燃煤烟气中零价汞控制技术研究进展

我国燃煤过程中汞的排放越来越引起国际社会的广泛关注。燃煤烟气中排放汞的形态主要以零价汞为主,将气态零价汞转化为易于脱除的二价汞是控制零价汞排放的有效途径。为此,文章对燃煤烟气中零价汞的转化机理以及控制技术现状进行了概括和总结,对不同零价汞控制技术的特点进行比较分析,并初步探讨了其发展趋势。结论得出应充分利用现有的烟气净化设备,经济有效地发挥其在烟气除汞方面的作用。     

燃煤烟气脱汞技术

汞主要包括单质汞Hg0和二价汞Hg2 2种.二价汞化合物比较稳定,易溶于水,易脱除;单质汞挥发性较高、水溶性较低,是最难控制的形态之一.介绍了几种燃烧后脱汞的方法及烟气脱汞技术研究现状.     

不同煤种对烟气中汞的形态和分布的影响

采用化学热平衡分析方法研究了不同煤种燃烧过程中汞元素的化学形态及其分布.选用的煤种为唐山烟煤、高平无烟煤、贵州六盘水贫煤、小龙潭褐煤、印尼褐煤及宜昌褐煤6个煤样,在50~700℃温度范围内,比较讨论了不同煤样在氧化性气氛中汞的化学形态和物理相.结果表明:烟气温度较低时,原煤中S元素含量对烟气中汞的形态和分布的影响占主导地位;而原煤中Cl-含量越多,低温时最容易实现从HgSO4到HgCl2的转化,高温时最难实现从HgCl2到单质Hg的转化;相对于其它煤种,S和Cl元素在褐煤燃烧过程中的这种影响相对弱些.     

燃煤火电厂汞排放因子测试设计及案例分析

在火电厂锅炉煤的燃烧中,汞的迁移是个复杂的过程.在炉内高温下,几乎所有的汞以气态形式停留于烟气中,随着烟气温度的降低,汞被再分配到粉煤灰、炉渣和空气中.采用测试和衡算的方法,对火电厂汞排放因子进行测试和分析.结果表明:汞的迁移分配与煤中汞的赋存量、粉煤灰中可燃物碳的含量及烟气温度相关.煤燃烧后,进入粉煤灰中的汞占煤中汞含量的12.7%～31.3%,进入炉渣中的汞占0.9%～12.8%,大部分汞排入大气中,占67.8%～82.2%.      

火电厂烟气中汞的分布特征和排放特点

调查南京市某一燃煤火电厂100 MW机组,在两种不同的工况下,对该锅炉废气中的汞污染物进行现场测试,选取三个监测点位,分别为静电除尘器进口、出口及湿法脱硫装置出口,分析煤质燃烧烟气中汞不同形态的监测结果,得到静电除尘器和湿法脱硫装置对汞的脱除效率,总结火电厂烟气中汞的污染物的分布特征及其排放特点。火电厂燃烧的废气中汞来源于煤质中的汞,主要以气相部分汞形态存在,90%以上的汞以气态汞形态排放到烟气中,固相部分汞含量较少。静电除尘器对总汞有着相当高的脱除效率,湿法脱硫装置对总汞的脱除率较低。     

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。     

污泥与煤在循环流化床混烧过程中的汞排放特性

在密相床截面积为0.23m×0.23m、高度为7 00m的循环流化床燃烧试验装置上进行了含汞污泥与煤的混烧试验.测试并分析讨论了污泥与煤混烧过程中汞的分布,探讨了Ca/S摩尔比、脱硫剂种类、过量空气系数等运行参数以及烟气成分对汞在烟气、飞灰和炉渣中形态分布的影响规律.结果表明,大部分汞进入烟气,且元素汞是混烧烟气中的主要存在形态.钙基脱硫剂对烟气中氧化态汞有较强的吸附脱除作用,CaO对汞的脱除效果要好于CaCO3.随着烟气中SO2、NOx浓度的增大,烟气中二价汞所占份额呈上升趋势.过量空气系数对烟气和灰渣中汞的浓度和形态分布有较大的影响.     

