脉冲放电等离子体烟气脱硫脱硝工业试验研究

40 000～50000 Nm3/h工业试验结果表明,烟气温度75～80℃,脱硫效率＞90%,脱硝效率＞40%,烟气温度90～95℃,脱硫效率＞80%,脱硝效率＞50%;脉冲能耗＜3 Wh/Nm3;随着温度升高,SO2热化学反应效率逐渐降低;随着氨硫化学计量比增大,氨泄漏逐渐增加,烟气温度90～95℃,氨泄漏增加更为迅速.并分析了副产物的成分,阐述了脱硫脱硝的机理,并探讨了烟气排放的温度.     

SNCR的喷雾与混合过程及其对脱硝效率的影响

研究了SNCR(选择性无催化还原)工艺过程中还原剂液滴向炉内的喷射轨迹、以及还原剂在炉内高温空间的蒸发和混合扩散问题,得到了循环流化床锅炉不同截面的还原剂浓度分布。由研究结果可知,随着雾炬的扩散,还原剂浓度分布更加均匀,有效覆盖区域增加。根据还原剂有效覆盖范围,可以预测在合适的温度窗口处烟气的有效脱硝效率,在此基础上对喷枪喷射的液滴参数进行了优化分析。研究了不同液滴粒径分布对还原剂喷射和扩散的影响,结果表明:液滴雾化粒径的适当增大可以使蒸发时间延长,从而使得炉内还原剂与烟气中NO_x更好地混合、增加还原剂的有效覆盖面积;此外,根据还原剂覆盖浓度也可对还原剂的使用量进行预测。     

Ce掺杂TiO2-V2O5-WO3催化剂在水泥窑脱硝中的应用

以经Ce掺杂后的TiO_2-V_2O_5-WO_3催化剂为材料,在新型干法水泥生产线窑尾布袋除尘器后进行了低温选择性催化还原(SCR)脱硝中试试验。结果表明,掺杂Ce降低了TiO_2-V_2O_5-WO_3催化剂的起活温度。当烟气流量为10 000m~3/h(空速约5 000h~(-1))、氨水流量为5L/h、烟气温度超过150℃时,脱硝效率可达50%以上。SCR脱硝系统中,5 000h~(-1)空速设计是可行的。Ce适宜作为TiO_2-V_2O_5-WO_3催化剂低温改性助剂。     

超低排放背景下燃煤电厂烟气控制技术费效评估

在煤电机组超低排放趋势背景下,煤电企业需积极开展燃煤电厂大气污染物排放控制关键技术研究,快速推进环保升级改造,以期实现低成本下燃煤机组大气污染物的超低排放。基于环境审计中成本效益估算原则,收集实际工程案例投资和运行参数,建立了烟气脱硫、脱硝技术费效数据库,评估了燃煤电厂典型大气污染物控制技术的费用效益。烟气脱硫技术中,循环流化床半干法单位装机容量的系统初投资、年运行费用分别为25.78万、5.68万元/MW,均高于石灰石/石膏湿法。烟气脱硝技术中,选择性催化还原(SCR)技术的效费比仅为1.15,显著低于选择性非催化还原(SNCR)技术(1.63)和SNCR/SCR联用技术(1.36),但SCR技术脱硝效率高达80%,而SNCR技术的脱硝效率仅为30%,因此脱硝技术选型时不宜将效费比作为唯一参考指标。     

平板玻璃工业窑炉烟气中低温SCR脱硝中试研究

我国平板玻璃工业正面临严峻的NOx控制形势,研究并推广玻璃窑炉高效脱硝技术对玻璃工业发展及大气环境保护均具有重要意义。选择性催化还原(SCR)脱硝技术是国内外公认效率最高的脱硝技术,然而该技术在玻璃窑炉中推广应用还面临诸多技术问题。本研究设计并建设了10 000 Nm3/h的平板玻璃工业窑炉中低温SCR脱硝中试装置,分析了玻璃窑炉烟气组分波动规律及其对SCR脱硝系统的潜在影响,考察了烟气温度、喷氨量控制和烟气处理量等工艺参数,开展了为期6 d的连续运行实验。这些在实际烟气中开展的研究为玻璃窑炉SCR脱硝技术研究分享了大量一手数据和经验。     

