International Journal of Ambient Energy

ISSN: 0143-0750 (Print) 2162-8246 (Online) Journal homepage: http://www.tandfonline.com/loi/taen20

Effect of biodiesel fuel properties and formation of

Nox emissions: A Review

K. Velmurugan & A.P. Sathiyagnanam

To cite this article: K. Velmurugan & A.P. Sathiyagnanam (2016): Effect of biodiesel fuel
properties and formation of Nox emissions: A Review, International Journal of Ambient Energy,
DOI: 10.1080/01430750.2016.1155486

To link to this article: http://dx.doi.org/10.1080/01430750.2016.1155486

Accepted author version posted online: 18

Feb 2016.

Submit your article to this journal

Article views: 4

View related articles

View Crossmark data

Full Terms & Conditions of access and use can be found at

http://www.tandfonline.com/action/journalInformation?journalCode=taen20

Download by: ["Queen's University Libraries, Kingston"] Date: 23 February 2016, At: 01:48
 Publisher: Taylor & Francis

Journal: International Journal of Ambient Energy

DOI: 10.1080/01430750.2016.1155486

Effect of biodiesel fuel properties and

formation of Nox emissions: A Review

t
K.Velmurugana,*, A.P.Sathiyagnanamb
Downloaded by ["Queen's University Libraries, Kingston"] at 01:48 23 February 2016

rip
a ,b
Department of Mechanical Engineering, Annamalai University, Tamilnadu, India.

c
Abstract

us
Biodiesel is revealed as an environmental friendly alternative fuel for CI engine
and it can palliate regulated and unregulated emissions. Biodiesel is substantially found to
reduce the emissions of hydrocarbons (HC), carbon monoxide (CO), and particulate matter
an
(PM), but increasing (10-15%) oxides of nitrogen (NOx) emissions compared with
conventional diesel fuel. The accurate cause for NOx emission is still vague. This paper
reviews the effect of biodiesel properties and formation of NOx emissions and it is classified
M

in three sections. The first section bestows the NOx formation mechanisms. The second
edition deals with the influence of formation and biodiesel properties on NOx emissions.
Finally, a few prevailing conclusions are epitomized, and more researches are pointed out.
d

Keywords:
e
pt

Biodiesel, NOx emission, Fuel properties, Formation of NOx

ce
Ac
 1. Introduction

The major feature of the air quality management is to reduce the harmful emissions
from internal combustion engines. The limit merits were lowered many times over the last
decapods and will be set to lower merits for the coming years. The regulations limited such
properties are EN-14214 in Europe and ASTM-D-6751-03 in USA. The biodiesel employed
in diesel engine produces a remarkable reduction in emissions of particulate matter, HC and
CO but increase in NOx emission about 10-23% compared to the diesel fuel. This increase in
NOx emission is described as biodiesel NOx effect. The term generally invokes to fatty acid
methyl or ethyl esters made from vegetable oils or animal fats, whose properties are adequate
to be used in diesel engines. The US Environmental Protection Agency (EPA) explicated

t
NOx as one of the precedent pollutants which influences respiratory system. Germany, US,
Downloaded by ["Queen's University Libraries, Kingston"] at 01:48 23 February 2016

rip
France, Argentina and Brazil are the top five biodiesel producing countries in the world.US is
the second largest biodiesel producing country in the world and predicts the market to reach
about 6453 million liters in 2020. Considering it worldwide, the prediction is about 45,291

c
million liters to complete the required energy demand. Therefore, more research work is

us
needed to conquer all the disadvantages against biodiesel combustion either by fuel or engine
modification. The reason for the biodiesel higher NOx effect is mainly owing to the property
of the biodiesel (Xue, Tony and Hansen 2011; Bora D and Baruah D 2012; Varatharajan K
an
and Cheralathan M 2012). Lin et al. (2011) proposed that the rich oxygen content of the
biodiesel results in complete combustion, reduction of HC and CO emissions but increased
high combustion temperature and NOx. Van Garpen et al. (2007) described that the reason for
M

the biodiesel NOx effect is due to changes in the chemical composition and the physical
properties of the fuel. Hence, it is mandatory to discuss the effect of fuel property on NOx
emission and revamp the antioxidant additives. The main objective of this paper is to present
d

the influence of biodiesel properties on formation of NOx emission.

e

2. NOx formation mechanisms

pt

Oxides of nitrogen (NOx) consist of nitric oxide (NO), nitrogen dioxide (NO2) and
nitrous oxide (N2O) and formed when nitrogen (N2) combines with oxygen(O2) but the
ce

majority(95%) of NOx produced is in the form of nitric oxide(NO). The NO production in

diesel engine requires a complete analysis of NOx formation mechanisms. This section
dispenses the oxides of nitrogen pathways such as thermal, prompt, and N2O mechanisms.
Ac

Predominantly, biodiesel contains no fuel-bound nitrogen, so NO formation by the fuel is

negligible.

2.1 Thermal NO

Thermal NOx is deduced by a set of highly temperature-dependent chemical

reactions. High combustion temperature (1700K) breaks the strong triple bond of nitrogen
molecules and forming highly reactive atomic nitrogen, which reacting with oxygen and
generates thermal NOx.

O + N2 ↔NO +N (1)
 N + O2 ↔ NO + N (2)

N +OH↔ NO + H (3)

The three reactions mentioned above are suggested by Zeldovich (1946).The

factors which influence thermal NO formation rate are combustion temperature,
concentrations of oxygen and nitrogen and residence time of the reaction products. The NO
formation rate can be imprecised in the post-combustion flame region by:

[NO] = k e-K/T [N2] [O2]1/2 t (4)

Where k and K are reaction constants, T is absolute temperature, and it is time. The above

t
equation indicates that thermal NO formation is an exponential function of temperature. The
Downloaded by ["Queen's University Libraries, Kingston"] at 01:48 23 February 2016

rip
zeldovich kinetics on temperature is the major tool used in the control of NO formation in
combustion systems.

c
2.2 Prompt NO

us
The prompt NOx is the salient mechanism in low temperature, fuel-rich
combustion processes and where residence times are short (Bowman 1975). Prompt NOx is
most pervasive in rich flames. The actual formation involves a complex series of reactions
an
and many possible intermediate species (Fennimore 1975).

CH + N2 ↔ HCN + N (5)
M

N + O2 ↔ NO + O (6)

HCN + OH ↔ CN + H2O (7)

d

CN + O2 ↔ NO + CO (8)
e

A number of species resulting from fuel fragmentation suggested as the source

pt

of prompt NOx in HC flames [e.g.CH, CH2, C, C2H]

ce

CH2 + N2 ↔ HCN + NH (9)

NO formations occur at much lower temperatures (below 750°C).

Ac

2.3 N2O pathway

The atomic nitrogen reacts with N2 to form N2O by a three body reaction [9].

O + N2 + M ↔ N2O + M (10)

Where M is a molecule to complete the reaction. The N2O formed from reaction (10) is then
react to form NOx

N2O + O ↔. NO + NO (11)
 This mechanism is dominant in combustion process under elevated pressure and
lean air fuel ratio conditions (Pandey et al. 2012).

