水泥窑炉烟气催化还原脱硝技术研究进展

水泥工业是NOx的高排放行业,现有的燃烧控制技术难以满足日益提高的环保要求,因此烟气脱硝技术在水泥工业的应用将势在必行.选择性催化还原(SCR)脱硝技术是脱硝率最高的烟气脱硝技术,在燃煤电厂已有较大规模的应用,但是在水泥工业中的研究和应用相对滞后.简要介绍了SCR脱硝技术工作原理及其在水泥窑炉的应用现状,总结了催化材料研究和应用进展,探讨了水泥窑炉NOx减排用SCR脱硝技术和催化材料的研究方向.     

烟气脱硝技术研究新进展

简介了国内外已工业应用的主要烟气脱硝技术如选择性催化还原法（SCR）、选择性非催化还原法（SNCR）和电子柬脱硝技术（EBA）的应用现状及其发展,并对近年来国内外发展的烟气脱硝新工艺、新技术的原理及研究现状进行了评述,最终展望了中国烟气脱硝技术的未来的发展方向。     

SCR脱硝系统烟道内流场优化

为了改善选择性催化还原法(SCR)催化剂上游烟气的流场、温度场和浓度场分布,基于CFD仿真分析技术,建立了整个脱硝系统三维模型,并通过优化导流板及整流格栅,使得速度标准偏差、浓度标准偏差、温度偏差、速度偏转角以及压降等性能指标都满足设计要求,在满足脱硝效率和氨逃逸率前提下,大大降低了烟气对催化剂层的冲刷,保证催化剂的使用寿命。最后,为了合理布置吹灰器,对优化结构下粉尘颗粒在烟道内的运动情况进行了仿真分析研究,为设计提供了依据。     

催化剂在选择性催化还原法烟气脱硝技术的选择研究

介绍了SCR、SNCR等脱硝技术,着重介绍了SCR烟气脱硝技术中催化剂的基本知识及常用的催化剂种类,阐述了燃煤电厂应用SCR技术对催化剂的要求,并分析了影响催化剂钝化的主要因素。     

燃煤烟气低温SCR脱硝中试研究

低温选择性催化还原(SCR)脱硝是国内外脱硝技术研发的热点,但目前主要集中在实验室小试范围,无法完全反映催化剂在实际烟气中的运行状况。在30 t/h循环流化床燃煤锅炉脱硫除尘装置后建设了2 000~5 000 m3/h的SCR脱硝中试装置,经系统研究发现,中试使用的蜂窝式催化剂对SO2和NO具有很强的吸附能力,且反应温度、喷氨速率和气体空速均会影响催化脱硝效率。为期5 d的连续运行实验结果表明,催化剂的脱硝效率一直稳定在30%~50%,并未发现明显的失活,这证明设计除雾除尘器、较大的混合器、混合器与反应器间较长的管路均有利于缓解催化剂因SO2、H2O和飞灰中的碱性金属导致的失活。     

失活商业SCR催化剂在线维护技术

商业SCR催化剂在工业运行过程中由于其复杂的工况条件存在容易中毒、失活的问题,故利用在线维护技术对其进行活性恢复具有巨大的商业发展前景。为了探究泡沫清洗技术对商业SCR失活催化剂进行在线维护方案的可行性,采用一系列表征手段对在线维护前、后的失活SCR脱硝催化剂进行了表征分析,包括SEM、EDS、XRD、BET和XPS等,并对在线维护最佳的溶液浓度参数进行了探究。研究发现:当稀硫酸浓度为0.4 mol·L~(-1),微孔渗透液质量分数为2%,活性添加剂质量分数为3%,在线维护效果最优;经过在线维护之后,催化剂团聚现象得到明显改善,碱金属中毒现象得到缓解,催化剂氧化性能和表面酸度增强,催化剂活性因而得到恢复,其最佳脱硝效率可达92%,具备良好的工业应用潜力。     

水泥厂氨排放标准存在的问题及氨排放控制

为控制水泥脱硝工程产生的氨排放问题,中国发布《水泥工业大气污染物排放标准》(GB 4915—2013)对水泥企业氨排放限值提出明确要求。但水泥脱硝设施同步配套的氨在线检测仪记录数据表明,多数水泥厂脱硝后的氨排放浓度远超过标准限值。为此,对照火电厂相关标准和技术规范,指出了水泥工业氨排放标准和技术规范文件中存在的问题。结合实际检测数据和国外相关文献,确认水泥工业存在"本底氨"排放,水泥原料、协同处理废弃物、生产工况变化是导致本底氨排放的主要原因。选择性非催化还原(SNCR)脱硝设施产生的氨逃逸将增加氨排放浓度,反应温度窗口、停留时间、氨/氮摩尔比(NSR)、喷射方案等均会影响氨逃逸浓度。优化水泥生产工艺、SNCR脱硝工艺或配套选择性催化还原(SCR)脱硝系统等方式可有效控制水泥厂本底氨及氨逃逸。     

