生活垃圾衍生燃料催化气化制备合成气

以生活垃圾衍生燃料RDF(refuse derived fuel)为原料,在750℃下进行了催化气化-改质实验,研究了氧气供应量、Ni基催化剂组分等操作要素对合成气生成特性的影响。结果表明:氧气供应量ER(equivalent ratio)的增加可以提高碳素转化率和冷气体效率;在Ni基催化剂中添加Mg、Ce、K、Ca和Zn等金属助剂可以有效改善改质催化性能,促进焦油分解,提高有效气体收率。在750℃温度条件下,控制供氧量ER=0.04时,通过催化气化-改质处理,可以从RDF获得H_2体积分数约29.00%的清洁合成气,冷气体效率和碳素转化率分别为44.41%和82.41%,合成气收率可达0.244 m~3·kg~(-1)(RDF)。     

城市干污泥热解气化

针对包头市南郊污水处理厂污水污泥,采用先热解后对热解残渣进行气化的方法探讨城市污泥的有效利用方式。污泥热解实验取升温速率(20~60℃·min-1)和终温(400~600℃)作为影响因素,得出各热解产物产率的变化规律。结果表明,污泥热解在终温为600℃时失重率达到57.53%,焦油产率在450℃达到峰值。污泥残渣的气化分别以水蒸气和CO2作为气化剂,探讨了800~1 000℃范围内的气化产品气组分变化规律。以水蒸气为气化剂时,污泥热解残渣的可制备富氢产品气,产品气中H2体积分数随着反应温度的增加而增加,1 000℃时H2含量可达68.83%,H2+CO含量达到81.36%,低位热值为9.18 MJ·Nm-3。以CO2作为气化剂时,产品气中富含CO,温度越高CO含量越高,1 000℃时到达最大值53.84%,产品气低位热值为7.25 MJ·Nm-3。     

城市生活垃圾热解重整制合成气计算分析

基于热化学平衡对热解重整制取合成气工艺进行了建模分析,考察了垃圾收到基水分M_(ar)、干燥基灰分A_d、热解装置入口垃圾含水率和合成气燃烧比例对能量转化率、干合成气产率、干合成气低位热值、合成气组分等的影响。结果表明:该工艺对于收到基低位热值大于6.7MJ·kg~(-1)的生活垃圾可以产生标况下低位热值高于5.3 MJ·m~(-3)的干合成气;垃圾收到基水分和干燥基灰分的增加会大幅降低能量转化率、干合成气产率和低位热值。     

生物质废弃物快速热解制取富氢气体的实验研究

采用管式炉对红松锯屑快速热解制取富氢气体进行了实验研究,分析了反应器温度、物料粒径和催化剂对热解产物组成的影响.结果表明高温能加快生物质快速热解进程,减少炭和焦油生成量,利于富氢气体的生成,800℃时气态产物比例可达56.9 wt.%,气态产物中H2体积分数由4.3%(500℃下)上升至17.2%,H2 CO体积分数达68.3%.小粒径能增大热解气态产物的比例,但对气态产物组成的影响很小,这可能与红松锯屑本身质地疏松有关.以与生物质直接混合方式添加的煅烧白云石能使热解产物中H2含量增加,但造成产气过程变缓,炭生成量增多,富氢气体总产量未能得到提高.     

天然气全氧燃烧尾气生活垃圾气化热力学分析

基于Aspen Plus模拟平台,运用吉布斯能最小化原理,以天然气全氧燃烧尾气(后续称为烟气)作为气化剂,选取反应温度和烟气流量与生活垃圾量比(E/M)作为影响因素,气化炉温度变化范围为400~1 500℃,E/M范围0~3.0,对几种典型生活垃圾(木屑、纸屑、塑料、橡胶和厨余)气化进行模拟计算。模拟结果表明,以烟气作为生活垃圾气化剂,可制备富氢产品气,产品气为中热值燃气。温度在800℃左右时,H2的体积分数达到峰值46.75%,反应温度大于800℃时,反应温度的增加对提升产品气的热值、CO的含量有一定作用,但H2的含量和产品气产率有所下降,反应温度过高增加气化的能源投入,反应温度应控制在800~1 000℃范围。高温烟气的过量导致产品气热值和品质下降,E/M宜控制在0.4~1.0区间范围。     

