粉煤灰源NaY沸石的制备及其对乙酸乙酯的吸附性能研究

采用粉煤灰合成沸石的方法既经济又环保,在乙酸乙酯吸附领域中具有巨大应用前景.遵循节能减排、废物再利用的环保原则,探索了3种不同Si/Al比的粉煤灰、结晶温度、结晶时间和碱浓度4个因素对合成NaY沸石的影响.XRD、氮气吸脱附实验及ICP结果表明,Si/Al比和水热结晶温度对高比表面积NaY沸石的合成影响最大.Si/Al比在1左右的粉煤灰合成的沸石比表面积较低,且晶形中存在大量的NaA沸石,而Si/Al比在2左右的粉煤灰合成了高比表面积且纯度较高的NaY沸石;3种粉煤灰均在65 ℃下合成NaY沸石,但在105 ℃下完全转化为方钠石.实验优化结果表明,最优合成条件为采用Si/Al为2左右的粉煤灰,在2 mol·L^-1碱浓度、65 ℃水热温度下结晶12 h.该条件下合成的NaY沸石比表面积高达654.86 m²·g^-1(比表面积最高的粉煤灰源沸石之一),是原粉煤灰比表面积的22倍左右,对乙酸乙酯的吸附量也由15.4 mg·g^-1增至108.2 mg·g^-1.     

利用粉煤灰合成沸石处理重金属污水研究

本研究中利用粉煤灰合成沸石对含有Cu^2 、Pb^2 、Cd^2 的制备水样进行批处理振荡实验，其吸附容量分别为9．56、0．89和0．25mg／l。实验证明，用合成沸石处理含重金属离子污水达到平衡所需的时间约为3h。对污水中重金属离子的去除率随pH值降低而降低，随沸石用量增加而增加。同等条件下，利用粉煤灰处理含Cu^2 的污水，其吸附容量仅为6．49mg／l，低于合成沸石。     

粉煤灰水热法合成沸石及其对氨氮吸附性能的研究

以粉煤灰为原料,采用NaOH碱熔融制得粉煤灰熟料,由水热法合成沸石产品。通过单因素试验和正交试验考察搅拌陈化时间、水热晶化时间、液固比对合成沸石的氨氮吸附容量的影响。试验结果表明:搅拌陈化时间为12 h、水热晶化时间为6 h、液固比为10时,合成的产品主要为P型沸石,其氨氮吸附容量达最大为6.15 mg/g,并以此为理论基础讨论其运用于水处理工艺中的可能。     

X型粉煤灰沸石吸附丙酮及其动力学研究

文章采用碱熔融水热法合成了X型粉煤灰沸石,通过XRD、XRF、SEM、氮气吸附等手段研究了该沸石的结构组成特点,考察了初始浓度、吸附温度和空速对X型粉煤灰沸石吸附丙酮的影响机制,在此基础上,进一步研究了X型粉煤灰沸石对丙酮的吸附动力学及吸附机理。结果表明：合成的X型粉煤灰沸石品质较高,平均粒径为0.83μm,平均孔径为3.2 nm,比表面积为165.8 m²/g,总孔容积为0.133 8 cm2/g,总孔容积为0.133 8 cm³/g;X型粉煤灰沸石吸附丙酮的过程中,初始浓度、空速和温度越高,穿透时间和饱和时间越短;在实验范围内,升高温度会导致吸附量显著降低,增加空速会使吸附量略有下降,而增加初始浓度会使吸附量明显增加,当温度为40℃,初始浓度为777.9 mg/m3/g;X型粉煤灰沸石吸附丙酮的过程中,初始浓度、空速和温度越高,穿透时间和饱和时间越短;在实验范围内,升高温度会导致吸附量显著降低,增加空速会使吸附量略有下降,而增加初始浓度会使吸附量明显增加,当温度为40℃,初始浓度为777.9 mg/m³,空速为75 h3,空速为75 h^(-1)时,X型粉煤灰沸石对丙酮具有最高的吸附量;Bangham模型和准一阶模型能更好地拟合丙酮在X型粉煤灰沸石上的吸附过程,说明丙酮在X型粉煤灰沸石表面的吸附更符合以物理吸附为主的孔道吸附。     

