粉煤燃烧过程中细粒子形成机理的研究

煤是一种有机沉淀岩，主要包括有机碳化合物和无机矿物。在燃烧的高温条件下，煤中的矿物质首先经历热分解和气化，当烟气冷却时，它们经过冷凝成核、凝结和团聚等作用，形成大量细粒子。这些细粒子的排放会对大气环境和人类健康造成严重的影响。研究燃烧过程中细粒子的形成机理将为其污染防治提供理论基础和科学依据。本文系统地综述了煤燃烧过程中矿物质和痕量元素的气化、冷凝成核、表面凝结、团聚的机理、模拟和预测方法以及细粒子形成机理的研究进展。     

燃烧过程颗粒物的形成及我国燃烧源分析

燃料燃烧会排放一次颗粒物和二次颗粒物,一次颗粒物中亚微米粒子主要是由于无机矿物质经蒸发-成核-凝结-凝并的途径形成的;超微米颗粒的产生不同于亚微米颗粒的形成,是由于破碎机理.二次颗粒物是由气态前驱体在大气中转化而成的.我国燃烧源主要是煤燃烧、燃油机动车和农村生活燃料等.深入认识颗粒物的形成及燃烧源的特征对有效控制颗粒物的排放是很有帮助的.     

燃烧过程颗粒物的形成及我国燃烧源分析

燃料燃烧会排放一次颗粒物和二次颗粒物,一次颗粒物中亚微米粒子主要是由于无机矿物质经蒸发-成核-凝结-凝并的途径形成的;超微米颗粒的产生不同于亚微米颗粒的形成,是由于破碎机理.二次颗粒物是由气态前驱体在大气中转化而成的.我国燃烧源主要是煤燃烧、燃油机动车和农村生活燃料等.深入认识颗粒物的形成及燃烧源的特征对有效控制颗粒物的排放是很有帮助的.     

燃煤引起的有机氯污染

氯是煤中的有害元素之一,煤燃烧时氯一部分以ＨＣｌ的形式释放出来,一部分则生成三致剧毒有机氯化物－－二恶英和呋喃。重点介绍了燃煤引起的有机氯化物地环境的污染与 及它的形成机理,形成条件、煤质影响和它的传输方式,对氯污染的评价与防治有重要的意义。     

燃煤电厂多环芳烃的生成与控制

多环芳烃 (PAHs)对人体健康的危害极大。本文综述了燃煤电厂煤燃烧过程中多环芳烃的生成机理 (直接释放、热解合成和高温缩合机理 )和影响因素 (煤种、温度、锅炉负荷、过剩空气系数、停留时间、钙硫比和一次风 /二次风比 ) ,在此基础上介绍了煤燃烧过程中多环芳烃的各种控制技术和方法     

燃煤电厂多环芳烃的生成与控制

多环芳烃（PAHs)对人体健康的危害极大。本文综述了燃煤电厂煤燃烧过程中多环芳烃的生成机理（直接释放，热解合成和高温缩合机理）和影响因素（煤种，温度，锅炉负荷，过剩空气系数，停留时间，钙硫比和一次风/二次风比）。在此基础上介绍了煤燃烧过程中多环芳烃的各种控制技术和方法。     

100 MW锅炉NaOH颗粒生成的数值模拟

煤粉燃烧过程中矿物质的气化、成核、凝结等过程是炉膛中亚微米颗粒形成的主要途径。本文运用CFD软件针对某100 MW锅炉内NaOH颗粒形成进行了数值研究，计算得到了炉内的温度分布、氧浓度分布和亚微米颗粒数量浓度和质量浓度分布。结果显示，亚微米颗粒的生成数量与温度具有强烈的相关性，温度较高的区域亚微米颗粒数量浓度较大，温度较低的区域则较小；而在炉膛的高温区内，NaOH颗粒的质量浓度并不是最高，而是最低，同时随着炉膛高度的增加，NaOH颗粒的质量浓度逐渐增加。计算结果为今后数值研究燃煤过程中亚微米颗粒的形成与演化奠定基础，为研究温度等燃烧条件对亚微米颗粒形成的影响、抑制其排放等方面提供了一种有效研究手段。     

粉煤灰烧制陶粒过程中二氧化硫的释放规律与形成机理

研究了粉煤灰烧制陶粒过程中烟气二氧化硫的释放规律,同时对烧结前后粉煤灰与陶粒中不同形态硫含量和硫平衡进行了分析,探讨了烟气中二氧化硫的来源和转化机理.结果表明,烟气中约55％的二氧化硫来源于硫酸盐的还原,其余主要来自有机硫燃烧和亚硫酸盐的分解.烧制每千克陶粒所产生的二氧化硫量约为7.8g.高温烧结过程中粉煤灰球内形成的还原性气氛导致了粉煤灰中硫酸盐向二氧化硫的还原转化.     

