碳基催化剂低温选择性催化还原氮氧化物的研究进展

氨选择性催化还原（SCR）技术广泛应用于固定源氮氧化物污染控制，该技术的核心是催化剂。目前，研制具有低温活性的催化剂是国内外该领域的热点。文章综述了活性炭、活性炭纤维、碳成型物为载体的催化剂，以氨为还原剂，低温选择性催化还原锅炉烟气氮氧化物（NOx）的研究现状，并对该技术的发展做了展望，特别提出了碳的另一同素异性体碳纳米管在低温选择催化还原NOx上的应用前景。     

以金属为载体催化剂上选择性催化还原Nox的研究

以Ni—Cr-Fe合金金属作为催化剂的载体,以复合型金属氧化物MnCr2O4作为催化剂主要活性成分,通过XRD和SEM等分析手段对催化剂进行表征。选择环状六碳芳香烃C6H6为还原剂,选择催化还原NOx的实验评价催化剂的催化活性。结果表明：催化剂活性组分负载均匀,催化剂具有良好的催化活性,NOx的最高转化率为78％,C6H6最高转化率为81％,CO的生成量很少,几乎全部生成CO2。制备的催化剂具有良好的氧化还原性能。     

MnOx-基催化剂低温NH3-SCR脱硝研究进展

锰氧化物(MnOx)基催化剂在氨选择性催化还原(NH3-SCR)脱除氮氧化物(NOx)的反应中具有高的低温催化活性.然而,目前,缺乏从分子原子水平认知控制MnOx基催化剂低温活性的关键机制,进而难以采用可控策略实现NOx在更宽的温度窗口和更低温度的高效催化转化.本文基于最新的研究进展,综述了催化剂制备方法、催化剂载体、...     

低温SCR脱硝催化剂过渡金属氧化物改性及硫中毒失活机制研究

以浸渍法制备MnOx-CeOx/ACF催化剂.在110~230℃温度范围内,MnOx-CeOx/ACF催化剂具有较好地低温选择性催化还原脱除NOx的活性.结果表明,该催化剂在150℃和230℃的脱硝效率分别达到80%和90%.加入Fe、Cu和V等过渡金属氧化物对MnOx-CeOx/ACF催化剂进行改性.该类过渡金属氧化物的加入对MnOx-CeOx/ACF的活性具有抑制作用.相比于MnOx-CeOx/ACF以及Cu和V改性的催化剂,Fe改性催化剂在一定时期内具有良好的抗SO2性能.在SO2存在下,Fe改性催化剂在初始6h内其脱硝效率保持在75%以上.X射线光电子能谱(XPS)和傅立叶转换红外光谱(FTIR)分析结果表明,催化剂失活包括两部分机制,一是形成硫酸铵盐,可粘附在催化剂表面使催化剂失活;另外一个机制是作为活性成分的锰铈等金属氧化物被SO2硫化形成金属硫酸盐.     

废物处理与综合利用

一般性问题X701200602197含钼氧化物对碳烟和NOx的催化去除特性/运新华…(上海交通大学机械与动力工程学院)∥上海交通大学学报/上海交通大学.-2005,39(11).-1886～1890环图N-42通过在MoO3上添加不同金属氧化物,制备了一系列含低熔点物质的催化剂。利用程序升温控制反应(TPR),探讨了紧接触、松接触不同条件下活性组分和载体对碳烟的催化氧化及NOx还原活性的影响,分析讨论了碳烟和NOx同时催化去除机理。实验结果表明,添加K和某些金属氧化物能改善碳烟和催化剂的接触,提高催化活性。NiO的添加使得NOx转换效率达到最高(38%),CuO的添加…     

