energies

Article
Soot Particle Size Distribution, Regulated and
Unregulated Emissions of a Diesel Engine Fueled
with Palm Oil Biodiesel Blends
Jun Cong Ge and Nag Jung Choi *
Division of Mechanical Design Engineering, Jeonbuk National University, Jeonju-si 54896, Korea; jcge@jbnu.ac.kr
* Correspondence: njchoi@jbnu.ac.kr; Tel.: +82-63-270-4765




Received: 6 October 2020; Accepted: 27 October 2020; Published: 2 November 2020


Abstract: In this study, five fuels including pure diesel (B0), pure palm oil biodiesel (B100), and their
blends (B10, B20, and B30) were investigated in relation to soot particle distribution and regulated
and unregulated emission characteristics in a common rail direct injection (CRDI) diesel engine.
The results indicated that CO, hydrocarbon (HC), and particulate matter (PM) regulated emissions
were effectively controlled to a very low level by combining the addition of palm oil biodiesel (POB) to
diesel with optimized engine operating conditions. Paper filters and TEM grids were used to capture
the diesel particles. All the PM primary particles were less than 100 nm in diameter observed by
TEM, and the average diameters of the PM primary particles for the biodiesel blends were distributed
between 20 and 26 nm. Unregulated emissions such as trace metals including Pb, Mn, and Ba were
found in the PM particles, and the xylene, toluene, and benzene unregulated emissions of B100 were
reduced by 55.68%, 21.56%, and 18.32%, respectively, compared to those of B0. Therefore, POB is an
excellent alternative fuel for diesel engines and has great application potential to solve the current
pollution problems of regulated and unregulated emissions.

Keywords: palm oil biodiesel; engine load; regulated emissions; unregulated emissions

1. Introduction
Diesel engines have been used widely in applications such as commercial vehicles, passenger cars,
power generators, and construction equipment due to their high thermal efficiency, reliability, and large
output power [1,2]. However, high nitrogen oxide (NOx) and particulate matter (PM) emissions are
significant drawbacks of diesel engines [3,4]. The large presence of NOx and PM emissions poses a
huge threat to the ecological environment and human health. Many researchers have reported that
the formation of haze is related to diesel engine emissions, and long-term exposure to haze pollution
will directly increase the morbidity and mortality of respiratory and cardiovascular diseases [5].
It is well known that the relationship between PM and NOx emissions is a tradeoff, which makes
it difficult to reduce PM and NOx simultaneously using traditional engine technology. Although
some new combustion technology, such as low temperature combustion (LTC) [6] and diesel exhaust
aftertreatment devices (e.g., DOC: Diesel Oxidation Catalyst; DPF: Diesel Particulate Filter; and SCR:
Selective Catalytic Reduction) [7], can limit the regulated emissions (i.e., CO, hydrocarbon (HC), NOx,
and PM) to a low value, they will increase purchase and maintenance costs, which is uneconomical.
In addition, these technologies do not have more information for the reduction of unregulated emissions
from diesel engines, such as trace metals (TMs) and volatile organic compounds (VOCs).
Generally, the ways to reduce engine emissions mainly include improving the fuel injection system
(e.g., fuel injection timing and pressure and single or multiple injection), optimizing the air–fuel ratio
(e.g., variable valve timing system and turbocharger), using exhaust aftertreatment systems (e.g., DOC,

Energies 2020, 13, 5736; doi:10.3390/en13215736 www.mdpi.com/journal/energies

Energies 2020, 13, 5736 2 of 16

DPF, and SCR), and improving fuel properties (e.g., biodiesel and oxygenated fuel). Considering the
cost and technical limitations of other alternatives, optimizing fuel properties has great application
potential to improve engine performance and emissions by using, for example, biodiesel, oxygenated
fuels, and fuel additives. The development and utilization of biodiesel has always been one of the most
important research topics for researchers all over the world due to its rich resource, green, renewable,
environmentally friendly, and other advantages.
Biodiesel, also known as a mixture of fatty acid methyl or ethyl esters, can be extracted from a
variety of renewable feedstocks, such as animal fats [8], vegetable oil [9], algal biomass [10], and waste
cooking oil [11], via transesterification; it can be used in diesel engines directly or by blending it with
diesel without any modification due to the fact that its fuel properties are similar to diesel [12]. Moreover,
biodiesel can effectively improve engine combustion efficiency and reduce CO, HC, and PM emissions
due to its high oxygen content and high cetane number [13]. However, using pure biodiesel for diesel
engines will lead to poor atomization, injector coking, cold start problems, high fuel consumption,
and other problems due to its high viscosity and low calorific value. Therefore, blending biodiesel
and diesel is a simple and effective way to solve the above problems. Many researchers have reported
that a variety of biodiesel–diesel blended fuels can effectively reduce CO, HC, and PM emissions,
such as waste cooking oil biodiesel [14], jatropha oil biodiesel [15], karanja oil biodiesel [16], canola oil
biodiesel [17], soybean oil biodiesel [18], and palm oil biodiesel [19]. However, numerous studies on
biodiesel have only focused on the torque, combustion pressure, fuel consumption, and endurance
in specific diesel engines (e.g., in single cylinder engines or engines with some modifications) [20]
under partial operating conditions (e.g., constant engine speed or load) [17,21]. There have been
few studies on PM morphology and unregulated emissions such as trace metals and VOCs from
diesel engines fueled with biodiesel blends. Salamanca et al. [22] used a Teflon filter to capture
particulate matter emitted from a diesel engine fueled with palm oil biodiesel, then dispersed the PM
in ethanol via an ultrasonic bath, and finally analyzed the size and morphology of the particles by TEM.
The disadvantage of this method is that the steps are too complicated and unequal to ensure that the
morphology of the particles does not change in the ultrasonic treatment process. Some semi-automatic
measurement methods have also been used to analyze the size of the primary particles [23,24]. On the
other hand, although Ferreira et al. [25] and Shukla et al. [26] studied the volatile organic compounds
(VOCs) and trace metals emitted from diesel engines, they did not report the relationship between the
emission and combustion characteristics.
Therefore, to further investigate the combustion and emission characteristics of palm oil biodiesel,
especially the morphology and microstructure of particles and unregulated emissions, including VOCs
and trace metals, this experimental investigation was carried out on a four-cylinder common rail direct
injection (CRDI) diesel engine without any modification at various engine loads from 0% to 100%.
Five palm oil biodiesel blends were selected as the main test targets. In this study, two simple and
practical PM primary particle capture methods were used, which provide an effective reference for
the analysis of PM morphology, including nanostructure and size. These methods have potential
application value for further analysis of the physicochemical characteristics of PM particles emitted
from diesel engines in the future.

