Combustion and Flame 134 (2003) 249 –260

Investigating the role of methane on the growth of

aromatic hydrocarbons and soot in fundamental
combustion processes
J. F. Roeslera,*, S. Martinota, C.S. McEnallyb, L.D. Pfefferleb, J.-L.
Delfauc, C. Vovellec
a
IFP, 1 et 4 av. de Bois-Préau, 92852 Rueil-Malmaison Cedex, France
b
Department of Chemical Engineering and Center for Combustion Studies, Yale University,
New Haven, CT 06520-8286 USA
c
Laboratoire de Combustion et Systèmes Réactifs, CNRS, 45701 Orléans Cedex 2, France

Received 30 November 2002; received in revised form 24 March 2003; accepted 1 April 2003

Abstract
Experimental results are presented on the effect of methane content in a non-aromatic fuel mixture on the
formation of aromatic hydrocarbons and soot in various fundamental combustion configurations. The systems
considered consist of a laminar flow reactor, a laminar co-flow diffusion flame burner, and a laminar, premixed
flame burner, all of which operate at atmospheric pressure. In the flow reactor, the experiments are performed at
1430 K, constant C-atom flow rates, 98% nitrogen dilution, C/O ratio ⫽ 2, and with fuel mixtures consisting of
ethylene and methane. The diffusion flames are performed with fuel mixtures of methane and ethylene diluted in
nitrogen to maintain a constant adiabatic flame temperature. The premixed flame experiments are performed with
n-heptane and methane mixtures at a C/O ratio ⫽ 0.67 with nitrogen-impoverished air. The results show the
existence of synergistic chemical effects between methane and other alkanes in the production of aromatics,
despite reduced acetylene concentrations. This effect is attributable to the ability of methane to enhance the
production of methyl radicals that will then promote production channels of aromatics that rely on odd-carbon-
numbered species. Benzene, naphthalene, and pyrene show the strongest sensitivity to the presence of added
methane. This synergy on aromatics trickles down to soot via enhanced inception and surface growth rates by
polycyclic aromatic hydrocarbon condensation, but the overall effects on soot volume-fraction are smaller due to
a compensating reduction in surface growth from acetylene. These results are observed under the very fuel-rich
environments existing in the flow reactor and diffusion flames. In the premixed flames, however, instabilities did
not permit investigation of conditions with sufficiently high equivalence ratios to perturb the aromatic and
soot-growth regions. © 2003 The Combustion Institute. All rights reserved.

Keywords: Soot; Aromatic hydrocarbons; PAH; Methane; Combustion; Flow reactor; Diffusion flame; Premixed flame

1. Introduction tion are complex. Early mechanistic models [1,2]

The molecular growth-processes leading to poly-
cyclic aromatic hydrocarbons (PAH) and soot forma-
* Corresponding author. Tel: ⫹(33)1-47-52-5811; fax:
⫹(33)1-47-52-7069.
E-mail address: john.roesler@ifp.fr (J.F. Roesler).
suggested that the first aromatic ring was formed by
the addition of acetylene to C4 radicals and that the
key growth process toward increasingly larger PAH
occurred by continuous addition of C2H2. Bi-aryl
formation by aromatic-ring addition was considered
feasible only in the case of aromatic fuels. This type
of pioneering model was able to reproduce most of