污泥与煤、木屑燃烧过程中重金属排放特性研究

为了考察燃料燃烧过程中重金属的迁移转化规律，对污泥、煤与木屑及其混合物在不同温度下氧气中燃烧灰渣中的重金属元素进行分析。结果表明，燃料中重金属在高温燃烧时表现出不同的挥发特性，大部分元素随着温度的升高挥发率增加，其中Cd、Pb和Zn元素挥发性较强，Cr、Cu和Ni挥发性较弱。污泥与木屑混合燃烧灰渣仍以污泥灰为主，重金属含量与污泥灰相近，污泥中混入煤后使灰中大部分重金属含量有所降低。燃烧过程会改变重金属存在形态，污泥与煤原料中以酸溶态和可还原态存在的重金属含量较高，具有较强的生物有效性和迁移性，而燃烧灰渣中酸溶态和可还原态含量显著下降，混合燃烧灰渣中除As外的其他重金属几乎全部以残渣态存在，其含量达到90％以上，焚烧过程有效降低了燃料灰渣中重金属的生物毒性。     

南京大气细粒子中重金属污染特征及来源解析

利用2011年1月、4月、7月和10月在南京市区和北郊采集的气溶胶样品，研究了南京大气细粒子中zn、Ph、Hg、As和cd5种重金属的污染水平，通过元素相关性分析和因子分析方法，对细粒子中这些重金属的污染来源进行了初步解析。结果表明，南京大气细粒子及其重金属污染严重，北郊普遍比市区严重；As严重超标，cd在南京北郊超标约5倍，zn在市区与北郊的质量浓度均高于其他重金属元素。每种重金属的浓度均随季节而变化。市区细粒子中，As和zn可能主要与燃煤、轮胎灰尘和建筑扬尘等有关，Pb、Hg和cd主要来自交通尘、城市垃圾焚烧等。北郊细粒子中，As、Hg和zn主要来源于燃煤、钢铁冶炼等工业，Pb和cd主要与农作物秸秆燃烧、汽车尾气、道路扬尘等影响有关。     

Formation of fine particles enriched by V and Ni from heavy oil combustion: Anthropogenic sources and drop-tube furnace experiments

The present study attempts to investigate the emission characteristics of fine particles with special emphasis on nickel and vanadium metal elements emitted from the heavy oil combustion in industrial boilers and power plant, which are typical anthropogenic sources in Korea. A series of combustion experiments were performed to investigate the emission characteristics of particles in the size range of submicron by means of drop-tube furnace with three major domestic heavy oils. Cascade impactors were utilized to determine the size distribution of particulates as well as to analyze the partitioning enrichment of vanadium and nickel in various size ranges. Experimental results were compared with field data of particle size distribution and metal partitioning at commercial utility boilers with heavy oil combustion. Such data were interpreted by chemical equilibrium and particle growth mechanism by means of computational models. In general, fine particles were the major portion of PM₁₀ emitted from the heavy oil combustion, with significant fraction of ultra-fine particles. The formation of ultra-fine particles through nucleation/condensation/coagulation from heavy oil combustion was confirmed by field and experimental data. Vanadium and nickel were more enriched in fine particles, particularly in ultra-fine particles. The conventional air pollution devices showed inefficient capability to remove ultra-fine particles enriched with hazardous transition metal elements such as vanadium and nickel.     