2. Experimental Setup and Procedure

2.1. Test Fuels

Five blended fuels were prepared through blending pure palm oil biodiesel at 0%, 10%, 20%, 30%,
and 100% by volume with neat diesel, which corresponded to B0, B10, B20, B30, and B100, respectively.
The specific properties of the tested fuels are listed in Table 1. As shown in Table 1, it can be clearly
seen that the palm oil biodiesel has a higher density, viscosity, cetane index, and lower calorific value
than diesel. Moreover, this biodiesel also contains about 11.26% oxygen. These important physical
properties are related to the combustion and emission characteristics described in Section 3.
Energies 2020, 13, 5736 3 of 16

Table 1. Properties of B0, B10, B20, B30, and B100.

Properties (Units) B0 B10 B20 B30 B100

Density (kg/m3at 15 ◦ C) 836.8 841 845 849 877
Viscosity (mm2 /s at 40 ◦ C) 2.719 2.893 2.991 3.173 4.56
Calorific value (MJ/kg) 43.96 43.43 42.83 42.31 39.72
Cetane index 55.8 - - - 57.3
Flash point (◦ C) 55 - - - 196.0
Oxidation stability (h/110 ◦ C) 25 - - - 9.24
Oxygen content (%) 0 - - - 11.26

2.2. Test Engine and Operating Methods

This experimental research was investigated in a four-cylinder turbocharged CRDI diesel engine
(2004 Hyundai Santa Fe, Ulsan, Korea) with a displacement of 1991cc. The tested engine was not
equipped with an exhaust aftertreatment system. The detailed engine specifications are summarized
in Table 2. Figure 1 shows a schematic of the experimental setup. An eddy-current-type eddy current
(EC) dynamometer was employed to control engine speed and engine load. Moreover, a high-precision
digital electronic weighing balance (GP-100K, A&D Co. Ltd., Tokyo, Japan) was used to measure fuel
consumption; the in-cylinder pressure was measured by a piezoelectric pressure sensor (Type 6056A,
Kistler Korea Co., Ltd., Gyeonggi-do, Korea). The in-cylinder pressure value with crank angle was
recorded from 200 engine cycles to calculate the heat release rate (HRR) for analyzing combustion
characteristics. All combustion data were acquired using a National Instruments PCI-6040E (National
Instruments, Austin, TX, USA) data acquisition (DAQ) board. The CO, HC, and NOx emissions were
measured by a MK2 (GreenLine MK2, Eurotron (Korea) Ltd., Seoul, Korea) and HPC-501 (Nantong
Huapeng Electronics Co., Ltd., Jiangsu, China) multi-gas analyzer. The smoke opacity of the exhaust gas
was measured with an OPA-102 (QROTECH Co., Ltd., Gyeonggi-do, Korea) smoke meter. Five engine
loads of 0, 35, 70, 105, and 140 Nm, corresponding to 0%, 25%, 50%, 75%, and 100%, were selected
as the main experimental variable to test the biodiesel blends. The engine speed and the pilot and
main injection timings were fixed at 1500 rpm, 24◦ before top dead center (BTDC), and 4◦ BTDC,
respectively. Detailed operating conditions are listed in Table 3. Figure 2 shows the detailed flow
charts of this experiment.

Table 2. Specifications of the test engine.

Engine Parameter Units Specifications

Type - turbocharged CRDI diesel engine
Number of cylinders - 4
Bore × stroke mm 83 × 92
Injector hole diameter mm 0.17
Compression ratio - 17.7:1
Max. power kW/rpm 82/4000

Table 3. Experimental and operating conditions.

Item Conditions
Test fuels B0, B10, B20, B30, B100
Engine loads 0%, 25%, 50%, 75%, 100%
Engine speed 1500 rpm
Fuel injection pressure 60 MPa
Pilot injection timing 24◦ BTDC
Main injection timing 4◦ BTDC
Intake air temperature 25 ± 3 ◦ C
Cooling water temperature 85 ± 3 ◦ C
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Energies 2020, 13, 5736 Cooling water temperature 85 ± 3 °C 4 of 16
Cooling water temperature 85 ± 3 °C

Figure 1. Schematic diagram of the experimental apparatus.

Figure 1. Schematic diagram of the experimental apparatus.
Figure 1. Schematic diagram of the experimental apparatus.

Figure 2. Flow chart for the engine experiment.

Energies 2020, 13, 5736 5 of 16

2.3. PM Sampling System and Analysis Method

To observe the structure and morphology of PM primary particles, a 400 mesh transmission
electron microscope (TEM) grid (Type: FCF400-Cu) was used to collect the PM primary particles from
all tested fuels at 25% and 75% loads. Then, the TEM (H-7650 with 0.2 nm resolution; Hitachi High
Technologies, Tokyo, Japan) and field emission scanning electron microscopy (FE-SEM; SUPRA 40 VP;
Carl Zeiss, Germany) were used to observe and analyze the micromorphology, nanostructure, and size
of the PM primary particles loaded on the TEM grid. The magnifications of the TEM and SEM were
200.00 and 250.00 KX, respectively. The diameter of the PM primary particles loaded on the TEM grid
was measured by ImageJ software. In addition, to further observe the effect of the biodiesel blends on
the PM emissions, the PM primary particles were also collected for one and two minutes on a soot
determination filter paper (Ø 45 mm) under full load. These samples were then analyzed by the above
SEM with a magnification of 1.00 KX.

2.4. Benzene, Toluene, and Xylene (BTX) Emissions Sampling System and Analysis Method
The exhaust gas emitted from the CRDI engine fueled with the five tested fuels at loads of
25% and 75% was collected in 5 L Tedlar (TDAP05, Aluminum Gas Sampling Bag, LKLABKOREA
Inc., Gyeonggi-do, South Korea) gas sampling bags. While collecting the gas, a stainless-steel pipe
with a diameter of 50 mm was used to cool the exhaust gas and maintain it at roughly 45◦ C. Then,
a high-precision air flow pump was employed to mix the collected gas with high-purity nitrogen
(99.99%) at a ratio of 1:19. In order to avoid a photochemical reaction between the BTX and NOx
emissions in the presence of sunlight, all BTX operations were carried out in the absence of sunlight. The
diluted BTX emissions were analyzed using a purge and trap analyzer (JDT-505II/2010GC/QP2010MS,
Japan Analytical Industry, Tokyo, Japan). The JDT-505II and 2010GC/QP2010MS were used for purge
and trap sampling and qualitative and quantitative analysis of BTX emissions, respectively. Detailed
testing methods have been documented in our previous studies [27].

2.5. Trace Metals Sampling System and Analysis Method

In general, the trace metals (TMs) are loaded on PM primary particles and then discharged into
the atmosphere with PM primary particles. Thus, in order to capture TMs, the PM primary particles of
all tested fuels were collected for five minutes on a soot determination filter paper (Ø 45 mm) under
full engine load. Then, an inductively coupled plasma mass spectrometer (ICP-MS; iCAP RQ; Thermo
Fisher Scientific) was used to measure the TMs. The detailed experimental steps were as follows: the
samples were first cut with scissors and placed in a Teflon vessel containing aqua regia (nitric acid:
hydrochloric acid = 1:3), reacted for 24 h at room temperature, and then the reaction solution with the
samples was heated to 180 ◦ C and microwaved for 20 min. After the temperature returned to room
temperature, the reaction solution with the samples was poured into a 50 mL tube and finally diluted
to a 50 mL precursor solution by adding 2% nitric acid solution for ICP-MS analysis.

