Fuel 191 (2017) 411–426

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Fuel
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Full Length Article

Development of a diesel-biodiesel-ethanol combined chemical scheme

and analysis of reactions pathways
Dario Alviso a,b,⇑, Federico Krauch a, Rodney Román a, Hernando Maldonado c,
Rogério Goncalves dos Santos d, Juan Carlos Rolón a, Nasser Darabiha c
a
Laboratorio de Mecánica y Energía, Facultad de Ingeniería, Universidad Nacional de Asunción, Campus Universitario, San Lorenzo, Paraguay
b
Laboratorio de Fluidodinámica, Facultad de Ingeniería, Universidad de Buenos Aires, Paseo Colón 850 CABA, Argentina
c
Laboratoire EM2C, CNRS, CentraleSupélec, Université Paris-Saclay, Grande Voie des Vignes, 92295 Châtenay-Malabry Cedex, France
d
Faculdade de Engenharía Mecánica da Universidade Estadual de Campinas – FEM/UNICAMP, Rua Mendeleyev, 200 – CEP 13083-860, Cidade Universitária ‘‘Zeferino Vaz”
Barao Geraldo, Campinas, SP, Brazil

a r t i c l e i n f o a b s t r a c t

Article history: Diesel-biodiesel-ethanol blends have been the focus of intense research quite recently. Diesel is a com-
Received 12 August 2016 plex fuel composed of hundreds of compounds indicating the difficulty of using diesel for experimental
Received in revised form 2 November 2016 studies associated with numerical simulations. Biodiesel is also a complex mixture of methyl esters.
Accepted 11 November 2016
When injected in a diesel engine in the pure form, it induces changes in combustion behavior which
can impact pollutants emission. Consequently simplified synthetic fuels, called ‘‘surrogate fuels”, with
shorter chain lengths and known physical chemical properties are chosen to carry combustion studies.
Keywords:
Finally, ethanol is one of the liquid alternative fuels most widely studied. The present paper focuses on
Diesel
Biodiesel
numerical studies of the combustion of diesel-biodiesel-ethanol blends using 0D auto-ignition delay
Ethanol and 1-D freely-propagating gaseous premixed flame configurations. The objective is to develop and val-
Kinetic modeling idate a new chemical scheme by carefully combining two existing chemical schemes from the literature.
Auto-ignition The first one is the scheme due to Andrae (2011) for the combustion of diesel-ethanol blends and the sec-
Freely propagating flames ond one is due to Luo et al. (2012) for a biodiesel surrogate. The approach consists of merging non com-
mon elementary reactions from both chemical schemes and analyzing the common reactions (having
different reaction constants) in both chemical schemes in order to chose most relevant chemical path-
ways from each scheme so that the resulting merged scheme gives a good prediction of the auto-
ignition delay and laminar flame speed.
Ó 2016 Elsevier Ltd. All rights reserved.

1. Introduction physical and chemical properties are chosen to carry combustion

Diesel is a complex fuel, which is derived from conventional
petroleum sources and is composed of hundreds of compounds.
Although the composition of petroleum-based diesel fuel is highly
variable, there are some trends; the carbon numbers of the compo-
nents range from approximately C 10
C 22 . An average carbon
number is 14 or 15. These characteristics indicate the difficulty
of using diesel for experimental studies associated with numerical
simulations [1].
In order to avoid these difficulties, simplified synthetic fuels,
called ‘‘surrogate fuels”, with shorter chain lengths and known
⇑ Corresponding author at: Laboratorio de Mecánica y Energía, Facultad de
Ingeniería, Universidad Nacional de Asunción, Campus Universitario, San Lorenzo,
Paraguay.
E-mail address: beto.alviso@gmail.com (D. Alviso).
studies.
Biodiesel is a complex mixture of methyl esters with different
chain lengths and degrees of saturation and can be used in pure form
or may be blended with diesel without major modifications in diesel
engines. However, changing the fuel in diesel engines induces
changes in combustion behavior which can impact pollutants
emission. Indeed, the use of biodiesel in diesel engines decreases
emission of pollutants such as carbon monoxide, unburned hydro-
carbons, and particulate matter, although a slight increase in
emissions of nitrogen oxides is observed in some cases [2,3].
Chemical kinetic mechanisms for hydrocarbon fuels have been
the focus of intense research for several decades. However, there
are less information on the combustion properties and pathways
of common liquid fuels. This is partly due to the difficulty in repre-
senting real fuels containing hundreds of components with a wide
variation in composition by surrogate fuels for the purpose of
chemical kinetic modeling. Nevertheless, due to the increasing

