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Ecotoxicology and Environmental Safety 121 (2015) 1621

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Production characterization and working characteristics in DICI engine

of Pongamia biodiesel
M. Srinivasa Rao n, R.B. Anand
Department of Mechanical Engineering, National Institute of Technology, Tiruchirappalli 620015, India

art ic l e i nf o

a b s t r a c t

Article history:
Received 10 December 2014
Received in revised form
13 July 2015
Accepted 27 July 2015
Available online 1 August 2015

Renewable energy plays a predominant role in solving the current energy requirement problems and
biodiesel is a promising alternative fuel to tide over the energy crisis and conserve fossil fuels. The
present work investigates an eco-friendly substitute for the replacement of fossil fuels and the experiments are designed to determine the effects of a catalyst in the biodiesel production processes. Pongamia
pinnata oil was utilized to produce the biodiesel by using catalysts namely KOH and NaOH and the
properties of the fuel were found by using Carbon Hydrogen Nitrogen Sulfur (CHNS) elemental analysis,
Fourier Transform Infrared (FTIR) Spectroscopy, Gas Chromatography & Mass Spectrometry (GCMS), and
Proton Nuclear Magnetic Resonance (1H NMR) Spectroscopy and the thermophysical properties were
compared with those of neat diesel. In continuation, the working characteristics of the biodiesel and
biodieselwater emulsions were accomplished in a four stroke compression ignition engine and the
results were compared to those of neat diesel. It was found that the exhaust emission characteristics like
brake specic carbon monoxide (BSCO), brake specic hydrocarbons (BSHC) and smoke opacity were
better for neat biodiesel (except brake specic nitric oxide BSNO) than those of neat diesel.
& 2015 Elsevier Inc. All rights reserved.

Diesel engine
Emission characteristics

1. Introduction
In the present global scenario, a rise in energy utilization and
ecological deprivation due to the rapid growth in technology, industrialization, population, automobiles and power plants affect
the health of living beings, deplete the ozone layer and lead to
global warming. The available energy resources are very limited
and are diminishing at a faster rate. In this perspective, various
non-edible vegetable oils are considered as the potential candidates to serve as a substitute fuel in diesel engines. However, the
vegetable oils and their methyl esters (biodiesel) have their own
limitations when they are used in diesel engines. Recovering the
energy resources from the environmental waste products and
throw away oils from the industry are an economically viable solution. In addition, the disposal of waste organic and inorganic
materials causes pollution of ground and surface water, obnoxious
odor and health hazards. For better environmental safety and the
implementation of strict regulations on emission norms over the
internal combustion engines, the biodiesel is a potential solution
for the replacement of fossil fuels in spite of its poor performance
characteristics in engines. Biodiesel is a chemical combination of
fatty acid methyl esters, non-toxic, biodegradable, sulfur free,

Corresponding author.
E-mail address: (M. Srinivasa Rao).
0147-6513/& 2015 Elsevier Inc. All rights reserved.

environmentally friendly, and renewable energy source with a

potential to reduce the level of pollutants in the exhaust emissions
of internal combustion engines as it is made from (non-edible)
vegetable oils and animal fats.
Ma and Hanna (1999) who carried out a broad review on
published literatures mentioned that the biodiesel is an alternate
for diesel and can be produced through processes like thermal
cracking (pyrolysis) and transesterication. Further, they mentioned that biodiesel has the advantage of reduced level of pollutants in the engine exhaust due to its oxygen content. Bartholomew (1981) conducted extensive experimental investigations
with the objective of using sunower oil in compression ignition
engine having a pre-combustion chamber. Based on the results he
suggested that the fuel blends which have less than 20% of sunower oil do not require any signicant hardware modications in
compression ignition engines and it is impractical to substitute
diesel of 100% by neat vegetable oil because of its high viscosity.
Atabani et al. (2012) surveyed relevant literatures on different
areas including biodiesel feedstock, production techniques, properties, troubles and possible solutions for using biodiesel, economic feasibility and the future of biodiesel. Consequently they
conrmed that biodiesels (Jatropha, Callophylum inaphyllum, and
Madhuca) have almost similar properties of diesel and meet the
standard specications of the ASTM and EN test methods. Beatrice
et al. (2010) conducted experiments on EURO 5 four-cylinder inline modern diesel engine by utilizing rapeseed methyl-ester,

