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1.
用于气态零价汞转化的催化剂研究   总被引:4,自引:0,他引:4  
零价汞的高效去除是燃煤烟气汞污染控制过程中的关键环节。为了促进烟气中的零价汞转化为易于去除的氧化态汞,分别考察了在有HCl存在时,几种过渡金属氧化物(Cu、Fe、Mn、Co和Zr)对零价汞氧化的催化作用,以筛选出性能较好的催化组分;为提高催化剂的抗SO2性能,分别尝试了利用几种金属元素(Sr、Ce、W和Mo)对催化剂进行掺杂改性的方法。结果表明,锰氧化物的催化作用最好,其最佳使用温度在573 K左右;SO2对零价汞的催化氧化有明显抑制作用,在无SO2及1 400 mg/m3SO2时锰催化剂对零价汞催化氧化效率分别为93%和78%。而Mo改性的锰氧化物催化剂的抗硫性能大幅提高,在1 400 mg/m3SO2存在的情况下其对零价汞的催化氧化效率可达到90%以上,较其他改性元素高。  相似文献   

2.
湿式烟气脱硫系统同时脱汞研究   总被引:3,自引:0,他引:3  
研究表明,湿法烟气脱硫装置(WFGD)可去除烟气中绝大部分Hg2+,但对单质汞的吸收效果不明显,因此研究提高湿法烟气脱硫系统中单质汞的氧化率的方法对控制汞的排放具有重要意义。综述了WFGD及在此系统中各种添加剂的脱汞性能,认为在添加剂中,气态的臭氧、液态的次氯酸和氯化钠稀溶液、 黄磷乳浊液、氢硫化钠溶液及EDTA的汞去除效果较好,且不会被SO2大量消耗,可在WFGD系统实现同时脱硫脱汞;而气态的氯气,液态的K2S2O8溶液虽然也有较好的汞去除效果,但因易被SO2或亚硫酸盐溶液消耗,当在WFGD系统中用其氧化单质汞时,需要对脱硫塔进行分层或其他改造,使烟气中的SO2被吸收后再控制汞,提高经济性。  相似文献   

3.
A goal of the acidic deposition control program in the United States has been to link emissions control policies, such as those mandated under Title IV of the US Clean Air Act Amendments (CAAA) of 1990, to improvements in air and water quality. Recently, several researchers have reported trends in the time series of pollutant data in an effort to evaluate the effectiveness of the CAAA in reducing the acidic deposition problem. It is well known that pollutant concentrations are highly influenced by meteorological and climatic variations. Also, spatial and temporal inhomogeneities in time series of pollutant concentrations, induced by differences in the data collection, reduction, and reporting practices, can significantly affect the trend estimates. We present a method to discern breaks or discontinuities in the time series of pollutants stemming from emission reductions in the presence of meteorological and climatological variability. Using data from a few sites, this paper illustrates that linear trend estimates of concentrations of SO2, aerosol SO42−, and precipitation-weighted SO42− and NO3 can be biased because of such complex features embedded in pollutant time series.  相似文献   

4.
Abstract

This paper is particularly related to elemental mercury (Hg0) oxidation and divalent mercury (Hg2+) reduction under simulated flue gas conditions in the presence of nitric oxide (NO) and sulfur dioxide (SO2). As a powerful oxidant and chlorinating reagent, Cl2 has the potential for Hg oxidation. However, the detailed mechanism for the interactions, especially among chlorine (Cl)-containing species, SO2, NO, as well as H2O, remains ambiguous. Research described in this paper therefore focused on the impacts of SO2 and NO on Hg0 oxidation and Hg2+ reduction with the intent of unraveling unrecognized interactions among Cl species, SO2, and NO most importantly in the presence of H2O. The experimental results demonstrated that SO2 and NO had pronounced inhibitory effects on Hg0 oxidation at high temperatures when H2O was also present in the gas blend. Such a demonstration was further confirmed by the reduction of Hg2+ back into its elemental form. Data revealed that SO2 and NO were capable of promoting homogeneous reduction of Hg2+ to Hg0 with H2O being present. However, the above inhibition or promotion disappeared under homogeneous conditions when H2O was removed from the gas blend.  相似文献   