http://dx.doi.org/10.1016/j.fuel.2016.11.039
0016-2361/Ó 2016 Elsevier Ltd. All rights reserved.
412 D. Alviso et al. / Fuel 191 (2017) 411–426
number of research works in the development of either kinetic
modeling or experimental database of these fuels, this field has
experienced a significant amount of recent developments.
Concerning diesel, there has been much recent progress in the
area of surrogate fuels for diesel. In the last few years, experiments
and modeling have been performed on higher molecular weight
components of relevance to diesel fuel [4].
Concerning biodiesel, methyl decanoate C 11 H22 O2 (MD) has
been proposed as a good surrogate due to the length of the hydro-
carbon chain. Several authors proposed detailed and skeletal kinet-
ics for this surrogate [5–9]. In addition to methyl decanoate
reaction mechanism, other surrogates have been recently proposed
[10–18]. In a previous work [19], we have combined two biodiesel
chemical schemes due to [6,13] in order to perform numerical
studies in a counterflow flame of combined methane-air and
biodiesel-air mixtures.
Finally, ethanol (C 2 H5 OH) is one of the liquid alternative fuels
most widely studied. In vehicles, it is mainly used as a fuel addi-
tive, especially blended with gasoline to enhance octane number
and improve combustion in spark-ignition engines, but also as a
renewable alternative fuel, specially in Brazil [2].
In recent years, systematic efforts have been made on the use of
biodiesel and ethanol fuels in diesel engines. Compared to diesel
fuel, the cetane number, flash point and calorific value of ethanol
are much lower, which restricts its direct application in diesel
engines. To overcome these difficulties, ethanol might be blended
with biodiesel, expected to improve the overall low temperature
flow properties, viscosity, heating value and cetane number. Mean-
while, if combustion could be shifted towards lower temperatures,
NOx and PM emissions could be reduced simultaneously [20].
Recently a skeletal scheme was constructed for biodiesel and
ethanol (referred as Bio-Ethanol) combustion by [20], consisting
of 116 species and 523 reactions. This scheme was validated by
performing 0-D ignition delay predictions, as well as 3-D numerical
simulations against the experimental results.
Diesel-biodiesel-ethanol blends have been the focus of intense
research quite recently [21–25]. Most of these works have been
done using a Diesel engine, however in our knowledge, none of
them concerns kinetic modeling.
The present paper concerns numerical studies of the combus-
tion of diesel-biodiesel-ethanol blends in a 0D constant-pressure
auto-ignition and 1-D freely-propagating gaseous premixed flame
configurations. The objective is to develop and validate a new
chemical scheme for the combustion of diesel-biodiesel-ethanol
blends while guaranteeing reproducing correctly the principal fea-
tures of the original pure fuels combustion characteristics. This is
done by carefully combining two chemical schemes: one originally
for the combustion of diesel/ethanol and the other for biodiesel.
The common reactions with different reaction constants in both
chemical schemes were identified and analyzed in order to obtain
reasonable results for the pure fuels separately.
Numerical simulations were performed using the REGATH pack-
age developed at EM2C laboratory [26–28], that takes into account
the detailed kinetics and multicomponent transport phenomena.
The new combined model was validated comparing auto-
ignition delays and laminar flame speeds of the pure fuels using
the combined model and the original models, as well as experimen-
tal results. Then, auto ignition delays and laminar flame speeds of
diesel-biodiesel and diesel-biodiesel-ethanol blends are presented.
2. Diesel and biodiesel chemical structure and schemes
2.1. Diesel chemical structure and chemical schemes
Diesel is a complex combination of hydrocarbons produced by
the distillation of crude oil. It consists of hydrocarbons having
carbon numbers predominantly in the range of C 10
C 20 . The com-
position varies widely, depending on the crude oils used, the refinery
processes available, the overall balance of product demand, and the
product specifications. North American diesel is composed by alka-
nes (25–50 vol.%), mono- and poly-aromatics (15–40 vol.%) and
cycloalkanes or naphtenes (mono- and polycyclic, 20–40 vol.%) [1].
There has been much recent progress in the area of surrogate
fuels for diesel. In the last few years, experiments and modeling
have been performed on higher molecular weight components of
relevance to diesel fuel. Chemical kinetic schemes have been devel-
oped for n-alkanes up to 16 carbon atoms. Also, there has been
experimental and modeling works on lower molecular weight sur-
rogate components such as n-decane and n-dodecane that are most
relevant to jet fuel surrogates, but are also relevant to diesel surro-
gates where simulations of the full boiling point range is desired
[4].
The choice of a surrogate depends on the chosen application
target. Extensive reviews of different types of diesel surrogate fuels
have been made by different authors [1,29,4].
Straight-alkanes are usually the most abundant components in
liquid fuels. For the past decades, surrogates with short carbon
chains, such as n-heptane, are usually employed as the surrogates
for diesel fuels. Moreover, chemical schemes for long-chain
straight-alkanes such as n-dodecane, n-tetradecane, and n-
hexadecane (HXN) have been developed owing to their compara-
ble boiling range to those of the diesel fuels [30].
Based on the review of Farrell et al. [1], toluene is recommended
as the near-term surrogate component for aromatics, by taking
into the considerations of the availability of kinetic schemes and
data for all aromatic compounds. Besides, toluene is often inte-
grated into various diesel surrogate fuel blends. For instance, a typ-
ical surrogate fuel is toluene reference fuel (TRF), a simple toluene/
n-heptane mixture. Corcione et al. [31] proposed a diesel surrogate
composed of 76 vol.% n-heptane and 24 vol.% toluene (TRF24) in
volume in the diesel spray in a constant volume vessel. Andrae
[32] proposed a chemical scheme for TRF blends and investigated
the auto-ignition by a single-zone adiabatic model both theoreti-
cally and experimentally. This scheme consists of a semi-detailed
description of toluene oxidation and skeletal mechanisms of iso-
octane and n-heptane. Andrae [32] chemical scheme has the dis-
tinction of including ethanol chemistry.
According to recent papers of Hernandez et al. [33,34], a mix-
ture of toluene and n-heptane was the best diesel surrogate in
comparison to other species surrogates. Luo et al. [35] have shown
that the ignition delay and smoke emission of TRF20 (80% n-
heptane/20% toluene in volume) were closer to that of diesel fuel
as compared with the pure n-heptane and TRF30 (70% n-
heptane/30% toluene in volume) fuel.
Following these works, in the present paper TRF20 (80% n-
heptane/20% toluene in volume) have been chosen as a diesel sur-
rogate and the chemical kinetics due to Andrae [32] has been used
as a base to carry out the numerical studies. As explained before,
this scheme includes ethanol chemistry, therefore, to simulate
diesel-biodiesel-ethanol blends combustion, chemical reaction
pathways for biodiesel are needed.
2.2. Biodiesel chemical structure and chemical schemes
Biodiesel is a complex mixture of methyl esters with different
chain lengths and degrees of unsaturation. Rapeseed-derived bio-
diesel (most produced around the world [36]) concentrations and
mole fractions has been estimated [19]. In comparison to the val-
ues found in literature [5], it corresponds to the classical composi-
tion of biodiesel obtained from this oil (see Table 1).
The structures of the components (methyl Palmitate, stearate,
oleate, linoleate and linolenate) show considerable similarities,
 D. Alviso et al. / Fuel 191 (2017) 411–426
Table 1
Composition of rapeseed-derived biodiesel.
Methyl ester CC (ppm) Mole fraction
Palmitate 417 4.74
Stearate 157 1.78
Oleate 5660 64.21
Linoleate 1866 21.16
Linolenate 715 8.11
each with a methyl ester attached to a large hydrocarbon chain
(see Fig. 1).
Due to the complex chemical structure of biodiesel, surrogate
fuels are also chosen to carry numerical combustion studies. Her-
binet et al. [5] developed a detailed chemical kinetic mechanism
for methyl decanoate (MD) including both low and high tempera-
ture chemistry. It consists of 3012 species and 8820 reactions.
Seshadri et al. [6] used the directed relation graph (DRG) method
of [37,38] to reduce Herbinet’s detailed mechanism to a skeletal
mechanism consisting of 125 species and 713 elementary reac-
tions. The model has been validated with experiments studying
the limits of ignition and extinction of MD in a counterflow diffu-
sion flame. Later, Glaude et al. [7] developed a detailed kinetic
mechanism using computer package EXGAS, consisting of 1251
species and 7171 reactions. To validate the mechanism, computed
results were compared to a new set of methyl decanoate experi-
mental results obtained in a jet-stirred reactor. In addition, Sarathy
et al. [8] developed a skeletal mechanism for MD consisting of 648
species and 2998 reactions from Herbinet’s detailed mechanism
using also DRG method. They have validated their results obtained
in a counterflow diffusion flame by their experimental profiles of
some reactant, intermediate, and product species obtained with
GC-MS technique with good agreement. Moreover, Dievart et al.
[9] developed from Herbinet’s detailed mechanism a detailed
kinetic scheme consisting of 2276 species and 7086 reactions
and the reduced it to generate two smaller schemes, one with
530 species and 2396 reactions, and the other with 238 species
and 1244 reactions. Both reduced schemes are in good agreement
with each other and with experiments for premixed flame condi-
tions, high temperature ignition delay and stirred reactor
speciation.
In addition to methyl decanoate chemical schemes, Herbinet
et al. [10] developed reaction mechanisms for two unsaturated
esters, methyl-5-decenoate and methyl-9-decenoate. Both
schemes were compared with rapeseed oil methyl esters experi-
