添加剂促进亚硫酸钙氧化的实验研究

在湿式石灰石-石膏法脱硫工艺中，副产物——亚硫酸钙的氧化是其中重要的化学过程。利用自行设计的实验室规模的反应装置，通过改变pH、亚硫酸钙浓度、空气流量、催化剂浓度和温度等条件，实验研究了多种添加剂对亚硫酸钙氧化的促进作用。实验结果可为湿法脱硫工艺的设计提供有益的参考。     

烟气脱硫过程锰催化氧化亚硫酸钙的研究

利用直径280 mm、高320 mm的间歇式搅拌槽,在MnSO4加入浓度为0～0.05 mol/L的情况下,对亚硫酸钙悬浮液进行了催化氧化实验研究.实验结果表明,锰离子的加入会改变亚硫酸钙的氧化机理及氧化过程,表现为终点氧化率和氧化速率的变化.当Mn2 浓度为0.05 mol/L时,亚硫酸钙的终点氧化率比未加入Mn2 时高30%;此外,与非催化反应过程相比,Mn2 的加入能使亚硫酸钙在一个更宽的浓度范围内(0.02～0.073 mol/L)和一个更宽的时间范围内(20～100 min)均保持较高的氧化速率水平.     

CFB烧结烟气脱硫灰亚硫酸钙热氧化条件优化

循环流化床(CFB)是一种常用的半干法烟气脱硫工艺,该工艺的副产物主要为脱硫灰。含有大量亚硫酸钙的脱硫灰较难被利用,致使大量脱硫灰堆积,给环境保护和企业生产带来了巨大的压力。亚硫酸钙的存在限制了脱硫灰在建材领域的应用,只有将其氧化为硫酸钙才能实现其资源化。脱硫灰热氧化主要采用了立式管式炉,分别考察了反应温度、反应状态、氧含量、水汽的含量对亚硫酸钙氧化的影响。结果表明:温度对脱硫灰氧化的影响最大,其次为气体流速、氧含量和水汽含量。反应温度与反应速率呈正相关;增加氧气含量可以提高反应速率,但当氧含量高于30%时,反应速率趋于稳定;反应器温度在350℃时,亚硫酸钙开始缓慢反应,在400℃、无预热气速为75 mL·min~(-1)时,亚硫酸钙最大转化效率达到86%,预热处理后最大转化率达到90%;当水汽量0.88 g·L~(-1)时,水汽量的增加会抑制氧化的进行;当水汽含量0.88 g·L~(-1)时,则会促进反应的进行。以上结果对指导脱硫灰热氧化处理和节能环保具有理论与实践意义。     

烟气脱硫中亚硫酸钙铁锰复合催化氧化优化

亚硫酸钙氧化是湿法石灰石/石膏法脱硫中十分重要的一个环节,优化亚硫酸钙氧化过程有助于降低湿法脱硫能耗和物耗。以Ca SO_3氧化速率(SOR)为研究对象,对比了Fe和Mn单独催化和复合催化的氧化效果,通过单因素和响应面法考察了p H、Fe/Mn比例和起始Ca SO_3浓度对SOR的单独和联合效应。结果表明,Fe和Mn复合催化的SOR明显高于单独催化。对SOR的影响大小依次为起始Ca SO_3浓度p HFe/Mn,Fe/Mn和起始Ca SO_3浓度的交互作用显著。Ca SO_3氧化的最佳条件为p H 4.5,Fe/Mn为0.37,起始浓度为17.83 mmol·L~(-1),优化的SOR为4.22 mmol·(L·min)~(-1)。结构表征结果表明,亚硫酸钙氧化首先生成Ca SO_4·2H_2O的(020)、(021)和(041)晶面,产物为Ca SO_4·2H_2O。     

燃煤炉窑烟气净化工艺及其装置的研究

在实验测试基础上,对燃煤烟气喷钙水浴复合脱硫工艺及设备进行了研究.实验表明,采用喷钙水浴复合脱硫工艺较单一喷钙或水浴具有更高的脱硫效果,且喷入的碳酸钙可得到充分利用.此外,还对钙硫比、喷钙方向及喷管插入水深等影响脱硫效率的因素进行了测试分析.     

