La_(1-x)Ce_xCu_yMn_(1-y)O_3/HZSM-5催化剂低温去除柴油机碳烟和NO_x

为实现对柴油机碳烟和NOx的低温同步去除,采用柠檬酸络合法制备分子筛负载钙钛矿型金属复合氧化物催化剂,应用X衍射分析仪(XRD)和电镜扫描仪(SEM)对催化剂性能进行表征,并在微型固定床反应器中对催化剂低温去除碳烟和NOx进行活性评价。利用程序升温反应(TPR)技术,进行催化剂活性评价、柴油机负荷和排放等特性实验。结果表明,A位用适量Ce部分取代La,B位用适量Cu部分取代Mn,可使碳颗粒燃烧温度降低,CO2选择性好,NOx转化率升高。La0.4Ce0.6Cu0.2Mn0.8O3/HZSM-5催化剂的最大NOx转化率为81.0%,Ti、Tm和Tf分别为250、350和475℃,表明该催化剂具有较好的催化活性,能在低温条件下去除碳烟和NOx。     

UV/H2O2/Fe-FeOxH2x-3和UV/H2O2工艺降解水中富里酸的研究

采用硼氢化钠还原法制备核-壳结构的Fe-FeO_xH_2x-3复合材料，研究了富里酸在UV/H₂O₂和UV/H₂O₂/Fe-FeO_xH_2x-3两种不同反应体系下的降解情况。结果表明，核-壳结构Fe-FeO_xH_2x-3的存在，提高了UV/H₂O₂降解富里酸的反应速率，TOC去除达到84%。采用XAD树脂吸附法对反应前后的富里酸进行化学分级表征，结果表明，富里酸经反应后憎水酸（HoA）、弱憎水酸（WHoA）和憎水中性物质（HoN）都有所减少，进而转化为亲水性物质（HiM）；用超滤膜法对富里酸进行物理分级表征，考察了富里酸在反应前后分子量分布的变化情况。同时，富里酸经过反应后生成的中间产物降低了三氯甲烷生成趋势。     

除氟活性铝氧化物(AlO_xH_y-F_n)的吸附除砷性能

以活性铝氧化物AlOxHy处理某高氟地下水的中试实验获得的吸附剂废料AlOxHy-Fn为对象,考察其对三价砷(As(Ⅲ))和五价砷(As(Ⅴ))吸附去除性能,并对吸附机理进行了探讨。研究显示,AlOxHy-Fn为多孔无定型且具有不规则表面的絮状结构,比表面积为218.88 m2/g,零电荷点pHZPC在pH为8左右;AlOxHy-Fn可快速吸附As(Ⅲ)和As(Ⅴ),且反应24 h后的平衡吸附量分别为0.60和3.41 mg/g,朗格缪尔模型可以很好地描述As(Ⅲ)和As(Ⅴ)在AlOxHy-Fn表面的吸附,且As(Ⅲ)和As(Ⅴ)的最大吸附容量分别为13.63和63.27 mg/g;AlOxHy-Fn在pH=4~10范围内对As(Ⅴ)去除率在90%以上,As(Ⅲ)在中性和弱碱性pH范围内吸附效果较好,但去除率仍在32%以下。AlOxHy-Fn表面性质、砷形态分布特征等对As(Ⅲ)与As(Ⅴ)的吸附有重要影响,电负性As(Ⅴ)较电中性As(Ⅲ)更容易吸附在AlOxHy-Fn表面。AlOxHy-Fn吸附除砷过程中,在pH为6时氟溶出量最低(0.40 mg/g),过高或过低pH均会导致氟溶出量增大;氟溶出量与As(Ⅴ)吸附量之间有明显正相关关系(R2=0.97),但与As(Ⅲ)吸附量无相关关系;铝溶出量在pH为4~10范围内均很低。将AlOxHy-Fn回用作为除砷吸附剂去除工业含砷废水的砷具有良好的技术经济可行性,且将As(Ⅲ)氧化为As(Ⅴ)是提高去除效果的重要手段。     

ZnO/Lix Ni1-xO光催化降解甲基橙的研究

采用溶胶凝胶法制备LixNi1-xO和ZnO粉体,利用球磨法制备ZnO/LixNi1-xO复合粉体,以紫外光为光源,通过降解甲基橙,研究了锂掺杂及n-p复合对氧化镍的光催化性能影响.结果表明:当投放量为0.1 g/L,x≤0.075(摩尔分数)的锂掺杂氧化镍均比未掺杂氧化镍的光催化活性高.当锂掺杂摩尔分数为0.025,...     