ments in a jet-stirred reactor. This comparison showed that
methyl-9-decenoate does a better job than methyl-5-decenoate
Fig. 1. Structures of the main components of rapeseed-derived biodiesel.
413
in reproducing the reactivity and the mole fraction profiles of
important species.
Furthermore, Herbinet et al. [11] developed mechanisms for C 9
to C 17 methyl esters, using the computer program EXGAS. The
schemes were subsequently validated by comparing experimental
data for methyl palmitate conversion in a jet stirred reactor with
simulations using methyl dodecanoate. The agreement in this com-
parison was reasonable and the reaction mechanism was able to
predict the qualitative behavior of the effect of temperature on
conversion percentage.
Naik et al. [12] developed a kinetic mechanism for two real bio-
diesel fuel molecules, methyl stearate ðC 19 H36 O2 Þ and methyl ole-
ate ðC 19 H34 O2 Þ. The resulting detailed reaction mechanism
includes more than 3500 species and more than 17,000 elementary
reactions. Due to the size of the resultant mechanism simplifica-
tions were necessary to reduce the amount of required computing
power. The chemical scheme produced a reasonable global agree-
ment with experimental data, but showed discrepancies with a sig-
nificant amount of the experimental data.
Brakora et al. [14] presented a multi-chemistry mechanism
developed by Ra and Reitz [39], consisting of 77 species and 216
reactions. They implemented their chemical scheme in a 3-D CFD
solver to simulate biodiesel combustion in the Sandia
compression-ignition optical research engine (SCORE) at different
engine loads. Combustion characteristics and NOx emissions at
both low and high loads were captured.
Later, Luo et al. [13] developed a detailed mechanism that con-
sists of 3299 species and 10,806 reactions for a tri-component bio-
diesel surrogate including methyl decanoate, methyl 9-decenoate
and n-heptane (chemical structures presented in Fig. 2). Methyl-
9-decenoate was chosen because the double bond is at the same
position as the one in methyl oleate and at the same location as
the first double bond in methyl linoleate and in methyl linolenate.
The detailed mechanism was then reduced with direct relation
graph (DRG, [37,38]), isomer lumping [40,41], and DRG-aided sen-
sitivity analysis (DRGASA [41]), which was improved to achieve a
larger extent of reduction. The skeletal mechanism consists of
115 species and 460 reactions. Extensive validations were per-
formed against 0-D simulations with the detailed mechanism
and experimental data for spatially homogeneous systems, 1-D
flames and 3D-turbulent spray combustion.
A new skeletal scheme for surrogate including methyl deceno-
ate (MD), methyl 5-decenoate (MD5D), and n-decane was pro-
posed by Chang et al. [18]. The final mechanism for the biodiesel
surrogate is composed of 60 species and 172 reactions. The mech-
anism was validated against experimental data, using ignition
delay times in shock tubes and major species concentrations in
jet-stirred reactors over wide operating conditions.
A skeletal reaction mechanism for the combustion of four-
component biodiesel comprising methyl decenoate, methyl-5-
decenoate, n-decane and methyl linoleate was recently proposed
by Liu et al. [17]. The objective of Liu et al. work was to develop
a mechanism for accurate modeling of the effect of the amount
of fatty acid methyl ester on biodiesel ignition and combustion.
Fig. 2. Biodiesel surrogates chemical structure.
414 D. Alviso et al. / Fuel 191 (2017) 411–426
In order to validate the feasibility of the new developed skeletal
mechanism, 0-D ignition delay testing, reflected shock tube exper-
iment validation and 3-D engine testing about cylinder pressure,
heat release rate and NOx emission trends were conducted at dif-
ferent conditions.
Concerning diesel-biodiesel blends, a compact combined reac-
tion mechanism for diesel engine simulations is proposed by Ng
et al. [15] through the combination of three-component mecha-
nisms using a chemical class-based approach. This mechanism
comprises the reaction schemes of methyl crotonate (MC), methyl
butanoate (MB) and n-heptane. The final mechanism comprises 80
species and 299 reactions. The compact-sized mechanism is vali-
dated against 234 test conditions ranging from initial temperatures
of 750–1350 K, pressures of 40–60 bar and equivalence ratios of
0.4–1.5.
A mechanism suitable to simulate biodiesel, diesel and their
blend fuels was presented by An et al. [16]. A tri-component skele-
tal reaction mechanism consisting of methyl decanoate, methyl-9-
decenoate, and n-heptane was developed for biodiesel combustion
in diesel engine. It comprises 112 species participating in 498 reac-
tions with the CO, NOx and soot formation mechanisms embedded.
Extensive validations were performed for the developed skeletal
reaction mechanism with 0-D ignition delay testing and 3-D
engine simulations.
In the present work, a chemical scheme for the simulation of the
combustion of diesel-biodiesel-ethanol blends is needed. The
scheme due to Andrae [32] developed for n-heptane-toluene
blends (TRF) has been chosen as a base and we combine it to the
scheme due to Luo et al. [13], which consists of 115 species and
460 reactions for the combustion of a biodiesel surrogate: methyl
decanoate(MD)/methyl 9-decenoate(MD9D)/n-heptane. This latter
scheme has already been combined to another scheme in our
recent paper [19]. As proposed by Luo et al. [13], 50% n-heptane,
25% methyl decanoate and 25% methyl-9-decenoate (vol) was the
biodiesel surrogate chosen to carry the numerical studies.
3. Numerical approach
The kinetic modeling for the combustion of diesel-biodiesel-
ethanol blends in a 0D constant-pressure auto-ignition and 1-D
freely-propagating flame were performed using the REGATH
package [26–28] with detailed thermochemical and transport
properties developed at EM2C laboratory. The inputs to each sim-
ulation include a chemical kinetic reaction mechanism, a dataset of
thermochemical properties and a dataset of transport properties.
Operating conditions for 0D auto-ignition diesel-biodiesel-
ethanol/air flames have been chosen considering the equivalence
ratio / ¼ 0:5; 1:0 and 1:5, for pressures of 1, 10 and 100 atm and
different temperatures (1000=T ¼ 0:5–1:42).
Operating conditions for 1D freely-propagating premixed
diesel-biodiesel-ethanol/air flames have been chosen considering
the equivalence ratio (/): from / ¼ 0:6 to / ¼ 1:4. The mixture
flow is kept at an initial temperature of 300 K and 470 K. The pres-
sure is equal to one atmosphere.
4. Kinetic modeling
In order to simulate diesel-biodiesel-ethanol/air flames, from
one side TRF20 (80% n-heptane/20% toluene in volume) has been
chosen as a surrogate of diesel fuel. The mechanism due to Andrae
[32] consisting of 150 species and 758 reactions has been chosen to
represent diesel/ethanol chemistry. On the other hand, 50%
n-heptane, 25% methyl decanoate and 25% methyl-9-decenoate
(vol) are considered as the surrogates to represent biodiesel. The
mechanism due to Luo et al. [13] with 115 species and 460
reactions has been chosen to represent biodiesel chemistry. Now,
to simulate diesel-biodiesel-ethanol/air flames, the two chemical
mechanisms should be merged, species representing these fuels
must indeed be present in a single reaction scheme.
The scheme proposed in this work will be designed from the
original oxidation framework of Andrae [32]. This chemical scheme
is used as a starting base model. Then additional species and reac-
tions which are present in the kinetic scheme of Luo et al. [13]
should be included in the Andrae’s scheme.
The common species in both chemical schemes are 30 (see
Table 2). Therefore, the new combined scheme will consist of
235 species; 150 from Andrae, and 85 from Zhaoyu Luo.
There are also 105 common elementary reactions in both mech-
anisms, but with different reaction constants. The new combined
scheme will have 1113 elementary reactions; 758 from Andrae,
and (460
105 ¼ 355) from Zhaoyu Luo.
This way of merging guarantees reproducing the principal ther-
modynamic features of the pure fuels combustion characteristics.
However, the common reactions (105) in both chemical schemes
should be carefully analyzed and chosen from one or the other
scheme in order to obtain reasonable results for the pure fuels
separately.
In order to identify the sensitive reactions for the estimation of
the pure fuels auto-ignition delay and flame speed, 5 packages
were made as explained below:
 Package I: 18 reactions containing species H2 ; OH; HO2 ; H2 O2
 Package II: 19 reactions containing species HCO; CH2 O;
CH3 O; CH3 OH
 Package III: 23 reactions containing species CH; CH2 ; CH3 ; CH4
 Package IV: 30 reactions containing species C 2 H6 ; C 2 H5 ; C 2 H4 ;
C 2 H3 ; C 2 H2 ; C 2 H5 CHO
 Package V: 15 reactions containing species C 7 H16 ; C 7 H15
2 ;
CH2 CO; HCCO
These 5 packages were chosen taking into account similar struc-
tures of species and reactions groups. These packages along with
the Arrhenius reaction constants of Andrae [32] and Luo et al.
[13] are given in Appendix (Tables 6–10). Some common species,
such as O; H; O2 ; H2 O; CO and CO2 , are present in more than one
package; whereas N 2 and pC 4 H9 species are not present in any
package.
The first important point to note in these tables is that, gener-
ally, Luo et al. [13] scheme gives forward and reverse constants,
while that of Andrae [32] gives only forward constants. Now, in
order to easily identify the common reactions with different for-
ward constants in both chemical schemes, we have highlighted
them in bold. As one can see, the number of these reactions is
not negligible. In fact, in Package I, 15 out of 18 reactions have dif-
ferent forward constants; in Package II, 14 out of 19 reactions; in
Package III, 17 out of 23 reactions; in Package IV, 23 out of 30 reac-
tions; and finally in Package V, 9 out of 15 reactions have different
forward constants.
Table 2
30 common species.
Common species
H2 ; OH; HO2 ; H2 O2
HCO; CH2 O; CH3 O; CH3 OH
CH; CH2 ; CH3 ; CH4
C 2 H6 ; C 2 H5 ; C 2 H4 ; C 2 H3 ; C 2 H2 ; C 2 H5 CHO
C 7 H16 ; C 7 H15
2 ; CH2 CO; HCCO
O; H; O2 ; H2 O; CO; CO2
N 2 ; pC 4 H9
 D. Alviso et al. / Fuel 191 (2017) 411–426 415

