An official website of the United States government
We perform spatially resolved measurements of light scattering of soot in atmospheric pressure counterflow diffusion flames to complement previously reported data on soot pyrometry, temperature and gaseous species up to three-ring polycyclic aromatic hydrocarbons (PAHs). We compare two flames: a baseline ethylene flame and a toluene-seeded flame in which an aliquot of ethylene in the feed stream is replaced with 3500 ppm of pre-vaporized toluene. The goal is twofold: directly adding an aromatic fuel to bypass the formation of the first aromatic ring, widely regarded as the main bottleneck to soot formation from aliphatic fuels, and assessing the impact of a common component of surrogates of transportation fuels on soot formation. The composition of the fuel and oxidizer streams are adjusted to ensure invariance of the temperature-time history, thereby decoupling the chemical effects of the fuel substitution from other factors. The doping approach enables the comparison of very similar flames with respect to combustion products, radicals and critical precursors to aromatic formation (C2–C5 species), in addition to the temperature-time history. Doping with toluene boosts the aromatic content and soot volume fraction relative to the baseline ethylene flame, but, surprisingly, the soot number density and nucleation rate are affected modestly. As a result, the observed difference in volume fraction in the toluene-doped flame is reflective of larger initial particles at the onset of soot nucleation. The nucleation rate when soot first appears near the flame is of the same order as the dimerization rate of single-ring aromatics, in contrast with the expectation that the dimerization of larger PAHs initiates the process. Even though in and of itself nucleation contributes modestly to the overall soot loading, nucleation conditions the overall soot loading by affecting the size of the initial particle, which ultimately affects subsequent growth.
more »
« less
Small aromatic hydrocarbons control the onset of soot nucleation
The gas-to-particle transition is a critical and hitherto poorly understood aspect in carbonaceous soot particle formation. Polycyclic Aromatic Hydrocarbons (PAHs) are key precursors of the solid phase, but their role has not been assessed quantitatively probably because, even if analytical techniques to quantify them are well developed, the challenge to adapt them to flame environments are longstanding. Here, we present simultaneous measurements of forty-eight gaseous species through gas capillary-sampling followed by chemical analysis and of particle properties by optical techniques. Taken together, they enabled us to follow quantitatively the transition from parent fuel molecule to PAHs and, eventually, soot. Importantly, the approach resolved spatially the structure of flames even in the presence of steep gradients and, in turn, allowed us to follow the molecular growth process in unprecedented detail. Noteworthy is the adaptation to a flame environment of a novel technique based on trapping semi-volatile compounds in a filter, followed by off-line extraction and preconcentration for quantitative chemical analyses of species at mole fractions as low as parts per billion. The technique allowed for the quantitation of PAHs containing up to 6 aromatic rings. The principal finding is that only one- and two-ring aromatic compounds can account for soot nucleation, and thus provide the rate-limiting step in the reactions leading to soot. This finding impacts the fundamental understanding of soot formation and eases the modeling of soot nucleation by narrowing the precursors that must be predicted accurately.
more »
« less
- Award ID(s):
- 1853150
- PAR ID:
- 10486813
- Publisher / Repository:
- Elsevier
- Date Published:
- Journal Name:
- Combustion and Flame
- Volume:
- 223
- Issue:
- C
- ISSN:
- 0010-2180
- Page Range / eLocation ID:
- 398 to 406
- Subject(s) / Keyword(s):
- Polycyclic aromatic hydrocarbons Soot Flames Capillary-sampling Gas chromatography
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
We perform spatially resolved measurements of temperature, gaseous species up to three-ring Polycyclic Aromatic Hydrocarbons (PAHs), and soot in atmospheric pressure counterflow diffusion flames. First, we characterize fully a baseline ethylene flame and then a toluene-seeded flame in which an aliquot of ethylene in the feed stream is replaced with 3500 ppm of prevaporized toluene. The goal is twofold: to investigate the impact of a common reference fuel component of surrogates of transportation fuels and bypass the main bottleneck to soot formation from aliphatic fuels, that is, the formation of the first aromatic ring. The composition of the fuel and oxidizer streams are adjusted to maintain a constant stoichiometric mixture fraction and global strain rate, thereby ensuring invariance of the temperature–time history in the comparison between the two flames and decoupling the chemical effects of the fuel substitution from other factors. Major combustion products and critical radicals are fixed by the baseline flame, and profiles of critical C2–C5 species precursors to aromatic formation are invariant in both flames. On the other hand, doping with toluene boosts the aromatic content and soot volume fraction, increasing the mole fraction of benzenoid structures and soot volume fraction by a factor of 2 or 3, relative to the baseline ethylene flame. This finding is consistent with the expectation that the formation of the first aromatic ring is no longer a bottleneck to soot formation in the doped flame. In addition, toluene bypasses completely benzene formation, opening a radical recombination pathway to soot precursors through the production of C14H14 (via dimerization of benzyl radical) and pyrene (through dimerization of indenyl radical).more » « less