镍基催化剂对污泥微波热解制生物气效能的影响

为实现污水污泥减量化、无害化及资源化的目标,在微波热解污水污泥基础上,进行了镍基催化剂对制取生物气效能影响的研究。采用元素分析对污泥元素进行检测,气/质联用分析(GC-MS)和气相色谱(GC)对热解生物气的组成和含量进行测定。实验结果表明,镍基催化剂的添加对微波热解污水污泥制取生物气有较大促进作用。5%添加量与800℃热解终温条件下具有最佳催化效果:生物气中H2、CO产量最大,H2产量由29 g/kg增加到35.8 g/kg,提升23.4%,CO产量由302.7 g/kg增加到383.3 g/kg,提升26.6%;同时催化剂还能提高热能利用效率,降低热解终温,即5%添加量在700℃热解终温时可达到空白800℃时的产气效果;镍基催化剂主要在500~600℃时发挥催化作用,加快了H2和CO的释放。微波热解污泥制取的生物气具有产量大、富含H2与CO等优点,可推动污水污泥的资源化进程。     

炼焦煤尾煤催化热解制取富氢燃料气

以炼焦煤原煤、尾煤为研究对象，采用微量热重、常量固定床实验装置对其在热解过程中的质量变化和气相产物进行了对比分析。考察了温度、6种催化剂（CaO、MgO、Fe、Ni、NaOH、A1）及其添加比例对炼焦煤尾煤热解制取富氢燃料气的影响。结果表明，尾煤中富集的无机矿物质对热解制取富氢燃料气有促进作用，单位尾煤热解H2产率要比原煤高出1．93％。温度是影响尾煤热解产气的重要参数，热解终温的上升有利于H2产量的提高，随终温800℃升高到950℃H，产量增长了32．59mL／g。在催化热解实验中，除Al和MgO对尾煤热解有抑制作用外，CaO、Fe、Ni及NaOH均对尾煤热解产H2有促进作用，以CaO和Fe效果最为明显。并且不同添加比例的CaO和Fe对热解制取富氢燃料有一定的影响。     

基于分区气化模型的MSW燃烧过程模拟研究

针对一种新型两段式生活垃圾分区气化燃烧装置,提出了基于分区气化模型的垃圾热转化过程数值模拟方法。该方法耦合化学反应动力学和流体动力学软件预测移动床层垃圾的气化以及炉内气相空间的燃烧过程。通过对组分及热值差异较大的2种生活垃圾在炉内的反应过程进行模拟,得到了炉内的气相组分、温度及流场的分布。结果表明,该方法能够很好地适用于复杂组分的垃圾热转化过程模拟研究。高水分、低热值的生活垃圾气化后再燃炉膛出口温度处于973~1 073 K,不利于二恶英的生成控制。前拱二次风的增加不仅加强了炉内的湍流扰动,而且加强了炉内主反应区的温度。经过对流场和温度场进行优化,烟气的停留时间延长,炉膛出口烟气中的可燃气体组分大大降低,而且NO的浓度降低了近一个数量级。     

餐厨垃圾中典型组分的裂解液化特征研究

利用实验室规模的实验装置管式加热炉进行餐厨垃圾热解实验,实验分析了反应温度对餐厨垃圾热解产物分布的影响,米饭、白菜、猪肉、塑料和纸5种原料在最佳温度下可实现热解油质量产率的最大化,分别为45.02%、24.55%、61.19%、73.77%和24.86%。其中,米饭和白菜热解油含水率较高,可达到30%~40%,将含水率降到15%后,测定热值分别为25.51 MJ/kg和17.75 MJ/kg。塑料和纸混合热解时,塑料热解过程的放热效应可缩小纸的热解温度区间,增加热解油产量。红外光谱分析厨余热解油包含多种含氧有机物。通过气质联用仪(GC-MS)分析塑料热解油和塑料与纸混合热解油在180℃以下蒸馏出的液相产物,主要组分为烷烃和烯烃,从成分和热值分析,与汽油、柴油相近。     

城郊乡村生活垃圾衍生燃料热解特性研究

将城郊乡村生活垃圾加工成粒径6.0 mm左右的垃圾衍生燃料(RDF),采用热重(TG)分析和红外光谱等研究其热解特性.结果表明:(1)在RDF挥发分阶段和生物质挥发分阶段,助燃添加剂处于活泼分解阶段,加入了30％(质量分数)秸秆、玉米芯等生物质作助燃添加剂后的RDF(以下简写为混合RDF)分子碎片正发生内部氢重排,总体挥发分产物较多,并且有明显的二次裂解,失重提高到4.85 mg,失重率约提高12％.在RDF与生物质重叠的碳固定阶段,助燃添加剂失重率有一定提高,热重微分(DTG)峰值速率增加,为RDF碳固定阶段的进一步热解提供了良好的支持.(2)快加热产气速率均大于慢加热.(3)热解终温越高,越有利气体析出.(4)RDF的热解固体产率随着热解终温的升高而降低,在850℃时为31.9％;热解气体产率随着热解终温升高而迅速升高,在850℃时可达49.8％.(5)根据红外光谱图,城郊乡村生活垃圾加工成的RDF中所含的氯元素基本上以HCl形式释放.(6)一级动力学反应可以准确地描述物料热解过程.     

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.