3. Results and Discussion

3.1. Combustion Characteristics

The combustion characteristics of the biodiesel blends can be quantified using in-cylinder pressure
(IP) and heat release rate (HRR). Figure 3 shows the influences of various biodiesel blends on IP at
engine loads from 0% to 100%. As shown in Figure 3, the combustion processes of all tested fuels
were the same, including a phase of premixed combustion and a phase of diffusion combustion, which
was the dual burning mode of diesel engine combustion [28]. On other hand, the peak IP of all tested
fuels appeared after top dead center (ATDC) 8◦ ~15◦ crank angle (CA) under all operating conditions.
This indicates that the CRDI diesel engine fueled with biodiesel blends could run well under various
loads, because peak IP occurring very close to TDC or before has a negative effect on engine knock and
durability [29]. Overall, all the biodiesel blends had similar pressure profiles to diesel at each load. The
Energies 2020, 13, x FOR PEER REVIEW 6 of 17
Energies 2020, 13, 5736 6 of 16
under various loads, because peak IP occurring very close to TDC or before has a negative effect on
engine knock and durability [29]. Overall, all the biodiesel blends had similar pressure profiles to
mixing
diesel atratio
eachof biodiesel
load. had little
The mixing ratioeffect on IP athad
of biodiesel 0% little
and 25%
effectloads.
on IP However,
at 0% and 25% the temperature
loads. However,and
pressure in the combustion chamber began to rise sharply and form a high
the temperature and pressure in the combustion chamber began to rise sharply and form a high temperature and pressure
combustion
temperatureenvironment
and pressure under mediumenvironment
combustion and high loads. Based
under on thisand
medium environment,
high loads.theBased
physical
on and
this
chemical properties of biodiesel activate, the negative effects of biodiesel,
environment, the physical and chemical properties of biodiesel activate, the negative effectssuch as high density and highof
viscosity,
biodiesel,weaken,
such as and
highthe oxygen
density and in high
biodiesel promotes
viscosity, combustion,
weaken, so that the
and the oxygen IP of B30 promotes
in biodiesel is greater
than that of B0;
combustion, so the
thatIPthe
of IP
B30ofincreased most than
B30 is greater at thethat
75%ofload, about
B0; the 2.05%
IP of B30 compared with B0.
increased most On75%
at the the
other hand, another disadvantage of biodiesel is its low calorific value compared
load, about 2.05% compared with B0. On the other hand, another disadvantage of biodiesel is its low to diesel, which
results
calorificinvalue
the IP of B100 being
compared lower
to diesel, thanresults
which that ofinB0the [30]. InB100
IP of addition,
beingthe peak
lower IP rose
than significantly
that of B0 [30]. In
with
addition, the peak IP rose significantly with increasing engine load for all tested fuels, whichquantity
increasing engine load for all tested fuels, which may be due to the increase in fuel may be
requirement and entrained-air
due to the increase volume.
in fuel quantity In Figure 3a,b,
requirement the in-cylindervolume.
and entrained-air pressure Incurve
Figurefor3a,b,
B100theat 0%
in-
and 25% low engine loads rose relatively earlier than other tested fuels at
cylinder pressure curve for B100 at 0% and 25% low engine loads rose relatively earlier than otherhigh loads. These results
were
testedinfuels
agreement
at highwith
loads.Dhar et al.
These [31]. were in agreement with Dhar et al. [31].
results

Figure 3. Effect
Figure 3. Effect of
of biodiesel
biodiesel blends
blends on
on in-cylinder
in-cylinder pressure
pressure at
at each
each engine
engine load.
load. (a)
(a) Engine
Engine load: 0%;
load: 0%;
(b)
(b) Engine
Engine load:
load: 25%;
25%; (c)
(c) Engine
Engine load: 50%; (d)
load: 50%; (d) Engine
Engine load:
load: 75%;
75%; (e)
(e) Engine
Engine load:
load: 100%.
100%.

Figure
Figure 4 4describes
describesthethevariation
variationofofthe
theHRR
HRRaccording
accordingto tovarious
various biodiesel
biodiesel blends
blends at
at each
each engine
engine
load. It can
load. It can be
be seen
seen that
that no
no significant
significant correlation
correlation can be drawn
can be drawn between
between the the biodiesel
biodiesel blends
blends and
and the
the
peak
peak HRR.
HRR. TheThe undulating
undulating peak peak HRR
HRR values
values of
of biodiesel
biodiesel blends
blends cancan bebe attributed
attributed to
to the
the following
following
reasons: (i) high
reasons: (i) high viscosity
viscosity and
and high
high density are not
density are not conducive
conducive to to fuel
fuel atomization;
atomization; (ii)
(ii) low
low calorific
calorific
value
value reduces the peak values of in-cylinder pressure and HRR; (iii) oxygen in biodiesel and
reduces the peak values of in-cylinder pressure and HRR; (iii) oxygen in biodiesel and aa high
high
cetane index improve combustion characteristics, which is helpful for increased in-cylinder
cetane index improve combustion characteristics, which is helpful for increased in-cylinder pressure pressure
and
and HRR.
HRR. The
The first
first and
and second
second reasons
reasons are
are negative
negative factors
factors onon increasing
increasing in-cylinder
in-cylinder pressure
pressure and
and
HRR,
HRR, and the third reason is a positive factor. Therefore, all the properties of biodiesel, including
and the third reason is a positive factor. Therefore, all the properties of biodiesel, including
both
both advantages
advantages and and disadvantages,
disadvantages, should
should bebe taken
taken into
into account
account when
when evaluating
evaluating the
the combustion
combustion
characteristics
characteristics of
of biodiesel
biodiesel blends.
blends.
Energies 2020, 13, 5736 7 of 16
Energies 2020, 13, x FOR PEER REVIEW 7 of 17

