Applied Energy 111 (2013) 827841

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Applied Energy
journal homepage: www.elsevier.com/locate/apenergy

Computational study of biodieseldiesel fuel blends on emission

characteristics for a light-duty diesel engine using OpenFOAM
Harun Mohamed Ismail a, Hoon Kiat Ng a,, Suyin Gan b, Tommaso Lucchini c
a
Department of Mechanical, Materials and Manufacturing Engineering, The University of Nottingham Malaysia Campus, Jalan Broga, 43500 Semenyih, Selangor Darul Ehsan, Malaysia
b
Department of Chemical and Environmental Engineering, The University of Nottingham Malaysia Campus, Jalan Broga, 43500 Semenyih, Selangor Darul Ehsan, Malaysia
c
Department of Energy, Politecnico Di Milano, Via Lambruschini 4, 20156 Milano, Italy

h i g h l i g h t s

 Relations between emissions and combustion are established for diesel and biodiesel.
 Biodiesel with lower ID and longer MCC produces less NOx.
 Inuence of fuel bound oxygen content is signicant during the MCC.
 Neat CME is best for both NOx and soot reduction across all the engine loads.
 Emissions reduction capability of biodiesel is enhanced/moderated by engine loads.

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

Article history: In this paper, emissions formation process and its interaction with the combustion event are established
Received 11 September 2012 for fossil diesel and the methyl esters of coconut (CME), palm (PME) and soy (SME) across three different
Received in revised form 17 May 2013 engine conditions. Here, the OpenFOAM open source CFD codes are utilised to simulate the in-cylinder
Accepted 24 May 2013
events. The ignition delay (ID) period and the timing of peak pressure are accurately predicted to within
Available online 19 June 2013
0.2 crank angle for all the test cases. The maximum error between the experimental and computed
peak pressure values across the test range is limited to below 4.5%. The change in the fuel type from fossil
Keywords:
diesel to biodiesel alters the physical and the chemical delays, both of which affect the overall ID period.
Biodiesel
Multi-component fuel
As a result, variations in the combustion behaviour and hence the emission characteristics are observed.
Diesel engine emissions Neat CME is found to produce both NOx and soot reduction across all the engine loads tested. The most
OpenFOAM signicant reduction in soot level is achieved at high load operation, while greatest NOx reduction is
recorded under low load condition when neat or B50 blends of the test biodiesel fuels are used. The best
operating condition to result in simultaneous soot and NOx reduction through the use of biodiesel is at
mid load condition with an engine speed of 2000 rev/min.
2013 Elsevier Ltd. All rights reserved.

1. Introduction
Compression ignition (CI) engine generally produce greater
thermal efciency than gasoline engine because of its higher com-
pression ratio. As a result, CI engine is increasingly favoured in re-
cent years as the leading propulsion system for ground
transportation. Nevertheless, due to depleting fossil fuel reserves
and increasingly stringent emissions standards, research efforts
are focused on developing more efcient CI engine through various
operating and fuelling strategies, as well as novel design concept of
the combustion system. One key research area that has gained
much attention in recent years is the use of biodiesel, which a
renewable and environmentally-friendly fuel. Biodiesel reduces
Corresponding author. Tel.: +60 3 89248161; fax: +60 3 89248017.
E-mail address: hoonkiat.ng@nottingham.edu.my (H.K. Ng).
carbon dioxide (CO2) emissions over its life-cycle because of its
low carbon cycle-time. By using biodiesel instead of fossil diesel,
the increase in atmospheric content of CO2 can be slowed down
thus mitigating the effects of global warming. Additionally, biodie-
sel can be used with minimal or no modications in existing diesel
engine due to its physicochemical properties which closely resem-
ble that of fossil diesel [1].
Despite these apparent advantages, there is still signicant
knowledge gap in the fundamental understanding of how biodiesel
impacts the engine output performance, combustion efciency and
emission characteristics. Neat and blends of biodiesel are reported
to reduce particulate matter (PM), hydrocarbons (HC) and carbon
monoxide (CO) emissions [2] in the exhaust stream. In contrast,
the effects on nitrogen oxides (NOx) are inconclusive. Some studies
have reported that an increase in NOx level is observed [24] when
biodiesel fuels are tested in unmodied engines. On the other

0306-2619/$ - see front matter 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.apenergy.2013.05.068
828 H. Mohamed Ismail et al. / Applied Energy 111 (2013) 827841

Nomenclature

ATDC after top-dead centre ME methyl esters

B0 100% diesel N2 nitrogen
B50 50% biodieseldiesel mixture NO nitrogen-monoxide
B100 100% biodiesel NOx nitrogen oxides
CAD crank angle degree O2 oxygen
CFD computational uid dynamics PM particulate matter
CO carbon monoxide PMC premixed combustion
CO2 carbon dioxide PME palm methyl ester
CME coconut methyl ester SME soybean methyl ester
CI compression ignition SOC start of combustion
HC hydrocarbon SOI start of injection
EOC end of combustion TDAC tabulation of dynamic-adaptive chemistry
EOI end of injection TDC top-dead centre
EVO exhaust valve opening Xi normalised data
HRR heat-release rate Zi maximum/minimum data
ID ignition delay k1, k2 normalisation range
IVC intake-valve closing
MCC mixing-controlled combustion