0010-2180/03/$ – see front matter © 2003 The Combustion Institute. All rights reserved.
doi:10.1016/S0010-2180(03)00093-2
250 J.F. Roesler et al. / Combustion and Flame 134 (2003) 249 –260
the major PAH and soot trends observed experimen-
tally in combustion processes [1,3,4]. However, it
neglected other reaction pathways that are increas-
ingly shown to be of importance.
In 1990, Miller and Mellius [5] published work
that suggested that benzene could be formed, in large
part, from the re-combination of the odd-carbon-
numbered, resonantly-stabilized propargyl radicals.
While this specific reaction is now well-recognized
and has been implemented in many recent kinetic
models [6-9], there is growing evidence that many
other such radical species are involved in the produc-
tion of at least the smaller PAH. This evidence is
found in various theoretical analyses of reaction
channels and in experimental flame and modeling
studies [10 –14].
If these reactions are indeed important, then add-
ing methane to the PAH and soot-forming regions in
combustion systems should, under some conditions,
promote their growth. The premixed flame results of
Senkan and Castaldi [15] that show a methane, lam-
inar, premixed, flat flame to produce more benzene
and PAH than a similar ethane flame confirm this line
of thought. More direct evidence of this effect of
methane was obtained in flow-reactor studies [16,17].
The addition of methane was found to enhance the
formation of aromatics and soot in n-heptane oxida-
tive pyrolysis. Detailed reaction mechanisms from
the literature were found to reproduce these effects,
provided PAH formation was appropriately described
with odd-carbon-numbered radical species.
The present work further investigates experimen-
tally the influence of methane as a parameter to be
considered in the formation of soot and PAH. Our
goal was to further quantify the effect, under flow-
reactor conditions, and to determine whether or not
these were applicable to classic, laminar, premixed
and diffusion flame conditions.
2. Experimental set-ups
2.1. The flow-reactor system
The flow-reactor device and the analytical tech-
niques for quantifying the composition of the sam-
pled products have been described in detail previ-
ously [17,18]. The reactor is made of quartz, with a
30-mm inside diameter. It is inserted in a three-zone
furnace. The premixed reactants are rapidly heated in
the first zone through a coiled 1.5-m-long tube with
an inside diameter of 4 mm. The flow enters the
larger-diameter test section and is laminarized by
passing through a porous quartz disk. The test section
is at atmospheric pressure and is isothermal within
5 K throughout a distance of 35 cm.
The product samples are quenched and collected
along the center-line axis by means of an oil-cooled
probe at 180°C. Only 20% of the total flow is sam-
pled; therefore, the measurements correspond to the
products along the center-line and not to the bulk
mean.
At the probe exit, the soot is filtered at 180°C, and
condensable species are then trapped. In a first pass,
the trap is at ambient temperature, and the low-mo-
lecular-weight gas-phase species, up to benzene, are
analyzed on-line with a Fourier-transform infrared
spectrometer (FTIR). The gas-phase species are then
collected for subsequent analysis by gas chromatog-
raphy (GC) with a flame ionization detector (FID) in
order to more accurately quantify the hydrocarbon
gas-phase species with up to eight carbon atoms. The
species quantified solely by FTIR are CO, CO2, and
H2O. The higher-molecular-weight species are col-
lected on a second pass, with the trap at dry-ice
temperature (⫺70°C) that is then washed with
CH2Cl2. The detailed speciation of the PAH from the
trap is obtained by GC-FID and GC-mass spectrom-
etry (MS) analysis. All other wetted surfaces (probe,
Teflon liner, and soot filter) are washed ultrasonically
with CH2Cl2. Analysis of the collected solutions
showed ⬍ 5% loss of any one of the reported PAH to
these surfaces. The total masses of condensable spe-
cies (hereafter referred to as “tar”) of molecular
weight, corresponding roughly to masses greater than
acenaphthylene, and the mass of soot (non-dichlo-
romethane-soluble, condensable species) are deter-
mined gravimetrically.
In the experiments presented here, the fuel was
initially C2H4 that was gradually substituted with
CH4 at a constant total-carbon molar content of 3%.
A mixture parameter characterizing the initial fuel
composition is defined as:
X CH4
␤⫽ (1)
X CH4 ⫹ 2X C2H4
and represents the fraction of fuel carbon injected as
methane. This parameter was varied from 0 to 0.5.
The oxygen content was also held constant to main-
tain a C/O ratio of ⬃2.0, leading to an equivalence
ratio varying slightly between 6 and 7 due to added
hydrogen in the presence of methane. The experi-
mental conditions investigated were for a tempera-
ture of 1430 K, atmospheric pressure, and a total flow
rate of 0.54 slpm (standard liters per minute) with
nitrogen as the carrier gas. The product samples were
collected at a fixed position of 0.25 m downstream of
the porous quartz disk, corresponding to a bulk mean
residence time of 0.42 s.
 J.F. Roesler et al. / Combustion and Flame 134 (2003) 249 –260 251