3. Reasons for biodiesel NOx effect

There are many factors playing the important role on NOx formation from diesel
engine. An enormous number of studies have shown that high isentropic bulk modulus of
biodiesel causes an artificial advance injection timing relative to petro-diesel, and higher NOx
emissions. The pump-line-nozzle (PLN) injection system causes an increase in the mass
delivery and residence time, which results in very high reaction temperature and NOx (Garner
et al. 2009). McCormick et al. (2012) used the common rail injection system and did not find
any increase in NOx emissions. But, Zhang and Boehman (2007) established higher NOx

t
Downloaded by ["Queen's University Libraries, Kingston"] at 01:48 23 February 2016

rip
emissions with common rail system, and deduced that injection timing shift alone could not
be the basis for biodiesel NOx effect. Benajes et al. (2008) exhibited significant impacts of
adiabatic flame temperature, heat release rate, and stoichiometric burning on NOx formation

c
in diesel engines. The adiabatic flame temperature of biodiesel is higher than petro-diesel
owing to complete combustion from fuel bound oxygen. But, Moneyem et al. (2001) found

us
that biodiesel has lower adiabatic flame temperature than petro-diesel. Kegl .B (2011)
suggested the higher heat release rate of biodiesel is the possible reason for the biodiesel NOx
effect. Szybist et al. (2005) perceived a lower rate of heat release for biodiesel fuel at all
an
loads. This result is additionally endorsed by extensive experimental work by Bittle et al.
(2009) the biodiesel fuel properties change might lead to an increased ignition delay.
M
Predominantly, longer ignition delay increases the premixed burn fraction which is important
for increased NOx formation (Musculus 2005).Due to the lower calorific value of biodiesel,
more quantity of fuel is injected into the cylinder which results in high temperature and NOx
d

(Sun, Caton and Jacobs 2010). Varuvel et al. (2012) found that the increased premixed
combustion of biodiesel is one of the reason for biodiesel NOx effect. Because premixed
e

combustion has higher oxygen concentrations and produces more NOx. Allen and watts
pt

(2009) indicated the sauter mean diameter of methyl ester varies from 5 to 40% higher than
petroleum diesel fuel. Thus, increase in sauter mean diameter reduces the premix phase of
combustion, causing an increase in the diffusion phase of combustion and NOx. During
ce

combustion, CH and OH radicals are continuously formed. OH radicals are formed during
high temperature reactions and CH radicals are formed during low temperature pre-
Ac

combustion reactions (Sakib et al. 2012). Brezinsky et al. (2009) stated that the high rate of
acetylene production from unsaturated methyl ester is the main reason for biodiesel NOx
effect and acetylene is responsible for CH radical generation and prompt NOx. Varatharajan
et al. (2011)described the factors such as higher heat release rate, adiabatic flame temperature
and stoichiometric burning might not be the major reasons for biodiesel NOx effect. The US
National Renewable Energy Laboratory [NREL] reported the prompt NOx is the major reason
for the biodiesel NOx effect and suggested the use of antioxidants as a prompt NOx control
strategies. Rajasekar et al. (2010) reviewed the NOx mitigation techniques for biodiesel fuels.

4. Effect of fuel properties on NOx emissions:

 Many researchers have suggested many possible reasons for the increase of NOx
emissions in the diesel engine using biodiesel as a fuel. There is an ubiquitous accordance
that no single factor is responsible for biodiesel NOx factor. John agudelo et al. (2010)
described a reduction of NOx formation by biodiesel over diesel fuel. But, the exact cause of
NOx emission is still ambiguous. The physical and chemical properties of fuel may vary
combustion temperature, residence time, position of injection, quantity of injection and NOx
emission. The fuel properties such as bulk modulus, oxygen content, cetane number,
viscosity, density, heat capacity, degree of saturation, surface tension and thermal
conductivity all have important effect on the engine emission and performance as well. The
physical and chemical properties of some common biodiesel fuels and their NOx emissions
are shown in table 1.

t
Downloaded by ["Queen's University Libraries, Kingston"] at 01:48 23 February 2016

rip
4.1 effect of bulk modulus of compressibility

Bulk modulus is a preferred injection system parameter is a measure of resistance

c
to compressibility. It increases with pressure, decreases with temperature but also caused by
velocity of sound and density of fuel. Boehman et al. described the impact biodiesel fuels on

us
the fuel injection timing in a diesel engine with in-line fuel injection system (Boehman et al.
2006). The higher bulk modulus of compressibility of vegetable oils and their methyl ester
lead to advanced injection timing. Lower bulk modulus of compressibility leads to retardation
an
of injection timing with paraffinic fuels (Yamane et al. 2001). Tat and Van garpen et al.
(2000) examined the effect of fuel property changes on injection timing and concluded that
M
the 1° of advanced injection timing is partially responsible for the increase in NOx emission.
They found that the densities, speed of sound and isentropic bulk modulus of unsaturated
methyl ester is higher than that of the saturated methyl ester (Tat and Van garpen 2002).Bulk
d

modulus can cause changes in fuel moreover; injection timing isentropic bulk modulus of
saturated fatty acid is alike to the conventional diesel fuel. The density, speed of sound and
e

the isentropic bulk modulus of the methyl ester showed approximately linear relationship
pt

with pressure at the temperature levels of 20° and 40°C (Van garpen and Tat 2003). Methyl
soy ester has high bulk modulus of compressibility, velocity of sound and also produces more
NOx. The bulk modulus effect on NOx emissions can be reduced by retarding the injection
ce

timing and by preheating the fuel. Biodiesel’s higher density tends to oppose the effect of
viscosity, speed of sound, and isentropic bulk modulus. Higher speeds of sound and
Ac

isentropic bulk modulus of biodiesel have no effect on the start of the injection. It is not
possible to discriminate the relative significance of the pump effect and the bulk modulus
effect on the timing (Tat and Van garpen 2004). Kegl (2011) compared the blends B100,
B75, B50 and B25 with diesel fuel and established that the injection delay decreases with
B100 and other blends because of higher values of bulk modulus. Besides, she observed that
mean injection of rate and pressure increases with higher content of biodiesel in blends.
Moneyem et al. (2001) described that 3° retardation of injection timing gave a 20.9%
reduction in NOx emissions for B100 fuel and it is compared with the standard injection
timing. For the same start of combustion, neat biodiesel fuels produced less NOx than the
diesel fuel. Fuel density has importance in diesel engine performance since the fuel injection
system operates on a volume metering system. Jatropha methyl ester has higher bulk modulus
 of compressibility than diesel fuel, due to this the pressure waves generated by the pump
plunger travels faster from pump end to the injector end, causes premature injection. Jatropha
methyl ester is burning close to the top dead centre (TDC) and the peak pressure is higher
than that of the diesel fuel. This is due to higher bulk modulus of jatropha methyl ester and it
causes early lift of the needle in the nozzle, causing advanced injection (Gumusa et al. 2012).
The higher value of bulk modulus leads to advanced injection timing which is responsible for
the increase in NOx emissions. The bulk modulus effect on NOx emissions can be reduced by
retarding the injection timing and by preheating the fuel.

