Effects of Oxygen on Soot Formation in Methane, Propane,

and n-Butane Diffusion Flames

6MER L. GtiLDER
National Research Council of Canada, Combustion Technology, IERT, Building M-9, Ottawa,
Ontario KlA OR6, Canada

Gverventilated coflow axisymmetric laminar diffusion flames of methane, propane, and n-butane were used
to study the influence of oxygen addition to the fuel side on soot formation. The line-of-sight soot volume
fractions and the visible flame profiles were measured as a function of axial location along the centerlines of
pure fuel flames, and the flames in which the fuel was diluted either with oxygen or nitrogen at selected
temperatures of the reactants, to maintain a constant adiabatic flame temperature. The relative influences of
dilution and direct chemical interaction effects of oxygen in the fuel gas mixture were quantified. It was
found that, when allowance was made for the influence of dilution and thermal effects, the addition of
oxygen to the methane diffusion flame chemically suppressed soot formation. This suppression was argued to
be due to the reduction in acetylene concentration in the pyrolysis products as the oxygen mole fraction in
methane was increased. The chemical influence of oxygen addition to methane decreased when the adiabatic
flame temperature was decreased by decreasing the temperature of the reactants. In propane and n-butane
flames, on the other hand, oxygen addition chemically enhanced soot formation. The degree of enhancement
was small for low mole fractions of oxygen, but increased with increasing oxygen. When oxygen is added to
the fuel side of a diffusion flame, two counteracting chemical effects are expected: Oxygen promotes fuel
pyrolysis and hence production of hydrocarbon radicals and H atoms which enhance soot formation. On the
other hand, aromatic radicals and critical aliphatic hydrocarbon radicals are removed by reactions with
molecular oxygen and oxygen atom. The net chemical influence is the difference of these two counteracting
effects.

