Subscriber access provided by Kaohsiung Medical University
Combustion
Laminar burning velocity of n-propanol and air mixtures at elevated mixture temperatures Amit Katoch, Ayush Chauhan, and Sudarshan Kumar Energy Fuels, Just Accepted Manuscript • DOI: 10.1021/acs.energyfuels.8b00997 • Publication Date (Web): 27 Apr 2018 Downloaded from http://pubs.acs.org on April 28, 2018
Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts.
is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.
Page 1 of 25 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Energy & Fuels
Laminar burning velocity of n-propanol and air mixtures at elevated mixture temperatures
1 2 3
Authors: Amit Katoch1, *, Ayush Chauhan2, Sudarshan Kumar1
4
1
5
Technology, Bombay, Mumbai, Maharashtra, 400076, India
6
2
7
Himachal Pradesh, 177005, India
8
CORRESPONDING AUTHOR: *Amit Katoch, (
[email protected])
Combustion Research Laboratory, Department of Aerospace Engineering, Indian Institute of
Department of Mechanical Engineering, National Institute of Technology Hamirpur,
9 10
Abstract:
11
The present work reports the measurement of laminar burning velocity for n-propanol and air
12
mixtures at 1 atm pressure with unburnt mixture temperature varying up to 620 K using
13
externally heated meso-scale diverging channels. Planar flames were stabilized in quartz
14
channels using externally heated meso scale diverging channel to create a positive
15
temperature gradient along the direction of fluid flow. Laminar burning velocity was
16
extracted using mass conservation principle at the flame surface and channel inlet. The
17
performance of six recent kinetic mechanisms was evaluated through comparison of the
18
predictions with present experimental results. A significant disagreement (≈ 22 %) was
19
observed between different mechanism predictions even at lower mixture temperatures of
20
335 K. The temperature exponent, α was extracted using power-law correlations and
21
observed to follow an inverted parabolic pattern with a minimum at slightly rich equivalence
22
ratio of 1.1, similar to other alcohol fuels.
23
Keywords: n-propanol, biofuel, laminar burning velocity, meso-scale channels, temperature
24
exponent
25
26
1 ACS Paragon Plus Environment
Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
1
Nomenclature:
2
Laminar burning velocity (m/s)
3
Temperature exponent
4
Φ
Equivalence ratio
5
,
Reference temperature (K)
6
,
Laminar burning velocity at reference temperature (m/s)
7
Mixture flow velocity at the inlet (m/s)
8
Tinlet
9
Ainlet Channel cross-section area at inlet (m2)
Mixture temperature at the channel inlet (K)
10
Tf
Mixture temperature at the flame stabilization location (K)
11
Af
Channel cross-section at flame stabilization location (m2)
12
13
14
15
16
17
18
19
20
2 ACS Paragon Plus Environment
Page 2 of 25
Page 3 of 25 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Energy & Fuels
1
1. Introduction:
2
Increasing green-house gas emissions and shrinking ice cover is becoming a major global
3
concern which is being directly linked to various combustion processes. The increasing
4
interest of the policy makers in the use of renewable fuels has led to the intensification of
5
research efforts towards understanding the production and combustion processes of biofuels.
6
During the past one decade, the interest in alcohol-based biofuels has increased significantly.
7
More than 90 % of the biofuel market is focused around bioethanol and other higher chain
8
derivatives of alcohols are also being looked upon as potential alternatives. More studies are
9
being conducted to understand the fuel behavior and performance with different types of 1-4
10
engines
. Apart from being renewable fuels, biofuels offer unique advantages in
11
combustion linked to the presence of additional oxygen content, which promotes clean
12
combustion resulting in less particulate generation, when compared to conventional
13
hydrocarbon fuels. In this context, a large number of studies have been reported with a focus
14
on assessing the engine performance with methanol, ethanol, butanol and pentanol isomers.
15
As compared to its isomer (isopropanol) and other alcohols from C1 to C5 group, n-propanol
16
has received little attention as a potential biofuel for combustion studies. Gautam et al.
17
investigated combustion characteristics of higher alcohol (n-propanol, n-butanol and n-
18
pentanol) blends with gasoline. They found that increased oxygen content from the alcohol
19
addition provided the blended fuels with improved knock resistance than a pure gasoline fuel.
