性能,具有较好的应用前景。     

Mn/TiO2和Mn-Ce/TiO2低温脱硝催化剂的抗硫性研究

在低温选择性催化还原(SCR)反应条件下考察了烟气残余SO2对Mn/TiO2和Mn-Ce/TiO2催化剂选择性催化还原活性的影响,同时对SO2的影响机理进行了探讨.结果发现,Mn/TiO2催化剂在SO2反应气氛中失活很快,硫铵盐的沉积和活性组分的硫酸化是催化剂失活的重要原因;Ce的加入可以有效地抑制催化剂活性组分的硫酸化,同时还能降低硫酸盐在催化剂表面的稳定性,从而可以提高催化剂的抗硫性.     

Effects of two sludge application on fractionation and phytotoxicity of zinc and copper in the soil

The potential harm of heavy metals is a primary concern in application of sludge to the agricultural land. A pot experiment was conducted to evaluate the effect of two sludges on fractionation of Zn and Cu in soil and their phytotoxicity to pakchoi. The loamy soil was mixed with 0%, 20%, 40%, 60% and 80% (by weight) of digested sewage sludge (SS) and composted sludge (SC). The additions of both sludges caused a significant raise in all fractions, resulting in that exchangeable (EXCH) and organic bound (OM) became predominance of Zn and organic bound Cu occupied the largest portion. There was more available amount of Zn and Cu in SS treatments than SC treatments. During the pot experiment, the concentration of Zn in EXCH, carbonate (CAR) and OM and Cu in EXCH and OM fractions decreased in all treatments, so their bioavailability reduced. Germination rate and plant biomass decreased when the addition rate was high and the best yield appeared in 20% mixtures at the harvest of pakchoi. The two sludges increased tissue contents of Zn and Cu especially in the SS treatments. Zn in pakchoi was not only in relationship to ΔEXCH and ΔCAR forms but also in ΔOM forms in the sludge-soil mixtures. Tissue content of Cu in pakchoi grown on SC-soils could not be predicted by ΔEXCH. These correlation rates between Zn and Cu accumulation in pakchoi and variation of different fractions increased with time, which might indicate that sludges represented stronger impacts on the plant in long-term land application.     

Intraspecific differences in effects of co-contamination of cadmium and

A hydroponic experiment was carried out to study intraspecific differences in the effects of different concentrations of cadmium (Cd)(0-10 mg/L) and arsenate (As(V)) (0-8 mg/L) on the growth parameters and accumulation of Cd and As in six wheat varieties Jing-9428, Duokang-1, Jingdong-11, Jing-411, Jingdong-8 and Zhongmai-8. The endpoints of wheat seedlings, including seed germination,biomass, root length and shoot height, decreased with increasing the Cd and As concentrations. Significant differences in seed germination, biomass, root length, shoot height and the accumulation of Cd and As were observed between the treatments and among the varieties (p ＜ 0.05). The lethal dosage 50% were about 20, 80, 60, 60, 80 and 20 mg As/L for Jing-9428, Duokang-1, Jingdong-11,Jing-411, Jingdong-8 and Zhongmai-8, respectively, and the corresponding values for Cd were about 30, 80, 20, 40, 60 and 10 mg Cd/L, respectively. Among the six varieties, Duokang-1 was found to be the most resistant to Cd and As toxicity, and Zhongmai-8 was the most sensitive to Cd and As co-contamination. The resistance of the six varieties was found dependant on the seedling uptake of Cd and As. Duokang-1 was the most suitable for cultivation in Cd and As co-contaminated soils.     

Toxic effects of acetochlor, methamidophos and their combination on nifH gene in soil