Measurement of ultrafine particle size distributions from coal-, oil-, and gas-fired stationary combustion sources

Currently, we have limited knowledge of the physical and chemical properties of emitted primary combustion aerosols and the changes in those properties caused by nucleation, condensation growth of volatile species, and particle coagulations under dilution and cooling in the ambient air. A dilution chamber was deployed to sample exhaust from a pilot-scale furnace burning various fuels at a nominal heat input rate of 160 kW/h(-1) and 3% excess oxygen. The formation mechanisms of particles smaller than 420 nm in electrical mobility diameter were experimentally investigated by measurement with a Scanning Mobility Particle Sizer (SMPS) as a function of aging times, dilution air ratios, combustion exhaust temperatures, and fuel types. Particle formation in the dilution process is a complex mixture of nucleation, coagulation, and condensational growth, depending on the concentrations of available condensable species and solid or liquid particles (such as soot, ash) in combustion exhausts. The measured particle size distributions in number concentrations measured show peaks of particle number concentrations for medium sulfur bituminous coal, No. 6 fuel oil, and natural gas at 40-50 nm, 70-100 nm, and 15-25 nm, respectively. For No. 6 fuel oil and coal, the particle number concentration is constant in the range of a dilution air ratio of 50, but the number decreases as the dilution air ratio decreases to 10. However, for natural gas, the particle number concentration is higher at a dilution air ratio of 10 and decreases at dilution air ratios of 20-50. At a dilution air ratio of 10, severe particle coagulation occurs in a relatively short time. Samples taken at different combustion exhaust temperatures for these fuel types show higher particle number concentrations at 645 K than at 450 K. As the aging time of particles increases, the particles increase in size and the number concentrations decrease. The largest gradient of particle number distribution occurs within the first 10 sec after dilution but shows only minor differences between 10 and 80 sec. The lifetimes of the ultrafine particles are relatively short, with a scale on the order of a few seconds. Results from this study suggest that an aging time of 10 sec and a dilution air ratio of 20 are sufficient to obtain representative primary particle emission samples from stationary combustion sources.     

Analysis and discussion on formation and control of primary particulate matter generated from coal-fired power plants

Particulate matter (PM) has been becoming the principal urban pollutant in many major cities in China, and even all over the world. It is reported that the coal combustion process is one of the main sources of PM in the atmosphere. Therefore, an investigation of formation and emission of fine primary PM in coal combustion was conducted. First, the sources and classification of coal-fired primary PM were discussed; then their formation pathways during the coal combustion process were analyzed in detail. Accordingly, the emission control methods for fine particles generated from coal-fired power plants were put forward, and were classified as precombustion control, in-combustion control, and postcombustion control. Precombustion control refers to the processes for improving the coal quality before combustion, such as coal type selection and coal preparation. In-combustion control means to take measures for adjusting the combustion conditions and injection of additives during the combustion process to abate the formation of PM. Postcombustion control is the way that the fine PM are aggregated into larger ones by some agglomeration approaches and subsequently are removed by dust removal devices, or some high-performance modifications of conventional particle emission control devices (PECDs) can be taken for capturing fine particles. Finally, some general management suggestions are given for reducing fine PM emission in coal-fired power plants.

ImplicationsThe analysis and discussions of coal properties and its combustion process are critical to recognizing the formation and emission of the fine primary PM in combustion. The measures of precombustion, in-combustion, and postcombustion control based on the analysis and discussions are favorable for abating the PM emission. Practically, some measures of implementation do need the support of national policies, even needing to sacrifice economy to gain environmental profit, but this is the very time to execute these, and high-performance PECDs, especially novel devices, should be used for removing fine PM in flue gas.     

A review of particle formation events and growth in the atmosphere in the various environments and discussion of mechanistic implications