INTRODUCTION formation. Wright [8] and Hura and Glassman

There is a growing interest in oxygen enrich-
ment applied to natural gas fired industrial
furnaces for the purpose of increasing the heat
flux from the flame. Adding oxygen to the air
stream or to the fuel stream, while keeping the
air-to-fuel ratio constant, elevates the combus-
tion temperature, and consequently, increases
the heat flux. Oxygen enrichment of the intake
air of internal combustion engines has also
been considered for a long time as a measure
to control exhaust pollutants (especially partic-
ulate emissions from diesel engines) and to
improve thermal efficiency [l, 21. A basic un-
derstanding of the role of oxygen addition to
diffusion flames has, therefore, some practical
implications.
Since the first observation of the presence of
small percentages of oxygen inside the flame
cone of a pure methane diffusion flame [3],
there have been several studies devoted to
deciphering the role of oxygen in soot produc-
tion and oxidation in diffusion flames of vari-
ous hydrocarbons. The addition of oxygen to
acetylene [4] and ethylene [5-121 enhances soot
OOlO-2180/95/$0.00
SSDI OOlO-2180(94)00217-G
[lo] observed an increase in soot upon oxy-
gen addition to propylene diffusion flames, al-
though Jones and Rosenfield [7] reported a
decreased rate of soot formation. Hura and
Glassman [lo] found that the presence of small
amounts of oxygen in ethylene causes a sub-
stantial increase in the radical pool (primarily
H atom) and, subsequently, increases the py-
rolysis rate over a wide range of temperatures.
This effect was found to be very weak in
the temperature range of interest in propane
flames which suggests that oxygen addition does
not have any significant catalytic effect on the
pyrolysis of alkanes [lo]. The observed sup-
pressive effect, when oxygen is added to pro-
pane and isobutane, was entirely attributed to
dilution [ll]. Wey et al. [131 observed a signifi-
cant increase in soot concentrations upon oxy-
gen addition to propane in an underventilated
Wolfhard-Parker diffusion burner flame. The
measured increase was much larger than that
would be expected due to an increase in flame
temperature resulting from oxygen addition
[13]. The findings of Du et al. [12] contrast
conclusions of Refs. 10 and 13. In a counter-
COMBUSTIONAND FLAME 101: 302-310 (1995)
Copyright 0 1995 by The Government of Canada
Published by Elsevier Science Inc.
EFFECTS OF OXYGEN ON SOOT FORMATION
flow diffusion flame, when allowance was made
for the dilution effect, oxygen addition (up
to 30%) to propane resulted in a significant
chemical suppressive effect on soot formation
[121. Oxygen addition caused the promotion of
soot formation as the oxygen mole fraction
approached 40% in the fuel gas mixture [121.
The other investigators reported very small
changes in soot formation with oxygen addition
to propane [6-8, 101.
In a near-sooting ethylene inverse diffusion
flame, Sidebotham and Glassman [14] observed
a shift towards species associated with oxida-
tion rather than an increase in the pyrolysis
intermediates, when oxygen was added to the
fuel side. They concluded that oxygen addition
does not enhance the ethylene pyrolysis rate
[14], and the enhancement of soot formation is
not due to an earlier transition to soot incep-
tion.
There is no study on the influence of oxygen
addition to methane in diffusion flames, except
the work reported by Saito et al. [15, 161 in
which the maximum oxygen mole fraction in
the fuel gas mixture was 0.045. Their results
indicated that the small percentages of oxygen
present in the pure methane diffusion flame do
not affect either the pyrolysis of the methane
or subsequent reactions leading to formation
of soot [151.
The objective of the present work was to
investigate the effects (thermal, dilution and
chemical) of oxygen addition on soot forma-
tion in overventilated coflow laminar diffusion
flames of methane, propane, and butane. The
emphasis was on methane, since no data exists
in the literature for oxygen mole fractions
higher than 0.045 in the fuel gas mixture. One
of the aims was to resolve the controversy
about the effect of oxygen addition to propane
on soot formation. Using the techniques em-
ployed previously [12, 17-191, the relative in-
fluences of dilution, thermal, and direct chemi-
cal interaction effects, as a result of oxygen
addition, on soot formation were quantified.
METHODOLOGY
When a gaseous diluent or additive is added to
the fuel side of a diffusion flame, one can
expect the influence of three potential effects
303
on soot formation [12, 191: (i) a dilution effect
resulting from the change in the amount of
carbon per unit mass of the fuel gas mixture,
(ii> a thermal effect due to a change in the
flame temperature field upon diluent addition,
and (iii) a direct chemical interaction (exclud-
ing the changes in chemical reaction rates as a
result of a change in temperature) due to
changes in species concentrations.
To assess the relative influences of the ther-
mal, concentration, and chemical effects of
gaseous additives on soot formation, the fol-
lowing parameters in the diluted and the undi-
luted flames should be taken into considera-
tion: the characteristic flame temperatures,
residence times, the flame diameters, and fuel
and oxidant mole fractions. In diffusion flames
of methane, propane, and butane, flame tem-
peratures are expected to change substantially
upon oxygen addition to fuel side. The adia-
batic flame temperature was taken as the indi-
cator of the temperature field of the low-
er regions of the flame where soot inception
and nucleation occur. The use of the adiabatic
flame temperature as the characteristic flame
temperature is justifiable, as discussed by Go-
mez and Glassman [20] and Axelbaum and
Law 1211.
The evidence for the correlation between
adiabatic flame temperatures and the mea-
sured temperatures in oxygen-added flames are
illustrated in Figs. 1 and 2. In these figures, the
symbols are experimental measurements and
the dashed lines represent the best fits ob-
tained by least squares. Figure 1 shows the
relationship between uncorrected thermocou-
ple measurements in a Wolfhard-Parker dif-
fusion burner and the adiabatic flame temper-
atures with various oxygen mole fractions Xo,
in ethylene [51. In ethylene and propane flames,
there is an almost perfect correlation between
measured maximum flame temperatures in a
counterflow diffusion flame and the adiabatic
flame temperatures at various oxygen concen-
trations Yo, in oxygen-enriched air [22] (Fig.
2). Also, the peak temperature increase in the
counterflow diffusion flames of ethylene, pro-
pane, and n-butane upon 10% oxygen addition
to fuel side were 29, 17, and 11 K, respectively
1101; Corresponding increases in calculated
adiabatic flame temperatures are 28, 17, and
304 b. L. GtiLDER

