Article

pubs.acs.org/EF

Laminar Burning Velocities of Dimethyl Carbonate with Air

Maxim E. Bardin,†,* Evgenii V. Ivanov,† Elna J. K. Nilsson,‡ Vladimir A. Vinokurov,†
and Alexander A. Konnov‡
†
Division of Physical and Colloid Chemistry, Department of Chemistry, Gubkin Russian State University of Oil and Gas, Moscow,
Russia 119991
‡
Division of Combustion Physics, Department of Physics, Lund University, 223 63 Lund, Sweden

ABSTRACT: Laminar burning velocities of dimethyl carbonate (DMC) + air flames at initial gas mixture temperatures of 298,
318, 338, and 358 K are reported. Nonstretched flames were stabilized on a perforated plate burner at atmospheric pressure, and
the laminar burning velocities were determined using the heat flux method. The overall accuracy of the burning velocities was
evaluated to be typically better than ±1 cm/s. The effects of unburned mixture temperature on the laminar burning velocity of
DMC were analyzed using the correlation SL = SL0 (Tu/Tu0)α. The present experimental results indicated that the power
exponent α reaches a minimum in slightly rich mixtures corresponding to the maximum burning velocity. Modeling of these
results has been attempted using the mechanism developed by Glaude et al. It was found that this model significantly
overpredicts laminar burning velocities of methanol, ethanol, and DMC; however, it accurately reproduces the temperature
power exponent α for dimethyl carbonate flames.

■ INTRODUCTION
Most of renewable nonfossil fuels (except hydrogen and
syngas) are oxygenated hydrocarbons. One of the important
advantages of oxygenates is that when used as additives or
alternative fuels under equivalent conditions they produce less
soot as compared to hydrocarbons. Environmental concerns,
however, may arise if oxygenated fuels or their intermediate
products are emitted from engines due to incomplete
combustion. This imposes additional constrains on the use of
many oxygenates and motivates the search for alternatives.
One of the attractive candidates to replace environmentally
hostile antiknock compounds such as methyl-tert-butyl ether is
dimethyl carbonate (DMC), C3H6O3,1 suitable as an additive
because of its low toxicity and persistence. An additional benefit
is that DMC can be produced from methanol and carbon
dioxide1,2 providing a sink (at least partial) for the greenhouse
gas, CO2. DMC is one of the widely adopted additives to
gasoline and diesel1 and was tested in a wide range of
concentrations from 1 to 20%,3 and 10−30%,4 up to 100%5 in
diesel engines. These tests showed contradictory results in
terms of NOx emissions: an increased proportion of DMC in
diesel fuel was found leading to increased3,5 or decreased4
formation of NOx in exhaust. Yet, in all cases. reduction of
smoke or soot particulates has been confirmed.
The suppression of soot production in diesel engines by
addition of oxygenates was explained by the reduction in
concentration of soot precursors in fuel-rich combustion
molecular wt %, its efficiency in soot suppression was found
inferior to that of methanol.
The model of Glaude et al.8 was developed by extension of a
detailed kinetic mechanism for dimethoxy methane and
dimethyl ether9 and validated using experimental species
profiles obtained in opposed flow diffusion flames at
atmospheric pressure.10 Glaude et al.8 concluded that their
model is in reasonable agreement with these measurements.
The model was later compared with species profiles obtained in
premixed low-pressure (30 Torr) flames of heptane with
addition of dimethoxy methane or DMC11 with overall
satisfactory agreement.
Many reaction rate constants in the DMC submechanism8
were estimated using analogy with other reactions or employing
rate rules proposed in, for example, ref 7. Although some new
theoretical12 and experimental13,14 results for pertinent rate
constants appeared since then, further development and
validation of the DMC combustion mechanism is hampered
by the lack of accurate experimental data for combustion
characteristics of DMC. For instance, such an important
parameter of any combustible mixture as the laminar burning
velocity has never been measured. The goals of the present
work were therefore (a) to determine burning velocities of
DMC in air at different initial temperatures at atmospheric
pressure, using the heat flux method; (b) to analyze their
temperature dependence, and (c) to compare these experi-
ments with predictions of the only available DMC combustion
mechanism.8