4.2 Effect of surface tension

Generally biodiesel fuels have higher latent heat of vaporization, viscosity and

t
Downloaded by ["Queen's University Libraries, Kingston"] at 01:48 23 February 2016

rip
surface tension than diesel. When surface tension decreases from pure methyl ester to the
diesel, NOx emission did not change significantly. Therefore, surface tension did not
contribute to the increased NOx (Yuan and Hansen 2009). Graboski et al. (2009) stated that

c
the surface tension of biodiesel is 22% higher compared to diesel. Higher viscosity and the
surface tension of fuel offer resistance to atomization during injection process. The sauter

us
mean diameter (SMD) is found to increase with increasing surface tension and viscosity.
Diesel spray properties, droplet size distribution and sauter mean diameter are influence by
fuel surface tension and viscosity. SMD of biodiesel fuels varies from 5 to 40% higher than
an
diesel fuel (Gopinath, Puhan and Nagarajan 2010). The surface tension increases with the
increase in unsaturation of the biodiesel. The high viscosity and surface tension of biodiesel
M
affect atomization by increasing the mean droplet size which increases the spray tip
penetration. The higher mean droplet size of biodiesel is due to the lower Weber number,
which is owing to the high surface tension (Rao 2011).Lee et al.(2005) described a method of
d

injection when using ultralow sulfur diesel and biodiesel on a common rail diesel engine.
They unveiled with a higher biodiesel blend ratio, a higher injection pressure is necessitated
e

due to the larger surface tension of biodiesel . Biodiesel combustion inside cylinder has less
pt

radiative heat transfer due to lees soot formation which can be a cause for NOx emissions
(Sun et al. 2010). Thus, higher surface tension of biodiesel disputes more shearing between
fuel molecules and poor atomization which steers to increase in NOx.
ce

4.3 Effect of fuel viscosity

Ac

Biodiesel has a higher viscosity than petro-diesel. Biodiesel has inferior

atomization and spray resulting in a larger mean liquid droplet diameter and a larger ignition
delay (Hoekman et al. 2012). Anderson et al. (2009) examined NOx as a function of viscosity
and they perceived an increase of NOx with increase in viscosity at low temperatures.
Moreover, the increased penetration length may occasionally cause air and fuel spray mixed
more slowly near the spray tip owing to slower velocities producing more time for NO
formation. Sathish et al. (2012) reported biodiesel has deep fuel spray penetration which will
lead to increase in physical delay and NOx formation. Biodiesel blends lead to delay in start
of combustion due to late injection and results in low thermal NOx formation. The reduction
in fuel viscosity lead to low fuel mass injection rate hence reduces the amount of combustible
air-fuel mixture leading to low NOx emissions. Higher viscosity of biodiesel fuel causes
 injector hole clogging and lubricant contamination. At 30°C, the viscosity of jatropha oil is
about 16 times greater than of conventional diesel. Fuels with high viscosity tend to form
larger droplets on injection which can cause poor combustion and increased NOx emissions.
Viscosity veers to high jet penetration and increasing mass to volume ratio of the fuel
injected. Increased penetration length cause slow mixing of air and fuel near spray tip owing
to less velocity procreate formation of NOx (Xingcai et al. 2008).The vegetable oils which are
high in polyunsaturated fatty acids (e.g. linoleic and linolenic acid) are less viscous, but
bestowed higher NOx emissions.

4.4 Effect of density

Evangelos et al .(2012) obtained lower density of fuel leads to lower NOx

t
Downloaded by ["Queen's University Libraries, Kingston"] at 01:48 23 February 2016

rip
emissions 10-12% by weight of oxygen in fuel conduct to commensurate lower energy
density, postulating greater mass of fuel to be injected in order to achieve the same engine
power output. Higher density of biodiesel increased the total injected mass and fuel mass

c
burnt during the impacting premixed combustion phase. Injection requires a different
optimization to reimburse for biodiesel higher value of density. Volumetrically operating

us
injectors inject greater mass of biodiesel than conventional diesel fuel. Higher density of
jatropha methyl ester, fuel results in poor atomization and low combustion efficiency. It leads
to reduction in engine power. The higher density creates increased injection pressure as well
an
as advanced injection timing. Because, more fuel accumulates inside the combustion chamber
temperature and forming higher rates of prompt NOx (Palash et al.2014). The lower
M
compressibility of and density of biodiesel cause the shorter ignition delay (or) earlier
injection timing that results in, advanced combustion. Higher density of biodiesel causes the
flow properties. So, additives mixed with the biodiesel did not work to improve the
d

performance of the engine. The pure biodiesel has higher density with the lower calorific
value produced higher BSFC. The lower energy density biodiesel sensibly impacts vehicle
e

performance and fuel economy (Shahabuddin et al.2013). Szybist et al. (2003) narrated that
pt

the density of biodiesel causes the rate of pressure rise within the fuel to ramp-up faster and
in turn inject earlier into the cylinder. Kook and Pickett (2012) narrated biodiesel has both
increased density and fuel-borne oxygen at 10.8%wt. Increased density results in increased
ce

cylinder penetration during fuel injection. It should enhance the mixing process, as increased
penetration will spread the mixture over a larger area. So, density increase combined with a
Ac

large proportion of fuel-borne oxygen should see a fairly large increase in the extent of the
premixed combustion. Density of fuel acts as a progenitor for a number of fuel properties
such as heating value and viscosity. Recent diesel engine fuel injection system computes the
fuel by volume. So, the changes the fuel density will affect the mass of fuel injected and NOx
(Alptekin and Canacki 2009). NREL report indicated that blending with a low density fuels
such as kerosene, aromatic diesel (or) Fischer Tropsch diesel is effective at reducing biodiesel
NOx emissions (McCormick et al.2003). Boehman et al. (2003) distinguished lower NOx
emissions with low density paraffinic fuels. The fuel densities do not consequentially affect
the total entrainment and mixing into the spray. For the same injection pressure atomization
of higher density biodiesel is poorer than the lower density biodiesel. The poor atomization
results in large fuel droplet diameter which increases the physical delay time period. This
 larger physical delay increases peak pressure which leads to increase in peak temperature
(Gopinath et al.2010). Thus, the NOx emission increases with the increase in biodiesel
density.

Table 1

Fatty acid profiles of Soybean, Cottonseed, Palm, Jatropha and Sunflower bio fuels (Liu et
al. 2010)

Table 2

Chemical and physical properties of jatropha kernel (Akbar et al.2009)

t
Downloaded by ["Queen's University Libraries, Kingston"] at 01:48 23 February 2016

rip
4.5 Effect of thermal properties

McCrady et al. (2007) found the vapour heat capacity and liquid thermal
conductivity of fuel influences heat transfer between the drop interior and the surface,

c
temperature distribution of gas mixtures surrounding the spray drops and fuel ratio. For

us
biodiesel, liquid thermal conductivity and vapour heat capacity are slightly lower than that of
the diesel. The low temperature combustion (LTC) mode can reduce the thermal contribution
to NOx emissions because of a low average temperature in the engine. LTC mode can reduce
an
NOx and other emissions as preserve a suitable thermal efficiency (Takeda et al. 1996).
Ruslala et al. (2013) stated that the thermal conductivity of biodiesel is about 30% lower than
that of diesel fuel. The predicted values of thermal conductivity for both densities are close
M

and good. The biodiesel fuel droplet heating and evaporation in conditions are relevant to
diesel engines using the effective thermal conductivity. The thermal diffusivity of biodiesel
vapour is much lower than that of diesel. The changes in thermal properties play significant
d

role on atomization and NOx formation rate (Ra et al.2008). Lujaji et al. (2010) conducted the
e

thermo gravimetric (TG) test on fuel samples and suggested a strong relationship between the
thermal characteristics and cetane number (CN) of fuel samples. Thermo gravimetric analysis
pt

is defined as a method of thermal analysis by which changes in chemical and physical

properties are measured as a function of increasing temperature or as a function of time. The
ce

vapour heat capacity of biodiesel is vaguely lower than that of the diesel fuel which effects
the thermal energy balance and temperature distribution of gas mixtures surrounding the
spray drops (Fazal et al.2011). Sun et al. (2010) described that biodiesel combustion inside
Ac

cylinder has less radiative heat transfer owing to less soot formation which is the main source
for the NOx emissions. Thus, the thermal conductivity, vapour heat capacity and thermal
diffusivity are the main origin for the increase in NOx emissions in biodiesel.

