Thermodynamic behaviour of sodium and calcium based sorbents in the emission control of waste incinerators

The dry treatment of flue gas produced by incineration processes is discussed thermodynamically. The study investigates the theoretical limits achieved by sodium and calcium based sorbents in the removal of the pollutant species HCl, NOx and SO2. Calculations were performed varying the temperature and the molar ratio between the amount of the injected alkaline sorbent and the content of the pollutant gaseous species in the flue gas. Results show that sodium cation based sorbents are more efficient than calcium based ones in the whole investigated temperature range (100-600 degrees C). The higher effectiveness of sodium based sorbents is particularly remarkable towards hydrogen chloride, whose concentration can always be reduced below the values set by the environmental regulations. Possible improvements in the treatment efficiency of combustion fumes obtainable with sodium based sorbents can be mainly summarised in a lower concentration of HCl in the treated gas and in a partial reduction of NOx concentration.     

Simultaneous control of Hg0, SO2, and NOx by novel oxidized calcium-based sorbents

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 sorption capacities (approximately 100 microg/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.     

The relationship between atmospheric pollutant emissions and fuel qualities of inland vessels in Jiangsu Province,China

Air pollution caused by ship exhaust emission is receiving more and more attention. The physical and chemical properties of fuels, such as sulfur content and PAHs content, potentially had a significant influence on air pollutant emissions from inland vessels. In order to investigate the effects of fuel qualities on atmospheric pollutant emissions systematically, a series of experiments was conducted based on the method of actual ship testing. As a result, SO2, PM and NOx emission rates all increased with the increase of main engine rotating speed under cruise mode, while PM and NOx emission factors were inversely proportional to the main engine rotating speed. Moreover, SO2 emission factor changed little with the increase of the main engine rotating speed. In summary, the fuel-dependent specific emission of SO2 was a direct reflection of the sulfur content in fuel. The PM emission increased with the increase of sulfur content and PAHs content in fuel. However, fuel qualities impacted little on NOx emissions from inland vessels because of NOx formation mechanisms and conditions.

Implications: Ship activity is considered to be the third largest source of air pollution in China. In particular, air pollutants emitted from ships in river ports and waterways have a direct impact on regional air quality and pose threat on the health of local residents owing to high pollutants concentration and poor air diffusion. The study on the relationship between air pollutant emissions and fuel quality of inland vessels can provide foundational data for local authority to formulate reasonable and appropriate policies for reducing atmospheric pollution due to inland vessels.     

半干法烟气脱硫新技术——粉末-颗粒喷动床技术

粉末 颗粒喷动床 (powder particlespoutedbed ,PPSB)是近几年来由日本研究人员开发的一种新的半干法烟气脱硫技术。本文介绍了PPSB的基本原理、优点以及在试验条件下所得到的影响因素和适宜的运行方式。PPSB在系统结构、废物处理、操作和费用方面比湿法有所提高 ,同时又比干法和其他半干法的去除率和吸收剂的利用率高。此外 ,对吸收剂研究结果表明 ,石灰石的脱硫效率虽然不及石灰 ,但是由于PPSB中吸收剂的停留时间长 ,气、固、液三相接触好的特点以及可以对石灰石进行研磨 ,因此 ,利用石灰石作吸收剂的PPSB完全可以达到理想的脱硫效率 ,同时也可以保持较好的经济性。但是 ,目前还没有大规模的试验和应用。所以PPSB是一项十分值得进一步开发和应用的烟气脱硫新技术。     

Effects of instrument precision and spatial variability on the assessment of the temporal variation of ambient air pollution in Atlanta, Georgia