20
Fernandez et al. 6, 7 investigated the performance of direct injection CI engine with n-butanol-
21
diesel and n-propanol diesel blends. The study revealed that n-propanol can be successfully
22
blended up to 25% by volume, without causing any significant change in combustion and
23
engine performance. Laminar burning velocity is a fundamental fuel parameter which
24
characterizes the reactivity, thermo-diffusivity and exothermic nature of a fuel. It is defined
25
as the steady propagation of a planar, adiabatic and one-dimensional reaction front into a
3 ACS Paragon Plus Environment
5
Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Page 4 of 25
1
relatively stationary mixture in a doubly infinite domain 8. It is widely used in the estimation
2
of turbulent burning velocity and validation of chemical kinetic mechanisms. For a particular
3
fuel-oxidizer mixture it’s value depends on initial pressure, unburnt mixture temperature and
4
equivalence ratio. The dependence of laminar burning velocity on initial mixture temperature
5
9
for constant pressure study is described as:
= , /,
6
(1)
7
where is the temperature exponent and a function of mixture type and equivalence ratio.
8
, is the laminar burning velocity at reference temperature , .
9
There are very few studies reported in literature on measurement of laminar burning velocity
10
of n-propanol-air mixtures at atmospheric pressure. Gong et al. 10 used the combustion bomb
11
method to measure atmospheric laminar burning velocities at 343 K and 393 K mixture
12
temperatures for an equivalence ratio range of 0.75 - 1.5. They used the linear extrapolation
13
scheme
14
obtained in the combustion bomb.
15
Veloo et al.
16
343 K mixture temperature and atmospheric pressure and used the non-linear stretch
17
extrapolation scheme suggested by Wang et al.
18
velocity. Galmiche et al.
19
using shadowgraphy in a spherical bomb. Non-linear correlations suggested by Kelly and
20
Law
21
values were reported for an unburnt mixture temperature of 423 K at atmospheric pressure.
22
Recently, Capriolo et al.
23
in the temperature range 323 -343 K.
15
11
to extrapolate the results to zero stretch from a spherically expanding flame
12
used the counterflow burner method to measure laminar burning velocities at
and Halter et al.
14
16
17
13
to obtain the unstretched laminar burning
extracted the burning velocities from the flame front evolution
were used for extrapolation of stretch. Laminar burning velocity
used the heat-flux method to measure laminar burning velocities
4 ACS Paragon Plus Environment
Page 5 of 25 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Energy & Fuels
Johnson et al.
1
18
developed a kinetic model using shock tube ignition delay studies to add
2
reactions pertaining to n-propanol and iso-propanol to the base chemistry of methanol and
3
ethanol. Galmiche et al.
4
experiments. Mann et al.
5
mixtures in argon-diluted oxygen mixtures and developed a new kinetic model based on the
6
mechanism of Johnson et al. 18 . The authors reported a reasonable agreement with measured
7
JSR (Jet Stirred Reactor) and laminar burning velocity data. However, they stated that there
8
was a disagreement with ignition delay predictions using Johnson et al. model 18. Togbe et al.
9
20
14
developed a model with species inputs from Jet-Stirred Reactor 19
reported ignition delay data for n-propanol and iso-propanol
and Galmiche et al. 14 reasoned that this could be ascribed to the exclusion of few oxidation
10
paths in their propanol sub-model which manifests due to absence of important oxygenated
11
intermediate species in JSR modelling. Gong et al.10 developed a detailed and reduced model
12
for simulating n-propanol combustion. These models were developed by modifying the
13
kinetics of Man et al.19 model with CHEM-RC software21. Liu et al.22 developed a combined
14
mechanism for C1-C5 alcohols. Frassoldati et al.
15
mechanism for n-propanol and iso-propanol combustion (Polimi CRECK group).
23
also proposed a detailed kinetic
16
To the authors’ knowledge, there are no studies reported in literature, which have reported
17
the variation of the laminar burning velocities at mixture temperature higher than 423 K,
18
variation of temperature exponent with equivalence ratio and comparison of various kinetic
19
models at higher mixture temperatures. Besides, there is no experimental data reported for
20
mixture temperature greater than 423 K to validate various kinetic mechanisms at still higher
21
temperatures. The externally heated diverging channel method has been used in previous
22
works to measure the laminar burning velocities of gaseous
23
mixture temperatures. Therefore, the motivation of the present work is to present the high
24
temperature laminar burning velocity data and associated temperature exponent variation
24-28
5 ACS Paragon Plus Environment
and liquid fuels
29
at higher
Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
1
with mixture equivalence ratio, which would be invaluable for further development and
2
validation of high temperature kinetic models for this fuel.
3
4
2. Details of experimental setup and numerical modeling
5
2.1. Experimental setup:
6
In the present work, the externally heated meso-scale diverging channel method is used. The
7
diverging channel is made of quartz material. Figure 1 shows the schematic diagram of the
8
present setup. The channel consists of an initial rectangular part with 25 mm × 2 mm
9
dimensions and 50mm length followed by a diverging section of 50 mm length. The starting
10
of the diverging channel is termed as inlet (X=0) and the divergence angle used in this study
11
are 10 and 15 degrees. The channel gap between the upper and lower quartz plates is varied
12
as 2 mm and 1.5 mm. The thickness of the channel plates is kept fixed at 2 mm.