2.2. The laminar co-flow diffusion flame system Table 1

Volumetric flowrates for the laminar diffusion flames*
The laminar co-flow diffusion flame burner and ␤ N2 CH4 C2H4 Ar
the analytical techniques have been described in de-
tail previously [19]. The flames are generated with an 0.00 500 0 220 7.27
atmospheric pressure, axisymmetric, co-flowing 0.03 484 11 213 7.15
burner. The fuel mixture flows from an un-cooled 0.05 468 23 206 7.04
0.08 452 35 199 6.93
12-mm-diameter vertical brass tube. The air flows
0.11 436 48 192 6.83
between this tube and a surrounding 108-mm inside- 0.14 417 61 183 6.68
diameter chimney. 0.18 397 75 175 6.53
Temperatures are measured with an un-coated 0.21 378 90 166 6.40
125-␮m wire-diameter/260-␮m junction-diameter 0.25 358 105 158 6.28
type R (Pt-Pt/13% Rh) thermo-couple. Further details 0.29 336 121 148 6.10
are provided elsewhere [20]. The relative and abso- 0.33 313 138 138 5.94
lute uncertainties in the results are estimated to be ⫾5 0.38 290 156 128 5.79
and ⫾50 K. The temperatures are corrected for radi- 0.43 267 176 118 5.66
ation heat-transfer effects using procedures described 0.48 239 195 105 5.44
0.54 211 216 93 5.25
in the paper cited above.
0.60 182 241 80 5.08
The reaction gases are sampled by means of a 0.67 154 271 68 4.98
quartz micro-probe. Analyses are then performed on- 0.74 124 309 54 4.92
line, with a commercial electron-impact/quadrupole 0.82 87 346 38 4.77
mass spectrometer (EQMS) and a custom-built pho- 0.90 46 384 20 4.54
to-ionization/time-of-flight mass spectrometer 1.00 0 421 0 4.25
(PTMS) [19]. The calibration mole fractions for
* (units are cm3/min at STP).
methane, acetylene, and benzene are determined by
direct comparison with room temperature mixtures of
known composition, while the rest are determined by
assuming that their PTMS sensitivity is the same as N2 was adjusted to maintain a constant adiabatic
for benzene. The concentrations of C2H4, CO, and N2 flame temperature of 2230 K. Argon was added to the
cannot be measured due to mutual molecular-mass fuel in order to match its concentration in air. It was
interference. The relative uncertainties in the hydro- also used as an internal standard to correct the con-
carbon mole fractions are estimated to be ⫾10%, and centration measurements for changes in the sample
the absolute uncertainties are estimated to be ⫾20% gas-flow rate generated by thermal effects and soot
(methane, acetylene, and benzene) or ⫹100/⫺50% deposition. The air flow around the fuel jet was main-
(all others). These uncertainties are acceptable, be- tained constant at 44.0 slpm. The total fuel jet flow
cause we are primarily interested in how the hydro- rates were specifically chosen to make the maximum
carbon mole fractions change as the fuel composition center-line temperature occur at a height of 71.4 mm.
is altered. The temperature profiles along the center-line axis
Soot-volume fractions are measured using laser- are then quite similar for the various conditions ob-
induced incandescence (LII) The incandescence is served here. Since these are buoyancy-driven flames,
excited at 1064 nm, as opposed to a visible wave- the center-line gas residence times are independent of
length, in order to eliminate interferences from PAH
this flow rate. Therefore, the time-temperature pro-
fluorescence. The incandescent signal is collected
files are nearly similar for all flames.
orthogonal to the excitation beam and is monitored at
Center-line profiles were measured for each spe-
wavelengths from 400 to 450 nm. This detection
cies in a subset of the flames in Table 1; then for each
range discriminates against C2 fluorescence. The spe-
cific details are similar to those provided elsewhere species, a height above the burner was identified
[21]. The relative uncertainty in the measurements is where its concentrations in each profile was within
estimated to be ⫾10%. 10% of the maximum; and then measurements of that
The experimental conditions investigated are species were made at that height in all of the flames
summarized in Table 1. In the present investigation, listed in Table 1. Thus, the final results are the max-
the composition of the fuel consisted of mixtures of imum concentrations of each species as a function of
CH4, C2H4, Ar, and N2. As with the flow-reactor ␤. The exception is methane, for which the measure-
experiments, the relative concentrations of CH4 and ment represents the maximum only for the lowest ␤
C2H4 were identified by the mixture parameter ␤ that values, whereas it represents the residual from the
was varied over its full range. The concentration of fuel at the higher ␤ values.
252 J.F. Roesler et al. / Combustion and Flame 134 (2003) 249 –260

Table 2
Initial conditions for the premixed flames

Flame 1 2

n-C7H16 (mole %) 5.3 4.6

CH4 (mole %) 0.0 3.5
O2 (mole %) 27.5 26.7
N2 (mole %) 67.2 65.2
␾ 2.12 2.16
T1(K) 450 450
C/O 0.67 0.67
P (atm) 1 1
U1 (cm/s at 450 K) 6.3 6.5

