燃煤电厂飞灰PM_(2.5)及PM_(2.5-10)中多环芳烃分布特性研究

通过试验装置从飞灰样品中分离出PM2.5和PM2.5-10灰样,利用GC-MS检测出其中USEPA建议优先检测的16种多环芳烃(PAHs)的质量分数,分析了这些多环芳烃在PM2.5和PM2.5-10中的分布特性.结果表明:PM2.5中PAHs的平均质量分数约为PM2.5-10中的1.86倍;PM2.5中三环、四环PAHs占主要部分,PM2.5和PM2.5-10中六环PAHs质量分数均较小;PM2.5和PM2.5-10对不同PAHs的吸附能力不同,PM2.5对二环、三环、四环PAHs的吸附能力强于PM2.5-10,而对五环、六环PAHs的吸附能力相对偏弱.     

柴油机燃用不同柴油的多环芳烃排放研究

在一台国-Ⅲ柴油机上,燃用G5、D1、D2、D3、和D4五种芳烃含量不同的柴油,对不同负荷下的排放特性进行了研究。利用PUF泡沫和聚四氟氯乙烯纤维滤膜串联法采集柴油机尾气中的气相和颗粒固相多环芳烃(PAHs),并采用气相色谱-质谱联用仪进行分析,重点研究了PAHs的排放特征。结果表明:燃用不同柴油时柴油机PM排放随负荷增加呈现先降后增的趋势。PAHs排放以气相为主,占总PAHs含量的90%以上,颗粒固相PAHs则低于10%;在柴油燃烧排放的总PAHs中萘和甲基萘含量最高,且不同油品燃烧排放的PAHs排放状况与油品中PAHs自身含量密切相关。不同柴油燃烧排放的气相PAHs均以2环和3环为主,而颗粒固相PAHs则以3环和4环为主。     

柴油公交车加装CDPF的非常规污染物排放特征分析

测试分析了柴油公交车安装催化型柴油机颗粒过滤器(catalyzed diesel particulate filters,CDPF)在瞬态测试循环工况下对非常规气态物、颗粒物中的碳质组分、芳香烃及其毒性的影响。研究结果表明:CDPF对挥发性有机物的减排率为57.6%,对柴油车颗粒物中总碳的减排率为70.4%,对柴油车颗粒中多环芳烃(PAHs)组分减排率为91.1%,CDPF对低环数的PAHs表现较高的减排率,而对其他环数的PAHs的减排率略低。CDPF能明显降低不同苯环PAHs的毒性当量,但对不同苯环PAHs的毒性当量比例影响不明显。     

双尺度小火焰模型预测混合层火焰中PAHs的生成

本文验证了双尺度过程变量小火焰方法在层流混合层火焰中的适用性,该方法通过增加额外的过程变量C_(PAHs)来提高传统过程变量小火焰方法对多环芳烃的预测能力。通过与直接数值模拟结果的先验和后验对比,证明了该方法的优越性。在后验验证中,由于对过程变量C_(PAHs)源项的偏低预测继而导致了对多环芳烃组分峰值的预测偏低。通过分析直接数值模拟结果中的小火焰分支,推测过程变量C_(PAHs)源项的偏低预测是小火焰的多维性造成的。     

柴油油品对发动机颗粒物中SOF及PAHs排放的影响研究

使用AVL全流采样(CVS)系统,在1台国Ⅴ车用重型柴油机上通过ESC循环试验研究了国Ⅲ、国Ⅳ、国Ⅴ车用柴油对发动机排放的影响,并利用气相色谱-质谱联用仪等设备对颗粒物中的可溶性有机物(SOF)和多环芳烃(PAHs)进行了对比分析.研究发现,在稳态工况下,改善燃油油品,PM排放大幅减少,PM中SOF比重明显升高,但PAHs排放总浓度明显下降;3种燃油的16种PAHs规律相近,只是芴、菲、蒽、荧蒽、芘、苯并(a)蒽、屈7种芳烃浓度基本上都呈减小趋势,尤其是浓度贡献率较大的芘,降幅达95.8％.     