氧化锌法处理低浓度SO_2烟气的模拟实验研究

文中介绍了氧化锌法脱硫的基本原理,总结了国内外研究及应用现状,同时详细叙述了模拟实验采用的流程、主要仪器,着重分析了不同SO2浓度下的吸收率以及亚硫酸锌的氧化率与氧化时间、浆液温度的关系,提出了实验过程中发现的问题及可采取的措施,为后期中试以及工业化应用提供了设计依据。     

火电厂烟气脱硫与软水处理

在过去的两年中,美国对烧富硫煤的发电厂以强化氧化模式进行了实验性烟气脱硫(FGD)洗涤器的大范围试验。结果证明,在双回路文丘里/鼓风塔系统的第一回路内,通过空气鼓风洗涤淤浆能有效地和可靠地达到废淤渣的完全氧化。已表明把亚硫酸钙氧化成硫酸钙将会显著地改进淤渣的质量;例如,当废液通过真空过滤时,其固体含量从55％(按亚硫酸钙计)增加到85％(按石膏计)。不仅是     

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。     

复合型除尘器除尘脱硫一体化工艺实验研究

试验研究了专利产品"高压静电滤槽复合型卧式除尘器"的除尘脱硫一体化工艺.试验表明,在布袋前方的末级电场中实行半干法脱硫工艺具有可行性,可达到除尘脱硫一体化目的.试验同时研究了钙硫比、脱硫灰循环率、饱和温距、喷水量和SO2浓度等对脱硫率的影响.该工艺适用于以低硫煤为燃料的锅炉进行除尘脱硫.     

Bio-SR工艺脱硫净化天然气影响因素试验研究

在对比天然气传统脱硫工艺的基础上,结合 Bio-SR工艺特点,分析了该工艺应用于天然气脱硫净化的可行性.通过单因素实验考察了H2S标准混合气浓度、初始Fe3 浓度、喷淋量、空塔停留时间、pH及压力等因素对脱硫率的影响,初步确定了适宜的控制参数.实验结果表明,该工艺对气量大、低H2S质量浓度(＜1.0 g/m3)的天然气有快速高效的净化作用,出气达到管输天然气标准.     

Evaluation of trichloroethene recovery processes in heterogeneous aquifer cells flushed with biodegradable surfactants

The ability of two biodegradable surfactants, polyoxyethylene (20) sorbitan monooleate (Tween 80) and sodium dihexyl sulfosuccinate (Aerosol MA), to recover a representative dense non-aqueous-phase liquid (DNAPL), trichloroethene (TCE), from heterogeneous porous media was evaluated through a combination of batch and aquifer cell experiments. An aqueous solution containing 3.3% Aerosol MA, 8% 2-propanol and 6 g/l CaCl(2) yielded a weight solubilization ratio (WSR) of 1.21 g TCE/g surfactant, with a corresponding liquid-liquid interfacial tension (IFT) of 0.19 dyn/cm. Flushing of aquifer cells containing a TCE-DNAPL source zone with approximately two pore volumes of the AMA formulation resulted in substantial (>30%) mobilization of TCE-DNAPL. However, a TCE mass recovery of 81% was achieved when the aqueous-phase flow rate was sufficient to displace the mobile TCE-DNAPL toward the effluent well. Aqueous solutions of Tween 80 exhibited a greater capacity to solubilize TCE (WSR=1.74 g TCE/g surfactant) and exerted markedly less reduction in IFT (10.4 dyn/cm). These data contradict an accepted empirical correlation used to estimate IFT values from solubilization capacity, and indicate a unique capacity of T80 to form concentrated TCE emulsions. Flushing of aquifer cells with less than 2.5 pore volumes of a 4% T80 solution achieved TCE mass recoveries ranging from 66 to 85%, with only slight TCE-DNAPL mobilization (<5%) occurring when the total trapping number exceeded 2 x 10(-5). These findings demonstrate the ability of Tween 80 and Aerosol MA solutions to efficiently recover TCE from a heterogeneous DNAPL source zone, and the utility of the total trapping number as a design parameter for a priori prediction of DNAPL mobilization and bank angle formation when flushing with low-IFT solutions. Given their potential to stimulate microbial reductive dechlorination at low concentrations, these surfactants are well-suited for remedial action plans that couple aggressive mass removal followed by enhanced bioremediation to treat chlorinated solvent source zones.     