基于实测的燃煤电厂汞迁移转化规律研究分析

为了研究某典型300 MW燃煤电厂汞迁移转化规律,对入炉煤、炉渣、石灰石、脱硫工艺水、石膏、脱硫废水、灰中的汞进行了取样测试。并采用EPA30B和安大略法实测了不同位置烟气中汞的形态分布情况。通过系统的汞质量平衡核算,得出各样品中汞所占的比例,在此基础上分析得到汞的迁移转化规律。结果表明,汞在煤渣中呈耗散状态,飞灰则具有一定富集汞的能力。袋式除尘器灰(0.016)的富集因子略高于电除尘器灰(0.094)的富集因子,可以看出袋式除尘器捕集颗粒汞的能力更强一些。烟囱排放的烟气是煤中汞的主要迁移方向,烟气经湿法脱硫系统后减少的汞主要富集在脱硫废水中,可以看出由湿法脱硫系统去除的汞大部分是可溶于水的二价汞。     

烟气污染综合治理的研究现状及发展趋势

烟气污染物大致分为气态污染物（SOx和NOx）、颗粒物和重金属.烟气综合治理的研究基础应先研究三类污染物之间、污染物与常用处理工艺之间以及不同污染物处理工艺之间的相互影响和作用.烟气污染综合治理的思路可归纳为工艺直接组合、集成控制与同时处理,其中以同时处理为最优.同时脱硫脱硝的研究趋势为等离子体技术与活性炭吸附技术,同时除尘脱汞的研究趋势则为汞在除尘过程中的迁移转化和汞的氧化剂和氧化方法的研究.     

脱硫废水添加对煤燃烧时汞析出特性的影响

为探究含氯脱硫废水溶液添加对煤燃烧时汞析出特性的影响,分别利用沉降炉和管式炉实验装置进行了3种煤在1200℃下的燃烧实验。实验时通过改变模拟脱硫废水溶液的添加量来控制燃煤中氯的质量分数分别为0.00%、0.02%、0.04%和0.06%。分析煤燃烧后烟气中汞浓度、吸收液、飞灰和煤灰中汞含量的变化情况发现:随着加氯量的增加,烟气中Hg0浓度逐渐降低,Hg2+浓度则逐渐升高,但对Hgt（气态总汞）浓度的提升效果相对较差。当加氯量为0.06%时,煤种B在沉降炉中燃烧后烟气中Hg0浓度下降约2.3 μg/m3,而Hg2+浓度提高约2.6 μg/m3,但Hgt浓度仅提高了0.3 μg/m3。氯的添加也会使飞灰中汞含量增加,煤灰中汞含量降低。通过综合对比分析沉降炉和管式炉实验结果发现:无论是否添加氯,煤在沉降炉中燃烧后烟气中Hg0比例均小于管式炉实验结果。当煤种B加氯量为0.06%时,在沉降炉和管式炉中燃烧后烟气中Hg0含量占比分别为50.6%和67.8%。此外,还发现3种煤粉在管式炉中加氯燃烧后汞的析出率提高趋势均较沉降炉明显。故含氯脱硫废水溶液的添加可以改变煤燃烧时汞的析出特性,且有利于促进烟气中Hg0的氧化,对燃煤烟气脱汞具有重要作用。     

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.     

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.     

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.     

Effect of sorbed and desorbed Zn(Ⅱ) on the growth of a green alga (Chlorella pyrenoidosa)

Toxic effect of Zn(Ⅱ) on a green alga (Chlorella pyrenoidasa) in the presence of sepiolite and kaolinite was investigated.The Zn-free clays were found to have a negative impact on the growth of C.pyrenoidosa in comparison with control samples (without adding any clay or Zn(Ⅱ)).When Zn(Ⅱ) was added,the algae in the presence of clays could be better survived than the control samples,which was actually caused by a decrease in Zn(Ⅱ) concentration in the solution owing to the adsorption of Zn(Ⅱ) on the clays.When the solution system was diluted,the growth of algae could be further inhibited as compared to that in a system which had the same initial Zn(Ⅱ) concentration as in the diluted system.This in fact resulted from desorption of Zn(Ⅱ) from the zinc-contaminated clays,although the effect varied according to the different desorption capabilities of sepiolite and kaolinite.Therefore the adsorption and desorption processes of Zn(Ⅱ) played an important part in its toxicity,and adsorption and desorption of pollutants on soils/sediments should be well considered in natural eco-environmental systems before their risk of toxicity to aquatic organisms was assessed objectively.