复合催化剂CuO-MnO_2-CeO_2/13X对烟气多环芳烃催化氧化性能研究

采用浸渍法制备复合催化剂Cu O-Mn O_2-Ce O_2/13X,并用全自动气体吸附仪、扫描电子显微镜和X射线衍射仪对其结构组成进行表征;同时在固定床中考察了Cu O-Mn O_2-Ce O_2/13X催化剂对燃煤烟气PAHs的催化降解性能。结果表明:Cu O-Mn O_2-Ce O_2/13X催化剂对烟气PAHs的总去除率为69%~75%,当Cu O、Mn O_2和Ce O_2的负载率分别为4%、7%和4%时对PAHs的去除效果最好。复合催化剂Cu O-Mn O_2-Ce O_2/13X对高环(5环、6环)PAHs的去除率比中低环的要高,对PAHs毒性当量有较好的去除效果,最高达到94%。催化剂中活性组分铜和锰的质量分数对PAHs的催化氧化性能影响较大,当铜锰比从1∶1变为4∶7时,PAHs去除率从69%提高到73%,加入助剂Ce O_2后PAHs去除率进一步增加到75%。     

树脂负载草酸铁光助类芬顿降解水中孔雀石绿

为了强化多相类芬顿反应的速率,在可见光下采用以草酸盐为配体的三价铁草酸络合物(Fe~(3+)C_2O_4/R)为催化剂催化过氧化氢降解水中孔雀石绿.结果表明,与Fe~(3+)/R相比催化剂Fe~(3+)C_2O_4/R具有更强的催化活性,能强化羟基自由基(·OH)的产生. 过氧化氢的初始浓度越高,反应速率越快,反应遵循一级反应动力学,反应速率常数与过氧化氢浓度具有很好的相关性.在pH值3～9的范围内,催化剂Fe~(3+)C_2O_4/R都能有效地对MG进行降解,最佳pH值为6.随着催化剂投量的增加,MG的去除效率明显提高.随着MG初始浓度的增加,MG的去除也由吸附为主转化为以氧化为主,但总体影响不大.催化剂重复使用后仍然具有较好的催化活性,说明铁在树脂表面负载比较牢固,催化剂具有反复使用的能力.反应中的氧化活性物种是羟基自由基和高价态铁同时共存.     

不同方法制备Co3O4催化剂CO-SCR性能及机制

氮氧化物(NOx)是造成细颗粒物、近地面臭氧等大气污染问题的重要前体物.随着大气污染治理行动的深入,对工业锅炉/窑炉烟气排放的NOx进行控制十分重要.采用不同方法制备了一系列Co_3O_4催化剂,考察了不同制备方法对CO选择性催化还原NO(CO-SCR)反应活性的影响,通过BET、XRD、Raman、HR-TEM和SEM等技术对该系列催化剂进行了表征.活性测试表明,以硫酸钴为前驱体用固态研磨法制备的Co_3O_4-S催化剂具有更优异的CO-SCR反应活性,且表现出较好的抗水蒸气性能,以醋酸钴为前驱体用固态研磨法制备的Co_3O_4-C催化剂显示出较好的抗水性能. NO氧化结果显示,催化剂的NO氧化效果越好,CO-SCR活性也越好. Raman表征结果显示,Co_3O_4-S表面可能含有更多的Co2+离子,从而有利于形成氧空位. H2-TPR结果表明,Co_3O_4-S催化剂的氧化还原性较好. HR-TEM表征发现Co_3O_4-S和Co_3O_4-O主要暴露(111)和(220)晶面,而更多(220)晶面的暴露可能更有利于反应的进行.     

锰银复合催化剂对NTP降解吸附态甲苯的影响

采用等体积浸渍法制备以13X分子筛为载体的Mn-Ag复合型催化剂,并用SEM、BET和FT-IR手段对催化剂进行表征。在介质阻挡放电反应器(DBD)中,考察了锰、银不同摩尔比和不同负载总量的催化剂对吸附态甲苯降解的影响。结果表明:当n(Mn)∶n(Ag)为1∶3时,Mn-Ag/13X催化剂对甲苯催化氧化活性最高,CO_2选择性为98.84%;不同摩尔比的催化剂对O_3分解性能顺序与对甲苯的催化氧化性能顺序一致,其顺序为n(Mn)∶n(Ag)1∶3>1∶5>1∶1>3∶1>5∶1>0∶0;Mn-Ag/13X(Mn∶Ag=1∶3)催化剂锰和银负载量对催化剂的吸附性能和催化活性有显著影响,随负载量的变化,吸附穿透时间大小关系为:2.5%Mn-Ag/13X≈7.5%Mn-Ag/13X>5%Mn-Ag/13X>10%Mn-Ag/13X;负载量为5%时,吸附穿透时间为125 min,CO_x浓度为4 669.82 mg/m~3,显示出最好的催化活性。     

