Paper # E13

Topic: Engine

5th US Combustion Meeting

Organized by the Western States Section of the Combustion Institute
and Hosted by the University of California at San Diego
March 25-28, 2007

Ignition of methane/ethane/propane mixtures at engine pressures

Viktorio Antonovski, Christopher Zinner, Alexander Barrett,
Danielle Kalitan, and Eric Petersen
Mechanical, Materials and Aerospace Engineering
University of Central Florida, Orlando, FL, USA
Abstract
Shock-tube experiments were conducted to investigate and further understand the impact of
higher-order hydrocarbons on methane-based fuels at elevated pressure. Measurements of ignition
times behind reflected shock waves were obtained for methane/ethane/propane/air mixtures; the
mixtures were methane-based (70-90% by volume), and ethane and propane were varied from 720% and 3-15%, respectively. The pressures, temperatures, and equivalence ratios varied from 1
to 58.6 atm, 1032 to 1577 K, and 0.5 to 2, respectively. The results show the effects of pressure,
temperature, stoichiometry, and hydrocarbon content on the combustion chemistry of the blends.
From the parametric analysis on the ignition data, in which equivalence ratios and mixture
compositions were varied, it was determined that hydrocarbon content has a much greater impact
on ignition delay time than does fuel mixture stoichiometry. Ignition delay time increases with
increasing equivalence ratios over a comparable range of temperatures.

1. Introduction
Because of its abundance and clean burning characteristics, natural gas is employed as a fuel
source for gas and steam turbines. In fact, the primary fuel for industrial gas turbines is natural
gas [1]. As the simplest hydrocarbon and the main constituent (about 97% by volume) of natural
gas, methane is of particular interest. In addition to methane, natural gas contains quantities of
ethane (C2H6), propane (C3H8), butane (C4H10) and other higher-order hydrocarbons in different
proportions depending on the geographic origin and purification processes. Future methanebased fuels however, may contain significant levels of these higher-order hydrocarbons.
In recent years, interest in fuel-flexible gas turbine engines has been expressed; in particular, the
level of influence varying compositions of higher-order hydrocarbons in methane-based fuel
blends exacts on combustion kinetics is desired [2]. Changes within the fuel content affect the
combustion chemistry and thus generate a dramatic impact on the existing gas turbine
combustors. These concerns are complicated by the reality that few, if any, data exist on the
fundamental effects of hydrocarbons in methane-based fuel blends at engine pressures. Of
particular interest to designers of power generation gas turbines are these effects at various
fuel/air mixture ratios, temperatures, and pressures [3].
Ignition delay time, one of the most significant combustion parameters, is heavily dependent
upon combustion chemistry. Accurate measurements of ignition delay times at typical gas
turbine pressures, temperatures, and stoichiometries could lead to improvements in efficiency
1