Toxic effects of two agrochemicals on nifH gene in agricultural black soil were investigated using denaturing gradient gel electrophoresis （DGGE） and sequencing approaches in a microcosm experiment. Changes of soil nifH gene diversity and composition were examined following the application of acetochlor, methamidophos and their combination. Acetochlor reduced the nifH gene diversity （both in gene richness and diversity index values） and caused changes in the nifH gene composition. The effects of acetochlor on nifH gene were strengthened as the concentration of acetochlor increased. Cluster analysis of DGGE banding patterns showed that nifH gene composition which had been affected by low concentration of acetochlor （50 mg/kg） recovered firstly. Methamidophos reduced nifH gene richness that except at 4 weeks. The medium concentration of methamidophos （150 mg/kg） caused the most apparent changes in nifH gene diversity at the first week while the high concentration of methamidophos （250 mg/kg） produced prominent effects on nifH gene diversity in the following weeks. Cluster analysis showed that minimal changes of nifH gene composition were found at 1 week and maximal changes at 4 weeks. Toxic effects of acetochlor and methamidophos combination on nifH gene were also apparent. Different nifH genes （bands） responded differently to the impact of agrochemicals： four individual bands were eliminated by the application of the agrochemicals, five bands became predominant by the stimulation of the agrochemicals, and four bands showed strong resistance to the influence of the agrochemicals. Fifteen prominent bands were partially sequenced, yielding 15 different nifH sequences, which were used for phylogenetic reconstructions. All sequences were affiliated with the alpha- and beta-proteobacteria, showing higher similarity to eight different diazotrophic genera.     

EDTA-enhanced phytoremediation of lead contaminated soil by Bidens maximowicziana

Phytoremediation is a potential cleanup technology for the removal of heavy metals from contaminated soils.Bidens maximowicziana is a new Pb hyperaccumulator,which not only has remarkable tolerance to Pb but also extraordinary accumulation capacity for Pb.The maximum Pb concentration was 1509.3 mg/kg in roots and 2164.7 mg/kg in overground tissues.The Pb distribution order in the B. maximowicziana was:leaf>stem>root.The effect of amendments on phytoremediation was also studied.The mobility of soil Pb and the Pb concentrations in plants were both increased by EDTA application.Compared with CK(control check),EDTA application promoted translocation of Pb to overground parts of the plant.The Pb concentrations in overground parts of plants was increased from 24.23-680.56 mg/kg to 29.07-1905.57 mg/kg.This research demonstrated that B.maximowicziana appeared to be suitable for phytoremediation of Pb contaminated soil,especially,combination with EDTA.     

Distribution and ecological effect of mercury in Laogang landfill, Shanghai, China

Laogang landfill near Shanghai is the largest landfill in China, and receives about 10000 t of daily garbage per day, Samples of topsoil and plants were analyzed to evaluate mercury pollution from the landfill. For topsoil samples, there were significant correlations among total mercury （HgT）, combinative mercury （Hgc） and gaseous mercury （HgG）, and content of total organic carbon （TOC）, but, no significantly relationship was found between Hg content and filling time. Hg content changes in vertical profiles with time showed that the average Hgv of profiles 1992, 1996, and 2000 was similar, but their average HgG was quite different. HgT was significantly correlated with Hgc in profile 1992 and 2000, and Hgv was significantly correlated with Hg6 in profile 1996. HgG/Hgv ratio in profile samples decreased in the order of （HgG,/HgT）1992〉（HgG/HgT）1996〉〉（HgG/HgT）2000. A simple outline of Hg release in landfill could be drawn： with increasing of filling time, degradation undergoes different biodegradation, accordingly, gaseous mercury goes through small, more, and small proportion to total mercury. Distribution of Hg in plants was inhomogeneous, following the order of leaf〉root〉stem. The highest value of leaf may be associated with higher atmospheric Hg from landfill. Ligneous plants （e.g. Phyllostachys glanca, Prunus salicina and Ligustrum lucidum） are capable of enriching more Hg than herbaceous plants.     

Arsenic uptake by arbuscular mycorrhizal maize （Zea mays L.） grown in an arsenic-contaminated soil with added phosphorus

The effects of arbuscular mycorrhizal (AM) fungus (Glomus mosseae) and phosphorus (P) addition (100 mg/kg soil) on arsenic (As) uptake by maize plants (Zea mays L.) from an As-contaminated soil were examined in a glasshouse experiment.Non-mycorrhizal and zero-P addition controls were included.Plant biomass and concentrations and uptake of As,P,and other nutrients,AM colonization,root lengths,and hyphal length densities were determined.The results indicated that addition of P significantly inhibited root colonization and development of extraradical mycelium.Root length and dry weight both increased markedly with mycorrhizal colonization under the zero-P treatments,but shoot and root biomass of AM plants was depressed by P application.AM fungal inoculation decreased shoot As concentrations when no P was added,and shoot and root As concentrations of AM plants increased 2.6 and 1.4 times with P addition,respectively.Shoot and root uptake of P,Mn,Cu,and Zn increased,but shoot Fe uptake decreased by 44.6%,with inoculation, when P was added.P addition reduced shoot P,Fe,Mn,Cu,and Zn uptake of AM plants,but increased root Fe and Mn uptake of the nonmycorrhizal ones.AM colonization therefore appeared to enhance plant tolerance to As in low P soil,and have some potential for the phytostabilization of As-contaminated soil,however,P application may introduce additional environmental risk by increasing soil As mobility.     