flame temperatures were quoted as 18 and 40

K, respectively [13].
In order to compensate for the thermal ef-
fect of oxygen addition to the fuel, the adia-
.A*
.’
.’
batic flame temperatures were kept constant
A.’ /ao.35
.’ /’ by changing the temperatures of the reactants.
.’ /
.’
/ 0.3 Thus, the observed changes upon oxygen addi-
.a’/ rJ /’
.’
.’ //0.22 tion would be only due to dilution and the
.’ /’
a
o/’ direct chemical interaction of oxygen. A sum-
,‘0.12
/’ mary of experimental conditions is tabulated in
/’ Wolfhard-Parker burner -
?? xo*=o
Fuel: Ethylene/Oxygen
5mm Above the Burner Exit
Tables l-4.
To determine the influence of dilution alone,
1 fuels were diluted with nitrogen while keep-
2400 2450 2500 2550
ing the adiabatic flame temperature fixed by
Adiabatic Flame Temperature, K
changing the temperatures of the reactants
Fig. 1. Correlation between thermocouple measurements
(Tables 1-4). The difference between the oxy-
in a Wolfhard-Parker diffusion burner and the calculated
adiabatic flame temperatures with various oxygen mole gen diluted and nitrogen diluted flames, at the
fractions in ethylene. X0* is the oxygen mole fraction in same adiabatic flame temperature, would give
the fuel stream. Dimensions in the legend box denote the the chemical influence of the oxygen on soot.
measurement locations with respect to the flame sheet. The dilution effects of nitrogen and oxygen
Experimental data, shown by symbols, are from
were considered equal for identical adiabatic
Chakraborty and Long [5].
flame temperatures and additive fractions, be-
cause both gases have similar transport proper-
12 K, respectively. Further, in the experiments ties.
of Wey et al. [13], the increases in the maxi- The line-of-sight average light extinction and
mum flame temperature were about 25 and 50 the flame diameter were measured, as a func-
K for 10 and 20% oxygen mole fraction, re- tion of the axial position, along the centerlines
spectively, in propane diffusion flames; corre- of methane, propane, and n-butane flames.
sponding increases in calculated adiabatic The fuel flow rates were 365, 119, and 81
ml/min, respectively, under all conditions
2200 2300
studied in this work.
Counterflow Diffusion Flame
,,90.28
; 2100 Yo> = Oxygen index of air 2200 ;
,I TABLE 1
I
a a
5 0.24 9”’ Summary of Experimental Conditions and Results
E 2000 #’ 2100 f
-,/
of Oxygen and Nitrogen Addition to Methane’
f 0.22,4 F
,,A 0.28 Oxygen Addition Nitrogen Addition
; 1900 /’ ,c 2000 ;
._ ._ (Tad = 2400 K) (Tad = 2400 K)
: : i”, (K) XN, F,
$ 1800 1900 T, (K) Xo, F,
i 670 0. 1. 670 0. 1.
I I 0.025 0.9 688 0.1 0.89
I 1700 1900 I 650
633 0.05 0.81 700 0.15 0.85
612 0.075 0.75 712 0.2 0.8
160 700 590 0.1 0.76
8 I 2200 2300 2400 2500 2600 2 b
Adiabatic Flame Temperature, K 565 0.125 0.66b
528 0.16 0.62’
Fig. 2. The relationship between measured maximum flame
temperatures in a counterflow diffusion flame and the “X0, and XN2 are the mole fractions of oxygen and
calculated adiabatic flame temperatures with various oxy- nitrogen in the fuel gas mixture, respectively, E is the
gen concentrations in the oxidizer stream. Yo, is the normalized maximum soot volume fraction, Tad is the
oxygen mole fraction in the oxidizer stream (oxygen index calculated adiabatic flame temperature, and T, is the tem-
of air). Experimental data, shown by symbols, are from perature of the reactants.
Vandsburger et al. [22]. b Corrected for residence time change.
EFFECTS OF OXYGEN ON SOOT FORMATION 305