CuO/AOCF类Fenton催化剂的制备及光催化性能

以偕胺肟纤维(AOCF)为载体,采用配位-沉淀法研制了一种新型的类Fenton催化剂CuO/AOCF.用SEM、EDS和XRD对CuO/AOCF的表面形貌、晶体结构和表面成分进行分析,结果显示:CuO纳米颗粒均匀分布在AOCF表面.以活性红染料为目标降解物及其去除率为评价指标,考察CuO/AOCF与H_2O_2组成类Fenton催化剂的光催化性能.结果表明:在氙灯光照作用下,0.6 g·L~(-1)CuO/AOCF、2 m L·L~(-1)H_2O_2、反应时间为80 min,活性红溶液几乎完全被降解.对比同质量粉体CuO,CuO/AOCF对光催化性能有着更好的促进作用.CuO/AOCF重复使用5次后降解率仍能大于80%.动力学研究表明,该类Fenton催化降解反应遵循一级反应动力学规律.     

金属氧化物降解六氯苯的活性比较及催化机理研究

以氧化铝(α-Al_2O_3、γ-Al_2O_3)、氧化钙(CaO)、过渡金属氧化物(Mn O_2、α-Fe_2O_3、γ-Fe_2O_3、Ni_2O_3、CuO)为催化剂,考察了催化剂种类、添加比例等因素对六氯苯(Hexachlorobenzene,HCB)降解效果和产物组分的影响.结果表明,催化效果随催化剂添加比例的提高显著增加.在反应温度为350℃,反应时间1 h,金属氧化物添加比例为100∶1的条件下,碱土金属氧化物CaO及过渡金属氧化物中的α-Fe_2O_3和Ni_2O_3降解活性较好,这3种氧化物对HCB的降解率分别达到65.5%、100.0%和100.0%,脱氯率D_1分别为54.4%、81.9%和77.5%.HCB降解有机产物分析结果显示,8种金属氧化物与HCB样品反应产物中均存在低氯代苯,在α-Fe_2O_3和Ni_2O_3的催化作用下有2~4氯代低氯苯检出,说明在降解过程中存在明显的逐级脱氯/加氢反应;与CaO反应后的产物中低氯代苯较少,经拉曼光谱定性分析,有无序碳的检出,说明除了脱氯/加氢还存在脱氯缩合反应.     

微波加热下苯的催化氧化性能研究

研究考察了微波加热与传统电炉加热两种不同加热方式下苯的催化氧化性能,同时考察了微波加热下铜锰质量比,铈掺杂量及焙烧温度变化对铜-锰-铈/分子筛催化剂催化氧化苯性能的影响,并对催化剂进行了SEM和XRD表征.结果表明,微波加热下苯的催化氧化性能优于电炉加热,微波的"局部热点"效应、偶极极化作用与稳定的床层反应温度保证了苯的高效催化氧化;铜∶锰∶铈质量比1∶1∶0.33和焙烧温度500℃下催化剂的活性最高,苯的起燃温度与完全燃烧温度分别为165℃和230℃.催化剂表征分析可知,铜、锰氧化物及铜锰尖晶石固溶物等活性相的存在保证了催化剂的高活性;稀土元素铈的掺杂促进了活性组分在催化剂表面的分散与规整化;高温焙烧可导致催化剂表面的烧结与活性组分的团聚,从而降低其催化氧化苯的活性.     