水泥生料中的微量组分对预分解炉SNCR脱硝性能的影响

采用石英制固定床反应器,在模拟水泥预分解炉气氛条件下考察了微量Al_2O_3、Mg O、Fe_2O_3、CaSO_4和CaF_2对SNCR脱硝性能的影响。结果表明,水泥生料中微量的Al_2O_3和Mg O对脱硝性能没有影响;Fe_2O_3会显著降低低温区的脱硝效率;CaSO_4对脱硝性能有轻微促进作用。CaF_2的存在能提高脱硝效率。Al_2O_3、Mg O、Fe_2O_3和CaSO_4共存时所表现的作用主要是对低温区脱硝的抑制,此时CaSO_4作用被掩盖。因此在新型干法水泥生产中,若要尽可能减轻生料里的微量组分对脱硝的不利影响,需要在不影响水泥性能的前提下,尽量降低生料中Fe_2O_3含量,且避免将预分解炉上的喷氨点设置在低温区域。     

CH_4对于尿素选择性非催化还原脱硝的影响研究

在加热的石英反应器中研究CH_4对于模拟烟气尿素选择性非催化还原(SNCR)脱硝过程的影响。结果表明:添加CH_4可使脱硝曲线向低温方向移动,提高低温下的脱硝效率及脱硝温度窗口宽度,但最佳脱硝效率略有降低,当CH_4添加比由0增大到6.0时,尿素SNCR最佳脱硝效率减少了近14百分点,最佳脱硝温度降低了200℃,当CH_4添加比为2.0时脱硝温度窗口宽度最大,为296℃;添加CH_4可以缓解尿素SNCR体系的NH_3、HNCO逃逸,NH3、HNCO的近零排放温度均下降约150℃,为控制CH_4逃逸,喷入CH_4时应尽量保证喷入处温度不低于850℃;添加CH_4会提高低温下尿素SNCR的N_2O生成浓度,因此低温下N_2O的排放问题要引起足够重视;温度低于1 000℃时,提高氨氮比可以增强CH_4对脱硝效率的促进作用,但高于1 000℃时则起抑制作用。     

烟道喷射石灰(石)烟气脱硫技术综述

本文介绍了近几年发展起来的一种简单、中效、适合燃烧中低硫煤的工业锅炉的烟气脱硫技术———烟道喷射石灰 (石 )烟气脱硫技术。从湿法、干法、半干法 3种工艺对烟道喷射烟气脱硫进行了介绍 ,并提出新型脱硫吸收剂是提高烟道脱硫效率的可行方法。最后指出烟道脱硫今后的研究方向     

二次风喷嘴角度对炉排式垃圾焚烧炉内燃烧及选择性非催化还原脱硝的影响

利用CFD技术,对某城市处理量为750 t·d~(-1)的垃圾焚烧炉内燃烧与选择性非催化还原脱硝(SNCR)过程进行建模分析,重点研究了二次风喷嘴角度的改变对焚烧炉内燃烧温度场的影响及其对提高SNCR脱硝效率的作用。模拟结果表明,焚烧炉二次风喷嘴角度调整为相互交叉45°,可以改善炉内燃烧状况,促进炉膛内烟气与空气的混合,使炉膛内温度场分布均匀,有利于SNCR还原反应;二次风喷嘴角度改变后,在一定程度上保证了SNCR系统喷入的尿素液滴在炉膛内的停留时间。与平行二次风相比,使用交叉二次风送风方案,前墙喷嘴脱硝效率提高4.8%,后墙喷嘴脱硝效率提高了19.7%。     

水泥厂氨排放标准存在的问题及氨排放控制

为控制水泥脱硝工程产生的氨排放问题,中国发布《水泥工业大气污染物排放标准》(GB 4915—2013)对水泥企业氨排放限值提出明确要求。但水泥脱硝设施同步配套的氨在线检测仪记录数据表明,多数水泥厂脱硝后的氨排放浓度远超过标准限值。为此,对照火电厂相关标准和技术规范,指出了水泥工业氨排放标准和技术规范文件中存在的问题。结合实际检测数据和国外相关文献,确认水泥工业存在"本底氨"排放,水泥原料、协同处理废弃物、生产工况变化是导致本底氨排放的主要原因。选择性非催化还原(SNCR)脱硝设施产生的氨逃逸将增加氨排放浓度,反应温度窗口、停留时间、氨/氮摩尔比(NSR)、喷射方案等均会影响氨逃逸浓度。优化水泥生产工艺、SNCR脱硝工艺或配套选择性催化还原(SCR)脱硝系统等方式可有效控制水泥厂本底氨及氨逃逸。     

Radionuclides and trace elements in fish collected upstream and downstream of Los Alamos national laboratory and the doses to humans from the consumption of muscle and bone

