不同气氛下燃煤SO2的排放规律研究

在立式管状电加热炉上对合山高硫煤在不同的气氛、温度以及Ca／S比的条件下进行了动态燃烧实验，对收集的气体产物进行了红外光谱分析，并讨论了CO2浓度以及温度等因素对SO2释放的影响。结果表明：不同浓度的CO2气氛对煤燃烧过程中硫的释放以及石灰石的固硫效率有着不同的影响，在高于900℃以后，较之空气气氛下，无论是否存在钙基固硫剂，其它三种02／C02气氛下S02的排放量都比较低，且在不同C02浓度下，温度对S02的排放影响不一致。     

纳米TiO2催化燃烧固硫的实验研究

通过纳米TiO2催化CaO燃烧后粉煤灰的成分分析和燃烧烟气中SO2含量的测定确定固硫效果,探讨了纳米TiO2添加量、Ca/S摩尔比、不同条件制备的纳米TiO2及燃烧温度对分析纯CaO固硫的影响,比较了纳米TiO2对不同煤种以及不同钙基固硫剂的固硫效果,并对反应产物进行了X射线衍射和扫描电镜分析.结果表明,纳米TiO2与CaO共同作用时,纳米TiO2最佳的添加量为8%;在Ca/S摩尔比为2、燃烧温度为850℃时纳米TiO2催化分析纯和工业纯CaO固硫效率达87.8%和60.3%,比不添加纳米TiO2时增加13.4%和29.6%.纳米TiO2对不同煤种燃烧时CaO固硫有较好地催化作用,能够促进SO2转化成SO3的本征反应,同时增加煤灰的孔尺寸,促进二氧化硫的扩散从而提高CaO的固硫效果.     

固硫煤和普通煤对SO2污染和健康危害的对比研究

探讨固硫煤与普通煤燃烧造成室内SO2污染及对健康的危害作用.将家兔分别喂养在燃烧固硫煤、普通煤和不烧煤的环境中连续观察90d,每天监测室内环境中SO2、CO的浓度;实验各时期测定家兔LYS含量和血清中SOD、GSH-PX、SA浓度.结果:固硫煤组SO224h平均浓度(2.68mg/m3)明显低于普通煤组(13.04mg/m3),但CO水平两组间无明显差异.实验90d后与实验前的GSH-PX值的差值比较,普通煤＞空白对照组＞固硫煤组,普通煤和固硫煤组间的差别有显著性意义(p＜0.05);SOD、SA、LYS值在实验期有所变化,但各组间的差别无显著性意义 (p＞0.05).结论:提示燃煤煤烟中SO2能影响生物体内SOD、GSH-PX、LYS、SA的浓度变化,燃烧固硫煤能明显降低SO2的污染,故使用固硫煤可减少燃煤煤烟对健康的危害.     

纳米助燃固硫添加剂的催化作用机理

溶胶.凝胶法制备的纳米TiO2作为CaO固硫添加剂,用热分析法对纳米TiO2催化煤燃烧以及催化CaO固硫的过程进行了实验研究.对燃烧后煤灰的孔径分布进行了分析.采用未反应收缩核模型对固硫反应的动力学过程进行表征.研究结果表明,纳米TiO2与CaO共同作用条件下对煤燃烧有明显的促进作用,即燃烧反应活化能E下降,同时纳米TiO2还能增大燃烧后煤灰的孔径,提高固硫率.氧气的存在抑制氧化钙的固硫转化率,纳米TiO2可以消弱氧气的抑制作用.对固硫反应的影响表现为在反应后期(即产物层扩散控制阶段),与固硫转化率和孔径分布的实验结果非常吻合;讨论了纳米TiO2催化燃烧催化固硫的机理,纳米TiO2导致碳晶格的扭曲,增加表面活性部位,加快氧气的吸附速度,使添加剂周围燃烧速度加快,煤灰孔隙增大从而强化燃烧,促进SO2转化成SO3的本征反应,促进二氧化硫向氧化钙内部的扩散从而提高CaO的固硫效果.     