HDTMA改性粉煤灰沸石对水中铬酸盐的吸附

以自制HDTMA-粉煤灰沸石为吸附剂,对铬酸盐的吸附进行了实验研究。讨论了吸附剂的投入量、废水pH值、吸附温度和吸附时间等各因素对Cr（VI）去除率的影响。研究表明：pH值对Cr（VI）的吸附效率无显著影响,且在HDTMA-粉煤灰沸石的投加量为20 g/L、吸附温度为30℃、吸附时间为60 min的条件下,Cr（VI）的去除率可达90%左右。     

粉煤灰合成沸石处理含氟水的研究

以粉煤灰为主要原料,通过碱融法可以制备对氟离子具有一定吸附性能的沸石,通过正交试验与单因素试验共同考察了陈化时间、晶化时间和固液比对沸石吸附性能的影响,最佳的合成条件是陈化时间为12 h、晶化时间为6h、固液比为1/10,在制作工艺方面为粉煤灰合成沸石提供了重要参考.     

水热条件对粉煤灰沸石离子交换性能的影响

沸石的离子交换性能是决定其应用价值的一个重要指标。为衡量粉煤灰沸石的应用性能,本研究主要考察了反应温度、反应时间以及添加剂等水热反应条件对合成粉煤灰沸石产品离子交换性能(CEC,Cation Exchange Capacity)的影响。结果表明,产品的CEC值随着反应温度和反应时间增加而增大,至120℃、6h达到最大。添加剂十六烷基三甲基溴化铵和95%乙醇有效促进了NaP1沸石的结晶过程,均可使产品CEC值提高10%以上。合成NaP1型粉煤灰沸石的最佳水热反应条件为:反应温度120℃,反应时间6h,液固比(mL/g)为8,氢氧化钠浓度为2mol/L,95%乙醇作为添加剂。所得粉煤灰沸石产品CEC值达到最大值198.31cmol/kg。     

水热合成温度对纳米TiO2特性及其可见光波段光催化性能的影响

以乙醇-丙酮-吡啶为溶剂，采用水热法制备了在可见光波段（≤450nm）具有良好光催化活性的纳米TiO2粉体,通过XRD、TEM、DTA、漫反射谱（DRS）与光电压谱等手段，研究了水热合成温度及250℃热处理对合成纳米TiO2粉体的材料特性，以及在可见光激发下纳米TiO2对甲基橙光催化降解的影响．结果显示，纳米TiO2晶型（锐钛矿）与粒径不随水热合成温度及热处理（250℃）条件的变化发生明显改变；各样品的表面吸附物状态以及可见光响应特性在未经热处理时随水热合成温度变化发生明显变化，而在经250℃热处理后则差异不明显；样品的表面吸附物状态、可见光响应以及可见光催化活性之间有显著关联，水热合成温度显著地影响了纳米TiO2粉体的表面吸附物状态及可见光催化活性。     

粉煤灰吸附去除弱酸性艳蓝印染废水

利用粉煤灰对弱酸性艳蓝印染废水进行了处理。研究表明：粉煤灰的粒径、灰水比、废水pH值以及振荡吸附时间对粉煤灰的吸附能力均有较大影响。在以下工艺条件下：20℃,粉煤灰的粒径200目,灰水比为1：30,pH为2．0,振荡吸附2．5h,弱酸性艳蓝印染废水经粉煤灰处理后,COD值由576mg／L降至71mg／L,COD去除率可达87．7％：废水色度可从10000倍降为50倍,色度的去除率达99．5％,出水pH为6．5。出水水质达到了国家印染废水一级排放标准(GB4287—92)。     

添加剂对垃圾焚烧飞灰熔融过程二不断噁英分解的影响

为了研究添加剂对垃圾飞灰熔融处理过程中二噁英分解特性的影响，选择碱性氧化物CaO和液体陶瓷(LC)2种添加剂，改变温度、气氛和熔融时间研究2种添加剂对二噁英分解率的影响．研究表明CaO对二噁英分解影响随气氛不同而改变，氧化气氛下，加入CaO使二噁英的分解率略微降低，而在还原气氛下则会使二噁英分解率升高．液体陶瓷添加剂对熔融过程二噁英分解有显著影响．1400℃时，随着LC添加比例由0增加到10％，二噁英分解率则从99．997％升高到100％．同时加入10％的LC可以使二噁英的完全分解温度由无添加剂时的1460℃降低至1100℃．     

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.     

