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1.
Fly ash is a potential alternative to activated carbon for mercury adsorption. The effects of physicochemical properties on the mercury adsorption performance of three fly ash samples were investigated. X-ray fluorescence spectroscopy, X-ray photoelectron spectroscopy, and other methods were used to characterize the samples. Results indicate that mercury adsorption on fly ash is primarily physisorption and chemisorption. High specific surface areas and small pore diameters are beneficial to efficient mercury removal. Incompletely burned carbon is also an important factor for the improvement of mercury removal efficiency, in particular. The C-M bond, which is formed by the reaction of C and Ti, Si and other elements, may improve mercury oxidation. The samples modified with CuBr2 , CuCl 2 and FeCl3 showed excellent performance for Hg removal, because the chlorine in metal chlorides acts as an oxidant that promotes the conversion of elemental mercury (Hg0) into its oxidized form (Hg2+). Cu2+ and Fe3+ can also promote Hg 0 oxidation as catalysts. HCl and O2 promote the adsorption of Hg by modified fly ash, whereas SO2 inhibits the Hg adsorption because of competitive adsorption for active sites. Fly ash samples modified with CuBr2 , CuCl2 and FeCl3 are therefore promising materials for controlling mercury emissions.  相似文献   

2.
The role of the gaseous pollutants, HCl and SO2, has been investigated in a laboratory-based atmospheric flow rig. Using an HCl level of 25 ppm at a pollutant bulk presentation rate 10 times that found typically outdoors, a degradation acceleration factor of about 20 times was obtained, together with realistic degradation products. HCl was found to be a more reactive gas than SO2, which was also studied at the 25 ppm level. This may be due either to factors involved in the adsorption of the gases on to the stone surfaces, or the extensive solubility of HCl, or the requirement of an extra step in the conversion of SO2 to sulphate, which would limit the overall reaction rate. The soluble degradation product CaCl2 is readily washed off the stone allowing continuous reaction, while the relatively insoluble CaSO4.2H2O can remain on, or in the stone surface regions and may inhibit or affect further reaction with SO2.The reaction of limestone with HCl gas is mass-transport limited and greater material losses arise in locations of higher HCl concentration and deposition velocity, i.e. a close-to-source effect is highlighted due to its high solubility and reactivity, but the HCl concentration is, of course, generally about one-fiftieth of that of SO2 outdoors. For SO2, with lower solubility and a necessary oxidation stage to form SO42−, comparatively high deposition velocities are applicable more widely from the source. The consequences include a widespread formation of relatively insoluble CaSO4.2H2O and consequent crust development.  相似文献   

3.
The influence of CO2 content and presence of SO2 on the sequestration of CO2 by municipal solid waste incinerator(MSWI) fly ash was studied by investigating the carbonation reaction of MSWI fly ash with different combinations of simulated flue gas.The reaction between fly ash and 100% CO2 was relatively fast;the uptake of CO2 reached 87g CO2/kg ash,and the sequestered CO2 could be entirely released at high temperatures.When CO2 content was reduced to 12%,the reaction rate decreased;the uptake fell to 41g CO2/kg ash,and 70.7% of the sequestered CO2 could be released.With 12% CO2 in the presence of SO2,the reaction rate significantly decreased;the uptake was just 17g CO2/kg ash,and only 52.9% of the sequestered CO2 could be released.SO2 in the simulated gas restricted the ability of fly ash to sequester CO2 because it blocked the pores of the ash.  相似文献   

4.
在双搅拌釜上实验测定了飞灰和废大理石浆液的脱硫率η及pH值随过程时间t的变化关系,计算了不同t时的传质速率Nm、液膜传质系数kL、气相总传质系数KG、气膜传质系数kG、传质系数之比KG/kG以及反应增强因子E等,并分析了飞灰和废大理石脱硫的传质-反应过程.实验和计算结果表明,当进口SO2体积分数为4000×10-6时,飞灰和大理石浆液脱硫均受液相阻力控制;pH值越低,KG/kG就越小,液相阻力控制也就越明显,在pH=4.5时,液相阻力占总阻力的90%; pH值越高,E就越大,化学反应对传质的影响也就越明显;pH=6时飞灰浆液具有与大理石浆液相近的脱硫率,达70%左右.  相似文献   

