Ni2+改性的Cu-ZSM-5催化分解NO的性能

研究Ni2+改性的Cu-ZSM-5催化剂在无氧和有氧气氛下的NO分解反应性能,考察Ni2+的加入量及加入方式对Cu-ZSM-5催化剂NO分解活性的影响.结果表明,先交换适量Ni2+再交换Cu2+的Ni-Cu-ZSM-5催化剂较单组分Cu ZSM-5催化剂有较高的高温(500℃～600℃)NO分解活性.在含5.5%O2的反应气氛中,Ni-Cu-ZSM-5在500℃下的NO分解率较之Cu-ZSM-5高出约20%,Ni2+的引入显著提高了催化剂的抗氧活性.就Ni2+对Cu-ZSM-5催化剂的可能改性机制进行了讨论.     

Ce3+(La3+))改性Cu-ZSM-5催化剂分解NO活性的研究

 采用一步离子交换法用稀土Ce³⁺(La³⁺对Cu-ZSM-5分子筛改性,并在固定床反应器中进行了催化剂分解NO活性和耐氧性的实验研究.结果表明,离子交换主要发生在分子筛铝羟基和桥联羟基上,其中交换后的铝羟基为活性中心.Ce³⁺更易于交换到桥联羟基上,使铜离子占据活性中心,较低的交换温度和浓度有利于制备高催化活性催化剂.改性Cu-ZSM-5分子筛催化剂可以显著降低活性反应温度和提高空速,在310～390℃的温度范围内,La-Cu-ZSM-5催化剂上NO转化率均在80%以上,表现出良好的活性和较宽的反应温度范围.在O₂体积含量低于9%时,Ce³⁺掺杂Cu-ZSM-5表现出良好的氧稳定性,NO转化率基本保持在84%.     

Cu/Al-Ce-PILC在丙烯选择性催化还原NO反应中的失活研究

采用聚合羟基复合阳离子合成交联黏土Al-Ce-PILC,经SO^2-₄改性后,以浸渍法制备了铜基交联黏土催化剂Cu/Al-Ce-PILC,并将其应用于C₃H₆选择性催化还原NO的反应,350℃时NO转化率达到最大值56％,700℃时下降至22％.为探究催化剂高温失活的原因,采用XPS、TPR、TGA、Py-IR和DSC对反应前后催化剂的物化性能进行了表征.结果表明,经过H₂预处理活化后活性组分Cu物种以Cu⁺形式存在,而高温反应后Cu物种除以Cu⁺和Cu²⁺ 2种形式存在外,还出现了少量CuO物种;高温反应过程中Al-Ce-PILC上结构羟基和SO^2-₄流失导致催化剂表面酸性减弱;此外,还存在表面积炭覆盖了部分活性中心并堵塞了催化剂孔道的现象.这三者的共同影响促进了C₃H₆深度氧化,抑制了NO还原,从而导致催化剂的失活.     

用TTC与INT-电子传递体系活性表征重金属对污泥活性的影响

研究了不同浓度的Cu²⁺、Zn²⁺、Cd²⁺、Hg²⁺、Ni²⁺、Pb²⁺和Ag⁺对污泥TTC和INT 电子传递体系活性产生的影响 ,比较了这 2个参数在表征污泥活性受重金属抑制时的灵敏性 .结果表明 ,各种重金属抑制污泥TTC 电子传递体系活性的IC₅₀小于抑制INT 电子传递体系活性的IC₅₀,TTC 电子传递体系活性反映重金属毒性作用的灵敏性大于INT 电子传递体系活性 .实验的重金属离子呈现出不同的毒性作用 ,以TTC 电子传递体系活性为评价参数 ,毒性顺序为 :Hg²⁺>Cd²⁺>Cu²⁺>Ag⁺>Zn²⁺>Ni²⁺>Pb²⁺,以INT 电子传递体系活性为评价参数 ,毒性顺序为 :Hg²⁺>Ag⁺>Cu²⁺>Cd²⁺>Zn²⁺>Ni²⁺>Pb²⁺.     