高炉瓦斯泥参与水煤浆燃烧固硫作用机理的研究

由于高炉瓦斯泥中多种组分均具有燃煤固硫的特性,因此,本研究通过将高炉尘泥混入到水煤浆中进行燃烧,在前期研究的基础上,结合XRD分析,研究了不同燃烧条件下高炉瓦斯泥对水煤浆固硫率的影响规律,以及尘泥中多元固硫体系在燃烧固硫中相互协调作用、热力学行为.结果表明,瓦斯泥添加量为30%,燃烧终温为800℃时,固硫率达到48.31%.主要原因是瓦斯泥多组分促进了耐高温脱硫产物3Ca O3·3Al2O3·Ca SO4的生成,降低了Ca SO4的分解,从而提高了水煤浆的固硫率.研究结果可为具有多元固硫体系的高炉尘泥及其它固废高附加值利用提供一定的技术参数和理论依据,也可为开拓研究新型、高效燃煤固硫剂提供理论基础,具有一定的经济价值和环境意义.     

添加剂CeO_2对煤粉燃烧中钙基固硫的影响

针对内蒙古某火电厂用煤,以CaCO3为固硫剂,CeO2为固硫添加剂,进行了箱式电阻炉定温固硫实验,分析了温度、钙硫比、添加剂CeO2对燃煤固硫率的影响;热重法分析了固硫添加剂CeO2对煤炭燃烧性能的影响。结果表明:加入CeO2低温下(850℃、950℃)促进了燃煤固硫,提高了燃煤固硫率,而在高温下(1 050℃),催化作用导致固硫剂表面孔隙迅速堵塞,降低产物层扩散控制阶段反应速率,抑制了固硫过程的进行;CeO2催化了煤炭挥发份和固定碳的燃烧,降低了固硫煤着火点温度和燃尽温度,改善了煤的燃烧性能;揭示了添加剂CeO2催化固硫和催化燃烧的作用机理。     

悬浮态水泥生料固硫效率试验研究

在水泥工业领域,水泥生料作为悬浮预热预分解系统脱硫过程中的固硫剂,为了研究固气比、温度、气体流速、SO2浓度以及水泥生料比表面积对悬浮态水泥固硫效率影响规律,采用水泥工厂的生料,利用悬浮电阻炉对水泥生料固硫效率进行试验研究,研究发现固气比和温度对水泥生料固硫效率影响较大。     

超细煤粉在氧化条件下NOx的释放特性实验研究

采用DTG(热重/差热分析仪)和GC-MS(气相色谱质谱联用仪)对鹤岗煤超细化煤粉进行燃烧试验,分析了粒径、氧气浓度、升温速率对NOx释放的影响.结果表明,不同粒径的鹤岗煤在氧气浓度为20%的燃烧条件下,NOx的析出均为单峰曲线;粒径对煤粉燃烧NOx释放有重要影响,超细化煤粉可以减少NOx的排放;在5.10、20℃/min升温条件下,随升温速率的增大NO和NO2的析出量也增加,并且NO的最大析出速率对应的温度随着升温速率的提高也提高;随着燃烧气氛氧气浓度的增高,NOx的析出量相应增加,并且NOx的最大析出速率对应温度相应降低.     

螯合电镀污泥的基本理化特性及燃烧特性

在研究某园区螯合电镀污泥基本理化特性的基础上,针对其含有一定量的有机物及高金属含量的特点,利用红外-热联用技术(TGFTIR)对污泥在空气气氛下的燃烧特性和燃烧过程释放的气体组成进行了研究.结果表明,污泥中的有机物在空气中的燃烧经过4个阶段,其中,有机物的热解、燃烧发生在230~431.01℃范围的第2和第3阶段;燃烧过程会释放CO2、水蒸气和微量NH3、SO2,燃烧温度和控氧量决定释放气体的组成;另外,燃烧过程存在重金属的挥发,可采用有机高分子重金属捕集剂的碱性水溶液喷淋烟气,捕集挥发出的金属,净化焚烧过程释放的酸性气体.考虑到污泥中有机质的充分燃烧、金属铬、铁和铝等金属氢氧化物的分解及部分金属的挥发,污泥焚烧温度应控制在450~500℃左右.研究结果可为此类污泥焚烧热处理提供理论和技术支持.     