Figure 4. Effect of biodiesel blends on heat release rate at each load. (a) Engine load: 0%; (b) Engine
Figure 4. Effect of biodiesel blends on heat release rate at each load. (a) Engine load: 0%; (b) Engine
load: 25%; (c) Engine load: 50%; (d) Engine load: 75%; (e) Engine load: 100%.
load: 25%; (c) Engine load: 50%; (d) Engine load: 75%; (e) Engine load: 100%.
3.2. Engine Performance
3.2. Engine Performance
Figure 5 shows the brake specific fuel consumption (BSFC) and the coefficient of variation of the
Figure
indicated 5 shows
mean the brake
effective pressurespecific fuel consumption
(COVimep) for all tested(BSFC) and the coefficient
fuels according to variousofloads.
variation of the
As shown
indicated mean effective pressure (COVimep) for all tested fuels according
in Figure 5a, with the increase in engine load from 25% to 100%, the BSFC of all tested fuels initially to various loads. As
shown in and
decreases Figure
then5a, with theslightly
increases increase in engine
at full load
load. The from
main 25% to
reason for100%, the BSFC
the decrease of all
is that thetested fuels
increasing
initially decreases and then increases slightly at full load. The main reason
percentage of fuel required for engine operation is less than the increasing percentage of brake powerfor the decrease is that the
increasing
due percentage
to relatively low heat of fuel
loss required
at medium forand
engine
highoperation
loads [32].is On
lessthe
than thehand,
other increasing
the BSFCpercentage
increases of
brake powerwith
significantly duean to increasing
relatively low heat ratio
biodiesel loss at
inmedium
diesel. This andishigh
a mainloads [32]. On the
contribution other hand,
to biodiesel the
having
aBSFC
lowerincreases
calorific significantly
value than diesel,with an increasing
leading biodiesel
to biodiesel andratio in diesel. This
biodiesel–diesel is a main
blends contribution
consuming more
to biodiesel
fuel to producehavingtheasame
lowerpower
calorific
as value
diesel.than diesel,
Other leading tohave
researchers biodiesel and biodiesel–diesel
also found these results [33]. blendsIn
consuming more fuel to produce the same power as diesel. Other researchers
Figure 5b, it can be seen that the COVimep is significantly reduced for all tested fuels as the load have also found these
results [33].
increases fromIn Figure
0% to 50% 5b, itbut
can be seen
then that theslightly
it increases COVimep is significantly
at the 75% and 100% reduced
loads. for
It isall tested
worth fuels
noting
as the
that theload increases
COVimep from
of all 0% to
tested 50%isbut
fuels much then it increases
lower than 10% slightly
underat allthe 75% andconditions.
operating 100% loads. It It
canis
worth noting that the COVimep of all tested fuels is much lower
be shown that the engine can run very stably under these parameters, because the upper limit ofthan 10% under all operating
conditions.isIt10%
COVimep can[34].
be shown that the engine can run very stably under these parameters, because the
upper limit of COVimep is 10% [34].
Energies 2020, 13, 5736 8 of 16
Energies 2020, 13, x FOR PEER REVIEW 8 of 17

Figure5.5.Variation
Figure Variationofof(a)
(a)brake
brakespecific
specificfuel
fuelconsumption
consumption(BSFC)
(BSFC)and
and(b)
(b)the
thecoefficient
coefficientof
ofvariation
variationof
of the
the indicated indicated
mean effectivemean effective
pressure pressure for
(COVimep) (COVimep) for various
various biodiesel biodiesel blends.
blends.

3.3.
3.3. Regulated
Regulated Emission
Emission Characteristics
Characteristics
Figure
Figure66 showsshows the the effect
effect of
of biodiesel blends on regulated regulated emission
emissioncharacteristics.
characteristics.As Asshown
showninin
Figure
Figure6a, 6a,the theCOCO emissions
emissionsare are
higher at 0%atload
higher 0% thanload atthan
other atoperating conditions,
other operating and CO emissions
conditions, and CO
decrease
emissionssignificantly as the loadas
decrease significantly increases.
the load The higherThe
increases. the engine
higher theload, the higher
engine load, the combustion
higher the
temperature and pressure,
combustion temperature and
and the more
pressure, and complete
the more combustion is, which contributes
complete combustion to the overall
is, which contributes to
decrease
the overall in CO emissions.
decrease in COThe slight increase
emissions. The slightin CO at full in
increase loadCOmay be due
at full loadtomay the belarge
dueamount
to the of fuel
large
amount ofto
consumed fuel consumed
obtain greaterto obtainpower,
output greateratoutput
which power,
time theatconcentration
which time the concentration
of oxygen of oxygen
in the combustion
in the combustion
chamber is reduced, chamber
therebyisslowing
reduced,downthereby theslowing
oxidation down ratetheofoxidation
CO [35]. rate Uyumazof COet[35]. Uyumaz
al. [34] noted
et al.CO
that [34]is noted
a harmfulthat exhaust
CO is a harmful
gas that exhaust
is mainly gas that isas
emitted mainly emitted
the result as the result
of incomplete of incomplete
combustion, and
combustion, and CO emissions increase when the temperature
CO emissions increase when the temperature and oxygen in the combustion chamber are insufficient. and oxygen in the combustion
chamber
In addition, areCO insufficient. In addition,
emissions decrease CO emissions
substantially as thedecrease
biodieselsubstantially
ratio in dieselasincreases.
the biodiesel ratio in
The reduction
diesel
of CO in increases.
B100 at The 50%reduction of CO than
load is greater in B100 that at under
50% load is greater
other operatingthanconditions
that underand other
is operating
about 82%
conditions
lower than thatand is of about
B0 under82%thelower than
same that of B0 This
conditions. under is the samebecause
mainly conditions. This is mainly
the oxygen contained because
in the
the oxygen
biodiesel playscontained
a decisive in the
role,biodiesel
increasing plays a decisive
the oxygen role, increasing
concentration during thetheoxygen concentration
combustion process
during
and the combustion
making the fuel burn process
moreand making the
thoroughly. fuel burn
Figure more thoroughly.
6b compares the unburned Figurehydrocarbon
6b compares (HC) the
unburned hydrocarbon (HC) emissions for all tested fuels. Based on the
emissions for all tested fuels. Based on the overall analysis, increasing the load from 0% to 100% has overall analysis, increasing
athe
muchloadsmaller
from 0% to 100%
effect on HC hasemissions
a much smaller
than oneffect on HC emissions
CO emissions. The range thaninonHC COconcentrations
emissions. Theat
range in HC concentrations at various loads is 65 ppm. The HC emissions
various loads is 65 ppm. The HC emissions for all biodiesel blends are less than those for diesel. for all biodiesel blends areThis
less than those for diesel. This reduction in HC emissions may be due
reduction in HC emissions may be due to changes in the stoichiometry of the spray caused by the to changes in the stoichiometry
of the spray
oxygen caused [36].
in biodiesel by theIn oxygen
addition, in the
biodiesel
biodiesel [36].hasIn addition, the biodiesel
a higher cetane has a than
index (57.3) higher thecetane
diesel
(55.8), resulting in more complete combustion in the cylinder, which also contributes to the lowalso
index (57.3) than the diesel (55.8), resulting in more complete combustion in the cylinder, which HC
contributes
emissions to the
[37]. low HC
As shown in emissions
Figure 6c, [37].
for allAstested
shown in Figure
fuels, the NOx 6c,emissions
for all testedincreasefuels, the NOx
significantly
emissions
with increase
the gradual significantly
increase in thewith
load.theThe gradual increase in of
NOx emissions theB0load.
andThe B100 NOx emissions
at 100% engineof load
B0 and are
B100 at 100% engine load are increased by 849.28% and 848.45%, respectively, relative to those at 0%
increased by 849.28% and 848.45%, respectively, relative to those at 0% load. In addition, the biodiesel
load. In addition, the biodiesel blend ratio in diesel fuel has a greater impact on NOx emissions at a
blend ratio in diesel fuel has a greater impact on NOx emissions at a high load than at a low load.
high load than at a low load. The diffusion flame combustion process dominates at a high load, and
The diffusion flame combustion process dominates at a high load, and the effect of engine control on
the effect of engine control on NOx emissions emitted from biodiesel is more significant. On the other
NOx emissions emitted from biodiesel is more significant. On the other hand, premixed combustion
hand, premixed combustion dominates at a low load, and the fundamental combustion effects are
dominates at a low load, and the fundamental combustion effects are more influential [38]. In Figure 6c,
more influential [38]. In Figure 6c, the overall analysis shows that the NOx emissions from the CRDI
the overall analysis shows that the NOx emissions from the CRDI diesel engine fueled with B100 are
diesel engine fueled with B100 are only 13.08% greater than those of B0. This is because the presence
only 13.08% greater than those of B0. This is because the presence of oxygen in biodiesel promotes
of oxygen in biodiesel promotes combustion and raises the temperature in the combustion chamber,
combustion and raises the temperature in the combustion chamber, resulting in slightly higher NOx
resulting in slightly higher NOx emissions from biodiesel than from diesel [39]. Moreover, the
emissions from biodiesel than from diesel [39]. Moreover, the increase in NOx is related to the presence
increase in NOx is related to the presence of unsaturated hydrocarbons in the fuel [40]. As shown in
of unsaturated hydrocarbons in the fuel [40]. As shown in Figure 6d, the smoke opacity is the lowest at
Figure 6d, the smoke opacity is the lowest at 0% engine load due to a high air/fuel ratio compared
0% engine load due to a high air/fuel ratio compared with other operating conditions. At 100% load,
with other operating conditions. At 100% load, there is a clear increase in smoke opacity due to a
there is a clear increase in smoke opacity due to a large amount of fuel consumption and a decrease in
large amount of fuel consumption and a decrease in oxygen concentration in the combustion
chamber. Therefore, it can be concluded that a higher load results in lower fuel oxygen content [41].
Energies 2020, 13, 5736 9 of 16