Oxidative dealkylation of five phenylurea herbicides by the fungus CunninghamellaechinulataThaxter

Microorganisms isolated from soil degrade phenylurea herbicides via two major pathways: (i) direct hydrolysis by an amidase leading to N,O-dimethylhydroxylamine, CO₂ and aniline¹ and (ii) N-dealkylation, which has been described as the first step in urea herbicide degradation by a variety of organisms including mammals, plants and microbial systems (for a review see reference 2).Until now no attempts have been made to investigate the mechanism of N-demethylation of substituted ureas in soil microorganisms, due to the instability of the N-hydroxymethyl intermediates. This reaction mechanism has only been described in detail in green plants^3–5. As among soil fungi Phycomycetes are known to demethylate phenylurea herbicides^6,7 this study has been made to identify intermediate hydroxymethyl compounds from urea herbicides, when incubated with the fungus $\text{Cunninghamella echinulata Thaxter}$.     

CuMnCeOx/Al2O3/CH催化剂的制备及微波催化燃烧VOCs性能

针对整体式催化剂载体比表面积小和涂层脱落等问题,采用聚乙二醇200 (PEG200) 为粘结剂在蜂窝堇青石 (CH) 载体表面涂覆氧化铝 (Al₂O₃) 涂层,等体积浸渍法制备CuMnCeO_x/Al₂O₃/CH催化剂,微波催化燃烧VOCs以考察其催化性能。结果显示,当酸铝比 ($ {{\text{n}}_{{H^+}}}/{{\text{n}}_{A{l^{3+}}}} $) 为 0.262 5、$ {{\text{m}}_{PEG200}}/{{\text{m}}_{A{\text{l}}OOH}} $为1.5时,PEG200与AlOOH以氢键连接得到分散度高的铝溶胶,涂覆煅烧后PEG的造孔效应改善了载体形貌,为活性组分的负载提供了更多附着位点。在甲苯初始质量浓度1 000 mg·m⁻³和处理气量0.12 m³·h⁻¹的实验条件下,CuMnCeO_x/Al₂O₃/PEG(1.5)/CH催化剂降解甲苯的T₉₀为200 ℃,比CuMnCeO_x/CH和CuMnCeO_x/Al₂O₃/PEG(0.0)/CH催化剂分别降低了62 ℃和53 ℃。SEM、BET和XRD等表征发现,片状γ-Al₂O₃涂层增大了载体比表面积和孔容,活性粒子更均匀地分布于催化剂表面,为VOCs氧化提供更多的有效活性位点;过渡金属氧化物表面丰富的活性位点和Cu⁺/Cu²⁺与Mn³⁺/Mn⁴⁺间价态转化产生的氧空穴提高了催化剂的催化活性和VOCs的矿化效果。该研究结果可为高活性催化剂的制备及其微波催化燃烧VOCs技术应用提供参考。     

H4SiW12O40/TiO2/beads光催化降解亚甲基蓝的研究

以钛酸四丁酯为原料,空心微珠为载体,采用溶胶凝胶法制备TiO₂/beads光催化剂载体,然后浸渍法制备出H₄SiW₁₂O₄₀/TiO₂/beads表面负载修饰型复合光催化剂,并运用SEM、XRD、FT-IR和DRS对催化剂进行表征和分析。研究了H₄SiW₁₂O₄₀/TiO₂/beads对亚甲基蓝降解的光催化活性,考察了光强度、pH值、曝气量、底物浓度和催化剂用量等对催化效率的影响。实验结果表明,在中性条件下,H₄SiW₁₂O₄₀/TiO₂/beads催化剂的投加量为0.25 g/L,浓度为7.5 mg/L的亚甲基蓝溶液在250 W的紫外灯和600 W的可见光灯下光照60 min降解率分别可达到94.5%和55%。     