Abstract

The purpose of this study was to determine radionuclide and trace element concentrations in bottom‐feeding fish (catfish, carp, and suckers) collected from the confluences of some of the major canyons that cross Los Alamos National Laboratory (LANL) lands with the Rio Grande (RG) and the potential radiological doses from the ingestion of these fish. Samples of muscle and bone (and viscera in some cases) were analyzed for ³H, ⁹⁰Sr, ¹³⁷Cs, ^totU, ²³⁸Pu, ^239,240Pu, and ²⁴¹Am and Ag, As, Ba, Be, Cr, Cd, Cu, Hg, Ni, Pb, Sb, Se, and Tl. Most radionuclides, with the exception of ⁹⁰Sr, in the muscle plus bone portions of fish collected from LANL canyons/RG were not significantly (p<0.05) higher from fish collected upstream (San Ildefonso/background) of LANL. Strontium‐90 in fish muscle plus bone tissue significantly (p<0.05) increases in concentration starting from Los Alamos Canyon, the most upstream confluence (fish contained 3.4E‐02 pCi g^‐1 [126E‐02 Bq kg^‐1]), to Frijoles Canyon, the most downstream confluence (fish contained 14E‐02 pCi g^‐1 [518E‐02 Bq kg^‐1]). The differences in ⁹⁰Sr concentrations in fish collected downstream and upstream (background) of LANL, however, were very small. Based on the average concentrations (±2SD) of radionuclides in fish tissue from the four LANL confluences, the committed effective dose equivalent from the ingestion of 46 lb (21 kg) (maximum ingestion rate per person per year) of fish muscle plus bone, after the subtraction of background, was 0.1 ± 0.1 mrem y^‐1 (1.0 ± 1.0 μSv y^‐1), and was far below the International Commission on Radiological Protection (all pathway) permissible dose limit of 100 mrem y^‐1 (1000 μSv y^‐1). Of the trace elements that were found above the limits of detection (Ba, Cu, and Hg) in fish muscle collected from the confluences of canyons that cross LANL and the RG, none were in significantly higher (p<0.05) concentrations than in muscle of fish collected from background locations.     

Patterns of volatile metabolites and nonvolatile trichothecenes produced by isolates of <Emphasis Type="Italic">Stachybotrys,Fusarium, Trichoderma,Trichothecium</Emphasis> and <Emphasis Type="Italic">Memnoniella</Emphasis>

We reported previously that trichodiene, a volatile trichothecene derivative, was produced by a Stachybotrys isolate, also known to produce highly cytotoxic, non-volatile, macrocyclic trichothecenes (satrotoxins). We investigated the relationship between the production of trichodiene and various non-volatile trichothecenes for several molds. Volatile metabolites were concentrated by adsorption on Tenax TA and analyzed by GC/MS, while non-volatile metabolites were separated by HPLC, derivatized and analyzed by GC/MS. Stachybotrys chartarum isolates producing macrocyclic trichothecenes secreted significantly larger amounts of trichodiene and other sesquiterpenes than isolates which only produced simple trichothecenes. The amounts of secreted trichodiene were relatively small in all cases. With the exception of Memnoniella, which excreted small amounts of sesquiterpenes, the other isolates produced varying amounts of sesquiterpenes, including trichodiene, as well as simple tricothecenes, no detectable trichodiene, but large amounts of griseofulvin derivatives. In Stachybotrys there is apparently a correlation between trichodiene and macrocyclic trichothecene production. In the remaining isolates, there was no simple relationship between trichodiene and non-volatile trichothecene synthesis. Trichodiene is produced in larger amounts by Stachybotrys isolates, which also produce satratoxins, but it will be difficult to utilize this metabolite to detect toxic isolates in buildings due to the relatively small amounts excreted.     

Radionuclides in deer and elk from Los Alamos national laboratory and the doses to humans from the ingestion of muscle and bone

