Fuel 225 (2018) 343–348

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Fuel
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Full Length Article

A comparative study on performance, combustion and emission T

characteristics of diesel engine fuelled by biodiesel blends with and without
an additive
⁎
M. Mohamed Musthafa , T. Ashok Kumar, T. Mohanraj, R. Chandramouli
School of Mechanical Engineering, SASTRA Deemed University, Thanjavur 613401, India

A R T I C LE I N FO A B S T R A C T

Keywords: Biodiesel is a fuel containing mono-alkyl esters which are derived from vegetable oils or animal fats. Biodiesel
Diesel fuels are well-adopted now a day’s having multiple benefits such as a renewable energy source, less pollutant
Palm oil methyl ester emissions of carbon monoxide, hydrocarbons and particulate matter and so on. The oxides of nitrogen (NOx)
Di-tert-butyl peroxide emissions reported in the literature are ambiguous for biodiesel blended fuels with reference to baseline diesel
Cetane number
NOx. Authors have come out with different conclusions of no change in NOx, a decrease NOx and an increase in
Performance
NOx. This study aims to reduce NOx emission of palm oil methyl ester blended with diesel fuel (B20), by using
Emissions
Chemical kinetics Cetane number improver-di-tert-butyl peroxide (DTBP) and to improve ignition performance of the test fuel.
Single cylinder, four stroke, water cooled diesel engine loaded by eddy current dynamometer was used for this
study. The engine was run with diesel, B20 fuel and B20 with 1% DTBP additive by volume basis. The per-
formance, combustion and emission results were compared. The results revealed that B20 with additives shows
an increased thermal efficiency by 2–3.5% and decrease specific energy consumption by 10–15% compared to
diesel and B20 fuel. Significant reduction of CO and NOx in trade off with slight increase in HC for the B20 fuel
without additives was observed.

1. Introduction
Diesel engines are used in wider application like transport vehicles,
marine engines, power generation and agriculture purpose because of
their lower fuel consumption, higher thermal efficiency and reduced
tail pipe emissions, compared to gasoline engine. The rapid exhaust of
crude oil reserves and increasing petroleum prices resulted in increases
the research interest in alternate fuels. In the recent years an im-
portance is given to the use of plant oils and its esters. The biodiesel is
focused more because of its environmental aspects and its potential as
an alternative fuel for diesel engines without any significant mod-
ification in existing engine [1]. Many researchers have suggested the
biodiesel as a replacement, either completely or partially blended, be-
cause they reduce the exhaust emissions. Biodiesel by weight contains
less carbon, sulphur, water and more oxygen than the petroleum diesel
[2]. Various studies have shown that with the decrease of carbon
monoxide (CO), carbon dioxide (CO2), particulate matter, sulphur
compounds (SOx), volatile organic compound and unburned hydro-
carbons except the NOx emissions [3]. NOx is formed by the oxidation
of nitrogen in the atmosphere at elevated temperature (above 1700 K),
and prompt NOx by the formation of free radicals in the flame front of
hydrocarbon flames. It is believed that the NOx formation is mainly due
to thermal (Zeldovich mechanism) and prompt or Fennimore me-
chanism. However, in biodiesel, a significant amount of NOx is formed
due the prompt or Fennimore mechanism (< 1000 K) [4] The National
Renewable Energy Laboratory (NREL) reported that di-tert-butyl per-
oxide (DTBP) and ethyl-hexyl nitrate (EHN), are Cetane improver for
reducing NOx up to 4% in B20 blends [5]. Residual methanol in bio-
diesel is responsible for a decrease in the Cetane number. The Cetane
number of biodiesel is always more than 47, which is higher than the
petroleum diesel [6]. Researchers report that Cetane index of biodiesel
and diesel is about 60 and 42 respectively. The higher the Cetane index
provides, the better the combustion and an improvement in the engine
thermal efficiency. Biodiesel having 10–11% excess oxygen by weight
resulting into complete combustion than diesel in an engine and high
Cetane number of fuel reduces the ignition delay period [7–10]. As
biodiesel is completely suspend with diesel, the blending of both fuels
in any ratio is possible and recommended in order to improve its
qualities. However, the differences in chemical nature of biodiesel and
petroleum diesel may cause effects in the physicochemical properties,
influencing engine performance and emissions [11]. From the literature
study, it is concluded that up to 20% of biodiesel with diesel fuel

⁎
Corresponding author.
E-mail address: mohamedmustafa@mech.sastra.edu (M.M. Musthafa).