-
On the heels of a recent study in an atmospheric pressure ethylene diffusion flame in which the transition from parent fuel molecule to Polycyclic Aromatic Hydrocarbons (PAHs) and, eventually, soot was studied by spatially resolved measurements of PAH concentrations and soot quantities, we extended the focus to diffusion flames with self- similar structure in the 0.101–0.811 MPa pressure range. To that end, we complemented pyrometry based measurements of soot volume fraction with light scattering measurements that, once corrected for beam steering, yielded soot particle size and number concentration profiles. A chemistry model, that had been validated for all species up to 3 ring aromatics in one of the flames investigated at each pressure and up to 4-rings for the flame at atmospheric pressure, was used to compare profiles of chemical species to those of soot quantities. Further analysis yielded the assessment of number nucleation rates of soot and their comparison to the dimerization rates of PAHs. Soot nucleation rate is consistent only with the dimerization of one- and two-ring PAHs, an observation that confirms findings in the atmospheric pressure flame. Changes in pressure and temperature have a progressively larger impact on the concentration of aromatics of increasingly larger molecular weight and, even more so, on soot volume fraction and nucleation rate. A four-fold increase in pressure from 0.101 MPa to 0.405 MPa increases the soot nucleation rate and PAH dimerization rate in flames with constant peak temperature, which is primarily a concentration effect on bimolecular collision rates; a similar but less pronounced effect is observed in the higher (0.405–0.811 MPa) pressure range. Changes in pressure and temperature tend to be progressively more consequential on aromatics of increasing molecular weight and soot.more » « less
-
Soot and its gaseous precursors are quantified in detail (precursors up to 166 amu, volume fraction, particle size, number concentration, and light emissivity dispersion exponent) in a laminar partially premixed counterflow flame of ethylene. The investigated flame has an equivalence ratio Φ = 2.43 and a mixture fraction Zst = 0.4, resulting in a distinct double-flame structure consisting of a rich premixed flame component and a diffusion flame component, both stabilized on the fuel side of the stagnation plane. The value of the equivalence ratio makes the premixed flame the dominant contributor to soot production, with soot being oxidized completely by OH from the diffusion flame component. Particle size is measured to increase quasi-monotonically, but remains within a few nanometers throughout the soot forming region. Aromatic species are primarily formed in the post flame region of the premixed flame. Their mole fractions peak close to the premixed flame and decrease as the diffusion flame is approached. The experimentally measured gaseous species are captured well by kinetic models, with the exception of two critical species in soot chemistry: benzene and naphthalene.more » « less
-
Soot is known for its enormous and pervasive negative impacts on human health and the environmental, but there much about soot that is not well known, including the precursors and chemical mechanisms involved in its formation. Many studies have characterized species associated with incipient particles, i.e., the first particles produced during soot formation. These studies provide insight into inception mechanisms, the pathways leading from gas-phase precursors to condensed-phase particles. Potential inception mechanisms involve one (or a combination) of two classes of pathways: physical nucleation, in which precursors undergo a thermodynamic phase change and are bound together by electrostatic forces, and chemical clustering, in which precursors react to form covalently bound clusters. In a recent paper, Shao et al.1 concluded that soot inception occurs through physical nucleation and claimed to have provided direct evidence of such a mechanism. We demonstrate that this conclusion is inconsistent with (1) the consensus of published work, (2) the data, theory, and analysis on which this conclusion is nominally based, and (3) the second law of thermodynamics. We show that, contrary to their conclusions, their experimental and theoretical results provide evidence for a chemical-clustering soot-inception mechanism.more » « less
- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1016/j.combustflame.2020.08.029