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     

甲烷预混火焰中芳香烃及多环芳烃形成的数值模拟

利用一种详细的化学动力学模型，模拟了甲烷层流预混火焰中芳香烃及多环芳烃(PAHs)的形成．结果表明，数值模拟与实验数据吻合得较好，可以用于预测同类型火焰中芳香烃及PAHs的形成．对不同工况条件下火焰的数值模拟结果显示，火焰当量比、压力对芳香烃及PAHs形成都有影响。     

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)。     

甲苯裂解形成碳烟和PAHs的试验研究

基于流动反应器,开展了甲苯裂解过程碳烟颗粒及其前驱物多环芳烃(PAHs)的形成规律的试验研究．选取了在950～1 450℃温度范围内3个不同停留时间(0.2 s、0.5 s、0.8 s)下,甲苯裂解反应形成碳烟颗粒粒径分布特性,以及2～7环19种颗粒态PAHs的成分谱特征,进一步分析了不同裂解条件下颗粒物的当量毒性．发现甲苯裂解颗粒的生成过程伴随着凝结、凝并和团聚等气溶胶动力学变化,裂解温度越高碳烟颗粒的几何平均粒径越大、颗粒质量越高,颗粒粒径随停留时间增加向大粒子方向偏移;PAHs的浓度随温度的变化多数呈单峰分布,部分呈双峰分布,这与构成分子中的芳香环数和停留时间相关;0.5 s颗粒中PAHs当量毒性高于0.8 s和0.2 s时,且峰值位于1 050℃左右．     

不同煤种燃烧生成多环芳烃的研究

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     

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.     

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。     

Comparative studies on steam gasification of ash-free coals and their original raw coals

Catalytic gasification of raw coals at mild condition is not realized yet mainly due to deactivation of catalysts via their irreversible interaction with mineral matters in coal. As a means to achieve repeated use of catalysts, four different ash-free coals (AFCs) containing less than 0.2 wt% ash are produced in this work. Steam gasification of ash-free coals (AFCs) and their parent raw coals of various ranks ranging from lignite (Eco) to coking coal (Posco) is performed in a fixed bed reactor at 700–900 °C. Regardless of the rank of the parent raw coals, all the AFCs behave like a highly carbonized coal such that their gasification rate are similarly slow and they exhibit relatively low H₂/CO ratio. The steam gasification and associated CO to CO₂ conversion of the AFCs are, however, significantly enhanced by K₂CO₃, resulting in the higher H₂/CO and CO₂/CO molar ratio.     

Formation of soot particles in methane and ethylene combustion: A reactive molecular dynamics study

A numerical analysis of the complete soot formation process was conducted in the combustion condition with methane and ethylene as initial fuel and oxygen as oxidant by applying the reactive molecular dynamics. The relative time of different periods during soot formation was quantitatively analyzed by a normalized time (t/t_g), and the effects of fuel type, temperature, and equivalent ratio on soot formation were further studied. The simulation results showed that there is little difference of the normalized time (t/t_g) of the different periods during soot formation between CH₄ and C₂H₄ combustion. The normalized time of the periods for fuel pyrolysis and initial PAHs formation, soot nucleation, and soot surface growth and particle coalescence are 27.7%, 12.3%, and 60%, respectively. The carbon atom number and C/H ratio of the final soot particles in ethylene combustion were approximately twice that of methane combustion, which was due to the high acetylene concentration during ethylene combustion promoting the formation of initial polycyclic aromatic hydrocarbons (PAHs). Increasing temperature significantly accelerated soot formation mainly by promoting soot coalescence process, while excessive temperature inhibited soot formation by accelerating soot fragmentation. Decreasing equivalence ratio mainly inhibited soot formation by reducing the concentrations of acetylene and PAHs during fuel pyrolysis and initial PAHs formation period. Assuming CH₃ and C₂H₃ free radical as the initial fuel could speed up soot formation process, while the hydroxyl (OH) had no obvious effect on soot formation process.     

Solubility and molecular composition of organic species in low-rank coals during sequential thermal dissolution in cyclohexane and methanol

In this study, six low-rank coals (LRCs) including two lignite samples and four subbituminous coals were sequentially dissolved in cyclohexane and methanol. The yields of cyclohexane-soluble portions (SPs) from the lignite are slightly lower than those from the subbituminous coals, while the yields of methanol SPs showed a linear correlation with the oxygen content and O/C ratio. The concentrations of n-alkanes and polycyclic aromatic hydrocarbons in the SPs of subbituminous coals are higher than those of the lignite, and the concentrations of phenols in the SPs are possibly associated with the content of aryl ether bonds in the LRCs.     

煤质对水煤浆气化性能的影响研究

煤质与气流床气化炉的匹配性至关重要,其不但影响气化炉的运行条件,也影响气化性能。本文选择了10种来自新疆和陕西北部的煤样进行了工业分析、元素分析、灰组成分析、灰熔点分析以及成浆性测试,并筛选出适合水煤浆气化的煤样。同时借助Aspen Plus软件对适合水煤浆气化的煤样在相同的煤浆浓度、碳转化率及操作压力条件下开展煤质对水煤浆气化性能影响的模拟分析。结果表明煤中灰含量越高,冷煤气效率和有效气含量越低,比氧耗和比煤耗越高;煤中O/C质量比和H/C质量比的增加也会导致冷煤气效率和有效气含量降低,比氧耗和比煤耗增加。因此从水煤浆气化经济性考虑,建议水煤浆气化煤质灰含量小于9.0wt%,煤中O/C质量比小于0.173,H/C质量比小于0.065。     