氯氧铁非均相催化过氧化氢降解罗丹明B

传统芬顿(Fenton)法因反应pH值低、产生大量铁泥等限制其规模化应用.采用化学气相转变法制备氯氧铁(FeOCl)纳米片,选择罗丹明B为模型污染物,研究FeOCl作为类芬顿催化剂催化过氧化氢(H_2O_2)降解罗丹明B性能.通过扫描电镜(FE-SEM)和X射线衍射光谱(XRD)等表征结果显示,FeOCl晶型结构完整、呈现纳米片状,可充分暴露催化活性位点.罗丹明B降解实验结果表明,H_2O_2投量为1. 67 mmol·L~(-1)时,投加200 mg·L~(-1)FeOCl,可使得罗丹明B去除率由15. 5%提高至100%(15 min). FeOCl的催化性能随pH升高而降低,初始pH为3、5和7时,反应15 min后罗丹明B去除率分别为100%、100%和84. 0%,初始pH提升至9,去除率则显著降低至57. 6%.与传统Fenton法比较,FeOCl催化H_2O_2的pH值范围明显拓展,在弱酸性和中性条件下表现出优良的催化性能.自由基淬灭实验表明,FeOCl/H_2O_2体系催化降解罗丹明B起主要作用的是羟基自由基(·OH).电子自旋共振波谱仪测定(EPR)结果表明,单独H_2O_2体系未检测出明显的自由基信号,而投加FeOCl使得·OH信号显著增强,·OH是降解罗丹明B的主要氧化活性物种.     

基于新型陶粒催化剂的H_2O_2/O_3多相催化氧化体系降解刚果红的研究

用自制陶粒催化剂与臭氧(O_3)、双氧水(H_2O_2)构建多相催化氧化体系降解水中的刚果红。采用电镜扫描、能谱分析与红外光谱等表征了陶粒催化剂,考察了反应时间、O_3浓度、H_2O_2投加量等因素下多相催化氧化体系对刚果红色度和COD去除率。结果表明:自制的陶粒催化剂表面较为粗糙,比表面积较大,反应后的陶粒催化剂表面较为平滑,比表面积较反应前减少;自制陶粒催化剂对H_2O_2催化能力差,但对O_3、H_2O_2/O_3具有较好的催化效果。当O_3浓度在1.2~3.8 mg/L时,陶粒/H_2O_2/O_3体系较O_3、H_2O_2/O_3对刚果红(100 mg/L)的脱色率分别平均提高了11.72%、15.32%,COD去除率分别提高了16.37%、24.29%,将陶粒引入O_3、H_2O_2/O_3体系中可减少O_3和H_2O_2的用量,提高体系的氧化性能,降低运行成本。     

Fe_2O_3-TiO_2-MnO_2/Al_2O_3催化臭氧化催化剂的制备及表征

以Al_2O_3为载体,采用浸渍-焙烧法制备了Fe_2O_3-TiO_2-MnO_2/Al_2O_3催化剂,使用SEM、EDX、BET和XRD方法对其进行了表征.以化工园区污水处理厂二级出水为目标降解物,考察了该催化剂在臭氧催化氧化过程中的催化活性.结果表明,浸渍液中Ti~(4+)、Mn~(2+)、Fe~(3+)的摩尔比为2:2:1、焙烧时间为4h和焙烧温度为500℃下制备出的催化剂对化工园区废水有较好的催化性能,在臭氧投加量为50mg/L,催化剂填充率为50%的条件下,反应60min后废水COD的去除率达到52.2%.三维荧光谱图显示,废水经臭氧催化氧化后,水中可见腐殖质类和UV腐殖质类物质可完全降解,同时有少量类富里酸生成.     

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.     

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.     

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.     

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.     

Potential of plant polyphenol oxidases in the decolorization and removal of textile and non-textile dyes

In this study an effort has been made to use plant polyphenol oxidases; potato （Solanum tuberosum） and brinjal （Solanum melongena）, for the treatment of various important dyes used in textile and other industries. The ammonium sulphate fractionated enzyme preparations were used to treat a number of dyes under various experimental conditions. Majority of the treated dyes were maximally decolorized at pH 3.0. Some of the dyes were quickly decolorized whereas others were marginally decolorized. The initial first hour was sufficient for the maximum decolorization of dyes. The rate of decolorization was quite slow on long treatment of dyes. Enhancement in the dye decolorization was noticed on increasing the concentration of enzymes. The complex mixtures of dyes were treated with both preparations of polyphenol oxidases in the buffers of varying pH values. Potato polyphenol oxidase was significantly more effective in decolorizing the dyes to higher extent as compared to the enzyme obtained from brinjal polyphenol oxidase. Decolorization of dyes and their mixtures, followed by the formation of an insoluble precipitate, which could be easily removed simply by centrifugation.     

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.