M. Srinivasa Rao, R.B. Anand / Ecotoxicology and Environmental Safety 121 (2015) 1621

brake specic hydrocarbons (g/kWh)
brake specic nitric oxide (g/kWh)
Fourier Transform Infrared Spectroscopy
GCMS Gas Chromatography & Mass Spectrometry
H NMR Proton Nuclear Magnetic Resonance Spectroscopy
Pongamia biodiesel
PBD2S5W 93% biodiesel 2% surfactant 5% water
PBD2S10W 88% biodiesel 2% surfactant 10% water


American Society for Testing and Materials

brake specic fuel consumption, (kg/kWh)
brake thermal efciency, (%)
brake mean effective pressure, (MPa)
before top dead center
crank angle
brake specic carbon monoxide (g/kWh)

soybean methyl-ester and FischerTropsh (GTL gas-to-liquid) and

the results were compared with those of EU certied diesel fuel. It
is concluded that for modern diesel engines, EGR is a promising
technique for the reduction of NOx emission among the tested
fuels. Sahoo and Das (2009) conducted optimization experiments
on the production of biodiesel from Jatropha, Karanja and Polanga
oils and reported that the maximum Jatropha, Karanja and Polanga
biodiesel yield obtained was 93%, 91% and 85%, respectively at the
optimum conditions. From the experiments they stated that the
optimum alcohol to oil ratio was 11:1, 11.5:1 and 12:1 and the base

catalyst of KOH as 1.1%, 1% and 0.9% for Jatropha, Karanja and

Polanga oil, respectively.
Sinha et al. (2008) produced rice bran oil methyl ester by using
methanol and NaOH catalysts and they achieved the biodiesel
yield of 93% at the conditions of alcohol/oil molar ratio of 9:1,
0.75% of catalyst (by weight), and 1 h reaction time at a temperature of 55 C. In addition, they reported that rice bran oil
methyl ester had comparable properties to those of neat diesel and
recommended it as a substitute to the neat diesel. Zagonel et al.
(2004) employed Soybean oil to produce biodiesel by using

Raw oil

Determination of Free
Fatty Acids (FFA)




Titration Method using 0.1 N KOH


Pre Treatment or
Acid Esterification

Base/Alkaline Catalyst
Acid Catalyst
Reactor Unit

Phase Separation

Methanol + KOH /

Reactor Unit

Methanol +

Phase Separation


Biodiesel with Impurities

Mono Ester
Low Temp. Maintains

Extra Glycerin

Distillation Process

Extra Methanol

Purification with Hot

Water washing

Heating at 120 oC




Determination of FFA



Removal of Moisture

Pure Pongamia Biodiesel

Fig. 1. Flow chart of production process of the Pongamia biodiesel.


M. Srinivasa Rao, R.B. Anand / Ecotoxicology and Environmental Safety 121 (2015) 1621

ethanol to form ethyl ester in the presence of KOH catalyst. Subsequently the Soybean ethyl ester was subjected under FTIR analysis and they have found the ester peak at around 1730 cm  1 and
at 9001500 cm  1, which conrmed the ester functional groups
availability. Aliske et al. (2007) carried out FTIR analysis on soybean oil methyl ester and compared it with neat diesel and reported that the ester peak for soybean biodiesel was found at an
absorbance peak of 17001800 cm  1.
India is a tropical country and has a suitable climate for the
development of Pongamia tree. Pongamia trees are found in forests, waste lands and road sides and India has potential for the
growth of these trees. The growth of Pongamia trees in waste
lands also eliminates soil erosion and leads to increase of rain fall.
The seeds obtained from Pongamia tree are crushed in an expeller
to obtain the oil. In these conditions, non-edible oil such as Pongamia raw oil is considered as a major renewable fuel for sustainable economic development. The present investigation is carried out to describe complete production process, thermophysical
properties and working characteristics of Pongamia biodiesel in a
four stroke compression ignition engine.