Fe2O3-Cr2O3/TiO2系列催化剂的结构和脱硝性能

研究以纳米TiO2为载体,浸渍负载过渡金属氧化物,以CO为还原剂的脱硝催化剂的脱硝性能。实验中以计算量的Ni(NO3)2和Fe(NO3)3混合溶液浸渍纳米TiO2粉末,室温下搅拌30 min至混合均匀,放入旋转蒸发器中,70℃下至水分蒸干为止;所得粉末在550℃下、空气气氛中焙烧4 h即得所需催化剂。用以上方法分别制备2%Fe2O3-10%Cr2O3/TiO2、4%Fe2O3-8%Cr2O3/TiO2、6%Fe2O3-6%Cr2O3/TiO2、8%Fe2O3-4%Cr2O3/TiO2与10%Fe2O3-2%Cr2O3/TiO2等5种催化剂样品。实验结果表明,制备的催化剂具有较好的结构,分散较为均匀。对于CO+NO反应,Fe2O3-Cr2O3/TiO2系列催化剂具有较好的催化活性,NO的转化率都达到了100%。其中,10%Fe2O3-2%Cr2O3/TiO2样品具有最好的低温活性,H2-TPR结果表明,这是由于10%Fe2O3-2%Cr2O3/TiO2催化剂更易于被CO预还原。     

Biotransformation of the fungicide pentachloronitrobenzene by Tetrahymenathermophila

The protozoan, $\text{Tetrahymena}$$\text{thermophila}$, metabolizes pentachloronitrobenzene to several products, including nitrite, pentachlorothioanisole and pentachloroaniline. The latter two metabolites were identified by gas chromatographymass spectrometry. Pentachlorothioanisole may be produced via a glutathione-dependent pathway, and two key enzymes of this pathway, glutathione transferase and thiol S-methyltransferase, have been detected in crude extracts of this microorganism.     

Biotransformation of N-phenyl-β-naphthylamine to β-naphthylamine in a laboratory sludge system

$\text{N}$-Phenyl-$\text{β}$-naphthylamine, a widely used rubber antioxidant and antiozonant, was biotransformed into $\text{β}$-naphthylamine, a potent carcinogen, in a laboratory sewage sludge system. $\text{β}$-Naphthylamine appeared to accumulate in the aqueous phase of the system while the undegraded parent compound appeared to be associated with the sludge solids.     

CdIn2S4/In2O3/BP复合可见光催化剂降解RhB及光催化灭活大肠杆菌

采用水热法制备了CdIn₂S₄和In₂O₃单品催化剂以及Cdln₂S₄/In₂O₃/黑磷(BP)三元复合光催化剂。利用X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、傅里叶红外光谱(FT-IR)、紫外-可见漫反射光谱(UV-vis DRS)、X射线光电子能谱(XPS)等对制备的催化剂进行表征分析。以罗丹明B(RhB)为目标降解物进行了降解实验,以大肠杆菌(E.coli)为目标进行了灭菌实验,分析了不同掺杂比例的Cdln₂S₄对所制备材料光催化性能的影响。从自由基捕获实验中分析出降解过程中起主要作用的活性物质。结果表明：CdIn₂S₄、In₂O₃、BP三者成功复合,复合的三元材料可提高In₂O₃对可见光的吸收,使其光催化活性得以增强;Cdln₂S₄/In₂O₃/BP对RhB的降解率和E.coli的灭菌率均优于单品催化剂,且5% Cdln₂S₄/In₂O₃/BP的光催化性能最好,光照120 min后,对RhB的降解率和对E.coli的灭菌率分别达到了94.7%和100%;在降解和灭菌过程中,·O₂⁻起主导作用。     

