Renewable and Sustainable Energy Reviews 52 (2015) 1566–1579

Contents lists available at ScienceDirect

Renewable and Sustainable Energy Reviews

journal homepage: www.elsevier.com/locate/rser

Study on stability, fuel properties, engine combustion, performance

and emission characteristics of biofuel emulsion
S.S. Reham a,n, H.H. Masjuki a, M.A. Kalam a,n, I. Shancita a, I.M. Rizwanul Fattah b, A.M. Ruhul a
a
Centre for Energy Sciences, Department of Mechanical Engineering, Faculty of Engineering, University of Malaya, 50603 Kuala Lumpur, Malaysia
b
School of Mechanical and Manufacturing Engineering, University of New South Wales, Kensington, 2033 NSW Australia

art ic l e i nf o a b s t r a c t

Article history: This study reviewed papers related to biofuel emulsion, principally assessing the use of biofuel emulsion.
Received 4 March 2015 The discussion is focused mainly on three active areas of emulsified biofuel, namely, exploration of
Received in revised form various factors affecting the preparation of stable emulsion and its fuel properties, investigation of the
4 June 2015
effect of water concentration on physicochemical properties of fuel, and observation of the improvement
Accepted 4 August 2015
and degradation of combustion, performance, and emission characteristics and the possible methods to
Available online 29 August 2015
enhance these characteristics.
Keywords: & 2015 Elsevier Ltd. All rights reserved.
Biofuel
Emulsion
Stability
Ignition delay
Emission
Performance
Combustion

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1567
2. Material and methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1567
3. Components and its preparation of emulsified biofuel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1568
3.1. Surfactant/emulsifier . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1568
3.2. Hydrophilic
lipophilic balance (HLB) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1568
3.3. Preparation of emulsified fuel. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1568
4. Stability of biofuel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1568
4.1. Stability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1568
4.1.1. Classes of stability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1568
4.1.2. Stability test method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1569
4.1.3. Factors affecting the stability of biofuel emulsion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1569
4.2. Comparative analysis physicochemical properties of tested biofuels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1571
4.2.1. Density . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1572
4.2.2. Viscosity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1572
4.2.3. Heating value . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1572
5. Combustion, performance and emission studies of emulsified biofuels . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1573
5.1. Combustion analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1573
5.2. Performance analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1573
5.3. Emission analysis. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1574
5.3.1. Hydro carbon (HC) emission . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1574
5.3.2. CO and CO2 emission. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1575

Abbreviations: BCO, Bio crude oil; BP, Brake power; BSEC, Brake specific energy consumption; BSFC, Brake specific fuel consumption; BTE, Brake thermal efficiency; CMC,
Critical micelle concentration; CNT, carbon nano tube; CO, carbon monoxide; CO2, Carbon-di-oxide; HC, Hydro-carbon; HLB, Hydrophilic-lipophilic balance; HRR, Heat
release rate; ID, Ignition Delay; JB, Jathropa biodiesel; JME, Jatropha Methyl Ester; NOx, Nitrogen oxides; O/W, Oil in water; O/W/O, Oil in water in oil; PAH, Polyaromatic
hydrocarbons; PM, Particulate matter; POME, Palm oil methyl ester; THC, total hydrocarbon; TP, Thevetia Peruviana; W/O, Water in oil
n
Corresponding authors. Tel.: þ 60 3 7967 4448; fax: þ 60 3 7967 5317.
E-mail addresses: syeda.reham.shahed@gmail.com (S.S. Reham), masjuki@um.edu.my (H.H. Masjuki), kalam@um.edu.my (M.A. Kalam),
rizwanul.buet@gmail.com (I.M. Rizwanul Fattah).

http://dx.doi.org/10.1016/j.rser.2015.08.013
1364-0321/& 2015 Elsevier Ltd. All rights reserved.
 S.S. Reham et al. / Renewable and Sustainable Energy Reviews 52 (2015) 1566–1579 1567

