Fuel 236 (2019) 1366–1376

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Full Length Article

Comparative compression ignition engine performance, combustion, and T

emission characteristics, and trace metals in particulates from Waste
cooking oil, Jatropha and Karanja oil derived biodiesels
Chetankumar Patela, Krishn Chandraa, Joonsik Hwangb, Rashmi A. Agarwala, Neeraj Guptaa,
Choongsik Baeb, Tarun Guptac, Avinash Kumar Agarwala,
⁎

a
Engine Research Laboratory, Department of Mechanical Engineering, Indian Institute of Technology Kanpur, Kanpur 208016, India
b
Engine Lab, Department of Mechanical and Aerospace Engineering, Korea Advanced Institute of Science and Technology (KAIST), 291 Daehak-ro, Yuseong-gu, Daejeon
305-701, Republic of Korea
c
Department of Civil Engineering, Indian Institute of Technology Kanpur, Kanpur 208016, India

GRAPHICAL ABSTRACT

ARTICLE INFO ABSTRACT

Keywords: In the present study, comparison of performance, combustion and emission characteristics of a single cylinder
Biodiesel compression ignition (CI) genset engine fueled by biodiesels derived from Waste cooking oil (WCO), Jatropha
Combustion and Karanja oils vis-á-vis baseline mineral diesel has been carried out. Performance and combustion in-
Performance vestigations were carried out at constant engine speed (1500 rpm) and six engine loads (0–100%). WCO bio-
Emission characteristics
diesel showed slightly higher heat release rate (HRR) than baseline mineral diesel, while it was slightly lower for
Particulates
Trace metals
Karanja and Jatropha biodiesels. Hydrocarbons (HC) and oxides of nitrogen (NOX) emissions were lower, while
carbon monoxide (CO) emission was relatively higher for biodiesels compared to baseline diesel. Smoke opacity
was higher for Karanja and Jatropha biodiesels compared to baseline diesel. WCO biodiesel exhibited com-
parable smoke opacity with baseline mineral diesel except at full load, where it was relatively lower. Particulates
were collected from the engine exhaust on a quartz filter paper using a partial flow dilution tunnel at 50 and
100% engine loads, for trace metal analysis using inductively coupled plasma optical emission spectroscopy
(ICP-OES). It was found that trace metals such as Ca, Cu, Fe, K, Mg, Na, Zn and Al showed higher concentrations
in particulates from all test fuels, while Ba, Cd, Cr, Mn and Mo showed relatively lower concentrations in the
particulates collected.

⁎
Corresponding author.
E-mail address: akag@iitk.ac.in (A.K. Agarwal).

