密相塔烟气脱硫技术试验研究

建立了密相塔烟气脱硫试验装置,并对烧结烟气进行了脱硫试验研究,验证了该工艺的可行性,并研究了主要因素对脱硫效率的影响.结果表明,钙硫比和近绝热饱和温度（approach to adiabatic saturation temperature,AAST）是影响脱硫效率的显著因素,循环灰浓度是保证系统脱硫效率的关键因素.在Ca/S比为1.2、密相塔出口烟气AAST=15℃、循环灰浓度为400g/m3条件下,系统能连续稳定运行,脱硫效率达92.5%以上,系统出口烟气中SO2浓度在150 mg/Nm3以下.     

半干半湿法烟气脱硫技术的工业应用研究

探讨了日本半干半湿法脱硫除尘系统和中国环境科学研究院半干半湿法烟气脱硫除尘示范系统的主要差别 ,研究了半干半湿法烟气脱硫技术在出塔烟气温度、钙硫摩尔比和循环粉煤灰返灰等方面对脱硫效率的影响。结果表明 ,在脱硫塔出口烟气温度为 78℃、m(循环粉煤灰返灰 )∶ m(石灰 )为 1∶ 4、n( Ca)∶ n( S) <1.2时 ,脱硫效率达 85 .1%;在 n( Ca)∶ n( S) =1.4时 ,脱硫效率可达 88.3 %。     

密相塔半干法烟气脱硫塔内加湿降温及其对脱硫效率的影响

为了实现密相塔半干法脱硫工艺的精确加湿进一步提高系统脱硫效率,利用推导出的传热传质计算方法,得到烟气温度降低和加水量的关系.结合3组密相塔半干法工程实际数据,发现理论计算值和实测值误差区间仅为2.9％ ～5.4％.通过选取河北某钢厂210 m2烧结烟气密相塔半干法脱硫项目实际在线检测数据,发现循环脱硫灰含湿量为3％的系统脱硫效率整体高于含湿量为5％和4％的样品,最大值达93.56％.通过粒度分析、扫描电镜、X射线衍射及差热-热重对2种不同含湿量的循环脱硫灰进行表征,结果表明,含湿量为3％的循环脱硫灰较含湿量为5％的样品粒径小、比表面积大,无团聚现象,物相分析还证实相对于含湿量为5％样品,其Ca(OH)2和结晶水含量少,几乎都是CaSO4和CaS03干态物质,因此脱硫反应进行彻底,脱硫效率较高.     

内循环流化床烟气脱硫技术的实验研究

通过对流化床烟气脱硫吸收塔塔顶和塔底结构的改进,开发出一种新的内循环流化床烟气脱硫工艺。该工艺以60～80目细砂作为主要床料,在流化气速为2～5m/s情况下,实现了绝大部分固体颗粒在脱硫塔内的内循环,从而强化了热质传递,避免了粘壁现象。考察了各种因素对脱硫效率的影响,结果表明,绝热饱和温度差是影响脱硫效率的显著因素,颗粒浓度是保证系统稳定运行的关键因素。在Ca/S为12和颗粒浓度为10kg/m3条件下,系统能连续稳定运行,脱硫效率达90%以上。     

旁通式烟气循环流化床脱硫特性的数值模拟

应用标准k-ε模型、DPM模型和物质输运与化学反应模型模拟烟气循环流化床脱硫的两相流动及化学反应,模拟结果和实验数据符合较好。提出了一种旁通式烟气循环流化床,并进一步研究了钙硫比和脱硫剂粒径对旁通脱硫塔脱硫效率的影响。结果表明,脱硫剂颗粒粒径从15μm增大到300μm时,旁通式脱硫塔的脱硫效率略有降低但变化不大;当钙硫摩尔比从0.8增大到1.3时,脱硫效率随之有明显的增加,当钙硫比大于1.3时,脱硫效率随钙硫比的增大略有增加。     

内循环流化床烟气脱硫技术的实验研究

通过对流化床烟气脱硫吸收塔塔顶和塔底结构的改进，开发出一种新的内循环流化床烟气脱硫工艺。该工艺以60～80目细砂作为主要床料，在流化气速为2～5m／s情况下，实现了绝大部分固体颗粒在脱硫塔内的内循环，从而强化了热质传递，避免了粘壁现象。考察了各种因素对脱硫效率的影响，结果表明，绝热饱和温度差是影响脱硫效率的显著因素，颗粒浓度是保证系统稳定运行的关键因素。在Ca／S为1．2和颗粒浓度为10kg／m^3条件下，系统能连续稳定运行，脱硫效率达90％以上。     

循环流化床烟气脱硫多层喷水技术

东南大学热能工程研究所建立了我国目前最大的循环流化床烟气脱硫试验装置，脱硫塔直径为600mm,处理烟气量达2000m^3/h。在此试验台上进行了循环流化床烟气脱硫多层喷水的试验研究，试验表明在多层喷水条件下，趋近饱各温度△T有较大降低，脱硫效率明显提高，提高了Ca的利用率，降低了运行费用。     

