CO2含量对污泥燃烧Fuel-N析出特性的影响

在模拟水泥分解炉气氛条件下,考察了CO_2浓度对污泥燃料N(Fuel-N)析出特性的影响,结果表明污泥Fuel-N的析出形式主要为NH_3、HCN及NO_x.在研究的CO_2浓度范围(体积分数0～35%)内,CO_2浓度的升高将消耗更多的含氮位点和H自由基,导致NH_3的析出受到抑制;而CO_2能直接氧化HCN或—CN官能团,导致HCN的析出随着CO_2浓度的升高逐渐降低.NO_x的析出量随CO_2含量的升高先减小后升高,在25%时达到最小值.NO_x的生成和还原反应是同步发生的,在燃烧温度和O_2含量一定的情况下,NO_x的析出主要受NO_x还原反应的影响,研究表明燃烧过程中同时存在NO_x的气相均相还原反应和气固异相还原反应.当CO_2浓度从0上升至25%时,CO_2分子与污泥焦反应生成的CO相对增加,在污泥焦表面的催化作用下,NO_x被CO还原的量增多,此时污泥焦对NO_x的气固异相还原占据主导地位;继续增加CO_2浓度至35%时,还原性气体HCN生成幅度下降较大,此时HCN、NH_3对NO_x的气气均相还原占据主导地位,导致NO_x的析出逐渐升高.     

废轮胎流化床热解半焦结构特性

以流化床反应器为主体对废轮胎热解半焦微观结构特性进行了研究.主要研究了热解温度、床料粒径、流化数等参数对热解半焦的比表面积、孔隙率、孔体积的影响.结果表明:半焦比表面积和孔隙率随温度变化过程中会在650℃或750℃出现一峰值,这表明对半焦品质而言,轮胎存在最佳的热解温度,采用较小粒径(0.135～0.304mm)床料时有使最佳热解温度下降的趋势;半焦孔隙率随流化数增加而减小;半焦比表面积随流化数的变化趋势与热解温度有关,550℃时流化数增加半焦比表面积减小,650℃时流化数增加半焦比表面积增大;半焦孔体积随温度的变化趋势与床料粒径有关,采用较大粒径(0.304～0.4mm)床料时,半焦孔体积随温度升高呈现先降后升的趋势,而采用较小粒径(0.135～0.304mm)床料时,半焦孔体积随温度升高呈现下降的趋势.     

深度脱水污泥焚烧过程中调理剂的热转化行为及其对重金属挥发的影响

采用化学热力学平衡分析方法,应用污泥实测数据模拟计算了深度脱水后污泥焚烧过程中调理剂的热转化过程及逸出产物,并预测了含Cl调理剂与CaO耦合作用对重金属迁移转化及排放的影响.研究结果表明,污泥添加单一调理剂Al_2(SO_4)_3、Fe_2(SO_4)_3、FeSO_4、AlCl_3及FeCl_3后,Fe和Al在高温下主要以Al_2O_3(s)和Fe_2O_3(s)存在,主要气态产物是HCl和SO_2.调理剂CaO和FeCl_3共存且含量增加时,焚烧过程中HCl(g)逸出过程变慢,并且Fe_2O_3(s)易于和CaO(s)作用导致Fe_2O_3(s)存在温度区间变窄.污泥未添加调理剂焚烧过程中,重金属Cd、Pb、Cr、Tl、Hg、As易于以Cd(OH)_2(g)、PbO(g)、CrO_2(OH)_2(g)、AsO(g)、Hg(g)、Tl(g)形式挥发,而Cu、Zn、Ni以其氧化物形式存在而难挥发.调理剂FeCl_3及CaO添加到污泥后,重金属(Cd、Pb、Cu、Zn、Ni、Hg、Tl)的分布受FeCl3的影响大于CaO,导致其形成重金属氯化物而挥发,而Cr和As与CaO作用生成CaCr_2O_4(s)、Ca_3(AsO_4)_2(s)热稳定化学物,抑制了Cr、As的挥发.当脱水污泥与含硫化物掺烧时,重金属(Pb、Cu、Zn、Ni)挥发受到Cl的影响大于S,在低温区间其主要以硫酸盐为主,在中高温区间以氯化物存在,而Hg和Tl不受硫化物影响.     