Table 3
7 combined schemes examined.

Scheme Package from Andrae Package from Z. Luo

I II III IV V I II III IV V
A x x x x x
B x x x x x
C x x x x x
D x x x x x
E x x x x x
F x x x x x
G x x x x x

Then, 7 chemical schemes were examined containing 1113

reactions; 758 from Andrae, 355 from Zhaoyu Luo, with 105 reac-
tions as presented in Table 3.

5. Results and discussion

5.1. Auto-ignition Simulations

5.1.1. Comparison of combined chemical schemes to the original

schemes
Pure diesel/air auto-ignition delays estimated as a function of
equivalence ratio (/ ¼ 0:5; 1:0 and 1:5), pressure (1; 10 and
100 atm) and temperature (1000=T ¼ 0:5–1:42) are presented in
Figs. 3–5. These figures show that all combined schemes repro-
duce fairly well the auto-ignition delays obtained by the original
scheme of Andrae [32], except for scheme D, which gives bad
results. However, some discrepancies were observed on the
branches of the curves with 10 atm pressure and temperature
ranging from 1000=T ¼ 1:1 to 1:4 at / ¼ 1:0 and 1:5 (Figs. 4b
and 5b, respectively). Schemes C and G seems to be slightly bet-
ter than others schemes, although the difference is not
significant.
Now, in order to quantify how much close are the combined
schemes auto-ignition delay results to the original scheme results,
rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
P ffi!
2
ðX
XÞ
we have presented in Table 4 standard deviations S ¼ n

of schemes A to G, related to the original schemes.

On the first line of this table corresponding to Andrae scheme
for diesel/air combustion, we note that the standard deviation of
the results obtained using scheme G is the smallest, followed very
closely by that of scheme C, while that of the scheme D is the lar-
gest, confirming the previous conclusions. These results clearly
show that the reactions pathways of the package II containing spe-
cies HCO; CH2 O; CH3 O; CH3 OH from Andrae scheme are very impor-
tant in the estimation of Diesel/air auto-ignition delay.
Then, we have plotted in Figs. 6–8 the auto-ignition delays of
pure biodiesel/air flames using the scheme of Luo et al. [13] and
the combined schemes A to G.
These figures show that Zhaoyu Luo results are not reproduced
as well as Andrae’s, and some discrepancies were observed, at
/ ¼ 0:5—1:5, for 100 atm pressure and temperature ranging from
1000=T ¼ 0:8 to 1:0 (Figs. 6c, 7c and 8c); moreover, at
/ ¼ 1:0
1:5, for 1 atm pressure and temperature ranging from
1000=T ¼ 1:1 to 1:4 (Figs. 7a and 8a) and at / ¼ 1:0
1:5, for
10 atm pressure and temperature ranging from 1000=T ¼ 1:0 to
1:2 (Figs. 7b and 8b).
This figure and the second line of Table 4 show that, the com-
bined scheme C is the one that best reproduces the results of
Zhaoyu Luo et al. 2012, and that scheme G also gives good results,
and scheme D is once again the one giving the worst results, show-
ing that the reactions pathways of the package II of species Fig. 3. Diesel/air auto-ignition delay as a function of pressure and temperature
HCO; CH2 O; CH3 O; CH3 OH are also very important in the estimation (/ ¼ 0:5) using the original scheme of Andrae 2011 and the combined model
of biodiesel/air auto-ignition delay. Schemes A through G (n-heptane was chosen for species delay detection).
416 D. Alviso et al. / Fuel 191 (2017) 411–426

Fig. 4. Diesel/air auto-ignition delay as a function of pressure and temperature Fig. 5. Diesel/air auto-ignition delay as a function of pressure and temperature
(/ ¼ 1:0) using the original scheme of Andrae 2011 and the combined model (/ ¼ 1:5) using the original scheme of Andrae 2011 and the combined model
Schemes A through G (n-heptane was chosen for species delay detection). Schemes A through G (n-heptane was chosen for species delay detection).

Table 4
In conclusion, Figs. 3–8 and Table 4 show that auto-ignition
Standard deviation of Schemes A to G auto-ignition delay results compared to those of
delay of both diesel and biodiesel surrogates are very sensitive to the original schemes of Andrae and Zhaoyu Luo.
the common reactions. In particular scheme C, where package I is
Scheme A B C D E F G
taken from Zhaoyu Luo et al. scheme and packages II to V from
Andrae scheme), is the one that gives reasonable results using both Andrae 0.12 0.13 0.11 0.33 0.15 0.15 0.10
Zhaoyu Luo 0.22 0.21 0.13 0.30 0.19 0.22 0.15
fuels separately, justifying the analysis of the common reactions,
instead of taking them directly from the original schemes (as done
in schemes A and B). Note that the elementary reactions of package
I contain species H2 ; OH; HO2 ; H2 O2 .
As one can see, auto-ignition results of the developed combined sel (see Table 4). This is quite convenient knowing that in a blend,
schemes are generally much better for diesel compared to biodie- diesel is usually the major component.
 D. Alviso et al. / Fuel 191 (2017) 411–426
Fig. 6. Biodiesel/air auto-ignition delay as a function of pressure and temperature
(/ ¼ 0:5) using the original scheme of Zhaoyu Luo et al. 2012 and the combined
model Schemes A through G (methyl decanoate was chosen for species delay
detection).
5.1.2. Diesel-biodiesel blends ignition delays
We have performed simulations using the combined scheme C
for a blend corresponding to B20 (20% in volume biodiesel, 80%
diesel). B20 is the most common blend used around the world.
Agarwal and Das [42] found out that B20 is the optimum biodiesel
blend giving maximum increase in thermal efficiency, lowest
brake-specific energy consumption (BSEC) and advantage in terms
of lower emissions. We have plotted auto ignition delays as a func-
tion of equivalence ratio, pressure and temperature in Fig. 9 for B0
(pure diesel), B20 and B100 (pure biodiesel).
417
Fig. 7. Biodiesel/air auto-ignition delay as a function of pressure and temperature
(/ ¼ 1:0) using the original scheme of Zhaoyu Luo et al. 2012 and the combined
model Schemes A through G (methyl decanoate was chosen for species delay
detection).
One can see that for all three equivalence ratios and pressures
the influence of adding biodiesel is not negligible. In fact, B20 igni-
tion delays curve is located, in average, at 20% from that of B0, and
80% from that of B100.
5.1.3. Diesel-biodiesel-ethanol blends ignition delays
Fig. 10 presents a comparison between numerical diesel-
biodiesel-ethanol blends ignition delays using scheme C as a func-
tion of equivalence ratio, pressure and temperature. The blends
correspond to BDE10 (10% biodiesel, 10% ethanol, 80% diesel) and
418 D. Alviso et al. / Fuel 191 (2017) 411–426
Fig. 8. Biodiesel/air auto-ignition delay as a function of pressure and temperature
(/ ¼ 1:5) using the original scheme of Zhaoyu Luo et al. 2012 and the combined
model Schemes A through G (methyl decanoate was chosen for species delay
detection).
BDE20 (10% biodiesel, 20% ethanol, 70% diesel) and B10 (10%
biodiesel, 90% diesel) (taken as a reference). In this figure, one
can see that adding ethanol does not change significantly the igni-
tion delays, at least up to 20%.
5.2. Laminar flame speed simulations
5.2.1. Comparison of combined chemical schemes to the original
schemes
We have first used the kinetic scheme proposed by Andrae [32]
and schemes A and B (all common reactions from Andrae and
Fig. 9. Diesel/biodiesel-air B20 blend auto-ignition delay as a function of equiva-
lence ratio, pressure and temperature using the combined model C (n-heptane was
chosen for species delay detection).
Zhaoyu Luo, respectively, see Table 3) to simulate 1-D freely-
propagating pure diesel/air premixed flames using 1D-PREMIXED
code within the REGATH package.
Pure diesel/air flame speeds estimated as a function of equiva-
lence ratio are presented in Fig. 11. This figure shows that the com-
bined scheme A reproduces fairly well the flame speed obtained by
the original scheme of Andrae [32] for rich flames. The scheme B
seems to be slightly better than scheme A for lean flames, although
the difference is very small.
We have next used the kinetic scheme proposed by Luo et al.
[13] and schemes A and B to simulate 1-D freely-propagating pure
biodiesel/air premixed flames. Pure biodiesel/air flame speed
 D. Alviso et al. / Fuel 191 (2017) 411–426
Fig. 10. Diesel/biodiesel/ethanol-air blends auto-ignition delay as a function of
equivalence ratio, pressure and temperature using the combined model C (n-
heptane was chosen for species delay detection).
estimated as a function of equivalence ratio are presented in
Fig. 12. This figure shows that the combined scheme A gives
slightly better results than scheme B, compared to those of the
original scheme of Luo et al. [13]. This is quite remarkable, as
scheme B has all the common reactions from Zhaoyu Luo, and
one would think that it would give better results than scheme A.
For scheme A, in the very lean zone (from / ¼ 0:6 to 0:7) the
results are very good, then, as equivalence ratio increases, the dif-
ference between scheme A and Zhaoyu Luo results also increases.
We have then examined the combined schemes C through G by
simulating 1-D freely-propagating pure diesel/air flames. We have
compared the flame speeds to those obtained using the original
419
Fig. 11. Diesel/air flame speed as a function of equivalence ratio, for T = 300 K and
p = 1 atm, using the original scheme of Andrae 2011 and the combined schemes A
and B.
Fig. 12. Biodiesel/air flame speed as a function of equivalence ratio, for T = 300 K
and p = 1 atm, using the original scheme of Zhaoyu Luo et al. 2012 and the
combined schemes A and B.
scheme of Andrae [32]. Flame speeds are plotted as a function of
equivalence ratio in Fig. 13. This figure shows that for all equiva-
lence ratios, schemes C, D, F, and G give reasonable results, how-
ever the combined scheme C reproduces best results close to
those obtained using the original scheme of Andrae 2011. The
results obtained from combined scheme E are far away from the
original scheme of Andrae 2011. These results clearly show that
the reactions pathways of the package III containing species
CH; CH2 ; CH3 ; CH4 from Andrae scheme are very important in the
estimation of Diesel/air flame speed.
Now, in order to quantify how much close are the combined
schemes flame speed results to the original scheme results, we
have presented in Table 5 standard deviations of schemes A to G,
related to the original schemes.
On the first line of this table corresponding to the scheme of
Andrae for diesel/air combustion, we note that the standard
deviation of the results obtained using scheme A is the smallest,
followed very closely by that of scheme C, whereas that of the
scheme E is the largest, confirming the previous conclusions.
Then, we have plotted in Fig. 14 the flame speeds of pure
biodiesel/air mixtures using the scheme of Luo et al. [13] and the
combined schemes C to G. This figure and the second line of Table 5
show that, the combined schemes C, F and G are the ones that best
420 D. Alviso et al. / Fuel 191 (2017) 411–426