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.     

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

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Single and joint effects of pesticides and mercury on soil urease

The influence of two pesticides including chlorimuron-ethyl and furadan and mercury （Hg） on urease activity in 4 soils （meadow burozem and phaeozem） was investigated. The soils were exposed to various concentrations of the two pesticides and Hg individually and simultaneously. Results showed that there was a close relationship between urease activity and organic matter content in soil. Chlorimuron-ethyl and furadan could both activate urease in the 4 soils. The maximum increment of urease activity by chlorimuronethyl was up to 14%-18%. There was almost an equal increase （up to 13%-21%） in the urease activity by furadan. On the contrary, Hg markedly inhibited soil urease activity. A logarithmic equation was used to describe the relationship （P〈0.05） between the concentration of Hg and the activity of soil urease in the 4 tested soils. Semi-effect dose （ED50） values by the stress of Hg based on the inhibition of soil urease in the 4 soils were 88, 5.5, 24 and 20 mg/kg, respectively, according to the calculation of the corresponding equations. The interactive effect of chlorimuron-ethyl or furadan with metal Hg on soil urease was mainly synergic at the highest tested concentrations.     

Isolation and preliminary characterization of a 3-chlorobenzoate degrading bacteria

A study was conducted to compare the diversity of 2-, 3-, and 4-chlorobenzoate degraders in two pristine soils and one contaminated sewage sludge. These samples contained strikingly different populations of mono-chlorobenzoate degraders. Although fewer cultures were isolated in the uncontaminated soils than contaminated one, the ability of microbial populations to mineralize chlorobenzoate was widespread. The 3- and 4-chlorobenzoate degraders were more diverse than the 2-chlorobenzoate degraders. One of the strains isolated from the sewage sludge was obtained. Based on its phenotype, chemotaxonomic properties and 16S rRNA gene, the organism S-7 was classified as Rhodococcus erythropolis. The strain can grow at temperature from 4 to 37℃. It can utilize several （halo）aromatic compounds. Moreover, strain S-7 can grow and use 3-chlorobenzoate as sole carbon source in a temperatures range of 10-30℃ with stoichiometric release of chloride ions. The psychrotolerant ability was significant for bioremediation in low temperature regions. Catechol and chlorocatechol 1,2-dioxygenase activities were present in cell free extracts of the strain, but no （chloro）catechol 2,3- dioxygenase activities was detected. Spectral conversion assays with extracts from R. erythropolis S-7 showed accumulation of a compound with a similar UV spectrum as chloro-cis,cis-muconate from 3-chlorobenzoate. On the basis of these results, we proposed that S-7 degraded 3-chlorobenzoate through the modified ortho-cleave pathway.     

Organochlorine pesticides in soils under different land usage in the Taihu Lake region, China

A field study was conducted in the Taihu Lake region, China in 2004 to reveal the organochlorine pesticide concentrations in soils after the ban of these substances in the year 1983. Thirteen organochlorine pesticides (OCPs) were analyzed in soils from paddy field, tree land and fallow land. Total organochlorine pesticide residues were higher in agricultural soils than in uncultivated fallow land soils. Among all the pesticides, ΣDDX (DDD, DDE and DDT) had the highest concentration for all the soil samples, ranging from 3.10 ng/g to 166.55 ng/g with a mean value of 57.04 ng/g and followed by ΣHCH, ranging from 0.73 ng/g to 60.97 ng/g with a mean value of 24.06 ng/g. Dieldrin, endrin, HCB and α-endosulfan were also found in soils with less than 15 ng/g. Ratios of p,p'-(DDD DDE)/DDT in soils under three land usages were: paddy field ＞ tree land ＞ fallow land, indicating that land usage inlfuenced the degradation of DDT in soils. Ratios of p,p'-(DDD DDE)/DDT ＞1, showing aged residues of DDTs in soils of the Taihu Lake region. The results were discussed with data from a former study that showed very low actual concentrations of HCH and DDT in soils in the Taihu Lake region, but according to the chemical half-lives and their concentrations in soils in 1980s, the concentration of DDT in soils seemed to be underestimated. In any case our data show that the ban on the use of HCH and DDT resulted in a tremendous reduction of these pesticide residues in soils, but there are still high amounts of pesticide residues in soils, which need more remediation processes.     