重金属对厌氧污泥电子传递体系活性影响研究

以2-氯酚（2-CP）厌氧降解污泥电子传递体系(ETS)活性为考察对象,研究了3种典型重金属元素Cu²⁺、Cd²⁺、Ni²⁺对ETS活性的影响,并比较了驯化过程对提高厌氧微生物抗重金属毒性的作用.重金属离子对厌氧污泥呼吸活性的抑制作用发生很快,在0.25 h内就已表现出来,并随金属浓度的增加而加剧.驯化前,3种金属的作用均表现为抑制,抑制作用的强弱顺序为Ni²⁺>Cd²⁺>Cu²⁺,抑制强度与金属离子在水溶液中的含量成正相关关系.采用低浓度金属离子驯化的方法可以有效改善重金属毒性.驯化后,Cu²⁺毒性的降幅约为10%,Cd²⁺毒性的最大降幅超过40%,Ni²⁺对污泥ETS活性的作用则基本表现为促进,最佳促进浓度约为70　mg/L.Ni²⁺对ETS活性的特殊激活作用可能与其能形成正四面体结构的络合物有关.驯化作用对改善金属毒性的效果：Ni²⁺>Cd²⁺> Cu²⁺.     

Effect of transition metal doping under reducing calcination atmosphere on photocatalytic property of TiO2 immobilized on SiO2 beads

TiO₂ immobilized on SiO₂ (TiO₂/SiO₂) have been prepared by sol-gel method and various ions of transition metals (Cr³⁺, Co²⁺, Ni²⁺, Cu²⁺, and Zn²⁺) were doped on the photocatalyst using wet impregnation method under reducing calcination atmosphere. The photocatalytic activity of metal doped TiO₂/SiO₂ towards phenol degradation under black light irradiation were investigated and compared with undoped TiO₂/SiO₂. The results showed that the photoresponse of Cu²⁺ and Zn²⁺ doped TiO₂/SiO₂ were larger than undoped TiO₂/SiO₂, indicating that the photogenerated carriers were separated more efficiently in Cu²⁺ and Zn²⁺ doped TiO₂/SiO₂. The reactivity was in the order of Cu²⁺ > Zn²⁺ > Ni²⁺ > Cr³⁺ > Co²⁺. The different photoreactivity was ascribed to combine effect of the different ionic radii and photocorrison tendency of the dopants. The sample was also characterized by surface analytical methods such as X-ray diffraction, scanning electron micrograph/electron dispersive X-ray analyzer and UV-Vis absorption spectrum.     

活性炭纤维负载氧化镧催化净化NO的实验研究

以ACF作为载体制备了负载不同质量分数La₂O₃的负载型催化剂,研究了它们催化净化NO的活性和活性的稳定性,同时对比研究了ACF、HNO₃/ACF净化NO的能力.正交实验结果表明,实验中最佳的氧气体积分数为5%,最佳空速为5 000 m³·(m³·h)^-1;催化实验结果表明,ACF的低温活性很差,HNO₃/ACF净化NO的低温活性很好,但是其活性的稳定性很差;负载了La₂O₃的ACF能大幅提升ACF净化NO的能力,其活性中心为La₂O₃,La₂O₃的最佳负载量为20%,350℃以上时,20% La₂O₃/ACF催化净化NO的效率均在95%以上,在200℃恒温条件下,其催化活性约能持续8h;催化剂的理化特征实验结果表明,ACF、HNO₃/ACF净化NO的机制与负载了La₂O₃的ACF净化NO的机制有着本质的区别.     

零价铁对重金属和硝酸根的同步去除研究

为考察零价铁粉(Fe^O)同步快速处理废水中多种污染物的可能性,研究了Fe^０同步处理Cu²⁺、 Ni²⁺、 Cr(Ⅵ)等重金属离子和硝酸根.实验结果表明,硝酸盐对重金属离子的去除无明显影响,而不同重金属离子则对硝酸盐的去除有不同的影响.Fe^０同步去除水中的NO^-₃和Cu²⁺时,明显地提高了硝酸盐的去除率和反应速度,反应120 min使NO^-₃的去除率从38.2%提高到了95.0％,相应反应速率常数k_obs也从0.004 3 min^-1提高到了0.033 9 min^-1,且k_obs与Cu²⁺的初始浓度呈线性关系.Fe^０同步去除水中的NO^-₃ 和Cu²⁺时,由于Cu²⁺的存在,使得铁还原NO^-₃的表观活化能由40.8 　kJ·mol^-1降低到21.1 　kJ·mol^-1. 从而加快了Fe^０还原NO^-₃的反应速度.Fe^０同步去除水中的NO^-₃ 和Ni²⁺时,它们之间的相互影响较小.Fe^０同步去除水中的NO^-₃和Cr(Ⅵ)时,溶液中的硝酸盐浓度几乎保持不变,Cr(Ⅵ)的存在明显阻碍了铁粉还原脱除硝酸盐反应的发生.     