化学沉淀分离-置换法提纯Al13的工艺研究

采用A1Cl3溶液和Na2CO3粉末在不同温度下制备了不同浓度的聚合氯化铝(PACl).以选定的中等浓度、高Al13含量的PACl为原液,研究了Al13与硫酸盐沉淀反应过程中SO4/Al摩尔比、反应体系起始总铝浓度的影响以及Al13硫酸盐与Ba(NO3)2置换反应过程中的Ba/SO4摩尔比、超声、温度等因素的影响.实验结果表明,在制备温度为50℃条件下,浓度在0.4～0.6mol/L范围的PACl含有较高的Al13.沉淀分离反应的最佳SO4/Al摩尔比为0.6∶1;生成的Al13硫酸盐沉淀物为正四面体状晶体.在Al13硫酸盐与Ba(NO3)2溶液置换反应过程中,Ba/SO4的最佳摩尔比为1∶1,反应温度及超声作用对置换反应的影响较小;提高Ba(NO3)2的起始浓度可以得到相应较高浓度的纯化Al13溶液.所得Al13纯度的统计平均值为92.1%.     

Effects of two sludge application on fractionation and phytotoxicity of zinc and copper in the soil

The potential harm of heavy metals is a primary concern in application of sludge to the agricultural land. A pot experiment was conducted to evaluate the effect of two sludges on fractionation of Zn and Cu in soil and their phytotoxicity to pakchoi. The loamy soil was mixed with 0%, 20%, 40%, 60% and 80% (by weight) of digested sewage sludge (SS) and composted sludge (SC). The additions of both sludges caused a significant raise in all fractions, resulting in that exchangeable (EXCH) and organic bound (OM) became predominance of Zn and organic bound Cu occupied the largest portion. There was more available amount of Zn and Cu in SS treatments than SC treatments. During the pot experiment, the concentration of Zn in EXCH, carbonate (CAR) and OM and Cu in EXCH and OM fractions decreased in all treatments, so their bioavailability reduced. Germination rate and plant biomass decreased when the addition rate was high and the best yield appeared in 20% mixtures at the harvest of pakchoi. The two sludges increased tissue contents of Zn and Cu especially in the SS treatments. Zn in pakchoi was not only in relationship to ΔEXCH and ΔCAR forms but also in ΔOM forms in the sludge-soil mixtures. Tissue content of Cu in pakchoi grown on SC-soils could not be predicted by ΔEXCH. These correlation rates between Zn and Cu accumulation in pakchoi and variation of different fractions increased with time, which might indicate that sludges represented stronger impacts on the plant in long-term land application.     

Intraspecific differences in effects of co-contamination of cadmium and

A hydroponic experiment was carried out to study intraspecific differences in the effects of different concentrations of cadmium (Cd)(0-10 mg/L) and arsenate (As(V)) (0-8 mg/L) on the growth parameters and accumulation of Cd and As in six wheat varieties Jing-9428, Duokang-1, Jingdong-11, Jing-411, Jingdong-8 and Zhongmai-8. The endpoints of wheat seedlings, including seed germination,biomass, root length and shoot height, decreased with increasing the Cd and As concentrations. Significant differences in seed germination, biomass, root length, shoot height and the accumulation of Cd and As were observed between the treatments and among the varieties (p ＜ 0.05). The lethal dosage 50% were about 20, 80, 60, 60, 80 and 20 mg As/L for Jing-9428, Duokang-1, Jingdong-11,Jing-411, Jingdong-8 and Zhongmai-8, respectively, and the corresponding values for Cd were about 30, 80, 20, 40, 60 and 10 mg Cd/L, respectively. Among the six varieties, Duokang-1 was found to be the most resistant to Cd and As toxicity, and Zhongmai-8 was the most sensitive to Cd and As co-contamination. The resistance of the six varieties was found dependant on the seedling uptake of Cd and As. Duokang-1 was the most suitable for cultivation in Cd and As co-contaminated soils.     

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.