https://doi.org/10.1016/j.fuel.2018.08.137
Received 16 May 2018; Received in revised form 20 June 2018; Accepted 30 August 2018
0016-2361/ © 2018 Elsevier Ltd. All rights reserved.
C. Patel et al.
1. Introduction
Diesel engines are widely utilized to satisfy small-to-large power
requirements for variety of on-road and off-road applications.
Conventional fossil fuels like diesel and gasoline have been utilized in
internal combustion (IC) engines for over a century. However such
fossil fuel resources are rather limited. In addition, they cause atmo-
spheric pollution and contribute to severe environmental problems.
Therefore it is important to search for alternative renewable fuels,
which can reduce harmful emissions and can be utilized in existing
engines without major hardware modifications. In this context, bio-
diesel has emerged as a promising alternative fuel for direct use in
stationary engines, either in pure form or in blended form with mineral
diesel (up to 20%), especially in transportation engines [1]. Since
emissions (gaseous and particulates) lead to severe health effects, it
becomes important to measure the toxicity potential of emissions from
biofuels before their large-scale implementation worldwide. Combus-
tion in the engine cylinder plays significant role in engine-out emis-
sions. Combustion process is the engine is generally characterized by in-
cylinder pressure (P), heat release rate (HRR) and combustion duration
(CD). Implicit molecular oxygen and higher cetane number of biodiesels
result in superior combustion compared to baseline mineral diesel. Lee
et al. [2] performed an experiment on a common rail direct injection
(CRDI) single cylinder diesel engine fuelled with unpolished rice oil and
soybean oil biodiesel blends to investigate its combustion character-
istics. They reported that ignition delay for biodiesel blends was shorter
because of higher cetane number of biodiesels compared to baseline
mineral diesel. Zhu et al. [3] investigated combustion characteristics of
biodiesel and reported higher peak in-cylinder pressure (Pmax) for
biodiesel at higher engine loads. Lin et al. [4] measured combustion
characteristics of vegetable oil methyl ester (VOME) in a single cylinder
direct injection engine. They reported relatively earlier start of com-
bustion (SoC) for biodiesel as well as higher HRR, due to its higher
oxygen content compared to baseline mineral diesel. Ozsezen et al. [5]
suggested that higher bulk modulus of compressibility of biodiesel leads
to relatively earlier fuel injection and higher fuel injection pressure
(FIP) leads to earlier SoC. Due to higher oxygen content compared to
baseline mineral diesel, biodiesel sprays undergo superior fuel-air
mixing, leading to shorter CD [4]. Kegl [6] noticed lower HRR for
biodiesel due to shorter ID and lower volatility. It leads to traces of fuel
accumulating in the combustion chamber, leading to relatively lower
HRR. Majority of researchers reported improvements in combustion
due to inherent fuel oxygen in biodiesels, however mixed trends were
reported for the HRR.
Influence of biodiesels on engine performance depends on the re-
lationship between fuel injection system and fuel properties such as
oxygen content, viscosity, calorific value, density etc. Biodiesel has
higher density than baseline mineral diesel hence higher fuel mass of
biodiesel is injected in the same injection duration, resulting in higher
brake specific fuel consumption (BSFC) [7]. Zhang et al. [8] in-
vestigated performance characteristics of Soybean oil biodiesel in a DI
diesel engine. They reported that BSFC of biodiesel (B100) was
∼15–18% higher than baseline mineral diesel, due to its lower calorific
value. Dhar and Agarwal [9] investigated combustion characteristics of
Karanja biodiesel in a CRDI diesel engine. They reported increase in
BSFC with increasing Karanja biodiesel blend concentration.
Diesel engines emit various gases as well as particulates. Gaseous
emissions include CO, HC and NOX while particulates comprise of nu-
merous organic and inorganic species. CO formation takes place mainly
due to oxygen-deficient combustion of fuel in the engine combustion
chamber. CO formation is lower in diesel engines compared to gasoline
engines because they operate with excess air (low equivalence ratio).
However, some CO is formed in locally oxygen-deficient zones of the
diesel engine combustion chamber [10]. A number of researchers re-
ported lower CO emission from biodiesel. Murillo et al. [11] conducted
emission investigations in a four stroke DI outboard diesel engine fueled
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Fuel 236 (2019) 1366–1376
by waste cooking oil biodiesel and reported 12% lower CO emission
compared to baseline mineral diesel. Dhar and Agarwal [12] in-
vestigated emission characteristics of Karanja biodiesel and blends in a
four cylinder DI diesel engine. They reported that at higher engine loads
and speeds, biodiesel/blends emitted lower CO compared to mineral
diesel. However Dhar et al. [13] reported higher CO emission due to
deficiency of oxygen in the combustion chamber at higher engine loads.
HC emission formation in the engine takes place due to several
reasons such as due to lack of oxygen in the combustion zones (i.e. high
equivalence ratio), crevices, quench-layer, porous deposits, absorption
by oil, bulk-quenching, late burning, and injector effects. In a diesel
engine, HC emissions form mostly at lower engine loads, primarily due
to impingement of fuel sprays on the cylinder walls and piston top, non-
uniform fuel distribution in the engine combustion chamber, over-
leaning (or over-mixing), and lower combustion chamber temperatures
[10]. Most researchers reported reduction in HC emissions from bio-
diesel. Attia and Hassaneen [14] utilized Waste cooking oil methyl
esters in a single cylinder DI engine and reported 15% reduction in HC
emissions compared to baseline mineral diesel. Gangwar and Agarwal
[15] investigated emission characteristics in an indirect injection (IDI)
transport engine fueled by biodiesel blended with mineral diesel and
reported that HC emissions were slightly lower in case of biodiesel
blend, compared to baseline mineral diesel. However Kegl et al. [6]
reported higher HC emissions from rapeseed oil biodiesel. HC emissions
were higher at lower engine speeds due to presence of unburned fuel in
the engine combustion chamber [6].
Most researchers reported higher NOX emissions upon using bio-
diesel/blends. Ozener et al. [16] conducted experiments using soybean
biodiesel blends (B10, B20 and B50) in a single cylinder diesel engine.
They reported increased NOX emissions by ∼6.95–17.62% compared to
baseline mineral diesel. Murillo et al. [11] also reported ∼20% increase
in NOX emissions compared to baseline diesel. Zhang et al. [8] observed
higher NOX emissions with soybean biodiesel blends compared to
baseline mineral diesel as well. An et al. [17] performed experiments on
Euro-IV diesel engine to investigate emission characteristics of 100%
biodiesel. They found that NOx emissions produced by 100% biodiesel
were actually lower than baseline mineral diesel. Gangwar and Agarwal
[15] investigated emission characteristics of Jatropha biodiesel and
blends in four cylinder medium duty IDI transportation engine. They
reported that biodiesel/blends produced higher NOX emissions com-
pared to baseline mineral diesel, which was largely due to presence of
fuel oxygen in biodiesel, that increased the formation of fuel NOX apart
from thermal NOX. Higher viscosity, lower volatility and presence of
bulky hydrocarbon molecules in biodiesel resulted in relatively inferior
atomization of biodiesel/blends. Inferior atomization of biodiesel/
blends may be the main reason for higher smoke opacity.
Emission of trace metals from CI engines is a major health and en-
vironmental concern. Numerous researchers investigated trace metal
concentrations emanating in the biodiesel exhaust. Shukla et al. [18]
conducted trace metal investigations of a four cylinder naturally aspi-
rated water cooled transport engine using 20% Karanja biodiesel blend.
They reported trace metals such as Ca, Fe, Cr, Cu, Mn, Pb, Ni, Ba and Cd
