不同煤种燃烧生态多环芳烃的研究

燃煤过程产生的多环芳烃类有机污染物烃具有强烈的致癌、致突变、致畸变等作用，日益受到广泛的重视。本文进行了不同煤种燃烧时多环芳烃的生成研究，比较了燃煤排放和原煤中含有的多环芳烃之间关系，研究了煤的固定碳、挥发份、灰份等组分对燃煤过程中多环芳烃排放的影响。     

燃煤流化床多环芳烃的研究现状

比较系统地讨论了燃煤流化床多环芳烃的研究现状。首先介绍了多环芳烃的理化性质、起源及其取样和分析。其次对流化床煤燃烧过程中燃烧参数对多环芳烃形成和排放的影响进行了探讨。最后给出了多环芳烃减量化方法和净化措施。     

石化污泥与煤混烧的流化床多环芳烃排放特性

在一座密相区截面为0.23 m×0.23 m、高度为7 m的循环流化床试验装置上进行了石化污泥与煤混烧多环芳烃排放特性的系统性试验研究.结果表明,污泥中多环芳烃含量远高于煤;随着二次风率的增大,烟气、飞灰和底渣中多环芳烃排放量均呈明显的下降趋势;随着空气过剩系数的增大,多环芳烃排放水平先下降后上升:石灰石的添加能有效抑制多环芳烃的生成,随着ca/S摩尔比增大,多环芳烃排放水平显著下降.各工况均以排放低环多环芳烃为主,且飞灰中多环芳烃排放量远高于底渣.     

电厂排放烟气中的小颗粒分布及多环芳烃研究

小颗粒物，及附着其上的有机污染物如多环芳烃(PAHs)对环境、健康的影响越来越受到关注，而人为源排放小颗粒的比例正逐渐升高。文章通过对燃煤电厂除尘器前后排放烟气小颗粒的多次采样和分析，得到了除尘器前后PM10，PM2．5的小颗粒物粒度分布，进一步得到燃煤电厂排放颗粒物的分散度。并计算得出除尘器对于不同粒径的颗粒物的脱除效率，试验表明除尘器对于大颗的脱除效率高于小颗粒。样品进行预处理后用气相色谱仪分析样品中的17种多环芳烃(包括美国四EPA推荐优先监测的16种多环芳烃)。     

流化床焚烧塑料垃圾多环芳烃的生成特性

研究了典型塑料垃圾PVC、PE和PS在流化床燃烧过程中多环芳烃的排放特性,分析了多环芳烃生成量随燃烧温度变化的情况.结果表明,PS燃烧产生多环芳烃随温度呈现单峰变化,800℃时最高;PVC则随温度呈指数减少的趋势;PE变化较为复杂.从总量看,多环芳烃生成量大小顺序为PS>PVC>PE.     

石化污泥与煤混烧时多环芳烃的排放特性

在管式固定床上进行了石化污泥与煤的混烧试验,着重研究了质量掺混比、燃烧温度和燃烧停留时间等因素对底渣中多环芳烃排放的影响.结果表明:随着污泥质量掺混比的增大,底渣中多环芳烃排放量呈明显上升态势;随着燃烧温度的升高,多环芳烃排放量先上升后下降;随着燃烧停留时间的增加,多环芳烃排放量呈明显的下降趋势,且存在一个临界停留时间.在各种工况条件下,低环多环芳烃排放量均高于高环多环芳烃排放量.     

燃烧方式对塑料垃圾燃烧时PAHs和PCDD／Fs排放的影响

为了找出燃烧方式对塑料垃圾焚烧过程中多环芳烃和二恶英排放的影响,在两种不同类型试验用燃烧反应器上进行了聚氯乙烯的燃烧试验.燃烧的烟气参考GB 86-5119和USEPA1613方法采用色质联用分析仪收集分析,对烟气中多环芳烃和二恶英的分布特征进行了观察.结果显示,聚氯乙烯在流化床燃烧反应器上燃烧时生成的多环芳烃和二恶英的总量要明显低于固定床燃烧反应器上的生成量.流化床燃烧方式能够抑制多环芳烃和二恶英的某些发生机制.多环芳烃和二恶英排放特征的关联关系非常明显,可以作为塑料垃圾燃烧过程中产生的二恶英的实时监测替代物.     

