湿法脱硫工艺中MnSO_4对CaSO_3氧化与溶解速率的控制研究

亚硫酸钙的氧化是湿式石灰石石膏脱硫工艺最关键的过程,其氧化程度最终影响到烟气中二氧化硫的脱除效率。在溶解特性实验中发现,pH的影响最为显著,且溶解温度越高,需要的溶解时间越长。在亚硫酸钙的氧化实验中,以硫酸锰作为催化剂,采用实验室鼓泡反应装置,研究温度、pH、硫酸锰浓度、亚硫酸钙浓度对亚硫酸钙氧化速率的影响。试验结果发现:在无催化剂时,亚硫酸钙的氧化速率基本不变,而加入硫酸锰后,氧化速率随着亚硫酸钙的浓度增加而增大,且随着温度、pH、硫酸锰浓度的升高呈先增高后下降的趋势。     

电石渣中杂质对亚硫酸钙氧化及石膏浆液脱水性能影响

为了考察电石渣中杂质(Na2S、SiO2及铁、镁、铝的氧化物等)在湿法烟气脱硫过程中对亚硫酸钙氧化及石膏浆液脱水性能的影响,通过建立亚硫酸钙氧化反应装置,对亚硫酸钙氧化及石膏浆液脱水过程进行了研究。研究表明:浆液中Na2S浓度越高,亚硫酸钙氧化受到的抑制作用越明显,Na2S浓度高于10.0 mmol/L时,浆液中亚硫酸根几乎不发生氧化反应,石膏平均粒径随Na2S浓度增加呈先降低后增大趋势。浆液中SiO2不影响亚硫酸钙氧化,但是浓度低于0.5 g/L时,石膏粒径分布更加集中,更有利于提高石膏浆液脱水性能。浆液中Fe2O3的存在有利于亚硫酸钙氧化,浓度在0.5～1.0 g/L时,对石膏浆液脱水性能有明显的改善作用。浆液中MgO、Al2O3的存在,对亚硫酸钙氧化影响不大,但降低了石膏浆液脱水性能。     

湿法烟气脱硫环境下亚硫酸钙强制催化氧化的研究

采用机械搅拌槽式反应器,对湿法烟气脱硫环境进行模拟以研究锰催化对亚硫酸钙氧化的影响。实验得出:湿法烟气脱硫环境下,当槽内亚硫酸钙浆液浓度很小时,锰离子催化氧化对SIV浓度是1.5级,对Mn2+浓度是0.5 级;随着亚硫酸钙浆液增加至某一浓度后,氧化反应开始遵循并行反应机理,即氧化反应包括SIV离子的非催化氧化反应和SIV离子的锰离子催化氧化反应,且锰离子的催化氧化反应对Mn2+浓度是0.5级。文中提出的氧化反应速率的试验公式可以用来对湿法烟气脱硫中的氧化过程进行模拟。     

非均相UV/Fe-Cu-Mn-Y/H2O2反应催化降解4BS染料废水

制备了负载在Na Y分子筛上的Fe Cu Mn Y复合催化剂,并对其在非均相UV Fe Cu Mn Y H2O2体系中催化氧化4BS染料废水进行了研究.结果表明,非均相UV Fe Cu Mn Y H2O2体系对4BS染料废水的处理具有很高的效率.在基准条件下,反应时间为20min时,废水中4BS的去除率达到了93 7%.与均相UV Fenton体系不同,非均相UV Fe Cu Mn Y H2O2体系在碱性条件下(pH=10 5)仍可高效去除CODCr.动力学研究得到催化氧化4BS废水的模型方程,该模型可以为非均相UV Fe Cu Mn Y H2O2体系处理高色度的实际染料废水提供指导.     