氧化镁烟气脱硫反应特性研究

利用实验室规模的鼓泡式反应装置,对比了碳酸钙、氧化镁和氧化镁/硫酸镁脱硫剂的反应活性,证实脱硫液中高浓度硫酸镁的存在是保证镁法脱硫效率高于钙法的重要因素,并考察了硫酸镁浓度、脱硫剂(氧化镁)浓度、烟气量、SO2浓度和吸收液温度等因素对脱硫效率的影响。结果表明,脱硫反应可以根据pH分为2个不同阶段;反应过程中脱硫效率随着硫酸镁浓度的增加而显著升高;烟气量增加将会导致脱硫效率有所下降;入口SO2浓度升高,脱硫效率下降;氧化镁浓度、温度对脱硫效率影响不显著。结合实验现象进行推断,氧化镁脱硫的反应过程受SO2在气液两相界面的传质扩散和其水解产物在液相的扩散控制。     

循环流化床烟气脱硫系统内压降的建模

循环流化床烟气脱硫系统中的压降是保证反应器安全运行的重要参数,了解反应器内的气固流动状况以及压降分布并对其加以调节是系统稳定运行的关键.通过分析循环流化床内气固两相的流动状态,基于一维轴向流动模型,研究循环流化床烟气脱硫系统内的压降轴向分布特性.模型预测结果表明,压降受烟气流速和循环流量影响下的变化趋势与实验结论一致,证明了模型的有效性.可以用于循环流化床内脱硫传质研究,以及为反应器的设计与运行提供指导.     

湿法烟气脱硫反应过程的实验研究

在石灰石/石膏湿法烟气脱硫中试台上,系统开展了浆液pH值、飞灰浓度、液气比、入口SO2浓度、烟气速度和氧化方式等对脱硫反应过程影响的实验研究。实验表明,脱硫效率随着石膏浆液pH值、液气比的升高而增加,且入口SO2浓度越高,液气比越低,影响效应越明显;脱硫效率随着烟气速度、烟气温度和入口SO2浓度的增加而下降;石膏浆液中飞灰含量对系统脱硫效率具有一定的促进作用:pH值>5.6,飞灰浸出液中Fe3+含量相对较低,Fe3+对脱硫反应过渡态催化氧化影响程度较轻,不同工况脱硫效率差别不大。pH值<5.6,飞灰浸出液中Fe3+含量随pH值降低而增大,增效效果逐渐显著;氧化方式对脱硫反应过程有明显的影响,强制氧化工艺的脱硫效率比自然氧化的高5%左右。     

Chloroaromatic pollutants in mussels incubated in two finnish watercourses polluted by industry

Concentrations of different chlorinated compounds were measured in mussels incubated in two polluted watercourses, a river (the River Kymijoki) and a lake (Lake Vanaja) for four weeks in summer 1995. The sum concentrations of polychlorinated phenols (PCP) and biphenyls (PCB) were both about 1 μg/g lipid weight (lw) in Lake Vanaja mussels, while in the River Kymijoki mussels PCPs were non-detectable and PCBs were measured 120 ng/g lIw. The concentrations of toxic polychlorinated dibenzo-p-dioxin (PCDD) and dibenzofuran (PCDF) congeners ranged between <17 and 370 pg/g Iw in Lake Vanaja mussels and between <38 and 11,000 pg/g lw in the River Kymijoki mussels. Polychlorinated diphenyl ethers (PCDE) were detected in the mussels incubated in the River Kymijoki (0.4–1.1 ng/g Iw), but not in those incubated in Lake Vanaja. Polychlorinated phenoxyanisoles (PCPA) were measured 33 ng/g lw and polychlorinated phenoxyphenols (PCPP) 300 ng/g lw in the mussels incubated in the River Kymijoki. PCPAs were also detected in reference samples, which were sediment and pike from the River Kymijoki and Baltic salmon, seal and white-tailed sea eagle.     

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.     

Book review

The Pesticide Manual ‐ A World Compendium, 8th Edition, C.R. Worthing, Editor and S.B. Walker, Assistant Editor, British Crop Protection Council, BCPC Publications Sales, Bear Farm, Binfield, Bracknell, Berkshire RG12 5QE, England. 1987, 1100 pp., UK £50; Overseas £56. ISBN 0–948404–01–9.     

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.     

Observations on the influence of water and soil pH on the persistence of insecticides

Abstract

The pH‐disappearance rate profiles were determined at ca. 25°C for 24 insecticides at 4 or 5 pH values over the range 4.5 to 8.0 in sterile phosphate buffers prepared in water‐ethanol (99: 1 v/v). Half‐lives measured at pH 8 were generally smaller than at lower pH values. Changes in half lives between pH 8.0 and 4.5 were largest (>1000x) for the aryl carbamates, carbofuran and carbaryl, the oxime carbamate, oxamyl, and the organophosphorus insecticide, trichlorfon. In contrast, half lives of phorate, terbufos, heptachlor, fensulfothion and aldicarb were affected only slightly by pH changes. Under the experimental conditions described half lives at pH8 varied from 1–2 days for trichlorfon and oxamyl to >1 year for fensulfothion and cyper‐methrin. Insecticide persistence on alumina (acid, neutral and basic), mineral soils amended with aluminum sulfate or calcium hydroxide to different pH values and four natural soils of different pH was examined. No correlation was observed between the measured pH of these solids and the rate of disappearance of selected insecticides applied to them. These observations demonstrate the difficulty of extrapolating the pH dependent disappearance behaviour observed in homogeneous solution to partially solid heterogeneous systems such as soil.     