5.2.2. Diesel-biodiesel blends flame speeds

In order to compare experimental and numerical flame speeds of
diesel-biodiesel blends, we have performed simulations using the
combined scheme C for a B20 blend, for T = 300 K and p = 1 atm.
We have plotted flame speeds as a function of equivalence ratio
in Fig. 15 for B0 (pure diesel), B20, and B100 (pure biodiesel). One
can see in this figure that for very lean (/ ¼ 0:6–0:7) mixtures
flame speeds of B0; B20, and B100 are very similar. However for
mixtures with / > 0:7 the influence of adding biodiesel is not neg-
ligible. In fact, for these flames, B20 flame speed curve is located, in
average, at 20% from that of B0, and 80% from that of B100, and
consequently B20 flame speeds are very close to B0 flame speeds.

5.2.3. Comparison of combined chemical schemes flame speeds to

experimental data
As the comparisons of combined schemes to the original models
show good agreement for both diesel and biodiesel flame speeds,
Fig. 13. Diesel/air flame speed as a function of equivalence ratio, for T = 300 K and
the next step is to verify that flame speeds obtained using the com-
p = 1 atm, using the original scheme of Andrae 2011 and the combined model bined scheme (and in a manner also the original schemes) are in
Schemes C through G. good agreement with experimental data.
In this sense, Chong et al. [43] performed simulations to obtain
laminar flame speeds of practical fuels including Jet-A1, diesel,
Table 5
Standard deviation of Schemes A to G flame speeds compared to the original schemes
palm methyl esters (PME) and blends of PME with diesel and Jet-
of Andrae and Zhaoyu Luo. A1 fuels using a jet-wall stagnation premixed flame configuration
and particle imaging velocimetry (PIV) technique. The experiments
Scheme A B C D E F G
were performed over a range of equivalence ratios at elevated tem-
Andrae 1.67 1.89 1.73 3.51 10.21 3.70 2.40 perature of 470 K and atmospheric pressure.
Zhaoyu Luo 7.88 8.74 6.71 13.76 21.65 6.24 6.57
Fig. 16 compares experimental diesel/air laminar flame speeds
due to Chong et al. 2011 and our numerical results obtained using
scheme C as a function of equivalence ratio for T = 470 K and
P = 1 atm. As one can see the agreement is very good, especially
for / ¼ 0:8–1:2. There is only a slight difference for very rich flames
(/ ¼ 1:2–1:4).
Fig. 17 gives a comparison between numerical B20/air laminar
flame speeds using scheme C and experimental results due to
Chong et al. 2011, as a function of equivalence ratio for T = 470 K
and P = 1 atm. As one can see the agreement is reasonable, and
the maximum flame speed is different for Chong et al. experiments
(/ ¼ 1:1) and scheme C simulation (/ ¼ 1:2).

5.2.4. Diesel-biodiesel-ethanol blends flame speeds

Fig. 18 presents a comparison between numerical diesel-
biodiesel-ethanol blends flame speed using scheme C as a function
of equivalence ratio for T = 300 K and P = 1 atm. The blends corre-
spond to BDE10, BDE20 and B10 (taken as a reference). In this fig-

Fig. 14. Biodiesel/air flame speeds as a function of equivalence ratio, for T = 300 K
and p = 1 atm, using the original scheme of Zhaoyu Luo et al. 2012 and the
combined schemes C through G.