5th US Combustion Meeting Paper # E13

Topic: Engine

and compactness of gas turbine combustors. Ignition times are also of practical interest because
of potential autoignition in lean, premixed burner systems [2,3]. Due to the exotic nature of the
fuel blends of this work, the data generated will be used to either validate or correct present
chemical kinetics mechanisms used in estimating methane-based fuel blend ignition delay times.
The impetus of the present study was to augment the sparse body of literature available regarding
ignition delay time measurements at high pressures (>30 atm) and various hydrocarbon fuel
blends. Measurements of ignition times behind reflected shock waves were obtained for
methane/ethane/propane/air mixtures; the mixtures were methane-based (70-90% by
composition), and ethane and propane were varied from 7-20% and 3-15%, respectively.
Provided in this paper is a background describing related works, the experimental setup of this
work, and a discussion of results from data accumulated thus far.
2. Background
Some recent studies evaluating the effects of hydrocarbons on methane-based fuels using the
shock-tube technique are Bourque et al. [4], de Vries and Petersen [5], and Petersen et al. [3,6].
In Bourque et al. [4], three fuel blends with methane content varying from 62.5% to 98.1% were
evaluated analytically using a new chemical kinetics model by calculating autoignition times and
flame speeds. Targeted pressures were 10, 20, and 40 atmospheres with temperatures ranging
from 700 to 1000 Kelvins for mixtures with equivalence ratios of unity. Some important results
from their parametric study include nonlinearities in predicted ignition delay times for various
mixtures, temperatures, and pressures. The ignition activation energies of the ignition delay time
curves varied with the activation energies decreasing with lower temperature and higher
pressure. These effects were more predominant in mixtures containing greater levels of higherorder hydrocarbons.
In de Vries and Petersen [5], the autoignition behavior of undiluted, ternary methane-based
mixtures containing hydrogen and various hydrocarbons such as ethane, propane, butane, and
pentane were analyzed behind reflected shock waves. The experiments were evaluated at an
average pressure of 20 atmospheres, target temperatures near 800 Kelvins, and an equivalence
ratio of 0.5. In Petersen and coworkers [6], shock-tube experiments were performed for
methane/propane fuel mixtures in ratios varying from 90/10% to 60/40% by volume for methane
and propane, respectively. Test pressures were from 5.3 to 31.4 atmospheres with test
temperatures as low as 1042 Kelvins. Equivalence ratios were varied from 0.5 to 3. A chemical
kinetics mechanism was also presented in this work.
From these same authors [3], a study was conducted in which seven different fuel-lean fuel/air
mixtures were investigated: two methane-only blends, two methane/hydrogen blends (80/20 and
60/40), two methane/ethane blends (90/10 and 70/30) and one methane/propane blend (80/20).
The temperatures in the experiments ranged from 1090 to 2001 K, and pressures from 0.54 to
25.3 atmospheres were covered. In general, the ignition delay times decreased with increasing
hydrocarbon levels, but no significant changes in the activation energies were observed when
compared to the methane-only results. As previously delineated, shock-tube experiments had yet
to be performed using the fuel blends and test conditions described herein.

5th US Combustion Meeting Paper # E13

Topic: Engine

3. Experimental Setup
Two shock-tube facilities were employed to gather the ignition delay time data presented. The
shock tube utilized for the higher-pressure experiments has a driver section 3.5 m (10 ft) and an
internal diameter of 7.62 cm (3 in). The driven section has a length of approximately 10.7 m (35
ft) with an internal diameter of 16.2 cm (6.38 in). All experiments were performed behind
reflected shock waves, and the ignition times were monitored at the endwall. The conditions
behind the reflected shock wave were resolved from the measured incident-shock wave velocity
and standard one-dimensional shock wave relations. The reaction was monitored using a
pressure transducer and a photomultiplier tube monitoring CH* chemiluminescence, and ignition
delay times were defined using the rapid increase in the endwall pressure signal (however, for
the present conditions, both endwall pressure and emission led to similar ignition times). Either
polycarbonate or aluminum diaphragms are used to attain the reflected-shock pressures. More
specific details concerning the physical layout, auxiliary components, and diagnostics of this
shock tube are presented in Petersen et al [7].
The 1-atm experiments were performed with a shock tube that has an overall length of 6.09 m
(20 ft). The square-profiled driven section has an internal wall height of 15.24 cm (4.30 in), and
the helium-pressurized driver section is 1.83 m (6.0 ft). Polycarbonate diaphragms were used to
provide the necessary reflected-shock pressures. A series of four sequentially spaced
piezoelectric pressure transducers are used in conjunction with gating timers (Fluke PM6666) to
obtain incident shock wave velocities. From this information, shock wave equations are used to
determine conditions behind reflected shocks. More details on the UCF shock-tube facility may
be found in Rotavera et al. [8]. Further details on the measurement of ignition delay times for
undiluted fuel-air mixtures can be found in Petersen et al. [9].
Nine mixtures were studied and are listed in Table 1. The mixtures have equivalence ratios of
0.5, 1, or 2.0 with fuel blend compositions of CH4/C2H6/C3H8 in ratios of 90/7/3%, 70/15/15%,
and 70/20/10%. The mixtures were prepared in a stainless steel mixing vessel. To acquire the
correct mixing percentages, the partial pressure method was used employing Daltons law. Gas
purities were ultra high purity for N2 and O2, and research grade for CH4, C2H6, and C3H8.
Table 1: Mixtures and compositions used in the present study.
Mixture #
1
2
3
4
5
6
7
8

