National Conference on Advances in Mechanical Engineering Science (NCAMES-2016)

Effects of Additives on Biodiesel/Diesel

Performance, Emission Characteristics,
Combustion Characteristics and Properties
Gangadhara Rao1, Kumar G N2, Mervin Herbert3
1
Associate Professor, Department of Mechanical Engineering,
Srinivas Institute of Technology, Valachil, Mangaluru, Karnataka State, India – 574143
2
Professor Department of Mechanical Engineering,
National Institute of Technology Karnataka, Surathkal., India
3
Assistant Professor, Department of Mechanical Engineering,
National Institute of Technology Karnataka, Surathkal., India

Abstract— Biodiesel as a renewable and sustainable
alternative fuel has gained importance in recent
times. Use of biodiesel has shown reduced power,
increased BSEC and increase in NOx emission.
Different additives are used along with diesel and
biodiesel for improving fuel properties, combustion
characteristics, engine performance and emission
characteristics. This article describes about the use
of additives for above mentioned purposes. It is
found that use of additives improved the
biodiesel/diesel properties like viscosity, flash and
fire points and pour points etc. Use of additives
reported no much improvement in engine
performance except few cases who reported to the
contrary. Combustion characteristics found to be
improved with use of additives. HC and PM
emissions reported to be reduced and NOX emission
was found to increase in some cases. Special NOx
inhibitor additives found to be more effective in
reducing the NOx emission.
Keywords — Biodiesel, organic, metallic, additives,
performance, combustion, emission.
I. INTRODUCTION
As a renewable, sustainable and alternative fuel
for compression ignition engines, biodiesel instead
of diesel has been increasingly fuelled to study its
effects on engine performance and emissions in the
recent years. Available literature reviews show that
use of bio diesel lead to reduced engine power,
increased BSEC because of reduction in heating
values of biodiesel. But use of biodiesel has shown
reduction in PM, HC and CO but increase of NOx
emission. Biodiesel favours to reduce carbon deposit
wear of key engine parts. [1]
Biodiesel fuel is an oxygenated fuel and sulfur
free fuel. These factors lead to complete combustion
and less exhaust emissions than diesel fuel.
Furthermore biodiesel has higher viscosity, density,
pour point, flash point and cetane number than diesel
fuel. Using biodiesel can help reduce the world‟s
dependence on fossil fuels and also has significant
environmental benefits [2].
Different additives are used along with diesel and
biodiesel. The purposes of these additives are to
improve the cold flow properties of the fuel and
engine performance and emission characteristics. In
this paper detailed review of effect of additives on
fuel properties, combustion characteristics engine
performance and emission from the engine is done.
A.Types of additives
Additives can be broadly classified as organic
additives and metal based additives. It can be further
classified as additives to improve the properties of
base fuel, additives used to improve the engine
performance, additives used to improve the emission
characteristics. Additives to improve the engine
performance can be further classified as pre-flame
additives, flame additives and post-flame additives.
A special class of additives which improve the
oxidation stability of biodiesel are under study.
NPAA (4-Nonyl phenoxy acetic acid), NPPD
(N-phenyl-1, 4-phenylene diamine), DPPD (N, N‟-
diphenyl-1, 4-phenylenediamine), Synthetic fatty
acids, Oxygenated diglyme are the examples for
organic additives. Nio, mno2,Fecl3,Mn,Mo,
O,Mg,SCD5,Magnallium(Al-Mg),CD3O4,ceo,Cu are
the examples for metal based additives. Gossypol,
pyrogallol (1-2, 3 trihydroxy benzene), Propyl
gallate (3,4,5-trihydroxy benzoic acid),
butylatedhydroxyanisole BHA(2-tert butyl 4-
methoxy phenol) are the examples for additives for
improving oxidation stability of biodiesel.
B. Effect of Additives on fuel properties
The additives are added to improve the
properties of base fuel. Gossypol was found to be
exogenous antioxidant for FAME‟s [3].Pyrogallol,
Propyl gallate, butylatedhydroxyanisole was found
decreasingly effective i.e. (Py>PG>BHA) in
improving oxidation stability of Magalocarpous oil
biodiesel [4].