Abstract

This paper summarizes radionuclide concentrations (³H, ⁹⁰Sr, ¹³⁷Cs, ²³⁸Pu, ^239,240Pu, ²⁴¹Am, and ^totU) in muscle and bone tissue of mule deer (Odocoileus hemionus) and Rocky Mountain elk (Cervus elaphus) collected from Los Alamos National Laboratory (LANL), Los Alamos, New Mexico, lands from 1991 through 1998. Also, the committed effective dose equivalent (CEDE) and the risk of excess cancer fatalities (RECF) to people who ingest muscle and bone from deer and elk collected from LANL lands were estimated. Most radionuclide concentrations in muscle and bone from individual deer (n = 11) and elk (n = 22) collected from LANL lands were either at less than detectable quantities (where the analytical result was smaller than two counting uncertainties) and/or within upper (95%) level background (BG) concentrations. As a group, most radionuclides in muscle and bone of deer and elk from LANL lands were not significantly higher (p<0.10) than in similar tissues from deer (n = 3) and elk (n = 7) collected from BG locations. Also, elk that had been radio collared and tracked for two years and spent an average time of 50% on LANL lands were not significantly different in most radionuclides from road kill elk that have been collected as part of the environmental surveillance program. Overall, the upper (95%) level net CEDEs (the CEDE plus two sigma for each radioisotope minus background) at the most conservative ingestion rate (50 lbs of muscle and 13 lbs of bone) were as follows: deer muscle = 0.22 mrem y^‐1 (2.2 μSv y^‐1), deer bone = 3.8 mrem y^‐1 (38 μSv y^‐1), elk muscle = 0.12 mrem y^‐1 (1.2 μSv y^‐1), and elk bone = 1.7 mrem y^‐1 (17 μSv y^‐1). All CEDEs were far below the International Commission on Radiological Protection guideline of 100 mrem y^‐1 (1000 μSv y^‐1), and the highest muscle plus bone net CEDE corresponded to a RECF of 2E‐06, which is far below the Environmental Protection Agency upper level guideline of 1E‐04.     

Leaching of seven pesticides currently used in cotton crop in Mato Grosso State—Brazil

This study aimed to evaluate the leaching of pesticides and the applicability of the Attenuation Factor (AF) Model to predict their leaching. The leaching of carbofuran, carbendazim, diuron, metolachlor, α and β endosulfan and chlorpyrifos was studied in an Oxisol using a field experiment lysimeter located in Dom Aquino – Mato Grosso. The samples of percolated water were collected by rain event and analyzed. Chemical and physical soil attributes were determined before pesticide application to the plots. The results showed that carbofuran was the pesticide that presented a higher leaching rate in the studied soil, so was the one representing the highest contamination potential. From the total carbofuran applied in the soil surface, around 6 % leached below 50 cm. The other pesticides showed lower mobility in the studied soil. The calculated values to AF were 7.06E-12 (carbendazim), 5.08E-03 (carbofuran), 3.12E-17 (diuron), 6.66E-345 (α-endosulfan), 1.47E-162 (β-endosulfan), 1.50E-06 (metolachlor), 3.51E-155 (chlorpyrifos). AF Model was useful to classify the pesticides' potential for contamination; however, that model underestimated pesticide leaching.     

Endosulfan in China 2—emissions and residues

Background, aim, and scope  Endosulfan is one of the organochlorine pesticides (OCPs) and also a candidate to be included in a group of new persistent organic pollutants (UNEP 2007). The first national endosulfan usage inventories in China with 1/4° longitude by 1/6° latitude resolution has been reported in an accompanying paper. In the second part of the paper, we compiled the gridded historical emissions and soil residues of endosulfan in China from the usage inventories. Based on the residue/emission data, gridded concentrations of endosulfan in Chinese soil and air have been calculated. These inventories will provide valuable data for the further study of endosulfan. Methods  Emission and residue of endosulfan were calculated from endosulfan usage by using a simplified gridded pesticide emission and residue model—SGPERM, which is an integrated modeling system combining mathematical model, database management system, and geographic information system. By using the emission and residue inventories, annual air and soil concentrations of endosulfan in each cell were determined. Results and discussion  Historical gridded emission and residue inventories of α- and β-endosulfan in agricultural soil in China with 1/4° longitude by 1/6° latitude resolution have been created. Total emissions were around 10,800 t, with α-endosulfan at 7,400 t and β-endosulfan at 3,400 t from 1994 to 2004. The highest residues were 140 t for α-endosulfan and 390 t for β-endosulfan, and the lowest residues were 0.7 t for α-endosulfan and 170 t for β-endosulfan in 2004 in Chinese agricultural soil where endosulfan was applied. Based on the emission and residue inventories, concentrations of α- and β-endosulfan in Chinese air and agricultural surface soil were also calculated for each grid cell. We have estimated annual averaged air concentrations and the annual minimum and maximum soil concentrations across China. The real concentrations will be different from season to season. Although our model does not consider the transport of the insecticide in the atmosphere, which could be very important in some areas during some special time, the estimated concentrations of endosulfan in Chinese air and soil derived from the endosulfan emission and residue inventories are in general consistent with the published monitoring data. Conclusions  To our knowledge, this work is the first inventory of this kind for endosulfan published on a national scale. Concentrations of the chemical in Chinese air and agricultural surface soil were calculated for each grid cell. Results show that the estimated concentrations of endosulfan in Chinese air and soil agree reasonably well with the monitoring data in general. Recommendations and perspectives  The gridded endosulfan emission/residue inventories and also the air and soil concentration inventories created in this study will be updated upon availability of new information, including usage and monitoring data. The establishment of these inventories for the OCP is important for both scientific communities and policy makers.     