5.
基于碳捕集的富氧燃煤烟气联合脱硫脱硝试验研究   总被引:1,自引:0,他引:1  
富氧燃煤烟气压缩液化CO2的高压低温工况为NO氧化为易溶于水的NO2提供了十分有利的条件.基于小型高压吸收试验装置,采用配制的富氧燃煤模拟烟气,在高压常温下进行了NO、SO2、O2与H2O的吸收反应试验.根据反应前后的气液产物分析,测定了不同组分比例与不同压力下混合气体中NO与SO2的转化率.NO氧化与吸收试验表明,NO转化为HNO3的比率随压力升高而增加,在0.5 ~2 MPa之间增加很快,在2 ~3 MPa之间增速趋丁平缓,压力达3 MPa以上时,90%以上的NO均转化为稀硝酸,且初始NO浓度越高,NO的转化率越大.混合气体中同时存在5O2与NO的联合吸收试验发现,只有少量的NO转化成了NO3-,SO2向H2SO4的转化率随压力升高而增加,初始SO2浓度越大,转化率越高.分析表明,SO2与NO同时存在时SO2先行转化为SO3,NO充当了催化剂,但SO2转化为SO3的一次转化率小于35%,反应酸液产物的多次循环能使SO2的转化率达到90%以上.建议的工艺流程中需采用两座吸收反应塔顺序脱除SO2与NO并回收稀酸溶液,有望在富氧燃煤发电捕集CO2系统中降低脱硫脱硝成本,部分地弥补富氧燃烧机组发电成本的增加.  相似文献   

6.
Controlled exposure of ice to a reactive gas, SO2, demonstrated the importance of the chemical composition of the ice surface on the accumulation of acidity in snow. In a series of bench-scale continuous-flow column experiments run at four temperatures (−1, −8, −30 and −60°C), SO2 was shown to dissolve and to react with other species in the ice-air interfacial region at temperatures approaching the melting point of ice. Experiments consisted of passing air containing SO2 through glass columns packed with 100μm ice spheres of varying bulk composition (0–5μM H2O2, and 0–1 mM NaCl), and analysing SO2 in the air and SO42− in the ice. At all temperatures (−60 to −1°C), increased retention volumes were found for increasing ionic strength and oxidant concentration. At the coldest temperatures and with no NaCl, increased retention volumes for −60 vs −30°C are consistent with SO2 uptake by physical adsorption. At warmer temperatures, −8 and −1°C, the observed tailing in the sorption curves indicated that other processes besides physical adsorption were occurring. The desorption curves showed a rapid decrease for the warmer temperatures, indicating the sorbed SO2 is irreversibly oxidized to SO42−. Results indicate that aqueous-phase reactions can occur below −8°C (i.e. −30 and −60°C). Results for different salt concentrations show that increasing ionic strength facilitates SO2 oxidation at colder temperatures, which is consistent with freezing point depression. One environmental implication is that snowpacks in areas with background SO2, can accumulate acidity during the winter months. As acidity accumulates, the solubility of SO2 will decrease causing a concomitant decrease in the air-to-surface flux of SO2. Modeling dry deposition of gases to snow surfaces should incorporate the changing composition of the ice surface.  相似文献   

7.
Wet deposition of soluble materials was monitored for a 7-month period in the vicinity of Mount Sakurajima, which has been very active since 1955. Data obtained for the ionic composition of samples were used as a basis for considering the scavenging of volcanic emissions by precipitation. Precipitation samples with pH < 4 were often collected in the vicinity of Mount Sakurajima during the course of the study. HCl, H2SO4 and HF were the primary contributors to the acidity of precipitation. The exCl/exSO42− mole ratio of precipitation was several times that of volcanic ash in the vicinity of the volcano and declined with distance from the volcano. Although most of the S in volcanic emissions is in the form of SO2, relatively little of this is washed out by precipitation in the immediate vicinity of the volcano. The deposition of S in the vicinity of the volcano can be adequately accounted for by assuming the scavenging of SO42− particles despite the relatively small share of total atmospheric S loading of particulate SO42− in the vicinity of Mount Sakurajima.  相似文献   