5.3.3. NOx emission . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1576

5.3.4. Smoke opacity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1576
5.4. Other biofuel emulsions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1576
6. Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1576
7. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1576
8. Recommendations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1577
Acknowledgement. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1577
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1577

emulsified fuel exhibits poor performance, it has a very significant

1. Introduction
The most popular fuels in today’s world are diesel, gasoline,
and natural gas. Each has their merits and demerits depending on
their usage as fuel. However, the limited availability of these fuels
restricts their use in the far future. Burning of fossil fuels in
vehicles results in serious environmental changes, which include
an increase in global surface temperature (global warming),
change in rainfall patterns, and rise in frequency of adverse
weather events. Moreover, stern regulations to control vehicle
emission are in place in many parts of the world. Emissions from
fossil fuels may be controlled with external devices and chemicals,
but only to a certain extent. To mitigate this problem, substantial
effort is being conducted globally to explore renewable energy
sources that can replace fossil fuels. The use of biofuels, particu-
larly biodiesel, has become popular among researchers. Biofuels
are considered an economically feasible option as alternate fuel
because of their improved emission characteristics. Although
burning of biodiesel results in reduced emissions of carbon
monoxide (CO), total hydrocarbon (THC), particulate matter
(PM), and polyaromatic hydrocarbons (PAH), the emission of
nitrogen oxides (NOx) is high [1–5]. Fuel emulsification is con-
sidered one of the techniques of introducing water to the combus-
tion chamber to reduce the emissions of NOx, smoke, and
particulate matter (PM) [6–15].
Emulsified biofuel emits much lower HC, CO, CO2, and NOx
compared with non-emulsified diesel and biodiesel [6,11,16–24].
Prakash et al. [25] found 35% lower HC emission in emulsified JME
compared with that in JME alone. Some studies found higher CO
emission for emulsified biodiesel. Qi et al. [26] found that
emulsified fuel emits larger CO than biodiesel at low and medium
engine loads, but the CO level is identical at high load. The
emission may vary with the concentration of water addition.
Raheman et al. [27] found reduced CO2 emission at higher loads
caused by improved combustion. Animal fats are used as fuels in
several studies [28–32], and they are becoming a good alternative
fuel in diesel engine [30,33,34]. The properties of animal fats
resemble those of diesel, but poor atomization limits their use.
Thus, emulsified animal fats are used for enhanced atomization
[11,29,35,36]. Although the emission and combustion character-
istics are favorable for emulsified biodiesel, the use of emulsion of
biofuel is still restricted because of its stability and performance in
engine.
Several consecutive and parallel steps must be completed
before the complete unstable mixture is formed [37–41]. Aggrega-
tion and flocculation occur in the early stage of de-emulsification,
and single droplets are formed by coalescence. Micro emulsions
are thermodynamically stable. To stabilize the macro emulsion,
dispersed phase should be prevented from being coalesced using
an emulsifier [42]. Brake-specific fuel consumption is increased
and brake power (BP) and torque decrease in the case of emulsi-
fied fuel [24,25,43–46]. High water content results in high BSFC as
the lower heating value of emulsified fuel is reduced [7]. Although
emission characteristic and combustion quality because of micro-
explosion. Studies showed that the ignition delay and micro-
explosion phenomena are strongly related to the improvement
of the combustion efficiency in the case of emulsified fuel
[13,40,47].
Numerous studies on biofuel emulsion have been conducted
[23,25,48–51], and a few review articles have also been published on
the emulsion of diesel and biodiesel [40,52–54]. Potential areas of
emulsified fuel, such as combustion, performance, emission, and
micro-explosion phenomena fuel, have been investigated. However,
detailed investigations on stability as a prime aspect in emulsion are
necessary. The fuel property of emulsified biofuel is different from
those of diesel and biodiesel. This area also needs to be analyzed to
investigate the limitations and advantages of emulsified biodiesel
application. Moreover, analysis of different type of emulsions and
their effect on fuel properties, performance, and emission character-