Data from the U.S. Environmental Protection Agency Air Quality System, the Southeastern Aerosol Research and Characterization database, and the Assessment of Spatial Aerosol Composition in Atlanta database for 1999 through 2002 have been used to characterize error associated with instrument precision and spatial variability on the assessment of the temporal variation of ambient air pollution in Atlanta, GA. These data are being used in time series epidemiologic studies in which associations of acute respiratory and cardiovascular health outcomes and daily ambient air pollutant levels are assessed. Modified semivariograms are used to quantify the effects of instrument precision and spatial variability on the assessment of daily metrics of ambient gaseous pollutants (SO2, CO, NOx, and O3) and fine particulate matter ([PM2.5] PM2.5 mass, sulfate, nitrate, ammonium, elemental carbon [EC], and organic carbon [OC]). Variation because of instrument imprecision represented 7-40% of the temporal variation in the daily pollutant measures and was largest for the PM2.5 EC and OC. Spatial variability was greatest for primary pollutants (SO2, CO, NOx, and EC). Population-weighted variation in daily ambient air pollutant levels because of both instrument imprecision and spatial variability ranged from 20% of the temporal variation for O3 to 70% of the temporal variation for SO2 and EC. Wind     

Estimates of emissions of SO2, NOx, HCl and NH3 from a densely populated region of the UK

Estimates of emissions of SO2, NOx, HCl and NH3 have been made for a densely populated region of the UK, the North-West of England, using data on power generation, incinerator plant capacity, fuel usage and animal and human population statistics. The spatial distributions of SO2 and NOx emissions are quite different, reflecting their different source strengths. The emissions from motor vehicles make up 52% of the NOx emissions from the North-West of England, whilst those from fossil-fuel-fired power stations make up 20%. The emissions of fossil-fuel-fired power stations make up 58% of SO2 emissions from the North-West. A large fossil-fuel-fired power station is the largest known point source for emissions of SO2, NOx and HCl. The largest contribution to NH3 emissions in the North-West is from cattle. Humans may contribute some NH3 to overall emissions but there is considerable uncertainty as to how much is emitted and what fraction of this is deposited within buildings. The uncertainties in the methodologies used are high-lighted and, where possible, recommendations are made as to how future emissions estimates might be improved. Potential reductions in emissions of SO2, NOx and HCl are discussed under basic scenarios of planned power station closures in the area and the compliance of the electricity generation industry with the European Community Directive on Large Combustion Plants.     

Investigation of selective catalytic reduction impact on mercury speciation under simulated NOx emission control conditions

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.     

H2O2溶液同时脱硫脱硝实验研究

二氧化硫和氮氧化物是电厂产生的主要大气污染物,研究焦点越来越集中在在一个反应器内实现同时脱硫脱硝。实验以H2O溶液作为吸收液,在自制的鼓泡反应器内,对模拟烟气进行同时脱硫脱硝的实验研究,实验结果表明：H2O浓度、反应温度、NO浓度、SO2浓度、烟气流量对脱除率影响显著,pH、氧含量对脱硝率影响不大。在整个实验范围内脱硫效率总是保持在98．5％以上,脱硝效率最高达到67．4％。     

生石灰孔结构对高温脱硫性能的影响

喷钙脱硫工艺的炉内脱硫率 ,不仅受工艺参数的影响 ,还与石灰石分解生成的新生CaO或直接喷入的CaO的表面结构有关。本研究用同一石灰石经不同方法 (煅烧、过烧、煅烧 -水合 -脱水等 )制备了四种具有不同比表面积和孔结构的生石灰。高温脱硫研究表明 :这四种不同孔结构的生石灰 ,具有不同的脱硫率。通过对高温脱硫前后吸着剂宏观结构变化的对比 ,发现半径小于 30 的孔易被反应产物堵塞 ,因而脱硫能力有限 ,而半径大于 5 0 的孔对脱硫更有效。本研究将为提高炉内喷钙的脱硫率、研制和开发高效脱硫剂提供新的途径。     

石灰石高温煤气脱硫的试验研究

采用天然石灰石做脱硫剂,在固定床上进行硫化氢高温脱除的试验研究,考察了脱硫剂粒径、反应温度、气速及高温煤气中H2对石灰石脱硫性能的影响,同时还用热重分析(TG)、扫描电镜(SEM)、X-射线衍射(XRD)等测试手段对脱硫剂的物相组成和结构等进行了表征。结果表明,脱硫剂的粒径对脱硫效果的影响很大,0.38～0.83 mm的石灰石脱硫效果最佳;温度对脱硫效果的影响比较复杂,最佳的操作温度为850℃;气速对脱硫效果的影响较明显,脱硫剂的穿透时间随气速的减小而加长;H₂对脱硫过程起阻碍作用,气速越小,这种阻碍作用越明显。     