13 14
Figure 1. Schematic of the experimental setup
15
The channel is heated from the bottom using an infrared heater where the heating rate can be
16
controlled using a voltage controller. The heating rate can be set to a maximum output power
6 ACS Paragon Plus Environment
Page 6 of 25
Page 7 of 25 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Energy & Fuels
1
of 1200 W to the infra-red heater. The external heating creates a positive and linear
2
temperature gradient along the length of the channel, similar to the principle of micro-flow
3
reactors
4
can be varied by altering the heating rate and the horizontal and vertical clearance between
5
the channel and the heater. Figure 2 shows the direct measurements of wall temperature
6
profile in transverse and axial direction for a flow condition of Uinlet = 0.88 m/s. The
7
transverse temperature profile shows a maximum deviation of 3 K amongst all the measured
8
values for a particular axial location. The axial temperature increases linearly along the
9
direction of the fluid flow with a temperature gradient of 2.58 K/mm.
30, 31
and earlier studies on diverging channel method
26-29
. This temperature profile
10 11
(a)
(b)
12
Figure 2. Temperature profile of the diverging channel walls along radial and axial direction
13
with infra-red heater for Uinlet = 0.88 m/s and an external heating rate of 600 W.
14
Since n-propanol is in liquid state at ambient conditions, it needs to be vaporized and mixed
15
with air to form a combustible mixture before entering the diverging channel. For this
16
purpose, air is preheated to a certain temperature, and the required mixture ratio is achieved
17
based on the saturation vapor pressure for the liquid fuel at that temperature. The air
7 ACS Paragon Plus Environment
Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
1
preheater consists of two plate type heaters of 1.5 kW rating each and the heating rate is
2
controlled through a PID temperature controller driven unit attached to an IR heater. The fuel
3
flow rates are very small and hence an infusion pump is used for controlled fuel metering.
4
The preheated air is directed into a heated copper tube where the fuel is injected using a
5
micro syringe. Due to high temperature of the incoming air, the fuel vaporizes instantly and
6
mixes with it to form a uniform combustible mixture. The entire flow path is heated using
7
tape heaters and insulated to avoid any chances of fuel condensation along the length of the
8
flow circuit. The mixture is ignited at the exit plane of the diverging channel. The domains
9
are studied starting from low inlet velocities to establish the flashback regimes. The flow
10
velocities are slowly increased to obtain stable flames. In the stable flame regimes, initially
11
negatively stretched flames are observed followed by planar flames and on further increasing
12
the inlet velocity positively stretched flames are observed till the flame moves out of the
13
channel 29. Figure. 3 shows a typical stabilized planar flame used for laminar burning velocity
14
evaluation of n-propanol-air mixture. This flame is stabilized for a mixture flow velocity of
15
Uinlet = 0.85 m/s and a mixture equivalence ratio of Φ = 0.9.
16 17
Figure 3. Direct photograph of a stabilized planar flame for Uinlet = 0.85 m/s at Φ = 0.9
18
conditions.
8 ACS Paragon Plus Environment
Page 8 of 25
Page 9 of 25 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Energy & Fuels
1
No cellular flames are observed, since the depth of the channel is very small (1.5 and 2.0
2
mm). The temperature profiles are measured a priori with heated airflow only. Planar flame
3
regimes are used for measuring the laminar burning velocity. At the point of flame
4
stabilization, the mixture temperature is assumed to be equal to the wall temperature and is
5
measured using a 0.25 mm K-type thermocouple of Omega make (accuracy ± 5 K). This is
6
substantiated by the fact that the Peclet number (Pe) corresponding to such low flow rates is
7
small
8
traverse system with an accuracy of 0.25 mm. The location of the stabilized flame is recorded
9
using a digital camera and further image processing is carried out. The burning velocity is
10
calculated using the mass balance relation at the channel inlet and the flame stabilization
11
location:
12
=
13
Where is the mixture flow velocity at the inlet (X = 0), Tinlet is the mixture temperature
14
at the channel inlet (with area, Ainlet), Tf is the mixture temperature at the flame stabilization
15
location (with area Af). The present measurements are accurate to ± 5 %, at all condition of
16
mixture equivalence ratio of temperature as discussed in previous studies 25, 27, 29, 33.
