高活性脱硫剂脱硫工艺的实验研究

对以粉煤灰为原料制备的高活性脱硫剂进行了半干法烟气脱硫实验研究，考虑添加剂、脱硫剂加入量、反应温度、烟气流量工艺因素的影响时该活性脱硫剂的脱硫性能；实验结果表明，加入添加剂后，脱硫效率提高1．5％～8．1％；当烟气流量〈2m^3／min，钙硫比取1．5—2．0范围时，脱硫效率较高；一定范围内反应温度变化对脱硫效率影响不大。     

半干半湿法烟气脱硫主要影响因素分析

建立了半干法气流床烟气脱硫实验反应装置。实验研究了温度、绝对含湿量和飞灰对烟气脱硫的影响。烟气温度在65～130℃之间,绝对含湿量通过改变蒸汽量调节,在0%～10%之间,并且采用飞灰一次加入来模拟返灰,石灰与粉煤灰的比例分别为1∶3,1∶5和1∶8。结果表明,没有水蒸气加入时,温度的升高对脱硫效率影响不大,加入水蒸气后温度为68℃左右时,脱硫效率最高;65℃时,绝对含湿量在73%时脱硫效率最高;在T=68℃、Ca/S=12时,与不加粉煤灰的脱硫剂相比,利用石灰/粉煤灰=1∶8的混合脱硫剂时,脱硫效率提高了128%。     

粗媒体颗粒流化床半干法烟气脱硫

开发了粗媒体颗粒流化床半干法烟气脱硫技术.在流化床内加入惰性粗媒体颗粒,改善脱硫剂与烟气的接触,延长脱硫剂在床内的停留时间,促进脱硫反应进行,提高脱硫效率和脱硫剂利用率.以工业用石灰石为脱硫剂,实验研究了粗媒体颗粒的加入量及其他操作条件对此过程脱硫效率的影响.结果表明:随着粗媒体颗粒粒径减小及床内加入量增加,烟气脱硫效率提高;随着Ca/S增大、饱和接近度降低、空速及脱硫剂颗粒粒径减小,脱硫效率提高.当粗媒体颗粒的静止床高为122 mm,饱和接近度为15～18℃、空速为2850 h-1、钙硫比为1.0～1.1、脱硫剂粒径为64μm时,脱硫效率可达90%以上.     

半干半湿法烟气脱硫主要影响因素分析

建立了半干法气流床烟气脱硫实验反应装置。实验研究了温度、绝对含湿量和飞灰对烟气脱硫的影响。烟气温度在65～130℃之间，绝对含湿量通过改变蒸汽量调节，在0％～10％之间，并且采用飞灰一次加入来模拟返灰，石灰与粉煤灰的比例分别为1：3，1：5和1：8。结果表明，没有水蒸气加入时，温度的升高对脱硫效率影响不大，加入水蒸气后温度为68℃左右时，脱硫效率最高；65℃时，绝对含湿量在7．3％时脱硫效率最高；在T=68℃、Ca／S：1．2时，与不加粉煤灰的脱硫剂相比，利用石灰／粉煤灰=1：8的混合脱硫剂时，脱硫效率提高了12．8％。     

粗媒体颗粒流化床半干法烟气脱硫

开发了粗媒体颗粒流化床半干法烟气脱硫技术。在流化床内加入惰性粗媒体颗粒，改善脱硫剂与烟气的接触。延长脱硫剂在床内的停留时间，促进脱硫反应进行，提高脱硫效率和脱硫剂利用率。以工业用石灰石为脱硫剂，实验研究了粗媒体颗粒的加入量及其他操作条件对此过程脱硫效率的影响。结果表明：随着粗媒体颗粒粒径减小及床内加入量增加，烟气脱硫效率提高；随着Ca／S增大、饱和接近度降低、空速及脱硫剂颗粒粒径减小，脱硫效率提高。当粗媒体颗粒的静止床高为122mm，饱和接近度为15～18℃、空速为2850h^-1、钙硫比为1．0—1．1、脱硫剂粒径为64μm时，脱硫效率可达90％以上。     