8.
The acid snow/rain model [describedin Part I, Kitada et al., Atmospheric Environment27A, 1061–1076, 1993] was applied to investigate transport/transformation/deposition of acidic species in association with snow-precipitating cloud over the Japan Sea in winter. The model results showed: (1) The snow-precipitating clouds generated by relatively weak convective motions tend to trap aerosols of sulfate and nitrate and soluble gases such as SO2 and HNO3 below cloud levels, thus keeping their concentrations at higher levels than those for no-cloud situations. The mechanisms involved are: transfer of gas- and aerosol-phase species to cloud-phase through absorption and nucleation scavenging, then their transfer from cloud to snow through riming, and subsequent release from sublimating snow back to gas- and aerosol-phases below cloud base. (2) In-cloud oxidation enhanced the overall conversion of SO2 to SO42− by some 25% with respect to no-cloud situation after 12 h. Furthermore, contributions to the oxidation were 77.4%, 21.1% and 1.5% for S(IV)H2O2, S(IV)O2 with catalysts of Fe3+ + Mn2+ and S(IV)O3 reactions, respectively. (3) The sulfate wet deposited by precipitating snow for 12 h was due mostly to in-cloud scavenging and in-cloud oxidation, i.e. 66% by nucleation scavenging and the remaining by in-cloud oxidation of S(IV), while the contribution of below-cloud scavenging was negligible. (4) The adsorption process of HNO3 onto the surface of falling snow was found to account for major below-cloud scavenging of snow, and thus in contrast to SO42−, the below-cloud scavenging contributed very significantly to the nitrate wet deposition. Throughout the stimulation, below-cloud scavenging was responsible for 75% of the snow-NO3 formation. Therefore, taking account of this process in acid snow models is important.  相似文献   

9.
A laboratory-based atmospheric flow chamber, using realistic presentation rates of SO2, NO and NO2 pollutants directed to various dry and wetted surfaces, has been employed to quantify the effects of the individual pollutants and the role of ozone as an oxidant. For the individual pollutant gases reacting with stone surfaces coming to equilibrium with 84% relative humidity (r.h.), chemical reaction in the presence of a moisture film proceeds and the extent of this reaction is related to pollutant gas solubility in the moisture film, i.e. SO2 > NO2 > NO. After dissolution in the moisture film, the pollutant gases are oxidized in the presence of catalysts associated with the stones. The additional presence of ozone promotes oxidation of the pollutant gases and thus their reaction with the stones. For SO2 pollutant, oxidation in the gas phase is not significant compared with that in the moisture film, with enhanced oxidation in the presence of catalysts. Ozone increases oxidation of NO and NO2 pollutant gases in the gas phase and moisture film; however, the oxidation of SO2 in the moisture film is more significant than that of NO or NO2. Wetting of the stone surfaces, in the absence of ozone, reveals the consistently greatest chemical reaction with SO2 compared with NO and NO2, which is related to SO2 solubility, oxidation in the presence of catalysts and production of sulphuric acid. Generally similar behaviour is evident of NO and NO2, but NO shows a reduced extent of chemical reaction, implying that its oxidation in surface water, in the presence of catalytic species, is slow and hence the reactants are lost in the form of run-off. In the additional presence of ozone, the SO2 pollutant gas gives rise to enhanced chemical reaction, whereas both NO and NO2 show lower extents of chemical reaction than for the dry stones. This arises from the relatively slow conversion of N2O5 in the liquid phase to nitric acid, allowing loss of reactants in run-off.  相似文献   