■
zones.6 Westbrook et al.6 used chemical kinetic modeling to
demonstrate that the percentage of fuel carbon converted to
soot precursors shows a close to linear decrease with the EXPERIMENTAL DETAILS
fraction (by mass) of oxygen in the fuel. A detailed kinetic Experiments in the present study have been performed using two
mechanism employed by Westbrook et al. for combustion setups. The first one is described in details in previous papers;15−17 the
modeling of heptane + DMC mixtures was a combination of
the model for heptane,7 a conventional surrogate for diesel, and Received: June 14, 2013
the only existing model for DMC, by Glaude et al.8 Revised: August 2, 2013
Remarkably, although DMC has very high oxygen content, 53 Published: August 20, 2013

© 2013 American Chemical Society 5513 dx.doi.org/10.1021/ef401108a | Energy Fuels 2013, 27, 5513−5517
Energy & Fuels
Figure 1. Schematic of the heat flux setup.
second setup is largely identical with some characteristics different, as
described in the following. A schematic view of the second heat flux
setup is shown in Figure 1. The heat flux burner consists of a plenum
chamber and a burner plate separated by a ceramic ring for thermal
insulation. They are kept at different temperatures using two separate
water baths. One water bath heats the burner plate to 368 K, while the
second one heats the plenum chamber and the unburned gas to the
required initial temperature from 298 to maximum of 348 K.
The experiments with the heat flux method are based on measuring
the temperature distribution in the perforated burner plate while
varying the flow rate of the fresh gas mixture. The distribution reflects
the heat loss of the flame to the burner and the heat gain of the
unburned gas as it passes through the burner plate. The temperature
distribution is measured by thermocouples (type T) inserted into
small holes in the perforated burner plate. The thermocouple readings
are registered by a 16-channel thermocouple input module, National
Instrument 9213.
When the flame is stabilized at velocities lower than the laminar
burning velocity, the burner plate will gain heat from the flame. If the
flame is stabilized at a velocity higher than the laminar burning
velocity, the burner plate will lose heat. By varying the gas flow until
the heat loss and heat gain are equal, resulting in a uniform
temperature distribution of the burner plate, the laminar burning
velocity is determined. Detailed description of the principles behind
the heat flux method is given by Bosschaart and de Goey.18
Mass flow controllers, MFC, (Bronkhorst High Tech) were used to
control the flow rate and mixture compositions. Liquid fuel was
evaporated using a controlled evaporator mixer, CEM (Bronkhorst).
The capacity of the CEM employed in the second setup is 5 times
larger than the one on the first setup. The fuel vapor was premixed
with the air before entering the burner (see Figure 1). A heating tube
between the CEM and the burner maintained the unburned mixture at
the desired temperature to avoid condensation. The temperature of
the heating tube was kept equal to that of the plenum chamber.
Error Analysis. Previous work estimates the uncertainty of the
burning velocity determined using the heat flux method to near ±0.5
cm/s at ϕ =1.0.18 This uncertainty is mainly based on errors due to
uncertainties of the MFCs and thermocouple scatter. While the same
type of error estimation is used for the MFC uncertainty,18 adding
errors due to calibration, a different method has been used to estimate
the errors related to the thermocouples in the present work. This
method, described in the following, will represent the error in the
burning velocity due to temperature scatter in a more rigorous way.
The measured temperatures are fitted to a function T(r) =
T(0)+βr2, where T(r) are the temperatures at different radial positions,
5514
Article
r. The β coefficient is dependent on the unburned gas velocity, vu. By
plotting β versus vu, the burning velocity can be found via interpolation
at β equal to zero. The slope of this interpolation is defined as the
sensitivity and indicates how the β coefficient varies with the unburned
gas velocity. The new approach to the error estimation is to calculate
the standard deviation of the linear fit coefficient (i.e., β) and to divide
this with the sensitivity derived from the β versus flow velocity
interpolation. This is the error in the burning velocity due to
thermocouple scatter. The total error in the burning velocity is
calculated adding the error due to thermocouple scatter and the
previously mentioned error from uncertainties in gas flow. The error in
concentration and equivalence ratio is solely based on uncertainties
from the MFCs and calibration.
Modeling Details. The Premix code from the Chemkin collection
was used for the flame modeling. All default parameters of the Premix
code were implemented with adaptive mesh parameter GRAD = 0.05.
This value was implied to ensure accurate grid-independent solution
with typical number of grid points around 400. The chemical kinetics
mechanism by Glaude et al.8 includes 102 species and 442 reactions.
According to the authors,8 this mechanism can treat dimethylcar-
bonate, dimethoxymethane, methylformate, methanol, ethanol, and
dimethyl ether oxidation.
■
RESULTS AND DISCUSSION
As explained above, the measurements of the laminar burning
velocities of DMC + air were conducted on two experimental
setups. The reason for this was that the two setups have
different capacities for fuel evaporation. In the absence of any
literature data for the burning velocity of DMC, it was initially
expected that the range of the Cori-flow mass flow controller
(MFC) and CEM on the first setup is sufficient for covering the
whole range of mixture composition, which then appeared not
to be the case. In the following, both series of measurements
are presented to illustrate consistency of the results. To ensure