in the exhaust. They also noticed reduction in particulate emissions
with increasing engine load. Dwivedi et al. [19] investigated trace
metals in the exhaust from a medium-duty transport engine by using
diesel and B20 (20% blend of biodiesel with diesel). They reported that
Pb, Cd, Na and Ni were mainly present in diesel exhaust particulates,
while Fe, Al, Zn, Cr and Mg were mostly found in B20 exhaust parti-
culates. Agarwal et al. [20] evaluated toxic potential of particulates
from Jatropha biodiesel blend (JB20) and baseline mineral diesel used
in a medium-duty transport engine. They reported higher trace con-
centrations of crustal elements such as Al, Ca, Fe and Mg, compared to
anthropogenic elements such as Cd, Cr, Cu and Zn in baseline diesel as
well as B20. They also reported that relatively lower trace metal con-
centrations were observed in particulates from B20 compared to base-
line diesel. Chellam et al. [21] measured trace metals in fine
C. Patel et al.
particulates in the environment and reported higher trace concentra-
tions of Al, Fe, Mg and Ti, which were attributed to resuspension of
road dust; while Zn, Cu and Ba were attributed to vehicular exhaust.
Wang et al. [22] measured trace metals emitted by diesel engine of a
vehicle and reported higher trace metal concentrations of crustal ele-
ments such as Al, Ca, Fe, Mg and Si compared to anthropogenic ele-
ments such as Ag, Ba, Cd, Co, Cr, Cu, Mn, Mo, Ni, Pb, Sb, Sr, Ti, V and
Zn in the exhaust particulates. Agarwal et al. [23] also conducted trace
metal investigations of a single cylinder diesel engine fueled with
straight vegetable oil (SVO) and mineral diesel at constant engine speed
of 1500 rpm. They reported higher trace concentrations of Fe, Mg, Ca
and Na compared to Cu, Ni, Pb and Zn in the engine exhaust particu-
lates. Singh et al. [24] measured trace metal concentrations in ambient
air in Delhi and reported higher concentrations of Al, Ca, Cd, Cr, Cu, Fe,
Mn, Ni, Pb, V and Zn. They investigated vehicular and anthropogenic
emissions related to combustion source, industrial processes and nat-
ural dust. They concluded that transport sector and natural dust were
the main sources of trace metals in the ambient particles.
There is hardly any study in the literature, which covered engine
performance, combustion, emissions and trace metal concentration in
the particulates from biodiesel, taken together. In this context, experi-
mental investigations were carried out for comparative engine perfor-
mance, combustion, emission characterisation and analysis of trace
metals in the exhaust particulates from a single cylinder diesel engine
fueled by Jatropha biodiesel (JB100), Karanja Biodiesel (KB100), Waste
cooking oil biodiesel (WCOB100) and mineral diesel at constant engine
speed of 1500 rpm.
2. Experimental setup
Experimental investigations for evaluation of engine performance,
combustion, emission characteristics and traces metals in particulates
were conducted in a single cylinder, DI diesel engine, which is typically
used in agriculture sector and for power backup. Table 1 shows the
technical specifications of the test engine and Table 2 shows the tech-
nical specifications of the injector nozzle. Table 3 shows the important
properties of the test fuels used in this study. Table 4 shows the fatty
acid composition of biodiesels. Fig. 1 shows the schematic of the engine
experimental setup.
The test engine was coupled to an AC alternator, which applied load
on the engine. A variac was used to control the engine load precisely by
dissipating the energy in a controlled manner. The engine was equipped
with a piezo-electric pressure transducer (Kistler, 6013C), a charge
amplifier (Kistler, 5015), a optical rotary shaft encoder (Encoders India,
ENC58/6) and a high speed combustion data acquisition system (High
Techniques, Win600e). K-type thermocouple was installed in the ex-
haust manifold for measuring the exhaust gas temperature. Exhaust gas
emission analyser (AVL, 4000) was used for measurement of CO, HC
and NOX. Table 5 shows the specifications and measurement principle
Table 1
Specifications of the test engine.
Engine Parameters Specifications
Manufacturer Kirloskar Oil Engines Ltd., India
Engine type Vertical, four-stroke, single-cylinder, constant speed,
direct injection, compression ignition engine
Rated power 7.4 kW at 1500 rpm
Bore/Stroke 102 mm/116 mm
Displacement volume 0.948 L
Compression ratio 17.5
Start of fuel injection 26° bTDC
timing
Nozzle opening pressure 200 bar
Cooling type Water cooling
Length/width/height 685/532/850 mm
BMEP at 1500 rpm 6.34 kg/cm2
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Table 2
Injector nozzle specifications.
Parameters Specifications
Number of nozzle holes 3
Nozzle hole diameter (mm) 0.29
Angle between two nozzle holes 120°
of the emission analyzer.
The analyzer gives raw emission values of each pollutant, however
for comparison, they need to be converted to mass emissions following
standard SAE protocols used for conversion of raw emissions into mass
emissions. Smoke opacity quantifies the presence of soot particles in the
engine exhaust. Smoke opacity was measured using smoke opacimeter
(AVL, 437).
Particles were collected using a partial flow dilution, which was
developed earlier in the Engine Research Laboratory of IIT Kanpur.
Fraction of exhaust gas passes through partial flow dilution tunnel,
which is mixed with preheated ambient air (clean) and they travel to-
gether, while undergoing unhindered mixing. The dilution ratio was
kept between 10 and 16 as per EPA protocols. This diluted exhaust gas
then passes through a filter assembly, where particles are collected on a
pre-conditioned Quartz filter (47 mm diameter).
Two punches of 16.6 mm diameter from the sample loaded 47 mm
diameter quartz filter paper were taken for other evaluations.
Remaining filter paper was digested in 15 ml conc. nitric acid (65%, GR
Merck) in a digestion vessel and heated to a temperature of 150–200 °C
for 2 h as per the standard procedure [31–33]. Afterwards, this filtrate
was added with Milli-Q water to make up 50 ml solution. These samples
were then analyzed by Inductively coupled plasma-optical emission
spectrometry (ICP-OES; Thermo Fisher, ICAP 6300 Duo). ICP-OES is an
analytical instrument used for detection of trace metals. Trace metal
laden liquid sample was introduced to the plasma that excites trace
metal atoms which emit electromagnetic radiations of specific wave-
lengths for each trace metal. The intensity of these radiations gives
information on specific concentration of each trace metal present in
particulates.
The test fuels used for these experiments included Jatropha bio-
diesel (JB100), Karanja biodiesel (KB100), Waste cooking oil biodiesel
(WCOB100) and baseline mineral diesel.
3. Results and discussion
3.1. Combustion investigations
In-cylinder pressure (P) is an important parameter to understand
combustion characteristics of test fuels in IC engines. Power output,
combustion and emission characteristics of an engine largely depend on
in-cylinder pressure-crank angle history. Fig. 2 shows the in-cylinder
pressure results for all test fuels at various engine loads. Maximum
cylinder pressure (Pmax) increased with increasing engine load due to
increased injected fuel mass with increasing engine load at constant
engine speed [34]. Biodiesel showed slightly higher in-cylinder pres-
sure compared to mineral diesel at all engine loads. This was due to
higher density of biodiesel, which led to its larger mass being injected
for same injection duration compared to baseline mineral diesel [12].
Variations in Pmax were largely affected by fraction of fuel burnt in
premixed combustion phase. Pmax variations also depend on the fuel
characteristics such as cetane number, volatility characteristics, oxygen
content, burn rate of accumulated fuel, and advanced start of injection
(SoI) and SoC timings [5]. It was also observed that with increasing
engine load, peak of the in-cylinder pressure shifted away from the top
dead centre (TDC).
Fig. 3 shows the HRR for all test fuels. HRR curves can be divided
into three main phases namely ignition delay, premixed combustion
C. Patel et al. Fuel 236 (2019) 1366–1376