FeSO4/Ac脱硫剂脱硫性能的研究

为寻找经济适用且具有较高效率的烟气脱硫方法．研制了FeSO4／Ac脱硫剂。并对FeSO4／Ac脱硫剂的脱硫性能进行了实验研究。实验研究结果显示,烟气中O2、水蒸气含量的多少及脱硫温度的高低会影响FeSO4／Ac脱硫剂的脱硫性能。实验证明,当n(O2):n(SO2)=7～10、n(H2O)：n(SO2)=3～5、脱硫温度取120℃时,FeSO4／Ac脱硫剂具有良好的脱硫性能,脱硫效率可达92．1％～96．8％。FeSO4／Ac脱硫剂能够再生重复使用。采用水蒸气加热再生法对FeSO4／Ac脱硫剂进行再生,实验结果显示,经4次加热法再生的FeSO4／Ac脱硫剂的脱硫效率仍能达到91％。     

螺旋切割强化湿法烟气脱硫的传质动力学

针对开发的新型静态螺旋切割强化湿法烟气脱硫技术,根据双膜理论从动力学角度建立了静态螺旋切割强化Ca(OH)_2溶液吸收烟气SO_2的动力学模型,并采用单因素实验探究了烟气SO_2浓度、烟气流量、脱硫剂浓度以及脱硫剂循环流量对传质速率的影响。结果表明:模型能较好地描述静态螺旋切割强化湿法烟气脱硫的实际过程,理论计算与实验数据都发现,烟气SO_2浓度、烟气流量、脱硫剂浓度以及脱硫剂循环流量的增加均有助于提高传质速率;但当脱硫剂浓度大于5%时,传质速率随脱硫剂浓度的增加改变不大。     

飞灰/水菱镁石新型复合脱硫剂的性能研究

采用飞灰和水菱镁石水合搅拌制备飞灰/水菱镁石新型复合脱硫剂,模拟湿法烟气脱硫过程,采用正交实验分析法探讨了液固比(质量比)、反应温度、搅拌速度以及鼓泡深度4个因素对脱硫效率的影响。结果发现:复合脱硫剂的比表面积增大,这有利于该复合脱硫剂与气相SO2的接触和反应,因而提高了脱硫效率。复合脱硫剂的最佳反应组合:液固比为15.0∶1.0、反应温度为常温(20℃)、搅拌速度为150r/min、鼓泡深度为2.0cm,该条件下脱硫效率为98.58%。     

烧结烟气脱硫剂性能的研究

为了提高脱硫效率和合理利用烧结过程中产生的机头灰,在半干法烟气脱硫剂生石灰中,加入一定量的烧结机头灰作为脱硫催化剂。在测定机头灰与生石灰化学成分、粒度和比表面积的基础上,研究和分析了机头灰与生石灰的质量配比对于脱硫效率的影响。结果表明,脱硫剂与机头灰在粒径分布和比表面积上都较接近,但经过消化活化后的混合脱硫剂的比表面积明显增大。当机头灰添加量为脱硫剂质量的2%～5%时,脱硫效率提高了2%～3%。机头灰与生石灰的胶凝反应以及机头灰中Fe2O3的催化作用是主要的作用机理。     

相对湿度对钙基脱硫剂干法烟气脱硫效率的影响

为得到干法烟气脱硫较优的相对湿度,并验证钙基脱硫剂在干法烟气脱硫中的可行性,在模拟干法烟气脱硫实验台上,研究了钙基脱硫剂在不同相对湿度(0～45%)条件下,脱硫剂的出口浓度、脱硫效率和固硫量。结果表明,在相对湿度从0变化至45%时,可以稳定运行的穿透时间由160 min增加到720 min,可达100%脱硫效率的运行时间由0增至580 min,脱硫剂的固硫量从43.37 mg增加到332.09 mg;增加相对湿度能显著提高烟气脱硫效率,在保证烟气不穿透物料且不出现黏壁现象的条件下,较优的相对湿度为45%。研究明确了在低相对湿度条件下此种脱硫剂的可行性并确定了较优化的干法脱硫湿度,为干法脱硫条件的选择提供了参考。     

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.     

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.     

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.     

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.     

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.     

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.     

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.     

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 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.