acceptable accuracy of the measurements the MFCs were
calibrated and in addition cross-check experiments with well-
characterized fuels were performed. This is a common
procedure before investigating new fuels and is even more
important when switching from experiments with one
potentially corrosive fuel to another one. It was discussed in
detail by Nilsson et al.17 how a chemically aggressive liquid can
result in malfunction of the experimental system and thus error
in experiments. In the present work, the first experimental rig
dx.doi.org/10.1021/ef401108a | Energy Fuels 2013, 27, 5513−5517
Energy & Fuels
was tested using ethanol + air flames at an initial gas mixture
temperature of 318 K, while the second one using methanol +
air flames at 298 K. The elevated initial temperature for ethanol
flames was chosen to avoid vaporization limitations at 298 K
discussed elsewhere20 and thus to cover a complete range of
equivalence ratios. These measurements are shown in Figure 2
Figure 2. Laminar burning velocities of C2H5OH + air at 318 K.
Symbols, experimental data; lines, modeling; triangles, present work;
circles, ref 16; squares, ref 20; solid line, model of Glaude et al.;8
dashed line, the Konnov mechanism.20
and compared with recent results from the same laboratory16
and with earlier data from a different laboratory20 using the
same heat flux method. Three series of measurements for
ethanol are in remarkable agreement especially in the near-
stoichiometric mixtures. Larger deviations are observed in rich
flames, which may be related to inaccuracies in the MFC
calibration manifested in apparent “shift” of the SL depend-
encies along the x-axis. New measurements of the laminar
burning velocity of methanol + air flames are compared with
recent results from the same laboratory16 in Figure 3. That
these earlier measurements for alcohols are accurately
reproduced proves a good operation of the setups. The results
obtained using the heat flux method have previously been
Figure 3. Laminar burning velocities of CH3OH + air at 298 K.
Symbols, experimental data; lines, modeling; triangles, present work;
circles, ref 16; solid line, model of Glaude et al.;8 dashed line, model of
Li et al.25
5515
Article
compared to results from other methods at room and elevated
temperatures for ethanol20,22,16,23 and methanol.16,24 The
comparisons showed significant scattering (typically up to 4−
6 cm/s) and possible reasons for it were discussed in the above
references. Linear correction for stretch implemented in the
earlier studies employing spherical or counter-flow flames was
identified as the main drawback of these methods. The heat flux
method was found in a very good agreement (within 2 cm/s)
with the recent data obtained using nonlinear stretch correction
(e.g., by Veloo et al.).21 Also shown in Figures 2 and 3 are the
modeling results that are discussed in the following.
Laminar burning velocities of dimethyl carbonate + air flames
have been measured at initial gas mixture temperatures of 298,
318, 338, and 358 K. The results are listed in Table 1 and
shown in Figures 4 and 5 to avoid too busy graphs. The
measurements performed on the different setups are shown
with different symbols; the agreement is within evaluated
experimental uncertainties confirming consistency of these
results. The experiments at 298 K were restricted to lean
mixtures due to vaporization limits of DMC; at higher
temperatures, a full range of equivalence ratios from 0.7 to
1.6 was covered. As can be seen from comparison with Figures
2 and 3, DMC burns significantly slower than alcohols at the
same initial temperatures.
Figures 4 and 5 present also burning velocities of DMC + air
calculated using the mechanism of Glaude et al.8 The modeling
significantly (by 7−10 cm/s) overpredicts experimental results
at all initial temperatures. To reveal the reasons for the model
disagreement with the experiment a sensitivity analysis could be
helpful. The sensitivity analysis indicates reactions affecting
calculated burning velocity; these reactions can be re-evaluated
and modified if the model performs correctly for other
conditions or for other subhierarchical fuels. However, this is
apparently not the case: the calculated burning velocities of
methanol (Figure 3) and ethanol (Figure 2) also largely deviate
from the experimental data. Most probably, the underlying
problem is in incorrect description of combustion chemistry of
common intermediates, such as CH3O radicals or form-
aldehyde. Recently, developed models available in the literature
do not show the same discrepancy with the measurements:
examples of the predictions using the Konnov mechanism20 or
the scheme of Li et al.25 are shown in Figures 2 and 3,
respectively.
The temperature dependence of the laminar burning velocity
is commonly described by the relation
SL = SL0(T /T0)α (1)
where T0 is the reference temperature and SL0 is the burning
velocity at this temperature. The power exponent α is known to
depend on equivalence ratio only (at a given pressure), which
allows for independent cross-check of consistency of the results.
Specifically, when plotted in a log−log scale the values of
burning velocity obtained at different temperatures are
expected to follow a straight line, which slope gives the
power exponent α. Possible outliers can be clearly identified
from such a plot and may indicate potential mistakes in
experiments. Figure 6 shows these plots for selected
equivalence ratios. The scattering of the experimental data
points around best fit trend lines never exceeds the evaluated
uncertainty and the reliability of the measurements is thus
confirmed. Good linear fits indicate that the data were not
corrupted by corrosion, fouling, or other malfunctioning of the
equipment. This is an important conclusion in the present case
dx.doi.org/10.1021/ef401108a | Energy Fuels 2013, 27, 5513−5517
Energy & Fuels Article