This review highlights recent observations from a large number of studies investigating formation and growth within different environments and discusses the importance of various mechanisms of particle formation and growth between the different environments. Whilst, several mechanisms for new particle formation which proposed the importance of each mechanism are still the centre of much debate. Proposed nucleation mechanisms include condensation of a binary mixture of sulphuric acid and water; ternary nucleation of sulphuric acid, water and a third molecule, most likely ammonia; ion-induced nucleation; secondary organic aerosol formation involving condensation of low- or non-volatile organic compounds and homogeneous nucleation of iodine oxides. Laboratory and modelling studies have shown these mechanisms can occur in the atmosphere although the contribution depends on the concentrations of precursor compounds present. In addition, atmospheric particle formation events are significantly affected by environmental factors, such as temperature, humidity and the surface area of pre-existing particles, which is also discussed here. One major problem hampering our current understanding is that these new particles are smaller than the lower size detection limit of most instruments and are only observed after some particle growth has occurred.Particles growth occurs through condensation of supersaturated vapours on the surface of the nucleated particles. This requires a lower degree of supersaturation than nucleation and thus condensation of the nucleating species reduces the rate of particle formation. Therefore, it is believed that particle growth often occurs through the condensation of other gases, including organic and inorganic compounds, than those responsible for nucleation. This decoupling of nucleation and growth means that the individual gases responsible for nucleation and growth can be unclear.Since observations of particle formation only occur following growth to observable sizes it is possible that a pool of undetectable particles exist at all times but are only observed following significant condensational growth.     

Measurement of Ultrafine Particle Size Distributions from Coal-, Oil-, and Gas-Fired Stationary Combustion Sources

Abstract

Currently, we have limited knowledge of the physical and chemical properties of emitted primary combustion aerosols and the changes in those properties caused by nucleation, condensation growth of volatile species, and particle coagulations under dilution and cooling in the ambient air. A dilution chamber was deployed to sample exhaust from a pilot-scale furnace burning various fuels at a nominal heat input rate of 160 kW/h^?1 and 3% excess oxygen. The formation mechanisms of particles smaller than 420 nm in electrical mobility diameter were experimentally investigated by measurement with a Scanning Mobility Particle Sizer (SMPS) as a function of aging times, dilution air ratios, combustion exhaust temperatures, and fuel types. Particle formation in the dilution process is a complex mixture of nucleation, coagulation, and condensational growth, depending on the concentrations of available condensable species and solid or liquid particles (such as soot, ash) in combustion exhausts. The measured particle size distributions in number concentrations measured show peaks of particle number concentrations for medium sulfur bituminous coal, No. 6 fuel oil, and natural gas at 40-50 nm, 70-100 nm, and 15-25 nm, respectively. For No. 6 fuel oil and coal, the particle number concentration is constant in the range of a dilution air ratio of 50, but the number decreases as the dilution air ratio decreases to 10. However, for natural gas, the particle number concentration is higher at a dilution air ratio of 10 and decreases at dilution air ratios of 20-50. At a dilution air ratio of 10, severe particle coagulation occurs in a relatively short time. Samples taken at different combustion exhaust temperatures for these fuel types show higher particle number concentrations at 645 K than at 450 K. As the aging time of particles increases, the particles increase in size and the number concentrations decrease. The largest gradient of particle number distribution occurs within the first 10 sec after dilution but shows only minor differences between 10 and 80 sec. The lifetimes of the ultrafine particles are relatively short, with a scale on the order of a few seconds. Results from this study suggest that an aging time of 10 sec and a dilution air ratio of 20 are sufficient to obtain representative primary particle emission samples from stationary combustion sources.     

Formation characteristics of aerosol particles from pulverized coal pyrolysis in high-temperature environments

The formation characteristics of aerosol particles from pulverized coal pyrolysis in high temperatures are studied experimentally. By conducting a drop-tube furnace, fuel pyrolysis processes in industrial furnaces are simulated in which three different reaction temperatures of 1000, 1200, and 1400 degrees C are considered. Experimental observations indicate that when the reaction temperature is 1000 degrees C, submicron particles are produced, whereas the particle size is dominated by nanoscale for the temperature of 1400 degrees C. Thermogravimetric analysis of the aerosol particles stemming from the pyrolysis temperature of 1000 degrees C reveals that the thermal behavior of the aerosol is characterized by a three-stage reaction with increasing heating temperature: (1) a volatile-reaction stage, (2) a weak-reaction stage, and (3) a soot-reaction stage. However, with the pyrolysis temperature of 1400 degrees C, the volatile- and weak-reaction stages almost merge together and evolve into a chemical-frozen stage. The submicron particles (i.e., 1000 degrees C) are mainly composed of volatiles, tar, and soot, with the main component of the nanoscale particles (i.e., 1400 degrees C) being soot. The polycyclic aromatic hydrocarbons (PAHs) contained in the aerosols are also analyzed. It is found that the PAH content in generated aerosols decreases dramatically as the pyrolysis temperature increases.     