微纳米气泡/UV/K2S2O8协同处理模拟垃圾渗沥液

以垃圾渗沥液中的主要污染物冰乙酸、正丁酸、正己酸和氨组成的混合物为处理对象,采用微纳米气泡联合紫外灯活化过硫酸盐法处理模拟垃圾渗沥液,考察了反应时间、过硫酸钾投加量、pH、紫外灯功率、微纳米气泡进气量对污染物去除效果的影响。结果表明：微纳米气泡对紫外灯活化过硫酸盐法有显著的协同作用。当反应时间为180 min、过硫酸钾投加量为4 g·L⁻¹、pH=6、紫外灯功率为10 W、微纳米气泡进气量为30 mL·min⁻¹时,污染物的去除效果最佳,COD去除率为60.68%,TOC去除率为48.05%,氨氮去除率为42.1%。自由基淬灭实验结合EPR表征结果表明,羟基自由基和硫酸根自由基为降解过程中主要的活性物质。溶液中无机碳含量增加,说明废水中有机物分解为二氧化碳和水。     

Uptake and bioaccumulation of three PCBs by Chlorellafusca

This paper reports the bioaccumulation of three PCBs (2,4′-dichlorobiphenyl, 2,4,6,2′-tetrachlorobiphenyl and 2,4,6,2′,4′-pentachlorobiphenyl) by the green alga $\text{Chlorella}$$\text{fusca}$ under various conditions. A probable pattern of the bioconcentration mechanism is suggested. No metabolites were extracted from algae or water 6 days after incubation with PCBs.     

Bioaccumulation of pentachlorophenol by killifish (Fundulussimilus)

Killifish ($\text{Fundulus}$$\text{similis}$) were exposed in the laboratory to pentachlorophenol (PCP) at concentrations of 57 to 610 μg PCP/L. Bioaccumulation reached a plateau value of about 53 by 168 hrs and remained at this level for at least 72 hrs. One-half the plateau value was reached in about 25 hrs. Following exposure, fish placed in PCP-free aquaria lost PCP rather slowly ($\text{t}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{～ 4.7}\text{days}$). The depuration data were suggestive of a pool of PCP which was lost more rapidly ($\text{t}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{～ 4.2}\text{hrs}$). The results of this study are compared to similar studies in other species. The bioaccumulation factors measured in this study agree relatively well with those in other marine species, but are lower than reported for fresh water species. Possible reasons for this difference are discussed.     

Biochemical alterations in Bubalusbubalis after repeated exposures to quinalphos

Oral administration of 0.7 mg/kg/day of quinalphos to mals buffalo calves for 28 consecutive days produced marked inhibition of erythrocyte acetylcholinesterase and elevation in serum levels of aminotransferases and phosphatases without inducing apparent toxicity. The enzymic alterations were more pronounced following 1.4 and 2.1 mg/kg/day doses of quinalphos, which were lethal within 4–17 days.     

Environmentally-induced cadmium tolerance in the grass Holcuslanatus L.

This paper reports results of a study on cadmium tolerance in the grass $\text{Holcus}$$\text{lanatus}$ which suggest that tolerance is inducible and can be lost in transplanting plants to uncontaminated soils.     

A/O_1/H/O_2工艺处理焦化废水硝化过程的实现及其抑制

针对焦化废水中的有毒污染物会对敏感易受干扰的硝化细菌产生不利影响从而破坏硝化过程稳定性的现象,采用A/O1/H/O2工艺处理焦化废水的实际工程为研究对象,根据工程运行的水质监测数据分析,发现几种主要污染物的浓度变化会对二级好氧段的硝化过程产生抑制影响。序批式毒性抑制实验结果表明,苯酚、硫氰化物和喹啉对硝化过程具有毒性抑制作用,半抑制浓度EC50分别为34.26、278.5和73.24 mg/L。当二级好氧工艺段运行正常时(C/N约4.3/1,pH8～8.5,DO 4～4.5 mg/L),出水氨氮浓度可低于5 mg/L,是由于焦化废水经厌氧/好氧/水解工艺后毒物浓度大幅下降,毒性得到削减,表明焦化废水生物处理A/O1/H/O2组合流化床工艺具有较强抵抗毒物抑制并实现高效的硝化作用。