10.
The importance of the three major aqueous reactions thought to be responsible for the in-cloud conversion of SO2 to SO42- was studied using the acidic deposition and oxidants model by supressing each reaction individually and all reactions simultaneously. The reactions are the oxidation of SO2 by H2O2, or O3 and catalytic oxidation by O2 in the presence of Fe and Mn. The model simulations were 19–24 April 1981. It was found that SO42- precipitation concentrations were generally more sensitive to H2O2 oxidation than to O3 oxidation. The contribution of catalytic oxidation of SO2 in the presence of Fe and Mn is insignificant everywhere and at all times. The contributions of H2O2 oxidation to SO42- in precipitation is strongest in light precipitation areas while O3 oxidation can be greater than H2O2 oxidation in heavy precipitation areas. The effect of supressing one reaction is mitigated by compensation through another mechanism. This is seem from the significant difference observed in the effects when individual suppressions were added together and when all reactions were suppressed simultaneously. From this, it is estimated that the contribution of aqueous oxidation of SO2 to SO42- in precipitation is approximately 50–80 per cent. Further simulations show that the relationship between SO2 emissions and SO42- production in the aqueous-phase through the oxidation reaction with O3 is always non-linear in view of the pH dependence of the reaction rates.  相似文献   

11.
OMS-2 nanorod catalysts were synthesized by a hydrothermal redox reaction method using MnSO4 (OMS-2-SO4) and Mn(CH3COO)2 (OMS-2-AC) as precursors. SO42 −-doped OMS-2-AC catalysts with different SO42 − concentrations were prepared next by adding (NH4)2SO4 solution into OMS-2-AC samples to investigate the effect of the anion SO42 − on the OMS-2-AC catalyst. All catalysts were then tested for the catalytic oxidation of ethanol. The OMS-2-SO4 catalyst synthesized demonstrated much better activity than OMS-2-AC. The SO42 − doping greatly influenced the activity of the OMS-2-AC catalyst, with a dramatic promotion of activity for suitable concentration of SO42 − (SO4/catalyst = 0.5% W/W). The samples were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), inductively coupled plasma optical emission spectroscopy (ICP-OES), NH3-TPD and H2-TPR techniques. The results showed that the presence of a suitable amount of SO42 − species in the OMS-2-AC catalyst could decrease the Mn–O bond strength and also enhance the lattice oxygen and acid site concentrations, which then effectively promoted the catalytic activity of OMS-2-AC toward ethanol oxidation. Thus it was confirmed that the better catalytic performance of OMS-2-SO4 compared to OMS-2-AC is due to the presence of some residual SO42 − species in OMS-2-SO4 samples.  相似文献   

12.
An earlier analysis of empirical associations between SO2 emissions and wet SO42− concentrations in central North America (Hilst and Chapman, 1990, Atmospheric Environment 24A, 1889–1901) showed that local wet SO42− concentrations were not proportional to SO2 emissions averaged over areas up to ∼106 km2. Because it is axiomatic that at a global level of averaging a proportionality between total S emissions and S deposition should exist, we have extended these analyses in an attempt to determine whether there is proportionality between S emissions and wet SO42− deposition. We have found that for the eastern half of central North America (an area of about 4.3 × 106 km2), the annual average wet SO42− concentration exhibits a linear-proportional dependence on anthropogenic SO2 emissions. However, the internal structure of this association for subareas of the eastern half of central North America suggests the “global” proportionality is achieved by a combination of imported SO2 from major source areas and an oxidant-limited conversion of SO2 to SO42− within the major source areas. If this inference is even approximately correct, a rollback SO2 control strategy for the eastern United States and southeast Canada should result in an immediate proportional decrease in wet SO42− concentrations in minor SO2 source areas, but no appreciable reduction of wet SO42− concentrations in major SO2 source areas until the oxidant limitation has been overcome.  相似文献   

13.
The concentrations of aerosols (NH4NO3, (NH4)2SO4 and NH4Cl) and of gases (HCl(g), HNO3(g), NH3(g) were determined by denuder methods under different conditions (in the absence of fog, before, during and after fog events). At this site situated in an urban region, high concentrations of the gaseous strong acids HCl(g) and HNO3(g) are observed. NH4Cl and NH4NO3 aerosols represent a major fraction of the Cl and NO3 aerosols (<2.4 μm)collected by denuders. During a fog event, very high concentrations of SO42− were found in small aerosols, which are attributed to the aqueous phase oxidation of SO2 under the influence of high pH due to the presence of NH3. Differences in SO42− concentrations measured in aerosols (<2.4 μm) and in fog droplets were probably due to mass-transport limitations of the SO2 oxidation. Ammonium sulfate aerosols represent in some cases a significant fraction of the total S present (SO2(g) + SO42−. Soluble aerosols and gases contribute to the composition of fogwater and are released again after fog dissipation.  相似文献   