Table 3
Important properties of test fuels.
Test Fuels Calorific Value (MJ/kg) Density (g/cm3) Kinematic Viscosity @ 40 °C (cSt) Cetane Number

Mineral diesel 44.73 0.832 2.45 > 52 [25]

Jatropha biodiesel (JB100) 41.5 0.857 4.66 60.74–63.27 [26]
Karanja biodiesel (KB100) 39.89 0.886 5.66 59.86–60.9 [27]
Waste cooking oil biodiesel (WCOB100) 39.35 0.878 3.32 51.34 [27]

Table 4
Fatty acid composition of Biodiesels.
Type of fatty acids Jatropha biodiesel (% w/w)[28] Karanja biodiesel (% w/w) [29] WCO biodiesel (% w/w) [30]

Myristic (C14H28O2) (C14:0) 0.1 0.09 0.24

Palmitic (C16H32O2) (C16:0) 17.7 17.17 13.12
Palmitoleic (C16H30O2) (C16:1) 0.8 0.0 0.82
Stearic (C18H36O2) (C18:0) 6.4 4.96 3.23
Oleic (C18H34O2) (C18:1) 41.8 44.51 33.4
Linoleic (C18H32O2) (C18:2) 32.9 21.25 39.2
Linolenic (C16H30O2) (C18:3) 0.2 3.5 4.33
Arachidic (C20H40O2) (C20:0) 0.1 1.61 0.39
Eicosenoic (C20H38O2) (C20:1) 0 0.0 0.47
Behenic (C22H44O2) (C22:0) 0 0.0 0.2
Euricic (C22H42O2) (C22:1) 0 2.02 0
Unknown components 0 4.89 4.6

and mixing controlled combustion. In the beginning, a negative heat Table 5

release is observed because of the vaporization of fuel accumulated Specifications of the emissions analyzer.
during the ignition delay period. HRR became positive immediately Emissions Resolution Range Measurement Principle
after the SoC. SoC takes place earlier for biodiesels compared to base-
line mineral diesel. This was due to higher cetane number of biodiesels/ NOx 1 PPM 0–5000 PPM Electrochemical Sensor
CO 0.01% (v/v) 0–10% (v/v) NDIR
blends. Ignition delays for biodiesels were shorter compared to baseline
HC 1–10 PPM 0–20000 PPM NDIR
mineral diesel. Combustion of test fuels started after the ignition delay CO2 0.1% (v/v) 0–20% (v/v) NDIR
period was over. Major part of combustion takes place in premixed
combustion phase, and the remaining heat is released in the mixing
controlled combustion phase. Peak of HRR (HRRmax) was observed to mineral diesel. It was observed that amongst three biodiesels, KB100
be in the premixed combustion phase since the fuel-air mixture burns and JB100 exhibited higher viscosities than WCOB100. Higher viscos-
very rapidly after the ignition delay period is over. HRRmax was higher ities of KB100 and JB100 resulted in relatively inferior atomization of
for WCOB100 compared to baseline mineral diesel while it was rela- these two test fuels, leading to slower burning compared to WCOB100.
tively lower for KB100 and JB100. This is mainly due to differences in This resulted in reduction in heat release in premixed combustion phase
composition and properties of biodiesels. Biodiesels have higher visc- and consequently lower HRRmax. While a number of researchers re-
osity and oxygen content but lower calorific value compared to baseline ported lower HRRmax in case of biodiesels [6,35,36], higher HRRmax

Fig. 1. Schematic of the engine experimental setup.