istics is also important for the effective and commercial use of
emulsified biofuel. These analyses are essential to justify the use of
emulsified biofuel as a replacement of fossil fuel.
Compared with other review papers, this paper primarily
focused on the stability of emulsified biofuel and different factors
affecting it, as well as the analysis of fuel property of different base
fuel emulsions and their combustion, performance, and emission.
Given that the addition of water changes the fuel properties, the
concentration of water is an important factor to be considered.
This review paper investigated the contribution of the water
concentration in emulsion preparation, fuel property, combustion,
performance, and emission. Unlike other review papers, the
current paper reviews emulsified biofuel alone without discussing
diesel fuel emulsion. This paper also suggests potential research
areas to mitigate the limitations of using emulsified biodiesel.
2. Material and methods
This review paper discusses different aspects of biofuel emul-
sion starting from a brief discussion of the constituents of emul-
sion to its performance and emission. The reader of this review
paper needs basic knowledge in emulsion, combustion of fuels and
also in diesel engine. This review paper will provide a great deal of
information on emulsified biofuel and its benefits/ shortcomings
on using compared to biodiesel and diesel fuel. This section
provides general knowledge on emulsified fuel, its components,
and preparation details for new readers. This section is summar-
ized and diverse with suitable citations for readers who want
further information about the synthesis of emulsion. The stability
of the prepared emulsified fuel is studied from different feedstock
and different types of emulsion. The fuel properties of emulsified
fuel are then analyzed. A comparative analysis of biofuel from
different feedstock and different types of emulsion has been
considered. To determine the variation in properties with the
addition of water, results are plotted into a single graph for
comparative analysis. Combustion, performance, and emission
1568 S.S. Reham et al. / Renewable and Sustainable Energy Reviews 52 (2015) 1566–1579
Table 1
List of paper cited for the discussed topic.
Topic
Components of emulsion
Preparation of emulsified biofuel
Stability and its classification and test method
Factors affecting the stability of biofuel emulsion
Comparative analysis physicochemical properties of tested biofuels
Combustion, performance and emission studies of emulsified biofuels
Other biofuel emulsion
analyses are conducted with emulsified biofuel from different
feedstock and types of emulsion. Studies using non-conventional
methods of preparing the emulsion are also discussed. Finally,
potential works and research areas have been highlighted to make
emulsified biofuel more acceptable and commercially feasible.
Table 1 lists the papers selected for different topics in this paper.
3. Components and its preparation of emulsified biofuel
An emulsion is a mixture of two or more immiscible liquids
[40,42]. In the mixture, one of the liquids exists in dispersed
droplets and the other is in continuous phase. Dispersed droplets
throughout the mixture are referred to as internal phase, and the
other one is termed as external phase [40,44,55]. Emulsified fuels
are emulsions composed of water and a combustible liquid (i.e.,
fuel), in which water is in the form of dispersed droplets [56]. As
oil and water are inherently immiscible with each other, a
surfactant/emulsifier is used to prepare emulsion [10,57].
3.1. Surfactant/emulsifier
A surfactant molecule has two parts: one has affinity for water
and the other has affinity for oil. The emulsifying agent or
surfactant forms a thin interfacial film between the two liquids
to decrease water surface tension and minimize the contact,
coalescence, and aggregation of the internal dispersed phase
[59–61]. Surfactants work spontaneously and aggregate in water
to form well-defined structures called association colloids [42].
With the increase in surfactant concentration, surface tension
decreases strongly until it reaches the critical micelle concentra-
tion (CMC). Above this concentration, surface tension remains
almost constant, and the capacity to solubilize hydrophobic sub-
stances also changes. Below CMC, the hydrophobic substances
poorly dissolve, and this phenomenon can be explained by
micelles. Micelles are the simplest structures of spherical or
cylindrical form, formed by surfactant molecules [42,62]. Below
the CMC, surfactants form monomers and a few micelles. With the
increase in the surfactant concentration, the monomer also
increases. However, this scenario changes above the CMC level.
The concentration of monomers remains constant and, new