A schematic of the burner assembly is shown

TABLE 2 in Fig. 3. The fuel nozzle of the burner is a
Summary of Experimental Conditions and Results stainless-steel pipe of 12.7 mm inner diameter.
of Oxygen and Nitrogen Addition to Methane” Air is supplied from a concentric converging
Oxygen Addition Nitrogen Addition
nozzle of 100 mm inner diameter. Both the air
CT,, = 2300 K) (Tad = 2300 K) and fuel streams are heated by regulated elec-
tric heaters. Temperatures of the reactants
r,(K) X0, F, T, (K) XNZ F,
were monitored by thermocouples near the
450 0. 1. 450 0. 1. exit of the fuel and air nozzles, and kept within
430 0.025 0.935 461 0.05 0.94 +2 K of the desired reactant temperature.
410 0.05 0.87 472 0.1 0.9
388 0.075 0.82 487 0.16 0.85
The fuel and the oxygen flow rates were mon-
363 0.1 0.78’ 499 0.2 0.81 itored by calibrated rotameters. The air, be-
336 0.125 0.756 531 0.3 0.71 fore exiting from the converging nozzle, passed
295 0.16 0.72’ through a bed of glass beads and a set of
a See footnote of Table 1. wire-mesh screens to prevent flame instabili-
’ Corrected for residence time change. ties. A flame enclosure made of flexible steel
mesh with appropriate holes protects the flame
from air movements in the room while provid-
TABLE 3 ing optical access. The burner assembly sits on
Summary of Experimental Conditions and Results a positioning platform with accurate vertical
of Oxygen and Nitrogen Addition to Propane” and horizontal movement capability.
The line-of-sight average soot volume frac-
Oxygen Addition Nitrogen Addition
(Tad = 2400 K) (Tad = 2400 K) tions along the centerline of the flames were
measured by the transmission of an Ar-ion
T, (K) X0, F, T, (K) XNz E
(5 14.5 nm) laser beam. The visible flame di-
592 0. 1. 592 0. 1. ameter was measured by a reading telescope
576 0.05 0.98 600 0.1 0.89 with an eyepiece. Typical flame diameters over
558 0.1 0.956 610 0.2 0.8
516 0.2 0.92’ 623 0.3 0.71
the lower half of the flames were around 5-10
457 0.3 0.96 641 0.4 0.61 mm. Each division of the scale on the eyepiece
371 0.4 0.89b 664 0.5 0.48 corresponds to 0.125 mm. The repeatability
300 0.46 0.9b and the reproducability of the flame diameter
‘See footnote of Table 1.
’ Corrected for residence time change.

Laminar i :Flexible steel

diffusion :mesh screen
TABLE 4 flame ----A_+ p
Summary of Experimental Conditions and Results
Air nozzle
of Oxygen and Nitrogen Addition to n-Butane’

Oxygen Addition Nitrogen Addition

(Tad = 2400 K) (T,, = 2400 K)

r,(K) Xo, F, T, (K) XN, c

586 0. 1. 586 0. 1.
574 0.05 0.97 592 0.1 0.9
561 0.1 0.946 600 0.2 0.81
528 0.2 0.91b 611 0.3 0.7
484 0.3 0.886 625 0.4 0.59
422 0.4 0.96 643 0.5 0.5
300 0.515 0.946