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C. Patel et al. Fuel 236 (2019) 1366–1376

Fig. 2. Variations in pressure vs. crank angle for the test fuels.

was reported by Dhar and Agarwal [12] for Karanja biodiesel.
Fig. 4 shows the cumulative heat release (CHR) for all test fuels.
CHR is an aggregate sum of heat release rate [12]. CHR decreases im-
mediately after the start of fuel injection because latent heat of va-
porization is absorbed by fuel droplets during their evaporation and
formation of premixed charge. CHR increased and reached a maximum
value for all test fuels after negative CHR initially. CHR of biodiesels
was higher than baseline diesel, which suggested that burning of bio-
diesels started at a later stage (mixing controlled combustion phase).
Due to higher viscosity of biodiesels, time required to mix with air was
relatively higher than that of mineral diesel due to relatively inferior
atomization in earlier stages of fuel spray in the engine cylinder. This
inferior atomization resulted in larger fuel droplets. It was also ob-
served that with increasing engine load, there was an increased

Fig. 3. Variations in HRR vs. crank angle for the test fuels.

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C. Patel et al.
Fig. 4. CHR vs. crank angle for the test fuels.
Fig. 5. MBF and combustion duration vs. load for the test fuels.
maximum CHR for test fuels because of larger fuel quantity consumed.
Fig. 5 shows the mass burn fraction (MBF) for all test fuels. MFB
10% was considered as SoC while MBF 90% was considered as end of
combustion (EoC). Combustion duration (CD) was taken as the
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Fuel 236 (2019) 1366–1376
difference between MBF 90% and MBF 10%. It was observed that SoC
for KB100 and JB100 were relatively advanced while it was slightly
retarded for WCOB100. However EoC was advanced for all biodiesels
compared to baseline mineral diesel. This was mainly attributed to
higher fuel oxygen content of biodiesels compared to baseline mineral
diesel. Higher viscosity and density of biodiesels resulted in slightly
inferior fuel-air mixing in the initial stages. This resulted in delayed
SoC, especially for WCOB100. However, it was partially compensated
by the fuel oxygen content of biodiesel after the combustion initiation
and then overall burn rate increased.
3.2. Performance and emissions investigations
Fig. 6 shows the engine performance characteristics of all test fuels
compared to baseline mineral diesel. All biodiesels showed higher BSFC
and lower brake thermal efficiencies (BTE) compared to baseline mi-
neral diesel. This was due to lower calorific values of biodiesels hence
more fuel quantities were required to produce same engine power
output as that of baseline mineral diesel. BSFC increased with in-
creasing proportion of biodiesel in the test fuel [13]. A number of re-
searchers also reported higher BSFC in case of biodiesels [12,16,37].
Emissions from IC engines are affected by engine operating para-
meters such as fuel type, air-fuel equivalence ratio, injection timing,
spray atomization characteristics, combustion chamber design, engine
load and speed etc. [38,39]. CO and unburned HC emissions are im-
portant because they represent chemical energy lost during combus-
tion, representing fuel which is not fully burnt in the combustion
chamber [5]. Other significant emissions from diesel engines are CO2,
NOX and smoke, which cause health problems and play significant role
in ozone formation. When the test engine is fuelled with biodiesel, SoI
gets advanced compared to baseline mineral diesel because of higher
density, kinematic viscosity and lower bulk modulus of compressibility
of biodiesel [5]. Advancement in SoI for biodiesels results in decreased
CO and HC emissions and lower smoke opacity. Some researchers
[40,41] retarded injection timing for biodiesels at higher engine loads
for reducing NOX emissions.
C. Patel et al. Fuel 236 (2019) 1366–1376