4.6 Effect of cetane number

The combustion and ignition quality of any fuel is measured with a dimensionless
parameter called cetane number (CN). Higher cetane number fuels veer to increase power
output, reduce exhaust smoke, combustion noise and exhaust odour and increase cold start
properties. Too low CN steers to engine misfiring, higher air temperature and incomplete
combustion (Totten 2003). Rao et al. (2010) stated that cetane number (CN) of biodiesel is
affected both premixed combustion and the combustion rate, besides affected the amount of
 NOx formation. Cetane number of biodiesel is always more than 47, which is higher than the
petroleum diesel because of its oxygen content which enhances more complete combustion
because some of the fatty acids in the fuel have very high octane number. The higher value of
CN cause operational muddles like incomplete combustion and smoke. Conventionally,
higher CN is equated with shorter ignition delay, lower average combustion temperatures and
decreased residence time less occurrence of knocking, hence less NOx formation. Knothe et
al. (1998) narrated highly saturated fatty compounds have higher CN. The number of CH2
group is also significant .The longer saturated chain and the larger the sizes of the alcohol
moiety in fatty esters have the higher CN. Zheng et al. (2008) distinguished that biodiesel
with a same CN to the diesel produced more NOx emissions than the diesel fuel. Higher
cetane value biodiesel exhibits low NOx emissions than low cetane value biodiesel. Wang et

t
al. (2000) have proposed that higher CN biodiesel veer to increase peak pressure and
Downloaded by ["Queen's University Libraries, Kingston"] at 01:48 23 February 2016

rip
temperature owing to shortened ignition delay which intensifies NOx formation. Furthermore,
Knothe (2005) described non linear relationship between ignition delay period and the CN.
Lower CN fuels are short chain branched and unveils good cold flow properties.

c
Additionally, knothe derived the effect of component structure on CN by using ignition

us
quality tester and affirmed that the CN of fuel increases with saturated fatty acid content.
Indicated higher cetane number (higher CN leading to shorter ignition delay) veers to
increase peak pressure and temperature and augmenting NOx formation. Unsaturated methyl
an
ester leads to lower CN (number of double bond increases). Coconut, palm, Tallow and used
cooking oil have higher cetane number and it is highly saturated. Bello et al. (2012) have
reported that the saturated biodiesel increases the cetane number. The cetane number of
M

rubber seed oil increased after transesterification from 46.3 to 52.56. The cetane number of
cashew seed oil increased after transesterification from 50 to 63 and Egusi mclon oil from 48
to 55. Cetane number tends to decrease with amount of unsaturation of the oil. The effect of
d

transesterification on the fatty acid profile is not very significant although the properties may
e

change as the result of the displacement. The net compositions remain essentially unchanged.
There is no benefit for biodiesel blended with diesel fuel as a fuel in diesel engine as far as
pt

performance indexed based on cetane number is concerned. Highly unsaturated biodiesel

have low cetane number and the converse. Cetane number of biodiesel can be increased by
ce

addition of cetane improvers (or) by structural modification of fuel. Increase in cetane

number from 45 to 50 may be expected to process larger NOx impacts than increase in cetane
number from 50 to 55. Cetane improver additives are infrequent to increase the cetane
Ac

number of fuels that have the CN above 55 and even in this case the additive would have to
add more than 8 CN’s (for a total CN of more than 63) (Song, Zello and Boehman 2004).
Wadumesthrige et al. (2008) derived the atmospheric oxidation of biodiesel augments CN of
fuel due to the formation of hydro peroxides, aldehydes and oligomers of fatty acid methyl
esters. Usta et al. (2005) observed the addition of cetane improvers DTBP and EHN are
efficacious in reducing biodiesel NOx emissions. Thus, the decomposition of nitrate cetane
improver forms NO and NO2 in eloquent quantities respective to the low engine out NOx
emissions from low temperature combustion (LTC).

4.7 Effect of fuel bound oxygen

 The presence of oxygen content in biodiesel properties complete combustion and
reduce the emission of HC, CO, PM and other pollutants. High combustion efficiency tends
to high reaction temperature and NOx formation . Ramadhas et al. (2005) reported the oxygen
content of biodiesel plays the important role in the NOx formation, and it causes to high local
temperature owing to excess hydrocarbon oxidation. The increased oxygen level increases
NOx formation during the combustion. Song et al. (2004) described that both the emdowment
of intake oxygen and the use of oxygenated fuels increase NOx emissions. NOx emission is
sensitive to oxygen content, adiabatic flame temperature and spray characteristics. Hulwan et
al. (2011) have observed the addition ethanol and diethyl ether with jatropha methyl ester
increased the NOx emission subsequently and can be a promising approach for using
biodiesel/ diesel blend conveniently without any modifications in the engine. The oxygen

t
content of biodiesel molecules element an increase in boiling point and reduces the rate of
Downloaded by ["Queen's University Libraries, Kingston"] at 01:48 23 February 2016

rip
droplet evaporation. Despite the NOx formation, the lower oxygen consumption efficiency of
biodiesel causes an increase in availability of oxygen to form NOx. Theodose et al. (1997)
observed that when the oxygen content is increased from 3% to 9% by oxygenated additives

c
results in increasing nitric monoxide emission and reducing the ignition temperature of

us
particulate emissions, smoke intensity. In contrast, Lapuerta et al.(2005) stated the oxygen
content of biodiesel do not cause any increase in NOx formation because diffusion
combustion arises mainly in regions with oxygen-fuel ratio around the stoichiometric one,
an
and it is 2.81 biodiesel and 3.58 for standard diesel fuel. The fuel bound oxygen generates a
permanent dipole moment in the molecule which is stronger hydrogen bending and it increase
molecular affinity of oxygenated fuels. It tends to reduction of free space between molecules
M

and decreasing its compressibility, accordingly increases NOx (Moser et al. 2009). Mueller
et al. (2009) found the fuel bound oxygen influences mixture stoichiometry at the lift-off
length that motives the NOx generation. Yuan et al. (2005) established no correlation between
d

oxygen content of fuel and NOx emissions. Biodiesel produces less soot formation than diesel
e

fuel because of fuel bound oxygen, reduced aromatic content, absence of sulphur and
unsaturated fatty acid contents. The reduced soot formation lessens the radiative heat transfer
pt

at elevated reaction temperature and more NOx generation. Sunilkumar et al. (2012) observed
the presence of oxygen in the fuel indicates complete combustion and absence of oxygen
ce

implies more amount of fuel for combustion which disturbs the stoichiometric air/fuel ratio.
Thus, decreasing fuel bound oxygen content may not be the right approach for reducing the
NOx emissions because subsistence of oxygen not only reduces particulate matter but also
Ac

mutagen city of the soot particles (Sharp, Howell and Jobe 2002).