’ See footnote of Table 1. Heated Fuel (t N 2 or 02) line

b Corrected for residence time change. Fig. 3. Schematic diagram of the diffusion flame burner
assembly.
306
measurements were within f 1 scale division.
The soot volume fraction F then can be calcu-
lated assuming Rayleigh extinction. The com-
plex refractive index of the soot particles was
taken as m = 1.89-0.48i, from Lee and Tien
[23], to be consistent with our previous soot
work. A schematic of the experimental rig was
reported previously [24].
RESULTS AND DISCUSSION
Methane
In order to assess the effect of the flame
temperature on soot formation in methane
flames, soot profiles were measured in pure
methane flames in which the adiabatic flame
temperature was changed from 2400 to 2228 K
by changing the temperature of the reactants
(Fig. 4).
Axelbaum et al. [17] and Axelbaum and Law
[21] and our previous work [18, 191 showed that
soot formation rate in diffusion flames is first
order in fuel mole fraction in the fuel gas
mixture, when the remainder of the fuel gas is
an inert diluent like nitrogen. It was further
demonstrated [18, 191 that maximum soot vol-
ume fraction in coflow diffusion flames scales
as follows:
Frn -xF,O . 7. exp( -E,/RT,J
1.4 -
METHANE
: 365mVmin
1.2 -
E
0 10 20 30 40 50 60
Height Above the Burner, mm
Fig. 4. The line-of-sight average soot volume fraction pro-
files, as a function of axial position, of methane flames
with different temperatures of the reactants. Correspond-
ing adiabatic flame temperatures are noted near the best
fit curves to the soot data points. For clarity, data for
Tad = 623 K are not shown.
6. L. GULDER
where X,,. is the mole fraction of fuel in the
fuel gas mixture, r is the characteristic resi-
dence time, E, is the activation energy, and
Tad is the adiabatic flame temperature. The
activation energy inferred from the experimen-
tal data was 200 kJ/mol [18, 193 for C, and
higher carbon number hydrocarbons.
The maximum soot volume fractions from
the soot profiles in Fig. 4 are plotted in Fig. 5
against the inverse of the Tad. The characteris-
tic residence time was taken as the square root
of the distance from the axial point of the first
appearance of soot to the axial location where
the maximum soot volume fraction is mea-
sured. In accordance with Eq. 1, the slope of
the best fit line in Fig. 5 yields an overall
activation energy of about 200 kJ/mol.
The variation of the soot volume fraction
profile with oxygen and nitrogen in methane
flames with Tad = 2400 K are shown in Figs. 6
and 7, respectively. Since the adiabatic flame
temperature is kept constant by changing the
temperature of the reactants, the observed ef-
fect in Fig. 7 is due to dilution only, whereas in
Fig. 6 it is due to combined effects of dilution
and direct chemical interaction of oxygen. The
normalized soot volume fractions for these two
sets of experiments, as summarized in Table 1,
are plotted together in Fig. 8. The maximum
(1) soot volume fractions of methane flames with
lo%, 12.5%, and 16% oxygen were corrected
for the changes in residence times in these
flames. Uncorrected values are also shown in
Fig. 8 with empty circle symbols. Nitrogen-di-
luted flames did not show any change in flame
heights or diameters with nitrogen fraction.
The reduction in maximum soot volume frac-
tion due to oxygen addition is more than that
can be attributed to the dilution effect, Fig. 8.
Oxygen addition to methane seems to chemi-
cally suppress the soot formation. The suppres-
sion effect is significant even with the small
fractions of oxygen in methane. This observa-
tion does not agree with the results of Saito
70 et al. [15, 161 who reported no effects of small
oxygen mole fractions (up to 0.045) in the
methane stream.
When oxygen is added to the fuel side of a
diffusion flame two counteracting chemical ef-
fects can be expected as far as the soot forma-
tion is concerned. Due to an accelerated chain
EFFECTS OF OXYGEN ON SOOT FORMATION

I / I

METHANE
METHANE
365 ml I min 1.6
365 ml / min

1.4 - T,,=2400K
E
g 1.2 -
s
‘S
1.0 -
?