oxygen2020,
Energies concentration inREVIEW
13, x FOR PEER the combustion chamber. Therefore, it can be concluded that a higher9 load of 17
results in lower fuel oxygen content [41]. In addition, smoke opacity decreases with the increase in the
In addition,
biodiesel smoke
blend ratioopacity decreases
in the diesel fuel, with the behavior
and this increase isin more
the biodiesel
obvious blend
at highratio in the
engine diesel
loads. fuel,
At 100%
and
load,this
thebehavior is more
smoke opacity ofobvious
B10, B20,atB30,
highand engine
B100loads. At 100%
are reduced byload,
30.26%,the47.23%,
smoke opacity
64.95%, of
andB10, B20,
90.78%,
B30, and B100compared
respectively, are reduced byB0.
with 30.26%,
These47.23%,
results64.95%,
are alsoand 90.78%,
easily respectively,
verified in Figure 7, compared with B0.
which shows the
These results are also easily verified in Figure 7, which shows the color depth
color depth of the filter papers covered with PM primary particles according to different collection of the filter papers
covered
times (1,with PM
2, and primary
5 min). Thisparticles
is mainlyaccording
because tothedifferent collection in
oxygen contained times (1, 2, and
biodiesel 5 min).
improves This is
diffusion
mainly because the oxygen contained in biodiesel improves diffusion combustion
combustion and promotes the post-flame oxidation of smoke during later expansion and exhaust and promotes the
post-flame oxidation of smoke during later expansion and exhaust processes.
processes. Additionally, soot formation is also associated with temperature and the soot volume Additionally, soot
formation is also
fraction (SVF) associated
[42,43]; with temperature
the oxygen contained in and the soot can
biodiesel volume
also fraction
improve(SVF) local[42,43];
anoxic the oxygen
conditions
contained
caused by fuel-rich zones. The biodiesel has a higher cetane number than diesel, which also The
in biodiesel can also improve local anoxic conditions caused by fuel-rich zones. can
biodiesel has combustion
increase fuel a higher cetane number
efficiency andthan diesel,
reduce which
smoke also can
opacity increase fuel combustion efficiency
[41].
and reduce smoke opacity [41].

6. Effect
Figure 6.
Figure Effectofofengine loads
engine on (a)
loads on CO,
(a) (b)
CO,hydrocarbon (HC), and
(b) hydrocarbon (c) and
(HC), nitrogen oxide (NOx)
(c) nitrogen emissions
oxide (NOx)
and (d) smoke
emissions opacity.
and (d) smoke opacity.

Figures 8 and 9 show the TEM and SEM images of the PM primary particles emitted from the CRDI
diesel engine fueled with biodiesel blends at 25% and 75% engine loads. As shown in Figures 8 and 9,
the diameters of the PM primary particles emitted from the CRDI diesel engine fueled with all tested
fuels are much smaller than 100 nm. Some of the PM primary particles are clustered together to form
micron-sized agglomerates. Figure 10 shows the PM particle diameter distribution for all biodiesel
blends. At 25% load, the average diameter of the PM primary particles for B0, B10, B20, B30, and B100
is 32.35, 25.66, 24.71, 23.91, and 22.79 nm, respectively; the minimum diameter of the PM primary
particles for all tested fuels is about 10 nm. At 75% load, the average diameter of the PM primary
particles for all tested fuels are slightly further reduced; for B0, B10, B20, B30, and B100 the average
diameter is 30.70, 24.02, 23.01, 21.96, and 20.71 nm, respectively. Moreover, for B0, the diameter of the
PM primary particles is mainly distributed between 15 and 50 nm with most particles having diameters
between 30 and 40 nm. For biodiesel blends, most of the PM primary particles have diameters mainly

Figure 7. Photograph of filter papers covered with particles (a), and the color depth of the filter papers
(b).
Energies 2020, 13, 5736 10 of 16

