超低排放下燃煤电厂氨排放特征

燃煤电厂采用SCR(选择性催化还原)脱硝过程消耗大量的氨,同时存在氨逃逸和氨排放问题.为了掌握超低排放燃煤机组的氨排放程度、脱硝氨逃逸情况以及各环保设施对氨的协同脱除能力,为燃煤电厂氨减排政策制定和氨减排技术研发提供支持.在京津冀大气污染传输通道城市中选取11个城市中的14台机组,采用例如DL/T 260—2012《燃煤电厂烟含脱硝装置性能验收试验规范》的标准方法用稀硫酸吸收烟气中的氨再结合分光光度测试方法,对环保设施多个位置的烟气中氨进行浓度测试.结果表明:①氨排放浓度介于0.05~3.27 mg/m3之间,平均约0.95 mg/m3,通过烟气排入大气中氨的浓度不高;②测试的14台机组中有7台机组(约50%)脱硝氨逃逸值高于设计值(2.28 mg/m3),说明脱硝氨逃逸超过设计值呈普遍现象,个别电厂脱硝氨逃逸严重,氨逃逸亟待解决;③环保设施对逃逸氨具有较好的协同脱除能力,平均脱除率约为64.86%.建议对于SCR脱硝氨逃逸严重的机组,对SCR出口烟道截面氮氧化物(NO_x)实施网格式测试,在此基础上实施精细化精准喷氨、优化流场、提高SCR脱硝运行水平(或采用专业化运维),从源头上减少氨耗量,降低系统能耗和氨排放.      

引入化学反应的600MW火电机组烟气SCR脱硝性能模拟

以600 MW火电机组现有SCR脱硝装置为研究对象,应用CFD软件完成建立模型、划分网格、选择数学模型、设置边界条件、模拟计算等工作,最终得出SCR脱硝系统流速分布及Cv值、压力损失、NH3分布及逃逸浓度等结果。结果表明:SCR脱硝系统流速分布均匀、偏差符合设计要求,NH3与烟气混合均匀,氨逃逸浓度低。     

600 MW燃煤机组脱硝超低排放性能对比评估

对燃煤机组脱硝超低排放进行改造前后的性能对比评估与研究,可为当前正在进行的超低排放改造提供指导与借鉴。以已实现脱硝超低排放的某600 MW燃煤机组SCR脱硝装置为例,评估了该机组脱硝装置超低排放改造前后的脱硝效率、入出口NO_x浓度分布、出口速度分布、氨逃逸、SO_2/SO_3转化率、系统阻力等运行参数,掌握了此台机组脱硝装置主要性能。试验结果表明,该机组SCR脱硝装置在进行超低排放改造后整体性能良好,较改造前各方面性能指标均有所改善,但仍存在流场不均、局部流速过高过低等问题,并相应提出了意见及建议。     

一种SCR脱硝装置喷氨混合系统的结构优化设计

氮氧化合物是主要的大气污染物之一,已经成为我国大气污染控制的重点。SCR(selective catalytic reduction)烟气脱硝技术因其脱硝效率高、运行稳定而成为目前应用最为广泛的烟气脱硝技术。当前SCR烟气脱硝工程存在的主要问题之一是氨气的逃逸率过高,喷氨混合系统的混合强度和均匀度是影响氨气逃逸率的重要因素。针对该问题采用计算流体动力学的方法优化设计了一种SCR脱硝装置喷氨混合系统,采用该种喷氨混合系统可以有效提高氨气与烟气在催化剂表面的混合均匀度,使氨气与烟气中的氮氧化物在催化剂表面充分反应,有效降低氨气逃逸率,同时降低SCR脱硝工程成本。     

某600MW燃煤电厂SCR蜂窝式脱硝催化剂性能检测与分析

脱硝催化剂性能检测与评估是SCR脱硝系统运行管理的一项重要工作,本研究对某600MW燃煤电厂在役蜂窝式脱硝催化剂性能进行了检测、分析,掌握了催化剂样品整体性能现状。检查了催化剂外观情况,对催化剂理化特性(微观比表面积、化学成分、机械性能(磨损率、抗压强度))、工艺特性(脱硝效率、活性、氨逃逸、SO2/SO3转化率)进行了检测。结果表明催化剂存在孔道及微孔堵塞、活性下降现象,活性下降约19%,超过设计值。通过对催化剂性能的检测分析,提出了SCR脱硝系统后续优化运行建议。     

Zn-W/TiO_2宽温度窗口SCR催化剂在燃煤烟气中的应用

为拓宽SCR催化剂的工作温度,研究宽温度窗口SCR催化剂在实际烟气条件中的应用对燃煤机组适应负荷波动、实现氮氧化物的超低排放具有重要意义。通过5×10~4 m~3/h的燃煤烟气污染物脱除试验平台,研究了Zn-W/TiO_2宽温度窗口SCR催化剂在不同温度窗口下的脱硝性能、氨逃率及连续运行300 h后催化剂效率及阻力的变化。结果表明:该催化剂在275～320℃性能稳定,当催化剂层温度为275℃、入口ρ(NO_x)为115.00～130.00 mg/m~3时,可保证NO_x出口浓度<20 mg/m~3。NH_3逃逸在低温窗口运行时略高于常规温度窗口,但仍<2.50 mg/m~3。综合各项指标分析,建议该催化剂运行效率<91.0%。     