i 0.8 -

0.6

0.4

0.2

4.1 4.2 4.3 4.4 4.5 0.0

(1 I Tad) 104, K-’
Height Above the Burner, mm
Fig. 5. The Arrhenius plot of the normalized maximum Fig. 7. The line-of-sight average soot volume fraction pro-
soot volume fractions versus the inverse of the adiabatic files, as a function of axial position, of methane flames at
flame temperature. selected temperatures of the reactants and nitrogen mole
fractions correspondmg to Tad = 2400 K.

branching, the oxygen added to the fuel side

promotes the pyrolysis of the fuel [25, 261 and
hence production of hydrocarbon radicals and
H atoms which enhance soot formation. On
the other hand, aromatic radicals and critical
aliphatic hydrocarbon radicals, like C,H, and
C,H,, are removed by reactions with molecu-
lar oxygen 1271 and oxygen atoms. The net
chemical influence is, then, the difference of
these two counteracting effects. The present
results indicate that the net chemical influence
of oxygen is suppressive in methane which has
a unique sooting behaviour quite different from
other alkanes [lo].
In the pyrolysis of pure methane, acetylene
is one of the major intermediates 1251. When
oxygen is added to methane (i.e., a rich pre-
mixed flame), the computed profile of H atoms
is higher than that calculated for pyrolysis, but

l.lr,, ,I,, ,I, ,1,,, ,a ,I, ,-

METHANE, 365 ml / min

0.8 -

0.8 -

0.4 -

0.2
F

-._
“”
0 10 20 30 40 50
Height Above the Burner, mm
0.00 0.05 0.10 0.15 0.20 0.25
Fig. 6. The line-of-sight average soot volume fraction pro-
Mole Fraction of Additive, XNz and X0
files, as a function of axial position, of methane flames at
selected temperatures of the reactants and oxygen mole Fig. 8. The variation of the isolated dilution add chemical
fractrons correspondmg to r,,, = 2400 K. effects of oxygen addition to methane, Tad = 2400 K.
308 6. L. GULDER

acetylene is no longer one of the important 1.1 .,.,,.,..,....,,..,,,,.,,,,,.I,,,,

intermediate species [2.5]. Acetylene is formed c PROPANE, 119 ml I min T& = 2400 K
.=
5 1.0
from vinyl and its consumption in methane e
L
oxidation is by OH, H, and predominantly by E 0.9
0 atoms [28, 291. A higher concentration of 2
> 0.6
H atoms (as compared with those of pure
g
methane pyrolysis), and the presence of OH ‘: 0.7
and 0 in oxygen-added methane diffusion i
flames, result in a lower acetylene concentra- ‘# 0.6
I
tion. If it is assumed that the soot formation 3.;N 0.5
mechanism is mainly controlled by a radical-
g
based acetylenic addition route leading to the 5 0.4
z
chemical growth of PAHs, then the reduction / J
V.”

in the acetylene concentration, as a result of 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
Mole Fraction oi Additive, XNz and X0
oxygen addition to methane, could be one of
the possible causes of the chemical suppres- Fig. 10. The variation of the isolated dilution kd chemical
sion of soot formation. effects of oxygen addition to propane, Tad = 2400 K.

The influence of oxygen at a lower adiabatic

flame temperature, Tad= 2300 K, is shown in
Fig. 9 (conditions are summarized in Table 2).
At a lower flame temperature, the chemical
suppressive effect of oxygen is clearly weaker.
Propane and Butane
Using the same technique employed for meth-
ane flames, relative influences of dilution and
direct chemical interaction effects of oxygen
addition to propane and butane were quanti-
fied as shown in Figs. 10 and 11 (Tables 3 and
4, respectively). When allowance is made for
the dilution effect, oxygen addition to propane
and butane enhances the soot formation chem-
ically, although the degree of enhancement is
small at low oxygen mole fractions in the fuel
gas mixture.
This observation for propane does not agree
with the results of [12] which showed a signifi-
cant chemical suppressive effect of oxygen ad-
dition (up to 30% oxygen mole fraction) on
soot, when allowance is made for thermal and
dilution effects. In Ref. 12 the maximum mea-
sured temperature increased 50 K (from 1990
to 2040 K) when 10% oxygen was added to
propane in a counterflow diffusion flame (mea-
sured increase was 130 K for 20% oxygen). In