micelles are formed with the increase in surfactant. The number
of surfactant in micelles is not constant but varies considerably,
thereby creating significant polydispersity. By reducing the hydro-
carbon chain length of the surfactant, the residence time in the
micelle can be changed [42].
3.2. Hydrophilic
lipophilic balance (HLB)
The HLB of a surfactant is a measure of the degree to which it is
hydrophilic or lipophilic, and it is determined by calculating values
for the different regions of the molecule. Surfactants are classified
according to their HLB value, which affects their usage. An optimal
value of HLB is necessary for the stabilization of emulsion [63]. In
Reference
[7,10,13,21,39,40,42,44,48,54–57,59–67]
[7,13,26,41,42,68–70]
[39,40,55,65,71,72,78-80]
[13,24,26,27,29,30,39,40,50,51,61,67,68,79,81,82,88–97,109–111]
[7,13,24,26,27,29,47,51,69,79,83,89,97–99]
[6,7,12,13,16,19,22,24–30,40,43–46,47,49–51,69,74,79,89,97–106]
[107,108]
general, surfactant molecules with low HLB, such as sorbitan ester,
polyglycerol polyricinoleate, and soy lecithin, are used for water in oil
(W/O) emulsions [21,39,64–66]. Koc et al. [7] used an anionic
surfactant (dioctyl sodium sulfosuccinate) with 98% purity and 10.2
HLB. The selection of such an anionic surfactant is for HLB balance
and can be used without a co-surfactant [7]. Low HLB values of 4–6
are used to produce W/O emulsion, [13,40,48,54,55,67], and higher
HLB values of 8–18 are used for oil in water (O/W) emulsions [13,48].
3.3. Preparation of emulsified fuel
Emulsified biodiesel can be two-phase (W/O) and three-phase
emulsion (oil in water in oil (O/W/O)). To produce water in biodiesel
emulsion, the base oil is mixed with lipophilic surfactant, added with
water, and evenly stirred via an electromagnetic stirring machine [13].
If the surfactant is hydrophilic, it is mixed with water instead of base
fuel. The mixture can be prepared using mechanical, electronic,
magnetic, or ultrasonic forces [7,41]. Micro emulsions are formed
instantaneously when all components are combined in required
proportions and usually do not need strong stirring or agitation.
[26,68]. Volume fraction of surfactant is generally significant in micro
emulsion [42]. Surfactants form semi-flexible elastic films at the
interface, and the interfacial tension of micro emulsions is very small
[42]. Generally, the three-phase emulsion is prepared using two-stage
emulsification method [69,70]. First, the O/W emulsion is prepared,
and an emulsifying and homogenizing machine is then used to stir the
biodiesel/surfactant mixture and simultaneously feed the O/W emul-
sion at a certain rate [69].
4. Stability of biofuel
4.1. Stability
Stability of emulsified fuel is one of the prime concerns to make
it commercially usable. Engine failure may occur if emulsified fuel
is destabilized during storage or engine operation. Durability of
this miscible state is a challenging issue. The destabilization of
emulsion depends on temperature, amount of surfactant, viscosity,
specific gravity, and water content [39,40,55,71,72].
4.1.1. Classes of stability
Water can co-exist with oil in four different states. Depending on
these states, the characteristics of the emulsion also vary. The four
states are stable, mesostable, unstable, and entrained water [78].
Some emulsions are highly stable and can be stored for several
months. The viscosity and elasticity of such emulsions increase over
time to at least three orders of magnitude higher than those of
starting oil. Mesostable emulsions possess the properties between
the stable and unstable emulsions. These emulsions are suspected to
have less sufficient stabilizing materials than destabilizing materials.
These emulsions may degrade to form layers of oil and stable
emulsions [78]. Unstable emulsion decomposes to oil and water
rapidly after mixing within a few hours. The viscosity of unstable
 S.S. Reham et al. / Renewable and Sustainable Energy Reviews 52 (2015) 1566–1579
emulsion is less than around 20 times greater than that of starting oil
[78]. Thus, viscosity may become an indicator of emulsion stability.
4.1.2. Stability test method
Stability test method: Stability can be measured in two ways: (1)
gravitational and (2) centrifugal stability tests. Gravitational stability
test is conducted by bottle test method [39,65]. The sample is kept in a
closed bottle in a fixed temperature region. At regular time intervals,
the phase separation of the sample is monitored visually [39]. The
least separated sample is considered more stable. The second method
is the centrifugal stability test [79,80]. Lin et al. [79] observed the
stability of emulsified biodiesel using centrifugal stability test. The fuel
samples were centrifuged at 3000 rpm for 5 min, and the test tubes
were kept motionless to observe the volume changes of the emulsion