distributed between 20 and 30 nm (see Figure 10b). As a result, with the increases in the biodiesel
mixing
Energies ratio and
2020, 13, engine
x FOR PEERload, the average diameter of the PM primary particles decreases. This may
REVIEW be
10 of 17
caused by increases in the combustion temperature and pressure in the combustion chamber and the
Figuresefficiency
combustion 8 and 9 showdue tothe TEM and
increased SEM images
biodiesel mixing ofratio
the PM
andprimary particles
engine load, emitted
thereby from the
increasing the
CRDI diesel
oxidation rateengine
of the PMfueled with biodiesel
primary particles.blends at 25%content
The oxygen and 75% in engine loads.fuel
the blended As shown
increasesin Figures
with the
8 and 9,of
addition the diameters
biodiesel of the
to the PMfuel,
diesel primary
which particles
improves emitted from the
the problem CRDI dieseloxygen
of insufficient enginein fueled with
the oil-rich
all tested
zone fuels are much
and promotes smaller thanof100
full combustion thenm.
fuel.Some of the PM
A similar primary particles
phenomenon was also areobserved
clusteredby together
Chong
ettoal.form
[42].micron-sized
On the otheragglomerates.
hand, the PMFigure primary 10 particles
shows the PM particle
emitted diameter
from diesel distribution
engines for all
mainly contain
biodiesel
solid carbonblends.
coresAt 25% load,mm),
(0.01~0.08 the average diameter
agglomerate of the PM
(0.05~1.0 mm)primary particles for
and adsorbed B0, B10, B20,
vapor-phase B30,
species,
and B100hydrocarbons,
adsorbed is 32.35, 25.66, liquid24.71, 23.91,
condensedand 22.79 nm, respectively;
hydrocarbon particles,theand minimum
hydrateddiameter of the PM
sulfate species [44].
primary particles for all tested fuels is about 10 nm. At 75% load, the
In general, HCs and other substances adsorbed on the surface of PM are more easily oxidized under average diameter of the PM
primary particlesand
high-temperature for all tested fuelsconditions.
high-pressure are slightlyTherefore,
further reduced; for B0,ofB10,
the decrease the B20, B30, anddiameter
PM particle B100 theis
average
also relateddiameter is 30.70,in24.02,
to the decrease 23.01, 21.96,
the substance and 20.71
adsorbed on thenm, respectively.
surface of the PMMoreover, for B0, This
primary particles. the
diameter of the PM primary particles is mainly distributed between 15 and
is consistent with the results reported by Li et al. [45]. They also pointed out that the change in the 50 nm with most particles
having
PM diameters
particle diameter between
is also30related
and 40 tonm. For
the biodiesel
fuel’s cetaneblends,
number;mosta of thecetane
high PM primary
number particles have
of biodiesel
diameters
resulted Figure
in amainly
6.short distributed
Effect between
loads on 20
of enginecombustion
premixed and
CO, 30
(a)period, (b)nm (seediffusion
Figure(HC),
ahydrocarbon
long 10b). As a(c)result,
and
combustion with
nitrogen
period, the increases
oxide
and (NOx)
increased
in the biodiesel
emissions
PM oxidation time. andmixing
(d) smokeratio and
opacity. engine load, the average diameter of the PM primary particles
decreases. This may be caused by increases in the combustion temperature and pressure in the
combustion chamber and the combustion efficiency due to increased biodiesel mixing ratio and
engine load, thereby increasing the oxidation rate of the PM primary particles. The oxygen content
in the blended fuel increases with the addition of biodiesel to the diesel fuel, which improves the
problem of insufficient oxygen in the oil-rich zone and promotes full combustion of the fuel. A similar
phenomenon was also observed by Chong et al. [42]. On the other hand, the PM primary particles
emitted from diesel engines mainly contain solid carbon cores (0.01~0.08 mm), agglomerate (0.05~1.0
mm) and adsorbed vapor-phase species, adsorbed hydrocarbons, liquid condensed hydrocarbon
particles, and hydrated sulfate species [44]. In general, HCs and other substances adsorbed on the
surface of PM are more easily oxidized under high-temperature and high-pressure conditions.
Therefore, the decrease of the PM particle diameter is also related to the decrease in the substance
adsorbed on the surface of the PM primary particles. This is consistent with the results reported by
Li et al. [45]. They also pointed out that the change in the PM particle diameter is also related to the
fuel’s cetane number; a high cetane number of biodiesel resulted in a short premixed combustion
period, a long diffusion combustion period, and increased PM oxidation time.
Figure 7. Photograph of filter papers covered with particles (a), and the color depth of the filter papers (b).
Figure 7. Photograph of filter papers covered with particles (a), and the color depth of the filter papers
(b).

Figure8.8.Comparisons
Figure ComparisonsofofTEM
TEMimages
imagesofof
the particulate
the matter
particulate (PM)
matter primary
(PM) particles
primary at 25%
particles andand
at 25% 75%
engine loads.loads.
75% engine
 Energies 2020, 13, x FOR PEER REVIEW 11 of 17
Energies 2020, 13, 5736 11 of 16
Energies 2020, 13, x FOR PEER REVIEW 11 of 17

Figure
Figure 9.9.
9.
Figure Comparisons
Comparisons of
Comparisonsof SEM
ofSEM images
SEMimages of the
images of
of the PM
the PMprimary
PM primaryparticles
primary particlesatat
particles at25%
25%
25% and
and
and 75%
75%
75% engine
engine
engine loads.
loads.
loads.

Figure 10. PM primary particle size (a) and its distribution at 75% engine load (b).
Figure10.
Figure 10. PM
PM primary
primary particle
particle size
size (a)
(a) and
andits
its distribution
distributionatat75%
75%engine
engineload
load(b).
(b).
Figure 11 presents the SEM images of filter papers without PM primary particles and filter
Figure
Figure
papers 1111presents
covered presents
with PM thethe
SEM SEM
primaryimages
imagesof filter
particles offrom papers
filterallpaperswithout
tested PM
without
fuels primary
at 100%PM load particles
primary andtofilter
particles
according andpapers
different filter
covered
papers withtimes
covered
collection PMwith
primary
(1 minPM and particles
primary fromAs all
particles
2 min). showntested
frominall fuels at 100%
tested
Figure theload
fuels
11, at according
100%
filter to different
loadwithout
paper according PM to collection
different
primary
times (1
collectionmin and
times 2(1min).
min As
and shown
2 in
min). Figure
As shown 11, the
in filter
Figure paper11, without
the
particles is made up of clear crisscrossing fibers with clearly visible voids between the fibers. AsfilterPM primary
paper particles
without PM is the
made
primary
up of clear
particles crisscrossing fibers with clearly visible voids between the fibers.
PM primary particles collected on the filter paper, the visible amount of fibers on the filter paperthe
is made up of clear crisscrossing fibers with clearly visible voids As the
betweenPM primary
the fibers.particles
As
collected
PM primary
decreased,on the
and filter
particles paper,
collected
the voids the visible
between on the amount
thefibers
filter were of filled
paper, fibers on
thewith the
visiblePMfilter
amount paper
primary of decreased,
fibers on
particles. and
the
With the voids
filter
increasingpaper
between
capturethe
decreased, fibers
and
time, thewere
the voids
amount filled
of with
between PM
visiblethe primary
fibers
fibers on the particles.
were filled
filter paperWith
with and increasing
PM primary
pores capture
between thetime,
particles. the
With
fibers amount
increasing
decreased of
visible
capture fibers
significantly,on
time, thethe filter
amount
which paper and
of visible
indicates pores between
fibers in
an increase onthe the
theamount fibers
filter paper decreased
of PMand significantly,
poresparticles
primary betweenon which
thethe
fibers indicates
filterdecreased
paper. an
increase
On theinother
significantly,thewhich
amount
hand, with of PM
indicates primary
increasing particles
biodiesel
an increase in the onamount
blend the filter
ratios ofpaper.
in diesel,
PM primaryOn the particles
especially other
for hand,
B100, with
onthe increasing
theamount
filter of
paper.
OnPMtheprimary
biodiesel blend
other particles
ratios
hand, inon
with the filter
diesel,
increasing paper
especially
biodieselisforsignificantly
B100, ratios
blend reduced.
the amount
in diesel,ofFewer
PM PM primary
primary
especially particles
forparticles
B100, the were
onamount
the filter
of
observed
paper by the
is significantly
PM primary SEM
particles on
reduced. B100 samples
Fewerpaper
on the filter compared
PM primary with other
particlesreduced.
is significantly samples.
were observed SEM
Fewerby PM allows the
theprimary morphology
SEM onparticles
B100 samples were
of PM primary
compared
observed with
by the particles
other
SEM samples.on filter
on B100 SEM paper
allows
samples tothebe morphology
compared observedwith in aofrelatively
other PM simple
primary
samples. SEM and clear
particles
allows on way.
thefilter These to
paper
morphology
ofobservations
be observed
PM primary in ademonstrate
relativelyon
particles that
filterpalm-oil-based
simple and
paperclearto way. biodiesel incan
These observations
be observed play an
a relatively important
demonstrate
simple and roleclear
that as away.reliable
palm-oil-based These
alternative
biodiesel
observations fuel
can play in reducing
an important
demonstrate particulate emissions
role as a reliablebiodiesel
that palm-oil-based from diesel
alternative engines.
canfuel playin an
reducing
importantparticulate
role asemissions
a reliable
from diesel engines.
alternative fuel in reducing particulate emissions from diesel engines.
Energies 2020, 13, 5736 12 of 16
Energies 2020, 13, x FOR PEER REVIEW 12 of 17