SO2对CoH-ZSM-5催化CH4还原NO催化性能的影响

研究了富氧条件下SO₂对CoH-ZSM-5上CH₄选择还原NO(CH₄-SCR)的影响,应用SO₂-TPSR,NO+(O₂)-TPD等方法研究了产生中毒的原因并定量研究了被毒化的活性位.反应在773 K进行时,加入体积分数78×10^-6SO₂,NO的转化率由72%逐渐降低并稳定在58%,提高反应温度至823 K,NO稳定转化率上升至62%.同时加入2.5     

两性复配修饰黏土对苏丹草修复Cu2+污染紫色土的影响

为了探索添加吸附材料对植物修复Cu²⁺污染土壤的影响,选取不同十二烷基二甲基甜菜碱 （BS-12）和十四烷基磺酸钠 （STS）复配修饰比例（50%BS-12+25%STS、50%BS-12+50%STS和50%BS-12+100%STS）的膨润土作为吸附材料,将其分别以1%的质量比加入到紫色土（PS）中,形成PS（对照）、PBS₂₅（50%BS-12+25%STS修饰膨润土混合紫色土）、PBS₅₀和PBS₁₀₀四种混合土样。采用盆栽实验对比苏丹草在0（CK）、50、100、200和500 mg/L Cu²⁺污染混合土样中的发芽率、株高、地上部和根系生物量,并分析混合土样和苏丹草对Cu²⁺污染的修复效果。结果显示,随着Cu²⁺处理浓度的增加,苏丹草在PS上的种子发芽率逐渐降低,而在各PBS土样上的发芽率基本保持先增加后稳定的趋势;不同Cu²⁺污染混合土样上的苏丹草株高均随生长时间的增加而增加。苏丹草地上部、根系干重和鲜重在PBS₂₅、PBS₅₀土样上均随Cu²⁺处理浓度的增大而降低,而在PS和PBS₁₀₀土样上均随Cu²⁺处理浓度的增加先增加后降低,峰值分别出现在200和100 mg/L的Cu²⁺处理。Cu²⁺污染处理下苏丹草各生理指标之间均保持中度以上正相关关系,且相关系数表现为PBS₁₀₀最高、PBS₂₅和PBS₅₀次之、PS最低的趋势。各混合土样对Cu²⁺的吸附能力表现为PBS₂₅ > PBS₅₀ > PBS₁₀₀ > PS,苏丹草对Cu²⁺的富集含量表现为PS > PBS₁₀₀ > PBS₅₀ > PBS₂₅的趋势,苏丹草联合两性复配黏土修复Cu²⁺污染紫色土的修复率达99%以上。     

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.     

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.     

基于综合水质标识指数和对应分析法的校园河道水质评价

以三峡大学的校园河道求索溪为研究对象,利用综合水质标识指数法确定求索溪水质类别,分析其水质时空变化规律,并利用对应分析法得出求索溪中不同监测点的主要污染因子.研究结果表明:求索溪整体的综合水质标识指数为7.423,整体水质为劣V类(地表水环境质量标准GB 3838-2002)且黑臭.从时间变化来看,求索溪4月份的水质最差,5月份次之,4、5月份所有监测点的水质都劣于V类且黑臭;8月份水质最好,水质为Ⅳ类;从空间分布来看,8个监测点综合水质标识指数均超过6.0,水质为劣V类,其中6号监测点的水质相对最好,监测点3号的水质相对最差;对应分析法得出求索溪的整体水体污染程度受总氮因子的影响最大,其次为总磷.该研究拟为求索溪及类似校园河道的水环境治理研究提供基础依据和参考.     

Effects of chitosan on growth of an aquatic plant (Hydrilla verticillata) in polluted waters with different chemical oxygen demands

Effects of chitosan on a submersed plant, Hydrilla verticillata, were investigated. Results indicated that H. venicillata could prevent ultrastructure phytotoxicities and oxidativereaction from polluted water with high chemical oxygen demand (COD). Superoxide dismutase (SOD) activity and malondialdehyde (MDA) contents in H. verticillata treated with 0.1% chitosan in wastewater increased with high COD (980 mg/L) and decreased with low COD (63 mg/L), respectively. Ultrastructural analysis showed that the stroma and grana of chloroplast basically remained normal. However, plant cells from the control experiment (untreated with chitosan) were vacuolated and the cell interval increased. The relict of protoplast moved to the center, with cells tending to disjoint. Our findings indicate that wastewater with high COD concentration can cause a substantial damage to submersed plant, nevertheless, chitosan probably could alleviate the membrane lipid peroxidization and ultrastructure phytotoxicities, and protect plant cells from stress of high COD concentration polluted water.     