5.
ABSTRACT

The capture of elemental mercury (Hg0) and mercuric chloride (HgCl2) by three types of calcium (Ca)-based sor-bents was examined in this bench-scale study under conditions prevalent in coal-fired utilities. Ca-based sorbent performances were compared with that of an activated carbon. Hg0 capture of about 40% (nearly half that of the activated carbon) was achieved by two of the Ca-based sorbents. The presence of sulfur dioxide (SO2) in the simulated coal combustion flue gas enhanced the Hg0 capture from about 10 to 40%. Increasing the temperature in the range of 65-100 °C also caused an increase in the Hg0 capture by the two Ca-based sorbents. Mercuric chloride (HgCl2) capture exhibited a totally different pattern. The presence of SO2 inhibited the HgCl2 capture by Ca-based sorbents from about 25 to less than 10%. Increasing the temperature in the studied range also caused a decrease in HgCl2 capture. Upon further pilot-scale confirmations, the results obtained in this bench-scale study can be used to design and manufacture more cost-effective mercury sorbents to replace conventional sorbents already in use in mercury control.  相似文献   

6.
High concentrations (>15 μm3 cm?3) of CaSO4, Ca(NO3)2 and (NH4)2SO4 were selected as surrogates of dry neutral, aqueous neutral and dry acidic inorganic seed aerosols, respectively, to study the effects of inorganic seeds on secondary organic aerosol (SOA) formation in irradiated m-xylene/NOx photooxidation systems. The results indicate that neither ozone formation nor SOA formation is significantly affected by the presence of neutral aerosols (both dry CaSO4 and aqueous Ca(NO3)2), even at elevated concentrations. The presence of high concentrations of (NH4)2SO4 aerosols (dry acidic) has no obvious effect on ozone formation, but it does enhance SOA generation and increase SOA yields. In addition, the effect of dry (NH4)2SO4 on SOA yield is found to be positively correlated with the (NH4)2SO4 surface concentration, and the effect is pronounced only when the surface concentration reaches a threshold value. Further, it is proposed that the SOA generation enhancement is achieved by particle-phase heterogeneous reactions induced and catalyzed by the acidity of dry (NH4)2SO4 seed aerosols.  相似文献   

7.
A new sampling device is described for the simultaneous collection of NH3, HNO3, HCl, SO2 and H2O2 in ambient air. The apparatus is based on air sampling by two parallel annular denuder tubes. The gases are collected by absorption in solutions present in the annulus of the denuder tubes. After a sampling time of 30 min at flow rate of 32 ℓ min−1 the solutions are extracted from the denuders and analyzed off-line. The detection limits of NH3, HNO3, HCL and SO2 are in the order of 0.1–0.5 μm−3. For H2O2 the detection limit is 0.01 μm−3. The reproducibility is 5–10% at the level of ambient air concentrations. Comparison of this novel technique with existing methods gives satisfactory results. The compact set-up offers the possibility of field experiments without the need of extensive equipment.  相似文献   

8.
Abstract

Selective catalytic reduction (SCR) technology increasingly is being applied for controlling emissions of nitrogen oxides (NOx) from coal-fired boilers. Some recent field and pilot studies suggest that the operation of SCR could affect the chemical form of mercury (Hg) in coal combustion flue gases. The speciation of Hg is an important factor influencing the control and environmental fate of Hg emissions from coal combustion. The vanadium and titanium oxides, used commonly in the vanadia-titania SCR catalyst for catalytic NOx reduction, promote the formation of oxidized mercury (Hg2+).