燃煤排放的新类型非多环芳烃类有机污染物

本文提出了非多环芳烃类（非ＰＡＨｓ）有机污染这一新的燃煤污染物排放类型。指出：常规能源的污染控制经验对于新能源的清洁开发与利用具有重要的借鉴意义。     

空煤比对煤部分气化多环芳烃排放的影响

为了研究空煤比对煤气化多环芳烃排放的影响,在一台小型常压流化床气化炉上进行了煤部分气化实验.经索氏萃取、K-D浓缩和硅胶层析纯化后,采用带荧光检测器和二极管矩阵检测器的高效液相色谱仪对半焦和煤气中16种多环芳烃进行了测定.实验结果表明,煤气中多环芳烃以低环和中环为主,半焦中多环芳烃以中环和高环为主;煤气和半焦中多环芳烃毒性当量质量浓度均集中在5环多环芳烃上,尤其是苯并(a)芘(BaP)和二苯并(a,h)荧蒽(DbA);当空煤比由2.25 m3/kg增加到3.83 m3/kg时,煤气和半焦中多环芳烃质量浓度和毒性当量质量浓度呈现出先增后减的变化趋势.     

混合塑料和煤在小型流化床中燃烧时多环芳烃的生成特性

为了明确城市固体废弃物中的塑料组分燃烧时生成的多环芳烃的特性,以及相应的抑制措施,在小型三段流化床上进行了混合塑料的燃烧试验,研究了不同燃烧温度时,以及相同一次风下二次风配比比例不同时多环芳烃的生成特性。并就混合塑料添加煤和不添加煤燃烧时多环芳烃的生成水平进行了比较。结果显示,混合塑料燃烧时,多环芳烃排放总量要比单组分燃烧多环芳烃量加权平均后的水平低;添加煤燃烧时,排放水平比不添加煤有明显的下降,在加20%的煤的时候排放水平最低;一次风量相同时,加适当比例(约0.20时)的二次风,可以取得抑制塑料垃圾生成多环芳烃的最佳效果。图12表1参8     

燃煤电厂飞灰碳含量与PAHs有机污染物吸附量之间相关性研究

以五家燃煤电厂为例，实验分析了飞灰总碳、元素碳、有机碳含量，并与飞灰中多环烃类（PAHs）有机污染物吸附量作了相关分析；此外研究了燃煤排放PAHs与炉前煤中PAHs的关联性，从煤化学、煤燃烧学角度探讨了PAHs的吸附反应机制，提出煤粉燃烧过程中PAHs的一种重要形成机制-未燃碳颗粒及吸附反应机制，指出飞灰中的碳位不仅是PAHs的重要吸附位，同时也是PAHs的重要反应位。     

不同煤燃烧方式多环芳烃生成特性的研究

研究比较了不同煤燃烧方式多环芳烃生成特性。固定床煤燃烧多环芳烃生成随温度升高出现了先增加后减少的趋势，流化床煤燃烧多环芳烃生成随温度升高而增加。流化床煤燃烧多环芳烃生成量要少于固定床燃烧方式，总量上低1～2个数量级。固定床燃烧(管式炉等)PAHs低温由热解生成，高温由前驱物生成。流化床燃烧PAHs低温由高环芳香性物质的热分解和缩聚反应生成，高温由小分子烃类的聚合。图12表1参13     

青山烟煤及其燃后飞灰中有机污染物分布的研究

采用色谱／质谱联用系统对青山烟煤及其燃烧产物－飞灰７Ｈ，１６Ｈ和２４Ｈ二氯甲烷索氏抽提液中脂肪烃、苯系物及多环芳烃等有机污染物的种类和含量进行了测量，得到了青山烟煤及其飞灰产物中有机污染物的分布特征。     

On the survivability and pyrosynthesis of PAH during combustion of pulverized coal and tire crumb