Table 1. Laminar Burning Velocities of DMC + Air Flames with Associated Uncertaintiesa
298 K 318 K 338 K 358 K
eq. ratio SL cm/s ±error SL cm/s ±error SL cm/s ±error SL cm/s ±error
0.65 13.05 0.35
0.7 16.45 0.42 18.00 0.32 20.25 0.34 23.25 0.44
0.7* 14.32 0.83 16.78 0.63
0.8 22.43 0.42 24.45 0.39 27.30 0.55 30.20 0.49
0.8* 20.89 0.97 23.31 0.62
0.9 26.34 0.46 29.14 0.40 32.15 0.47 35.76 0.57
0.9* 25.09 0.77 28.43 0.57
1 28.96 0.47 32.15 0.44 35.13 0.49 39.01 0.56
1* 28.07 0.74 31.38 0.61
1.1 32.98 0.45 36.17 0.48 39.87 0.56
1.2 31.87 0.60 35.13 0.49 38.67 0.59
1.3 29.19 0.57 31.95 0.54 35.64 0.63
1.4 24.51 0.99 27.24 0.59 29.75 0.65
1.4* 24.43 0.89
1.5 19.99 1.28 21.30 0.67 24.80 0.99
1.5* 19.64 1.64
1.6* 15.69 2.00
a
Asterisk denotes measurements performed on the first setup.