reproduces the results of Zhaoyu Luo et al. 2012, better than

Scheme A. For lean flames (/ ¼ 0:6–0:7) the agreement is very
good. Finally, scheme E is again the one which gives the worst
results, showing that the reactions pathways of the package III of
species CH; CH2 ; CH3 ; CH4 are also very important in the estimation
of biodiesel/air flame speed.
In conclusion, Figs. 11–14 and Table 5 show that flame speeds of
both diesel and biodiesel surrogates are very sensitive to the com-
mon reactions. In particular scheme C is again the one that gives
reasonable results using both fuels separately (as for auto-
ignition results), and therefore making the validation of the new
scheme more comprehensive.
As for auto-ignition results, flame speed results of the
developed combined schemes are generally much better for diesel Fig. 15. Laminar flame speed of different diesel - biodiesel blends as a function of
compared to biodiesel (see Table 5). equivalence ratio, for T = 300 K and p = 1 atm.
 D. Alviso et al. / Fuel 191 (2017) 411–426
Fig. 16. Comparison between simulated diesel/air laminar flame speed using
scheme C with experimental due to Chong et al. 2011 as a function of equivalence
ratio, for T = 470 K and P = 1 atm.
Fig. 17. Comparison between simulated B20/air laminar flame speeds using
scheme C with experimental results due to Chong et al. 2011 as a function of
equivalence ratio, for T = 470 K and P = 1 atm.
Fig. 18. Diesel - biodiesel - ethanol blends flame speeds using scheme C as a
function of equivalence ratio, for T = 300 K and P = 1 atm.
ure, one can see that adding ethanol does not change significantly
the flame speed, at least up to 20%. Unfortunately, no experimental
data was found in the literature for this triple blend.
421
6. Conclusions
This paper has presented numerical studies of the combustion
of diesel-biodiesel-ethanol blends in a 0-D constant-pressure
auto-ignition and 1-D freely-propagating gaseous premixed flames
configurations.
A new chemical scheme was developed and validated by care-
fully combining the schemes proposed by Andrae 2011 (diesel/
ethanol) and Zhaoyu Luo et al. 2012 (biodiesel). This guarantees
reproducing the principal features of both fuels combustion
thermochemical characteristics. The new combined scheme, con-
sists of 235 species and 1113 elementary reactions.
In addition, the common reactions with different reaction con-
stants (which are 105) in both chemical schemes were identified
and analyzed in order to obtain reasonable results using the pure
fuels separately. In order to identify the sensitive reactions for
the estimation of the pure fuels auto-ignition delays and flame
speeds, 5 reaction packages containing particular species were cre-
ated. Then, 7 chemical schemes called A to G were developed using
these packages.
We have first simulated pure diesel/air and biodiesel/air auto-
ignition delays estimated as a function of equivalence ratio, pres-
sure and temperature. In conclusion, it was shown that auto-
ignition delay of both diesel and biodiesel surrogates are very sen-
sitive to the common reactions. In particular, scheme C (containing
species H2 ; OH; HO2 ; H2 O2 from the scheme of Zhaoyu Luo et al. and
the rest of common reactions from Andrae scheme) is the one that
gives reasonable results using both fuels separately, justifying the
analysis of the common reactions, instead of taking them directly
from the original schemes.
Auto-ignition delays results of the developed combined scheme
are generally much better for diesel, compared to biodiesel. Taking
into account that in a practical blend, diesel is usually the major
component, this is quite convenient.
Then, numerical diesel-biodiesel and diesel-biodiesel-ethanol
blends auto-ignition delays using scheme C were presented. The
blends corresponded to B20 (20% biodiesel, 80% diesel), BDE10
(10% biodiesel, 10% ethanol, 80% diesel) and BDE20 (10% biodiesel,
20% ethanol, 70% diesel). It was shown that B20 ignition delays
curve is located, in average, at 20% from that of B0 (pure diesel),
and 80% from that of B100 (pure biodiesel). Moreover, it was
shown that adding ethanol does not change significantly the igni-
tion delays, at least up to 20%.
In addition, we have used the kinetic schemes proposed by
Andrae 2011 and Zhaoyu Luo et al. 2012, as well as the combined
schemes A through G, to simulate 1-D freely-propagating pure die-
sel and pure biodiesel premixed flames, respectively. In conclusion,
flame speeds of both diesel and biodiesel surrogates are also very
sensitive to the common reactions in both mechanisms, and in par-
ticular to some reactions packages. Scheme C is again the one giv-
ing reasonable results using both fuels separately, and therefore
making the validation of the new scheme more comprehensive.
As the comparison of combined schemes to the original
schemes showed good agreement for both diesel and biodiesel
flame speeds, the next step was to verify that the flame speeds
obtained using the developed scheme (and in a manner also the
original schemes) are in good agreement with experimental data.
A comparison between numerical diesel/air flame speeds
obtained using the combined scheme C and experimental flame
speeds due to Chong et al. 2011 was presented. Very good
agreements especially for / ¼ 0:8–1:2 were obtained. However a
slight difference was observed for very rich flames (/ ¼ 1:2–1:4).
Concerning diesel-biodiesel blend B20, a comparison between
numerical B20/air flame speeds using scheme C and experimental
flame speeds due to Chong et al. 2011 showed reasonable
agreements.
422 D. Alviso et al. / Fuel 191 (2017) 411–426

Then, a numerical diesel-biodiesel-ethanol blends flame speeds Appendix A

using scheme C was presented. The blends corresponded to BDE10
and BDE20. It was shown that adding ethanol does not change sig- Tables 6–10.
nificantly the flame speed (as for auto-ignition), at least up to 20%.
Unfortunately, no experimental data was found in the literature for
this triple blend.

Table 6
Package I (species H2 ; OH; HO2 ; H2 O2 ). Reaction rate coefficients given in the form k ¼ AT n expð
E=RTÞ. Units are mol cm cal s.

Reactions Andrae [32] Luo et al. [13]

A n E A n E
O þ OH ¼ O2 þ H 2.0E+14
0.4 0 1.015E+13
0.01
1.330E+02
REV 3.547E+15
0.41 1.660E+04
O þ H2 ¼ OH þ H 5.0E+04 2.67 6290 5.080E+04 2.67 6.292E+03
REV 2.667E+04 2.65 4.880E+03
OH þ H2 ¼ H2 O þ H 2.1E+08 1.52 3450 2.160E+08 1.51 3.430E+03
REV 2.298E+09 1.40 1.832E+04
OH þ OH ¼ O þ H2 O 4.3E+03 2.7
2486 1.465E+05 2.11
2.904E+03
REV 2.970E+06 2.02 1.340E+04
H þ H þ M ¼ H2 þ M 1.0E+18
1.0 0 1.146E+20
1.68 8.200E+02
REV 4.577E+19
1.40 1.044E+05
O þ O þ M ¼ O2 þ M 1.9E+13 0
1788 6.165E+15
0.50 0.000E+00
REV 4.515E+17
0.64 1.189E+05
H þ O þ M ¼ OH þ M 6.2E+16
0.6 0 4.714E+18
1.00 0.000E+00
REV 9.880E+17
0.74 1.021E+05
H þ OH þ M ¼ H2 O þ M 1.6E+22
2.0 0 4.500E+22
2.00 0.000E+00
REV 1.912E+23
1.83 1.185E+05
H þ HO2 ¼ H2 þ O2 4.3E+13 0 1411 1.660E+13 0.00 8.230E+02
REV 3.164E+12 0.35 5.551E+04
H þ HO2 ¼ OH þ OH 1.7E+14 0 874 7.079E+13 0.00 2.950E+02
REV 2.027E+10 0.72 3.684E+04
O þ HO2 ¼ O2 þ OH 3.3E+13 0 0 3.250E+13 0.00 0.000E+00
REV 3.252E+12 0.33 5.328E+04
OH þ HO2 ¼ H2 O þ O2 1.9E+16
1.0 0 2.890E+13 0.00
4.970E+02
REV 5.861E+13 0.24 6.908E+04
H2 O2 þ H ¼ OH þ H2 O 1.0E+13 0 3576 2.410E+13 0.00 3.970E+03
REV 1.269E+08 1.31 7.141E+04
H2 O2 þ H ¼ HO2 þ H2 1.7E+12 0 3755 6.025E+13 0.00 7.950E+03
REV 1.041E+11 0.70 2.395E+04
H2 O2 þ O ¼ OH þ HO2 6.6E+11 0 3974 9.550E+06 2.00 3.970E+03
REV 8.660E+03 2.68 1.856E+04
CO þ O2 ¼ CO2 þ O 2.5E+12 0 47,700 1.050E+12 0.00 4.254E+04
REV 7.950E+15
0.80 5.123E+04
CO þ OH ¼ CO2 þ H 1.5E+07 1.3
758 1.750E+05 1.95
4.348E+02
REV 4.629E+11 0.76 2.499E+04
HO2 þ CO ¼ CO2 þ OH 5.8E+13 0 22,934 1.570E+05 2.18 1.794E+04
REV 1.189E+08 1.71 7.991E+04

Table 7
Package II (species HCO; CH2 O; CH3 O; CH3 OH). Reaction rate coefficients given in the form k ¼ AT n expð
E=RTÞ. Units are mol cm cal s.