hand, there are also studies documenting that biodiesel fuels such
as palm methyl ester (PME) and coconut methyl ester (CME)
reduce the formation of NOx [5,6] especially for engine operation
with exhaust gas recirculation (EGR) [4]. Other reported works
indicate that the variation in the engine-out NOx is due to system
responses, such as a change in the fuel injection timing and the ef-
fects of turbocharger and EGR [4,7,8]. On a fundamental level, the
difference in the combustion attributes such as ignition delay (ID)
period, combustion phasing and ame temperature among various
biodiesel fuels is reported as the main cause for the observed dif-
ferences in the NOx level [3,915]. It is challenging to ascertain ex-
actly the impact on engine-out behaviour when different biodiesel
fuels are used mainly because the fundamental understanding of
the effects of thermophysical properties and oxidation chemistry
of the biodiesel fuels on combustion and emissions processes is
limited. Different biodiesel fuel types, coupled with the varying de-
gree of blending level with fossil diesel result in a diverse physical
and chemical attributes such as density, kinematic viscosity, ash
point, heating value, molecular structures and reaction kinetics.
Therefore, these fuels behave differently under different range of
engine operating conditions. As a result, comprehensive studies
on this area are required in order to fully understand and conclu-
sively determine the benets and drawbacks of biodiesel fuels
[16,17] in terms of their combustion and emission behaviours.
Set against this background, this study aims to characterise the
emissions prole from the combustion of CME, PME and soy
methyl esters (SME) and their blends as compared to fossil diesel.
A computational uid dynamics (CFD) approach is used together
with an experimental engine test-bed study to capture the
corresponding physical and chemical events governing the com-
bustion of these fuels in a light-duty diesel engine. Here, the Open-
FOAM open source CFD code is utilised for the simulation. A set of
numerical experiments are performed to elucidate the key effects
of CME, PME and SME at 0% (B100) diesel mixture and 50% diesel
mixture (B50) on the emission characteristics under a constant
engine speed of 2000 rev/min and at engine load values of
0.5 kW (low), 1.5 kW (mid) and 2.5 kW (high). For the emission
analysis, the in-cylinder conditions is resolved spatially and
temporally to determine the governing factors giving rise to the
observed NOx and soot levels at the exhaust valve opening (EVO)
time. Correlations between combustion behaviour and emission
characteristics are established for fossil diesel, CME, PME and
SME over a range of engine conditions. In addition, detailed
explanations of the in-cylinder conditions, fuel attributes and com-
bustion characteristics responsible for the recorded variations in
NOx and soot trends are also presented.
2. Engine experimental setup and CFD sub-model formulations
2.1. Heat-release rate (HRR) analysis
The assumptions and calculation of the HRR prole are pre-
sented in this section. The heat release due to combustion is deter-
mined from the First Law of Thermodynamics for both the
experimental and simulated data. Using the change in pressure
and volume per unit of crank angle degree, the net rate of heat re-
lease is calculated using Eq. (1), where c is the adiabatic exponent
with a value of 1.35 [18,19], p is the in-cylinder pressure and V is
the volume as a function of crank angle.
dQ net c dm 1 dp
p V 1
dh c  1 dh c  1 dh
Variations in the HRR proles and the associate combustion
behaviour are classied according to three distinctive features as
shown in Fig. 1. The rst two categories are known as the premixed
combustion (PMC) and the mixing-controlled combustion (MCC).
The combustion is predominantly governed by the chemical reac-
tion rate in the PMC phase [18], whereas the burn rate in the MCC
phase (or sometimes known as the diffusion-burn phase) is con-
trolled by the locally available oxygen concentration and the local
mixing process which is dictated by the level of turbulent intensity
[18,19]. Finally, the third category of combustion falls in between
these two extreme features, with balanced PMC and MCC phases.
In this study, the test fuels are observed to undergo longer PMC
phase relative to the MCC phase under low load condition due to
the shorter fuel injection duration. Similarly, test fuels with long
ID period tend to have more fuel mass burnt during the PMC phase
and is indicated by the high peak HRR value. Here, the MCC phase
is short and for some cases, it is negligible. Test fuels exhibiting
shorter ID period or under high engine load conditions typically
produce longer MCC phase. Due to the shorter time for fuel and
air to mix from the short ID period or the longer fuel injection
duration to accommodate higher fuel mass required at high load,
the PMC phase is negligible as compared to the MCC phase as
shown in Fig. 1.
 H. Mohamed Ismail et al. / Applied Energy 111 (2013) 827841 829

55
PMC-Dominated
High peak PMC/MCC-Balanced
45 PMC MCC-Dominated

Heat-Release Rate / [J/CAD]

Medium peak
PMC
35
Balanced PMC
Low peak and MCC phases
25
PMC
Short or negligible
diffusion-burn
15 period

5
Longer
diffusion-burn
period
-5
-15 -5 5 15 25 35 45
Crank Angle / [degrees]

Fig. 1. Denition of the combustion phases utilised in this study.