Fig. 7 shows CO, HC, NOX emissions and smoke opacity for all test
fuels. CO emission is largely affected by the air-fuel ratio. Other im-
portant factors affecting CO emission are inadequate fuel-air mixing,
presence of fuel-rich mixtures in the combustion chamber, lack of re-
sidence time and oxygen concentration required for oxidizing CO to
CO2 [42]. CO emission from diesel engine is a measure of incomplete
combustion since it is an intermediate combustion product generated
when incomplete combustion of hydrocarbon fuels takes place inside
the combustion chamber. CO emission was higher at low engine loads,
slightly lower at medium engine loads and higher again at high engine
loads. Inferior fuel spray atomization results in higher CO emission at
lower engine loads however combustion of test fuels improves at
medium engine loads. At higher engine loads, fuel injection quantity is
higher, which requires more time to burn however lower available time
for combustion results in higher CO emission. CO emission was higher
from biodiesels compared to baseline mineral diesel at most experi-
mental conditions. This was due to relatively higher viscosity of bio-
diesel, which led to inferior spray atomization and larger droplet size
distribution [43]. Higher droplet size distribution, inferior spray ato-
mization and lower fuel injection pressure (FIP) for single cylinder
genset engine resulted in incomplete combustion of biodiesels. Another
important factor responsible for relatively higher CO emission from
biodiesels is the presence of long chain unsaturated fatty acid molecules
in biodiesels, and relatively higher boiling range, which leads to rela-
tively inferior fuel vaporization [44]. These factors lead to higher CO
emission from biodiesels compared to baseline mineral diesel. However
some researchers also reported lower CO emission from biodiesels
[45–48].
HC emission formation takes place due to incomplete combustion
and unburnt charge left in the crevice volume. Level of hydrocarbons in
the exhaust gas is specified in term of HC concentration [16]. Wide
Fig. 6. Performance characteristics of all test fuels.
varieties of hydrocarbon species are observed in the exhaust gas.
Composition of HC emissions is significantly influenced by the fuel
composition [4]. Fuel containing higher proportion of aromatics and
olefins produces higher HC emissions. At lower BMEP, raw HC emis-
sions are relatively lower but they increase with increasing BMEP. HC
mass emissions were higher for low engine loads and they decreased
with increasing engine load. Biodiesels emitted lower HC emissions
compared to baseline mineral diesel, primarily due to incomplete
combustion of the biodiesel, owing to higher viscosity however more
complete combustion was promoted by fuel oxygen and higher cetane
number [14,15]. Biodiesels have higher concentration of long-chain
saturated and unsaturated fatty acids and very low concentration of
short-chain carbon structures, but higher fuel oxygen content, which
resulted in a relatively lower HC emissions from biodiesels [49]. Man
et al. [50] and Mosarof et al. [51] also reported relatively lower HC
emissions from biodiesels.
NOx consists of two gases mainly: nitric oxide (NO) and nitrogen
dioxide (NO2). NO is the predominant oxide of nitrogen generated in
the engine combustion chamber. Fuel oxygen, high peak combustion
temperature and residence time at peak temperature are responsible for
formation of NO in a CI engine. NO is formed when local peak tem-
perature in the combustion chamber exceeds the critical temperature
and molecules of oxygen and nitrogen combine in the cylinder. NO gets
oxidized to NO2 under suitable conditions and contributes to NOx
emissions. NOX emissions from biodiesels were lower than baseline
mineral diesel, due to lower heat release from biodiesels during pre-
mixed combustion phase, which reduced the peak combustion chamber
temperature, leading to lower NOX emissions from biodiesels.
WCOB100 exhibited relatively higher HRRmax but lower NOX emissions.
Mixed NOx emission trends were reported by various researchers. Lin
et al. [48] reported lower NOX emissions but Mosarof et al. [51] and
Sayin et al. [52] reported higher NOX emissions from biodiesels.
Fig. 7. Exhaust emissions from all test fuels. Diesel particulates consist of combustion generated carbonaceous
material (soot), with organic species absorbed onto it [31,35]. Parti-
culate formation takes place due to incomplete combustion of

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Table 6
Health risk potential of trace metals on humans.
Trace Metal Health Risks

Ca ▪ Calcium reacts with oxygen and forms Calcium Oxide.

▪ Calcium oxide causes eyes/nose/throat/skin irritation in addition to causing Bronchitis and Pneumonia. [54]
Cu ▪ Exposure to Copper traces cause feeling of cold, mild nasal and eye discomfort and irritation. [55]
Ba ▪ High level Ba exposure causes gastrointestinal, cardio-vascular, and muscular effects along with hypokalemia.[56]
Cr ▪ Higher levels of inhalation of hexavalent chromium Cr(VI) cause irritation to nose, and throat, leading to runny nose, sneezing, coughing, itching and a burning
sensation.[57]
Cd ▪ Breathing air with high levels of Cd traces can severely damage lungs, leading to death.
▪ Breathing air with lower levels of Cd over a long period results in kidney disease due to Cd buildup in kidney. [58]
Fe ▪ Prolonged exposure of Iron oxides for many years may cause benign pneumoconiosis (siderosis). [54].
K ▪ Exposure to K traces cause irritation of nose/throat/lungs and causes sneezing/coughing. [59]
Mg ▪ Mg traces exposure cause irritation of nose/throat/lungs and metal fume fever. [60]
Mn ▪ Inhalation of a large traces of Mn or its fumes causes irritation of lungs and may lead to pneumonia. [61]
Mo ▪ Inhalation of Mo traces cause irritation of nose and throat, headache, fatigue, loss of appetite, muscle and joint pain. [62]
Na ▪ Inhalation of NaOH traces in particulates can cause irritation of the membranes of the nose/throat and respiratory tract [63]
Zn ▪ Inhalation of Zn traces results in metal fume fever with symptoms such as fatigue/fever/cough etc. [64]
Ni ▪ Chronic inhalation exposure to Ni leads to respiratory issues, including asthma, decreased lung function and bronchitis. [65]
Pb ▪ Pb is carcinogenic in nature. [66]
Sr ▪ Inhalation of Sr traces causes irritation of nose/throat and lungs.
▪ Repeated exposures may cause damage of lungs/heart/liver and kidneys.
▪ It affects the nervous system. [67]

hydrocarbon fuels and lubricating oils. Smoke opacity is a measure of

particulates present in the exhaust. Higher smoke opacity was observed
from KB100 and JB100. Biodiesels have higher oxygen in the fuel
molecule compared to baseline mineral diesel. However, viscosity of
KB100 and JB100 was twice that of baseline mineral diesel, whereas
the viscosity of WCOB100 was slightly higher than the viscosity of
baseline mineral diesel. Higher viscosity, particularly at lower FIPs
resulted in inferior spray atomization due to higher Sauter Mean Dia-
meter (SMD) of the spray droplets, especially in case of KB100 and
JB100. Higher viscosity of KB100 and JB100 played a dominant role in
higher smoke opacity observed from these fuels and suppressed the
advantage of additional fuel oxygen present. WCOB100 exhibited al-
most similar smoke opacity as that of mineral diesel, primarily due to
positive role of additional fuel oxygen but only marginally higher fuel
viscosity, which resulted in almost similar spray atomization but su-
perior combustion. This effect was reflected to a greater degree under
full load conditions and WCOB100 exhibited the lowest smoke opacity.
Mixed trends of smoke opacity are reported in the open literature.
Monyem and Vangarpen [46] and Ozturk [53] reported lower smoke
opacity while Sayin et. al. [52] reported higher smoke opacity upon
using biodiesels.