Metin Guru et al [5] studied the effect of
organic compounds of Mn, Mg, Cu and Ca metals as

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National Conference on Advances in Mechanical Engineering Science (NCAMES-2016)
additives for improving the diesel fuel properties. It
was found that organic based Manganese gave
greatest decrease in freezing point. This additive
reduced the freezing point to 12.40C at the rate of
dosage of 54.2µmol Mn/L diesel fuel. It was
established that the cetane number of diesel fuel
without additive was 46.22 whereas the cetane
number 48.24 for diesel fuel with optimum amount
of dosage. It was observed that the organic based
Manganese reduces the viscosity and flash point. An
Organic based Manganese additive was found to
improve the properties of pomace oil methyl ester
biodiesel [6].Doping the fuel at a ratio of 12µmol/l
oil methyl ester led to a 20.37% decrease in viscosity,
70C fall in flash point and reduced the pour point
from 00C to -150C.
Chicken fat methyl ester has the advantage of
having a high cetane number, being non-corrosive,
clean and renewable, while having certain
disadvantages such as a high freezing point, high
viscosity and high flash point. In a study Magnesium
based additive was synthesized stoichiometricaly at
2250C for 1 hour in a 1 litre glass reactor. Effects of
[7] the additive on pour point, viscosity and flash
point of raw chicken fat methyl ester were
investigated by dosing additives upto 16µmol/l.
Increase in additive concentration from 0 to
16µmol/l resulted in lower freezing point, viscosity
and flash point. A dosage of 16µmol Mg into the
chicken fat methyl ester a causes a 70C pour point
decrease. Viscosity and flash point tests were carried
out with and without the Mg additive. The increase
from in magnesium concentration from 0 to
16µmol/l lead to decrease from 5.184 to 4.812 in
viscosity. With the same Magnesium additive
concentrations flash point was decreased from 129 0C
to 1220C. The additive causes reductions in the flash
point, viscosity and pour point compared to fuel
without additives. The synthesized additives such as
polyisobutylene (PIB)-succinimides showed same or
better detergent-dispersant properties compared to
the conventional diesel and biodiesel blends. They
also provided corrosion inhibiting and lubricity
improving effects when applied in diesel fuel, 5%
biodiesel containing diesel fuel and 100% biodiesel
[8].
M De Torres et al [9] studied the effect of CFPP
(cold filter pour point) additives on biodiesel fuel
and improvement in bad behaviour at low
temperatures. In this study, it has been shown that
how the presence of free fatty acids in the starting
materials for producing biodiesels can be used for
synthesizing additives able to improve cold flow
properties of biodiesel from reused oils. The study of
crystallization patterns of pure derivatives by DSC
and optical microscopy revealed the improvement of
cold properties of biodiesel. Blends of biodiesel with
upto 5% of some of these compounds allowed a
decrease of CFPP.
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A few more research work is needed in the area
of effect of additives improving the properties of
diesel/biodiesel.
C. Effect of additives on biodiesel engine
performance
Most of the researches on the performance
characteristics of diesel engine when additive was
used along with biodiesel report that effect of
additive on the performance of diesel engine fuelled
with biodiesel was not much significant. In a study
conducted by Kalam. M.A. et al [10] on effect of
adding NPAA additive in B20 palm biodiesel to the
extent of 1% additive showed better performance
such as improved brake power, lower SFC.
A bio solution made of natural organics was used as
an additive in a research [11]. Experimental results
in this work demonstrate that emulsified bio-
solution/palm biodiesel/diesel blends have the
advantage of saving energy upto the extent of 16%
reduced fuel consumption.
Ali Keskin et al [12] studied the effect of
synthesized Mn and Ni based additive in biodiesel
produced out of tall oil. Fatty acids and resinic acids
were obtained from crude tall oil by distillation
method. Tall oil methyl ester was produced from
fatty acids. Resinic acids were reacted with NiO and
mno2 stoichiometrically for the production of
metallic fuel additives. Each metallic fuel additive
was added at the rate of 8µmol/l and12µmol/l to
make mixture of 60%tall oil methyl ester/40% diesel
fuel (TE60) for preparing test fuels. Biodiesel fuels
were tested in an unmodified direct injection diesel
engine at full load condition. Specific fuel
consumption of diesel fuel increased by 6%.
However in comparison with TE60 it showed trend
of decreasing with adding additives. A different
study conducted by Ali Keskin et al [13] on the
influence on tall oil biodiesel of Mg and Mo
additives based fuel additives. The engine torque and
power output values did not change much in
comparison with fuel without additives. A study was
conducted by G.R.Kannan et al [14] on the effect of
ferric chloride (fecl3) additive with waste cooking
palm oil based biodiesel. The metal based additive
was added to biodiesel at a dosage of 20µmol/l. The
study revealed that fecl3 added biodiesel resulted in a
decrease of brake specific fuel consumption (BSFC)
of 8.6% while the brake thermal efficiency was
increased by 6.3% for constant speed test at
1500rpm.