2.2. Light-duty diesel engine experimental setup 2.3. Computational mesh and initial conditions

Simulations are conducted for a light-duty diesel engine with a A 90o sector mesh is generated to take advantage of the symme-
quiescent, bowl-in-piston combustion chamber conguration. The try imposed by the four equally-spaced injector nozzle holes in-
test engine has a compression ratio of 19.1:1 and a displacement stalled centrally. Hexahedral mesh type is employed here to
volume of 347 cm3. A mechanical fuel injection system delivers construct the mesh for the volume of the combustion chamber as
the fuel through an injector which has four equally-spaced holes. shown in Fig. 2. The initial conditions of intake pressure and tem-
The air-cooled engine operates at speeds between 1500 and perature at the intake valve closing (IVC) time are 1.23 bar and
3500 rev/min and loads between 0.5 and 2.5 kW. The engine bore 300 K, respectively. Here, the dynamic mesh layering utility of
and stroke dimensions are given as 80 mm and 69 mm, respec- mesh topological change library (lib-ICE) [2022] is utilised for
tively. Table 1 summarises the key specications of the test engine the modelling of the compression and expansion strokes. The mesh
used in this study. The test engine is coupled to an asynchronous with a cell size of 2.0 (radial)  2.5 (axial)  2.0 (azimuthal) mm is
motor mounted on an engine test stand, which forms the central used throughout the study because this resolution is found to pro-
pairing of the test bed. Engine responses such as torque, exhaust duce similar accuracy but with shorter computing time as com-
temperature, specic fuel consumption, equivalence ratio and vol- pared to that from a ner resolution mesh. Further details on the
umetric efciency are measured from the sensors contained within mesh congurations are reported by Ismail et al. [14,15].
the engine test stand [6]. Tailpipe emissions are measured using a
Bosch BEA350 gas emissions analyser and a Bosch RTM 430 smoke
2.4. Formulation of the CFD sub-model
opacimeter. The experimental data is recorded at fully warm, stea-
dy state engine conditions. Details of the experimental measure-
Details of the CFD submodel used which was implemented in
ments and results have been reported elsewhere [5,6].
OpenFOAM open source CFD code under the Lib-ICE library as
developed by Lucchini et al. [22] is described in this section. Here,
the in-cylinder ows and turbulence effects are calculated using
the commonly used RNG k-e turbulence model [14,23]. The liquid
Table 1
Engine specications and test conditions for the CFD simulation study.
spray structures are predicted using the Huh injector model to rep-
resent the injector and fuel droplets primary spray break-up
Engine specications
[14,22]. Fuel spray atomisation is modelled using the modied
Engine type Light-duty diesel
Piston type Bowl-in-piston
Cylinder head type Flat cylinder head
Displacement volume per-cylinder 347 cm3
Compression ratio 19.1:1
Stroke 69 mm
Bore 80 mm
Connecting rod length 114.5 mm
Intake valve closing (IVC) 140 ATDC
Exhaust valve opening (EVO) 140 ATDC
Engine speed 15003500 rev/min
Load (kW) Speed (rev/min) Fuel (B100) Fuel (B50)
Validation test range
0.5 2000 CME CME
0.5 2000 PME PME
0.5 2000 SME SME
1.5 2000 CME CME
1.5 2000 PME PME
1.5 2000 SME SME
2.5 2000 CME CME
2.5 2000 PME PME
2.5 2000 SME SME
Fig. 2. 90 Sector mesh of the test engine.
830 H. Mohamed Ismail et al. / Applied Energy 111 (2013) 827841
Huh and Gosman model, where the model constants of C4 and C5
are set to 3 and 2 [14,22,24], respectively for all the test cases.
The secondary break-up is simulated using the KelvinHelmoltz
and RayleighTaylor model [14]. The heat transfer process from
the in-cylinder gasses to the chamber walls is modelled using the
Hans and Reitz correlation [14,15,25]. On the other hand, heat
transfer between the discrete and gas phases is determined using
the RansMarshall correlation [14,15,20]. The Bai and Gosman cor-
relation is utilised to predict the dynamics characteristics of drop-
lets wall interactions on the piston bowl wall surface [14,15].
Further details about the spray model constants as well as model
implementations and validations have been reported extensively
[14,15,2022,26].
Twelve thermo-physical and transport properties are identied
to have signicant inuences on the fuel spray and vapour
structures. These are density, vapour pressure, heat of vaporisa-
tion, liquid heat capacity, vapour heat capacity, second-virial coef-
cient, liquid dynamic viscosity, vapour dynamic viscosity, liquid
thermal conductivity, vapour thermal conductivity, surface tension
and vapour diffusivity. Fuel properties generally depend on the
presence of various molecular groups, for example, petroleum die-
sel comprises hundreds of molecules ranging from n-heptane, n-
decane and iso-octane. In this study however, the surrogate fuel
species approach is adopted where the properties are based on
the chemical compositions and structures of the few important
groups in the fuels over a wide temperature range. Here, the spray
characteristics of diesel fuel are dened by the thermo-physical
and transport properties of C14H30 surrogate. The properties of
CME, PME and SME developed by Ismail et al. [15] are utilised
for the neat biodiesel fuels. For the B50 biodieseldiesel blends,
the properties of neat biodiesel are mixed with that of C14H30 using
multi-component modelling approach at 50% blend ratio.
For the fuel oxidation chemistry, two widely utilised and well
validated chemical kinetics mechanisms for diesel [14,27] and bio-
diesel [14,15,18], respectively are employed in this study. A mod-
ied n-heptane mechanism is used to represent the combustion
of diesel fuel [14,27]. On the other hand, the BOS-V2 mechanism
containing 113 species and 399 reactions with integrated NOx
reaction kinetics as developed by Ismail et al. [14] is employed to
represent the combustion chemistry of CME, PME and SME fuels.
The different fuels are modelled by varying the mass composition
ratio of saturated and unsaturated component with respect to indi-
vidual fuel type [14]. When the biodiesel fuel changes from CME to
PME and SME, the level of unsaturation for the fuel component is
varied from 20% to 50% and 80%, respectively to match the typical
unsaturation levels present in the actual biodiesel fuel [14,15,18].
Here, two global reactions are used to represent the saturated
and unsaturated components in biodiesel fuels [14]. These reac-
tions link the fuel molecules decomposition into sub molecules
of methyl decanoate (MD), methyl butanoate (MB), methyl (E)-2-
butenoate (MB2D) and n-heptane) [14,15]. This is to ensure the en-
ergy release during the combustion process closely matches that of
the actual biodiesel fuel [14,15,18]. The use of these reduced mech-
anisms is strategic here in order to limit the otherwise long run-
time of the 3D CFD simulation for the test cases.
In this study, only thermal NOx formation is deemed important
under this engine setup and conditions. Thermal NOx formation
typically occurs in oxygen rich (lean combustion) region with high
temperature, which is commonly observed downstream of the
ame front in the burnout gas zones [19]. Thermal NOx mechanism
involves the reactions of molecular nitrogen and atomic nitrogen
with oxygen and oxygen containing radicals. For the prediction
of in-cylinder NOx evolution here, the extended Zeldovich mecha-
nism is integrated into the fuel combustion chemistries. The mech-
anism also includes NO formation via N2O pathways, as well as
NO2 formation as previous experimental studies have indicated
that NO2 can be between 10% and 30% of the total exhaust NOx
emission. The NOx level computed in the simulation here is the
summation of NO and NO2.
Finally, a phenomenological model is used to predict the soot
emissions. The Hiroyasu approach is employed to describe the
formation of soot, while its oxidation process is estimated by the
NagleStrickland and Constable model. In order to obtain compa-
rable soot data set, both the experimental and simulated data set
is normalised using Eq. (2). Here, Zi is the input or output variable
and k1 ; k2 is the ranges of the function [28]. The data is norma-
lised between the range of 0 and 1 such that the experimental
and computed data are in the same scale for ease of comparison.
!
Z i  Z min
i
xi k1 k2  k1 2
Z max
i  Z min
i
For the computation of the combustion event, each computa-
tional cell is assumed to be a homogeneous system. The chemical
mechanism as described above are implemented to estimate the
PMC and MCC combustion phases. The chemical reaction rates
are calculated by an ordinary differential equation (ODE) stiff sol-
ver using an operator-splitting technique. For each time-step Dt,
the ODE solver maps the initial composition w0 = w(t0) to the re-
acted value w(t0 + Dt) which is a unique function of w0 called the
reaction mapping, (w0). The composition array is dened by
w fY i ; . . . ; Y Ns ; p; Tg, where Yi is the species mass fraction, Ns the
number of species, T the temperature and p the pressure. However,
direct-integration of the full chemistry is computationally
demanding. For this reason, the proposed combustion model works
in combination with the tabulation of dynamic-adaptive chemistry
(TDAC) algorithm [14,21,29]. Such approach combines mechanism
reduction and tabulation techniques that are both performed
on-the-y in each cell during the simulation. Signicant speed-
up factors compared to direct-integration are ensured (>300),
allowing semi-detailed mechanism to be used for complex CI en-
gine simulations.
3. Results and discussion
A total of 18 engine test points are utilised to validate and
assess the emission characteristics of six biodiesel fuel type and
blends in comparison with fossil diesel. The validated fuels are
CME, PME and SME at 0% (B100) diesel mixture and 50% diesel
mixture (B50). The selection of B50 biodieseldiesel mixture is to
allow a feasible number of test points to be conducted, while still
allowing sufcient differences to be observed in the test results.
The engine speed is maintained at 2000 rev/min and the engine
load is varied from low (0.5 kW) to mid (1.5 kW) and high
(2.5 kW) loads as given in Table 1. A medium engine speed is
chosen here because it lies within the typical operating range of
on-road vehicles and also within the engines drivability limits.
Meanwhile, the chosen engine loads are set between engine idling
condition and the maximum loads achievable for all the test fuels
[5].
3.1. Validation
Fig. 3af shows the comparison between experimental and sim-
ulated in-cylinder pressure trace and HRR for the six test fuels at
three different engine load conditions. Generally, good levels of
accuracy are achieved in the prediction of the ID period, peak pres-
sures, pressure traces and HRR proles. The change in combustion
behaviour from PMC to MCC phase due to prolonged fuel injection
period is also clearly captured for all the simulations. Additionally,
the ID period and the timing of peak pressure are predicted within
0.2 crank angle degrees (CAD) across the entire engine loads
 H. Mohamed Ismail et al. / Applied Energy 111 (2013) 827841
(a) CME(B50) (b) PME(B50)
Pressure / [bar]
(d) CME(B100) (e) PME(B100)
Pressure / [bar]
Crank Angle Degrees / [CAD] Crank Angle Degrees / [CAD]
Fig. 3. Pressure trace and HRR for low, mid and high load operations at 2000 rev/min for (a) CME (B50), (b) PME (B50), (c) SME (B50), (d) CME (B100), (e) PME (B100), and (f)
SME (B100).
tested. The maximum error between experimental and computed
peak pressure values across the test range is limited to below
4.5%. Furthermore, the timing of the peak pressure varies only by
1.5 CAD of the experimental data for all the test fuels and engine
loads.
Fig. 4af illustrates the calculated and measured engine-out
NOx and soot emissions at EVO timing. The majority of the test
cases have a maximum percentage error between the predicted
and measured values within an acceptable limit of 8.7% for NOx
and 13.5% for soot. Both the NOx and soot trends for all the tests
are also well predicted. Further details of the CFD engine valida-
tions against the experimental results have been reported by Is-
mail et al. [14]. Based on this validation exercise, it can be
concluded that the selected CFD models and model constants are
able to accurately predict the in-cylinder combustion and emission
characteristics with acceptable error tolerance limits.
3.2. NOx emissions
In this study, thermal NOx is computed as the summation of NO
and NO2 as discussed above [21]. Fig. 5 illustrates the percentage
variations in NOx levels at EVO when diesel fuel is substituted by
different biodiesel fuel blends at different engine load conditions.
Here, the variation in NOx levels is computed with respect to the
level produced by diesel fuel. The percentage of NOx variation is
determined using Eq. (3), where NOx,fuel is the NOx concentration
produced when using different fuels and NOx,B0 is the NOx level
from the combustion of diesel fuel. Here, the computation is based
on the NOx level at EVO for each fuel. From this, the impact of dif-
ferent fuels and engine loads on the NOx emission can be identied.
NOx;fuel  NOx;B0
% Change NOx  100%
NOx;B0
The unique fuel attributes and combustion characteristics inu-
encing the temporal evolution of NOx throughout the combustion
period are found to eventually determine the nal level of NOx ex-
hausted. This study shows that the differences in fuel unsaturation
831
(c) SME(B50)
Rate of Heat-Release
/ [J/CAD]
(f) SME(B100)
Rate of Heat-Release
/ [J/CAD]
Crank Angle Degrees / [CAD]
level, fuel bound oxygen content, ID period and combustion behav-
iour due to the use of various fuels signicantly affect the NOx evo-
lution process. These factors are discussed as follows.
3.2.1. Inuence of fuel types
Neat and B50 blend of CME are found to give the lowest NOx per
unit of fuel mass injected across the engine loads tested, as illus-
trated in Fig. 6. Among the B50 blends of biodiesel fuels, B50
SME produces the highest NOx emission index (EI), followed by
B50 PME and nally B50 CME throughout the different engine
loads. This observation is also applicable for the various neat bio-
diesel fuels. The use of neat and B50 blend of CME consistently re-
sults in a reduction of exhaust NOx level, as well as giving the
highest percentage of NOx reduction at all the tested engine loads
as shown in Figs. 5 and 6. On the other hand, neat and B50 blends
of PME and SME are found to signicantly reduce NOx level in the
exhaust stream only at certain values of engine load, while they
produce higher NOx at other load conditions. For example, higher
NOx level as compared to that of diesel fuel is produced when
B50 blends of SME, neat PME and neat SME are used at mid-load
condition, whereas neat PME and SME result in greater NOx emis-
sion at high load condition.
The reason for the observed trends lies in the way NOx is pro-
duced in CI engines. The NOx formation process is dictated by
two main in-cylinder conditions, namely the local temperatures
and oxygen concentrations. High temperature and the presence
of oxygen promote NOx formation [18,19,30]. These in-cylinder
conditions are in turn controlled by the engine operating condi-
tions, fuel chemical and physical attributes, as well as the combus-
tion characteristics. The inuence of engine operating conditions
on NOx emission is mainly through the start of injection (SOI)
timing. Here, biodiesel fuels tend to have an advanced SOI as
compared to diesel fuel as a direct result of the higher bulk modu-
3 lus and viscosity. Advanced SOI typically leads to higher in-cylin-
der temperature due to the cumulative effects of combustion and
piston-assisted compression early in the compression stroke
[18,19,30]. As such, the residence time of high temperature, com-
bustion products is longer. Consequently, greater NOx level is re-
corded when the SOI timing is advanced as shown in Fig. 7. This
832 H. Mohamed Ismail et al. / Applied Energy 111 (2013) 827841