Laboratory study on the high-temperature capture of HCl gas by dry-injection of calcium-based sorbents

This is a laboratory study on the reduction of combustion-generated hydrochloric acid (HCl) emissions by in-furnace dry-injection of calcium-based sorbents. HCl is a hazardous gaseous pollutant emitted in significant quantities by municipal and hazardous waste incinerators, coal-fired power plants, and other industrial furnaces. Experiments were conducted in a laboratory furnace at gas temperatures of 600-1000 degrees C. HCl gas diluted with N2, and sorbent powders fluidized in a stream of air were introduced into the furnace concurrently. Chlorination of the sorbents occurred in the hot zone of the furnace at gas residence times approximately 1 s. The sorbents chosen for these experiments were calcium formate (CF), calcium magnesium acetate (CMA), calcium propionate (CP), calcium oxide (CX), and calcium carbonate (CC). Upon release of organic volatiles, sorbents calcine to CaO at approximately 700 degrees C, and react with the HCl according to the reaction CaO + 2HCl <=> CaCl2 + H2O. At the lowest temperature case examined herein, 600 degrees C, direct reaction of HCl with CaCO3 may also be expected. The effectiveness of the sorbents to capture HCl was interpreted using the "pore tree" mathematical model for heterogeneous diffusion reactions. Results show that the thin-walled, highly porous cenospheres formed from the pyrolysis and calcination of CF, CMA, and CP exhibited high relative calcium utilization at the upper temperatures of this study. Relative utilizations under these conditions reached 80%. The less costly low-porosity sorbents, calcium carbonate and calcium oxide also performed well. Calcium carbonate reached a relative utilization of 54% in the mid-temperature range, while the calcium oxide reached an 80% relative utilization at the lowest temperature examined. The data matched theoretical predictions of sorbent utilization using the mathematical model, with activation energy and pre-exponential factors for the calcination reaction of 17,000 K and 300,000 (g gas/cm2/s/atm gas), respectively. Thus, the kinetics of the calcination reaction were found to be much faster (approximately 500 times) than those of the sulfation reaction examined previously in this laboratory.     

Improving urban air quality in China: Beijing case study

China is undergoing rapid urbanization because of unprecedented economic growth. As a result, many cities suffer from air pollution. Two-thirds of China's cities have not attained the ambient air quality standards applicable to urban residential areas (Grade II). Particulate matter (PM), rather than sulfur dioxide (SO2), is the major pollutant reflecting the shift from coal burning to mixed source pollution. In 2002, 63.2 and 22.4% of the monitored cities have PM and SO2 concentrations exceeding the Grade II standard, respectively. Nitrogen oxides (NOx) concentration kept a relatively stable level near the Grade II standard in the last decade and had an increasing potential in recent years because of the rapid motorization. In general, the air pollutants emission did not increase as quickly as the economic growth and energy consumption, and air quality in Chinese cities has improved to some extent. Beijing, a typical representative of rapidly developing cities, is an example to illustrate the possible options for urban air pollution control. Beijing's case provides hope that the challenges associated with improving air quality can be met during a period of explosive development and motorization.     

Simultaneous removal of nitrogen oxide/nitrogen dioxide/sulfur dioxide from gas streams by combined plasma scrubbing technology