Pomace oil methyl ester blended with diesel fuel
can be used as an alternative fuel in the conventional
diesel engine without any major modification. An
organic based Manganese (Mn) additive improved
engine performance along with the base fuel
properties [6]. Metin Guru et al [7] studied the
chicken fat biodiesel with synthetic Mg additive in a
single cylinder DI diesel engine for its effects on
engine performance. Organic based synthetic
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Magnesium additive was doped into biodiesel blends
by 12µmols of Mg. Engine tests were run with diesel
fuel (EN590) and a blend of 10% chicken fat
biodiesel and diesel fuel (B10) at full load operating
conditions and different engine speeds from
1800rpm to 3000rpm. The results showed that the
engine torque was not changed significantly with
addition of 10% chicken fat biodiesel, while specific
fuel consumption increased by 5.2% due to lower
heating value of biodiesel. A.S. Ramadhas et al [15]
experimentally proved that the3 diethyl ether could
be used as an additive with biodiesel to improve
performance characteristics.
An experimental investigation has been carried
out on the effects of „injection pressure‟ on
performance and emission characteristics of CI
engine using Jatropha Curcus As biodiesel with
SCD5 additive. Tests were conducted on single
cylinder four stroke water cooled compression
ignition engine to evaluate the feasibility of blends
of JME with SCD5 additive. The performance of J20
with SCD5 additive shows less specific energy
consumption and highest brake thermal efficiency
[16].
IRGANOR NPA was added to POME-Diesel
blended fuels especially for B20+1% combination in
a study conducted by M.Shahabuddin et al [17].
Along with B20+1% several form of biodiesel is
used in this experiment namely B100 (pure bio
lubricant), B20, B20+2% and compared with
ordinary diesel. It is found that B20+1% produces
1.73% and 9% higher brake power compared to fuel
B20 and ordinary diesel respectively. Also it is
found that B20+1 consumes 26% and 6% lower SFC
compared with fuels B20 and ordinary diesel.
Ali Keskin et al [18] studied the influence of
metallic based fuel additives such as synthesized Mn
and Mg based additives on engine performance. The
metallic based additives were produced by
synthesizing of resinic acids (abeetic acid) with
mno2 and mgo. These additives were doped into
diesel fuel at the rate of 8µmol/l and 16µmol/l for
preparing test fuels. The fuels with and without
additives were tested in a direct injection diesel
engine at full load condition. Maximum reduction in
SFC was recorded as 4.16%. Power and Torque
values of engine were increased slightly by Mn
based additive at some engine speeds.
V Sajith et al [19] conducted experimental
investigation on effects of Cerium oxide nano
particle fuel additives on biodiesel derived from
jatrophacurcus. Engine performance tests were
conducted on the diesel engine with standard
biodiesel oil and modified fuel. The results show
that the brake thermal efficiency of diesel engine
improved by addition of Cerium oxide in the fuel.
The Cerium oxide nano particles present in the fuel
promote longer and more complete combustion
compared to the base fuel as Cerium oxide acts as an
oxygen buffer thus increases the efficiency. It also
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has been observed that the improvement in the
efficiency generally increases with dosing levels of
nanoparticles.
D. Effect of additive on biodiesel combustion
characteristics
Researches are carried out on the effect of
additive on biodiesel combustion characteristics in a
diesel engine. Ferrocene was used as additive in a
study conducted by C.J.Du et al [20]. Two engine
configurations were tested, standard aluminium
piston with normal engine deposits and engine
cleaned to “new engine condition”, with piston
replaced with a thermal barrier coated piston. It is
found that 30 and 40% burn angles were advanced
while 5 and 60% burn angles remained unchanged.
Eji Kinoshita et al [21] experimentally found that the
ignition delay of biodiesel became longer by adding
crude glycerine to biodiesel.
Hu Li et al [22] investigated the effect of a
multifunctional diesel fuel additive package used
with rapseed oil (RSO) as a fuel in DI heavy duty
diesel engine. The results showed that use of
multifunctional fuel additive package reduced the
ignition delay, increased the premixed combustion
duration (PCD), improved the combustion stability,
reduced deposit build up on fuel injectors and
prevented the deterioration of engine.
G.R.Kannan et al [12] investigated the effect of
FeCl3 as a fuel borne catalyst (FBC) for waste
cooking palm oil based biodiesel for combustion
characteristics. FBC added biodiesel showed higher
cylinder gas pressure, heat release rate and shorter
ignition delay at optimized operating conditions.