Emission Index NOx / [(g/s)/(kg/s)]

Emission Index NOx / [(g/s)/(kg/s)]

140 1.0 140 1.0
(a) Low-0.5kW 0.9 (d) Low-0.5kW 0.9
130 130

Normalised Soot / [-]

Normalised Soot / [-]

0.8 0.8
120 120
0.7 0.7
110 110 0.6
0.6
100 0.5 100 0.5
0.4 90 0.4
90
0.3 0.3
80 80
0.2 0.2
70 70 0.1
0.1
60 0.0 60 0.0
100 1.0 100 1.0
Emission Index NOx / [(g/s)/(kg/s)]

Emission Index NOx / [(g/s)/(kg/s)]

(b) Mid-1.5kW (e) Mid-1.5kW
0.9 0.9
90 90
0.8 0.8

Normalised Soot / [-]

Normalised Soot / [-]
80 0.7 80 0.7
0.6 70 0.6
70
0.5 0.5
60 60
0.4 0.4

0.3 50 0.3
50
0.2 0.2
40 40
0.1 0.1

30 0.0 30 0.0
Emission Index NOx / [(g/s)/(kg/s)]

Emission Index NOx / [(g/s)/(kg/s)]

70 (c) High-2.5kW 1.0 70 (f) High-2.5kW 1.0

65 0.9 65 0.9
0.8 0.8
Normalised Soot / [-]

Normalised Soot / [-]

60 60
0.7 0.7
55 0.6 55 0.6
50 0.5 50 0.5

45 0.4 45 0.4
0.3 0.3
40 40
0.2 0.2
35 0.1 35 0.1
30 0.0 30 0.0
B0 CME(B50) PME(B50) SME(B50) B0 CME PME SME

Measured-NOx Calculated-NOx Measured-Soot Calculated-Soot

Fig. 4. Emission index of NOx and normalised soot for (a) B50 blend at low load (0.5 kW), (b) B50 blend at mid load (1.5 kW), (c) B50 blend at high load (2.5 kW), (d) B100 at
low load (0.5 kW), (e) B100 at mid load (1.5 kW), and (f) B100 at high load (2.5 kW). Comparisons are made between experimental and simulation data.

