水热老化条件对Cu/ZSM-5催化剂NH3-SCR反应的影响

针对Cu/ZSM-5高温水热失活的问题,通过浸渍法合成了Cu/ZSM-5催化剂,并对该催化剂进行了不同温度和不同H_2O(g)含量的水热老化。采用比表面积分析、SEM观察、X射线衍射分析、H_2-程序升温还原、X射线光电子能谱分析对Cu/ZSM-5催化剂的理化性能进行了表征。分别研究了不同水热老化条件下Cu/ZSM-5催化剂的NH_3-SCR性能和水热失活机理。结果表明,经水热处理后,各Cu/ZSM-5催化剂的NH_3-SCR性能均有所降低。随着老化温度的提高,催化剂的分子筛载体出现结构坍塌,比表面积减小,孔容积增大,但仍保持MFI结构,老化温度的提高同样使催化剂活性Cu~(2+)减少并一部分转化为CuO微晶,而H_2O(g)含量的变化对催化剂的物理化学结构的影响较小。在高温水热老化过程中,温度对催化性能劣化的影响大于水蒸汽含量,是催化剂失活的主要原因。     

焙烧温度对层柱粘土催化剂Cu/Ti-PILCs催化丙烯还原NO反应的影响

制备了钛层柱粘土负载铜催化剂Cu/Ti-PILCs,用于有氧条件下C3H6选择性还原NO反应,考察了焙烧温度对Cu/Ti-PILCs的催化活性、孔结构和表面活性物种状态的影响。500℃焙烧的Cu/Ti-PILCs具有最佳的催化活性。Cu/TiPILCs的孔结构在600℃焙烧温度下具有良好的热稳定性。H2-TPR和SEM显示,在500℃焙烧的Cu/Ti-PILCs上,铜物种高度分散,主要以活性物种Cu2+的形式存在。700℃焙烧引起较小孔的孔结构崩塌,使得催化剂比表面大幅降低,且高温焙烧下Cu/Ti-PILCs形成没有催化活性的铜氧化物团聚体,导致了催化活性的大幅降低。     

铜铈掺杂六铝酸盐的脱硝性能

用共沉淀法制备用于脱除NO的六铝酸盐催化剂LaMxAl12-xO19(M =Cu,Ce,CuCe).用XRD、H2-TPR和BET对催化剂进行了结构和物性表征.用微型催化反应装置考察了催化剂在CO选择性催化还原NO中的活性.结果表明,Cu离子易于进入六铝酸盐晶格内,形成完整的六铝酸盐结构.Ce离子不易于进入六铝酸盐晶格内,主要以CeO2的形式存在.在CO+ NO条件下,3种催化剂都表现出较好的脱硝活性,LaCuCeAl10O19中由于Cu离子与Ce离子间产生协同作用,该催化剂的脱硝活性有所增加.加入SO2后,3种催化剂都有不同程度的失活现象发生,其中LaCuAl11O19催化剂受SO2中毒影响最严重,LaCuCeAl10O19催化剂的脱硝活性在三者中最好.     

F和S共掺V_2O_5/TiO_2催化剂对NH_3-SCR活性的影响

在V_2O_5/TiO_2催化剂基础上进行非金属改性载体的研究。采用溶胶凝胶法、浸渍法制备了一种新的氟、硫共掺杂氧化钒/氧化钛催化剂,探讨了新型催化剂对低温SCR活性的影响。并通过比表面积测试(BET)、X射线衍射实验(XRD)、H2和NH3的化学吸附特性测试(H2-TPR、NH3-TPD)等技术对催化剂的理化性能进行表征。研究结果表明,氟、硫掺杂催化剂提高了低温SCR活性,拓宽了活性温度范围,在F与S摩尔比为x3时,获得了最佳的脱硝性能。     

CaH_2对Cu-Ce-La-ZSM-5催化分解NO性能的影响

实验采用一步离子交换法制备Cu-Ce-La-ZSM-5催化剂,然后采用共混法制得Cu-Ce-La-ZSM-5/CaH2催化剂。采用扫描电镜(SEM),电感耦合等离子体发射光谱(ICP-AES),X射线衍射(XRD),红外(FTIR)以及NO吸脱附(NO-TPD)对催化剂进行表征。结果显示CaH2的加入使得催化剂中铜离子存在形式发生变化,催化剂表面变光滑洁净,并且吸附NO能力增强。NO催化分解实验的结果表明CaH2提高了催化剂活性和抗氧性。CaH2助催性是由于其受热分解过程中产生的H2能将Cu2+还原为具有催化活性的Cu+,同时使催化剂表面洁净光滑更容易吸附NO。     