https://doi.org/10.1016/j.fuel.2018.03.147
Received 27 February 2017; Received in revised form 16 March 2018; Accepted 20 March 2018
0016-2361/ © 2018 Elsevier Ltd. All rights reserved.
M.M. Musthafa et al. Fuel 225 (2018) 343–348

resulted in better performance, controlled combustion and emission of Table 2

diesel engine [12–15]. Likewise, chemical additives such as di-tert-butyl Physiochemical properties of test fuels.
peroxide (DTBP), ethyl hexyl nitrate (EHN) and Di-ethyl ether (DEE) Properties Diesel Palm oil biodiesel B20 fuel B20 with DTBP
also can be blended directly to diesel and biodiesel blends by some
researches. To date, there has been a significant amount of research Density (g/cc) 0.832 0.873 0.845 0.8402
Viscosity at 40 °C (cSt) 2.74 4.5 3.5 2.62
work carried out in these areas, and many articles have been published
Flash Point (°C) 46 92 65 57
in these topics. A few of the papers related to this work are discussed in Fire point (°C) 51 124 97 85
this section (i) Wang et al. [9] have investigated the effects of DTBP Calorific value (kJ/kg) 45,500 42,144 44,300 45,400
blend with biodiesel on combustion and emissions of the diesel engine. Cetane Number 49 53 52 58
Their results show that the ignition delay and combustion duration is
reduced by 1.2°CA and 3°CA respectively with addition of 0.75% DTBP
in biodiesel, the maximum cylinder pressure was reduced by 2.5%. HC, catalysed transesterification method. Methanolic solution prepared by
CO and NOx emission decreased by 42.7%, 13.9% and 15.7% respec- 1% potassium hydroxide (KOH) is mixed with 30% of methanol by
tively. (ii) Venkateswarlu et al. [16] have studied the performance and volume of oil. The prepared solution is added into the 60 °C heated
emissions characteristics of a diesel engine by B30 fuel blended with an refined oil, is stirred for one hour at 50 °C and is finally transferred into
additive of 0.5% and 1% on volume of Di tertiary butyl peroxide along a conical flask and allowed to settle for next 24 h. Two layers are
with EGR rate is varied from 0% to 20%. They found that an increase in formed in the flask, the dense bottom layer is separated out and the
thermal efficiency and decrease in specific fuel consumption, cylinder remaining biodiesel is washed with distilled water heated up to
pressure and exhaust emissions of carbon monoxide, hydro carbon, NOx 50–60 °C in three times to get pure biodiesel. By this process, 92%
and smoke opacity. (iii) Kumar et al. [17] have investigated on the biodiesel yield is obtained. The prepared biodiesel properties are tested
effect of biodiesel fuel blended with ethyl hexyl nitrate (EHN) and ex- as per ASTM standard and the same is listed in the Table 2.
haust gas recirculation on diesel engine performance and emissions.
They found that the biodiesel with Cetane improver under 20% EGR 2.3. Experimental setup
reduces NOx emissions by 33% when compared to baseline fuel of diesel
without EGR. (iv) Ramakrishna et al. [18] have studied the effect of The experimental test rig consists of a compression ignition engine,
Ethyl Hexyl Nitrate (EHN) as an additive to the diesel-biodiesel blends eddy current dynamometer as loading system, fuel supply system for
on engine performance and emissions. They found that an increase in both diesel and biodiesel supply, water cooling system, lubrication
BTE and cylinder pressure, emissions of CO and NOx were reduced with system; and various sensors and instruments integrated with compu-
increase in EHN percentage. (v) Di-ethyl ether up to 0–5% on some terized data acquisition system for online measurement of load, air and
vegetable oils such as POME, Neem oil resulting in better performance fuel flow rate, instantaneous cylinder pressure, injection pressure, po-
and improved emission on CI engine [19]. (vi) Di-ethyl ether (0–12%) sition of crank angle. Fig. 1 shows the photographic view of the ex-
on Jatropha oil 20% and diesel 80% blend provides best results when perimental setup used in the laboratory to conduct the present study.
compared to conventional diesel [20]. In fact, it is now possible to Table 3 gives the technical specifications of different components used
examine the effect of DTBP additive to Palm oil biodiesel blends (B20) in the test rig. Windows based engine performance analysis software
on engine performance, combustion and emission through mainstream package ‘Engine soft’ is provided for online thermal performance eva-
literature reviews. luation. The thermal performance parameters include brake power,
brake mean effective pressure, brake thermal efficiency, volumetric
2. Materials and methods efficiency, brake specific fuel consumption, exhaust gas temperature,
heat equivalent of brake power and heat equivalent of exhaust gas. The
This section describes DTBP properties, biodiesel preparation pro- emissions such as Nitrogen oxides (NOX), Carbon monoxide (CO), Hy-
cedure, properties of the test fuels and experimental setup. drocarbon (HC), Carbon dioxide (CO2), Oxygen (O2) and air-fuel ratio
were measured by Delta 1600L exhaust gas analyser.
2.1. Di-tert-butyl peroxide (DTBP)
3. Results and discussions
DTBP is available 100 ml bottle pack. It is an organic compound -
consisting of a peroxide group flanked by two tert-butyl groups. It is The effect of Di-tert-butyl peroxide additive added to palm oil me-
amongst the most stable organic peroxides. The peroxide bond under- thyl ester on engine performance and emissions are discussed in this
goes homolysis at temperatures > 100 °C, and for this reason di-tert-
butyl peroxide is commonly used as a radical initiator in organic
synthesis and polymer chemistry. Its chemical formula is C8H18O2 and
other properties as per supplier specification are listed in the Table 1.