Figure11.
Figure 11.Comparisons
Comparisons of
of SEM
SEM images
images of
of paper
paper filters
filters covered
covered with
with different
different amounts
amounts of
of particles.
particles.

3.4.
3.4.Unregulated
UnregulatedEmission
EmissionCharacteristics
Characteristics
Figure12a
Figure 12acompares
comparesthe theconcentrations
concentrations of of three
three trace metals (TMs)(TMs) (Mn,
(Mn, Ba,
Ba, and
andPb) Pb)emitted
emittedatat
100%engine
100% engine load
load fromfromall all
thethe biodiesel
biodiesel blends.
blends. TheTheTMsTMsin theinexhaust
the exhaust emissions
emissions show show different
different trends
trends
with thewith
changethe ofchange
the palmof the palm biodiesel
biodiesel blendingblending ratio in
ratio in diesel diesel
fuel. fuel.proportion
A high A high proportion
of biodieselof
biodiesel does not keep the TMs at a very low level, and Shukla et al. [26]
does not keep the TMs at a very low level, and Shukla et al. [26] also found similar results. This also found similar results.
Thisbe
may may be attributed
attributed to some to comprehensive
some comprehensive effect affecting
effect affecting TM changes,
TM changes, such assuch
fuelas fuel properties,
properties, engine
engine operating conditions, and atomization effects during fuel injection. Patel et
operating conditions, and atomization effects during fuel injection. Patel et al. [46] and Shukla et al. [26] al. [46] and Shukla
et al. [26]
pointed outpointed
that thereoutare
thatthree
theremain
are three
sourcesmainof sources
TMs in an of TMs
enginein an engine
exhaust exhaust
system: (i)system: (i) those
those present in
present
fuels frominproduction,
fuels from production,
processing, and processing, and transportation;
transportation; (ii) those
(ii) those present present
in wear debris in from
wear friction
debris
from friction
between between
different engine different engine components,
components, such as pistons, suchpiston
as pistons,
rings,piston rings,
cylinder cylinder
liner, liner,seats;
and valve and
valve seats; and (iii) those present in lubricating oil from metal additives. Patel
and (iii) those present in lubricating oil from metal additives. Patel et al. [46] also pointed out that et al. [46] also pointed
outvariations
the that the variations in engine
in engine loads loads atspeed
at constant constant speed
are also veryareimportant
also very for important
TM changes, for TM changes,
because the
because the lubricating oil composition and wear debris will be affected.
lubricating oil composition and wear debris will be affected. Therefore, the engine operating conditions Therefore, the engine
operating
play conditions
an important roleplay an important
in the concentration role inofthe
TMsconcentration
emitted from of TMs emitted
the CRDI fromengine.
diesel the CRDIOverall,
diesel
engine.
the Overall,are
TM changes theaffected
TM changesby a are affected
variety by a variety
of complex of complex
factors such as factors such as fuellubricating
fuel composition, composition, oil
lubricating oil composition, and engine operating conditions. In addition,
composition, and engine operating conditions. In addition, TM emissions from diesel engines TM emissions fromarediesel
very
engines
low, thus are
theyvery low, thustothey
are difficult are difficult
capture and analyzeto capture and analyze
by general analysisby general analysis
techniques. Therefore, techniques.
detailed
Therefore, detailed analysis of the specific formation mechanism of TM emissions
analysis of the specific formation mechanism of TM emissions from diesel engines needs to be further from diesel engines
needs to be further studied in the future.
studied in the future.
Figure 12b shows the concentrations of benzene, toluene, and xylene (BTX) emissions from the
Figure 12b shows the concentrations of benzene, toluene, and xylene (BTX) emissions from the
CRDI diesel engine fueled with palm oil biodiesel–diesel blends at 25% and 75% loads. BTX are
CRDI diesel engine fueled with palm oil biodiesel–diesel blends at 25% and 75% loads. BTX are volatile
volatile organic compounds (VOCs). VOCs are numerous and complex, and the most common ones
organic compounds (VOCs). VOCs are numerous and complex, and the most common ones that pose
that pose the greatest threat to human health and the environment are BTX. Therefore, BTX are
the greatest threat to human health and the environment are BTX. Therefore, BTX are regarded as the
regarded as the main research object in this study. It was observed that the trends of BTX emissions
main research object in this study. It was observed that the trends of BTX emissions are significantly
are significantly affected by the load and biodiesel blend ratio. BTX emissions decrease with
affected by the load and biodiesel blend ratio. BTX emissions decrease with increasing engine load
increasing engine load and biodiesel concentration in diesel. The overall analysis indicates that
and biodiesel concentration in diesel. The overall analysis indicates that benzene emissions from all
benzene emissions from all fuels are the greatest, followed by xylene (total o-xylene and p-xylene)
and toluene. Similar results have been reported by other researchers [47–49]. Moreover, Liu et al. [50]
Energies 2020, 13, 5736 13 of 16