2. Materials and methods

2.1. Biodiesel production
Based on the rigorous literature survey, the present investigation was attempted to establish the practicability of production of
Pongamia biodiesel from Pongamia raw oil by using base catalysts
such as Potassium Hydroxide (KOH) and Sodium Hydroxide
(NaOH). The process involved in the production of Pongamia
biodiesel from Pongamia raw oil is shown in Fig. 1. The commercially available Pongamia raw oil was heated to a temperature of
120 C for half an hour to remove the excess water content in the
raw oil. For identifying the suitable biodiesel production process,
the Free Fatty Acid (FFA) value is an essential parameter and in this
case it was found to be 8.2%. Since the FFA value was greater than
1%, both acid esterication and base transesterication processes
were required for the production of biodiesel, as otherwise base
transesterication alone is enough.
2.1.1. Acid esterication
Acid esterication or pretreatment is a process through which
the FFA value of raw vegetable oil is reduced to less than 1% by
using suitable acid catalyst(s) such as H2SO4, H3PO4 and HCl. In the
present investigation, the high FFA value of the Pongamia raw oil
was reduced in the presence of sulfuric acid (H2SO4). The schematic layout of the biodiesel production setup is shown in Fig. 2
and the setup consists of a reactor unit, which comprises a 2 l

borocil ask, reux condenser (Reux condenser is connected to

the reactor unit to prevent the loss of alcohol through evaporation.), motorized mechanical stirrer, electric heater and a temperature control unit and a separator funnel setup that consists of
a separation funnel and a drain stop. The molar ratio of methanol/
oil, amount of the catalyst, reaction temperature, and the reaction
time are the key parameters in the biodiesel production process.
Based on the predened molar ratio of methanol/oil (6:1), a specied quantity of raw oil was taken in the reactor ask and heated
to a temperature of 60 C. When the oil reached the specied
temperature (60 C), a dened quantity of methanol and sulfuric
acid (1 vol%) were added to it and the mixture was continuously
stirred by the mechanical stirrer that was set at a speed of
600 rpm for a period of 1 h (reaction time). Then the mixture was
transferred to the separation funnel setup and allowed to settle
over a night. Due to the difference in density, the water was settled
down at the lowest region, the oil having low FFA value was settled in the middle region and the mixture of alcohol (methanol) of
H2SO4 was stayed at the top. Initially, the settled water was removed from the ask through the drain tap. Subsequently, the oil
having a low FFA value was collected for the base transesterication process and the top layer was discarded as waste. The FFA
value of the oil was determined to verify the pretreatment process
and the acid value was measured as 1.59 mg KOH/g and the corresponding FFA value is 0.79%. After the completion of the acid
esterication process, the reactor ask was cleaned for the base
transesterication process.
2.1.2. Base transesterication
For the base transesterication process, the treated oil was
transferred to the reactor ask where it was heated to a temperature of 60 C and the temperature was maintained with the
help of the temperature control unit. A specied quantity of the
mixture of the base catalyst (KOH, 1% by weight) and methanol
were mixed with the oil (molar ratio as 6:1) and the mixture was
continuously stirred for 2 h.
The nal product was again poured into the separating funnel
where the content was allowed to settle down over a night. Due to
the difference in density of the liquids, two layers were formed;
the lower layer that contains glycerol and heavy impurities was
discarded through the drain tap and the upper layer that contains
methyl ester with alcohol was collected separately. The collected
mixture (methyl ester alcohol) was puried through the distillation process, by washing it with hot water to remove the remaining impurities and nally the moisture content was eliminated by heating. Subsequently to the study, the catalyst effect in
terms of biodiesel yield, the biodiesel was produced by using
NaOH catalyst in the similar base transesterication process. Based
on the biodiesel outcome, it was observed that the biodiesel yield
in the case of KOH is more than that of NaOH because of higher
solubility of KOH in methanol and easier separation of glycerol
when using KOH as a catalyst and larger amount of soap formation
in the case of NaOH. In addition, the fuel characterization tests like
Fourier Transform Infrared Spectroscopy (FTIR), Gas Chromatography & Mass Spectrometry (GCMS), and Proton Nuclear Magnetic Resonance (1H NMR) Spectroscopy on biodiesels were produced by using KOH and NaOH and the properties were found to
be identical for both the biodiesels.
2.2. Characterization of Pongamia biodiesel

Fig. 2. Schematic layout of biodiesel production setup.