2.3. The laminar, premixed flame system

The laminar, premixed flame burner and corre-

sponding analytical techniques have been described Fig. 1. Flow-reactor concentrations of CO, CO2, and H2O
measured as a function of the initial mixture parameter ␤.
in detail elsewhere [22]. The fuel is vaporized and
Lines are curve fits to the data.
mixed with oxygen and nitrogen in a pre-burner
chamber. The burner surface consists of a porous
plate made of 0.5-mm-diameter holes uniformly dis- 3. Results and discussion
tributed over an area 40 mm in diameter at atmo-
spheric pressure. The initial gas temperature is fixed
3.1. The flow-reactor system
by heating the burner surface and up-stream feed line
to 450 K, a temperature which prevents fuel conden-
Figures 1 through 7 show the evolution of species
sation. Gas samples are collected by means of a
concentration as a function of the fuel-mixture pa-
quartz micro-probe. The probe moves along the cen-
rameter ␤, as measured at a point 25 cm down-stream
ter-line axis of the flame. The sampling orifice of the
from the porous quartz disk, corresponding to a bulk
probe is 0.1 mm, and the down-stream pressure is
mean residence time of 0.42 s.
maintained at 1 kPa. The sampled gases are then
The concentrations of CO, CO2, and H2O are
stored in glass bottles for subsequent analysis by GC.
nearly constant (Fig. 1). These species are formed
The hydrocarbon species were quantified with an
predominantly before the porous disk in the pre-heat
Al2O3/KCl column coupled to a FID. Quantification
of N2, O2, H2, and CO was performed with a molec-
ular-sieve column coupled to a thermal-conductivity
detector, while for CO2 and H2O, a Porapak-Q was
used. Aromatic species heavier than benzene were
not measured with these techniques. Soot-volume
fractions were measured by He/Ne laser-light atten-
uation at 670 nm, with a soot refractive index of
1.57– 0.46i [23].
The experimental conditions investigated are
summarized Table 2. Two flames are compared, both
at the same pressure and temperature. The difference
is that in one case, the fuel is only n-heptane (␤ ⫽ 0),
whereas in the second, ⬃ 10% of the total carbon is
injected in the form of methane (␤ ⫽ 0.1). Flames
with larger fractions of methane were unstable with
the given N2/O2 mixture composition. The C/O is
maintained constant, which slightly raises the equiv-
alence ratio from 2.12 to 2.16. Oxygen and nitrogen
flow rates are also maintained. The effects on species Fig. 2. Flow-reactor concentrations of H2, C2H2, CH4, and
concentration profiles and on soot production are pC3H4 measured as a function of the initial mixture param-
then observed. eter ␤. Lines are curve fits to the data.
 J.F. Roesler et al. / Combustion and Flame 134 (2003) 249 –260
Fig. 3. Flow-reactor concentrations of C2H4, C4H4, C4H2,
and aC3H4 measured as a function of the initial mixture
parameter ␤. Lines are curve fits to the data.
regions on a very short time scale compared to that of
PAH growth. The slightly varying concentrations ex-
press changes in the chemistry in this region as the
fuel mixture composition changes. These variations
are not very important, as these species have little
interaction with the PAH and soot-growth processes.
For detailed information regarding the evolution of
species concentrations along the reactor axis, the
reader is referred to reference [17].
Fig. 4. Flow-reactor concentrations of single-ring aromatic
species as a function of the initial mixture parameter ␤.
Lines are curve fits to the data.
253
Fig. 5. Flow-reactor concentrations of the poly-aromatic
species that show the strongest rise when the initial mixture
parameter ␤ is increased. Lines are curve fits to the data.
The concentrations of CH4, C2H2, pC3H4, and H2
are displayed in Fig. 2. As would be expected, when
the relative amount of methane in the fuel increases,
so do the amounts of H2 and CH4 during the reaction.
In contrast, the amount of acetylene decreases. As
previously noted [17], the propyne in this system
varies proportionally with the three former species
due to a near partial equilibrium of the global reac-
tion
Fig. 6. Flow-reactor concentrations of the poly-aromatic
species that show a mild rise when the initial mixture
parameter ␤ is increased. Lines are curve fits to the data.
254 J.F. Roesler et al. / Combustion and Flame 134 (2003) 249 –260
Fig. 7. Flow-reactor concentrations of tar, soot, and total
PAH measured by GC analysis as a function of the initial