Experimental study on the coal tar hydrocracking process over different catalysts

In the paper, the results of the study on a laboratory process of hydrocracking of coal tar are presented. High-temperature coal tar was hydrocracked in an autoclave reactor, at 400–413 °C and 7,3–9,6 MPa over 5 different, hydrocracking catalysts to study the yields and characteristics of the products. Liquid products were obtained with a yield of 88–92 wt.% and gas products with a yield of 12–8 wt.%. After dehydration by azeotropic distillation, liquid products were separated on the oil fraction boiling below 360 °C, and pitch fractions boiling above this temperature. In the balance of distillation, it is clear that only the cracking activity of NiW/Al₂O₃ and Y zeolite catalysts is so high that the raw material containing 5 vol.% fraction boiling below 200 °C provides a product comprising approx. 12,5 vol.% of this fraction. The influence of five different catalysts on the yield of 18 poly aromatic hydrocarbons (PAHs) in the hydrocracking products have been investigated by GC/MS. The results indicate that NiW/Al₂O₃ and Y zeolite catalysts have the highest catalytic activity for light aromatic formation (the highest yield of fraction boiling below 200 °C) and aromatic condensed aromatic cracking (PAHs). After the hydrocracking NiW/Al₂O₃ catalyst, the total yields of PAHs decrease 52.7% as that of raw coal tar.     

Experimental and kinetic modeling study of PAH formation in methane coflow diffusion flames doped with n-butanol

In order to understand the interactions between butanol and hydrocarbon fuels in the PAH formation, experimental and kinetic modeling investigations were combined to study methane laminar coflow diffusion flames doped with two inlet mole fractions of n-butanol (1.95% and 3.90%) in this work. Mole fractions of flame species along the flame centerline were measured using synchrotron VUV photoionization mass spectrometry. A detailed kinetic model of n-butanol combustion, extended from a recent published n-butanol model, was provided in this work to reproduce the fuel decomposition and the formation of benzene and PAHs in the investigated flames. Numerical simulations were performed with laminarSMOKE code, a CFD code specifically conceived to handle large kinetic mechanisms. The simulation results were able to follow the observed effects of n-butanol addition from the experimental results. In particular, unsaturated hydrocarbons, especially C6–C16 aromatics, were predicted satisfactorily. The reaction flux analysis revealed that benzene precursors, especially C3 radicals, increase significantly with increasing inlet mole fraction of n-butanol. This enhances the formation of phenyl and benzyl radicals, which are important PAH precursors. Reactions of benzyl, phenyl radicals and benzene with C2–C3 species are the major formation pathways for indene and naphthalene. And PAHs with more carbon atoms are dominantly formed from naphthyl and indenyl radicals.     

高水分煤在流化床中燃烧时NO_x的排放特性

通过数值计算,研究了高水分煤在流化床中燃烧时ＮＯ的排放特性及其形成的主要影响因素。结果表明煤中的水分,床内的ＣＯ浓度和空－燃比等都对于ＮＯ转换率有较大影响。     

Soot formation characteristics and PAH formation process in a micro flow reactor with a controlled temperature profile

A micro flow reactor with a controlled temperature profile was examined with regard to its capabilities to investigate soot formation characteristics of rich methane/air mixtures and the formation process of polycyclic aromatic hydrocarbons (PAHs) of rich acetylene/air mixtures. In the experiment for a methane/air mixture, four kinds of flame and soot responses to equivalence ratio (1.5–4.5) and inlet mean flow velocity (5–40 cm/s) were observed: soot formation without a flame; a flame with soot formation; a flame without soot formation; and neither a flame nor soot formation. Soot formation was observed at high equivalence ratio and low flow velocity. Sooting limits depending on equivalence ratio and flow velocity (residence time) were successfully identified by the present micro flow reactor. To investigate the PAH formation process, the micro flow reactor was employed for a rich acetylene/air mixture at equivalence ratios of 4, 5 and 6 at an inlet mean flow velocity of 2 cm/s and gas sampling experiments were conducted at temperatures from 600 to 1000 K. Temperature dependence of mole fractions of benzene, styrene, naphthalene, phenanthrene, indene, acenaphthylene and biphenyl was successfully obtained and larger PAHs such as pyrene and coronene were not observed in this study. One-dimensional computation with the ABF 2.99 mechanism predicted a benzene mole fraction three times higher than the experimental result. The modification of the ABF 2.99 mechanism using recent benzene reactions greatly improved the prediction of the benzene mole fraction. The rate of production analysis was carried out and PAH formation in the micro flow reactor was investigated in detail.