Oxides of nitrogen (NOx) [nitrogen oxide (NO) + nitrogen dioxide (NO2)] and sulfur dioxide (SO2) are removed individually in traditional air pollution control technologies. This study proposes a combined plasma scrubbing (CPS) system for simultaneous removal of SO2 and NOx. CPS consists of a dielectric barrier discharge (DBD) and wet scrubbing in series. DBD is used to generate nonthermal plasmas for converting NO to NO2. The water-soluble NO2 then can be removed by wet scrubbing accompanied with SO2 removal. In this work, CPS was tested with simulated exhausts in the laboratory and with diesel-generator exhausts in the field. Experimental results indicate that DBD is very efficient in converting NO to NO2. More than 90% removal of NO, NOx, and SO2 can be simultaneously achieved with CPS. Both sodium sulfide (Na2S) and sodium sulfite (Na2SO3) scrubbing solutions are good for NO2 and SO2 absorption. Energy efficiencies for NOx and SO2 removal are 17 and 18 g/kWh, respectively. The technical feasibility of CPS for simultaneous removal of NO, NO2, and SO2 from gas streams is successfully demonstrated in this study. However, production of carbon monoxide as a side-product (approximately 100 ppm) is found and should be considered.     

锅炉烟气联合脱硫脱氮技术

硫氧化物和氮氧化物是燃煤锅炉排放的主要污染物 ,传统分步脱硫脱氮设备昂贵且效率不高 ,而联合脱硫脱氮技术具有很大的优越性 ,如可以减小系统的复杂性、具有更好的运行性能、较低的成本及较小的占地面积 ,因此实现在一个系统内同时脱硫脱氮的工艺成为国内外烟气净化技术的研究重点。对近年来国内外各种联合脱硫脱氮技术的脱除原理、研究现状、应用情况和主要优缺点进行了论述 ,并对各工艺的经济技术指标给予了多方面的比较。通过对两类烟气联合脱硫脱氮技术 (炉内联合脱除和烟气中联合脱除 )的分析、综合和比较 ,找出了我国今后脱硫脱氮技术的研究重点 ,从而为脱硫脱氮技术的进一步开发和改进提供参考     

Tolerance to SO2, NO2 and their mixture in Plantago major L. populations

The possible evolution of tolerance to NO2, alone or in combination with SO2 was investigated in three populations of Plantago major L., originating from Hyde Park in central London (polluted site), Ascot (clean site) and The Netherlands. Screening for sensitivity to the pollutants was carried out by means of chronic fumigations with NO2 or NO2 plus SO2 and acute fumigations with SO2, NO2 or their mixture. The Hyde Park population showed smaller growth reductions induced by the pollutant mixture, than did the other populations. In contrast no differential response in terms of foliar injury was observed after an acute fumigation with SO2+ NO2, but the Hyde Park population was the most sensitive to NO2 alone. The results indicate that selection for tolerance to SO2 does not confer tolerance to NO2 alone or the pollutant mixture.     

A statistical assessment of saturation and mobile sampling strategies to estimate long-term average concentrations across urban areas

The objectives of this study were: (1) to quantify the errors associated with saturation air quality monitoring in estimating the long-term (i.e., annual and 5 yr) mean at a given site from four 2-week measurements, once per season; and (2) to develop a sampling strategy to guide the deployment of mobile air quality facilities for characterizing intraurban gradients of air pollutants, that is, to determine how often a given location should be visited to obtain relatively accurate estimates of the mean air pollutant concentrations. Computer simulations were conducted by randomly sampling ambient monitoring data collected in six Canadian cities at a variety of settings (e.g., population-based sites, near-roadway sites). The 5-yr (1998-2002) dataset consisted of hourly measurements of nitric oxide (NO), nitrogen dioxide (NO2), oxides of nitrogen (NOx), sulfur dioxide (SO2), coarse particulate matter (PM10), fine particulate matter (PM2.5), and CO. The strategy of randomly selecting one 2-week measurement per season to determine the annual or long-term average concentration yields estimates within 30% of the true value 95% of the time for NO2, PM10 and NOx. Larger errors, up to 50%, are expected for NO, SO2, PM2.5, and CO. Combining concentrations from 85 random 1-hr visits per season provides annual and 5-yr average estimates within 30% of the true value with good confidence. Overall, the magnitude of error in the estimates was strongly correlated with the variability of the pollutant. A better estimation can be expected for pollutants known to be less temporally variable and/or over geographic areas where concentrations are less variable. By using multiple sites located in different settings, the relationships determined for estimation error versus number of measurement periods used to determine long-term average are expected to realistically portray the true distribution. Thus, the results should be a good indication of the potential errors one could expect in a variety of different cities, particularly in more northern latitudes.     