型煤催化固硫的研究

本试验发现Fe_2O_3对型煤固硫有催化作用,当型煤中Fe_2O_3含量在6‰时,固硫率最高,比在同等条件下不加Fe_2O_3时约增加10%左右。在温度小于500℃时,固硫率和Fe_2O_3关系曲线只出现极大值,大于500℃时,则同时出现极大极小值。它的催化固硫动力学行为比较复杂,温度小于500℃,Fe_2O_3含量小于6‰时,它起催化作用;Fe_2O_3含量大于6‰时,它与CaO形成固熔体,因而影响了活性。型煤催化固硫率的高低主要取决于温度低于470℃这一阶段,提高型煤固硫率的关键是要求型煤在500℃之前升温速度不能太快,为此可设计一型煤预热装置,此装置温度控制在470℃以下,型煤在装置中停留时间不超过半小时。Fe_2O_3的加入主要加快了CaO+SO_2→CaSO_3这一主反应的速度,并对硫的最后形态CaSO_4起一定稳定作用。     

抗生素菌渣热解及气态污染物排放特性的研究

抗生素菌渣的热解行为受其热解条件的影响,而明确热解条件对抗生素菌渣热解特性的影响是其热解资源化和无害化的前提。通过在固定床反应器中热解抗生素菌渣(以土霉素菌渣为例),采用热重分析法研究升温速率、菌渣粒径、添加剂(CaO、CeO_2、Na_2CO_3)等热解条件对抗生素菌渣热解特性的影响,并利用傅里叶红外光谱仪(FTIR)分析了其热解过程中SO_2、HCN、NH_3、NO等气态污染物的排放规律。结果表明:抗生素菌渣的热解主要分为两个阶段,即在200~600℃温度区间,抗生素菌渣内有机质充分热解,挥发分大量析出,抗生素菌渣的质量损失从95%降低至40%左右,且在370℃达到最大失重速率9%/min,而在600~900℃温度区间,热解焦继续热解,抗生素菌渣的质量损失从40%降低至30%左右,直至稳定;升温速率的改变对热解焦剩余量的影响较小,但随着升温速率的提高,其热解速率加快;菌渣粒径越小,其热解速率越快,分解越彻底,热解焦的剩余量越少;添加剂能够改善抗生素菌渣的热解活性,降低热解反应的活化能,并可以促进氮、硫元素的转化,使热解气体中HCN、NH_3、NO、SO_2的排放浓度降低。     

改进燃烧技术控制NO_x的生成

一、前言日本巴韦日立公司根据最近社会上对降低NO_x的要求,开发了以实验燃烧炉为主体的低NO_x燃烧器,本文就液体燃料燃烧作一介绍。 (一)燃烧型NO_x和温度型NO_x 众所周知的氮氧化物有下列几种。 NO(一氧化氮);NO_2(二氧化氮);N_2O(氧化二氮);N_2O_3(三氧化二氮);     

前体物与气象因子对珠江三角洲臭氧污染的影响

利用2012年中国气象局广州番禺大气成分站的O_3、NO_x逐时浓度数据,广州观象台逐时的温度、相对湿度以及风向风速数据,统计分析了2012年O_3前体物(NO_x)以及气象因子对珠江三角洲(以下简称珠三角)地区臭氧浓度的影响.研究发现:O_3和NO_x均表现出单峰结构的月变化特征,且分别于10月和3月达到峰值,为(104.9±68.0)μg/m~3,(131.1±122.1)μg/m~3.O_3的日变化为单峰分布,午后的浓度较高,而NO_x浓度于早晚高峰有增加,且夜间浓度高于白天.NO_x对O_3有显著的滴定作用,O_3浓度随着NO_x浓度的增加呈现指数形式下降.高温低湿条件有利于O_3的形成.与NO_x类似,O_3浓度随着温度和相对湿度的增大以指数形式相应的增大和减小.当珠三角地区受偏西风控制时,下风向地区的O_3浓度最高,而当珠三角地区盛行偏北风时,下风向地区的O_3浓度最低,且该方向所对应的NO_x浓度最高,表明广州城区的NO_x对O_3的滴定作用显著.珠三角地区发生光化学污染的关键性因子主要为20~40μg/m~3的NO_x浓度,高于27°C的气温,低于55%的相对湿度以及受偏西风控制.分析发现10月份O_3的形成主要受VOCs控制,且烯烃的O_3生成潜势贡献最大,为69%,而烷烃和芳香烃的贡献分别为15%、16%.     