20
15
Positive value indicates
10 increase in NOx as
compared to diesel
5
NOx Variations / [%]

0
-5
-10
-15
-20
-25 Negative value indicates
reduction in NOx as
-30 compared to diesel
-35
B0 CME(B50) PME(B50) SME(B50) CME PME SME
0.5kW 1.5kW 2.5kW

Fig. 5. Variations of NOx level at EVO when the base fuel (diesel) is substituted by biodiesel fuels at different engine loads.
 H. Mohamed Ismail et al. / Applied Energy 111 (2013) 827841 833

140 16 140 12

Emission Index NOx / [(g/s)/(kg/s)]

(a) Low-0.5kW (d) Low-0.5kW
Emission Index NOx / [(g/s)/(kg/s)]

130 14 130
10
120 12 120

Soot / [g/kW.hr]

Soot/[g/kW.hr]
8
110 10 110

100 8 100 6

90 6 90
4
80 4 80
2
70 2 70

60 0 60 0
100 80 100 (e) Mid-1.5kW 80
(b) Mid-1.5kW

Emission Index NOx / [(g/s)/(kg/s)]

Emission Index NOx / [(g/s)/(kg/s)]

90 70 90 70

60 60
80 80

Soot/[g/kW.hr]
Soot/ [g/kW.hr]
50 50
70 70
40 40
60 60
30 30
50 50
20 20

40 40 10
10

30 0 30 0

70 (c) High-2.5kW 300 70 (f) High-2.5kW 300

Emission Index NOx / [(g/s)/(kg/s)]

Emission Index NOx / [(g/s)/(kg/s)]

65 250 65 250
Soot/ [g/kW.hr]

Soot/ [g/kW.hr]
60 200 60 200

55 150 55 150

50 100 50 100

45 50 45 50

40 0 40 0
B0 CME(B50) PME(B50) SME(B50) B0 CME PME SME

Calculated-NOx Calculated-Soot

Fig. 6. Predicted emission index of NOx and normalised soot for (a) B50 blend at low load (0.5 kW), (b) B50 blend at mid load (1.5 kW), (c) B50 blend at high load (2.5 kW), (d)
B100 at low load (0.5 kW), (e) B100 at mid load (1.5 kW), and (f) B100 at high load (2.5 kW). Comparisons are made with fossil diesel fuel.

trend is only prominent at high engine load condition when the

145 fuel injection period is long. At low load when the fuel injection
period is signicantly shorter, the trend is less clear due to the
125 close-coupled interactions of other factors as discussed next.
NOx / [(g/s)/(kg/s)]

In general, the difference in the chemical composition between

105
biodiesel and diesel fuels causes the variations in the combustion
85 characteristics and hence the NOx emissions. For the biodiesel fuels
studied here, CME only has 20% by mass of unsaturation level, PME
65 with 50% and nally SME has the highest level of unsaturation of
45 80%. As a result of the low unsaturation level, CME has the highest
cetane number with shortest ID period as compared to PME, diesel
25 and SME as evident in Fig. 8. Due to the short ID period, CME
-11.2 -11 -10.8 -10.6 -10.4 -10.2 -10 -9.8 -9.6 exhibits longer and more dominant MCC phase than the PMC
Start of Injection (SOI) / [degree] phase across all the different engine loads. The MCC phase is
mainly governed by the turbulent intensity and the local oxygen
0.5kW 1.5kW
2.5kW Linear (0.5kW) concentration, and is typically less complete and less efcient than
Linear (1.5kW) Linear (2.5kW) that of the PMC phase [19]. Therefore, the combustion temperature
during the MCC phase is usually lower than that of the PMC phase
Fig. 7. NOx level as a function of SOI timing at different engine load conditions. [18,19]. On the other hand, premixed combustion affords higher
834 H. Mohamed Ismail et al. / Applied Energy 111 (2013) 827841

60
250 (a) 0.5kW
40

Heat release-Rate / [J/CAD]

200

NOx / [(g/s)/(kg/s-fuel)]
20

150
0

100
-20

50
-40
SME (B100) has shortest NOx
formation window, late SOC and
0 short combustion duration -60
100
(b) 1.5kW
90

Heat Release-Rate / [J/CAD]

80
NOx / [(g/s)/(kg-fuel/s)]

70
NOx formation rate
60 increases when
combustion
50 phasing changes
from MCC to PMC
40

30

20

10

0
-15
5 -10 -5 0 5 10 15 20 25 30 35 40 45
5
90
(c) 2.5kW
80
NOx formation rate

Heat Release-Rate / [J/CAD]

increases when
70 combustion
NOx / [(g/s)/(kg-fuel/s)]

phasing changes
60 from MCC to PMC

50

40 NOx formation
"freezes" at 25o ATDC
for all the tested fuels
30 regardless of fuel type

20

10

0
-15
-15 -10
-10 -5
-5 0
0 5
5 10
10 15
15 20
20 25
25 30
30 35
35 40
40 45
45
Crank Angle / [degrees]

Diesel(B0) CME(B50) PME(B50)

SME(B50) CME(B100) PME(B100)
SME(B100)

Fig. 8. HRR and evolution of NOx level for all the test fuels at (a) 0.5 kW, (b) 1.5 kW and (c) 2.5 kW.

combustion efciency which results in higher combustion temper-
ature [18,19]. In addition, CME is also found to burn at lower ame
temperature as compared to PME and SME due to the lower fuel
unsaturation levels as illustrated in Fig. 9. Studies by Ban-Weiss
et al. [31] showed that fuels with higher unsaturation level tend
to have higher adiabatic ame temperature (dened as the highest
temperature of a fuel burning at equilibrium conditions). Conse-
quently, CME produces lower local in-cylinder temperatures as
compared to PME, SME and diesel fuels throughout the combustion
period due to the compounding effects of the aforementioned fac-
tors. Here, the overall in-cylinder temperature during the combus-
tion of neat and B50 blend of CME is relatively low when compared
with other test fuels, resulting in lower NOx emission.
3.2.2. Inuence of fuel blends
From Figs. 5 and 6, signicant reduction in NOx is achieved at
mid and high loads with B50 blend of PME. B50 blend of SME also
produces lower NOx at high load, but the emission level is still
 H. Mohamed Ismail et al. / Applied Energy 111 (2013) 827841 835

NO NO 5o ATDC Temperature
(mole fraction)

Diesel (B0) Diesel with lower

proportion of local in-
cylinder T and NO

SME (B50)

CME with lower proportion of

PME (B50) local in-cylinder T and NO as
compared to SME
T (oK)

CME (B50)

SME with higher

SME (B100) proportion of local in-
cylinder T and NO

PME (B100)

CME with lower proportion of

CME (B100) local in- cylinder T and NO as
compared to SME

Fig. 9. 2-D contour plots at the plane of spray axis for local in-cylinder NO mass fractions and local temperature at 5 ATDC when the engine is running at 2.5 kW. 5 ATDC is
strategically chosen here because all the test fuels undergo the MCC phase and produce the greatest concentrations of high temperature gases at this point.