17
2.2
18
Laminar flame speeds were calculated from kinetic mechanisms using PREMIX code 34. It is
19
a FORTRAN code used for modelling 1-D steady premixed freely propagating laminar
20
flames. The governing differential equations for flame dynamics are solved using implicit
21
finite difference schemes along with steady and transient temporal schemes. The schemes
22
employ a coordinate system, which is a fixed point on the flame. In the solution, the flame
23
speed is an Eigen-value of the scheme, wherein, it is the inlet velocity at which flame is
24
stabilized at a fixed location. The steady state solver TWOPNT solves the non-linear
32
. The thermocouple is traversed within the channel with the help of an accurate
(2)
Numerical Simulations
9 ACS Paragon Plus Environment
Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Page 10 of 25
1
governing equations using a damped Newton’s method. Soret effect was taken into
2
consideration for all simulations. Mixture-averaged values were used to account for transport
3
parameters. The adaptive grid parameters were set to stiff values with CURV= 0.03 and
4
GRAD= 0.01. Table 1 gives a brief summary of various mechanisms used for simulations.
5
Gong et al. 10 have proposed a detailed and reduced model. Here, only the detailed model has
6
been used for comparison, since the difference between the predictions from the detailed and
7
reduced model is less than 0.4 %. The following models from literature are used for
8
simulating n-propanol combustion.
9
Table 1. Summary of various n-propanol mechanisms Mechanism Johnson et al.-2011-18 Galmiche et al.-2011-14 Polimi CRECK-2011-23 Man et al.-2014-19 Gong et al. (detailed)-2015 10 Gong et al. (reduced)-2015 10 Liu et al.-2016-22
Species 237 93 225 238 260 91 161
Reactions 1415 663 7645 1448 1653 706 622
10 11
3. Results & Discussions
12
3.1 Effect of initial mixture temperature on laminar burning velocity
13
10 ACS Paragon Plus Environment
Page 11 of 25 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Energy & Fuels
1
Figure 4. Comparison of laminar burning velocity with mechanism predictions for the lean
2
case of Φ = 0.7
3
Figure 4 and 5 show the variation of laminar burning velocity with temperature ratio for lean
4
mixtures. The unburnt mixture temperature has been normalized with a reference temperature
5
of 300 K (Tu,0) to obtain the temperature ratio. The present data is fitted with power law
6
correlations to obtain the trends across the complete temperature range investigated in the
7
present experiments studies. For the lean case of Φ = 0.7 shown in Figure 4, the kinetic
8
model predictions of Polimi CRECK
9
mechanism
14
23
gives the highest predictions, whereas the Galmiche
predicts the lowest values. For Φ = 0.7, the trend obtained from experimental 23
and Gong (D) mechanism
10
10
values lies between the predictions of Polimi CRECK
11
predictions. Figure 5 shows the measurements of predictions of laminar burning velocities for
12
Φ = 0.9 conditions. For Φ = 0.9, the trend line is in good agreement with the predictions of
13
various mechanisms ( Johnson 18, Man 19, Gong (D) 10 and Liu 22 ).
14
15 16
Figure 5. Comparison of laminar burning velocity with mechanism predictions for the lean
17
case of Φ = 0.9 11 ACS Paragon Plus Environment
Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Page 12 of 25
1
Figure 6 and Figure 7 show the variation of the laminar burning velocity with temperature
2
ratio for rich mixture conditions with Φ =1.1 and 1.3 respectively. On the richer side, as
3
shown in Figure 6, for Φ = 1.1, the trends are similar to those at Φ = 0.9. However, at Φ = 1.3
4
the predictions from various kinetic models of Johnson et al.
5
CRECK
6
show a good match with a slight over prediction at higher mixture temperatures.
23
18
, Mann et al.
are much higher than present results. Here, Gong (D)
10
and Liu
19
and Polimi
22
mechanisms
7 8
Figure 6. Comparison of laminar burning velocity with mechanism predictions for the rich
9
case of Φ =1.1
10
12 ACS Paragon Plus Environment
Page 13 of 25 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Energy & Fuels
1
Figure 7. Comparison of laminar burning velocity with mechanism predictions for the rich
2
case of Φ = 1.3
3
4
5
6
7
3.2 Influence of mixture equivalence ratio on temperature exponent
8
The value of the temperature exponent, α is obtained at each mixture equivalence ratio by
9
fitting a power-law correlation to the variation of laminar burning velocity with mixture
10
temperature. Figure 8 shows the variation of temperature exponent, α with equivalence ratio,
11
Φ. Since there is no other data reported in the literature for the variation of temperature
12
exponent, α with equivalence ratio, Φ, only the kinetic model predictions are shown in the
13
figure for comparison purpose. It is to be noted that all the mechanism predictions show a
14
qualitative inverted parabolic variation with a minimum value of temperature exponent, α for
15
slightly rich mixtures.