The properties of Pongamia biodiesel, Pongamia raw oil and

neat diesel were determined by using ASTM test procedures and
the values are given in Table 1. The ash point of Pongamia biodiesel is higher than that of neat diesel and the high ash point
makes the biodiesel safer than neat diesel in terms of handling and

M. Srinivasa Rao, R.B. Anand / Ecotoxicology and Environmental Safety 121 (2015) 1621


storage. The properties of different samples of Pongamia biodiesel

that was obtained by using alkaline catalysts (KOH, NaOH) have
been compared with those of neat diesel and found almost similar
2.3. CHNS analysis
The elemental analysis of the fuel samples was carried out in a
Carbon Hydrogen Nitrogen Sulfur (CHNS) elemental analyzer
(Model: Elementar Vario EL III-Germany) to know the elemental
composition. The fuel samples were burned in the presence of
excess oxygen. The products of combustion in a CHNS analysis
(CO2, H2O, N2 and SO2) were analyzed through the system by
Helium (He) carrier gas. The combustion products were measured
quantitatively by means of a non-dispersive IR absorption detection spectrum and the level of N2 was determined via a thermal
conductivity detector. By using the level of C, H, N and S, the
oxygen content was evaluated. The elemental composition of
biodiesel and neat diesel are shown in Table 2.
2.4. Fourier transform infrared spectroscopy (FTIR) results
Fourier Transform Infrared Spectroscopy (FTIR) was carried out
to analyze the probable functional groups and the bands corresponding to various stretching and bending vibrations in the fuel
samples by using a Perkin Elmer Spectrum Analyzer that was
equipped with the detector and set in the range of 4000
400 cm  1. Fig. 3 shows the FTIR spectrum of neat diesel and
Pongamia biodiesel. In the gure, the wave number (cm  1) is
shown on the X-axis, the absorbance (%) is shown on the Y-axis
and the resolution is 4 cm  1 and 4 scans. There are two regions to
analyze the biodiesel and neat diesel, such as region I with wave
number (10001300) and region II with wave number (1700
1800). The regions I and II do not exist in neat diesel spectra as
compared to Pongamia biodiesel spectra. There are other regions
where wave numbers (28003000) are present in both Pongamia

% Transmittance






Pongamia biodiesel












Fig. 3. FTIR spectrum of neat diesel and Pongamia biodiesel.











Wave number cm -1

biodiesel and neat diesel due to the absorption of infrared by the

CH olenic bonds. The FTIR spectrum of neat diesel represents
the presence of hydrocarbons; mainly CH3 and CH2 long chain
hydrocarbons. Pongamia biodiesel contains long chain hydrocarbons and the strong and sharp absorbance peak at 1741 cm  1;
represents the C O stretching known as esters. Further, the ester
peak at 1168 cm  1 representing the CO stretch is also found.
Based on the observations, neat diesel has hydrocarbons whereas
Pongamia biodiesel has ester compounds.
2.5. Gas Chromatography and Mass Spectrometry results
Gas Chromatography (GC) and Mass Spectrometry (MS) were
used to analyze the chemical constituents of fuels by using a gas
chromatograph and a mass spectrometer (Model: PerkinElmer
Clarus 500). Fig. 4 shows the chromatogram of Pongamia biodiesel
in which the retention time in minutes is shown in the X-axis and
the intensity in % is shown in the Y-axis. From the results, it can be
observed that the main constituents of Pongamia biodiesel are
methyl esters and the details are shown in Table 3.

H NMR spectroscopy results

Proton Nuclear Magnetic Resonance (1H NMR) Spectroscopy is

a powerful technique that is being used in the determination of
the chemical structure of organic compounds. The quality of the
biodiesel was analyzed by using the 1H NMR with chloroform as a
solvent (Make of 1H NMR Spectroscopy analyzer: BRUKER, Switzerland, model: Avance 400 MHz). The strong singlet at 3.6 ppm
(refer Fig. 5(a)) shows the presence of methyl ester (CH3OCOR)
group in Pongamia biodiesel. It is observed from the Fig. 5(a), a
triplet near the value of 0.8 ppm can be seen and it is related to
terminal methyl protons of hydrocarbons, a duplet at 1.2 ppm indicates the methylenes protons of carbon chain, a long singlet at
1.6 ppm indicates the -carbonyl methylene protons, a triplet at
near 2.3 ppm indicates -carbonyl methylenes, and the peaks related to unsaturation at 2.0, 2.8 and 5.3 ppm assigned to allylic,
bis-allylic and olenic hydrogens, respectively. 1H NMR spectrum
of neat diesel (Fig. 5(b)) shows clusters of peak at 0.92.8 and 6.8
8.0 ppm and they signify aliphatic hydrogens and aromatic hydrogens, respectively.