2.2. Biodiesel preparation

The refined Palm oil was obtained from local market. Biodiesel was
prepared from the refined Palm oil in a laboratory by simple base

Table 1
Properties of di-tert-butyl peroxide.
Molecular weight 146.23
Specific gravity@25 °C (g/cc) 0.785–0.796
Melting point Below 40 °C
Active Oxygen 10.75%
Boiling point 109–111 °C
Solubility Soluble in most organic solvent; insoluble in
water
Fig. 1. Photographic view of engine setup.

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M.M. Musthafa et al. Fuel 225 (2018) 343–348

Table 3
Engine specification.
Make Kirloskar-TV1
Rated output 3.5 kW
Bore 87.5 mm
Stroke 110 mm
Compression ratio 14:1–18:1
Dynamo meter arm length 185 mm
Rated speed 1500 rpm
Engine loading device Eddy current dynamo meter

Fig. 4. Comparison of exhaust gas temperature against brake power for the test
fuels.

biodiesel is blended with diesel (B20), there is less than 2% change in

Fig. 2. Comparison of brake thermal efficiency against brake power for the test
fuels.
experimental study. The test was conducted three times to verify the
output and engine exhaust emission data. However, the average value is
used for further calculation and graphical representation.
3.1. Engine performance
Figs. 2–4 show the comparison of the variation in brake thermal
efficiency, brake specific energy consumption and with load for the test
fuels.
fuel energy content. The lower energy content of biodiesel blend re-
flects into slightly reduced performance than diesel fuel. However, the
addition of DTBP in the B20 blends slight increases in brake thermal
efficiency. The reason might be the cetane improver of DTBP can at-
tribute to the reduction of fuel consumption rate. Larger oxygen con-
tent, increase in Cetane number, lower density, and viscosity of fuel can
also direct to complete combustion. The similar observation and results
were also found by some authors [16,21,22].
3.1.2. Brake specific energy consumption vs load
Fig. 3 shows the variation of brake specific energy consumption
(BSEC) against load for the test fuels. While comparing the result of
different calorific value fuels, BSEC is best option rather than specific
fuel consumption [23]. It was observed that there is an increased trend
of BSEC for B20 fuel and reduced tendency for blending of DTBP to the
B20 fuel compared to diesel. The reduction in BSEC can be ascribed to
shorten ignition delay by enhancing Cetane number resulting in better
combustion. Moreover, the reduction in fuel viscosity and density are
liable for this decrement [24,25]. Few researchers also obtained similar
observation and results [16,21,22].

3.1.1. Brake thermal efficiency vs load
From the Fig. 2, it is observed that B20 fuel with additive shows
higher efficiency than B20 and diesel fuel. Pure biodiesel will have
energy content 5–10% lowers than diesel. When 20% in volume of
3.1.3. Exhaust gas temperature vs load
Fig. 4, shows the variation of exhaust gas temperature with brake
power for test fuels. The exhaust gas temperature increased with the
increase in load because more fuel was supplied to meet the power
requirement. An increase in fashion of exhaust gas temperature for B20
fuel and decrease trend for B20 with additive compared to diesel fuel.
The reason could be B20 fuel may burn during the late combustion
phase due to poor volatility. DTBP added B20 fuel may pilot to com-
plete combustion of fuel due to enhanced Cetane number which shorten
an ignition delay period.

3.2. Engine emissions

Results on hydrocarbon, carbon monoxide and nitric oxide emission

measurements at various loads for diesel, B20 and B20 with additive
fuels are presented in the Figs. 5–7. In general biodiesel reduces emis-
sions of carcinogenic compounds by as much as 85% compared with
petro diesel.