Impact of spiked concentrations of Cd,Pb, As and Zn in growth medium on elemental uptake of Nasturtium officinale (Watercress)

This study is aimed at investigating the impact of water quality on the uptake and distribution of three non-essential and toxic elements, namely, As, Cd and Pb in the watercress plant to assess for metal toxicity. The plant was hydroponically cultivated under greenhouse conditions, with the growth medium being spiked with varying concentrations of As, Cd and Pb. Plants that were harvested weekly for elemental analysis showed physiological and morphological symptoms of toxicity on exposure to high concentrations of Cd and Pb. Plants exposed to high concentrations of As did not survive and the threshold for As uptake in watercress was established at 5 ppm. Translocation factors were low in all cases as the toxic elements accumulated more in the roots of the plant than the edible leaves. The impact of Zn on the uptake of toxic elements was also evaluated and Zn was found to have an antagonistic effect on uptake of both Cd and Pb with no notable effect on uptake of As. The findings indicate that phytotoxicity or death of the watercress plant would prevent it from being a route of human exposure to high concentrations of As, Cd and Pb in the environment.     

Butyltin compounds in sediment and fish from the Polish Coast of the Baltic Sea

Concentrations of mono- (MBT), di- (DBT), and tri-(TBT) butyltin compounds were measured in eggs, liver, and muscle of nine species of fish from four regions of the Baltic Sea - the Firth of Vistula, the Gulf of Gdańsk, Puck Bay, and the mouth of the Vistula River. The overall concentration ranges among all the fish sampled from the four sites were: < 7 to 79 ng/g for MBT, 6 to 1100 ng/g for DBT, 7 to 3600 ng/g for TBT, and 16 to 4800 ng/g for total BTs, on a wet wt basis. The highest concentration of total BTs was found in herring liver from the Firth of Vistula (4800 ng/g, wet wt) and in roach muscle from Puck Bay (3300 ng/g, wet wt), while the least concentration was found in burbot eggs and liver from the Vistula River (39 and 32 ng/g, wet wt, respectively). TBT was the major form of BTs present in most samples analyzed. Sediment samples collected from shipyards in the Gulf of Gdańsk contained butyltin concentrations ranging from 1.2 to 46 μg/g (dry wt) for MBT, 2.0 to 42 μg/g for DBT, and 2.6 to 40 μg/g for TBT. As with the fish, the majority of the BTs in sediment were present as TBT, which suggested recent exposure of the aquatic environment of the region to TBT.     

Malathion-induced sublethal toxicity on the hematology of cricket frog (Fejervarya limnocharis)

The effect of malathion [diethyl(dimethoxythiophosphorylthio)succinate] at sublethal concentration (0.006 ppm) on hematological parameters of the cricket frog (Fejervarya limnocharis) was studied for 24 hrs to 240 hrs of exposure and remarkable hematological alterations were observed. The study on hematological parameters revealed a highly significant decrease (P < 0.01) in the total erythrocytes count in malathion-exposed animals from 24 hours to 96 hrs of exposure as compared to control. Significant decreases (P < 0.01) of hemoglobin and packed cell volume were also observed from 48 hrs to 240 hrs. A significant increase (P < 0.01) in leucocytes count was noted throughout the exposure period. Elevated numbers of lymphocytes and eosinophils as found in the present study revealed lymphocytosis as well as eosinophilia, suggesting that this was a result of direct stimulation of the immunological defense due to the presence of a toxic substance or may be associated with tissue damage. The cytomorphological and cytopathological study of erythrocytes and leucocytes in malathion-exposed frogs at 0.006 ppm concentration revealed various cytotoxic effects at different exposure times. It was noted that the size and the shape of the erythrocytes were subjected to variation in different blood disorders.     

Relation between forest vegetation, atmospheric deposition and site conditions at regional and European scales

Several monitoring programs have been set up to assess effects of atmospheric deposition on forest ecosystems. The aim of the present study was to evaluate effects on the understorey vegetation, based on the first round of a regional (the Netherlands) and a European forest monitoring program. A multivariate statistical analysis showed surprisingly similar results for both data sets; the vegetation appeared to be largely determined by the ‘traditional’ factors soil, climate, and tree species, but there was a small but statistically significant effect of atmospheric deposition. The effects of deposition include a slight shift towards nitrophytic species at high N deposition in the European network, and towards acidophytic species at high S-deposition in the Dutch network. The relatively small effect of atmospheric deposition is understandable in view of the very large natural variation in environmental conditions. Time series of both vegetation and environment are needed to assess deposition effects in detail.