Figure 4. Laminar burning velocities of DMC + air at 298 K and 338
K. Symbols, experimental data; lines, modeling; circles, results from
the first setup at 298 K; diamonds, results from the second setup at
298 K; triangles, results from the second setup at 338 K; solid line,
modeling at 338 K; dashed line, modeling at 298 K.
Figure 5. Laminar burning velocities of DMC + air at 318 K and 358
K. Symbols, experimental data; lines, modeling; circles, results from
the first setup at 318 K; diamonds, results from the second setup at
318 K; triangles, results from the second setup at 358 K; solid line,
modeling at 358 K; dashed line, modeling at 318 K.

where the results were obtained sequentially on two setups and
at different temperatures over extended period of time.
Experimentally derived power exponents α at different
equivalence ratios are shown in Figure 7. The error bars on
the experimental points in Figure 7 include the uncertainties in
the individual burning velocity data points, presented in Table
1, and the uncertainty in the fit using eq 1. The uncertainties of
α progressively increase from lean toward rich mixtures due to
somewhat higher uncertainty in the burning velocities of rich
mixtures and due to reduced temperature range, as the
measurements at 298 K were not fully accessible. The present
experimental results indicated that the power exponent α
reaches a minimum in slightly rich mixtures corresponding to
the maximum burning velocity, which is further substantiated
by the modeling. The occurrence of this type of minimum has
recently been validated for methane,19 ethanol,20 and acetone.17
Also shown in Figure 7 are the power exponents α derived
from the modeling. Even though the laminar burning velocities
5516
of DMC + air are significantly overpredicted (see Figures 4 and
5), the agreement with the modeling in Figure 7 is excellent
and the trend is clear; the power exponent goes through a
minimum for slightly rich mixtures. A similar trend was
observed in ethanol flames,20 although not to the same extent:
while models notably overpredicted ethanol laminar burning
velocities in lean and near-stoichiometric mixtures (see Figure
2), the agreement with the power exponents was somewhat
better in these flames as compared to rich mixtures. One may
conclude, therefore, that the comparison of the experimental
and calculated power exponent coefficients provides an
independent tool (target) for model validation and development.
■ CONCLUSIONS
Laminar burning velocities of dimethyl carbonate + air flames at
initial gas mixture temperatures of 298, 318, 338, and 358 K
have been measured for the first time, using the heat flux
method. Special care has been taken to ensure proper operation
dx.doi.org/10.1021/ef401108a | Energy Fuels 2013, 27, 5513−5517
Energy & Fuels
Figure 6. Log−log plot of selected laminar burning velocities of DMC
+ air flames at atmospheric pressure and different initial temperatures.
Equivalence ratio: 0.7 (open diamonds); 0.8 (solid diamonds); 0.9
(solid triangles); 1.0 (crosses); 1.1 (solid squares); 1.2 (solid circles);
1.3 (open squares); 1.4 (open circles); 1.5 (open triangles).
Figure 7. Correlation coefficient α as a function of equivalence ratio.
Diamonds, experimental data; line, modeling.
of the experimental setups, which was controlled by measuring
burning velocities of two well-characterized alcohols: methanol
and ethanol. Moreover, the measurements performed at two
setups were demonstrated to agree within the evaluated
uncertainties. The overall accuracy of the burning velocities
was evaluated to be typically better than ±1 cm/s. The effects
of unburned mixture temperature on the laminar burning
velocity of DMC were analyzed using the correlation SL =
SL0(Tu/Tu0)α. The present experimental results indicated that
the power exponent α reaches a minimum in slightly rich
mixtures corresponding to the maximum burning velocity.
Modeling of these results has been attempted using the
mechanism developed by Glaude et al.8 It was found that this
model significantly overpredicts laminar burning velocities of
methanol, ethanol, and DMC; however, it accurately
reproduces the temperature power exponent α for dimethyl
carbonate flames. It can be pointed out that since the
development of the base mechanism9 understanding of reaction
rates of many of the intermediate and reactive species of
importance in the model have improved significantly. It is likely
that an update of reaction rate constants for the fundamental
reactions governing laminar burning velocities will significantly
improve the performance of the model.
5517
■
Article
AUTHOR INFORMATION
Corresponding Author
*E-mail: max_bardin@mail.ru.
Author Contributions
The manuscript was written through contributions of all
authors. All authors have given approval to the final version of
the manuscript.
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
Financial support of the Ministry for Science and High
Education of Russian Federation by the Federal Target
Programme “Human Potential” 2009-2013 Project Grant No.
14.B37.21.1959 is gratefully acknowledged.
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