4.8 Effect of fuel composition

Sara Pinzi et al. (2013) stated that biodiesel refers to methyl (or) ethyl esters derived
from vegetable oils by the transesterification process. Biodiesel transesterifies from vegetable
oil is higher in esters of unsaturated fatty acids and from animal fat is higher in esters of
saturated fatty acids. Saturated fatty acids possess no carbon-carbon double bond and
unsaturated fatty acids possess one or more double bond. A fatty acid with one double bond
is called mono unsaturated fatty acid and fatty acid with two or more double bond is called
poly unsaturated fatty acid. The fatty acids are indicated by XX: Y, where XX signifies the
 number of carbon atoms in the fatty acid chain and Y the number of double bonds. NOx
emissions are found to increase as chain length with exception of C18:0 and the degree of
unsaturation of fatty acid methyl ester increased. Generally biodiesel has the common fatty
esters of C16 and C18. Fatty acids comprise palmitic acid (C16:0), stearic acid (C18:2), oleic
acid (C18:1), linoleic acid (C18:2) and linolenic acid (C18:3) whereas, palmitic and stearic
acids are saturated fatty acids and others are unsaturated fatty acids (Knothe 2009).
McCormick (2011) established that the biodiesel direct effect on NOx emissions. Iodine
number (IV) is a measure of degree of unsaturation of the fatty acid. When the iodine value
of biodiesel increases, NOx emission increases. High iodine number indicates a high degree
of unsaturation. Knothe et al. (2006) selected three fatty acid methyl esters of methyl laurate,
methyl palmitate and methyl oleate for exhaust emissions. NOx emission increased with

t
methyl oleate (about 6%) and decreased with both palmitate(4%) and laurate (5%). NOx
Downloaded by ["Queen's University Libraries, Kingston"] at 01:48 23 February 2016

rip
emissions are reduced (around 15.5-16%) with dodecane and hexadecane, which showed
little chain-length dependence. The unsaturated fatty acid double bond disputes less linear
chains, consequently leaving less space for molecules to squeeze closer simultaneously and

c
reduces compressibility. Ban-Weiss et al. (2007) derived the biodiesel double bonded

us
molecules have higher adiabatic flame temperature which increases NOx emission. Glaude et
al. (2010) reported adiabatic flame temperature of biodiesel is equal to or lower than diesel
fuel.
an
Table 3
M
Average composition of triacylglycerol (Gutierrez and Barron 1995)

Tat et al. (2007) tested the unsaturated soybean biodiesel and noted that
unsaturated biodiesel reduces NOx emission. Pattamaprom (2012) derived performance and
d

emission tests using palm olein and palm stearin (co-products of palm oil refining process)
e

biodiesel fuels and concluded that higher chain length olein produced more NOx than the
short chain length stearin. The position of double bonds and configurations (cis or trans)
pt

influence the physical properties of biodiesel. The unsaturated fatty acids in the cis
configuration and it is converted into trans configuration by isomerisation. The physical
ce

properties of trans configured unsaturated fatty acids are equivalent to fully saturated fatty
acids. Hass et al. (2007) strived to reduce NOx emissions by using reformulated biodiesel and
observed that isomerised biodiesel increased NOx emissions by 2.7%. Besides, they tested
Ac

tranesterified soy polyols (fatty acids containing hydroxyl group) as fuel and initiated a
decrease in NOx emissions. The number of double bonds in unsaturated fatty acid is reduced
by hydrogenation or by blending a suitable amount of saturated methyl ester to the biodiesel.
Chapman et al. (2003) tested the blend of caprylic acid methyl ester (C8:0) and capric acid
methyl ester (C10:0) with B100 and obtained a NOx reduction of 2.8% to the conventional
diesel fuel. They also attempted on hydrogenated fatty acid and found no reduction in NOx.
High degree of saturation and longer chain length of fatty acids owing to increase in cloud
point which causes clogging of fuel filters and fuel lines. Many approaches have been
initiated to reduce the cloud point of biodiesel including: properties of feed stocks; blending
with petro diesel and the use of additives and conducted the emission test with soybean
methyl ester and found the % reduction in NOx e mission which has an unsaturated to
 saturated fatty acid ratio of 5.7 (Smit et al. 2010). The saturated components like methyl
palmitate and methyl stearate could be fraternized with a higher tendency to produce NOx
than unsaturated components present in the biodiesel.

5. Summary of the findings and conclusion

1. Biodiesel has appreciably higher NOx emission than conventional diesel fuel. The
majority of NOx formed in biodiesel will decompose at the low temperatures of exhaust.
But, owing to very low reaction rate at the exhaust temperature, a part of formed NOx
remains in exhaust which leads to higher NOx emission.

2. Various factors are granted to increase biodiesel NOx emissions: advanced injection

t
timing, increased adiabatic flame temperature, decreased spray cone angle, higher
Downloaded by ["Queen's University Libraries, Kingston"] at 01:48 23 February 2016

rip
viscosity and higher oxygen content. The higher bulk modulus of biodiesel leads to
increase in NOx emissions owing to the advanced injection timing.

c
3. Generally, thermal NO is a preeminent mechanism in the combustion process. But,

us
prompt NO contributes quite in biodiesel combustion. Biodiesel combustion is a low
temperature reaction and the change in thermal NOx could not be the vital reason
biodiesel NOx effect.
an
4. Preheating of biodiesel efficaciously decreases viscosity, density and surface tension
which eminently improves injection of biodiesel by contributing to better fuel atomization
at elevated temperatures of the biodiesel.
M

5. High oxygen content in the biodiesel than the diesel fuel, reduce emissions like HC.CO
and PM but increases NOx. The presence of oxygen in biodiesel results in higher heat
d

release throughout the premixed phase combustion which is the main source for increased
e

NOx emissions.
pt

6. Biodiesel has a high cetane number that entails shorter ignition delay and reductions of
NOx emissions are expected. Nevertheless, NOx emission is increased at elevated
combustion temperatures due to the advanced combustion timing and longer residence
ce

period.

7. NOx emissions are correlated with iodine value of fatty acid ester. The fuel composition
Ac

has many effects on bulk modulus of compressibility, adiabatic flame temperature, degree
of saturation and cetane number and changes in these properties play a significant role in
NOx formation.

8. Biodiesel NOx emission could be minimized by optimizing the compression ratio, fuel
injection pressure and fuel injection timing. When biodiesel is used in the CI engine with
antioxidant additives, proportionate amount of NOx is reduced. This is due to the
suppuration of free radical generation from antioxidants.

9. NOx emissions also can be reduced by modification of fuel properties, quality of feed
stocks, engine parameters etc., Additionally, NOx can be reduced by modifying the engine
 setup by promoting catalytic converter, water injection system, Exhaust Gas Recirculation
(EGR) system etc.,

Further studies will be needed to regulate the impact of fuel atomization on biodiesel
NOx and influence of fuel composition on prompt NOx generation. Moreover,
modifications of biodiesel feedstock giving lowest NOx emission are also needed.

References

Xue,J., E. Tony, A. Hansen, A. 2011. ‘‘Effect of biodiesel on engine performance and

emissions,” Renewable and Sustainable Energy Reviews 15: 1098-116.

t
Downloaded by ["Queen's University Libraries, Kingston"] at 01:48 23 February 2016

rip
Bora, D., and D. Baruah .2012.‘‘Assessment of tree seed oil biodiesel. A comparative review
based on biodiesel of a locally available tree seed.” Renewable and Sustainable Energy
Reviews 16: 1616-29.

c
us
Varatharajan, K., and M. Cheralathan. 2012. ‘‘Influence of fuel properties and composition
on NOx emissions from biodiesel powered diesel engines.” Renewable and Sustainable
Energy Reviews 16: 3702-3710.
an
Lin, L., Z. Cunshan, S. Vittayapadung, S. Xiangqian, and D.Mingdong. 2011.
‘‘Opportunities and challenges for biodiesel fuel”. Applied Energy 88: 1020-31.
M

Tat, M., J. Van Garpen and P.Wang. 2007. ‘‘Fuel property effects on injection timing,
ignition timing, and oxides of nitrogen emissions from biodiesel fuelled engines,” ASAE 50
(4): 1123-1128.
d

Zeldovich, Y.B. 1946.‘‘The oxidation of nitrogen in combustion and explosions.” Acta

e

Physicochim 21: 577–628.

pt

Bowman, C. 1975. ‘‘Kinetics of pollutant formation and destruction on combustion.” Prog

Energy Combust Sci 1:33–45.
ce

Fennimore, C. 1975. ‘‘Formation of nitric oxide in premixed hydrocarbon flames. In: 13th
symposium on combustion.” The Combustion Institute 13: 373–80.
Ac

Heywood, J. 1998. ‘‘Internal combustion engines fundamentals. New York: McGraw- Hill
international edition.