Enzymatic oxidation of aqueous pentachlorophenol

The influence of the nonionic surfactant Tween 80 on pentachlorophenol （PCP） oxidation catalyzed by horseradish peroxidase was studied. The surfactant was tested at concentrations below and above its critical micelle concentration （CMC）. Enhancement of PCP removal was observed at sub-CMCs. The presence of Tween 80 in the reaction mixture reduced enzyme inactivation which occurred through a combination of free radical attack and sorption by precipitated products. A simple first-order model was able to simulate time profiles for enzyme inactivation in the presence or absence of Tween 80. At supra-CMCs, the surfactant caused noticeable reductions in PCP removal, presumably through micelle partitioning of PCP which precluded the hydrophobic PCP molecule from interacting with the enzyme.     

Decomposition of alachlor by ozonation and its mechanism

Decomposition and corresponding mechanism of alachlor, an endocrine disruptor in water by ozonation were investigated. Results showed that alachlor could not be completely mineralized by ozone alone. Many intermediates and final products were formed during the process, including aromatic compounds, aliphatic carboxylic acids, and inorganic ions. In evoluting these products, some of them with weak polarity were qualitatively identified by GC-MS. The information of inorganic ions suggested that the dechlorination was the first and the fastest step in the ozonation of alachlor.     

Degradation of metabolites accumulated of benzo[a]pyrene by coupling Penicillium Chrysogenum with KMnO4

Several main metabolites of benzo[a]pyrene （BaP） formed by Penicillium chrysogenum, Benzo[a]pyrene-1,6-quinone （BP 1,6- quinone）, trans-7,8-dihydroxy-7,8-dihydrobenzo[a]pyrene （BP 7,8-diol）, 3-hydroxybenzo[a]pyrene （3-OHBP）, were identified by high-performance liquid chromatography （HPLC）. The three metabolites were liable to be accumulated and were hardly further metabolized because of their toxicity to microorganisms. However, their further degradation was essential for the complete degradation of BaP. To enhance their degradation, two methods, degradation by coupling Penicillium chrysogenum with KMnO4 and degradation only by Penicillium chrysogenum, were compared; Meanwhile, the parameters of degradation in the superior method were optimized. The results showed that （1） the method of coupling Penicillium chrysogenum with KMnO4 was better and was the first method to be used in the degradation of BaP and its metabolites; （2） the metabolite, BP 1,6-quinone was the most liable to be accumulated in pure cultures; （3） the effect of degradation was the best when the concentration of KMnO4 in the cultures was 0.01% （w/v）, concentration of the three compounds was 5 mg/L and pH was 6.2. Based on the experimental results, a novel concept with regard to the bioremediation of BaP-contaminated environment was discussed, considering the influence on environmental toxicity of the accumulated metabolites.     

Impact of atrazine and nitrogen fertilizers on the sorption of chlorotoluron in soil and model sorbents

Sorption of chlorotoluron in ammonium sulfate, urea and atrazine multi-solutes system was investigated by batch experiments. The results showed application of nitrogen fertilizers to the soil could affect the behavior of chlorotoluron. At the same concentration of N, sorption of chlorotoluron decreased as the concentration of atrazine increased on the day 0 and 6 in soil, respectively. The sorption of chlorotoluron increased from 0 to 6 d when soils were preincubated with deionized water, ammonium sulfate and urea solution for 6 d. That indicated incubation time was one of the most important factors for the sorption of chlorotoluron in nitrogen fertilizers treatments. The individual sorption isotherms of chlorotoluron in rubbery polymer and silica were strictly linear in single solute system, but there were competition sorption between pesticides or between pesticides and nitrogen fertilizers. That indicated the sorption taken place by concurrent solid-phase dissolution mechanism and sorption on the interface of water-organic matter or water-mineral matter.