基于线性控制的SCR脱硝分区喷氨工业性试验

为了分析SCR脱硝分区喷氨技术的应用效果,采用1 000 MW、750 MW、500 MW三种工况的分区喷氨脱硝装置进行工业性试验。结果表明:A侧反应器和B侧反应器出口NOx相对标准偏差≤19.7%,氨逃逸率小于2.28 mg/m3(标态、干基、6%O2),出口NOx排放浓度小时均值小于50 mg/m3(标态、干基、6%O2);在锅炉燃烧较为稳定的情况下,基于出口NOx浓度场线性反馈控制的分区喷氨技术可以实现SCR出口全截面NOx浓度的均匀分布。     

导流板对脱硝反应器运行的影响分析

在SCR脱硝系统中,流场均匀性的研究主要是通过计算流体动力学CFD与冷态试验模拟相结合的手段来进行,通过加设导流板对流场进行优化,从而为SCR工程设计提供最优流场建议。本文对多个SCR工程的现场安装和运行情况进行跟踪检查,监测出口NOx浓度和氨逃逸率,观察催化剂磨损情况和导流板积灰、变形现象,从多角度考察导流板的优化效果。     

南京市典型钢铁企业氨逃逸的排放特征分析

对南京市典型钢铁企业工艺流程开展调查研究,采用便携式激光光谱法对主要工序进行测试,通过氨排放浓度分析,可以看出氨排放浓度范围为0.1～382mg/m³,差异显著,初步分析氨主要来源为SNCR和SCR脱硝设施的氨逃逸;参照炼焦化学和我省锅炉排放标准氨排放限值,35.2%的排放口氨排放超标排放,超标倍数范围为0.24倍～47倍,主要集中在焦炉和烧结工序;最后根据分析结论为环境管理提出建议。     

水泥炉窑中低温催化脱硝技术中试性能

利用中低温SCR脱硝技术路线对水泥窑炉进行深度脱硝,设计建设了烟气处理量为10000m³/h的SCR中试实验装置,考察了在SNCR装置后烟气中未能反应的NH₃进一步在SCR（selective catalytic reduction）装置的脱硝效果,并分析了不同入口NO_x浓度对脱硝率的影响.结果表明,所研究的水泥厂仅采用SNCR（selective non-catalytic reduction）和低氮燃烧技术,能够将烟气中的NO_x控制在100~135mg/Nm³,在不喷氨的状态下SCR系统的脱硝效率可达到50%以上,说明SNCR反应存在着一定懂得氨逃逸;在SCR系统补充喷射氨气后,SCR脱硝效率有显著的提升,可提到至80%以上.通过低氮燃烧、SNCR与SCR等脱硝技术的联合使用,可将水泥炉窑烟气中NO_x的排放浓度控制在50mg/Nm³以内,满足超低排放要求;将经过较长时间稳定运行后催化剂从系统中取出,进行成分、孔径分布和脱硝活性对比,结果表明催化剂内部微孔会被部分堵塞,导致比表面积降低,但经吹扫处理催化剂的脱硝效率可恢复,说明催化剂在水泥窑炉烟气条件下长期运行未出现中毒现象.     

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.     

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.     

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.     

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.     

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.     

Removal of heavy metals from sewage sludge by low costing chemical method and recycling in agriculture

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Isolation and preliminary characterization of a 3-chlorobenzoate degrading bacteria

A study was conducted to compare the diversity of 2-, 3-, and 4-chlorobenzoate degraders in two pristine soils and one contaminated sewage sludge. These samples contained strikingly different populations of mono-chlorobenzoate degraders. Although fewer cultures were isolated in the uncontaminated soils than contaminated one, the ability of microbial populations to mineralize chlorobenzoate was widespread. The 3- and 4-chlorobenzoate degraders were more diverse than the 2-chlorobenzoate degraders. One of the strains isolated from the sewage sludge was obtained. Based on its phenotype, chemotaxonomic properties and 16S rRNA gene, the organism S-7 was classified as Rhodococcus erythropolis. The strain can grow at temperature from 4 to 37℃. It can utilize several （halo）aromatic compounds. Moreover, strain S-7 can grow and use 3-chlorobenzoate as sole carbon source in a temperatures range of 10-30℃ with stoichiometric release of chloride ions. The psychrotolerant ability was significant for bioremediation in low temperature regions. Catechol and chlorocatechol 1,2-dioxygenase activities were present in cell free extracts of the strain, but no （chloro）catechol 2,3- dioxygenase activities was detected. Spectral conversion assays with extracts from R. erythropolis S-7 showed accumulation of a compound with a similar UV spectrum as chloro-cis,cis-muconate from 3-chlorobenzoate. On the basis of these results, we proposed that S-7 degraded 3-chlorobenzoate through the modified ortho-cleave pathway.     

Single and joint effects of pesticides and mercury on soil urease

The influence of two pesticides including chlorimuron-ethyl and furadan and mercury （Hg） on urease activity in 4 soils （meadow burozem and phaeozem） was investigated. The soils were exposed to various concentrations of the two pesticides and Hg individually and simultaneously. Results showed that there was a close relationship between urease activity and organic matter content in soil. Chlorimuron-ethyl and furadan could both activate urease in the 4 soils. The maximum increment of urease activity by chlorimuronethyl was up to 14%-18%. There was almost an equal increase （up to 13%-21%） in the urease activity by furadan. On the contrary, Hg markedly inhibited soil urease activity. A logarithmic equation was used to describe the relationship （P〈0.05） between the concentration of Hg and the activity of soil urease in the 4 tested soils. Semi-effect dose （ED50） values by the stress of Hg based on the inhibition of soil urease in the 4 soils were 88, 5.5, 24 and 20 mg/kg, respectively, according to the calculation of the corresponding equations. The interactive effect of chlorimuron-ethyl or furadan with metal Hg on soil urease was mainly synergic at the highest tested concentrations.