A three phase biodiesel emulsion of oil in water
drops- in oil (O/W/O) and O/W/O biodiesel
emulsion containing aqueous ammonia were
prepared and tested for burning quality in a study
conducted by Cheng-Yuan Lin and Hsia-An Lin [23].
The experimental results showed that the burning of
O/W/O biodiesel emulsion and the O/W/O emulsion
containing aqueous ammonia had larger fraction of
fuel burnt and thus larger heat release rate than neat
biodiesel if water content is not considered for
calculations of heating value.
An experimental investigation was conducted
by D.H.Qi et al [24] to evaluate the effects of using
diethyl ether and ethanol as additive to
biodiesel/diesel blends on the combustion
characteristics of a direct injection diesel engine.
Test fuels were denoted as B30 (30% biodiesel and
70% diesel in volume), BE-1(5% diethyl ether, 25%
biodiesel and 70%diesel in volume) and BE-2 (5%
ethanol, 25% biodiesel and 70% diesel in volume)
respectively. At Lower engine loads, the peak
pressure rise rate and peak heat release rate of BE-1
were almost similar to those of B30 and higher than
those of BE-2. At higher engine loads the peak
pressure rise rate and peak heat release rate of BE-1
were highest and those of B30 were lowest. Here
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BE-1 exhibited better combustion characteristics
than BE-2 and B30.
E.Effects of additives on biodiesel/diesel emission
characteristics.
The use of biodiesel leads to the substantial
reduction in PM, HC and CO emissions
accompanying with imperceptible power loss.
Increase in fuel consumption and increase in NOx
emission on conventional diesel engines with no or
fewer modifications. The use of additives along with
biodiesel should aim of reduction in PM, HC and
CO emissions with inhibition of NOx. Sometimes
special NOx inhibitors are added to reduce NOx
emission. The following presents detailed review of
effects of additives on engine emission
characteristics.
In a study conducted by K.Varatharajan and
M.Cheralathan [25] on adding NPPD and DPPD
additives on emission characteristics is done. Here
NPPD means N-phenyl-1, 4-phenylene diamine and
DPPD means N, N‟-diphenyl-1, 4-phenylenediamine.
These are basically antioxidant additives added to
biodiesel for improving oxidation stability of
biodiesel. Results show that significant reduction in
NOx could be achieved by the addition of
antioxidants but smoke, CO and HC emissions were
found to have increased.
Cheng-Yuan Lin et al [23] successfully used
aqueous NH3 in three phase mixture of O/W/O for
improving its NOx inhibition. M.A. Kalaam and H.H.
Masjuki [10] used NPAA additive to control NOx
and CO emissions of Palm diesel in diesel engine. It
is found that palm diesel with additive (B20X)
reduces NOx, CO and HC emissions. In an
experimental work emulsified bio solution/palm-
biodiesel/diesel blends were tested for their emission
characteristics [11]. When compared with premium
diesel fuel reduced emissions of PM by 90.1%and
total poly acrylic aromatic hydrocarbon (PAH) by
69.3% and BaPeq(benzol[a] pyrene equivalent)
concentration by 69.6% were observed.
Robert L McCormick et al [26] studied the
effect of fuel additive and blending approaches to
reducing NOx emissions from biodiesel.
Polyisobutylene (PIB) a high molecular weight
polymer fuel additive was extensively tested in
heavy duty diesel engines to determine its effect on
both controlled and uncontrolled exhaust emission
by Donel. R. Olson et al [27].Particulate matter
emissions were reduced of the order of 60%. All
PAHs were reduced.
Performance and emission studies of diesel
engine using diethyl ether as oxygenated fuel
additive were conducted by KapilanNatesan [28]. It
was found that emissions were considerably reduced.
Hang .Z.H et al [29] aimed to investigate the
combined application of fumigation methanol and a
diesel oxidation catalyst for reducing emissions of
an in use diesel engines. The fumigation method
ISSN: 2231-5381 http://www.ijettjournal.org
resulted in a significant increasing in hydrocarbon
(HC), carbon monoxide (CO) and nitric oxide (NO 2)
emissions but decrease in nitrogen oxides (NOx),
smoke opacity and particulate matter (PM)
concentration.
M.Shahabuddin et al [17] studied the effect of
emission characteristics of CI engine fuelled with
POME biodiesel/diesel blends. They found that
B20+1 reduces CO, NOx and CO2 emissions as
compared to other fuels such as B100, B20, B20+2.