Inhalation health effects of fine particles from the co-combustion of coal and refuse derived fuel

This paper is concerned with health effects from the inhalation of particulate matter (PM) emitted from the combustion of coal, and from the co-combustion of refuse derived fuel (RDF) and pulverized coal mixtures, under both normal and low NO_x conditions. Specific issues focus on whether the addition of RDF to coal has an effect on PM toxicity, and whether the application of staged combustion (for low NO_x) may also be a factor in this regard.

Ash particles were sampled and collected from a pilot scale combustion unit and then re-suspended and diluted to concentrations of 1000 μg/m³. These particles were inhaled by mice, which were held in a nose-only exposure configuration. Exposure tests were for 1 h per day, and involved three sets (eight mice per set) of mice. These three sets were exposed over 8, 16, and 24 consecutive days, respectively. Pathological lung damage was measured in terms of increases in lung permeability.

Results show that the re-suspended coal/RDF ash appeared to cause very different effects on lung permeability than did coal ash alone. In addition, it was also shown that a “snapshot” of lung properties after a fixed number of daily 1-h exposures, can be misleading, since apparent repair mechanisms cause lung properties to change over a period of time. For the coal/RDF, the greatest lung damage (in terms of lung permeability increase) occurred at the short exposure period of 8 days, and thereafter appeared to be gradually repaired. Ash from staged (low NO_x) combustion of coal/RDF appeared to cause greater lung injury than that from unstaged (high NO_x) coal/RDF combustion, although the temporal behavior and (apparent) repair processes in each case were similar. In contrast to this, coal ash alone showed a slight decrease of lung permeability after 1 and 3 days, and this disappeared after 12 days. These observations are interpreted in the light of mechanisms proposed in the literature. The results all suggest that the composition of particles actually inhaled is important in determining lung injury. Particle size segregated leachability measurements showed that water soluble sulfur, zinc, and vanadium, but not iron, were present in the coal/RDF ash particles, which caused lung permeabilities to increase. However, the differences in health effects between unstaged and staged coal/RDF combustion could not be attributed to variations in pH values of the leachate.     

Size-segregated chemistry of particulate dicarboxylic acids in the Arctic atmosphere

Gas–particle interactions of low-molecular-weight dicarboxylic acids were studied at a coastal Arctic site during the summer. Size segregated measurements with a Berner low-pressure impactor displayed up to four modes for ionic compounds: an Aitken mode, an accumulation mode, and two supermicron modes. The lower supermicron mode was ascribed to sea-salt, whereas the upper mode consisted mostly of species associated with continental particles. All four modes could be identified for oxalic acid, with the lower supermicron mode being the dominant. Malonic acid displayed a supermicron mode but was not found in the submicron size range. Succinic acid had an accumulation mode and, in a few samples, a supermicron mode. Glutaric acid displayed sometimes and accumulation mode, sometimes a supermicron mode, and occasionally both. The most probable formation pathway for submicron oxalic and glutaric acid was condensation from the gas phase, even though production in cloud droplets cannot be ruled out either. A slightly different formation pathway may have been important for submicron succinic acid production. Supermicron oxalic acid was probably formed by condensation from the gas-phase, by heterogeneous reactions occurring on the surface of pre-existing sea-salt and continental particles, or in cloud droplets. A larger mass median diameter for supermicron malonic and glutaric acid might be indicative of liquid-phase production in aqueous sea-salt particles. Evidence on possibly substantial sampling artifacts related to measuring dicarboxylic acids using filters were also obtained.     

煤粉再燃的半工业炉试验

从系统NOx还原效果，主燃区，再燃区和燃尽区内NOx的分解几方面对煤粉再燃效果进行半工业炉试验研究。虽然主燃区NOx生成量与主燃区过量空气系数成正比，系统NOx还原率却在主燃区过量空气系数一1．10时呈现最大值；再燃区还原性气氛有利于NOx的还原，但富氧氛围也可以实现一定NOx分解，燃尽区内煤粉异相还原占主要地位。以基础工况和再燃工况下的锅炉尾部NOx排放量的差值来计算系统NOx还原率可以更好地体现锅炉系统的再燃脱硝能力。