2
2
2
1
1
1
0.5
0.5

Fuel Blend (CH4/C2H6/C3H8)

90/7/3 %
70/15/15 %
70/20/10 %
70/20/10 %
70/15/15 %
70/20/10 %
90/7/3 %
70/15/15 %

XCH4
0.1444
0.0953
0.0971
0.0781
0.0521
0.0521
0.0411
0.0261

XC2H6
0.0113
0.0205
0.0281
0.0061
0.0111
0.0151
0.0032
0.0058

XC3H8
0.0051
0.0205
0.0141
0.0029
0.0111
0.0076
0.0015
0.0058

XO2
0.1761
0.1812
0.1806
0.1916
0.1945
0.1943
0.2001
0.2022

XN2
0.6631
0.6825
0.6801
0.7213
0.7312
0.7309
0.7541
0.7601

0.5

70/20/10 %

0.0271

0.0081

0.0041

0.2016

0.7591

5th US Combustion Meeting Paper # E13

Topic: Engine

4. Results and Discussion

Ignition delay time data of select mixtures are graphed in Figs. 1-6. These figures relate the
ignition times with the inverse of temperature. The experimental average pressures and related
temperatures are provided in each figure for each individual mixture.
In this work, the average pressures range between 1.2 and 53.4 atmospheres. Figures 1, 2, and 6
depict mixtures 1, 4, and 9, and three average pressures are shown. Figures 4 and 5 represent
mixtures 7 and 8 and are arranged into two average pressure groups. These average pressures
vary from 5.7 to 29.7 atmospheres. Figure 3 illustrates mixture 5 with the ignition delay data
grouped into 4 sets by average pressures, ranging from 1.4 to 29.9 atmospheres. Figures 7 and 8
provide an examination of the influence of stoichiometry and hydrocarbon content on the
methane-based mixtures. Figure 7 depicts mixtures 2, 5, and 8 with equivalence ratios of 2.0, 1.0,
and 0.5 for similar average pressures. Figure 8 compares the fuel lean (=0.5) mixtures 7, 8, and
9 for similar average pressures.

Ignition Times (s)

1000

100
Mixture 1
Pave=1.2 atm, T= 1322-1577 K
Pave=5.5 atm, T= 1253-1526 K
Pave=15.4 atm, T=1156-1405 K

10
6.5

7.0

7.5
4

8.0

8.5

-1

10 /T (K )
Figure 1: Ignition delay time results for mixture 1. The curves represent best fits to the data.

5th US Combustion Meeting Paper # E13

Topic: Engine

Ignition Time (s)

1000

100
Mixture 4
Pave= 28.5 atm, T= 1208-1447 K
Pave= 42.1 atm, T= 1288-1553 K
Pave= 53.4 atm, T= 1160-1270 K

10

1
6.5

7.0

7.5
4

8.0

8.5

-1

10 /T (K )
Figure 2: Ignition delay time results for mixture 4. The curves represent best fits to the data.

Ignition Times (s)

1000

100
Mixture 5
Pave= 1.4 atm, T= 1265-1413 K
Pave= 7 atm, T= 1093-1383 K
Pave= 19.7 atm, T= 1085-1327 K
Pave= 29.9 atm, T= 1065-1147 K

10
7.0

7.5

8.0

8.5
4

9.0

9.5

-1

10 /T (K )
Figure 3: Ignition delay time results for mixture 5. The curves represent best fits to the data.

5th US Combustion Meeting Paper # E13

Topic: Engine

Ignition Time (s)

1000

100
Mixture 7
Pave= 5.7 atm, T=1182-1456 K
Pave= 29.7 atm, T=1096-1355 K

10

7.0

7.5

8.0
4

8.5

9.0

-1

10 /T (K )
Figure 4: Ignition delay time results for mixture 7. The curves represent best fits to the data.

Ignition Time (s)

1000

100
Mixture 8
Pave=6.6 atm, T= 1166-1427 K
Pave=18.8 atm, T= 1060-1325 K

10

7.0

7.5

8.0
4

8.5

9.0

9.5

-1

10 /T (K )
Figure 5: Ignition delay time results for mixture 8. The curves represent best fits to the data.