制备工艺对V_2O_5/TiO_2 SCR催化剂脱硝性能的影响

围绕SCR脱硝催化剂制备工艺中活性组分负载顺序和钒助溶剂2个关键因素,分别制备了钒钨体系和钒钼体系催化剂,比较了不同条件下制备的催化剂的脱硝活性,并利用X射线光电子能谱分析(XPS)、程序升温还原(H2-TPR)和程序升温脱附(NH3-TPD)等手段进行表征。结果表明,活性组分与助剂同时负载制备的催化剂,其低价钒和化学吸附氧的比例最高,钒的还原温度最低,酸性位数量最多,表现出最好的脱硝活性;相较于常规助溶剂单乙醇胺,以草酸为助溶剂制备的催化剂,其低价钒和化学吸附氧比例更高,氧化还原性能和表面酸性更强,脱硝活性更好。     

NiO-MgO复合金属氧化物催化分解N_2O

采用溶胶凝胶法制备了一系列不同Ni/Mg比的NiO-MgO复合氧化物催化剂,并考察了其N_2O催化分解性能。结果表明,NiO-MgO催化剂的N_2O催化分解活性明显优于单一NiO和MgO,当MgO含量为5%时,NiO-MgO复合金属氧化物上N_2O分解活性最佳。XRD、H2-TPR和XPS结果表明,Ni2+是催化分解N_2O的主要活性位点。Mg不作为活性组分,但可通过Ni、Mg之间强烈的相互作用提高催化剂氧化还原能力,进而促进N_2O的催化分解。此外,Mg的加入促进了催化剂中NiO的形成。     

Mn-CeOx/钛基层柱粘土(Ti-PILCs)低温选择性催化还原催化剂的钙中毒研究

以钛基层柱粘土(Ti-PILCs)为载体,制备了Mn-Ceox/Ti-PILCs低温选择性催化还原(SCR)催化剂,采用浸溃法模拟了催化剂钙中毒,研究了不同含钙量对催化剂活性的影响,并运用NH3-程序升温脱附(TPD)、H2-程序升温还原(TPR)及X射线光电子能谱(XPS)表征,分析了钙对催化剂的失活作用.结果表明:...     

Y_2O_3/AC催化剂的烟气同时脱硫脱硝性能

采用等体积浸渍法制备了一系列不同负载量的x%Y_2O_3/AC(x=2、4、6、8和10)同时脱硫脱硝催化剂,以CO为还原气,考察该催化剂同时脱硫脱硝催化活性。采用X射线衍射仪(XRD)、H2-程序升温还原(H2-TPR)、比表面积(BET)对催化剂进行了表征。在不同负载量的催化剂中,6%Y_2O_3/AC表现出较好脱硫脱硝效果,SO_2和NO的T90%分别约为365℃和367℃。经HNO_3预处理过的活性炭载体制备的催化剂脱硝效果明显改善,催化剂预硫化可以显著提高脱硫脱硝活性,在550℃硫化的催化剂效果最好,NO和SO_2的T90%分别约为368和362℃,在380℃时脱硫脱硝率均可达到95%以上。     

低温非钒基NH3选择性催化还原催化剂的技术需求和研究进展

低温脱硝技术对于氮氧化物(NOx)的脱除意义深远,而NH3选择性催化还原(NH3-SCR) NO技术不仅在燃煤工厂里有应用,也在移动源的NOx的脱除上有应用的潜能.在低温NH3-SCR技术领域,很多非钒基的催化剂材料因其优异的催化性能受到重视.简述了低温SCR技术在能源、水泥、冶金行业的技术需求,并着重介绍了各种催化剂的SCR活性、不同催化剂的催化机制和抗SO2、H2O性能.并由此得出未来工业脱硝对催化剂的高SCR催化活性、高的N2选择性以及良好的抗SO2和H2O性能的要求.     

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.     

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.     

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.     

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 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.     

Biochemical interaction of six op delayed neurotoxicants with several neurotargets

Abstract

Five organophosphorous insecticides: Leptophos, EPN, Cyano‐fenphos, trichloronate and salithion proved to cause irreversible ataxia not only to chicken but also to mice and sheep. TOCP was included as a reference. Cyanofenphos blocked the catecholamine B‐receptor binding activity with ³H‐norepinephrine at a level similar to that of the specific inhibitor propranolol in the mouse heart preparation. In the lamb heart preparation, the B‐receptor was more sensitive to Leptophos, salithion and TOCP than to propranolol. The six compounds and their oxons were screened for their in‐vitro inhibition to monamine oxidase (MAO), acetyl cholinesterase (AChE) and neurotoxic esterase (NTE) in the brain of either mouse, lamb or chicken. It is believed that their AChE inhibition stands for their acute toxicity, while NTE inhibition is responsible for their paralytic ataxia.