Energies 2020, 13, x FOR PEER REVIEW 13 of 17

fuels are the greatest, followed by xylene (total o-xylene and p-xylene) and toluene. Similar results
have been
found that reported
the reduction by other researchers
of toluene [47–49].
was related Moreover,
to the additionLiu et al. [50] found
of oxygenated fuels.that
Thesethechanges
reduction in
of toluene was related to the addition of oxygenated fuels. These changes
BTX emissions may be mainly due to the combined effects of the following factors: (i) high engine in BTX emissions may
be mainly
load, due tostudies
with many the combined
showing effects
that theofhigh-temperature
the following factors: (i) high engine
and high-pressure load, withformed
environment many
studies showing that the high-temperature and high-pressure environment
by a high load can promote BTX degradation; (ii) unsaturated hydrocarbon chains from biodiesel, formed by a high load can
promoteunsaturated
because BTX degradation; (ii) unsaturated
hydrocarbons hydrocarbon
are the precursors chains from
responsible forbiodiesel,
the formation because unsaturated
of aromatic and
hydrocarbons are the precursors responsible for the formation of aromatic
polycyclic aromatic hydrocarbons; (iii) pyrolysis products from diesel fuel, such as C2H4 and and polycyclic aromatic
C3H6,
hydrocarbons;
whose presence(iii) pyrolysis
increases theproducts from diesel
concentration fuel, such
of benzene; (iv) as C2 H4 and C3 Hproperties
physicochemical 6 , whose presence
of BTX,
increases the concentration of benzene; (iv) physicochemical properties
which decide whether BTX are easily degraded; (v) a high cetane number and high oxygen of BTX, which decide whether
content
BTX
in are easily
biodiesel, degraded;
which improve (v)combustion
a high cetane number and
characteristics andhigh oxygen
promote BTX content in biodiesel,
degradation; which
(vi) exhaust
improve
gas combustion
temperatures, characteristics
because low exhaust and promote BTX
temperature degradation;
is not conducive to (vi)BTX
exhaust gas temperatures,
degradation, especially
for benzene; and (vii) other factors that are not conducive to BTX degradation, suchbenzene;
because low exhaust temperature is not conducive to BTX degradation, especially for and (vii)
as inappropriate
other factors that are not conducive to BTX degradation, such as inappropriate
engine operating parameters (e.g., low injection pressure), and shortcomings of biodiesel (e.g., high engine operating
parameters
viscosity and (e.g.,
highlow injection
density). pressure),
Thus, it may and shortcomings
be concluded of biodiesel
that the “positive(e.g., highofviscosity
effects” and high
high engine load
and oxygen content in biodiesel and its high cetane number outweigh the “negative effects” content
density). Thus, it may be concluded that the “positive effects” of high engine load and oxygen of high
in biodiesel
viscosity andand high itsunsaturated
high cetane hydrogen
number outweigh
from the the “negative
biodiesel effects” ofinhigh
documented this viscosity and high
study, resulting in
unsaturated hydrogen from the biodiesel documented in this study,
the reduction of BTX associated with increased biodiesel blend ratios and engine load. resulting in the reduction of BTX
associated with increased biodiesel blend ratios and engine load.

Figure 12. Trace metals (a) and peak area of benzene, toluene, and xylene (BTX) emissions (b) for all
Figure 12. Trace metals (a) and peak area of benzene, toluene, and xylene (BTX) emissions (b) for all
tested fuels.
tested fuels.
4. Conclusions
4. Conclusions
To expand research on combustion, soot particle distribution, and regulated and unregulated
To expand
emissions research
from diesel on combustion,
engines fueled with soot
palmparticle distribution,
oil biodiesel, a series and regulated and
of experiments wereunregulated
carried out
emissions from diesel engines fueled with palm oil biodiesel, a series of experiments
on a CRDI diesel engine with a constant speed of 1500 rpm under wide engine loads from 0% to 100%. were carried out
on
Theamain
CRDIconclusions
diesel engineare with a constant
summarized speed of 1500 rpm under wide engine loads from 0% to
as follows:
100%. The main conclusions are summarized as follows:
1. The influence of biodiesel blends on in-cylinder pressure and HRR has little change compared
1. Thewithinfluence of biodiesel
pure diesel. blends on
The low calorific in-cylinder
value and highpressure
viscosityand HRRoil
of palm has little change
biodiesel resultscompared
in higher
with pure diesel. The low calorific value and high viscosity of palm oil biodiesel
brake specific fuel consumption (BSFC) than diesel, with an average of about 11.96% higher results in higher
for
brake specificblends
all biodiesel fuel consumption (BSFC)
under all engine than diesel,
operating with
loads. TheanCOVimep
average offorabout 11.96% higher
all biodiesel blendsforis
all biodiesel
much lower blends under
than 10%, whichall engine operating
shows that loads.
the CRDI Theengine
diesel COVimep for all
without anybiodiesel blendscan
modification is
much lower
run very thanunder
stably 10%, all
which showsconditions.
operating that the CRDI diesel engine without any modification can
2. run very stably
Compared to B0under all operating
fuel, the CO, HC, andconditions.
smoke opacity are significantly reduced, while the NOx
2. Compared to B0 fuel, the CO, HC, and
emissions are increased slightly under all enginesmoke opacity
loadsareinsignificantly reduced,
the CRDI diesel while
engine the NOx
fueled with
emissions are increased
B10, B20, B30, and B100,slightly underMoreover,
respectively. all engine the
loads
PMinprimary
the CRDI diesel for
particles engine fueled
all test fuelswith
are
B10,
muchB20, B30, than
smaller and B100,
100 nm respectively.
in diameter.Moreover,
The diameterthe of
PM primary
these particles
particles furtherfor all test fuels
decreases with are
the
much smaller than 100 nm in diameter. The diameter of these particles further
increases in engine load and the biodiesel mixture ratio. At 75% load, the average diameters of decreases with
the increases in engine load and the biodiesel mixture ratio. At 75% load, the average diameters
of the PM primary particles for B0, B10, B20, B30, and B100 are 30.70, 24.02, 23.01, 21.96, and
Energies 2020, 13, 5736 14 of 16

the PM primary particles for B0, B10, B20, B30, and B100 are 30.70, 24.02, 23.01, 21.96, and 20.71
nm, respectively, which are 5.10%, 6.39%, 6.88%, 8.16%, and 9.13% lower than those at 25% load.
3. Unregulated emissions such as trace metals (TMs) including Pb, Mn, and Ba are found in the
engine emissions, and the Pb content is the highest, followed by Mn and Ba. The TM changes are
affected by a variety of complex factors such as fuel composition, lubricating oil composition,
and engine operating conditions. Of the BTX hydrocarbons, benzene is the highest in the emissions
from all fuels, followed by xylene and benzene. BTX emissions are decreased by increased engine
load and biodiesel content in diesel fuel.

Author Contributions: Methodology, J.C.G.; validation, J.C.G. and N.J.C.; investigation, J.C.G.; data curation,
J.C.G.; writing—original draft preparation, J.C.G.; writing—review and editing, J.C.G. and N.J.C.; funding
acquisition, J.C.G. and N.J.C. All authors have read and agreed to the published version of the manuscript.
Funding: This research was supported by the Basic Science Research Program through the National Research
Foundation of Korea (NRF) funded by the Ministry of Education (No. 2019R1I1A1A01057727) and supported by
the Korea government (MSIT) (No. 2019R1F1A1063154).
Acknowledgments: The authors would like to thank the teachers from the Center for University-Wide Research
Facilities (CURF) at Jeonbuk National University (JBNU) for their help in performing the morphology of the
PM particles.
Conflicts of Interest: All authors declare no conflict of interest.

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