Reactions Andrae [32] Luo et al. [13]

A n E A n E
HCO þ M ¼ H þ CO þ M 1.9E+17
1.0 17,000 1.86E+17
1.00 1.70E+04
REV 1.403E+16
0.62 1.67E+03
HCO þ O2 ¼ HO2 þ CO 7.6E+12 0 406 2.71E+10 0.68
4.69E+02
REV 4.283E+09 0.99 3.31E+04
HCO þ H ¼ CO þ H2 1.2E+13 0.25 0 7.34E+13 0.00 0.00E+00
REV 2.211E+12 0.66 8.82E+04
HCO þ O ¼ CO þ OH 3.0E13 0.000 0 3.02E+13 0.00 0.00E+00
REV 4.775E+11 0.64 8.68E+04
HCO þ O ¼ CO2 þ H 3.0E13 0.000 0 3.00E+13 0.00 0.00E+00
REV 1.255E+18
0.55 1.12E+05
HCO þ OH ¼ H2 O þ CO 1.0E14 0.00 0 1.02E+14 0.00 0.00E+00
REV 3.269E+13 0.55 1.03E+05
CH3 þ HCO ¼ CH4 þ CO 1.2E14 0.00 0 2.65E+13 0.00 0.00E+00
REV 7.286E+14 0.21 8.98E+04
CH2 O þ O2 ¼ HCO þ HO2 6.0E13 0.00 40,660 8.07E+15 0.00 5.34E+04
REV 2.499E+14
0.06 1.39E+04
CH2 O þ OH ¼ HCO þ H2 O 3.4E09 1.18
447 7.82E+07 1.63
1.05E+03
REV 4.911E+06 1.81 2.90E+04
 D. Alviso et al. / Fuel 191 (2017) 411–426 423

Table 7 (continued)

Reactions Andrae [32] Luo et al. [13]

A n E A n E
CH2 O þ H ¼ HCO þ H2 1.3E08 1.62 2166 5.74E+07 1.90 2.74E+03
REV 3.388E+05 2.19 1.79E+04
CH2 O þ O ¼ HCO þ OH 1.8E13 0.00 3080 6.26E+09 1.15 2.26E+03
REV 1.940E+07 1.42 1.60E+04
CH3 þ CH2O ¼ CH4 þ HCO 7.8E
8 6.10 1967 3.83E+01 3.36 4.31E+03
REV 2.063E+02 3.20 2.10E+04
CH2 O þ HO2 ¼ HCO þ H2 O2 3.0E12 0.00 13,000 7.10E
03 4.52 6.58E+03
REV 2.426E
02 4.11 5.77E+03
CH2 O þ HðþMÞ ¼ CH3 OðþMÞ 5.4E11 0.454 2600
REV 6.800E+13 0.00 2.62E+04
CH3 O þ O2 ¼ CH2 O þ HO2 6.3E10 0.00 2600 4.38E
19 9.50
5.50E+03
REV 1.416E
20 9.82 2.11E+04
CH3 O þ H ¼ CH2 O þ H2 2.0E13 0.00 0 2.00E+13 0.00 0.00E+00
REV 1.232E+11 0.66 8.13E+04
CH3 þ OHðþMÞ ¼ CH3 OHðþMÞ 6.3E13 0.0 0
REV 1.900E+16 0.00 9.17E+04
CH3 OH þ H ¼ CH3 O þ H2 4.2E6 2.1 4868 3.60E+12 0.00 6.09E+03
REV 1.676E+11 0.21 5.87E+03
CH3 OH þ OH ¼ CH3 O þ H2 O 1.32E4 2.53 960 5.13E+05 2.13 2.45E+03
REV 2.541E+05 2.24 1.71E+04

Table 8
Package III (species CH; CH2 ; CH3 ; CH4 ). Reaction rate coefficients given in the form k ¼ AT n expð
E=RTÞ. Units are mol cm cal s.

Reactions Andrae [32] Luo et al. [13]

A n E A n E
CH3 þ HðþMÞ ¼ CH4 ðþMÞ 1.3E16
0.63 383 2.108E+14 0.00 0.000E+00
CH4 þ H ¼ CH3 þ H2 2.2E04 3.00 8750 6.140E+05 2.50 9.587E+03
REV 6.727E+02 2.95 8.047E+03
CH4 þ OH ¼ CH3 þ H2 O 1.6E06 2.10 2460 5.830E+04 2.60 2.190E+03
REV 6.796E+02 2.94 1.554E+04
CH4 þ O ¼ CH3 þ OH 1.0E09 1.5 8604 4.396E+05 2.50 6.577E+03
REV 2.528E+02 2.93 3.625E+03
CH4 þ HO2 ¼ CH3 þ H2 O2 1.8E11 0.00 18,700 7.046E+04 2.50 2.100E+04
REV 4.468E+04 2.25 3.462E+03
CH2 þ CH4 ¼ CH3 þ CH3 4.3E12 0.0 10,030 2.460E+06 2.00 8.270E+03
REV 1.088E+03 2.75 1.057E+04
CH3 O þ H ¼ CH3 þ OH 1.0E14 0.0 0 1.562E+16
0.84
5.821E+03
REV 7.226E+11 0.00 5.484E+03
CH3 þ OH ¼ CH2 þ H2 O 7.5E06 2.0 5000 5.600E+07 1.60 5.420E+03
REV 1.476E+09 1.19 1.647E+04
CH3 þ HO2 ¼ CH3 O þ OH 8.0E12 0.00 0 1.000E+12 0.27
6.875E+02
REV 6.190E+12 0.15 2.455E+04
CH4 þ O2 ¼ CH3 þ HO2 7.9E13 0.00 56,000 2.018E+07 2.13 5.321E+04
REV 1.160E+05 2.23
3.022E+03
CH3 þ O ¼ CH2 O þ H 8.4E13 0.0 0 5.540E+13 0.05
1.360E+02
REV 3.873E+15
0.15 6.841E+04
CH3 þ O2 ¼ CH3 O þ O 2.9E13 0.0 30,481 7.546E+12 0.00 2.832E+04
REV 4.668E+14
0.45 2.880E+02
CH3 þ O2 ¼ CH2 O þ OH 1.9E12 0.0 20,315 5.870E+11 0.00 1.384E+04
REV 1.175E+11 0.19 6.566E+04
CH2 þ O2 ¼ CO2 þ H þ H 3.3E21
3.3 2867 2.270E+12 0.00 1.000E+03
REV 0.000E+00 0.00 0.000E+00
CH2 þ O ¼ CO þ H þ H 5.0E13 0.0 0 5.000E+13 0.00 0.000E+00
REV 0.000E+00 0.00 0.000E+00
CH2 þ H ¼ CH þ H2 1.0E18
1.56 0 1.000E+18
1.56 0.000E+00
REV 3.233E+15
0.92 1.050E+03
CH2 þ OH ¼ CH þ H2 O 1.1E07 2.0 3000 1.130E+07 2.00 3.000E+03
REV 3.887E+05 2.53 1.894E+04
CH þ O2 ¼ HCO þ O 3.3E13 0.0 0 3.300E+13 0.00 0.000E+00
REV 9.272E+12 0.16 7.121E+04
CH þ O ¼ CO þ H 5.7E13 0.0 0 5.700E+13 0.00 0.000E+00
REV 2.774E+15 0.00 1.760E+05
CH þ OH ¼ HCO þ H 3.0E13 0.0 0 3.000E+13 0.00 0.000E+00
REV 5.069E+14 0.00 8.811E+04
CH2 þ H ¼ CH þ H2 1.0E18
1.56 0 2.700E+11 0.67 2.570E+04
REV 1.897E+11 0.67 2.873E+04
CH þ H2 O ¼ CH2 O þ H 5.7E12 0.0
751 1.713E+13 0.00
7.550E+02
REV 8.372E+14 0.00 5.752E+04
CH þ CO2 ¼ HCO þ CO 3.4E12 0.0 690 1.700E+12 0.00 6.850E+02
REV 2.565E+11 0.00 6.646E+04
424 D. Alviso et al. / Fuel 191 (2017) 411–426

Table 9
Package IV (species C 2 H6 ; C 2 H5 ; C 2 H4 ; C 2 H3 ; C 2 H2 ; C 2 H5 CHO). Reaction rate coefficients given in the form k ¼ AT n expð
E=RTÞ. Units are mol cm cal s.