relatively higher than that of diesel at mid load condition. Never- exhausted as compared to using neat SME. Likewise, the use of B50
theless, the use of B50 blend of SME is able to lower the NOx level blend of CME enhances the NOx reduction capability as compared
836 H. Mohamed Ismail et al. / Applied Energy 111 (2013) 827841
to neat CME but only at mid and high loads, as shown in Fig. 5. The
reason for this observation is mainly attributed to the impact of
different fuel-bound oxygen content in the biodiesel blends.
In order to elucidate the observed NOx trend, the link between
combustion characteristics and fuel-bound oxygen content must
rst be established. For example, both B50 blend and neat PME
produce different NOx emission although they exhibit similar com-
bustion behaviour under all the engine loads tested with a well-
distributed PMC and MCC phases. During the PMC phase, fuel
and air are well-mixed prior to combustion to produce a more
complete combustion and higher combustion temperature which
is ideal for NOx formation [18,19,30]. Here, the additional fuel-
bound oxygen content in neat PME is unable to further enhance
the combustion and the NOx formation rate. However, the effects
of fuel-bound oxygen become more apparent during the MCC
phase where the higher fuel-bound oxygen level in neat PME pro-
motes a more complete MCC phase than that of the B50 blend. This
raises the combustion efciency with higher local in-cylinder tem-
perature, encouraging greater NOx formation rate and also higher
NO productions via the N2 reactions with the excess oxygen during
the MCC phase [18,19,30]. The same arguments are applicable to
explain the difference in NOx level for both the neat and B50 blends
of CME and SME.
There are two main conclusions that can be deduced from here.
Firstly, the inuence of fuel-bound oxygen content is only signi-
cant during the MCC phase. If two biodiesel fuels have similar com-
bustion behaviour but with different level of fuel-bound oxygen
content, the fuel with higher oxygen level is expected to produce
greater NOx during the MCC phase. For a set of two biodiesel fuels
with distinct combustion behaviour, the inuence of fuel-bound
oxygen is dependent on other factors such as the ID period, unsat-
uration levels and the nature of the combustion process itself. As
an illustration, neat CME and diesel produce longer MCC and
PMC phase, respectively under mid load condition. Here, neat
CME is expected to produce more NOx due to the higher fuel-bound
oxygen level. As both the fuels exhibit signicantly different com-
bustion characteristics, lower NOx emission is produced for neat
CME instead due to the lower unsaturation level, shorter ID and
longer MCC period. Although neat CME has excess oxygen from
the fuel to increase the combustion efciency and the combustion
temperature during the MCC phase, it is not sufcient to compen-
sate for the low local ame temperature produced due to the lower
unsaturation level. Secondly, it can be concluded that employing
B50 blends of CME, PME and SME essentially enhances the NOx
reduction capability of these biodiesel fuels as compared to the
neat form under mid and high load conditions. At low engine loads
however, the use of B50 blends of CME, PME and SME moderates
the NOx reduction capability of the neat biodiesel fuels.
3.2.3. Inuence of engine load
An increase in NOx level at EVO is observed when the engine
load is decreased as shown in Fig. 6, with highest NOx emission re-
corded at low engine load for all the test fuels. At low load, the fuel
injection period is short where fuel delivery is mostly completed
before the start of combustion (SOC). Therefore, the combustion
process is predominantly PMC as shown in Fig. 8, which burns
more completely and results in elevated local in-cylinder temper-
ature. This leads to greater NOx formation for all the test fuels at
low load as compared to mid and high load condition. Using diesel
and neat SME in Fig. 6a and d as an illustration, these fuels give
highest NOx emission at low load because they produce longer ID
period as evident in Fig. 8. Therefore, greater fraction of fuel mass
is burnt during the PMC phase rather than the MCC phase for both
the neat SME and diesel fuels. As a result, signicantly higher con-
centration of NOx is generated.
From this study, it is found that low engine load operation of
0.5 kW on this engine setup benets the most from the use of bio-
diesel to reduce NOx emission as shown in Figs. 5 and 6. Although
all the test fuels produce higher NOx level at low load, the magni-
tude of NOx reduction is enhanced when diesel is substituted with
neat or B50 blends of biodiesel fuels as illustrated in Fig. 5. For in-
stance, neat CME is able to reduce NOx by 33.68% at low load, but
only lowers the NOx level by 4.80% and 9.25% at mid and high load
conditions, respectively. Similar trend is also observed for the other
biodiesel fuels tested. In fact, neat PME and SME lose their NOx
reduction capability at mid and high engine load operations. Here,
neat PME exhausts higher NOx relative to that of diesel fuel by
5.17% and 6.02% at mid and high load, respectively, whereas neat
SME produces 17.55% and 6.15% greater NOx emission at mid and
high load, respectively. It can be deduced that NOx reduction is
most signicant at low engine load, followed by high load and
lastly mid load condition when the diesel is replaced with neat
or B50 blends of biodiesel fuels. Based on this, a general trend on
the NOx reduction capability of the tested biodiesel fuels at differ-
ent engine loads is illustrated in Fig. 10.
The fundamental reason for the observed trend as in Fig. 10 is
due to the fact that all the fuels undergo signicant changes in
their respective combustion behaviour at different engine loads.
At low load, the fuel injection period is typically short. Here, diesel
fuel has the longest ID period where fuel mass is fully injected be-
fore SOC which results in a dominant PMC phase as shown in Fig. 8.
When diesel fuel is replaced with biodiesel fuels, substantial quan-
tity of fuel mass is burnt during the MCC phase. For example, the
combustion behaviour shifts to MCC phase with neat CME. The
MCC phase leads to a much lower temperature as compared to
PMC [18,19,23,30]. Therefore, in-cylinder local temperatures are
lowered for biodiesel fuels and this moderates the NOx production
signicantly [18,19,30]. At mid and high load conditions on the
other hand, fuel injection period is prolonged. Therefore, large pro-
portion of fuel mass is burnt in the MCC phase for all the fuels.
Fig. 8 shows that the change in combustion characteristic is
deemed insignicant between diesel and biodiesel fuels. As such,
varying the fuel type does not enhance the NOx reduction capabil-
ity of biodiesel as shown in Figs. 5 and 10. In conclusion, the engine
load signicantly inuences the ability of different biodiesel fuel to
reduce NOx emission. The magnitude and ability of NOx reduction
of the neat biodiesel fuels are enhanced at low engine load, while
this is moderated at higher engine loads, as portrayed in Fig. 5.
3.3. Soot emissions
Soot is mainly formed during the MCC phase in the rich com-
busting liquid core region of the spray jet where the equivalence
ratio is between 1.5 and 4 and the local temperature is between
1400 K and 2000 K [18]. At higher load, the MCC phase is longer
due to the extended fuel injection period. This leads to a longer res-
idence time of the combustion products inside the rich combusting
core region, which is partly responsible for the greater soot forma-
tion rate at mid and high engine load conditions [19,30]. Therefore,
fuels which exhibit dominant MCC phase tend to produce higher
soot level [18,19,30].
At above 2000 K, the soot precursors are pyrolised and oxidised.
Different fuels have different onset and rate of soot oxidation pro-
cess, depending on the local in-cylinder temperature and the avail-
ability of O and OH free radicals. Here, soot oxidation becomes less
effective at lower temperature and lower concentrations of O and
OH radicals [32,33]. Soot oxidation also ceases at a saturation level
once the local in-cylinder temperature is below 2000 K, typically
towards the end of combustion (EOC) [32,33].
Fig. 11 illustrates the percentage variations in soot level at EVO
when diesel fuel is substituted by various biodiesel fuels at different
 H. Mohamed Ismail et al. / Applied Energy 111 (2013) 827841 837

Biodiesel Fuel NOx Reduction Ability as

Increasing NOx
reduction ability

Compared to Diesel / [%]

Highest NOx reduction
magnitude is achieved at
low load

Lowest NOx reduction Increasing

magnitude is achieved at engine load
mid load

Engine Load /[kW]