3.2.1. Hydrocarbon emission vs load

The flame quenching near the cylinder walls is one of the reason for
the formation of higher HC emission [26]. The variation of hydrocarbon
Fig. 3. Comparison of brake specific energy consumption against brake power (HC) emission against the load for the test fuels is shown in Fig. 5. A
for the test fuels. reduction in HC emission was observed for B20 fuel at entire load

345
M.M. Musthafa et al.
Fig. 5. Comparison of hydro carbon emissions against brake power for the test
fuels.
Fig. 6. Comparison of carbon monoxide emissions against brake power for the
test fuels.
Fig. 7. Comparison of NOx emissions against brake power for the test fuels.
spectrum compared to diesel fuel due to an oxygenated biodiesel blend
which leads to complete the combustion [27]. However, the additive
with B20 fuel showed an increase in tendency of HC emission. The
reason might be an additive help to increase the Cetane number of the
346
Fuel 225 (2018) 343–348
blend results in shortening the time available for fuel-air mixing. Hence,
the premixed combustion duration shortens, and the diffusion com-
bustion duration extend. It is prominent as an inhomogeneous air-fuel
mixture during the diffusion combustion process generates more HC
emission.
3.2.2. Carbon monoxide emission
Carbon monoxide emission variations in percentage against the load
for the test fuels are shown in Fig. 6. CO produces in rich air –fuel
mixture regions due to the non availability of oxygen to promote CO
concentration in the fuel [28]. As seen from Fig. 6, the emission of CO
for B20 fuel is lower than diesel fuel for entire load spectrum due to the
presence of excess oxygen in biodiesel, which supports complete com-
bustion of fuel inside the cylinder chamber. On the other hand, B20
with DTBP reduces 10–15% of CO emission than B20 fuel. The reduc-
tion may be attributed to the chemical structure of DTBP (C8H18O2)
which enhances more oxygen in the fuel blend. This might have led to
complete combustion.
3.2.3. NOx emission
From the Fig. 7, it was noted that with the use of B20 fuel, the NOx
level increases up to 9.5% compared to diesel fuel. However, addition
of DTBP to B20 fuel has shown the positive response on reduction of
NOx between 11 and 14%. The reason was due to the additive in the
blend increases Cetane number of the fuel and accelerating ignition.
This results in decreases the ignition delay by shortening the time of
premixed combustion phase. The fall in combustion temperature results
NOx reduction in the emission. It is evident that the exhaust gas tem-
perature is also reduced [Fig. 4]. Many researchers have reported the
similar results of NOx reduction with addition of ignition improver to
biodiesel blends [16,29–31].
3.3. Combustion analysis
The combustion analyses are represented in Figs. 8–10 which in-
clude the study of cylinder pressure, ignition delay period and cumu-
lative heat release rate.
3.3.1. Cylinder pressure vs crank angle
Fig. 8 shows the cylinder pressure versus crank angle variation for
diesel, B20 and B with DTBP fuels. A decrease in maximum cylinder
pressure was observed for B20 fuel with additive compared to diesel
operation. The reason might be that B20 with DTBP fuel ignite earlier
and finishes the combustion earlier than diesel and the duration of high
temperature combustion for this fuel is shorter than that of diesel. This
means that the premixed combustion duration for the blend with
Fig. 8. Comparison of cylinder pressure against crank angle for the test fuels.
M.M. Musthafa et al.
Fig. 9. Comparison of ignition delay period against brake power for the test
fuels.
Fig. 10. Comparison of cumulative heat release rate against crank angle for the
test fuels.
additive is lower than that of diesel which reduces the tendency of NOx
formation significantly. B20 fuel show slight decrease in the trend of
maximum cylinder pressure than diesel fuel due to less heating value
and mixture formation is not up to the level.
3.3.2. Ignition delay period
Fig. 9, shows the variation of ignition delay period duration with
brake power for diesel, B20 and B20 with DTBP fuel. The period be-
tween the start of fuel injection into the combustion chamber and the
start of combustion is called ignition delay period. The ignition delay
period of the tested fuel decreases with the increasing load. The results
showed that the addition of DTBP to B20 fuel, the ignition delay was
shortened by 1.6°CA and 2.3°CA compared with diesel and B20 fuel. It
might be due to enhancing of Cetane number by the use of additive.
3.3.3. Cumulative heat release rate
The Heat Release Rate (HRR) is a critical parameter to characterise
the combustion of fuel. The combustion performance was measured
using ‘Engine soft’ software which was interfaced with the engine.
Fig. 10 represents the cumulative heat release of test fuels such as
diesel, B20 with and without additives against crank angle. From the
figure, it is observed that the cumulative heat release was decreased for
B20 fuel due to the lower heating value of blend which increases the
