Pd-W-Cu/γ-Al_2O_3催化氢还原脱硝的基本性能研究

采用浸渍法制备Pd-W-Cu/γ-Al2O3催化剂,用XRD和SEM方法对该催化剂进行了表征.以氢气作为还原剂,在间歇式反应器中对催化还原地下水中硝酸盐进行了实验研究,考察了催化剂制备方法对催化还原硝酸盐性能的影响.结果表明,W的添加改善了Pd的分散性,提高了催化剂的活性和选择性.金属Pd/W/Cu质量比、浸渍顺序和焙烧温度对催化性能有较大影响.Pd/W/Cu质量比为3∶1∶1,Pd、Cu和W3种金属组分同时浸渍,焙烧温度为400℃时,催化剂的活性和选择性最高.在NO3--N初始浓度为100mg·mL-1条件下,催化反应60min后水中NO3--N和NO2--N浓度均为0mg·mL-1,NH4+-N浓度为2.5mg·mL-1.     

氮氟掺杂二氧化钛(N,F-TiO2)的制备及可见光催化活性的研究

以氨水为氮源,氢氟酸为氟源,采用溶胶-凝胶法制备了氮氟掺杂二氧化钛(N,F-TiO2)光催化剂,并通过X-射线衍射(XRD)和扫描电镜(SEM)技术对其晶型和形态进行表征.最后以酸性红B为模型污染物,探讨了N和F加入量、焙烧温度、焙烧时间、照射时间、催化剂用量、溶液初始浓度和照射功率等因素对N,F-TiO2可见光催化活性的影响.结果表明,制备的N,F-TiO2以锐钛型为主,N和F的掺杂对TiO2的晶相没有明显改变,但可以扩大TiO2的可见光响应范围.当N和F的加入量均为2.0%,且在500℃下焙烧40 min时,得到的N,F-TiO2的可见光催化活性明显高于单N或单F掺杂的TiO2(N-TiO2或F-TiO2).对于50 mL浓度为10.0 mg·L-1的酸性红B溶液,当催化剂加入量为1.5 g·L-1,128W光照3.0 h,溶液pH=5.6时,去除率为85.40%.适当延长光照时间至4.0 h,降解率几乎可达100%.另外,研究还证明了N,F-TiO2催化可见光降解过程中有.OH自由基生成.     

H_3PW_(12)O_(40)/TiO_2可见光下光催化降解孔雀石绿的研究

以钛酸四丁酯为原料,采用溶胶-凝胶法制备TiO2光催化剂,然后浸渍法制备出H3PW12O40/TiO2复合型光催化剂,并运用XRD、SEM、FT-IR和DRS对催化剂进行表征和分析.研究了可见光光照下H3PW12O40/TiO2对孔雀石绿降解的光催化活性,考察了浸渍量、催化剂用量、底物浓度、pH值对光催化降解率的影响.实验表明,在pH=5条件下,H3PW12O40/TiO2催化剂用量为0.3g.L-1,浓度为10mg·mL-1的孔雀石绿溶液在2L·min-1曝气、300W可见光下光照4h后光催化降解率为78%,比TiO2光催化活性提高了24%.     

负载型Mn-Co/TiO2催化剂的制备及其低温NH3选择催化还原NO

采用浸渍法制备了一系列以成型TiO2为载体的Mn-Co/TiO2低温SCR催化剂,研究分析了活性组分担载量、Mn含量、焙烧温度、焙烧时间等制备参数和进口NO浓度、空速、O2体积分数、NH3/N2摩尔比等操作条件对催化剂脱硝反应活性的影响.结果表明:活性组分担载量为30%,Mn/(Mn+Co)摩尔比为80%,在500℃下焙烧6 h得到的Mn-Co/TiO2催化剂具有较高的NO转化率;在进口NO浓度为600×10-6、O2体积分数6%、空速10000 h-1、150℃条件下,NO脱除率接近100%.     

制备条件对低温NH_3-SCR脱硝催化剂Mn-Ce/TiO_2结构与性能的影响

采用溶胶凝胶法制备了Mn-Ce/TiO2催化剂,以NH3为还原剂,通过程序升温反应考察其选择性催化还原NO的催化性能.同时,着重探讨了焙烧温度、焙烧时间、活性物质负载量及Mn、Ce负载比例对催化剂结构和性能的影响,并用BET、XRD等对催化剂进行了表征.结果表明,活性组分负载量由0增至20%时,NO转化率随着负载量的增加而提高,当(Mn+Ce)质量分数为20%,催化剂活性最高,此后随着活性组分负载量的增加,NO转化率明显下降;Mn与Ce的负载比例为0.85∶0.15时,催化剂比表面积最大,为112.31m2·g-1;焙烧温度500℃时催化剂晶相均为TiO2锐钛矿型结构,焙烧温度升高至600℃,催化剂晶相为TiO2锐钛矿型和金红石型混合结构,且催化剂比表面积急剧减小;焙烧时间对催化剂晶相结构影响不大,焙烧时间为5h时,Mn-Ce/TiO2的脱硝性能最好.     

