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FeO纳米颗粒介导的1-甲基萘氧化热解过程中的分子生长与碳烟生成

FeO nanoparticle mediated molecular growth and soot inception from the oxidative pyrolysis of 1-methylnaphthalene.

作者信息

Herring M Paul, Potter Phillip M, Wu Hongyi, Lomnicki Slawomir, Dellinger Barry

机构信息

Department of Chemistry, Louisiana State University, Baton Rouge, LA 70803, USA.

出版信息

Proc Combust Inst. 2013;34(1):1749-1757. doi: 10.1016/j.proci.2012.07.057.

Abstract

While it is well documented iron oxide can reduce soot through burnout in the oxidative regions of flames, it may also impact molecular growth and particle inception. The role of FeO nanoparticles in mass growth of soot from 1-methylnapthalene (1-MN) was studied in a dual-zone, high-temperature flow reactor. An iron substituted, dendrimer template was oxidized in the first zone to generate ~5 nm FeO nanoparticles, which were seeded into the second zone of the flow reactor containing 1-MN at 1100°C and = 1.4-5.0. Enhanced molecular growth in the presence of FeO nanoparticles resulted in increased yields of polycyclic aromatic hydrocarbons (PAH) and soot compared to purely gas-phase reactions of 1-MN at identical fuel-air equivalence ratios. This also resulted in an increase in soot-number concentration and a slight shift to smaller particles with increasing addition (from no addition to 3 mM) of FeO. Introduction of FeO nanoparticles resulted in the formation of stabilization of environmentally persistent free radicals (EPFRs), including benzyl, phenoxyl, or semiquinone-type radicals as well as carbon-centered radicals, such as cyclopentadienyl or a delocalized electron in a carbon matrix. At the high concentrations in the flow reactor, these resonance-stabilized free radicals can undergo surface-mediated, radical-radical, molecular growth reactions which may contribute to molecular growth and soot particle inception.

摘要

虽然有充分的文献记载表明氧化铁可以通过火焰氧化区域中的烧尽来减少烟灰,但它也可能影响分子生长和颗粒形成。在双区高温流动反应器中研究了FeO纳米颗粒在1-甲基萘(1-MN)烟灰质量增长中的作用。在第一区将铁取代的树枝状聚合物模板氧化以生成约5nm的FeO纳米颗粒,然后将其注入到流动反应器的第二区,该区在1100°C且当量比φ=1.4 - 5.0的条件下含有1-MN。与在相同燃料空气当量比下1-MN的纯气相反应相比,在FeO纳米颗粒存在下分子生长增强,导致多环芳烃(PAH)和烟灰的产率增加。这也导致烟灰数浓度增加,并且随着FeO添加量的增加(从无添加到3mM),颗粒略微向更小尺寸偏移。引入FeO纳米颗粒导致环境持久性自由基(EPFR)的形成,包括苄基、苯氧基或半醌型自由基以及碳中心自由基,如环戊二烯基或碳基质中的离域电子。在流动反应器中的高浓度下,这些共振稳定的自由基可以进行表面介导的自由基 - 自由基分子生长反应,这可能有助于分子生长和烟灰颗粒的形成。

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