14.
The design philosophy, construction and use of two exposure test systems are described, in which the objective is to simulate the degradation of stone samples under, respectively, the ‘dry’ and ‘wet’ deposition of atmospheric pollutants. Some element of realistic acceleration is possible in certain experiments. Particular emphasis is placed upon using known presentation rates of the pollutants, both in respect of typical depositions of pollutants and their oxidation products appropriate for an industrial atmosphere. In the dry deposition rig, SO2, NO2, NO, HCl and the oxidant O3 are presented individually or together at realistic deposition rates. In the wet deposition apparatus, SO2−4, NO3 and Cl at a pH of 3.5, simulating ‘acid rain’ but in a more concentrated form, are deposited. The dry deposition chamber can be operated at constant relative humidity (typically 84%) with pre-dried or precisely wetted stones to simulate episodic rain wetting, or using other methods of wet/dry cycling, which are also a feature of the wet deposition chamber. Heating and cooling of the samples is also possible, as is the use of shaped or coupled stones of different kinds such as are found in a building facade. The results are illustrated in terms of data on the weight change, the anion content of stone and run-off, the pH change of run-off and the total calcium reacted, using Portland stone, as a prelude to later papers in which behaviour of a whole matrix of stone types and environments is presented and discussed. Such an approach permits the eventual production of ‘pollutant-material response’ relationships and damage functions for comparison with and prediction of external exposure results.  相似文献   

15.
A long-term study of aerosol SO42− concentrations ([SO42−]) has been conducted at Mayville in the western and Whiteface Mountain in the northeastern New York State. From 1975 to 1988, 2382 daily aerosol samples were collected at Whiteface Mountain using high-volume samplers. Similarly, 1863 samples were collected at Mayville for the 1981–1988 period. Both sites are downwind of large SO2 sources in the Midwest. Whiteface Mountain is located approximately 600 km to the northeast of Mayville. The [SO42−] at Mayville were approximately twice that of Whiteface Mountain. The highest concentrations at both locations were observed in summer and the lowest during winter. Photochemical reactions appear to be the primary reason for this behavior. Air trajectories (Hefter model) were used to relate the observed [SO42−] with the upwind SO2 source regions. In addition, a method based on V/Se ratios was used to resolve SO42− contributions between Midwestern sources and those in the East Coast. Approximately, two-thirds or more of the total SO42− at the two sites was derived from the Midwestern emissions. At Whiteface Mountain the [SO42−] for summer months from 1975 to 1988 suggest a decrease of approximately 3% per year between 1978 and 1988. A similar decrease was also observed in SO2 emissions.  相似文献   

16.
Measurements of the dry deposition of pollen were made during the months of May and June 1987 in northern Wisconsin, using a smooth surrogate surface. Samples were taken on a raft located on Little Rock Lake and at a nearby field monitoring station. Rain samples were also collected at the field station. The wet SO42− flux was 102.7 mg m−2, compared with a dry SO42− flux of 118 mg m−2 at the field monitoring site and 45 mg m−2 at the lake site.The SO42− content of pollen ranged from 0.2 to 0.8% of the weight of the pollen, and NO3 concentrations were an order of magnitude lower. Between 9 and 22% of the pollen weight was available as total organic carbon (TOC) upon addition to water.The addition of pollen to distilled water produced an acid reaction, due to organic acids and not inorganic acidity.  相似文献   