Ali Keskin et al [13] conducted emission test on
diesel engine fuelled with Tall oil biodiesel. A single
cylinder DI diesel engine was used in these tests. CO
emission and smoke opacity decreased by 56.42%
and by 30.43% respectively. In general low NOx and
CO2 emissions were measured with the biodiesel
fuels. Tall oil resinic acids were reacted with MgO
and MoO2stoichiometrically for production of metal
based fuel additives. Same authors conducted
another investigation with synthesized NiO and
MnO2 additives with TOME for emission
characteristics [12]. CO emission and smoke opacity
decreased upto 64.28% and 30.91% respectively.
Low NOx emissions was also observed in general for
biodiesel fuels. A manganese based additive was
used in a study to investigate the effects on the
polycyclic aromatic hydrocarbon (PAHs) emission
from naturally aspirated heavy duty diesel powered
engine by His-Hsien Yang et al [30]. A similar turbo
charged engine was tested and compared with
natural-aspirated one for PAH emissions. The
concentrations of 21 individual PAH‟s (gas particle
phases) and the metal element (Mn) of the
particulate from the engine exhaust and the diesel
fuel respectively were determined. Engine exhaust
(PAHs and Mn) was collected over the modified
JAMA J-13 mode by a PAH sampling system. By
adding 400mg/kg of Mn based additive in the diesel
fuel the reduction fraction of mean total PAH
(gas+particle phase) emission was 37.2% while for
the 10 higher molecular weight PAHs the mean
reduction factor was 64.5%.In a particular study the
metallic based additive in diesel it is found that
additive decreased the CO emission and smoke
opacity by 16.35% and 29.82% respectively. NO x
emission was measured higher and CO2 was not
changed considerably with metallic based additives
[18].Valentine et al [31] experimentally observed
that bimetallic platinum and Cerium diesel fuel
borne catalyst reduces the engine emissions. In a
separate study conducted by Metin Guru et al[14] by
using Mg based additive in waste chicken fat
biodiesel in a single cylinder direct injection(DI)
diesel engine it is found that CO and smoke
emissions decreased by 13% and 9% respectively
but NOX emission increased by 5%.
In an experimental investigation on the effects
of Cerium oxide nanoparticle fuel additive on
biodiesel derived from Jatropha [19], it is found that
emission levels of hydrocarbon and NOx are
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appreciably reduced with the addition of Cerium
oxide nanoparticle. In an investigation done by
D.Ganesh et al[32] on the effect of Nano fuel
additive {Magnalium(Al-Mg) and cobalt oxide
(CO3O4)} on emission reduction in a [1]
biodiesel(Jatropha) fuelled CI engine, it is found that
nono fuel additive resulted in maximum reduction
about 60% in UBHC and 50% reduction in CO at
[2]
full load and 75% load respectively. Yanangan et al
[33] investigated the burning characteristics of fuel
droplets of JME containing nano and micron sized
Al particles by varying its size. Al particle
[3]
significantly reduces the emission of CO2, NOx.
Husnawan et al [34] showed that using post
flame MgO additive successfully diminished [4]
poisonous exhaust gasses from diesel and vegetable
oil based biodiesel blends. These gasses are HC,
NOx and CO. Use of metal based additive such as [5]
MgO combined with oxygenated additive (palm-
polyol) found reducing NOx from biodiesel-diesel
[6]
blended fuel combination.
A study was conducted by Mahesh C.V et al [16]
on emission characteristics of CI engine using
JatrophaCurcus as biodiesel with SCD5 additive. [7]
They found that as the amount of SCD5 additive
with JME increases the HC, CO, and smoke density
in exhaust decreases. [8]
II. CONCLUSIONS [9]
From the literature available following
conclusions can be drawn.
1. Adding different types of additives found that [10]
increased oxidation stability of base fuel,
decrease the freezing point, reduce the viscosity,
decrease the flash point and reduce the pour [11]
point of base fuel. Additives improved the
detergent-dispersant properties of
diesel/biodiesel blends [12]
2. Performance of diesel/biodiesel blended engines
grossly have not shown much improvement. But
[13]
in some cases it was reported that there were
marginal decrease in SFC and little increase in
brake thermal efficiency [14]
3. Additives in diesel/biodiesel blends are found to
improve the combustion characteristics.
Improved combustion stability, reduced deposit [15]
buildup, shorter ignition delay, better heat
release rate are observed with the additives. But
in some researches increased delay period and [16]
reduced heat release rate were reported.
4. Additives in general improved the emission
characteristics of diesel/biodiesel fuelled
engines. The addition of antioxidant additives [17]
reduced NOx emission. Emission characteristics
like CO, HC, NOx, PM, PAH and soot and
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smoke opacity are keenly observed and
additives found to improve these characteristics.
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