燃煤电厂烟气Hg排放特征及其吸附脱除技术研究进展

对比了中美燃煤电厂烟气Hg排放限值,统计、分析了中国燃煤电厂烟气Hg排放特征,按美国现役机组低阶煤、非低阶煤的Hg排放限值要求,我国燃煤电厂Hg排放达标率分别仅为25. 8%、70. 9%,实施烟气Hg排放控制是非常必要的。对活性炭、改性飞灰、钙基吸附等国内外吸附脱Hg技术进行综述,基于此指出了干粉活性炭、改性飞灰吸附脱汞技术的后续研究重点,并提出开发廉价、高效、可循环再生使用的Hg吸附剂是未来重要的研究方向,可为我国燃煤电厂吸附脱Hg技术研究及工程实施提供参考。     

燃煤机组超低排放改造对汞的脱除效果研究

燃煤烟气中汞污染的控制是目前重要的环保课题之一,燃煤电厂利用现有的脱硝、脱硫、除尘设备去除汞,文章分析燃煤电厂烟气净化设备超低排放改造后汞的排放水平,说明现有废气处理设施超低排放改造,既能有效降低烟尘、二氧化硫、氮氧化物排放浓度,也有利于汞的去除,燃煤机组超低排放改造后汞的排放浓度远低于现行0.03 mg/m3的限值;通过分析燃煤电厂现有烟气净化设备对汞的协同去除效果和脱除汞的原理,提出了未来燃煤烟气汞污染控制措施的建议.     

小型燃煤机组烟气重金属排放特征研究

100 MW以下燃煤机组呈单台容量小、总台数大的特点,是燃煤重金属污染的主要排放源之一.选择7台12 MW燃煤机组,采用美国环境保护局Method 29法现场检测燃煤机组烟气重金属排放浓度,分析烟气中Hg、Pb、Cr、As的排放特征;采集机组产生的飞灰和底灰,分析除尘技术对重金属的富集特性.结果表明:100 MW以下燃煤机组烟气中重金属经脱硝除尘脱硫装置协同控制后,ρ（Hg）为0.20~0.44 μg/m3,烟气Hg以气态形式存在,其占比为100.0%;ρ（Pb）为0.5~2.6 μg/m3,烟气Pb主要以气态形式存在,其占比为38.7%~92.1%;ρ（As）为0.6~3.0 μg/m3,烟气As主要以气态形式存在,其占比为67.8%~100.0%;ρ（Cr）为3.6~23.9 μg/m3,烟气Cr主要以颗粒态形式存在,其占比为65.8%~99.2%.飞灰富集Hg、Pb、Cr、As的能力大于底灰.重金属主要富集于飞灰中的细颗粒物中,采取除尘技术可有效协同控制烟气中的Hg、Pb、Cr、As;飞灰中重金属元素Hg、Pb相对富集系数均与煤中硫含量呈负相关,半干法脱硫+袋式除尘技术对飞灰富集Hg有促进作用.小型燃煤机组烟气重金属Hg、Pb、Cr、As的排放因子分别为0.002 2~0.005 1、5~17、42~160、7~24 mg/t.研究显示,100 MW以下燃煤机组与100 MW及以上燃煤机组烟气重金属Hg、Pb、Cr、As排放特征不同,100 MW以下燃煤机组烟气Hg排放浓度较小,二者烟气Pb、Cr、As排放浓度相近,选用湿式电除尘技术可进一步降低烟气Hg、Pb、Cr、As的排放浓度.      

燃煤电厂重金属排放与周边土壤中重金属污染特征及健康风险

为揭示燃煤电厂烟气中重金属排放对周边土壤环境的影响.以石家庄地区6座燃煤电厂为研究对象,测定了燃煤电厂烟囱入口烟气中As、Cd、Cr、Cu、Pb、Hg和Ni这7种重金属元素,同时对电厂周边土壤中重金属含量进行了测试分析,并对其进行了源解析和健康风险评价.结果表明,各燃煤电厂烟气经过一系列烟气污染物控制措施净化后,烟气中不同重金属元素的排放量范围为0.11~6.32 mg ·（MW ·h）^-1,Cu、Cr和Ni是主要排放污染物.各电厂向大气环境中排放的7种重金属元素总量在33.56~275.71 kg ·a^-1之间.燃煤电厂周边表层土壤中Cr、Cu、Pb、Hg和Ni这5种重金属元素含量平均值均高于河北土壤背景值,且超出背景值1.16~2.32倍.电厂周边土壤中重金属含量与烟气中重金属排放量具有一定相关性.不同风向上土壤中重金属含量随距电厂距离的增大,呈现出先增大后逐渐减小趋势.源解析表明煤炭燃烧排放对电厂周边土壤重金属的贡献率最大,达到41.4%,其次为工业排放,占比为23.6%,交通运输排放占比为19.6%.总而言之,人为活动对土壤重金属富集起主导作用,约占84.6%.健康风险评估显示电厂周边土壤中重金属元素的健康风险整体处于可接受范围内.     