3.3. Trace metal concentrations in particulate

Trace metals emitted in the particulates from diesel engines lead to

adverse environmental and health effects. Table 6 shows the health
risks on trace metal exposure to humans.
Three major sources of trace metals in particulate from an engine
are (i) wear debris generated by friction/wear of different components
such as piston, rings, cylinder liner etc. in the combustion chamber; (ii)
Organo-metallic additives in the lubricating oil, and (iii) fuel-bound Fig. 8. Trace concentrations of Ba, Ca, Cd, Cr, Cu in particulates from all test
trace metals [68,69]. Fuel-bound trace metals include Ca, K, Na and fuels.
Mg, whereas lubricating oil origin trace metals include Zn, Cu and Al
[70]. Concentration of trace metals in the fuel depends on various
composition and is therefore affected by the engine load in this constant
factors such as crude oil type used, catalysts used in petroleum refining
speed test engine. Fuel-borne trace metals and particulate emissions
process, and the synthesis process followed. ICP-OES was used to de-
increased with increasing engine load due to injection of higher fuel
termine trace metal concentrations in particulates emitted by the en-
quantity. Trace metal content may not increase in the same proportion
gine. Some of these metals were below the detection limit of the in-
as that of increase in particulate emissions at 100% load, which might
strument. Detected trace metals with reasonable degree of confidence
be the reasons for overall reduction in trace metal concentration per
included Ba, Ca, Cd, Cr, Cu, Fe, K, Mg, Mn, Mo, Na, Ni, Pb, Sr, Zn and
unit mass of particulates [18].
Al. Engine operating conditions play important role in determining the
Fig. 8 shows trace concentrations of Ba, Ca, Cd, Cr and Cu in exhaust
concentration of the trace metals in particulates. Contribution of trace
particulates. Source of Ca in particulates are lubricating oil additives,
metals is determined by the wear debris as well as lubricating oil