specific fuel consumption by 9.5%, as compared to petroleum diesel
fuel. The cumulative heat release of fuel B20 with additive is higher
347
Fuel 225 (2018) 343–348
than that of diesel fuels. This is because the ignition performance of fuel
blend was improved by DTBP. There is the enhanced Cetane number of
blend having lower ignition delay period which in turn increases the
efficiency of the engine and reduces the combustion temperature. This
is evident from Figs. 3 and 4. A similar trend was observed while the
engine was operated with biodiesel blend with additive [6,8,10].
3.4. Kinetic study of di-tert-butyl peroxide decomposition
The influence of DTBP additive to diesel and biodiesel blend has
given better performance and improved emissions are explained with
the following mechanistic reaction model.
The comprehensive kinetic model for adiabatic decomposition of
DTBP using Batch CAD simulation tool developed by Lizuka and
Surianarayanan [32], have been taken and added to this study.
The major reaction for oxidation of DTBP is generally considered to
occur via fission of weak peroxide ROeOR bonds at a temperature
above 393 K and readily undergoes dissociation at higher temperatures
to two RO radicals, and it is widely used as a radical source, reaction
initiator. The initial stable intermediates in the thermal decomposition
or combustions of DTBP are acetone (CH3COCH3) and methyl radical
(CH3). The reaction to be studied here is the decomposition of di-tert-
butyl peroxide, which occurs mainly via the process,
(CH3)3 COOC (CH3)3 → (CH3)3 CO+ (CH3)3 CO
These radicals internally rearrange very quickly; primarily forming
acetone (CH3COCH3) and a methyl radical (CH3).
(CH3)3 CO·→CH3 COCH3 + ·CH3
In the presence of oxygen, the development of a flame exhibits a
two-stage ignition, where the first stage, at lower temperatures, in-
volves the thermal decomposition of DTBP to acetone. This second
high-temperature ignition process involves chain-branching reactions
for the combustion of acetone and ethane [33]. The acetone produced
during the decomposition is stable and remains in the cycle until the
main ignition promoting reactions beginning at a temperature of ap-
proximately 1100 K. It is appealing to assign the advance in combustion
timing of the main fuel due to the presence of CH3. The resulting slight
increase in the temperature is enhanced by further compression of the
mixture. Although the oxidation of di-tert-butyl peroxide is highly
exothermic, and causes an initial temperature rise, most of the effec-
tiveness of di-tert-butyl peroxide stems from chemical origins. Results of
this study showed that the role of DTBP is to reduce the ignition delay
of the base fuel through rapid heat release, rather than by radicals
produced by decomposition during the base fuel ignition delay. This
work suggests that DTBP is capable of increasing the initial temperature
via its thermal decomposition in a very short time which results in
better performance of an engine. DTBP has been recognized as an ef-
fective Cetane improver and has a potential advantage to improving
emissions at comparable level than the diesel fuel [6,8,10,16,25].
4. Conclusion
The performance and emission characteristics of diesel engine
running on three different fuels Viz., diesel, B20 and B20 with DTBP
were experimentally investigated. A comparative study was made be-
tween effect of DTBP additive to B20 fuel and without additive to B20
fuel on engine performance and emission with base line diesel opera-
tion. The result of B20 with DTBP influences that.
• Brake thermal efficiency was increased by 2% than diesel and 3.5%
than B20 fuel.
• Brake specific energy consumption was reduced by 10% than diesel
and 15% than B20 fuel.
• Carbon monoxide emission is significantly reduced than diesel.
• NO and exhaust gas temperature decreases with penalty in slight
x
M.M. Musthafa et al.
increase in HC emission.
• NO emission is decreased by 13–15% than B20 fuel and 7–9% than
x
diesel.
• The addition of DTBP not only enhances the performance but also
reduces ignition delay.
• Peak cylinder pressure decreases slightly lower than diesel and B20
fuel.
• Heat release rate slightly increases than diesel fuel.
Finally, the experimental study suggested that the addition of 1%
DTBP by volume to biodiesel blend has best alternate fuel to improve
the performance and the emission characteristics of conventional diesel
engine without any modification.
Suggestion for the development of work
The above conclusions have been arrived in constant speed diesel
engine running on B20 with 1% of DTBP additive. Better results may be
attained at different engine speed and as well as with different con-
centration of DTBP and diesel/biodiesel blend.
Acknowledgement
The authors express their sincere thanks to Prof. R. Sethuraman,
Vice-Chancellor, SASTRA Deemed University, Thanjavur, for granting
permission to publish this research work and providing fund for the
purchase of VCR engine test rig.
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