The work reported in this paper focuses on the impact of SCR on elemental mercury (Hg0) oxidation. Bench-scale experiments were conducted to investigate Hg0 oxidation in the presence of simulated coal combustion flue gases and under SCR reaction conditions. Flue gas mixtures with different concentrations of hydrogen chloride (HCl) and sulfur dioxide (SO2) for simulating the combustion of bituminous coals and subbituminous coals were tested in these experiments. The effects of HCl and SO2 in the flue gases on Hg0 oxidation under SCR reaction conditions were studied. It was observed that HCl is the most critical flue gas component that causes conversion of Hg0 to Hg2+ under SCR reaction conditions. The importance of HCl for Hg0 oxidation found in the present study provides the scientific basis for the apparent coal-type dependence observed for Hg0 oxidation occurring across the SCR reactors in the field.  相似文献   

9.
Abstract

Efforts to develop multipollutant control strategies have demonstrated that adding certain oxidants to different classes of Ca-based sorbents leads to a significant improvement in elemental Hg vapor (Hg0), SO2, and NOx removal from simulated flue gases. In the study presented here, two classes of Ca-based sorbents (hydrated limes and silicate compounds) were investigated. A number of oxidizing additives at different concentrations were used in the Ca-based sorbent production process. The Hg0, SO2, and NOx capture capacities of these oxidant-enriched sorbents were evaluated and compared to those of a commercially available activated carbon in bench-scale, fixed-bed, and fluid-bed systems. Calcium-based sorbents prepared with two oxidants, designated C and M, exhibited Hg0 sorp-tion capacities (~100 μg/g) comparable to that of the activated carbon; they showed far superior SO2 and NOx sorption capacities. Preliminary cost estimates for the process utilizing these novel sorbents indicate potential for substantial lowering of control costs, as compared with other processes currently used or considered for control of Hg0, SO2, and NOx emissions from coal-fired boilers. The implications of these findings toward development of multipollutant control technologies and planned pilot and field evaluations of more promising multipollutant sorbents are summarily discussed.  相似文献   

10.
The rate of incorporation of radiolabeled sulfur dioxide has been determined in submicron sized ammonium sulfate droplet aerosols with and without catalytic metal ions (Fe3+, Mn2+). The sulfate droplets were generated by nebulizing solutions with a multiple jet Collison nebulizer and aged up to 30 min in a 10 m3 plug-flow reaction duct. Radiolabeled 35SO2 was metered into purified air to provide a concentration of 5 ppm.Three different atmospheres were studied: SO2 in purified air, SO2 in the presence of ammonium sulfate aerosol (1 mg m−3, 1 μm MMAD), and SO2 in the presence of ammonium sulfate aerosol containing Fe3+ and Mn2+ ions. No measurable SO2 conversion was detected in samples from atmospheres without the catalytic metal ions. A net SO2 conversion rate equivalent to 0.02 % h−1 was observed in the presence of Fe3+ and Mn2+ ions.  相似文献   

11.
Sodium hypochlorite (NaClO) has been widely used as a chemical additive for enhancing nitrogen oxide (NOx; NO + NO2), sulfur dioxide (SO2), and mercury (Hg0) removals in a wet scrubber. However, they are each uniquely dependent on NaClO(aq) pH, hence making the simultaneous control difficult. In order to overcome this weakness, we sprayed low liquid-to-gas (L/G) ratio (0.1 L/Nm3) of NaClO(aq) to vaporize quickly at 165 °C. Results have shown that the maximized NOx, SO2, and Hg0 removals can be achieved at the pH range between 4.0 and 6.0. When NOx and Hg0 coexist with SO2, in addition, their removals are significantly enhanced by reactions with solid and gaseous by-products such as NaClO(s), NaClO2(s), OClO, ClO, and Cl species, originated from the reaction between SO2 and NaClO(aq). We have also demonstrated the feasibility of this approach in the real flue gases of a combustion plant and observed 50%, 80%, and 60% of NOx, SO2, and Hg0 removals, respectively. These findings led us to conclude that the spray of NaClO(aq) at a relatively high temperature at which the sprayed solution can vaporize quickly makes the simultaneous control of NOx, SO2, and Hg0 possible.