1373
C. Patel et al.
Fig. 9. Trace concentrations of Fe, K, Mg, Mn, and Mo in particulates from all
test fuels.
water and grease. Ca trace concentration was 7.73–33.54 mg/g of
particulates at 50% engine load. WCOB100 exhibited 10.5% higher but
JB100 and KB100 exhibited 42.7 and 74.5% lower Ca trace con-
centrations compared to baseline mineral diesel at 50% engine load. Cu
trace concentration range was 3.31–11.44 mg/g of particulates at lower
engine loads. Cu trace concentrations for JB100, KB100, WCOB100
were 66, 70.9, 43.5% lower respectively compared to baseline mineral
diesel at 50% engine load. Sources of Cu traces in particulates included
bearings and bronze bushings. Presence of Cu in fuel and lubricating oil
additives also contribute to its higher concentration in particulates.
Fuel droplets strike cylinder walls, leading to fuel dilution of lubricating
oil, in addition to partial combustion of lubricating oil. Traces of Ba, Cd
and Cr were comparatively lower in particulates from biodiesels at 50%
load. Ba exhibited trace concentration in the range of 0.06–0.23 mg/g
of particulates, which primarily originated from lubricating oil ad-
ditives, water and grease. Trace concentration of Ba were 69.5% and
44.8% lower for JB100 and KB100 respectively while 12.9% higher for
WCOB100 compared to baseline mineral diesel at lower load condition.
Cr traces were in the range of 0.2–0.5 mg/g of particulates at similar
load conditions. JB100, KB100 and WCOB100 exhibited 49.6, 59.2 and
13.9% lower Cr trace concentration compared to baseline mineral
diesel, primarily due to lower wear rate of Cr coated piston rings be-
cause of relatively superior lubrication properties of biodiesels [71].
Sources of Cr traces in particulates include wear of compression rings,
crankshaft, gears, bearings and cylinder liner plating [71]. Negligible
Cd trace concentration was observed in the particulates.
Fig. 9 shows trace concentrations of Fe, K, Mg, Mn and Mo in par-
ticulates. Higher trace concentrations of Fe, K and Mg in test fuels lead
to their higher trace concentrations in particulates. Higher Fe traces
were detected in biodiesel particulates compared to baseline mineral
diesel, which primarily originated from wear of cylinder liner, piston,
rings, valves, valve guide, gears and shafts [71]. Highest Fe trace con-
centration was observed in KB100 particulates (14.21 mg/g of
1374
Fuel 236 (2019) 1366–1376
Fig. 10. Trace concentrations of Na, Ni, Pb, Sr, Zn in particulates from all test
fuels.
particulates), followed by JB100 and WCOB100 (8 mg/g of particu-
lates) at 50% engine load. The lowest Fe trace concentration was in
diesel (∼4.43 mg/g of particulates) at 50% engine load. Trace con-
centrations decreased at 100% engine load. K traces in particulates
originated from coolant and lubricating oil additives [71]. Highest trace
concentration of K was observed for WCOB100 (15.2 mg/g of particu-
lates), followed by mineral diesel (11.83 mg/g of particulates). Trace
concentrations of K were relatively lower for KB100 and JB100 (∼8.53
and 3.71 mg/g of particulates respectively) compared to baseline diesel.
Source of Mg in particulates included wear of bearings, additive
depletion, supercharger and gearbox housing [71]. Mg showed higher
trace concentration in WCOB100 (∼4.41 mg/g of particulates), fol-
lowed by diesel (∼3.22 mg/g of particulates), JB100 and KB100 (2.08
and 1.5 mg/g of particulates respectively).
Mn traces in particulates originated from steel-shafts and valves.
Significantly lower traces of Mn were observed in particulates from all
test fuels. Trace concentration of Mn in mineral diesel origin particu-
lates was 0.22 mg/g, while JB100, KB100 and WCOB100 exhibited
44.2, 12.4 and 2.1% lower Mn trace concentrations respectively com-
pared to baseline mineral diesel. Mo traces in particulates originated
from lubricating oil additives and wear of piston rings [71]. Trace
concentration of Mo were observed to be very low in particulates from
all test fuels. Traces of lubricating oil might enter the combustion
chamber at higher engine loads during combustion of WCO biodiesel.
This would have resulted in increased Mo trace concentration in case of
WCO biodiesel.
Fig. 10 shows trace concentrations of Na, Ni, Pb, Sr and Zn in par-
ticulates from all test fuels. Na and Zn traces showed significant pre-
sence in the engine exhaust particulates.
Trace concentrations of Na were observed to be the highest amongst
all trace metals in particulates. Na in particulates originated from lu-
bricating oil additives and coolant. Mineral diesel and WCOB100
C. Patel et al.
showed significantly higher concentrations of 74.1 and 76.62 mg/g of
particulates respectively while JB100 and KB100 exhibited relatively
lower trace concentrations (38.72 and 26.24 mg/g of particulates re-
spectively) compared to baseline mineral diesel.
Zn in particulates originated from bearings, lubricating oil ad-
ditives, plating, brass components and neoprene seals. Highest trace
concentration of Zn were observed in baseline mineral diesel (9.37 mg/
g of particulates), while they were in the range of ∼3–6 mg/g of par-
ticulates for all biodiesels at 50% engine load and ∼3.11–5.44 mg/g of
particulates at 100% engine load.
Ni, Pb and Sr traces were in relatively lower trace concentrations
compared to others trace metals in particulates. Trace concentration of
Ni was 0.71 mg/g of particulates for baseline mineral diesel, while for
WCOB100, KB100 and JB100, it was 5.82, 3.5 and 3.17 mg/g of par-
ticulates respectively. Ni traces originated from the lubricating oil,
where it is usually added as Nickel ethoxyethylxanthate in very small
concentration, in order to improve the lubrication quality. Pb traces in
particulates originated from bearings, grease and paint. Trace con-
centration of Pb was observed to be ∼0.57 mg/g of particulates from
baseline mineral diesel and WCOB100 at 50% engine load, while it was
∼0.24 mg/g of particulates from KB100 and JB100.
Trace metal concentrations in particulates reduced at 100% engine
load, compared to lighter engine loads. The concentration of most trace
metals in particulates was found to be lower from test engine fuelled
with biodiesels.
4. Conclusions
Experimental investigations were carried out to assess the perfor-
mance, combustion, emissions, and trace metal concentrations in par-
ticulates from different biodiesels comapred to baseline mineral diesel.
Differences in fuel properties of biodiesels due to different feedstocks
has significant effect on its combustion and emission characteristics.
Biodiesels exhibited slightly higher in-cylinder pressure compared to
baseline mineral diesel. HRRmax was relatively higher for WCOB100,
while it was relatively lower for KB100 and JB100 compared to base-
line mineral diesel due to relatively lower viscosity of WCOB100 than
KB100 and JB100. Inherent fuel oxygen content of biodiesels ac-
celerated the combustion during mixing-controlled combustion phase,
which resulted in overall lower combustion duration for biodiesels
compared to baseline mineral diesel. HC and NOX emissions were re-
latively lower while CO was relatively higher from biodiesels compared
to baseline mineral diesel. BSFC was higher, while BTE was lower for
biodiesels compared to baseline mineral diesel. Higher viscosities of
KB100 and JB100 resulted in higher smoke opacity compared to
baseline mineral diesel, while WCOB100 showed equivalent smoke
opacity except at higher engine loads. Significant trace concentrations
of metals were observed in the exhaust particulates. Ca, Cu, Fe, K, Mg,
Na, Zn, and Al showed higher presence of particulates at 50% engine
load, while Ba, Cd, Cr, Mn and Mo showed relatively lower trace con-
centrations. All trace metal concentrations in particulates reduced at
100% engine load, compared to lighter engine loads. The concentra-
tions of most trace metals in particulates were found to be lower from
engine fuelled with biodiesels, suggesting that emission from biodiesel
fuelled engines are more environmentally benign from trace metal
emission point of view comapred to baseline mineral diesel, however
they need to evaluated for the toxicity of adsorbed hydrocarbons point
of view.
Acknowledgements
Financial support from Department of Science and Technology,
Government of India (INT/KOREA/P-23 dated 06-07-2015) to the
Indian side and from National Research Foundation of Korea
(2014K1A3A1A19067560) to the Korean side under Indo-Korea Joint
International Cooperation Project is gratefully acknowledged. These
1375
Fuel 236 (2019) 1366–1376
funding enabled exchange visits of researchers for conducting experi-
ments and for consumables required in the experiments in this study.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.fuel.2018.08.137.
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