1.1

1 METHANE, 365 ml I min T.,, = 2300 K j s

‘E 1.0
t?
L
8 0.9
Dilut/on Effect 1

$ 0.6

aE 0.7 -

B o.6 j
B 0.5f
p
Oxygen z 0.4 -
C$gw&correcled
P

0.4t. 0.3
0.0 0.1 0.2 0.3 0.4 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7

Mole Fraction of Additive, X,v* and X0 Mole Fraction of Additive, XNz and X0
1
Fig. 9. The variation of the isolated dilution an> chemical Fig. 11. The variation of the isolated dilution and chemical
effects of oxygen addition to methane, Tad = 2300 K. effects of oxygen addition to butane, Tad = 2400 K.
EFFECTS OF OXYGEN ON SOOT FORMATION
a similar flame [lo], on the other hand, the
corresponding increase was measured as 17 K
(from 1859 to 1876 K). The calculated adia-
batic flame temperature increase for 10% oxy-
gen addition to propane is 17 K (39 K for 20%
oxygen), which agrees with the measurements
reported in Ref. 10 but far smaller than those
in Ref. 12. Further, measurements of Wey
et al. [131 in propane diffusion flames showed
about 25 and 50 K increase for 10% and 20%
oxygen mole fractions, respectively, which agree
closely with the calculated adiabatic flame
temperature changes. The discrepancy in the
temperature increase upon oxygen addition to
propane seems to be the reason for conflict-
ing results of the present work and those of
Ref. 12.
It seems that the net balance of the two
counteracting chemical effects of oxygen ad-
dition is to enhance the soot formation in
propane and butane flames. Although it was
argued that the oxygen addition does not have
any significant catalytic effect on the pyrolysis
of propane [lo], the present results and the
results of Wey et al. 1131claim otherwise.
It should be noted that flames which contain
high percentages of oxygen in the fuel stream
may not be strictly characterized as diffusion
flames.
A final observation is that the data in Figs.
8-11, showing the behaviour of soot as a result
of nitrogen dilution, agree with the first order
dependence of soot formation on initial fuel
concentration in the fuel gas mixture, as per
Eq. 1.
CONCLUDING REMARKS
The influence of oxygen addition to the fuel
side on soot formation in overventilated ax-
isymmetric laminar diffusion flames of meth-
ane, propane, and n-butane was investigated.
The relative influences of dilution and direct
chemical interaction effects of oxygen mole
fraction in the fuel gas mixture on soot forma-
tion were quantified.
When allowance is made for the influence of
dilution and temperature, addition of oxygen
to methane chemically suppresses soot forma-
tion. This suppression was argued to be due to
the reduction in acetylene concentration in the
309
pyrolysis intermediates, as the oxygen fraction
in methane is increased. The chemical influ-
ence of oxygen addition to methane decreases
when the adiabatic flame temperature is de-
creased by decreasing the temperature of the
reactants.
For higher alkanes, propane and n-butane,
oxygen addition enhances the soot formation
by direct chemical interaction. This enhance-
ment is small for low mole fractions of oxygen,
but increases as the oxygen fraction is in-
creased. The observed chemical enhancement
of soot formation is the net balance of the two
counteracting chemical effects of oxygen addi-
tion to propane and n-butane.
I thank M. F, Baksh for his capable assistance
with the experimental work. The work described
herein has been supported by National Research
Council’s internal funds (Sub-project CSF 02)
and by the PERD Program (Project no. 15113).
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Received 21 April 1994; revised 16 August 1994