Fig. 10. General trend of the NOx reduction ability for various biodiesel fuels at different engine loads.

engine load conditions. Here, the variation in soot levels is
calculated with respect to the level produced by diesel fuel.
The percentage of soot variation is determined using Eq. (4), where
sootfuel is the soot level produced with different fuels and sootB0 is
the soot level from diesel combustion (all expressed in g/(kW.h)).
Here, the percentage change of soot is computed based on the soot
level at EVO for each fuel. The impact of different fuels and the inu-
ence of engine load on soot emission can then be appropriately
determined.
sootfuel  sootB0
% Change soot  100%
sootB0
The temporal evolution and nal amount of soot exhausted is
predominantly affected by the characteristics of the fuel used
and the resulting combustion process. As before, factors governing
the pattern of soot variation when different fuels are used are dis-
cussed below. These include fuel unsaturation level, fuel bound
oxygen content, ID period and combustion behaviour.
3.3.1. Inuence of fuel types
At mid and high engine load operations, lowest soot emission is
produced by the combustion of neat or B50 blend of CME followed
by that of the PME. The use of either neat or B50 blend of SME gives
the highest soot level, as evident in Fig. 6. This trend is reversed at
low load, where highest soot emission is given by CME, followed by
PME and lastly SME for both the neat and B50 blends of the
biodiesel fuels. This is mainly attributed to the unique combustion
behaviour displayed by each of the fuel, the local in-cylinder tem-
peratures and the concentrations of freely available O and OH rad-
icals for soot oxidation. At low load, the inuence of combustion
characteristic is more apparent. Fuels undergoing mainly PMC such
as neat SME have less soot emission since soot formation rate is
typically low in premixed ame [19] as illustrated in Fig. 12.
However, the availability of free radicals for soot oxidation is
more dominant at mid and high loads. Under these conditions,
combustion of fuels such as neat and B50 blend of SME is observed
4 to produce lower levels of important free radicals for soot oxida-
tion such as O and OH. These fuels generally exhibit shorter com-
bustion duration with early EOC here, which gives rise to lower
local in-cylinder temperatures of less than 2000 K during the
expansion stroke as evident in Fig. 13. At this low temperature
range, the formation rates of these free radicals are substantially
suppressed since the governing reactions are all high temperature
class reactions [32,33]. As a result, lower concentrations of O and
OH free radicals are present for soot oxidation throughout the
combustion period as shown in Figs. 14 and 15. Due to these ef-
fects, neat and B50 blend of SME give rise to lower soot decompo-
sition rate and thus higher soot emission when compared with that
of CME or PME under mid and high loads conditions. From here,
the most promising fuel for soot reduction is neat CME under
mid and high load operations. However, neat SME produces the
lowest soot emission under low load condition.

450

350 Positive value indicates

increase in soot as
compared to diesel
Soot Variations / [%]

250

150

50

-50
Negative value indicates reduction in
soot as compared to diesel
-150
B0 CME(B50) PME(B50) SME(B50) CME PME SME
Fuel Type
0.5kW 1.5kW 2.5kW

Fig. 11. Variations of soot level at EVO when the base fuel (diesel) is substituted by biodiesel fuels at different engine loads.
838 H. Mohamed Ismail et al. / Applied Energy 111 (2013) 827841

60
(a) 0.5kW
100
40

Heat release-Rate / [J/CAD]

80
20
Soot / [g/kW.hr]
60
0
SME (B100) and diesel have
40 lowest soot formation due to
100 % premixed-burn -20

20 -40

0 -60
160
(b) 1.5kW
140

Heat Release-Rate / [J/CAD]

120

100
Soot / [kg]

80

60

40

20 Shift in soot formation

timing according to SOC
0
300 85
(c) 2.5kW
75
250
65 Heat Release-Rate / [J/CAD]

200 55
Soot / [g/kW.hr]

Shift in the timing

for soot formation
according to SOC 45
150
35

100 25

15
50
5

0 -5
-15 -10 -5 0 5 10 15 20 25 30 35 40 45
Crank Angle / [degrees]
Diesel(B0) CME(B50) PME(B50) SME(B50)
CME(B100) PME(B100) SME(B100)

Fig. 12. HRR and evolution of soot level for all the test fuels at (a) 0.5 kW, (b) 1.5 kW and (c) 2.5 kW.

3.3.2. Inuence of fuel blends
The ability of biodiesel to reduce soot content under all the test
conditions is generally moderated as compared to the neat fuels
when B50 blends of the biodiesel fuels is utilised. This is clearly
portrayed in Figs. 6 and 11. This is mainly due to the inuence of
ID period and the fuel-bound oxygen level. Firstly, B50 blends of
CME, PME and SME have shorter ID period than their respective
B100 counterparts. Therefore, B50 blends tend to undergo longer
MCC phase as shown in Fig. 12. Secondly, B50 blends of the biodie-
sel have less concentration of fuel-bound oxygen. Therefore, B50
blends produce richer diffusion ames during the longer MCC
phase. Consequently, each of the tested B50 biodiesel blends gives
rise to relatively higher soot level from the compounding effects of
shorter ID and lower fuel-bound oxygen content. Here, the use of
B50 blends is found to moderate the soot reduction capability of
CME, PME and SME biodiesel fuels.
3.3.3. Inuence of engine load
An increase in soot level is observed when engine load is raised
from low to high values, with greatest soot level registered at high
 H. Mohamed Ismail et al. / Applied Energy 111 (2013) 827841 839

30 70

EOC, CA90 / [Crank Angle]

EOC, CA90 / [Crank Angle]

28 (a) 1.5kW (b) 2.5kW
65
26
60
24
22 55
20 50
18 45
16
40
14
12 35
10 30
Diesel CME PME SME CME PME SME Diesel CME PME SME CME PME SME
(B50) (B50) (B50) (B50) (B50) (B50)
CA90 CombDuration

Fig. 13. Combustion duration and the timing when 90% mass fraction of fuel burnt at (a) 1.5 kW and (b) 2.5 kW.

1.0E-10
(a)
Shorter combustion duration
8.0E-11 of biodiesels causes less
free radical availabe for soot
O / [mole fraction]

oxidation

6.0E-11

4.0E-11

2.0E-11
Shift in O formation
timing is according
to SOC
0.0E+00
1.0E-09

9.0E-10 (b)
Shorter combustion duration
of biodiesels causes less
8.0E-10
free radical availabe for soot
OH / [mole fraction]

oxidation
7.0E-10

6.0E-10

5.0E-10

4.0E-10

3.0E-10

2.0E-10 Shift in the OH

formation timing is
1.0E-10 according to SOC

0.0E+00
-15 -10 -5 0 5 10 15 20 25 30 35 40 45 50 55 60
Crank Angle / [degrees]
Diesel(B0) CME(B50) PME(B50)
SME(B50) CME(B100) PME(B100)
SME(B100)

Fig. 14. Evolution of the mole fractions for (a) O and (b) OH at 1.5 kW.