16
13 ACS Paragon Plus Environment
Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Page 14 of 25
1
Figure 8. Comparison of temperature exponent variations with equivalence ratio for n-
2
propanol and air mixtures with predictions from detailed mechanisms
3
Prior to 2010, many studies reported linear decrements or constant values of α for different
4
hydrocarbon fuels. Konnov
5
variation of temperature exponent for various hydrocarbon fuels. Similar variation of
6
temperature exponent, α is obtained through a series of experiments at different equivalence
7
ratios as shown in Figure 8. The temperature exponent variation with equivalence ratio can be
8
fitted with a second-order polynomial as: = 2.3688Φ% − 5.2376Φ + 4.5889. The present
9
values are in good agreement with the predictions of Gong et al.
35
discouraged such variations and justified a non-monotonic
10
and Liu et al.
22
10
mechanisms for lean conditions and with a slight under prediction for stoichiometric and rich
11
mixtures. The error bars associated with each equivalence ratio were evaluated using the least
12
squares method proposed by Alekseev et al.
13
from kinetic models is significantly higher than the current measurements indicating a
14
possibility of over prediction of laminar burning velocities at higher mixture temperatures by
15
these kinetic models.
16
3.3
17
Figure 9 and Figure 10 show the comparison between the present results with predications of
18
various kinetic models and available experimental data at different mixture temperatures of
19
343 K and 423 K respectively. It is interesting to note that at both 343 K and 423 K
20
temperatures, Polimi CRECK
21
Galmiche mechanism
22
mechanism follow closely across the complete range of equivalence ratios.
36
. The prediction of temperature exponent, α
Laminar burning velocity at low and elevated temperatures
14
23
mechanism predicts the highest values, whereas the
predicts the lowest values. Predictions using the Gong et al.
14 ACS Paragon Plus Environment
10
Page 15 of 25 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Energy & Fuels
1 2
Figure 9. Comparison of laminar burning velocity with experimental data and predictions
3
from mechanisms at 343 K
4
At 343 K, the present data is in good agreement with the data of Veloo et al.
5
equivalence ratios, except at Φ ≥ 1.2. A significant difference of nearly 7 cm/s on the lower
6
side is observed for Φ ≥ 1.2 conditions. It is interesting to see that, for lean and stoichiometric
7
conditions, the heat flux method measurements reported by Capriolo et al.
8
higher than the predictions of all kinetic models.
9
15 ACS Paragon Plus Environment
17
12
at all
are relatively
Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Page 16 of 25
1
Figure 10. Comparison of laminar burning velocity with experimental data and predictions
2
from mechanisms at 423 K
3 4
Figure 11. Comparison of laminar burning velocity with experimental data and predictions
5
from mechanisms at 500 K
6
At 423 K mixture temperature, it is interesting to note that the measurements of Galmiche et
7
al.
8
predictions of their kinetic model. The measurements reported by Gong et al.
9
using spherical flame method with non-linear extrapolation model are quite close to the
10
measurement of Galmiche et al. 14. There exists very little difference between the two despite
11
a significant difference in the mixture temperature. However, it is to be noted that both these
12
experimental measurements are significantly lower than all other mechanism predictions and
13
present measurements at 423 K mixture temperature.
14
using spherical flame method and linear extrapolations model follow closely with the
16 ACS Paragon Plus Environment
10
at 393 K
Page 17 of 25 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Energy & Fuels
1 2
Figure 12. Comparison of laminar burning velocity with experimental data and predictions
3
from mechanisms at 600 K
4
Figure 11 shows a detailed comparison of present measurements with various kinetic model
5
predictions at 500 K and Figure 12 shows similar comparison at 600 K mixture temperature.
6
The data for comparison was obtained using temperature exponents shown in Fig. 8 through
7
interpolation for specific mixture temperatures at each equivalence ratio. It can be seen that
8
Polimi CRECK mechanism
9
Galmiche mechanism 14 predicts the lowest values across all equivalence ratios, for both 500
10
K and 600 K mixture temperatures. The difference is predictions is as large as 26 % at 600 K.
11
The present data shows a close agreement with Gong et al.
12
difference of about 4 cm/s at 600 K. Various other kinetic models (Johnson 18, Man 19 , Liu 22
13
) predict a close agreement with the present experimental results at different mixture
14
temperatures and equivalence ratios as clear from Figures. 9-12.
15
3.4
16
To present the sensitivity analysis, the model of Gong et al.
17
consistently good agreement with the present experimental results. The objective of the
23
predicts highest values of laminar burning velocity and
10
mechanism with a maximum
Sensitivity Analysis
17 ACS Paragon Plus Environment
10
was used as it has shown a
Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Page 18 of 25
1
present analysis is to identify the key reactions and their influence on the variation of laminar
2
burning velocity with varying mixture temperature and equivalence ratios. The normalized
3
sensitivity coefficient of laminar burning velocity with respect to the reaction rate constant is
4
given by the correlation: ,-./ , 01 =
5
sensitive to laminar burning velocity are plotted in Figure 13. It is well known that the
6
laminar flame speed is directly proportional to the concentrations of H and OH radicals.