Removal of cadmium using MnO2 loaded D301 resin

MnO2 loaded weak basic anion exchange resin D301 （Anion exchange resin, macroreticular weak basic styrene） as adsorbent has been prepared and applied to the removal of cadmium. The adsorption characteristics have been investigated with respect to effect of pH, equilibrium isotherms, removal kinetic data, and interference of the coexisting ions. The results indicated that the Cd^2＋ could be efficiently removed using MnO2 loaded D301 resin in the pH range of 3-8 from aqueous solutions with the co-existence of high concentration of alkali and alkaline-earth metals ions. The saturate adsorption capacity of the Cd^2＋ was 77.88 mg/g. The adsorption process followed the pseudo first-order kinetics. The equilibrium data obtained in this study accorded excellently with the Langmuir adsorption isotherm.     

Evaluation of phytoextracting cadmium and lead by sunflower, ricinus, alfalfa and mustard in hydroponic culture

Soil contaminated with heavy metals cadmium(Cd)and lead(Pb)is hard to be remediated.Phytoremediation may be a feasible method to remove toxic metals from soil,but there are few suitable plants which can hyperaccumulate metals.In this study,Cd and Pb accumulation by four plants including sunflower(Helianthus annuus L.),mustard(Brassica juncea L.),alfalfa(Medicago sativa L.), ricinus(Ricinus communis L.)in hydroponic cultures was compared.Results showed that these plants could phytocxtract heavy metals, the ability of accumulation differed with species,concentrations and categories of heavy metals.Values of BCF(bioconcentration factor)and TF(translocation factor)indicated that four species had dissimilar abilities of phytoextraction and transportation of heavy metals.Changes on the biomass of plants,pH and Eh at different treatments revealed that these four plants had distinct responses to Cd and Pb in cultures.Measurements should be taken to improve the phytoremediation of sites contaminated with heavy metals,such as pH and Eh regulations,and so forth.     

Effect of coagulation pretreatment on the fouling of ultrafiltration membrane

The purpose of this study is to understand the effect and mechanism of preventing membrane fouling, by coagulation pretreatment, in terms of fractional component and molecular weight of natural organic matter （NOM）. A relatively higher molecular weight （MW） of hydrophobic compounds was responsible for a rapid decline in the ultrafiltration flux. Coagulation could effectively remove the hydrophobic organics, resulting in the increase of flux. It was found that a lower MW of neutral hydrophilic compounds, which could remove inadequately by coagulation, was responsible for the slow declining flux. The fluxes in the filtration of coagulated water and supernatant water were compared and the results showed that a lower MW of neutral hydrophilic compounds remained in the supernatant water after coagulation could be rejected by a membrane, resulting in fouling. It was also found that the coagulated flocs could absorb neutral hydrophilic compounds effectively. Therefore, with the coagulated flocs formed on the membrane surface, the flux decline could be improved.     

Penetration analysis of elements and bioleaching treatment of spent refractory for recycling

Acidithiobacillus ferrooxidans ATCC23270 and Acidithiobacillus thiooxidans TM-32 were used for bioleaching of spent refractories of aluminium and copper melting furnaces for their recycling.Firstly,penetration of elements into aluminium melting furnace refractory was investigated and it was found that up to 7 cm from surface was contaminated.Comparison on leaching efficiency by the strains ATCC23270 and TM-32 found that the strain ATCC23270 could treat larger amount of the refractories than the strain TM-32 could do.In the experiment of bioleaching of spent refractory aluminium melting furnace by the strain ATCC23270,high leaching efficiency were obtained on Al,Si,and Ca,and extremely low leaching performance was,however,shown on the rest of elements i.e.,Na,Mn,and Zn.Under the strain TM-32 use,relatively high leaching performance was recognized on Al,Si,Ca,Na,Mn,and Zn.In the experiment of bioleaching for spent refractory copper melting furnace,almost the same leaching trends were shown on Cu,Zn,Al,and Si under the strains ACTT23270 and TM-32 uses.