The chemical stability of formulations of some hydrolyzable insecticides in aqueous mixtures with hydrolysis catalysts

Abstract

The active ingredients in commercial formulations of malathion, oxamyl, carbaryl, diazinon, and chlorpyrifos diluted to “spray tank”; concentrations with buffered distilled or natural water of pH 4–9 were stable for at least 24 hr. Formulations of trichlorfon were not stable at pH 7 or above but disappearance rates were slower than for the pure chemical in homogeneous solution. Cupric ion was observed to be an effective catalyst for the hydrolysis of a variety of pure organophosphorus insecticides but did not catalyze hydrolysis of the active ingredients of the formulations examined. Increasing the dilution of the formulation increased the susceptibility of malathion, oxamyl, and carbaryl to hydrolysis.     

Organochlorine compounds in a three-step terrestrial food chain

The concentrations of 15 organochlorine chemicals (PCBs and pesticides) were studied in a Central European oak wood food chain system: Great tit (Parus major), caterpillars (Tortrix viridana, Operophtera brumata, Erannis defoliaria), and oak-leaves (Quercus robur). Juvenile tits receive organochlorines from the mother via egg transfer and, eventually to a greater extent, from the caterpillar food source during nestling period. The concentrations of PCB 153 (2,2′,4,4′,5,5′-hexachlorobiphenyl, the most abundant in this study) was found in leaf material at ca. 1 ng/g, in caterpillars 10 ng/g, and in bird eggs 170 ng/g on an average and on a dry mass basis.     

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.     

Radionuclides in pinon pine (Pinus edulis) nuts from los alamos national laboratory lands and the dose from consumption

Abstract

One of the dominant tree species growing within and around the eastern portion of Los Alamos National Laboratory (LANL), Los Alamos, NM, lands is the pinon pine (Pinus edulis). Pinon pine is used for firewood, fence posts, and building materials and is a source of nuts for food—the seeds are consumed by a wide variety of animals and are also gathered by people in the area and eaten raw or roasted. This study investigated the (1) concentration of ³H, ¹³⁷Cs, ⁹⁰Sr, ^totU, ²³⁸Pu, ^{239, 240}Pu, and²⁴¹ Am in soils (0‐ to 12‐in. [31 cm] depth underneath the tree), pinon pine shoots (PPS), and pinon pine nuts (PPN) collected from LANL lands and regional background (BG) locations, (2) committed effective dose equivalent (CEDE) from the ingestion of nuts, and (3) soil to PPS to PPN concentration ratios (CRs). Most radionuclides, with the exception of ³H in soils, were not significantly higher (p < 0.10) in soils, PPS, and PPN collected from LANL as compared to BG locations, and concentrations of most radionuclides in PPN from LANL have decreased over time. The maximum net CEDE (the CEDE plus two sigma minus BG) at the most conservative ingestion rate (10 lb [4.5 kg]) was 0.0018 mrem (0.018 μSv); this is far below the International Commission on Radiological Protection (all pathway) permissible dose limit of 100 mrem (1000 μSv). Soil‐to‐nut CRs for most radionuclides were within the range of default values in the literature for common fruits and vegetables.     

Degradation and sorption of imidacloprid in dissimilar surface and subsurface soils

Degradation and sorption/desorption are important processes affecting the leaching of pesticides through soil. This research characterized the degradation and sorption of imidacloprid (1-[(6-chloro-3-pyridinyl)-methyl]-N-nitro-2-imidazolidinimine) in Drummer (silty clay loam) and Exeter (sandy loam) surface soils and their corresponding subsurface soils using sequential extraction methods over 400 days. By the end of the incubation, approximately 55% of imidacloprid applied at a rate of 1.0 mg kg^?1 degraded in the Exeter sandy loam surface and subsurface soils, compared to 40% of applied imidacloprid within 300 days in Drummer surface and subsurface soils. At the 0.1 mg kg^?1 application rate, dissipation was slower for all four soils. Water-extractable imidacloprid in Exeter surface soil decreased from 98% of applied at day 1 to > 70% of the imidacloprid remaining after 400 d, as compared to 55% in the Drummer surface soil at day 1 and 12% at day 400. These data suggest that imidacloprid was bioavailable to degrading soil microorganisms and sorption/desorption was not the limiting factor for biodegradation. In subsurface soils > 40% of ¹⁴C-benzoic acid was mineralized over 21 days, demonstrating an active microbial community. In contrast, cumulative ¹⁴CO₂ was less than 1.5% of applied ¹⁴C-imidacloprid in all soils over 400 d. Qualitative differences in the microbial communities appear to limit the degradation of imidacloprid in the subsurface soils.