Fe2O3/MIL-53(Al)催化类芬顿氧化性能及其作用机制研究

以MIL-53(Al)和铁盐为原料,采用浸渍-焙烧的方法,制备了Fe_2O_3/MIL-53(Al)类芬顿催化剂.通过扫描电子显微镜(SEM)、射透射电子显微镜(TEM)、X射线衍射仪(XRD)、傅里叶变换红外光谱仪(FTIR)及X射线光电子能谱仪(XPS),对Fe_2O_3/MIL-53(Al)、MIL-53(Al)及Fe_2O_3 3种材料的理化性质进行了表征.以亚甲基蓝为相关材料催化类芬顿反应氧化性能的指示剂,考察了Fe_2O_3/MIL-53(Al)、MIL-53(Al)及Fe_2O_3 3种材料催化类芬顿反应的活性.探讨了Fe_2O_3/MIL-53(Al)催化活性强化的相关作用机制.研究结果表明,Fe_2O_3/MIL-53(Al)的物化结构特征是以赤铁矿为主的纳米Fe_2O_3颗粒均匀、离散地分布在MIL-53(Al)之上,纳米Fe_2O_3颗粒尺寸大多集中在1～5 nm.与未负载纳米Fe_2O_3相比,其分散性和颗粒尺寸都展现出潜在优越性.Fe_2O_3/MIL-53(Al)材料催化类芬顿反应降解水溶液中亚甲基蓝的效果是未负载纳米Fe_2O_3的4.8倍(以反应速率常数计),且TOC去除率亦有明显优势.自由基猝灭实验结果表明Fe_2O_3/MIL-53(Al)催化类芬顿降解污染物的主要活性氧类物质为羟基自由基.MIL-53(Al)孔结构发达、孔分布均匀及孔尺寸较小且均一等结构特征,导致负载其中的Fe_2O_3具有孔道负载量大、颗粒分布离散且均匀、颗粒粒径小且均一等特点,从而强化了纳米Fe_2O_3催化类芬顿反应氧化降解水中污染物的性能.     

砂砾质地表不同粒径颗粒地球化学特征分析

风沙运动造成地表沉积物组分发生改变,伴随其沉积物地球化学特征发生改变。选取苏宏图洪积扇扇缘戈壁、沙积洼地地表沉积物,基于X射线衍射仪、扫描电镜能谱仪进行其不同组分矿物、地球化学元素测试。结果表明:风沙运动导致不同地表沉积物的风蚀和风积情况不同,但其均处于化学风化的初、中级阶段,具有相似性;该砂砾质地表不同粒径组分以石英、长石、云母、方解石等矿物为主,各沉积物组分矿物衍射峰强具有显著差异性;该区域不同粒径颗粒化学元素组成以SiO_2、Al_2O_3、Fe_2O_3为主,约占总含量的85%左右,沉积物颗粒粒径越大,SiO_2含量越多,Fe_2O_3、MgO、CaO、TiO_2等氧化物表现为在细颗粒组分中富集,而Al_2O_3、K_2O、Na_2O等随颗粒粒径变化无显著差异。     

河北廊坊市区大气中NO、NO_2和O_3污染特征研究

对廊坊市区为期3a(2013年1月~2015年12月)4个监测站点的NO、NO_2、NO_x和O_3浓度和气象要素进行了逐时连续观测.在此期间,廊坊市大气环境中的NO、NO_2、NO_x和O_3的平均浓度(×10~(-9))分别为15.10、23.00、38.10、23.25.结果显示:NO平均浓度最大值出现在07:00~09:00左右,与机动车排放增强和混合层高度较低有关;O_3呈现单峰分布并在15:00~16:00之间达到峰值;廊坊市臭氧周末效应可能原因是周末道路交通NO_x排放高峰比工作日排放大约晚2h,更有效地促进臭氧的生成.廊坊环境大气NO_x浓度与交通排放分别存在大约2~3h的滞后效应.春夏秋冬四季的NO_2平均光解速率(min~(-1))依次为:0.128、0.398、0.315、0.117,并在14:00~16:00达到峰值,NO-NO_2和O_3分别为NO_x的二次多项式、反比例函数.京津冀中小城镇NO_x浓度主要与局地污染物的输送和扩散有关,OX(NO_2+O_3)浓度受北京、天津等大都市区域传输影响突出,区域源贡献最高发生在16:00~18:00.     

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.     

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.     

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.     

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.     

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.     

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.     

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.