Results are presented on the emissions of semivolatile polycyclic aromatic hydrocarbons (PAH) from the combustion of a pulverized bituminous coal and ground waste automobile tires. Streams of fuel particles were injected at steady-state steady-flow conditions, and burned inside an isothermal drop-tube furnace, in air, at a gas temperature and gas residence time of 1150°C and 0.75 s, respectively. Combustion occurred under either very fuel-lean conditions (bulk equivalence ratio, φ < 0.5) or substantially fuel-rich conditions (φ = 1.6–1.9). Emissions from fuel pyrolysis, in the absence of oxygen, were also examined. The survivability of the fuel-PAHs during combustion/pyrolysis was assessed by examining the reactants (fuels) and the products of their oxidation/pyrolysis. The PAH species in the effluent of combustion were: 1) qualitatively compared with indigenous PAH constituents of the input fuels, and 2) quantitatively contrasted with known amounts of deuterium-labeled PAH standards, which were absorbed on the input fuels. No PAHs were detected in the effluent of combustion of either fuel under sufficiently fuel-lean conditions, e.g., φ < 0.5. This indicated that the PAH constituents of the input fuels, either indigenous or adsorbed, as well as those formed by pyrosynthesis in either the diffusion volatile flames or during the heterogeneous oxidation of the chars were destroyed. Significant amounts of PAHs were detected in the effluent of the combustion of both fuels under sufficiently fuel-rich conditions, e.g., φ > 1.6 and, especially, under pyrolytic conditions in N₂. These PAHs were mostly attributed to pyrosynthesis since none of the deuterated PAHs, adsorbed on the fuels, survived the combustion process. Small amounts of the labeled compounds, however, survived under purely pyrolytic conditions. These results were confirmed with separate experiments, where deuterium-labeled PAH standards were adsorbed on highly porous calcium/magnesium oxide or mullite particles. Again, small amounts of some PAHs survived in high-temperature pyrolytic conditions, but none in oxidative environments. These observations suggest that pyrosynthesis is the major contributing mechanism to the PAH emissions from the combustion of these fuels. Survivability of parent PAHs may be a minor mechanism at very high equivalence ratios.

Finally, both fuels were mixed with powders of calcium magnesium acetate (CMA), calcium carbonate (CaCO₃), and calcium oxide (CaO), all of which are known sulfur reduction agents, at a molar Ca/S ratio of 1. Combustion of the fuels mixed with CMA or CaCO₃ generated enhanced amounts of PAHs, while combustion with CaO had no effect on the PAH emissions.     

The effect of coal size on PM2.5 and PM-bound polycyclic aromatic hydrocarbon (PAH) emissions from a domestic natural cross-draft stove

Residential coal combustion has played an important role in the domestic energy supply of Northern China for many decades and will do so for the foreseeable future, although it is also an important contributor to severe air pollution. Meeting the daily cooking and spacing-heating demands of rural residents in an eco-friendly manner necessitates cleaner-burning technologies for residential coal combustion. Several reports have suggested that appropriately sized coal be beneficial for optimizing the performance of domestic coal-fired stoves. The effects of coal size (<1.6 cm, 1.6–2.0 cm, 2.0–2.5 cm and >2.5 cm) on fine particulate matter (PM_2.5) and sixteen U.S. Environmental Protection Agency (EPA) priority polycyclic aromatic hydrocarbons (16-PAHs) emissions from a natural cross-draft stove, operating in different phases (ignition, high power heating, low power heating, ramping up and high power cooking) were analyzed in this study. Results indicated that decreasing the coal size enhanced thermal efficiency and reduced pollutant emissions. When the coal size decreased from >2.5 cm to <1.6 cm, the average emission factor (EF) of PM_2.5 over a complete combustion sequence decreased from 3.12 to 1.42 mg/MJ_net, and the EF of PM-bound total PAHs decreased from 44.9 to 10.9 μg/MJ_net. The corresponding toxic equivalent quantity (TEQ) decreased from 1.25 to 0.38 μg/MJ_net. Emissions and energy efficiencies varied markedly between the various combustion phases, adequate air supply during the high power heating and cooking phases reduced the EFs of PM_2.5 and PAHs, while the low power heating phase produced relatively more pollutants due to a fuel-rich condition.     

Emissions of organic hazardous air pollutants during Chinese coal combustion

This paper provides a general investigation of the emissions of organic hazardous air pollutants (HAPs) during the combustion of several typical Chinese coals. First, the distribution of four types of HAP, i.e., aliphatics, cyclic hydrocarbons, monoaromatic compounds and PAHs, in the CH₂Cl₂ extracts of six Chinese coals were studied and the influences of the extractive times and coal varieties were also evaluated. Second, the partitioning of these HAPs in the flue gas during coal combustion in a small-scale reactor were investigated, depending on oven temperatures (500 °C, 600 °C, 700 °C, 800 °C, 900 °C) and coal varieties. The behaviors of HAP in the combustion flue gas were compared with those in the CH₂Cl₂ extracts. Finally, combustion was conducted at given conditions in two laboratory-scale reactors: a fluidized bed and a fixed bed. Two coals (Shengmu bituminous coal and Xunhuan anthracite coal) and one coke were considered in this case. The HAP partitioning both in flue gases and in ashes were evaluated and compared between the two combustors.     