Sorption of 1-naphthol by plant cuticular fractions

The contribution of aliphatic-rich plant biopolymer to sorption of hydrophobic organic compounds is significantly important because of their preservation and accumulation in the soil environment,but sorption mechanism is still not fully understood.In this study, sorption of 1-naphthol by plant cuticular fractions was examined to better understand the contributions of respective fraction.Toward this end,cuticular materials were isolated from the fruits of tomato by chemical method.The tomato cuticle sheet consisted of waxes (6.5 wt%),cuticular monomer (69.5 wt%),and polysaccharide (24.0 wt%).Isotherms of l-naphthol to the cuticular fractions were nonlinear (N value (0.82-0.90)) at the whole tested concentration ranges.The KodKow ratios for bulk cuticle (TC1),dewaxed cuticle (TC2),cutin (TC4),and desugared cuticle (TC5) were larger than unity,suggested that tomato bulk cuticle and cutin are much powerful solption medium.Sorption capability of cutin (TC4) was 2.4 times higher than the nonsaponifiable fraction (TC3).The 1-naphthol interactions with tomato cuticular materials were governed by both hydrophobic-type interactions and polar (H-bonding) interactions. Removal of the wax and polysaccharide materials from the bulk tomato cuticle caused a significant increase in the sorption ability of the cuticular material.There was a linear negative trend between K_(oc) values and the amount of polysaccharides or fraction's polarities ((N O)/C);while a linear positive relationship between K_(oc) values and the content of cutin monomer (linear R~2=0.993) was observed for present in the cuticular fractions.Predominant sorbent of the hydrophobic organic compounds (HOCs) in the plant cuticular fraction was the cutin monomer,contributing to 91.7% of the total sorption of tomato bulk cuticle.     

Alterations of organ histopathology and metallolhionein mRNA expression in silver barb, Puntius gonionotus during subchronic cadmium exposure

Common silver barb,Puntius gonionotus,exposed to the nominal concentration of 0.06 mg/L Cd for 60 d,were assessed for histopathological alterations(gills,liver and kidney),metal accumulation,and metallothionein(MT)mRNA expression.Fish exhibited pathological symptoms such as hypertrophy and hyperplasia of primary and secondary gill lamellae,vacuolization in hepatocytes,and prominent tubular and glomerular damage in the kidney.In addition,kidney accumulated the highest content of cadmium,more than gills and liver.Expression of MT mRNA was increased in both liver and kidney of treated fish.Hepatic MT levels remained high after fish were removed to Cd-free water.In contrast,MT expression in kidney was peaked after 28 d of treatment and drastically dropped when fish were removed to Cd-free water.The high concentrations of Cd in hepatic tissues indicated an accumulation site or permanent damage on this tissue.     

Seed selections for crystallization of calcium phosphate for phosphorus recovery

Seed induces and promotes the crystallization of calcium phosphate, and acts as carrier of the recovered phosphorus （P）. In order to select suitable seed for P recovery from wastewater, three seeds including Apatite （AP）, Juraperle （JP） and phosphate-modified Juraperle （M-JP） were tested and compared. Batch and fixed-bed column experiments of seeded crystallization of calcium phosphate were undertaken by using synthetic wastewater with 10 mg/L P phosphate. It shows that AP has bad enduring property in the crystallization process, while JP has better performance for multiple uses, and M-JP is a hopeful seed for P recovery by crystallization of calcium phosphate.