7
Across all the equivalence ratios, the results indicate that the burning velocity is most
8
sensitive to the main chain branching reaction: H + O2O + OH which shows the highest
9
positive contribution. The sensitivity contribution of this reaction increases as the mixture
10
moves from lean to rich equivalence ratios. In the lean regime, this reaction competes with
11
H+O2(+M)HO2(+M) reaction. The negative sensitivity of this reaction decreases as the
12
mixture equivalence ratio changes from lean to stoichiometric regime and becomes almost
13
non-existent at very rich conditions, at Φ=1.3. The next main reaction accelerating the flame
14
speed is the CO oxidation reaction: CO + OHCO2 + H, which contributes primarily in the
15
leaner regime. With an increase in equivalence ratio, the quantity of the hydroxyl radicals
16
decreases, thereby decreasing the sensitivity of this reaction. The water recombination
17
reaction: H+OH+M H2O + M which retards the flame, shows slightly increasing
18
sensitivity as equivalence ratio increases at 335 K. However, at 600 K, the contribution
19
remains identical for compared equivalence ratios.
23 24
4
∗ 3
37, 38
. Sixteen reactions which are most
18 ACS Paragon Plus Environment
Page 19 of 25 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Energy & Fuels
1 2
(a)
(b)
3
Figure 13. Normalized sensitivity coefficients for the laminar burning velocity of n-propanol
4
+ air mixtures at (a) 335 K and (b) 600 K.
5
Decomposition reaction of formyl radicals: HCO + M H + CO + M produces flame
6
accelerating radicals H and CO. This reaction shows only slight changes as equivalence ratios
7
increases. In a generic sense, both the negative and positive contributions from the reactions
8
decrease in terms of their sensitivity magnitude with increasing temperature. The only
9
reaction involving the fuel (n-propanol) showing any sensitivity is: NC3H7OH + H
10
C3H6OH-3 + H2, which contributes only for the rich case of Φ = 1.3. As the equivalence
11
ratio increases, the burning velocity becomes sensitive to the methyl recombination reaction:
12
CH3+H(+M)CH4(+M). This is a chain terminating reaction, where methyl radical acts as a
13
sink for the H radical to produce CH4, thus slowing down the rate of flame propagation.
14
Another radical termination reaction: HCO+H CO + H2 shows its presence only for the
15
rich case at 335 K However, as the temperature increases to 600 K, it starts influencing the
16
stoichiometric mixtures as well. Another such temperature bias is observed for the reaction:
17
HO2 + OH H2O + O2. At 335 K, this reaction influences the lean and stoichiometric
18
domains, whereas at 600 K, it affects only the lean regime. The participation of the vinyl 19 ACS Paragon Plus Environment
Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Page 20 of 25
1
radical happens for rich mixtures in a competing manner, where the reaction C2H3 + H
2
C2H2 + H2 slows down the flame and the reaction C2H2+H (+M) C2H3(+M) accelerates
3
it. The contribution from the latter reaction is slightly higher, thus leading to a net production
4
of the vinyl radicals.
5
Conclusions
6
New high temperature laminar burning velocity measurements were carried out using the
7
externally heated meso-scale diverging channel method employing planar flames for n-
8
propanol and air mixtures upto unburnt mixture temperatures of 620 K at atmospheric
9
pressure. The effect of mixture temperature on laminar burning velocity was investigated
10
through power law correlations for experimental measurements. The variation in temperature
11
exponents was studied for lean, stoichiometric and rich mixtures to assess the effects of
12
equivalence ratio. An inverted parabolic variation was observed with a minimum at slightly
13
rich mixture. The detailed mechanism by Gong et al.
14
measured values even for high temperatures across studied equivalence ratios except for
15
slight over-prediction at Φ=1.3. Therefore, the discrepancies in the kinetic parameters of
16
various mechanisms, particularly for rich mixtures need further investigation.
10
was observed to closely predict the
17
18
19
Acknowledgement:
20
The authors would like to acknowledge the financial support for this work from Department
21
of Science and Technology (DST), Govt. of India wide grant no. SB/S3/COMB-001/ (2014).
22 23
References
24
20 ACS Paragon Plus Environment
Page 21 of 25 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Energy & Fuels
1
1. Yusri, I. M.; Mamat, R.; Najafi, G.; Razman, A.; Awad, O. I.; Azmi, W. H.; Ishak, W. F.
2
W.; Shaiful, A. I. M., Alcohol based automotive fuels from first four alcohol family in
3
compression and spark ignition engine: A review on engine performance and exhaust
4
emissions. Renewable and Sustainable Energy Reviews 2017, 77, 169-181.