3. Results and discussion

Neat diesel


% Transmittance


Fig. 4. Chromatogram of Pongamia biodiesel.

The molar ratio of methanol/oil, catalyst amount, reaction

temperature, and reaction time are the key parameters in biodiesel
production. Potassium Hydroxide (KOH) and Sodium hydroxide
(NaOH) are selected as the base catalysts in the transesterication
process. A Pongamia biodiesel yield of 84% and 68% is obtained
with KOH and NaOH catalyst respectively, in the identical production process conditions like reaction temperature 60 C, reaction time 2 h, catalyst 1% by weight and methanol to oil molar


M. Srinivasa Rao, R.B. Anand / Ecotoxicology and Environmental Safety 121 (2015) 1621

Fig. 5. 1H NMR spectrum of Pongamia biodiesel.

In continuation of the production of biodiesel, the biodiesel

was subjected to characterization, chemical and thermophysical
analysis, the neat biodiesel and biodiesel water emulsions were
examined in terms of their working characteristics in a compression ignition engine. A test rig that consisted of a single cylinder,
four stroke, naturally aspirated, air-cooled, Direct Injection Compression Ignition (DICI) engine, AC alternator for loading, dataacquisition system, comprising a Kistler piezoelectric pressure
transducer (Model: 6613CA) and a crank-angle encoder, AVL 444
digital Di Gas analyzer, and AVL 437 smoke opacity meter were
employed. The technical specications of the engine, data-acquisition system and pressure transducer are mentioned in Table 4. A
Kistler piezoelectric pressure transducer was mounted on the cylinder head to measure the instantaneous in-cylinder gas pressure
and a crank angle indicator xed on the output shaft of the engine
measured the corresponding crank angle. The data acquisition
system was used to collect, store and analyze the pressure sensor
data during the engine testing. The level of CO, unburned hydrocarbons, CO2, O2 and NO were measured by the digital di-gas
analyzer and the smoke opacity was measured by the smoke
meter. The exhaust gas temperature was measured by a k-type
chromealumel thermocouple. The percentage uncertainty of
various instruments and the measured/calculated quantities are
listed in Table 5. All test runs were carried out by starting and
warming up the engine with neat diesel and then switching over
to the test fuel; Neat biodiesel/water emulsion biodiesel. At the
end of the test, the engine was set to run with the neat diesel to
wash out the traces of the test fuel in the fuel line and the injection
system. The experiments were conducted at a constant speed of
1500 rpm by varying the brake load; and each test was repeated a
minimum of three times to conrm the repeatability.
The waterPongamia biodiesel emulsion fuel PBD2S5W was
prepared by a mechanical homogenizer in the proportion of 93% of
biodiesel, 2% of surfactants (mixture of Span 80 and Tween 80) and
5% of water (by volume). Similarly, PBD2S10W fuel (88% of
biodiesel 2% of surfactants 10% of water) was also prepared.
Prior to the experimentation, water emulsion Pongamia biodiesel
fuels were subjected to the settling and sedimentation tests and it
was found that all the fuel samples were stable for more than ve

Neat Diesel









0.08 0.15 0.23


0.38 0.45 0.53

bmep (MPa)
Fig. 6. Variation in BSFC and BTE with respect to bmep.