Implications: The simple spray of NaClO(aq) at temperatures above 165 °C can cause the simultaneous removal of gaseous NOx, SO2, and Hg0 by its quick vaporization. Their maximized removals are achieved at the pH range between 4.0 and 6.0. NOx and Hg0 removals are also enhanced by gaseous and solid intermediate products generated from the reaction of SO2 with NaClO(aq). The feasibility of this approach has been demonstrated in the real flue gases of a combustion plant.  相似文献   


12.
Several wet chemical methods have been used or suggested for the determination of SO2 concentrations in air pollution work. These include the iron-O-phenanthroline procedure reported by Stephens and Lindstrom, the Scaringelli-modified West-Gaeke method and the Schulze method. This paper describes a laboratory study to evaluate the usefulness of the iron-o-phenanthroline procedure and is directed to individuals concerned with the analysis of gases from the exhaust of gas turbine engines and other combustion processes, including stationary power plants. The variables considered were: range of usefulness in terms of concentration of SO2, efficiency of collection, effect of contaminants, specifically oxides of nitrogen, olefin and aldehyde and effect of storage prior to spectrophctometric measurement. The Stephens-Lindstrom method was found to be suitable for measuring higher levels of SO2 concentrations. It can accurately measure amounts totalling 6000 µl of SO2 and above whereas the other mentioned methods are generally used for lower levels. Collection efficiency was satisfactory. Contaminants, particularly oxides of nitrogen, are a problem only at low levels of SO2. NO2 interference may be eliminated by absorption of the NO2 on Ultraport S impregnated with ANEDA/H2SO4 solution. Temperature control during SO2 addition is necessary. Storage of exposed reagents prior to measurement produce only small errors if stored at 0°C or at room temperature.  相似文献   

13.
Numerical simulations have been carried out with a model consisting of clear-air chemistry, in- cloud chemical reactions, and dynamic processes of cloud development in order to examine the time history of cloudwater pH and sulfate production in a cumulus cloud and the relationship between pollutant precursors and corresponding acidic chemical species in wet deposition. Preliminary results indicate that the molar ratio SO42−/NC3 in cloud water increases as the ratio SO2/NO2 increases, that the relationship between the increase of precursor SO2/NO2 and the increase of SO42−/NO3 in cloud water is nonlinear, and that the degree of this nonlinearity becomes more significant for cases when the cloud condensation nuclei content in air is assumed to be invariant.  相似文献   

14.
EN 14791 is a European Standard Reference method for the measurement of SO2 in emissions. This standard is based on a wet-chemical method in which SO2 present in flue gases is absorbed into an absorption solution containing hydrogen peroxide, and analyzed as sulfates after sampling. This study presents the results obtained when three portable automated measuring systems (P-AMS), based on Fourier-transform infrared (FTIR) spectroscopy, non-dispersive infrared (NDIR) and ultraviolet-fluorescence (UV) techniques, were compared to the Standard Reference Method for SO2 (EN 14791) in order to verify whether they could be used as alternative methods (AM) to EN 14791. In the case of FTIR, the measurements were performed from hot and wet gas, without any conditioning. UV-fluorescence analyzers were equipped with dilution probes and one NDIR applied a permeation dryer, whereas the other had a chiller. Tests were carried out at concentration ranges from 0 to 200 mg/m3(n) and from 0 to 800 mg/m3(n) for testing of equivalency according to CEN/TS 14793 using a test bench. Equivalency test criteria were met for all tested P-AMS except for NDIR at the lower range. The SO2 results measured with NDIR and the chiller were lower compared to the set-up with NDIR and permeation. This was most probably due to the chiller causing absorption of SO2 in the condensate. Tests were also carried out at field conditions, measuring the SO2 emissions from a boiler combusting mainly bark. The same phenomena were observed in these tests as during the test bench study, i.e. the measurement set-up with NDIR and the chiller gave the lowest results. These data demonstrated that the tested alternative methods (FTIR, UV-fluorescence, and NDIR) could be used instead of the standard reference method EN 14791, thus providing real-time calibration of automated measuring systems. It must however be emphasized that when measuring water-soluble gases, such as SO2, the choice of suitable conditioning technique is critical in order to minimize losses of the studied component in the condensate.