5
2. Awad, O. I.; Mamat, R.; Ali, O. M.; Sidik, N. A. C.; Yusaf, T.; Kadirgama, K.; Kettner,
6
M., Alcohol and ether as alternative fuels in spark ignition engine: A review. Renewable and
7
Sustainable Energy Reviews 2018, 82, 2586-2605.
8
3. Rajak, U.; Nashine, P.; Singh, T. S.; Verma, T. N., Numerical investigation of
9
performance, combustion and emission characteristics of various biofuels. Energy
10
Conversion and Management 2018, 156, 235-252.
11
4. Wong, K. I.; Wong, P. K., Adaptive air-fuel ratio control of dual-injection engines under
12
biofuel blends using extreme learning machine. Energy Conversion and Management 2018,
13
165, 66-75.
14
5. Gautam, M.; Martin, D., Combustion characteristics of higher-alcohol/gasoline blends.
15
Proceedings of the Institution of Mechanical Engineers, Part A: Journal of Power and
16
Energy 2000, 214, (5), 497-511.
17
6. Campos-Fernández, J.; Arnal, J. M.; Gómez, J.; Dorado, M. P., A comparison of
18
performance of higher alcohols/diesel fuel blends in a diesel engine. Applied energy 2012, 95,
19
267-275.
20
7. Campos-Fernandez, J.; Arnal, J. M.; Gomez, J.; Lacalle, N.; Dorado, M. P., Performance
21
tests of a diesel engine fueled with pentanol/diesel fuel blends. Fuel 2013, 107, 866-872.
22
8. Law, C. K., Combustion physics. Cambridge university press: 2010.
23
9. Turns, S. R., An introduction to combustion, 2000. MacGraw Hill, Boston, Massachusetts,
24
US 2000.
21 ACS Paragon Plus Environment
Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
1
10. Gong, J.; Zhang, S.; Cheng, Y.; Huang, Z.; Tang, C.; Zhang, J., A comparative study of n
2
-propanol, propanal, acetone, and propane combustion in laminar flames. Proceedings of the
3
Combustion Institute 2015, 35, (1), 795-801.
4
11. Matalon, M.; Matkowsky, B., Flames as gasdynamic discontinuities. Journal of Fluid
5
Mechanics 1982, 124, 239-259.
6
12. Veloo, P. S.; Egolfopoulos, F. N., Studies of n-propanol, iso-propanol, and propane
7
flames. Combustion and Flame 2011, 158, (3), 501-510.
8
13. Wang, Y.; Holley, A.; Ji, C.; Egolfopoulos, F.; Tsotsis, T.; Curran, H., Propagation and
9
extinction of premixed dimethyl-ether/air flames. Proceedings of the Combustion Institute
10
2009, 32, (1), 1035-1042.
11
14. Galmiche, B.; Togbe, C.; Dagaut, P.; Halter, F.; Foucher, F., Experimental and detailed
12
kinetic modeling study of the oxidation of 1-propanol in a pressurized jet-stirred reactor
13
(JSR) and a combustion bomb. Energy & fuels 2011, 25, (5), 2013-2021.
14
15. Kelley, A. P.; Law, C. K., Nonlinear effects in the extraction of laminar flame speeds
15
from expanding spherical flames. Combustion and Flame 2009, 156, (9), 1844-1851.
16
16. Halter, F.; Tahtouh, T.; Mounaïm-Rousselle, C., Nonlinear effects of stretch on the flame
17
front propagation. Combustion and Flame 2010, 157, (10), 1825-1832.
18
17. G. Capriolo, V.A. Alekseev, A.A. Konnov, Laminar Burning Velocities of C3 Alcohol
19
Isomers at Atmospheric Pressure. 8th European Combustion Meeting, 18-21 April 2017,
20
Dubrovnik, Croatia 2017.
21
18. Johnson, M. V.; Goldsborough, S. S.; Serinyel, Z.; O’Toole, P.; Larkin, E.; O’Malley, G.;
22
Curran, H. J., A Shock Tube Study ofn- andiso-Propanol Ignition. Energy & Fuels 2009, 23,
23
(12), 5886-5898.
22 ACS Paragon Plus Environment
Page 22 of 25
Page 23 of 25 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Energy & Fuels
1
19. Man, X.; Tang, C.; Zhang, J.; Zhang, Y.; Pan, L.; Huang, Z.; Law, C. K., An
2
experimental and kinetic modeling study of n-propanol and i-propanol ignition at high
3
temperatures. Combustion and Flame 2014, 161, (3), 644-656.
4
20. Togbe, C.; Dagaut, P.; Halter, F.; Foucher, F., 2-Propanol oxidation in a pressurized jet-
5
stirred reactor (JSR) and combustion bomb: experimental and detailed kinetic modeling
6
study. Energy & fuels 2011, 25, (2), 676-683.