半干法烟气脱硫灰改性及应用

文章主要对半干法脱硫灰中亚硫酸钙的氧化转化进行研究。半干法脱硫灰中亚硫酸钙对建材质量具有一定影响,通过筛选合适的催化-氧化剂体系对其进行了氧化改性。试验得到了一种复合催化剂,成功用于半干法脱硫灰改性。结合蒸压砖的生产工艺,使亚硫酸钙在生产过程中实现了部分转化,生产的蒸压砖能达到JC239-2001《粉煤灰砖》MU10强度等级。     

乙醇胺热降解-氧化降解循环过程及SO2在其中的影响

使用半连续式不锈钢搅拌反应釜,研究了质量分数30%的乙醇胺(MEA)水溶液(CO2负载量0.4 mol·mol-1)的热降解-氧化降解循环过程,旨在探讨循环过程对MEA降解的影响,以及SO2对MEA热降解、氧化降解和循环过程产生的影响.其中,热降解的实验条件为120℃,降解时间为2周,在密闭反应器内进行;氧化降解的实验条件为55℃,约121.59 kPa,向溶液中持续通入模拟烟气,总气量为7.5 L·min-1,其中包括2%CO2、0~150 ppm SO2和空气.实验结果表明,在先进行热降解再进行氧化降解的过程中,MEA的热降解产物N-(2-羟乙基)乙二胺等会在氧化降解的过程中发生进一步反应,且原本氧化降解中生成的亚硝酸根会有部分进一步被氧化,生成硝酸根.在循环过程中,MEA的整体降解程度比单独进行热降解、氧化降解实验中有所提高.研究表明,添加亚硫酸根会加剧热降解中的氨气生成量,而在氧化降解中,SO2又表现出了明显的抑制作用.在循环过程中,这两者均有体现,SO2仍起到一定的抑制降解的作用.     

半干法脱硫灰中亚硫酸钙催化氧化研究

半干法脱硫灰因脱硫过程中产生的脱硫副产物(脱硫灰)中Ca SO3含量高,成为了其处置与综合利用的技术瓶颈。本文通过对Ca SO3催化氧化实验研究,筛选出了低温下能够有效催化亚硫酸钙氧化的催化剂——硫酸锰。并从催化剂添加量、反应温度、反应时间等影响因素对硫酸锰催化氧化亚硫酸钙的影响进行了实验研究。结果表明,硫酸锰在室温下能够实现对亚硫酸钙的催化氧化,解决半干法脱硫灰资源化利用过程中亚硫酸钙含量高的问题。     

动态气升式环流反应器对生物除磷的强化作用

采用模拟污水,通过厌氧-好氧交替过程研究了活性污泥生物除磷过程.在实验过程中,通过周期性通入空气和氮气的实验方法,采用气升式环流反应器和普通鼓泡塔进行对比,在研究反应器的传质性能的基础上,进一步对反应器内的活性污泥形态和生物除磷性能进行了观察和测定.实验表明,相对于普通鼓泡塔,动态气升式环流反应器对活性污泥的生物除磷过程有明显的强化作用,磷的去除率提高了30%.      

二氧化硫在潮湿气溶胶表面的氧化速率研究

将稳定同位素方法应用于闽南地区SO₂在潮湿气溶胶表面氧化动力学研究中,在对大气中SO₂的稳定硫同位素及大气气溶胶中可溶性硫的硫稳定同位素丰度的测定的基础上,用硫稳定同位素动力学方程计算SO₂在潮湿气溶胶表面氧化速率与均相氧化速率比?结果表明:漳州地区潮湿气溶胶表面SO₂非均相和均相氧化速率之比:K非/K均为1.13,厦门地区SO₂非均相和均相氧化速率之比:K_非/K_均为0.36,这种差异主要是由相对湿度不同引起的。      

铈掺杂Ru/Al2O3催化臭氧氧化降解邻苯二甲酸二甲酯

考察了铈(Ce)的掺杂对Ru/Al2O3催化臭氧氧化邻苯二甲酸二甲酯(DMP)溶液过程的影响.结果表明,Ce的掺杂可以显著提高臭氧氧化的效果,反应100min后,TOC的去除率可以由原催化剂的61.3%提高到75.1%,而单独臭氧氧化仅有14.0%.在实验范围内,Ru和Ce同时浸渍催化效果较好,且活性组分的溶出最少,Ce的最佳掺杂量为1.0%.通过催化剂吸附试验、单独臭氧氧化试验、Ce的均相催化试验及Ru-Se/Al2O3催化剂的非均相催化实验,证明Ru-Ce/Al2O3催化剂对DMP溶液臭氧氧化体系TOC的去除率达到50%,这是基于Ru-Ce/A12O3催化剂的非均相催化作用.     

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.     

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.     

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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