The variation of street air levels of PAH and other mutagenic PAC in relation to regulations of traffic emissions and the impact of atmospheric processes

The occurrence of particle associated PAH and other mutagenic PAC was determined in 1996 in the street air of Copenhagen. In addition, particle extracts were tested for mutagenicity. The measurements were compared with previous measurements in 1992/1993. The levels had decreased in this period. The decrease was caused by an implementation of light diesel fuels for buses and the exchange of older petrol-driven passenger cars with catalystequipped new ones. About 65% of the reduction was caused by the application of the light diesel fuels. Under special conditions, chemical processes in the atmosphere produced many more mutagens than the direct emissions. The concentrations of S-PAC and N-PAC were 10 times lower than those of PAH, while the levels of oxy-PAH were in the same order of magnitude as those of PAH. Benzanthrone, an oxy-PAH, is proposed to be formed in the atmosphere in addition to direct emissions. Benzo(a)pyrene, often applied as an air quality criteria indicator, was photochemically degraded in the atmosphere. A strong increase in the mutagenic activities was observed to coincide with a depletion of benzo(a)pyrene.     

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.     

Teratological effects of pesticides in vertebrates: a review

Abstract

In the last decades, the use and misuse of pesticides in the agriculture have increased, having a severe impact on ecosystems and their fauna. Although the various effects of pesticides on biodiversity have been already documented in several studies, to our knowledge no consistent overview of the impact of pesticides in vertebrates, both terrestrial and aquatic, is available. In this review, we try to present a concise compilation of the teratogenic effects of pesticides on the different classes of vertebrates – mammals, birds, reptiles, amphibians and fish.     

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.     

Knowledge transfer initiative between molecular biologists and environmental researchers and regulators

A Natural Environment Research Council (NERC) funded Knowledge Transfer (KT) workshop was held in the United Kingdom (UK) to identify the needs and opportunities in the application of molecular biology and ‘omics’ techniques to environmental monitoring and risk assessment. Attendees highlighted a lack of effective communication between end-users and researchers as well as difficulties with data interpretation as reasons behind the slow uptake of molecular biology and omics techniques. A number of promising areas in which new techniques could be implemented at a practical level in the very near future were identified, thereby raising the profile of these recent technologies and providing vital proof of concept work. Molecular taxonomy, bacterial source tracking and pre-screening of chemicals for potential toxicities were all viewed as areas in which omics and molecular techniques could have immediate value, with the aim of reducing cost, increasing efficiency and providing more comprehensive data of improved quality.     

Sorption and predicted mobility of herbicides in Baltic soils

This study was undertaken to determine sorption coefficients of eight herbicides (alachlor, amitrole, atrazine, simazine, dicamba, imazamox, imazethapyr, and pendimethalin) to seven agricultural soils from sites throughout Lithuania. The measured sorption coefficients were used to predict the susceptibility of these herbicides to leach to groundwater. Soil-water partitioning coefficients were measured in batch equilibrium studies using radiolabeled herbicides. In most soils, sorption followed the general trend pendimethalin > alachlor > atrazine～ amitrole～ simazine > imazethapyr > imazamox > dicamba, consistent with the trends in hydrophobicity (log K_ow) except in the case of amitrole. For several herbicides, sorption coefficients and calculated retardation factors were lowest (predicted to be most susceptible to leaching) in a soil of intermediate organic carbon content and sand content. Calculated herbicide retardation factors were high for soils with high organic carbon contents. Estimated leaching times under saturated conditions, assuming no herbicide degradation and no preferential water flow, were more strongly affected by soil textural effects on predicted water flow than by herbicide sorption effects. All herbicides were predicted to be slowest to leach in soils with high clay and low sand contents, and fastest to leach in soils with high sand content and low organic matter content. Herbicide management is important to the continued increase in agricultural production and profitability in the Baltic region, and these results will be useful in identifying critical areas requiring improved management practices to reduce water contamination by pesticides.