Pandey, R., A. Rehman, and R. Sarviya.2012.‘‘Impact of alternative fuel properties on fuel

spray behaviour and atomization.” Renewable and Sustainable Energy Reviews 16: 1762–78.

Garner, S., R.Sivaramakrishnan, and K. Brezinsky. 2009.‘‘The high pressure pyrolysis of

saturated and unsaturated C7 hydrocarbons.” Proc Combust Inst 32: 461-7.

McCormick, R., J.Alvarez, and M. Graboski. 2012. ‘‘Effects of biodiesel blends on vehicle
emissions.US National Renewable Energy Laboratory 14:121-129.
 Zhang, Y., and A. Boehman. 2007. ‘‘Impact of biodiesel on NOx emissions in a common rail
direct injection diesel engine.” Energy Fuel 21:2003–12.

Benajes, J., S. Molina, C. Gonzalez, and R. Donde .2008.‘‘The role of nozzle convergence
in diesel combustion.” Fuel 87: 1849-58.

Monyem, A., J. Van Garpen, and M.Canakci. 2001. ‘‘The effect of timing and oxidation on
emissions from biodiesel-fuelled engines.” Trans ASAE 44: 35–42.

Kegl, B. 2011.‘‘Influence of biodiesel on engine combustion and emission characteristics.”

Applied Energy 88:1803-12.

t
Downloaded by ["Queen's University Libraries, Kingston"] at 01:48 23 February 2016

rip
Szybist, J., Kirby, S., and Boehman, A.2005.‘‘ NOx emissions of alternative diesel fuels: a
comparative analysis of biodiesel and FT diesel.” Energy Fuel 19: 1484–92.

Bittle, J., Knight, B., and Jacobs, T.2009. ‘‘The impact of biodiesel on injection timing and

c
pulse width in a common-rail medium-duty diesel engine. Paper presented at the SAE power

us
train, fuels and lubricants 2009 fall meeting, San Antonio.” SAE : 01-2782.

Musculus, M. 2005.‘‘Measurements of the influence of soot radiation on in cylinder

temperatures and exhaust NOx in a heavy duty diesel engine.” Society of Automotive
an
Engineers : 01-0925.

Sun, J., J.A. Caton, and T.J. Jacobs.2010.‘‘Oxides of nitrogen emissions from biodiesel-
M

fuelled diesel engines.” Progress in Energy and Combustion Science 36: 677–95.

Varuvel, E., N. Mrad, M. Tazerout, and F. Aloui.2012.‘‘Experimental analysis of bio fuel

as an alternative fuel for diesel engines.” Applied Energy 94: 224–31.
d

Allen, C.K., K. Watts, and R. Ackman.1999. ‘‘Predicting the surface tension of biodiesel
e

fuels from their fatty acid ester composition.” Journal of the American Oil Chemistry Society
pt

76: 317–23.

Saqib, M., M.W. Mumtaz, A. Mahmood, and M.I. Abdullah.2012.‘‘Optimized biodiesel

ce

production and environmental assessment of produced biodiesel.” Biotechnology and

Bioprocess Engineering 17: 617–23.
Ac

Varatharajan, K., M. Cheralathan, and R. Velraj.2011. ‘‘Mitigation of NOx emissions from

Jatropha biodiesel fuelled DI diesel engine using antioxidant additives.” Fuel 90: 2721-
2725.

Rajasekar, E., A. Murugesan, R. Subramanian, and N. Nedunchezhian.2010.‘‘ Review of

NOx reduction technologies in CI engines fuelled with oxygenated biomass fuels.”
Renewable and Sustainable Energy Reviews 14: 2113–21.

John, A., B. Pedro, and V. Adriana Patricia.2010. ‘‘Evaluation of nitrogen oxide emissions
and smoke opacity in a HSDI diesel engine fuelled with palm oil biodiesel.” Revista Faculted
De Ingenieria Universidad De Antioquia 51: 69-78.
 Boehman ,A., D. Morris, J. Szybist and E. Esen.2006. ‘‘The impact of the bulk modulus of
diesel fuels on fuel injection timing.” Fuel 18: 1877-1882.

Yamane, K., A. Ueta, Y. Shimamoto.2001.‘‘Influence of physical and chemical properties of

biodiesel fuels on injection, combustion and exhaust emission characteristics in a direct
injection compression ignition engine.” International Journal of Engine research 2(4): 249-
61.

Tat, E., H. Van Garpen, S. Soylu, M. Canakci, A. Monyem, and S. Wormley.2000. ‘‘The
speed of sound and isentropic bulk modulus of biodiesel at 21 ◦C from atmospheric pressure
to 35 MPa.” American Oil Chemical Society 77: 285–9.

t
Tat, E., and H. Van Garpen.2002.‘‘Physical properties and composition detection of
Downloaded by ["Queen's University Libraries, Kingston"] at 01:48 23 February 2016

rip
Biodiesel –diesel fuel Blends.” American Society of Automotive Engineers 026084:28-31.

Van Garpen, J., and M. Tat. 2003. ‘‘Measurement of biodiesel speed of sound and its impact
on injection timing.” National Renewable Energy Laboratory SR-510-31462.

c
us
Tat, E., and H. Van Garpen.2004. ‘‘Fuel property effects on injection timing, ignition timing
and oxides of nitrogen emissions from Biodiesel-fuelled engines.”American Society of
Automotive Engineers pp: 046081.
an
Kegl, B.2011. ‘‘Numerical analysis of injection characteristics using biodiesel fuel.” Fuel 85:
pp. 2377–87.
M

Gumusa, M., C. Sayina, and M. Canakci.2012.‘‘ The impact of fuel injection pressure on the
exhaust emissions of a direct injection diesel engine fuelled with biodiesel–diesel fuel
blends.” Fuel 95:pp. 486–494.
d

Yuan, W., and A. Hansen. 2009.‘‘Computational investigation of the effect of biodiesel fuel
e

properties on diesel engine NOx emissions.” International Journal of Agricultural Biological

Engineering 2: pp. 41- 46.
pt

Graboski, MS., R.L. McCormick. 1998. ‘‘Combustion of fat and vegetable oil derived fuels
ce

in diesel engines.” Progress in energy and combustion science 24:125-64.

Gopinath, A., S. Puhan, and G. Nagarajan.2010. ‘‘Numerical modelling of oxides of

nitrogen based on density of biodiesel fuels.” International Journal of Energy and
Ac

Environmental 1:313–20.

Rao, P.V. 2011. ‘‘Experimental investigation on the influence of properties of jatropha

biodiesel on performance, combustion and emission characteristics of a DI-CI engine.” World
academy of Science, Engineering and Technology 03; 23-29.

Hoekman, SK., A. Broch, C. Robbins, E. Ceniceros, and M. Natarajan.2012.‘‘ Review of

biodiesel composition, properties and specifications.” Renewable and Sustainable Energy
Reviews 16:143-169.