engine load across all the test fuels as shown in Figs. 6 and 12. At between 1.5 and 4 [19]. Therefore, lower amount of soot is formed
low load, the fuel injection period is short and this leads to a for all the test fuels at low load as compared to mid and high load
majority of the fuel mass to be delivered before SOC. As such, the conditions.
combustion is predominantly PMC, which is well mixed and burns Under low load operation, only the use of neat SME reduces the
more completely than the MCC [18,19,30]. Soot is typically formed soot level relative to that of the diesel fuel, as illustrated in Figs. 6
in the rich combusting diffusion ame region where the tempera- and 12. Generally, both neat SME and diesel generate reasonably
ture is between 1400 K and 2000 K and the equivalence ratio is low soot levels here. This is due to the fact that neat SME produces
840 H. Mohamed Ismail et al. / Applied Energy 111 (2013) 827841

1.8E-10
(a)
1.6E-10

1.4E-10 Shorter combustion duration

of biodiesels causes less free

O / [mole fraction]
radical availabe for soot
1.2E-10 oxidation

1.0E-10

8.0E-11

6.0E-11

4.0E-11

2.0E-11 Shift in O formation

timing is according to
SOC
0.0E+00
1.6E-09 In-cylinder local

(b)
temperature is more
important in determining
1.4E-09 soot oxidation rate
Shorter combustion duration
of biodiesels causes less free
OH / [mole fraction]

1.2E-09
radical availabe for soot
oxidation
1.0E-09

8.0E-10

6.0E-10

4.0E-10

2.0E-10 Shift in OH formation

timing is according to
SOC
0.0E+00
-15 -10 -5 0 5 10 15 20 25 30 35 40 45 50 55 60
Crank Angle / [degrees]
Diesel(B0) CME(B50) PME(B50) SME(B50)
CME(B100) PME(B100) SME(B100)

Fig. 15. Evolution of the mole fractions for (a) O and (b) OH at 2.5 kW.

the longest ID period among the test fuels followed by diesel fuel,
resulting in only PMC for both the fuels. However, soot produced
from the use of neat SME is lower due to the additional oxygenated
effect of the biodiesel fuel. Here, neat SME burns much leaner than
diesel combustion, hence producing less overall soot content.
It is also found that the ideal engine operation for soot reduc-
tion on this engine setup is at high load of 2.5 kW when using neat
biodiesel fuels, as shown in Figs. 6, 11 and 12. The soot reduction
capability when using biodiesel fuels is generally enhanced when
the engine load is raised from low to high values. For example, neat
SME is only able to reduce soot content by 27.84% as compared to
diesel at low load, while at mid and high load conditions, it can
reduce soot by 46.42% and 55.89%, respectively. This trend is also
observed for the other biodiesel fuels tested. In fact, neat and
B50 blends of CME and PME lose their ability to reduce soot at
low load condition all together. Here, CME and PME combustion
produce 185342% higher soot level than that recorded by diesel
combustion.
From this study, the unique combustion behaviour produced
with various test fuels at different engine loads is shown to deter-
mine the soot level. At low load condition when the injection per-
iod is short, fuels such as neat SME and diesel which exhibit long ID
period undergo pure PMC as shown in Fig. 12. When neat and B50
blends of CME, PME and SME (except neat SME) are used instead,
shorter ID period results and leads to early SOC before the end of
injection (EOI). Here, MCC phase dominates where higher soot le-
vel is formed. Under mid and high load operations however, fuel
mass delivered is burnt in both the PMC and MCC phases for all
the test fuels due to the relatively longer injection period. Variation
in the combustion behaviour becomes less apparent with different
fuels and no longer governs the observed difference in the soot lev-
els. Instead, the effect of fuel bound oxygen content becomes the
dominant factor here. Although the oxygenated effect of the bio-
diesel fuels has negligible inuence to arrest further soot formation
during the PMC phase due to the well-mixed nature of the combus-
tion process itself, higher concentration of fuel bound oxygen con-
tent does promote more complete and leaner combustion in the
MCC phase which can inhibit soot formation rate and lower the
soot level in the exhaust stream.
Conclusively, engine load signicantly inuences the soot
reduction ability of the biodiesel fuels. The amount of soot reduc-
tion magnitude and the ability of biodiesel fuels to reduce exhaust
soot are enhanced at mid and high load conditions, while these are
moderated at low engine load operation.
4. Conclusions
The conclusions presented here describe the combined effects
of the chemistry and thermo-physical properties of the selected
biodiesel fuels on the emissions characteristics for this specic test
 H. Mohamed Ismail et al. / Applied Energy 111 (2013) 827841
engine conguration. The unsaturation level and fuel bound oxy-
gen content of the biodiesel fuels are all-important in determining
the ID period and the combustion behaviour, which consequently
affect the NOx and soot formation processes. The inuence of fuel
bound oxygen content on NOx and soot formation is particularly
apparent during the MCC phase. Among the tested biodiesel fuels,
neat CME is found to be the best fuel for both NOx and soot reduc-
tion across all the three engine loads tested. The optimum operat-
ing condition to result in the simultaneous soot and NOx reduction
through the use of biodiesel is at mid load condition and at an en-
gine speed of 2000 rev/min. However, the level of emissions reduc-
tion is not as great as those observed under low load for NOx or
high load for soot. Pertinent ndings of this study are summarised
as follows:
 Advancement in SOI timing due to the use of biodiesel fuels in
typical rotary-type injection system contributes to the increase
in NOx level at mid and high engine load conditions.
 Fuels with lower unsaturation level result in shorter ID period
and hence exhibit more dominant MCC phase to produce less
NOx, where lowest NOx is observed for CME, followed by PME
and nally SME.
 The use of B50 blends of CME, PME and SME enhances the NOx
reduction capability of the neat biodiesel fuels, particularly at
mid and high load conditions.
 Engine load signicantly affects the exhaust NOx levels, where
the ability of biodiesel fuels to reduce NOx is enhanced at low
load while this is moderated at higher engine load operations.
 Neat CME is found to be most effective in reducing soot level at
mid and high load operations, whereas neat SME produces low-
est soot level under low load condition.
 The use of B50 blends is shown to moderate the soot reduction
capability of neat CME, PME and SME under different engine
load conditions.
 Engine load signicantly inuences the soot emissions, where
the ability of the biodiesel fuels to reduce soot level is enhanced
at mid and high engine load operations while this is moderated
at low engine load condition.
 When neat and B50 blends of biodiesel fuels are used, most
prominent soot and NOx reductions are achieved at high and
low engine loads, respectively.
From this study, the optimum choice of fuel types and blends at
different engine operating conditions are established. These should
form the necessary design and operating guidelines for both the
fuelling and engine strategies, which are of interest particular to
the automotive community. Additionally, unique fuel additives
can be developed to alter the chemical and physical attributes of
the biodiesel fuels such that simultaneous reduction in both NOx
and soot can be achieved across different engine operations.
Acknowledgements
This work was supported by the Ministry of Science, Technol-
ogy and Innovation (MOSTI) Malaysia under the Grant No. 03-02-
12-SF0045. The Faculty of Engineering at the University of Notting-
ham Malaysia Campus is also acknowledged for its support to-
wards this project.
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