BTE (%)

3.1. Working characteristics of C.I. engine

days. In addition, the most of the fuel properties of Pongamia

biodiesel were comparable with the neat diesel and hence no
hardware modications were carried out for using these fuels
(biodiesel and their water emulsions) in the existing engine setup.
The performance of the engine with Pongamia biodiesel, water
emulsion biodiesels and neat diesel are described in terms of
brake specic fuel consumption and brake thermal efciency at
different brake mean effective pressures of the engine and the
variation of these parameters is shown in Fig. 6. It can be observed
that the BSFC decreases with increase in bmep for all the test fuels.
The BSFC is high for neat biodiesel when compared to that of neat
diesel due to the lower energy content of biodiesel. It can also be
observed that water emulsion biodiesels have higher BSFC than
that of neat diesel and neat biodiesel because of prolonged ignition delay due to the decrement in the cetane number (on the
account of water addition). Further, it can be observed from the
gure that BTE increases with the increase in bmep for all the test
fuels and the BTE is the maximum for neat diesel among the other
test fuels. The decrease in BTE for biodiesel could possibly be due
to the combined effect of their lower caloric value and higher
viscosity. The BTE of water emulsied biodiesel fuels is slightly
higher than neat biodiesel as an effect of micro explosion phenomenon and enhancement in combustion efciency. Similar results were obtained by Sadhik Basha and Anand (2011).
The engine exhaust emission characteristics with Pongamia
biodiesel, water emulsion biodiesels and neat diesel are presented

BSFC (kg/kWh)

ratio as 6:1.

M. Srinivasa Rao, R.B. Anand / Ecotoxicology and Environmental Safety 121 (2015) 1621

Neat Diesel




BSNO (g/kWh)


Smoke opacity (%)

lower BSNO while PBD2S5W (with 5% of water) high BSNO than

neat diesel because of the presence of percentage of the water to
decrease the peak combustion temperature.

4. Conclusions

The present experimental investigations were conducted on

the production and characterization of the Pongamia biodiesel.
Subsequently, the performance and emission characteristics of a
diesel engine using Pongamia biodiesel, water emulsion biodiesels
and neat diesel were investigated. Based on the results, the following specic conclusions are drawn:



 Pongamia raw oil can be used as an alternative feedstock for


 Pongamia biodiesel yield of 84% and 68% were obtained with

biodiesel production.

BSHC (g/kWh)




BSCO (g/kWh)



KOH and NaOH catalyst respectively in identical production

process conditions like reaction temperature 60 C, reaction
time 2 h, catalyst 1% by weight and methanol to oil molar ratio
as 6:1.
Gas Chromatography and Mass Spectrometry (GCMS) studies
were performed to analyze the chemical constituents of fuels.
FTIR analysis shows that neat diesel has hydrocarbons whereas
Pongamia biodiesel has ester compounds.
The biodiesel and two water emulsions of biodiesel can be used
directly as fuel in compression ignition engine without any
hardware modications as their fuel properties are comparable
with those of neat diesel.
The level of NO emission was lower for water emulsied biodiesel (PBD2S10W) compared to biodiesel and neat diesel.


Appendix A. Supplementary Information








Supplementary data associated with this article can be found in

the online version at

bmep (MPa)
Fig. 7. Variation in BSCO, BSHC, Smoke opacity and BSNO with respect to bmep.

in terms of brake specic carbon monoxide (BSCO), brake specic

hydrocarbons (BSHC), smoke opacity and brake specic nitric
oxide (BSNO) at different brake mean effective pressure (bmep) of
the engine in Fig. 7. It can be concluded from the gure that the
variation of pollutants level (BSCO, unburned BSHC) in exhaust
gases is low for biodiesel when compared to that of neat diesel due
to more oxygen molecules presence in the biodiesel. The variation
in the pollutants level (BSCO, BSHC) decreases with the increase in
the engine bmep for all the test fuels. In addition, from the gure
that the water emulsied biodiesel exhibits high BSCO and BSHC
emissions compared to neat biodiesel due to the adverse effect of
water addition that leads to incomplete combustion.
Further the smoke opacity for Pongamia biodiesel is comparatively less than that of neat diesel because biodiesel has more
oxygen content and it is effected as improved combustion phase. It
is further noticed from the gure that the reduction of smoke
emissions for the biodiesel emulsion fuel compared to biodiesel is
due to the presence of water vapor in the combustion chamber
(micro explosion effect), further it leads to dilution in the concentration of black smoke (Saravanan et al., 2013; Sadhik Basha
and Anand, 2011; Kannan and Anand, 2011; Armas et al., 2005;
Crookes et al., 1992). BSNO emission is high for biodiesel compared
to the neat diesel due to its high oxygen content and peak combustion temperature. Fig. 7 illustrates that the two emulsions
show different behavior; PBD2S10W (with 10% of water) produces

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