Nettles-Anderson, S., and D. Olsen.2009. “Survey of straight vegetable oil composition

impact on combustion properties,” Society of Automotive Engineers 01: 0487, 2009.
 Sathish, S., S.K. Sai Narenthiran, S. Srinivasan, A. Arul Authithiyan, and E. Britto
sebestiraj.2014. ‘‘An experimental study of 3-pentanone and hexane on NOx emission
derived CI engine from a soy biodiesel.” Journal of Energy Research and Environmental
Technology 1-5.

Xingcai, Lu., M.A. Junjun, J. Libin, Z. Huang.2008.‘‘Simultaneous reduction of NOx

emission and smoke opacity of biodiesel-fuelled engines by port injection of ethanol.” Fuel
87:1289-96.

Evangelos, G., L. Giakoumis, D. Constantine, and R. Rakopoulos.2012.‘‘Exhaust emissions

of diesel engines operating under transient conditions with biodiesel fuel blends.” Progress in

t
Energy and Combustion Science 38(5): pp. 691–715.
Downloaded by ["Queen's University Libraries, Kingston"] at 01:48 23 February 2016

rip
Palash, SM.,M.A. Kalam, H.H. Masjuki, M.I. Arbab, B.M. Masum and A. Sanjid.2014.
‘‘Impacts of NOx reducing antioxidant additive on performance and emissions of a multi
cylinder diesel engine fuelled with jatropha biodiesel blends.” Energy Conversion and

c
Management 77:577-585.

us
Shahabuddin, M., A.M. Liaquat, H.H. Masjuki, M.A. Kalam, and M. Mofijur. 2013.
‘‘Ignition delay, combustion and emission characteristics of diesel engine fuelled with
biodiesel.” Renewable Energy and Sustainable Energy Reviews 21:623-632.
an
Szybist, JP., and A.L. Boehman.2003. ‘‘Behaviour of a diesel injection system with biodiesel
fuel.” Society of Automotive Engineers 01:1035-1039.
M

lptekin, E., Canakci, M.2009. “Determination of the density and the viscosities of biodiesel-
diesel fuel blends.” Renewable Energy 33: pp. 2623–30.
d

McCormick, R., J. Alvarez, and Graboski, M. 2003. “NOx Solutions for biodiesel.” National
e

Renewable Energy Laboratory Technical Report No. NREL/ SR-510-31465.

pt

Boehman, A., M. Alam, J. Song, R. Acharya, J. Szybist, and V. Zello.2003. “Fuel

formulation effects on diesel fuel injection, combustion, emissions and emission control.”
ce

Proceedings of diesel engine emissions reduction conference. pp. 1-9.

Kook, S., and L. Pickett. 2012. “Liquid length and vapour penetration of conventional,
Fischer–Tropsch, coal-derived, and surrogate fuel sprays at high-temperature and high-
Ac

pressure ambient conditions.” Fuel 93: pp. 539–548.

McCrady, J., V. Stringer, A. Hansen, and C. Lee. 2007. “Computational analysis of biodiesel
combustion in a low-temperature combustion engine using well defined fuel properties,” SAE
Int. J. Engines 116: pp. 434–43.

Takeda, Y., K. Nakagome, and N. Keiichi N.1996. “Emission characteristics of premixed

diesel combustion with extremely early staged lean fuel injection.” Society of Automotive
Engineers : paper 9611163.
 Kolodnytska, R., A.Q. Monsour, and S.S. Sergei.2013.“Biodiesel fuel droplets: Transport
and thermodynamic properties.” 25th European conference on liquid atomization and spray
systems [ILASS]: pp 1-7.

Ra, Y., and R. Reitz .2008.“Effects of fuel physical properties on diesel engine combustion
965 using diesel and bio-diesel fuels.”Society of Automotive Engineers .Paper No.01-1379.

Lujaji, F., A. Bereckzy, C.S. Novak, and Mbarawa.2010. “Cetane number and thermal
properties of croton oil, biodiesel, 1- butanol and diesel blends.” World Congress on
Engineering pp:2078-0966.

Totten, G.2003. “Fuels and lubricants handbook: technology, properties, performance, and

t
testing.”ASTM 4 :pp.414-419.
Downloaded by ["Queen's University Libraries, Kingston"] at 01:48 23 February 2016

rip
Rao, PV., S. Clarke, R. Brown, and W. Kaishen.2010. “Influence of Iodine value on
combustion and NOx emission characteristics of a DI diesel engine.” The 40th Australian
Chemical Engineering Conference, Engineers Australia 5:19-145.

c
us
Knothe, G., K. Bagby, and Ryan.1998.“Precombustion of fatty acids and esters of biodiesel.
A possible explanation for differing cetane numbers.” Journal of the American Oil Chemical
Society 75: 1007-1013.
an
Zheng, M., M. Mulenga, G. Reader, M. Wang , D. Ting, and J. Tjong.2008. “Biodiesel
engine performance and emissions in low temperature Combustion.” Fuel 87: pp. 714–22,
2008.
M

Wang, W., D. Lyons, W. Clark, and N. Gautam.2000.“Emissions from nine heavy trucks
fuelled by diesel and biodiesel blend without engine modification.” Environmental Science
d

and Technology 34: pp. 933–9, 2000.

e

Knothe, G.2005. “ Dependence of biodiesel fuel properties on the structure of fatty acid
alkyl esters.” Fuel Processing Technology 86: pp. 1059–70.
pt

Knothe, G., A. Matheaus, and T. Ryan.2003. “Cetane numbers of branched and straight-
ce

chain fatty esters determined in an ignition quality tester.” Fuel 82: pp.971–975.

Bello, EJ., F. Out, and A. Osasona.2012.“ Cetane number of three vegetable oils, their
biodiesels and blends with diesel fuel.” Journal of Petroleum Technology and Alternative
Ac

Fuels 3(5); pp. 52-57.

Wadumesthrige, W., J. Smith, J.Wilson, and S. Salley.2008. “Investigation of the parameters

affecting the cetane number of biodiesel.” Journal of the American Oil Chemical Society 85:
pp. 1073–83.

Usta, N.2005. “An experimental study on performance and exhaust emissions of a diesel
engine fuelled with tobacco seed oil methyl ester.” Energy Conservation and Management
46: pp. 2373–86.
`
 Ramadhas A.S., C. Muraleedharan, and S. Jayaraj.2005. “Performance and seed emission
evaluation of a diesel engine fuelled with methyl esters of rubber oil.” Renewable Energy
30:1789-1800.

Song, J., V.Zello and A. Boehman. 2004. “Comparison of the impact of intake oxygen
enrichment and fuel oxygenation on diesel combustion and emissions.” Energy Fuel 18: pp.
1282–90. 2004.

Hulwan, D., and S. Joshi.2011. “Performance, emission and combustion characteristic of a

multi cylinder DI diesel engine running on diesel–ethanol– biodiesel blends of high ethanol
content.” Applied Energy 88: pp.5042–55.

t
Theodose Constantine. 1997. “Experimental investigation to specify the effect of oxygenated
Downloaded by ["Queen's University Libraries, Kingston"] at 01:48 23 February 2016

rip
additive content and type on DI diesel engine performance and emissions.” Society of
Automotive Engineers 4: pp 01-0097.

Lapuerta, M., O. Ormas, R. Ballesteros, J. Rodriguez, and Fernandez. 2005. “Diesel

c
emissions from bio fuels derived from Spanish potential vegetable oils.” Fuel 84: pp 773-

us
780.

Moser, B., A.Williams, M. Haas and R. McCormick.2009.“ Exhaust emissions and fuel
properties of partially hydrogenated soybean oil methyl esters blended with ultra low sulphur
an
diesel fuel.” Fuel Processing Technology 90: 1122–28.