低温NH3-SCR催化剂及脱硝机理研究进展

为了开发高活性、高抗性的低温NH_3选择性催化还原(NH_3-SCR)催化剂,介绍了4种主要低温脱硝催化剂(贵金属、分子筛、炭基材料和过渡金属氧化物)脱硝活性以及抗硫抗水性能的研究成果,分析了基于原位红外和密度泛函方法的低温脱硝研究。分析认为:由一种或多种金属材料组合的NH_3-SCR催化剂一般具有良好的低温活性,但抗硫、抗水性能有待进一步提升;催化剂的表面酸性酸量特性和活性位点暴露数量与抗硫抗水性能密切相关,脱硝机理有助于分析SO_2和水蒸气对脱硝过程的影响机制。     

固定源氨选择性催化还原脱硝催化剂研究进展

固定源NH₃选择性催化还原(NH₃-SCR)脱硝技术是目前最有效的固定源氮氧化物排放控制技术.催化剂是NH₃-SCR脱硝技术的核心,其中,金属氧化物催化剂的应用最为广泛.国内外学者就固定源NH₃-SCR金属氧化物催化剂反应活性及其中毒机制进行了大量研究和探索.本文梳理了钒基、锰基、铈基、铁基以及铜基等固定源NH₃-SCR催化剂体系的研究进展,总结了对催化剂活性具有毒害作用的二氧化硫、碱金属和重金属的中毒机制及耐毒对策,并对目前存在的问题作出思考,进一步展望了未来固定源NH₃-SCR脱硝技术的发展趋势.     

Fe-MnOx-CeO2/ZrO2低温催化还原NO性能研究

以纳米ZrO2为载体,用浸渍法制备出Fe-MnOx-CeO2/ZrO2催化剂,考察了活性组分配比和助剂负载量对催化剂低温NH3选择性催化还原NO活性的影响,并对催化剂进行了XRD、SEM、EDS和BET表征;探讨了温度、H2O和SO2对Fe-MnOx-CeO2/ZrO2催化剂低温下NH3选择性催化还原NO的影响,结果表明,无SO2和H2O条件下,8%Fe-10%MnOx-CeO2/ZrO2催化剂具有良好的催化活性和稳定性.120℃时,催化剂的脱硝效率为85.23%,当温度升至180℃时,脱硝效率可达到92.0%.SO2和H2O共存条件下,催化剂易失活,采用傅立叶变换红外光谱对各反应阶段的催化剂进行了表征,对其失活机制进行深入研究,结果表明,催化剂失活的主要原因是催化剂表面硫酸铵盐的沉积和催化剂本身活性成分的硫酸盐化.     

分子筛负载CoO_x催化剂用于苯的催化氧化

采用等体积浸渍法合成了不同负载量的Co O_x/HZSM-5催化剂用于苯催化氧化反应,并采用XRD、低温氮气吸附、NH_3-TPD及H_2-TPR技术对催化剂的结构、孔性质、比表面积、酸性及氧化还原性能进行表征。催化反应结果发现,HZSM-5分子筛表面分散的Co Ox颗粒显著提高了HZSM-5的苯催化氧化活性,10%Co O_x/HZSM-5催化剂表现出最优的催化活性和良好的催化稳定性。材料表征结果表明分子筛表面丰富的酸中心以及Co O_x活性组分的低温可还原性是影响Co O_x/HZSM-5催化剂催化性能的关键因素。     

Ag-Al2O3催化剂选择性催化还原稀薄燃烧NOx的研究

本研究主要考察了丙烯为还原剂 ,溶胶 凝胶和共沉淀两种方法制备的Ag Al2 O3催化剂的活性 ,实验结果表明Ag(5 ) Al2 O3(SG)催化剂具有最高的活性。同时详细考察了C3H6 浓度、NO浓度和空速等因素对Ag(5 ) Al2 O3(SG)催化剂活性的影响 ,实验结果表明该催化剂在高空速条件下仍然具有良好的性能。此外 ,还考察了乙烯、丙烷和辛烷为还原剂 ,Ag(5 ) Al2 O3(SG)催化剂的活性 ,实验结果表明以辛烷为还原剂 ,该催化剂还原NOx 的活性 ,特别是低温活性明显提高     

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.     

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.     

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.     

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.     

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.     

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.