mixture parameter ␤. The concentrations are expressed in
terms of their carbon-atom equivalent. Lines are curve fits to
the data.
CH 4 ⫹ C 2H 2ºH 2 ⫹ pC 3H 4
The relation yields:
共CH 4兲共C 2H 2兲
共 pC 3H 4兲 ⫽ K eq
共H 2兲
The present results confirm again that Keq has a
value of 20 at 1430 K. In general, acetylene and
hydrogen are present in larger proportions than meth-
ane in fuel-rich combustion products. Therefore, ad-
dition of methane will generate a larger relative con-
centration change of itself than of H2 and C2H2.
Furthermore, at iso-carbon content, a change in meth-
ane is twice that of acetylene. These effects will
promote propyne formation.
The concentrations of ethylene, allene, vinyl-
acetylene, and diacetylene are displayed in Fig. 3. For
ethylene, its concentration increases by a factor of 2,
despite the reduced amount injected. This result is
due to the fact that, at the extent of reaction observed,
ethylene is being produced primarily as a product in
the decomposition of the larger quantities of meth-
ane. However, at an earlier reaction time, for a posi-
tion only 1 cm down-stream from the quartz disk, the
concentration of C2H4 rises only by 10%, to a value
near 1,000 ppm. Thus, in the earlier oxidation region,
methane acts more as an inhibitor in the decomposi-
tion of ethylene. The allene profile follows the trend
of its propyne isomer. Vinylacetylene has a profile
that remains rather flat (only a 20% increase) and
follows closely a partial-equilibrium tendency with
the global reaction C2H4 º C2H2 ⫹ H2. As for
diacetylene, its concentration decreases dramatically,
much more so than acetylene, a trend that is coherent
with partial equilibrium of the global reaction 2C2H2
º C4H2 ⫹ H2.
The evolution of single-aromatic-ring hydrocar-
bons is shown in Fig. 4. Here, we observe a strong
increase in benzene as ␤ increases. The maximum of
this species was not reached in the present set of
experiments. This increase is attributed to the en-
hanced production of propyne and allene, which
would lead to larger quantities of propargyl radicals
and accelerate the production of benzene via:
C 3H 3 ⫹ C 3H 3ºC 6H 6 (4)
In contrast, phenylacetylene increases much less
and attains a maximum at ␤ ⫽ 0.25. This is easily
attributable to the reduced C2H2 and enhanced H2
concentrations that eventually off set the effect of the
increased benzene in the growth steps. Toluene, on
the other hand, increases by a factor of 5, due to the
fact that it further feeds on methyl radicals in its
formation process from benzene.
The PAH shown in Fig. 5 and Fig. 6 display
profiles of two types. The examples of the first type,
(2)
naphthalene and pyrene, show trends similar to ben-
zene, with an increased growth of about a factor of
2.5. The examples of the second type, acenaphthyl-
ene, fluoranthene, phenanthrene, and C18H10 (this
(3)
curve most likely represents cyclopenta(c,d)pyrene
concentrations but possibly contains other indistin-
guishable minor isomers), show trends more like that
of phenylacetylene. This suggests that there are those
PAH whose growth depends more directly on the
presence of odd-carbon-numbered species and those
PAH whose growth depends more on even-carbon-
numbered hydrocarbons. Obviously, the cyclopenta
aromatics and acetylenated aromatics require the ad-
dition of acetylene, and these are found in the PAH
category showing lesser growth.
It is difficult to assess what the dominant reaction
pathways are exactly; however, some conclusions
may be reached as to what some pathways are not,
particularly regarding acetylene addition. The main
path to naphthalene is not likely to be from succes-
sive C2H2 addition reactions to phenyl, as in the
hydrogen-abstraction-carbon-addition (HACA)
mechanism [1]. The concentration of acetylene de-
creases as ␤ increases, and, assuming that the con-
centration of phenyl radicals varies proportionally to
benzene, it is not possible for such reactions to induce
the observed 2.5-fold increase in C10H8. Similar rea-
soning holds for a pathway involving C4H2 addition
to phenyl. This leaves many other possible pathways,
such as the addition of C4H4 to phenyl [6,24], the
recombination of cyclopentadienyl radicals [10,12],
 J.F. Roesler et al. / Combustion and Flame 134 (2003) 249 –260
the addition of propargyl to toluene [11,19], or the
addition of C2H2 to an o-xylyl radical, followed by
dehydrogenation. This last pathway is the main
source of naphthalene during the oxidation of o-
xylene [25]. It was found to dominate in methane