Implications: Portable automated measuring systems (P-AMS) provide real-time information about emissions and their concentrations, thus offering significant advantages compared to wet-chemical methods. This study presents results which can be used as a validation protocol to show that the tested P-AMS techniques (FTIR, NDIR, UV-fluorescence) could be used instead of EN 14791 (CEN 2017a) as alternative methods (AM), when paying attention to the selection of an appropriate conditioning technique.  相似文献   

15.
The influence of dissolved NO2 and iron on the oxidation rate of S(IV) species in the presence of dissolved oxygen is presented. To match the conditions in the real environment, the concentration of iron in the reaction solution and trace gases in the gas mixture was typical for a polluted atmosphere. The time dependence of HSO3, SO42−, NO2 and NO3 and the concentration ratio between Fe(II) and total dissolved iron were monitored. Sulphate formation was the most intensive in the presence of an SO2/NO2/air gas mixture and Fe(III) in solution. The highest contribution to the overall oxidation was from Fe-catalysed S(IV) autoxidation. The reaction rate in the presence of both components was equal to the sum of the reaction rates when NO2 and Fe(III) were present separately, indicating that under selected experimental conditions there exist two systems: SO2/NO2/air and SO2/NO2/air/Fe(III), which are unlikely to interact with each other. The radical chain mechanism can be initiated via reactions Fe(III)–HSO3 and NO2–SO32−/HSO3.  相似文献   

16.
Wet and dry deposition as collected by a bucket were measured at two sites in southeastern Michigan for two years. The precipitation had an average pH of 4.27 and a SO2−4 to NO3 ratio of 2.0. Particulate dry deposition velocities of 0.6 cm s−1 for SO2−4 and NO3 and > 2 cm s−1 for Cl, Ca2+, Mg2+,Na+ and K+ were calculated. The ambient particle composition, dry bucket collection and wet deposition were compared at two sites, one urban and the other rural. Higher ambient particle concentrations and dry deposition rates were measured at the urban site than the rural site, indicating the influence of local emissions. However, local emissions had no effect on the wet deposition concentrations. The influence of more distant source regions was examined by separating the precipitation events by wind direction. The events from the south and east had the highest SO2−4 to NO3 ratios, which corresponded to the areas with the highest sulfur emissions. NO3 showed no directional dependence.Wet deposition was examined for the effect of storm type and seasonal trends. Contrary to a recent study on Long Island, we found higher concentrations of H+, SO2−4 and NH+4 in winter rain compared to snow. The wet deposition concentrations of H+, SO2−4, and NH+4 were highest in the summer, while only Na+ and Cl concentrations were highest in the winter, presumably due to winter road salting. The total deposition of acidic ions was highest in the summer and lowest in the winter, due both to lower concentrations and lower precipitation volumes in the winter. The dry deposition as collected by a bucket accounted for 1 % of total H+ deposition, 21 % of SO2−4 deposition, 27% of NO3 deposition, 50% of Cl deposition and 61 % of Ca2+ deposition.  相似文献   

17.
The oxidation rates of sodium sulphite in bulk sea water solutions have been measured and found to be second order in [S(IV) ]. The reaction is much faster than in pure water due to chloride ion catalysis. The rate of absorption of SO2 into sea-salt aerosols at various relative humidities has also been studied using a radioactive tracing technique. The reaction was found to be zero order in gas phase SO2 concentration over the range 0.1–2 ppm. The reaction rate in the aerosols is several orders of magnitude faster than in sea water presumably due to the higher concentrations of Cl and other ions. The reaction rates both in the bulk solutions and in the aerosols were found to be faster for artificially prepared ‘sea water’ than for natural sea water, probably due to the absence of organic inhibitors.The conversion rates of SO2 in marine or coastal atmospheres due to this reaction are estimated for various salt concentrations and relative humidities. In favourable circumstances it could be competitive with other mechanisms. A possible effect of this reaction on the deposition rate of SO2 to the sea is noted.  相似文献   