Thermodynamic analysis and kinetic modelling of dioxin formation and emissions from power boilers firing salt-laden hog fuel

Both organic chlorine (e.g. PVC) and inorganic chlorides (e.g. NaCl) can be significant chlorine sources for dioxin and furan (PCDD/F) formation in combustion processes. This paper presents a thermodynamic analysis of high temperature salt chemistry. Its influence on PCDD/F formation in power boilers burning salt-laden wood waste is examined through the relationships between Cl2, HCl, NaCl(g) and NaCl(c). These analyses show that while HCl is a product of combustion of PVC-laden municipal solid waste, NaCl can be converted to HCl in hog fuel boilers by reactions with SO2 or alumino-silicate materials. Cl2 is a strong chlorinating agent for PCDD/F formation. HCl can be oxidized to Cl2 by O2, and Cl2 can be reduced back to HCl by SO2. The presence of sulphur at low concentrations thus enhances PCDD/F formation by increasing HCl concentrations. At high concentrations, sulphur inhibits de novo formation of PCDD/Fs through Cl2 reduction by excess SO2. The effect of NH3, CO and NOx on PCDD/F formation is also discussed. A semi-empirical kinetic model is proposed. This model considers both precursor and de novo formation mechanisms. A simplified version is used as a stack emission model. The kinetic model indicates that stack dioxin emissions will increase linearly with decreasing electrostatic precipitator (ESP) efficiency and exponentially with increasing ESP temperature.     

等离子体技术应用于气相污染物治理综述

近年来利用等离子体技术对气态污染物的氧化分解研究受到了广泛的关注.介绍了等离子体概念、分类及产生方法,简述了非平衡等离子体技术对气体污染物的降解原理,较全面地介绍了等离子体技术在脱硫、脱硝以及降解挥发性有机物(VOCs)等方面的研究.最后指出了今后等离子体处理废气的应用研究方向.     

Modeling sorbent injection for mercury control in baghouse filters: II--pilot-scale studies and model evaluation

Activated carbon injection for Hg control in a 500-lb/hr pilot-scale coal-fired furnace equipped with a fabric filter for particulate control was evaluated at different operating conditions. The pilot-scale tests showed that Hg removal was improved at lower temperatures and higher C/Hg ratios. The two-stage mathematical model developed to describe Hg removal using powdered activated carbon injection upstream of a baghouse filter was used to obtain Langmuir isotherm parameters as a function of temperature by fitting the model to a subset of experimental data. The predictive capability of the model was then tested by comparing model calculations with additional experimental data from this system obtained using different operating temperatures and sorbent to Hg ratios. Model predictions were in good agreement with experimentally measured Hg removal efficiency. Based on the model predictions, Hg removal in the duct appears to be limited and higher C/Hg ratio, lower operating temperature, and longer cleaning cycle of the baghouse filter should be utilized to achieve higher Hg removal in this system.     

Effect of solution pH on SO2, NO(x), and Hg removal from simulated coal combustion flue gas in an oxidant-enhanced wet scrubber

This paper presents a study on the simultaneous removal of SO2, NO(x) and Hg (both Hg0 and Hg2+) from a simulated flue gas by oxidant injection in a bench-simulated wet limestone scrubber for a wide range of slurry pH. The slurry pH strongly influenced the chemical mechanism in the scrubber and, therefore, affected pollutant removal. This paper also examines the potential ClO2(gas) reemission from a developed multipollutant scrubber at different slurry pHs. To better understand the chemical mechanisms at each slurry pH and to apply a mass balance to the process, detailed product ion analyses were performed for all experiments. Ion analysis covered three different chlorine species (chlorite, chloride, chlorate), sulfate, nitrite and nitrate. Different NO(x) removal efficiencies and mechanisms were found in acidic and alkaline pHs in the multipollutant scrubber. The acidic solution was favorable for NO and Hg0 oxidation, but increasing the slurry pH above 7.0 was disadvantageous for NO and Hg oxidation/removal. However the rate of NO(x) absorption (by percentage) was higher for the alkaline solution.