5th US Combustion Meeting Paper # E13

Topic: Engine

Ignition Times (s)

1000

100
Mixture 9
Pave=1.5 atm, T= 1194-1390 K
Pave=7.1 atm, T= 1113-1384 K
Pave=18.9 atm, T= 1063-1346 K

10

7.0

7.5

8.0

8.5
4

9.0

9.5

-1

10 /T (K )

Ignition Times (s)

Figure 6: Ignition delay time results for mixture 9. The curves represent best fits to the data.

1000

Stoichiometry Comparison
Mix 2, P=17.8 atm, =2.0
Mix 5, P=19.7 atm, =1.0
Mix 8, P=18.8 atm, =0.5

100
7.0

7.5

8.0

8.5
4

9.0

9.5

10.0

10.5

-1

10 /T (K )
Figure 7: Effect of Stoichiometry for three mixtures having an identical fuel composition of
CH4/C2H6/C3H8 in ratios of 70/15/15%. Activation energies appear to increase slightly with
decreasing equivalence ratios at pressures on the order of 19 atm.

5th US Combustion Meeting Paper # E13

Topic: Engine

Ignition Times (s)

1000

100
Mixture Comparison
Mix 7, P= 5.7 atm
Mix 8, P= 6.6 atm
Mix 9, P= 7.1 atm

10

7.0

7.5

8.0
4

8.5

9.0

-1

10 /T (K )
Figure 8: Comparison of the three fuel blends of this study at pressures on the order of 6.5 atm
with fuel lean (=0.5) equivalence ratios. While the increase in heavier hydrocarbons leads to
faster ignition, there is no significant difference between the relative amounts of ethane and
propane (mixtures 8 and 9)

From the presented figures it could be stated that increases in pressure reduce ignition delay
times, as expected. The slopes of the average pressure curves indicate that the ignition activation
energies of these reactions follow a linear behavior when plotted on a log scale. The parametric
analyses in Fig. 7 implies that varying the stoichiometry of a fuel blend under the same average
pressures has no major effect on the magnitude of the ignition delay times when compared to the
effect of pressure and level of heavier hydrocarbons in the blend. Nonetheless, it can be seen that
the slopes of the curves are slightly affected by variances in equivalence ratio.
Comparing mixtures 7, 8, and 9 in Fig. 8 reveals that a greater level of similarity exists between
ignition times for mixtures 8 and 9 than between either 7 and 8 or 7 and 9. This condition is
likely attributed to the similarities in hydrocarbon composition for mixtures 8 and 9 (i.e., both
have 70% methane and 30% ethane and propane combined). As a consequence of the fact that
there is little difference in ignition delay timing for mixtures 8 and 9, and because these two
mixtures share a similarity in their concentrations of ethane and propane relative to methane, it
may be concluded that increasing hydrocarbon content leads to shorter ignition delay times at
pressures on the order of 6.5 atmospheres, although the type of heavier hydrocarbon (either C2H6
or C3H8) is not important.
Complete results and data tables will be provided in future publications.
5. Summary
Nine mixtures were tested using the shock tube methodology for the purpose of
observing the effect of hydrocarbons on methane-based fuels at higher pressures. The impetus of
8

5th US Combustion Meeting Paper # E13

Topic: Engine

this study was the lack of ignition delay time data found in the literature for methane-based
mixtures with higher-order hydrocarbons at higher pressures. The fuel blends used were
CH4/C2H6/C3H8 having percentages of 90/7/3%, 70/15/15%, and 70/20/10%. From the resulting
graphs, it was evaluated that the ignition delay times were only slightly affected by the change in
stoichiometry and that increasing pressure values and hydrocarbon composition produce smaller
ignition times.
Acknowledgments
The work herein was sponsored by Rolls-Royce Canada, with Dr. Gilles Bourque as
contract monitor. We wish to thank Mouna Lamnaouer, Shatra Reehal, Brandon Rotavera,
Christopher Aul, and Derek Lambe for their assistance in performing some of the experiments.
References
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]

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