燃煤电厂石灰石-石膏湿法脱硫系统中痕量元素的迁移分布规律

燃煤电厂是煤炭消耗的主力军,煤炭在燃烧过程中,大量痕量元素随烟气排出.随着我国环保要求的不断提高,燃煤电厂的痕量元素排放受到广泛关注.石灰石-石膏湿法烟气脱硫(WFGD)系统不仅能高效吸收烟气中的SO₂,同时影响痕量元素的迁移分布.本研究对安徽省3个超低排放燃煤电厂的WFGD系统中进/出口烟尘、石灰石、工业水、污泥、石膏和脱硫废水等环境样品进行了采集,研究了Cr、As、Cd、Pb和Hg等痕量元素的迁移分布特征.结果表明：(1)WFGD系统对烟尘中痕量元素的去除率在95%以上,脱硫污泥中Cr、As和Hg浓度分别为29.9～52.2、12.5～36.7和2.2～6.5 mg/kg,约为石膏中Cr、As和Hg浓度的7～9倍.(2)元素质量平衡分析表明,痕量元素主要来源于烟气和石灰石,主要输出为污泥和石膏,废水中仅富集少量Cd.研究显示,脱硫石膏和污泥的处置及再利用过程中需着重关注痕量元素的环境影响.     

某600 MW机组燃煤电厂Hg的分布、排放特征及迁移、释放规律

为全面表征某600 MW超低排放燃煤机组的Hg分布特征及迁移、释放规律,开展了现场实测研究。结果表明:煤中Hg含量的平均值为310 μg/kg,炉渣、粉煤灰、石膏、废水、烟气中Hg的分布系数分别为1.9%、37.5%、34.6%、0.8%、24.8%;整个烟气治理系统的总Hg脱除效率为74.7%,最终总Hg排放为6.0 μg/m3,SCR脱硝、烟气冷却器对Hg0转化效率分别达到44.2%、30.4%,低低温电除尘器几乎实现Hgp完全脱除,WFGD对Hg2+脱除效率达到80.7%;该电厂Hg一次释放量达到783 kg/a(其中,大气直排188 kg/a),二次释放量为334 kg/a。该成果可为燃煤电厂烟气Hg排放控制标准出台及控制技术的选择提供借鉴。     

燃煤工业锅炉重金属排放特征研究

通过对6台燃煤工业锅炉污染物控制装置前后烟气中重金属浓度进行测试,考察了静电除尘器(ESP)、湿法脱硫装置(WFGD)和脱硫除尘一体化装置对烟气中重金属排放的影响。研究结果表明:ESP对烟气中的重金属有较好的捕集效果,对Pb、Cd、Cr的去除效率均为50%以上,通过对2台工业锅炉烟气中重金属排放测试发现,静电除尘器对Hg的去除率分别为45.70%和29.63%;经WFGD装置洗涤后,烟气中Hg、Pb、Cd的浓度均低于10μg/m3;脱硫除尘一体化技术对Hg、Pb和Cd的去除效果不明显,4号锅炉烟气脱硫后Pb的排放浓度高达65.76μg/m3。ESP+WFGD烟气处理装置较脱硫除尘一体化装备能够更好地控制烟气中重金属的排放。     

燃煤电厂排放烟气与大气中BaP的污染

本文通过对山西大同、神头、平定、漳泽地区大气中苯并(a)茈(以下称BaP)浓度的监测和全省十多个燃煤电厂烟道排放粉尘中BaP的检测,阐明燃煤电厂排放烟气与大气中BaP污染的关系。     

燃煤电厂烟气汞的排放及控制研究

随着环保意识的增强,燃煤电厂汞污染越来越受到人们的关注,对燃煤电厂烟气汞污染的控制也逐渐成为热点。介绍了燃煤电厂烟气中汞的排放形态及特性,分析了燃煤电厂烟气汞形态转化的影响因素,综述了有关燃煤电厂烟气中汞污染控制技术及研究进展,讨论了燃烧前脱汞、燃烧中脱汞和燃烧后脱汞技术,特别分析了利用现有烟气脱硫设备吸收法脱汞、吸附法脱汞、催化氧化脱汞的技术,并对燃煤电厂烟气脱汞技术的前景进行了展望,提出结合现有烟气净化设备同时脱汞的设想。     

基于监测数据的我国燃煤电厂汞排放分析

燃煤是最大的人为汞排放源之一,我国已加强对燃煤电厂的汞排放控制要求。通过对16家燃煤电厂32台机组的汞排放情况进行全要素监测,分析总结出符合我国燃煤电厂特点的汞排放情况:我国燃煤机组中的汞质量平衡范围在70%~130%是合理的;燃烧后的汞经过烟气污染物处理设施后,70%以上进入粉煤灰和脱硫石膏,经烟气排入外环境的平均不足30%;安装SCR脱硝装置有助于烟气中汞的去除;除尘、脱硫设施对烟气中汞平均去除效率为38.5%、52.5%;各污染物控制设施对烟气中汞的总协同去除效率平均为74.1%,说明我国燃煤机组现有的污染物处理设施的协同控制对降低烟气中的汞排放有较好的作用。     

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.     

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.     

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.     

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.     

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.