The effect of air staged combustion on NOx emissions in dried lignite combustion

Experiments were carried out in a multi-path air inlet one-dimensional furnace to assess NOx emission characteristics of the staged combustion of BRXL lignite and its dried coals. The impact of moisture content, multiple air staging, pulverized coal fineness and burnout air position on NOx emissions under deep, middle and shallow air-staged combustion conditions. Moreover, the impact of blending coals on NOx emissions was investigated in this paper. The unburned carbon concentration in fly ash was also tested. Experimental results based on the combustion of BRXL lignite and its dried coals show that NOx emissions can be reduced drastically by air-staged combustion. NOx emissions reduce with the increase of the air that is staged and the distance between the burner and burnout air position. Dried coal of BRXL lignite emits a smaller amount of NOx than that of BRXL lignite. However, the dried degree of BRXL lignite is closely related to R₉₀ fineness. Dried coal with optimal moisture content yields least NOx emissions. When deep or middle staged combustion was adopted, the application of multi-staged combustion is conducive to NOx reduction. However, when shallow staged combustion was adopted, NOx emissions are higher in multi-staged combustion than that in single-staged combustion with M_S = 0.54. Thus, the existence of a certain concentration of O₂ in reduction zone would significantly reduce NOx emissions. The blending coals that dried coals of BRXL lignite were blended with bituminous coals emit a larger amount of NOx than that of the dried coal alone. NOx emissions decrease with the increase of the proportion of dried coal in the blending coal. Moreover, the unburned carbon concentration in fly ash of dried coal in staged combustion is lower than that of BRXL lignite in staged combustion. On the whole, the dried coal of BRXL lignite is conducive to NOx reduction in staged combustion.     

粒度对循环流化床锅炉燃烧影响的试验研究

循环流化床燃烧技术具有高效,低污染,燃料适应性广的优点,燃用福建无烟煤的循环流化床锅炉在福建沿海地区得到了广泛开展,取得了许多的成果,但是普遍存在的问题是飞灰含炭量太高,热效率不高。在一台75 t.h-1的循环流化床锅炉上对三种不同粒度的福建无烟煤进行了燃烧试验,测量了炉膛各段的温度水平,获得了粒度对底渣、飞灰的粒径分布及其含炭量和热效率等的影响特性,并针对燃用福建无烟煤的循环流化床锅炉的优化燃烧提出了一些建议,对锅炉的运行具有一定的指导意义。     

柴油机排气中可溶性有机物排放的特性

通过柴油机台架试验,在一款柴油机上加装氧化型催化转化器(DOC)装置,研究了DOC前/后排气颗粒物中可溶性有机物(SOF)和固相多环芳烃(PAHs)的变化趋势,分析了不同转速和负荷对SOF及PAHs排放的影响以及排气中SOF及PAHs排放在排气过程中的变化规律.结果表明:DOC能明显降低排气中SOF及PAHs排放,SOF最高减排为50.69%,PAHs最高减排为83.28%,同时PAHs的毒性当量最高降低为49.31%.随着柴油机转速增加,燃烧过程后燃增加,排气中SOF及PAHs有增加的趋势,而随负荷的增加,缸内燃烧温度升高,各成分氧化速率加快使得SOF及PAHs排量逐渐降低.随排气输运距离增加,排气组分冷凝现象加重致使SOF及PAHs排量明显升高.     

Analysis of the co-combustion of sewage sludge and coal by TG-MS

Combustion of sewage sludge may be a viable solution for its management in some cases and so is its co-combustion with coal. The aim of the present paper is to study the behavior of three different sludges during combustion and the modifications of combustion parameters that take place when sludges are mixed with coal, all measurements being done by thermogravimetry. The combustion of pyrolyzed sewage sludges has also been studied, related to the possibility of combining combustion with pyrolysis when trying to valorize sludges by producing active carbon. From the burning profile data it has been possible to observe that a rapid devolatilization occurs during sludge combustion compared to coal and previously pyrolyzed sludge. The exact temperatures of devolatilization and of maximum speed of weight loss have also been ascertained together with differential thermal analysis and measurements of gas emissions during combustion. The behavior of the sludges tested is qualitatively similar but quantitatively different, so tests have to be carried out before they are put in the furnace.