Soot nanostructure evolution from gas turbine engine, premixed and diffusion flame: Equivalence ratio, flame temperature, and fuel dependencies.

Open Access
Author:
Huang, Chung-hsuan
Graduate Program:
Energy and Mineral Engineering
Degree:
Doctor of Philosophy
Document Type:
Dissertation
Date of Defense:
August 22, 2014
Committee Members:
  • Randy Vander Wal, Dissertation Advisor
  • Randy Vander Wal, Committee Chair
  • Andre Louis Boehman, Committee Member
  • Adrianus C Van Duin, Special Member
  • Thomas Litzinger, Special Member
Keywords:
  • Soot nanostructrue
  • AAFEX II
  • Premixed flame
  • diffusion
  • bunsen
  • SERDP
  • ChemKin
  • fullerenic soot
  • curvature
  • cyclopentadiene.
Abstract:
Combustion generated soot impacts human health and climate. Particulate emissions from combustors on jet aircraft are relevant to each area, occurring at ground level and at altitude. One of the advantages of alternative fuels is their potential for reducing emission levels. Comparative field-testing of alternative fuels for their emissions was conducted in the Alternative Aviation Fuel Experiment II (AAFEX II), a NASA-led ground-based field campaign. In this study, particulate emissions from a CFM-56-2C1 engine aboard a DC-9 aircraft were characterized by HRTEM and XPS for nanostructure, carbon speciation and surface chemistry. Fuels studied included JP-8, a 50:50 (JP-8 & HRJ) blend, Hydrotreated Renewable Jet (HRJ), and a Fischer-Tropsch (FT) synthetic fuel. Soot nanostructure and surface chemistry are examined across engine power levels from 4% to 100%. Nanostructure ranged from amorphous (reflecting organic carbon) to graphitic (reflecting elemental carbon) as characterized by lamellae length analysis. With JP-8 fuel, soot particle bonding chemistry, as inferred from the XPS ratio for sp2/sp3 carbon is compared to soot nanostructure evolution. Increasing lamellae length is found to strongly correlate with increasing sp2/sp3 ratio with increasing engine power – suggesting a change in species identity contributing to the soot growth process. Comparisons between fuels for the same power levels yielded insights into differences in soot processes as dependent upon initial fuel. Soots from the renewable HRJ and FT fuels exhibit significant nanostructure at each power level, rather than the progression as observed for JP-8. This difference is associated with differences in the soot formation environments as dependent upon fuel. To further examine the correlation between chemical environment and soot structure as manifested on different physical length scales, primary particle size versus lamellae length was compared. For JP-8 and its blend with HRJ, there is correlation with engine power, i.e. each spatial metric increases with increasing power, suggesting common underlying cause(s) for both observations. For the HRJ and FT fuels, there is no discernable trend. These results are interpreted in terms of the aromatic content of the JP-8 and blended fuels and their different pyrolysis kinetics compared to paraffinic components of the fuels. Observations of fullerenic nanostructure, particularly evident in soots from the pure paraffinic fuels were interpreted as reflecting partial premixing in order to produce the C5 membered rings for lamellae curvature. This led to the hypothesis defining this study: Partially premixed combustion produces soot with fullerenic nanostructure. Curvature is that one special feature of nanostructure that can be related back to particular gas phase specie(s), namely cyclopentadiene and PAHs containing 5-membered rings. This hypothesis was tested in the following two laboratory flame studies. Partial premixing within simple gas jet diffusion flames has a very long history – stemming back to the Bunsen flame. Yet HRTEM data of soot from such flames appears absent. In the first study cyclopentane was used as fuel to test lamellae curvature dependence upon C5 species. Modest curvature was observed – given competing fuel pyrolysis and ring dehydrogenation to yield cyclopentadiene, referred to as C5. Using benzene as the primary fuel with partial premixing tested the chemical path for C5 production – proceeding through partial benzene oxidation yielding the phenoxy radical followed by CO loss to produce C5. A strong variation of lamellae curvature with oxygen content in the primary fuel stream was observed – reflecting the increasing C5 production rate. Generality of the nanostructure dependence upon partial premixing and associated change in gas phase chemistry (compared to pure thermal pyrolysis) was demonstrated using an ordinary laboratory Bunsen burner with ethylene as fuel. In absence of partial premixing, soot production is well described by the HACA mechanism, C6 PAHs with observed flat lamellae, without curvature, dissimilar to observations here accompanying partial premixing. In the third study, the main goal was to test two main parameters – adiabatic flame temperature (2000K) and fuel/air equivalence ratio (Φ = 2.0) – for their relative impact on soot nanostructure formation. The soots were collected from a burner-stabilized flat flame burning the petroleum-based JP-8, synthetic FT, and surrogate – iso-Octane/n-Dodecane, m-Xylene/n-Dodecane, and n-Dodecane – fuels on a McKenna burner. Images from high-resolution transmission microscopy (HRTEM) show that for the same equivalence ratio of Φ = 2.0 with temperature maintained constant, soot from the FT fuel has significant curvature compared to soot from the JP-8 fuel, as also found in FT-derived soot from the jet engine. This comparative observation indicates two major findings. First is that the soot nanostructure depends upon initial fuel composition – and by extension molecular structure. Similar findings from diesel engine studies have also been documented by Yehliu (2010) 1. Second is that fuel pyrolysis pathways and products also depend upon the fuel components. Adjustment of flame adiabatic temperature suggests a temperature threshold for realization of such differences. Soot nanostructure comparisons with a surrogate fuel mixture of n-dodecane/m-xylene (75:25 wt.%) further illustrate pyrolysis processes and intermediates as dependent upon fuel molecular structure and components present. To further compare the experimental results, CHEMKIN with the SERDP mechanism using the burner-stabilized flame model was carried out and processed for the three surrogate fuels, iso-Octane, n-Dodecane, and m-Xylene at various reaction temperatures and fuel/air equivalence ratios. Both the C5H5/C6H6 ratio and C3H3 profiles were distinctly different between the pure n-dodecane and m-xylene/n-dodecane mixture. That the C3H3 profile is also the main difference between the iso-octane and surrogate fuel mix suggests that C3H3 participation in 5-membered ring formation is also key to introduction of 2-D curvature in lamella – especially given that the highest curvature is observed for FT fuel soot. Moreover, by these results the higher C5H5 observed for the surrogate mixture is an inferred consequence of the different C3H3 profile. Presently these calculated values are only used to interpret the observed curvature differences, as threshold values or the concentration dependency of curvature upon particular species are currently unknown. The goal of this study was to build a bridge between molecular gas phase species and the soot nanostructure. Initial observations of nanostructure curvature in jet engine soot prompted interest. Current chemical kinetic models can address fuel breakdown, thermal and oxidatively assisted, PAH formation and growth all via detailed kinetics, followed by soot inception via their physical and chemical coalescence. Thereafter soot models are particle based and use measured growth rates and aerosol dynamics to account for increasing soot mass and aggregate formation. No modeling studies have yet addressed the link between gas phase species with any aspect of soot nanostructure. As shown here soot nanostructure can reflect its origin, specifically the species forming the soot lamellae. The novelty of two-dimensional curvature is that it can be related uniquely to C5 species, via known chemical pathways – involving oxygen directly or indirectly. The oxygen concentration in the primary fuel stream defines the level of partial premixing. Therein lies the origin of the hypothesis that partial premixing leads to (recognizable) curvature in soot lamellae. Definition of the operative range of Φ and temperature will constitute future work for C5 production and its manifestation as curvature in nanostructure.