oxidative pyrolysis at an equivalence ratio of 12 [26],
based on a modeling study using the detailed reaction
mechanism of Marinov et al. [12]. This pathway
possibly becomes important at the higher values of ␤.
As with naphthalene, it seems very unlikely for
the production pathways of pyrene to involve exclu-
sively HACA reaction steps that describe PAH
growth by successive C2H2-addition reactions [1].
This holds, whether the HACA sequence is initiated
from benzene, naphthalene, or phenanthrene. Given
the decrease in acetylene content, it is difficult to
expect the successive HACA steps to yield the ob-
served 3-fold increase. In order to account for the
strong increase in pyrene, other reaction pathways
thus need to be considered, such as biaryl addition
with isomerization [11,27–29] or addition reactions
involving the cyclopentadiene moiety [10].
Regarding the formation of tar (Fig. 7), there
appears to be either large uncertainty in the data or
some contrasting trends as methane is added. The
global trend is nonetheless an increase, consistent
with the chromatographable PAH. For means of com-
parison, we have included the trend of the estimated
total measured PAH mass obtained by chromatogra-
phy and by assuming a response factor of unity for all
FID unidentified peaks. A similar curve, but with the
C12 and lighter species removed, is also shown.
These lighter species evaporate during the weighting
and are not accounted for in the tar [17]. The large
difference between the tar and GC-PAH curves
shows that there remains a large portion of unre-
solved soot-precursor matter, much as observed in
premixed flame [30] and flow-reactor studies [31].
Optical analysis [32] reveals this matter to contain a
significant fraction of aliphatic structures. This matter
is therefore not presently taken into account in cur-
rent soot-precursor models that consider only con-
densed PAH.
Despite the large increase in tar and PAH, there is
no observed enhanced soot formation. This result
contrasts with previous experiments that used n-hep-
tane instead of ethylene [17], which gave a 2-fold
increase in soot production at ␤ ⫽ 0.1. While the
exact reason for these differences has not yet been
assessed with certainty, we speculate that they orig-
inate from changes in soot induction times that are
affected by residual oxygen from the oxidative re-
gion. The amount of this oxygen (under 500 ppmv)
and the impact of methane on this quantity vary with
the initial fuel type. In addition, the oxidative chem-
istry is fast, and the conditions under which it occurs
255
Fig. 8. Laminar, co-flow diffusion-flame maximum temper-
ature and soot-volume fraction along the center-line axis as
a function of the mixture parameter ␤.
are not well-controlled, as it takes place before en-
trance of the gases into the test section. A more
thorough investigation would require gathering soot-
concentration profiles along the reactor axes under all
conditions. While the present data show no increase
in soot, they show no decrease either, a fact that
would be anticipated by mere observation of acety-
lene and hydrogen concentration changes. This result
suggests that soot growth under the observed condi-
tions occurs from the combination of enhanced in-
ception and PAH surface addition, compensated by
reduced acetylene surface addition.
To conclude this section, these flow-reactor data
have confirmed earlier results, in which methane was
mixed with n-heptane [17] at a fixed ␤ of 0.1. Here,
with mixtures of C2H4 and CH4, we observe again
that increasing the proportion of methane, with 0 ⬍ ␤
⬍ 0.5 at constant carbon content, generates a pro-
nounced increase in the formation of aromatic spe-
cies. The data are rich in information for testing
PAH-formation pathways. They show that the forma-
tion of PAH up to at least 4 aromatic rings is not
always dominated by acetylene addition.
Having assessed these effects in ideal flow-reactor
conditions, we next investigate their relevance to
practical flame conditions.
3.2. Diffusion-flame results
The laminar, co-flow, diffusion-flame system rep-
resents a system of more practical relevance than the
flow reactor. The parameter of prime interest is the
maximum soot-volume fraction, which is shown in
Fig. 8 as a function of ␤. An overall maximum is
reached at ␤ ⫽ 0.4. This variation in soot loading is
observed to have the reverse effect on the maximum
256 J.F. Roesler et al. / Combustion and Flame 134 (2003) 249 –260