气相中芥子气模拟剂2-CEES在SO42-/TiO2上的光催化消除

与传统洗消法相比,光催化技术消除军用毒剂具有高效和无二次污染等优点,但TiO2 的活性较低且易于失活以致难于实际使用.采用稀硫酸对TiO2 进行表面修饰制备出了SO2 -4/TiO2 催化剂,在连续流动微分反应器上考察其对芥子气模拟剂2 chloroethylethylsulfide(2 CEES)的光催化降解活性和稳定性,并与TiO2 进行了比较.结果表明,硫酸化处理不但可提高TiO2 的活性也可提高其活性稳定性,其中以2 0 0℃焙烧所得样品ST2 0 0的性能最好.还研究了反应温度和水蒸气对ST2 0 0上2 CEES光催化降解的影响,发现在90℃反应,催化剂有较高的活性和稳定性;当给2 CEES初始浓度<6 1 μL·L-1 的体系中添加30 . 5mL·L-1 的水蒸气时,催化剂可维持长久的高活性.还发现将SO2 -4/TiO2 负载在γAl2 O3 、SiO2 和木质活性炭(AC)上可提高SO2 -4/TiO2 的活性和稳定性,其中以SiO2 载体最佳.     

纳米金红石TiO2的转晶及声催化降解偶氮品红的研究

利用超声波结合过氧化氢(H2O2)使纳米金红石型TiO2转晶,制备出了大约含有30%锐钛相的转晶纳米TiO2.通过TiO2催化超声降解偶氮品红的研究证实了转晶纳米TiO2粉末具有明显的声催化活性.除此之外,还考察了各种因素对转晶纳米TiO2催化超声降解偶氮品红反应的影响.结果表明,在转晶纳米TiO2催化剂的作用下,偶氮品红的超声降解效果明显优于使用纳米金红石型和纳米锐钛型TiO2的情况.偶氮品红的声催化降解过程符合一级动力学反应.在超声波频率40 kHz、输出功率50 W、催化剂用量1000 mg·L-1、pH为5.00、温度为20℃、偶氮品红水溶液初始浓度20 mg·L-1的条件下,照射40 min时的降解率即可达到75%以上.     

絮凝污泥制备光催化剂及降解活性艳红K-2BP研究

利用絮凝污泥制备复合光催化剂,研究了其对模拟染料废水活性艳红K-2BP的光催化降解效率,并采用X射线衍射仪对其进行了结果表征。详细考察了催化剂煅烧温度、催化剂中钛含量、催化剂投加量、溶液pH值等不同条件对活性艳红K-2BP染料废水的光催化降解效果。实验结果表明,聚硅硫酸钛的n(Ti)∶n(Si)=5∶1,投加量为200mg/L,絮凝pH=5时的絮凝污泥在600℃煅烧2h制得复合光催化剂具有较高活性,当复合光催化剂投加量为500mg/L,光催化反应pH为4时光催化活性最好,此时对50mg/L的活性艳红K-2BP的降解率可达到97.2%。     

凹凸棒石吸附氧化催化剂对甲醛的脱除研究

以酸改性凹凸棒石为载体,采用浸渍法以不同金属氧化物做活性组分进行了脱除甲醛的活性组分筛选,通过正交实验优化制备氧化锰凹凸棒吸附氧化催化剂工艺条件.结果表明,负载9%(质量分数)的锰氧化物,300℃焙烧4h制备的粒度为40～60目的凹凸棒吸附氧化催化剂在初始浓度为9.5552mg·m-3的甲醛空气中,24h时对甲醛的吸附量可达到0.188mg·g-1,甲醛脱除率达到98.35%.傅立叶变换红外光谱(FTIR)及X射线衍射(XRD)测试表明,凹凸棒吸附氧化催化剂对空气中的甲醛在室温下起到了吸附与催化氧化的作用.     

SnO2/TS-1纳米材料及光催化降解工业染料研究

以SnCl_4·5H_2O为原料,钛硅分子筛TS-1为载体,采用超声溶胶-凝胶法制备了负载型催化剂SnO_2/TS-1,并对该催化剂进行X射线衍射、扫描电镜、透射电镜、比表面积等表征.以罗丹明B作为模拟废水(20 mg·L~(-1)),系统研究了催化剂SnO_2/TS-1纳米材料制备条件与影响光降解性能的主要因素,并对印染企业的实际印染染料进行降解.结果表明:在pH=7.0~8.0下,经450℃焙烧制备了球形SnO_2/TS-1(SnO_2负载量为42%)纳米催化剂,比表面积为270 m~2·g~(-1),平均孔径为46.81 nm;在高压汞灯(λ_(max)=365 nm)光照60 min,催化剂用量为30 mg的条件下,催化剂对实际应用的工业染料罗丹明B、酸性蓝、活性黑、RGFL黄、酸性红A-2BF的降解率分别为96.44%、99.85%、99.78%、96.15%、94.65%,TOC与COD的下降率分别为89.3%~96.4%和81.6%~90.4%,且催化剂稳定性较好.     

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.     

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.     

Removal of heavy metals from sewage sludge by low costing chemical method and recycling in agriculture

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