18.
Size-fractionated particles were collected at two sites from July 2004 to April 2006 in Shanghai. The mercury in particles was extracted and divided operationally into four species: exchangeable particulate mercury (EXPM), HCl-soluble particulate mercury (HPM), elemental particulate mercury (EPM) and residual particulate mercury. The total particulate Hg concentration during the study period ranged from 0.07 ng m?3 to 1.45 ng m?3 with the average 0.56 ± 0.22 ng m?3 at site 1, while 0.20 ng m?3–0.47 ng m?3 with the average 0.33 ± 0.09 ng m?3 at site 2, which is far higher than some foreign cities and comparable to some cities with heavy air pollution in China. The Hg mass content also displayed evident size distribution, with higher value in PM1.6–3.7, somewhat higher or lower than the source profile. EXAM was only found in the summer, HPM have higher percentage in summer and fall rather than in winter and spring. The different mercury species showed different correlation to temperature, relative humidity, wind speed. HPM positively depends on temperature at both sites which implies the importance of mercury transformation on particles. In foggy days TPM increased greatly, but HPM didn't vary greatly as anticipated. Instead, RPM gained a distinguished increase. It demonstrated that aqueous reaction and complex heterogenic reactions in droplet might happen in acidic environment. The correlation of mercury with other pollutants including SO2, NO2, CO and PM10 varies with the different mercury forms. Hybrid single-particle lagrangian integrated trajectories (HYSPLIT) model was used to back trace air mass at different representative days and results indicated that transportation from Huabei Plain will increase mercury concentration in winter and fall to some extent. The possible existing compounds and their atmospheric behavior of HPM, EPM and RPM were calculated and the compared to analyze its implication on atmospheric mercury cycle.  相似文献   

19.
A study of major atmospheric particulate sulfate species was conducted during 30 July 1980–1983 September 1980 in Sterling Forest, a rural area in Tuxedo, NY, not affected by major local sources of pollution. In situ measurements of total sulfate, sulfuric acid and ammonium sulfate ammonium bisulfate were made using Thermal Analysis-Flame Photometric Detection (TA-FPD). These measurements were compared to the total sulfate and strong acid (H+) concentration measured in simultaneously collected 12 h, treated quartz filter samples. The concentration of NH4HSO4 was inferred from the difference between the total strong acid concentration and the sulfuric acid measurements, so that total sulfate and acid concentrations could be balanced. A major sulfate pollution episode occurred during the period of 27–29 August. The concentration of H+ showed an excess above that necessary to account for the TA-FPD H2SO4 measurement, indicating the presence of NH4 HSO4. The maximum 12 h average concentrations of H2SO4, NH4HSO4 and (NH4)2SO4 were 5.18, 11.42 and 10.08 μg m−3 as SO42− respectively, and were measured from 9:15 to 21:15 on 28 August. The study demonstrated the usefulness of concurrent measurements of airborne particulate sulfate by filter extraction and TA-FPD to identify acidic sulfate species.  相似文献   

20.
Fe2O3 and CeO2 modified activated coke (AC) synthesized by the equivalent-volume impregnation were employed to remove elemental mercury (Hg0) from simulated flue gas at a low temperature. Effects of the mass ratio of Fe2O3 and CeO2, reaction temperature, and individual flue gas components including O2, NO, SO2, and H2O (g) on Hg0 removal efficiency of impregnated AC were investigated. The samples were characterized by Brunauer–Emmett–Teller (BET), X-ray diffraction (XRD), scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS). Results showed that with optimal mass percentage of 3 % Fe2O3 and 3 % CeO2 on Fe3Ce3/AC, the Hg0 removal efficiency could reach an average of 88.29 % at 110 °C. Besides, it was observed that O2 and NO exhibited a promotional effect on Hg0 removal, H2O (g) exerted a suppressive effect, and SO2 showed an insignificant inhibition without O2 to some extent. The analysis of XPS indicated that the main species of mercury on used Fe3Ce3/AC was HgO, which implied that adsorption and catalytic oxidation were both included in Hg0 removal. Furthermore, the lattice oxygen, chemisorbed oxygen, and/or weakly bonded oxygen species made a contribution to Hg0 oxidation.  相似文献   

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