Fig. 9. Laminar, co-flow diffusion-flame maximum species Fig. 10. Laminar, co-flow diffusion-flame species maximum
concentrations along the center-line axis as a function of the concentrations along the center-line axis as a function of the
mixture parameter ␤: C2H2, CH4, and C3H4. Lines are curve mixture parameter ␤: C6H6, C7H8, and C8H6. Lines are
fits of data. curve fits of data.

measured temperatures, also shown in Fig. 8. As the

species and soot are then also promoted (see Fig. 8,
soot loading increases, the temperature decreases due
Fig. 10, and Fig. 11).
to thermal radiation losses. The results further suggest that acetylene addition
The soot profile shows the existence of a syner- to phenylacetylene is neither the only nor the domi-
gistic effect of methane, in the sense that for ␤ ⬍ 0.6, nant pathway for the production of naphthalene. As ␤
the values reached exceed those of either the diluted increases, we see that all even-carbon-numbered spe-
ethylene flame or the methane flame. As discussed cies have decreasing concentrations, and that species
below, this synergistic effect is at least partly attrib- requiring an obviously direct addition of acetylene
utable to chemical factors that are similar to those for their production have decreasing concentrations
observed in the flow reactor. Measurements were also
made in similar flames without any nitrogen dilution,
and in that case, the soot-volume fractions decreased
monotonically from the neat ethylene flame to the
neat methane flame. However, the soot-volume frac-
tions in the intermediate flames were still larger than
the weighted contribution of the neat flames. This
result suggests that the same synergistic effects were
present but were outweighed by: 1) the decrease in
flame temperature as methane was added; and 2) the
very large difference in the sooting tendency of the
two fuels.
We now look at species concentration variations
with ␤. The maximum center-line acetylene concen-
trations decrease as methane is added, as shown in
Fig. 9, because the ethylene is being replaced by a
fuel that forms acetylene less readily. In contrast, the
C3H4 concentrations increase, because the increase in
methane is proportionately larger than the decrease in
acetylene. The benzene concentrations also increase Fig. 11. Laminar, co-flow diffusion-flame species maximum
(see Fig. 10), which shows the importance of propar- concentrations along the center-line axis as a function of the
gyl radicals as benzene precursors, just as in the mixture parameter ␤: C10H8 and C12H8. Lines are curve fits
flow-reactor results. The growth of larger aromatic of data.
 J.F. Roesler et al. / Combustion and Flame 134 (2003) 249 –260
Fig. 12. Laminar, co-flow diffusion-flame species maximum
concentrations along the center-line axis as a function of the
mixture parameter ␤: C4H4, C4H2, and C10H6. Lines are
curve fits of data.
relative to their parent aromatic. Indeed, phenylac-
etylene and phenyldiacetylene (C10H6 in Fig. 13)
decrease relative to benzene, and acenaphthylene de-
creases relative to naphthalene. Thus, the HACA
mechanism may not be able to fully explain the
increasing naphthalene. Analogously, neither can the
reaction of vinylacetylene addition to phenyl that was
recently suggested and incorporated in a detailed
reaction mechanism by Appel et al. [6].
Fig. 13. Laminar, premixed flame species-concentration
profiles: C7H16 and C2H4. Lines are curve fits of data. Flame
1: without CH4; flame 2: with CH4.
257
In an earlier study, some of the current authors
have shown that propargyl addition to benzyl is a
viable channel toward naphthalene production [19].
Here, this channel could well explain the observed
growth in naphthalene, since toluene concentrations
(Fig. 10) remain relatively flat, while C3H4 concen-
trations increase up to values of ␤ ⫽ 0.6. These two
species should be indicative of the relative amounts
of benzyl and propargyl. It is not clear, however, why
the toluene profile is so flat. This contrasts strongly
from the flow-reactor data, in which toluene displays
the strongest increase of all aromatic species and
illustrates that kinetic interpretation from these dif-
fusion flames is rather speculative and needs the
support of detailed, kinetic modeling or of other re-
active systems.
Finally, while the cyclopentadienyl pathway
[10,12] may exist, the concentration of cyclopenta-
diene decreases monotonically by a factor 4 as ␤
increases. Such a trend tends to discredit the rele-
vance of the above pathway in these co-flow diffu-
sion flames and corroborates the observations of
McEnally and Pfefferle [19].
In summary, the results show that adding methane
to ethylene diffusion flames promotes soot formation
via a synergistic, chemical mechanism that is similar
to the one observed in the flow-reactor experiments.
The results also confirm the need to consider PAH
growth pathways that include odd-carbon-numbered
species.
3.3. Premixed-flame results
The premixed-flame experiments investigated two
mixture conditions, one with pure n-heptane as fuel
(␤ ⫽ 0), and the other consisting of a mixture of
n-heptane and methane, with ␤ ⫽ 0.1. The choice of
these conditions was motivated by earlier flow-reac-
tor experiments with n-heptane [17]. The fact that
ethylene is not used is a secondary consideration, as
the present study aims at identifying the role of meth-
ane in various combustion configurations. Further-
more, the chemistry in premixed flames is such that
n-heptane is rapidly consumed in the low-tempera-
ture region to form predominantly ethylene. This is
observed in Fig. 13, which shows the rapid conver-
sion of n-heptane into ethylene under both flame
conditions. Although not measured specifically for
these flames, previous studies [22] indicate that the
temperature profile should reach a maximum at the
point of ethylene disappearance, i.e., at 4 mm down-
stream from the burner.
The soot measurements, extending to 20 mm
down-stream from the burner, are given in Fig. 14.
Overall, we see that there is a negligible effect of the
presence of methane on the production of soot. Ob-
258 J.F. Roesler et al. / Combustion and Flame 134 (2003) 249 –260
Fig. 14. Laminar, premixed flame soot-volume fractions.
Lines are curve fits of data. Flame 1: without CH4; flame 2:
with CH4.
servation of the measured intermediate gas-phase
species shows that the concentration profiles of H2
and C2H2 are nearly unchanged by the presence of
methane. The final concentration of H2 is, however,
slightly higher in flame 2 as would be expected, since
the C/O is preserved but the C/H ratio decreases.
Figure 15 shows the profiles of methane and benzene.
The methane in flame 2 generates a perturbation only
in the low-temperature regions of the flame. Eventu-
ally, oxidation reduces the methane concentration to
nearly the same value as in flame 1. Although the
Fig. 15. Laminar, premixed flame species-concentration
profiles: CH4 and C6H6. Lines are curve fits of data. Flame
1: without CH4; flame 2: with CH4.
methane concentration in flame 2 is considerably
enhanced in the early flame region, the concentration
of propyne is actually slightly reduced. This is ex-
plained by modeling analysis that shows propyne to
derive predominantly from the decomposition of n-
heptane in this region. As a consequence, contrary to
the diffusion-flame and flow-reactor results, the ad-
dition of methane slightly reduces the concentration
of benzene. Since the post-flame reaction paths are
similar, no large change in other aromatic species or
soot concentrations are expected.
The results relate well to experimental observa-
tions discussed by Glassman [33], which showed
sooting limits in premixed flames at a fixed adiabatic
temperature to be more related to the number of C-C
bonds than to the fuel structure. This conclusion was
explained by the fact that much of the fuel charac-
teristics are destroyed in the oxidizing region before
the sooting region. Harris and Weiner [34] also
reached a similar conclusion regarding the minor role
of fuel structure in premixed flames, provided the
C/H ratio does not change significantly. For the
present data, where the C/O ratios remain close to
those of the sooting limits and the C/H ratio changes
little, the same reasoning can be applied to explain
the weak effect of methane substitution. A more
distinct effect may possibly have been observed for
mixtures at higher values of ␤, in which case, less-
diluted flames or the use of Ar for dilution would be
required for stabilization purposes. Here, we focused
on realistic fuel/air flames for practical consider-
ations. Within stability limits of these flames, no
enhanced sooting or aromatic-species production was
observed.
4. Summary and conclusions
The effect of methane content on the formation of
PAH and soot production in a non-aromatic fuel
mixture was investigated in three fundamental com-
bustion processes, including a laminar flow reactor, a
laminar co-flow diffusion-flame burner, and a lami-
nar, premixed flame burner. The results varied sig-
nificantly with the combustion system used.
In the flow reactor, increasing the content of
methane at constant carbon content showed PAH
concentrations to increase. This increase reached a
factor 2.5 within the range of conditions observed
and could have possibly been larger at still higher
methane contents. The total mass of heavy hydrocar-
bons, or tar, also rose, while the soot concentration
stayed constant.
In the diffusion flames, increasing the methane
fraction of fuel carbon while decreasing that of eth-
ylene also generated increases in PAH concentration
 J.F. Roesler et al. / Combustion and Flame 134 (2003) 249 –260
and soot, if the ethylene was nitrogen-diluted, that
could be attributed to synergistic chemical effects. If
the ethylene was not diluted with nitrogen, then the
soot concentrations decreased monotonically, but
synergistic effects were still evident.
In contrast to the other two systems, the pre-
mixed flame results showed no synergy in the pres-
ence of methane. The maximum amount of methane
that could be used and the maximum attainable
equivalence ratio were limited, due to flame instabil-
ities. For the conditions attained, the detailed flame
structures suggested that the methane contained in
the fuel was primarily consumed by the oxygen,
leading to a virtually unperturbed flame in the PAH
and soot-growth regions.
The synergy of methane with other alkanes to
produce PAH is attributable to the ability of methane
to produce methyl radicals that will then promote
production channels of aromatics that rely on odd-
carbon-numbered species. This is clearly the case for
benzene that is formed from the propargyl recombi-
nation reaction. As for further aromatic growth, the
HACA mechanism could merely be enhanced by the
increased formation of benzene. However, the data
strongly suggest otherwise. Indeed, in conjunction
with decreasing acetylene concentrations, the acety-
lenated or cyclopenta fused aromatics, which require
direct addition of acetylene, show lesser growth than
aromatics for which various growth channels involv-
ing odd-carbon-numbered species have been specu-
lated in the literature. This is the case for naphtha-
lene, for which proposed production channels have
been the recombination of cyclopentadienyl radicals
and the addition of benzyl and propargyl. Regarding
soot, the synergy must arise from the enhanced PAH
that act either as precursors or surface growth species
in reactions that compensate for the lesser growth by
acetylene addition.
These results show the complexity of PAH chem-
istry and the important role of methyl radicals and of
odd-carbon-numbered species in the growth process.
These data should provide a good basis for testing
detailed reaction mechanisms by specifically sensi-
tizing the reactions with odd-carbon-numbered spe-
cies. Clearly, the HACA mechanism does not fully
describe the molecular growth process in many ap-
plications.
From a practical point, the results suggest that
methane is not an actual soot promoter in flame
situations. However, it does interact synergistically
with alkane fuels to produce more PAH and soot than
would otherwise have been expected. Finally, these
effects of methane are more likely to occur in diffu-
sion flames than in premixed flames.
259
Acknowledgments
Co-authors C.S. McEnally and L.D. Pfefferle
gratefully acknowledge financial support from the
National Science Foundation and the US Environ-
mental Protection Agency.
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