Mueller, C., A.Boehman, and G.Martin.2009. “An experimental investigation of the origin
M

of increased NOx emissions when fuelling a heavy-duty compression-ignition engine with soy
biodiesel.”SAE International Journal of Fuels and Lubricants 2: pp. 789-816.
d

Yuan, W., C. Hansen, M. Tat, J. Van Garpen, and Z. Tan.2005. “Spray, Ignition, and
Combustion Modelling of Biodiesel Fuels for Investigating NOx emissions.” American
e

Society of Automotive Engineers 48 (3): pp. 35-42, 2005

pt

Sunil Kumar, R., A. Chaube, and Shashi Kumar Jain.2012. “Experimental evaluation of CI
engine performance using diesel blended with jatropha biodiesel. International Journal of
ce

Energy and Environment 3: pp.471-484.

Sharp, C., S.Howell, and J. Jobe.2002. “The effect of biodiesel fuels on transient emissions
from modern diesel engines, part 1 regulated emissions and performance.” Society of
Ac

Automotive Engineers 45: Paper No. 2002-01-1967.

Sara, P., P. Rounce, J.M. Herreros, A. Tsolako, and M.P.Dorado.2013.“The effect of

biodiesel fatty acids composition on combustion and diesel engine exhaust emissions.” Fuel
104: pp 170-182.

Knothe, G.2009. “Improving biodiesel fuel properties by modifying fatty ester Composition.”
Energy Environmental Science 2: pp. 759–66.

McCormick, R., M. Graboski, T. Alleman, A. Herring, and S.Tyson.2011.“Impact of

biodiesel source material and chemical structure on emissions of criteria pollutants from a
heavy-duty engine.” Environmental Science Technology 35: pp. 1742–47.
 Knothe, G., C. Sharp, and T. Ryan. 2006.“Exhaust emissions of biodiesel, petro diesel, neat
methyl esters, and alkanes in a new technology engine.” Energy Fuel 20: 403–408.

Ban-Weiss, G., Y. Chen, B. Buchholz and R. Dibble.2007. “A Numerical Investigation into

the Anomalous Slight NOx Increase When Burning Biodiesel; A New (Old) Theory.” Fuel
Processing Technology 88: pp. 659-67.

Glaude, P., R.Fournet, R. Bounaceur, and M. Moliere.2010.“Adiabatic flame temperature

from bio fuels and fossil fuels and derived effect on NOx emissions.” Fuel Processing
Technology 91: pp. 229–35.

t
Tat, M., S.Paul, and J.Garpen.2007. “Exhaust emissions from an engine fuelled with
Downloaded by ["Queen's University Libraries, Kingston"] at 01:48 23 February 2016

rip
biodiesel from high-oleic soybeans.” Journal of the American Oil Chemical Society 84: pp.
865–869.

Pattamaproma, C.,W. Pakdeeb and S. Ngamjaroena . 2012. “Storage degradation of palm-

c
derived biodiesels: its effects on chemical properties and engine performance.” Renewable

us
Energy 37(1): pp. 412–8.

Hess, A., M. Hass, and T. Foglia. 2007. “Attempts to reduce NOx exhaust emissions by
using reformulated biodiesel.” Fuel Processing Technology 88: pp. 693–699.
an
Chapman, E., M. Hile, M. Pague, J. Song, and A.Boehman.2003.“ Eliminating the NOx
emissions increase associated with biodiesel.” American Chemical Society Division of Fuel
M

Chemistry 48: pp. 639–40.

Smit, P., Y. Ngothai, D. Nguyen, and B. Neill .2010. “Improving the low temperature
d

properties of biodiesel: methods and consequences.” Renewable Energy 35: pp. 1145–51.
e

Liu, HP., S. Strank, M.Werst, R. Hebner, and J. Osara. 2010.“Combustion emissions

modelling and testing of neat biodiesel fuels.” Proceedings of the ASME International
pt

Conference on Energy Sustainability 12; pp 17-22.

ce

Akbar, E., Z. Yaakob, S.K. Kamarudin, M. Ismail and J. Salimon.2009. “Characteristic and
composition of Jatropha curcus oil seed from Malaysia and its potential as Biodiesel
Feedstock.” European journal of Scientific Research 29(3). pp 396-403.
Ac

Gutierrez, VR., and Barron.1995. “Method for analysis of triacylglycerols.” Journal of

Chromatography Biomedical Application 671:133-168.

Lee, C.S., S.W. Park and S.I. Kwon .2005. “An experimental study on the atomization and
combustion characteristics of biodiesel blended fuels”. Energy Fuel 19: 2201-2208.

Gopinath, A., P. Sukumar, and G. Nagarajan.2010. “Numerical modelling of oxides of

nitrogen based on density of biodiesel fuels.” International journal of energy and
environment 1(2): 313-320.
 Fazal, M., A. Haseeb and H. Masjuki .2011. “Biodiesel feasibility study, an evaluation of
material compatibility; performance; emission and engine durability.” Renewable and
sustainable energy reviews 15:1314-21.

t
Downloaded by ["Queen's University Libraries, Kingston"] at 01:48 23 February 2016

c rip
us
an
M
e d
pt
ce
Ac
 Table 1

Fatty acid profiles of Soybean, Cottonseed, Palm, Jatropha and Sunflower bio fuels

Fatty acid Structure Soybean Cottonseed Palm Jatropha Sunflower

Lauric C12:0 - - 1.0 - -
C13H26O2
Myristic C14:0 0.2 0.8 2.1 0.1 -
C15H30O2
Palmitic C16:0 10.2 22.9 44.3 14.2 -
C17H34O2
Margaric C17:0 - - - - -
C18H36O2
Stearic C18:0 4.6 3.1 2.2 7.0 -

t
C19H38O2
Downloaded by ["Queen's University Libraries, Kingston"] at 01:48 23 February 2016

rip
Oleic C18:1 22.2 18.5 44.4 44.7 -
C19H36O2
Linoleic C18:2 54.6 54.2 5.2 32.8 -
C19H34O2

c
Linolenic C18:3 8.2 0.5 0.2 0.2 -
C19H32O2

us
Arachidic C20:0 - - - 0.2 0.3
C21H42O2
Gadoleic C20:1 - - - - -
C21H40O2
an
Behenic C22:0 - - - - -
C23H46O2
Lignoceric C24:0 - - - - -
C25H50O2
M

Table 2
d

Chemical and physical properties of jatropha kernel

e

Parameter Value
pt

%FFA as oleic acid 2.23±0.02

Iodine Value 103.62±0.07
ce

Peroxide Value 1.93±0.012

Saponification value 193.55±0.61
Density@20°C(g/ml) 0.9031
Ac

Percent oil content (kernel) 63.16±0.35

Viscosity at room temperature 42.88
Physical state at room temperature Liquid
Values are mean± standard deviation of triplicate determinations
 Table 3

Average composition of triacylglycerol

Triacylglycerol Relative composition (%)

OOL 22.99
OLL 17.91
MPP+000 16.69
POL 14.99
POO 9.74
PLL+MOL 7.11
Nd 3.63

t
SOO 2.54
Downloaded by ["Queen's University Libraries, Kingston"] at 01:48 23 February 2016

rip
PLP+MOP 1.89
POP 0.92
POS 0.63

c
MM 0.50
CC 0.40

us
PP an 0.35

Prominent polyunsaturated triglyceride = OOL, OLL, POL, PLL+ MOL, SOO

Monounsaturated triglyceride = MPP+ OOO+ POO, PLP+MOP, POP

M
e d
pt
ce
Ac