17.
超低排放燃煤电站三氧化硫的迁移和排放特征   总被引:3,自引:0,他引:3  
赵毅  韩立鹏 《环境科学学报》2019,39(11):3702-3708
采用美国环保署(USEPA)method 8推荐的方法,对典型超低排放燃煤电站满负荷工况下的燃煤、烟气、飞灰、渣进行三氧化硫监测.实验结果表明:燃煤电站超低排放环保设备对三氧化硫的总脱除率为71.86%,大气三氧化硫排放浓度为1.5 mg·m~(-3)(气体体积为标准大气压下的体积,下同).选择性脱硝催化剂(SCR)前烟气中三氧化硫生成量为二氧化硫的0.46%,在SCR催化剂SO_2/SO_3的转化率为0.58%,空气预热器内气态三氧化硫浓度显著降低.低温电除尘(LLT-ESP)内三氧化硫与飞灰结合得到脱除,LLT-ESP细灰中三氧化硫含量为粗灰的1.38倍.湿法脱硫系统(WFGD)对三氧化硫的脱除率为48.45%.超低排放燃煤电站大气三氧化硫排放因子EF_煤、EF_电分别为17.13 mg·kg~(-1)、4.41 mg·kW~(-1)·h~(-1).估算2018年我国燃煤电站三氧化硫大气排放总量约为3.99万t·a~(-1).  相似文献   

18.
A novel ferruginous active absorbent, prepared by fly ash, industrial lime and the additive Fe(VI), was introduced for synchronous abatement of binary mixtures of SO2–NOx from simulated coal-fired flue gas. The synergistic action of various factors on the absorption of SO2 and NOx was investigated. The results show that a strong synergistic effect exists between Fe(VI) dose and reaction temperature for the desulfurization. It was observed that in the denitration process, the synergy of Fe(VI) dose and Ca/(S + N) had the most significant impact on the removal of NO, followed by the synergy of Fe(VI) and reaction temperature, and then the synergy of reaction temperature and flue gas humidity. A scanning electron microscope (SEM) and an accessory X-ray energy spectrometer (EDS) were used to observe the surface characteristics of the raw and spent absorbent as well as fly ash. A reaction mechanism was proposed based on chemical analysis of sulfur and nitrogen species concentrations in the spent absorbent. The Gibbs free energy, equilibrium constants and partial pressures of the SO2–NOx binary system were determined by thermodynamics.  相似文献   

19.
A novel ferruginous active absorbent, prepared by fly ash, industrial lime and the additive Fe(VI), was introduced for synchronous abatement of binary mixtures of SO2–NOx from simulated coal-fired flue gas. The synergistic action of various factors on the absorption of SO2 and NOx was investigated. The results show that a strong synergistic effect exists between Fe(VI) dose and reaction temperature for the desulfurization. It was observed that in the denitration process, the synergy of Fe(VI) dose and Ca/(S + N) had the most significant impact on the removal of NO, followed by the synergy of Fe(VI) and reaction temperature, and then the synergy of reaction temperature and flue gas humidity. A scanning electron microscope(SEM) and an accessory X-ray energy spectrometer(EDS)were used to observe the surface characteristics of the raw and spent absorbent as well as fly ash. A reaction mechanism was proposed based on chemical analysis of sulfur and nitrogen species concentrations in the spent absorbent. The Gibbs free energy, equilibrium constants and partial pressures of the SO2–NOx binary system were determined by thermodynamics.  相似文献   

20.
石灰石脱硫反应活性的研究   总被引:5,自引:0,他引:5       下载免费PDF全文
脱硫剂石灰石的反应活性对流化床燃煤锅炉的脱硫效果影响很大。目前,国内外主要采用动力学方法,通过测定固态CaO的硫酸盐化程度来推断石灰石的反应活性。但是这在石灰石中含有许多其它杂质成分时是不够全面的,因为这些杂质成分对石灰石的脱硫反应活性影响很大,不能忽视。为此,通过测定流化床入口和出口的SO2浓度变化来判断加入床中的石灰石样品的反应活性。由于凡是能引起SO2浓度变化的物质都与石灰石的反应活性有关,从而克服了原有方法仅考虑CaO重量变化的片面性。本文也采用了动力学方法建立了石灰石反应动力学模型,并利用线性化方法对其反应速率常数K进行线性估计,建立了石灰石化学成分与活性关系的数学模型。  相似文献   

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