Reactions Andrae [32] Luo et al. [13]

A n E A n E
CH3 þ CH3 ðþMÞ ¼ C2 H6 ðþMÞ 2.1E16
0.97 620 1.880E+50
9.72 1.073E+05
C 2 H5 þ HðþMÞ ¼ C 2 H6 ðþMÞ 5.2E17
0.99 1580 5.210E+17
0.99 1.580E+03
C2 H6 þ H ¼ C2 H5 þ H2 5.4E02 3.50 5210 1.150E+08 1.90 7.530E+03
REV 1.062E+04 2.58 9.760E+03
C2 H6 þ O ¼ C2 H5 þ OH 3.0E+07 2.0 5115 3.550E+06 2.40 5.830E+03
REV 1.721E+02 3.06 6.648E+03
C2 H6 þ OH ¼ C2 H5 þ H2 O 7.2E+06 2.0 864 1.480E+07 1.90 9.500E+02
REV 1.454E+04 2.48 1.807E+04
C2 H6 þ O2 ¼ C2 H5 þ HO2 5.0E+13 0 55,000 6.030E+13 0.00 5.187E+04
REV 2.921E+10 0.33
5.930E+02
C2 H6 þ CH3 ¼ C2 H5 þ CH4 5.5E
01 4.0 8300 1.510E
07 6.00 6.047E+03
REV 1.273E
08 6.24 9.817E+03
C2 H6 þ HO2 ¼ C2 H5 þ H2 O2 1.3E+13 0 20,460 3.460E+01 3.61 1.692E+04
REV 1.849E+00 3.60 3.151E+03
C2 H4 þ H þ M ¼ C2 H5 þ M 1.1E+12 0.454 1822 5.400E+11 0.45 1.820E+03
C2 H5 þ CH3 ¼ C2 H4 þ CH4 1.1E+12 0 0 1.180E+04 2.45
2.921E+03
REV 2.390E+06 2.40 6.669E+04
C2 H5 þ H ¼ CH3 þ CH3 4.9E+12 0.35 0 3.269E+17
0.93 3.100E+02
REV 6.840E+12 0.10 1.060E+04
C2 H5 þ O2 ¼ C2 H4 þ HO2 1.1E+10 0
2190 7.561E+14
1.01 4.749E+03
REV 8.802E+14
0.96 1.813E+04
C2 H5 þ O2 ¼ C2 H4 þ HO2 1.1E+10 0
2190 4.000E
01 3.88 1.362E+04
REV 4.656E
01 3.93 2.700E+04
C2 H3 þ HðþMÞ ¼ C2 H4 ðþMÞ 6.1E12 0.27 280 1.360E+14 0.17 6.600E+02
C2 H4 þ H ¼ C2 H3 þ H2 5.4E14 0.0 14,900 5.070E+07 1.93 1.295E+04
REV 1.601E+04 2.44 5.190E+03
C 2 H4 þ O ¼ CH3 þ HCO 8.1E06 1.88 180 8.564E+06 1.88 1.830E+02
REV 3.333E+02 2.60 2.614E+04
C2 H4 þ OH ¼ C2 H3 þ H2 O 2.0E13 0.00 5940 2.090E+06 2.01 1.160E+03
REV 7.021E+03 2.41 8.292E+03
C2 H4 þ CH3 ¼ C2 H3 þ CH4 5.0E11 0.00 15,000 6.620E+00 3.70 9.500E+03
REV 1.440E+00 4.02 5.472E+03
CH þ CH4 ¼ C 2 H4 þ H 6.0E13 0.0 0 6.000E+13 0.00 0.000E+00
REV 3.573E+14 0.00 5.548E+04
H þ C2 H2 ðþMÞ ¼ C2 H3 ðþMÞ 3.1E11 0.58 2590 5.600E+12 0.00 2.400E+03
C2 H3 þ O2 ¼ C2 H2 þ HO2 5.2E15
1.26 3310 2.120E
06 6.00 9.484E+03
REV 1.087E
05 5.91 2.404E+04
C2 H3 þ O2 ¼ CH2 O þ HCO 1.1E23
3.29 3890 1.700E+29
5.31 6.500E+03
REV 7.987E+27
4.88 9.345E+04
C2 H3 þ CH3 ¼ C2 H2 þ CH4 2.1E13 0.00 0 3.920E+11 0.00 0.000E+00
REV 3.497E+14
0.19 7.078E+04
C2 H3 þ H ¼ C2 H2 þ H2 4.0E13 0.00 0 3.000E+13 0.00 0.000E+00
REV 2.932E+13 0.25 6.924E+04
C2 H3 þ OH ¼ C2 H2 þ H2 O 2.0E13 0.0 0 5.000E+12 0.00 0.000E+00
REV 5.200E+13 0.15 8.413E+04
C 2 H2 þ O ¼ CH2 þ CO 6.1E6 2.00 1900 6.940E+06 2.00 1.900E+03
REV 6.531E+04 2.32 5.077E+04
C 2 H2 þ O ¼ HCCO þ H 1.4E7 2.00 1900 1.350E+07 2.00 1.900E+03
REV 3.732E+08 1.07 1.535E+04
OH þ C2 H2 ¼ CH2 CO þ H 2.2E
4 4.5
1000 3.236E+13 0.00 1.200E+04
REV 1.136E+20
1.55 3.596E+04
OH þ C 2 H2 ¼ CH3 þ CO 4.8E
4 4.0
2000 4.830E
04 4.00
2.000E+03
REV 3.495E
06 4.64 5.212E+04
C 2 H5 þ HCO ¼ C 2 H5 CHO 1.8E13 0.0 0 1.810E+13 0.00 0.000E+00
REV 1.500E+27
3.21 8.704E+04

Table 10
n
Package V (species C 7 H16 ; C 7 H15
2 ; CH2 CO; HCCO). Reaction rate coefficients given in the form k ¼ AT expð
E=RTÞ. Units are mol cm cal s.

Reactions Andrae [32] Luo et al. [13]

A n E A n E
CH2 þ CO þ M ¼ CH2 CO þ M 8.1E+11 0.5 4510 8.10E+11 0.00 0.00E+00
CH2 CO þ H ¼ CH3 þ CO 5.9E+06 2.0 1300 1.10E+13 0.00 3.40E+03
REV 2.40E+12 0.00 4.02E+04
CH2 CO þ H ¼ HCCO þ H2 3.0E+07 2.0 10,000 2.00E+14 0.00 8.00E+03
REV 3.00E+09 0.64
1.10E+03
CH2 CO þ O ¼ CO2 þ CH2 1.8E+12 0 1350 1.75E+12 0.00 1.35E+03
REV 1.24E+10 0.68 5.17E+04
CH2 CO þ O ¼ HCCO þ OH 2.0E+07 2.0 10,000 1.00E+13 0.00 8.00E+03
REV 7.88E+07 0.62
2.51E+03
 D. Alviso et al. / Fuel 191 (2017) 411–426 425

Table 10 (continued)

Reactions Andrae [32] Luo et al. [13]

A n E A n E
CH2 CO þ OH ¼ HCCO þ H2 O 1.0E+07 2.0 3000 1.00E+13 0.00 2.00E+03
REV 1.60E+09 0.53 7.79E+03
HCCO þ O ¼ H þ CO þ CO 1.0E+14 0 0 8.00E+13 0.00 0.00E+00
REV 0.00E+00 0.00 0.00E+00
HCCO þ O2 ¼ OH þ CO þ CO 2.9E+07 1.7 1000 4.20E+10 0.00 8.50E+02
REV 0.00E+00 0.00 0.00E+00
CH þ CO þ M ¼ HCCO þ M 5.0E+13 0 0 6.50E+15 0.00 5.88E+04
REV 1.79E+10 1.61
8.27E+03
CH þ CH2 O ¼ CH2 CO þ H 9.5E+13 0
515 9.46E+13 0.00
5.15E+02
REV 1.62E+15 0.00 6.91E+04
CH þ HCCO ¼ C 2 H2 þ CO 5.0E+13 0 0 5.00E+13 0.00 0.00E+00
REV 1.72E+17 0.00 1.65E+05
C 7 H16 þ H ¼ C 7 H15
2 þ H2 2.60E06 2.40 4469 2.60E+06 2.40 4.47E+03
REV 3.93E+03 2.74 1.13E+04
C 7 H16 þ OH ¼ C 7 H15
2 þ H2 O 9.40E07 1.61
35 9.40E+07 1.61
3.50E+01
REV 6.15E+05 1.95 2.19E+04
C7 H16 þ HO2 ¼ C7 H15
2 þ H2 O2 3.36E13 0.00 17,690 1.12E+13 0.00 1.77E+04
REV 4.35E+11 0.01 8.16E+03
C 7 H16 þ O2 ¼ C 7 H15
2 þ HO2 4.00E13 0.00 50,190 4.00E+13 0.00 5.01E+04
REV 1.10E+09 0.67
5.41E+02

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