基于生命周期评价的选择性催化还原脱硝技术还原剂的选择研究

应用生命周期评价(LCA)方法,以燃煤电厂选择性催化还原(SCR)脱硝技术中还原剂的选择为研究对象,对液氨与尿素的生产、运输、存储与供应、脱硝及废液处理5个过程进行了清单分析,着重分析了液氨与尿素的生产、运输的能耗及其对环境的影响。计算结果表明,尿素对环境的负面影响大于液氨对环境的负面影响。因此,如果从对环境的影响看,燃煤电厂SCR脱硝技术在选择还原剂时,应采用对环境负面影响小的液氨。     

炼焦炉应用SCR烟气脱硝的中试研究

随着国家环保新标准的发布,焦化炉烟气的NOx排放将会得严格的控制。结合神华乌海能源有限公司6#炉侧线烟气脱硝中试项目,介绍了SCR脱硝技术原理、中试实验的工艺流程;测试了实验过程中反应温度、不同空速以及氨氮比对脱硝效率的影响;同时对中试系统的稳定性进行了为期4 d的连续测试。在实际烟气中开展的中试实验为焦化炉SCR脱硝技术的研究分享了一手数据及经验。     

脱硝催化剂孔结构及其脱硝特性的研究

选择性催化还原脱硝技术(SCR)所采用的催化剂多数为多孔介质,其内部孔隙有助于提高催化剂的反应活性。文中采用浸渍负载法,通过改变制备温度制备出不同孔结构的催化剂样品,采用N2吸附法对其孔结构进行测定和分析,并对不同孔结构的催化剂样品进行了脱硝实验。研究表明:煅烧及干燥温度对催化剂孔结构有很大的影响,比表面积越大,其催化剂内的孔分布宽度越窄,平均孔径越小;在活性温度范围(360～390℃)内,脱硝过程中主要是属于化学反应过程控制,脱硝效果随着比表面积的增大而增强;在非活性温度范围内,脱硝过程同时受到气体扩散过程及化学反应过程控制。     

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.     

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.     

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.     

土壤中砷的化学平衡

本文比较详细地综述了砷的化学特性,环境背景值及来源和循环,土壤中砷的三大化学平衡即沉淀溶解平衡,氧化还原平衡,吸附解吸平衡,以及微生物对砷的转化。     

Elemental uptake by edible herbs and lettuce (Latuca sativa)

The total concentration of toxic elements (aluminum, cadmium, chromium and lead) and selected macro and micro elements (iron, manganese, copper and zinc) are reported in six leafy edible vegetation species, namely lettuce, spinach, cabbage, chards and green and red types of Amaranth herbs. Although spinach and chards had greater than 125 mv of iron, both the amaranthus herbs recorded > than 320 μ g g^{? 1} dry weight. In both the spinach and chard species, the Mn and Zn levels were appreciable recording > 225 μ g g^{? 1} and 150 μ g g^{? 1} dry weight, respectively. Aluminum concentrations were (in μ g g^{? 1} dry weight) lettuce (10), cabbage (11), spinach (167), chards (65), amaranthus green (293) and amaranthus red (233). All the micro and macro elements and the toxic elements (Ni, Cr, Cd and Pb) elements analyzed, were below the recommended maximum permitted levels (RMI) in vegetables. Further the elemental uptake and distribution of the nine elements, at three growth stages of the lettuce plant grown on soil bed under controlled conditions are detailed. In the soil, except for iron (16%), greater than 33% of the other cations were in exchangeable form. Generally in the lettuce plant, roots retained much of the iron (> 224 μ g g^{? 1}) and aluminum (> 360 μ g g^{? 1}), while leaves had less than 200 μ g g^{? 1} of iron and 165 μ g g^{? 1} of Al. Although the concentrations of elements marginally decreased with growth, the lettuce leaves had significant amounts of Mn (30 μ g g^{? 1}), Zn (50 μ g g^{? 1}) and Cu (3.6 μ g g^{? 1}). Some presence of lead in leaves (2.0 μ g g^{? 1}) was noticed, but all the toxic and other elements analyzed were well below the RMI values for the vegetables.     

The dissipation of nonlyphenol in stream and pond water under simulated field conditions

Abstract

The dissipation of 1.0 ppm nonylphenol in stream and pond water, incubated in flasks at 16°C under simulated field conditions up to 44 days indicated that the half‐life was 2.5 days if the flasks were open, and 16 days if they were closed. A transformed product was detected in the closed flasks.

Translocation of nonylphenol in water occurred when treated water samples were incubated in the presence of sediment. After 10 days, nonylphenol was detected only in the sediment, but not in water (detection limit = 10 ppb). About 80% of the nonylphenol was degraded in 71 days, but no degradation occurred if the water and the sediment were autoclaved prior to incubation.