7
21. Sun, W.; Chen, Z.; Gou, X.; Ju, Y., A path flux analysis method for the reduction of
8
detailed chemical kinetic mechanisms. Combustion and Flame 2010, 157, (7), 1298-1307.
9
22. Liu, X.; Wang, H.; Zheng, Z.; Liu, J.; Reitz, R. D.; Yao, M., Development of a combined
10
reduced primary reference fuel-alcohols (methanol/ethanol/propanols/butanols/n-pentanol)
11
mechanism for engine applications. Energy 2016, 114, 542-558.
12
23. Frassoldati, A.; Cuoci, A.; Faravelli, T.; Niemann, U.; Ranzi, E.; Seiser, R.; Seshadri, K.,
13
An experimental and kinetic modeling study of n-propanol and iso-propanol combustion.
14
Combustion and Flame 2010, 157, (1), 2-16.
15
24. Varghese, R. J.; Kishore, V. R.; Akram, M.; Yoon, Y.; Kumar, S., Burning velocities of
16
DME (dimethyl ether)-air premixed flames at elevated temperatures. Energy 2017, 126, 34-
17
41.
18
25. Varghese, R. J.; Kolekar, H.; Hariharan, V.; Kumar, S., Effect of CO content on laminar
19
burning velocities of syngas-air premixed flames at elevated temperatures. Fuel 2018, 214,
20
144-153.
21
26. Akram, M.; Kumar, S., Measurement of Laminar Burning Velocity of Liquified
22
Petrolium Gas Air Mixtures at Elevated Temperatures. Energy & Fuels 2012, 26, (6), 3267-
23
3274.
24
27. Akram, M.; Saxena, P.; Kumar, S., Laminar Burning Velocity of Methane–Air Mixtures
25
at Elevated Temperatures. Energy & Fuels 2013, 27, (6), 3460-3466.
23 ACS Paragon Plus Environment
Energy & Fuels 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
1
28. Paidi, S. K.; Bhavaraju, A.; Akram, M.; Kumar, S., Effect of N2/CO2 dilution on laminar
2
burning velocity of H2–air mixtures at high temperatures. International Journal of Hydrogen
3
Energy 2013, 38, (31), 13812-13821.
4
29. Katoch, A.; Asad, M.; Minaev, S.; Kumar, S., Measurement of laminar burning velocities
5
of methanol–air mixtures at elevated temperatures. Fuel 2016, 182, (Supplement C), 57-63.
6
30. Kumar, S.; Maruta, K.; Minaev, S.; Fursenko, R., Appearance of target pattern and spiral
7
flames in radial microchannels with CH4-air mixtures. Physics of Fluids 2008, 20, (2),
8
024101.
9
31. Maruta, K.; Kataoka, T.; Kim, N. I.; Minaev, S.; Fursenko, R., Characteristics of
10
combustion in a narrow channel with a temperature gradient. Proceedings of the Combustion
11
Institute 2005, 30, (2), 2429-2436.
12
32. Dubey, A. K.; Tezuka, T.; Hasegawa, S.; Nakamura, H.; Maruta, K., Study on sooting
13
behavior of premixed C 1 –C 4 n -alkanes/air flames using a micro flow reactor with a
14
controlled temperature profile. Combustion and Flame 2016, 174, 100-110.
15
33. Akram, M.; Kishore, V. R.; Kumar, S., Laminar Burning Velocity of Propane/CO2/N2–
16
Air Mixtures at Elevated Temperatures. Energy & Fuels 2012, 26, (9), 5509-5518.
17
34. Kee, R. J.; Grcar, J. F.; Smooke, M. D.; Miller, J.; Meeks, E., PREMIX: a Fortran
18
program for modeling steady laminar one-dimensional premixed flames. Sandia National
19
Laboratories Report 1985, (SAND85-8249).
20
35. Konnov, A. A., The effect of temperature on the adiabatic laminar burning velocities of
21
CH4−air and H2−air flames. Fuel 2010, 89, (9), 2211-2216.
22
36. Alekseev, V. A.; Christensen, M.; Konnov, A. A., The effect of temperature on the
23
adiabatic burning velocities of diluted hydrogen flames: A kinetic study using an updated
24
mechanism. Combustion and Flame 2015, 162, (5), 1884-1898.
24 ACS Paragon Plus Environment
Page 24 of 25
Page 25 of 25 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Energy & Fuels
1
37. Turanyi, T., Applications of sensitivity analysis to combustion chemistry. Reliability
2
Engineering & System Safety 1997, 57, (1), 41-48.
3
38. Zhao, Z.; Li, J.; Kazakov, A.; Dryer, F. L., Temperature-dependent feature sensitivity
4
analysis for combustion modeling. International Journal of Chemical Kinetics 2005, 37, (5),
5
282-295.
6
25 ACS Paragon Plus Environment