layer in their study. The least separated sample is accepted to have
better stability. The centrifugal test is more suitable than the gravita-
tional test method because the former is relatively simple and can be
completed within a shorter time period [80].
4.1.3. Factors affecting the stability of biofuel emulsion
Stability of emulsion is influenced by many factors. The primary
factors are as follows: (1) type of emulsifier use, which depends on
base fuel; (2) concentration of emulsifier; (3) HLB value of emulsifier;
(4) concentration of water; and (5) type of emulsion prepared. The
concentration of water is the most significant factor and should be
considered carefully during preparation because it can change the fuel
properties of emulsified biofuel. To enhance the stability of the
emulsion, co-surfactants and additives are also used by many
researchers [26,81]. A co-surfactant is used to improve the migration
of surfactant at O/W emulsion for better stabilization [26]. The
following sub-sections discuss different factors that play important
roles in the stability period of the emulsion.
4.1.3.1. Effect of HLB values on emulsion stability. A wide range of
HLB values can be used to make a biofuel emulsion. Among them,
the optimal HLB value that gives the highest stability needs to be
selected, which depends on the type of emulsion prepared. Lin
et al. [79] found that the emulsion with HLB 13 results in the
highest stability when using Span 80 and Tween 80 together. The
author explained that the increase in hydrophilic emulsifier Tween
80 promotes the coverage capability of the dispersed water phase
with the inner biodiesel phase. Meanwhile, Span 80 is a lipophilic
emulsifier that enhances the adhering effect between the outer
biodiesel phase and O/W phase. Therefore, for the preparation of
three-phase emulsion, an HLB value of 13 gave the highest
stability. Raheman et al. [27] prepared three samples with HLB
values of 4.3, 5, and 6. They found the highest stability of
emulsified fuel with an HLB value of 5 using 93% Span 80 and
Fig. 1. Influence of mixing speed and surfactant concentration on emulsion
stability [50].
1569
7% Tween 80.While using combination of two surfactants the HLB
value is calculated by the following Eq. (1).
HLBAB ¼ ½ðH A  W A Þ þ ðH B  W B Þ=ðW A þ W B Þ ð1Þ
here A and B are two different surfactants. H denotes the HLB
value and W denotes the weights of the particular surfactant
shown in subscript.
4.1.3.2. Effect of surfactant dosage and type of emulsifier used on emulsion
stability. Surfactant plays a key role in the formation of biofuel
emulsion. Therefore, the type of surfactant and its concentration
play an important role in the stability of emulsion. The type of
emulsifier may vary depending on the base fuel. In that case, the
emulsifier with optimal performance should be used for the
preparation of emulsion. Roila Awang et al. [50] used seven potential
emulsifiers and screened out the best one. The amount of surfactant to
be used during emulsion has a specific range as it strongly influences
emulsion stability [61]. At low concentrations of surfactants, emulsions
are unstable because of oil droplet agglomeration. By contrast, at high
concentrations, rapid coalescence occurs and destabilizes the mixture
because of polydispersity of surfactant micelles formed at the W/O
interface as explained by Wasa et al. [82]. Thus, the emulsion is best
stabilized at an optimal level of surfactant concentration. This range
may vary with the base biofuel used for the emulsion. Kerihuel et al.
[29] kept their surfactant dosage within 2
8% to achieve stable
emulsion using animal fat as base fuel. For palm oil emulsion, the
highest stability is found at 1–2% surfactant concentration [50]. An
interesting observation is found from their study as well; the emulsion
system with 0.5% surfactant increases its stability when the mixing
speed is increased from 500 rpm to 1300 rpm (shown in Fig. 1) [50].
Therefore, the mixing speed is another factor that increases stability.
4.1.3.3. Effect of co-surfactant on emulsion stability. Co-surfactants
are primarily used to improve stabilization of emulsions and
reduce the amount of emulsifier usage. Synergism between the
surfactant and co-surfactant is the main factor that determines the
stability of the emulsions and structure of the co-surfactant [81].
Another use of co-surfactant is to prepare micro emulsions. For
this case, alcohol is generally used as a co-surfactant [26,68,88]. Qi
et al. [26] used Span 80 for ethanol-biodiesel
water emulsion,
and ethanol was selected as a co-surfactant. The type of alcohol to
be used depends on its miscibility with the base oil. Senthil Kumar
and Jaikumar [51] used ethanol over methanol because the former
has better mixing ability with waste cooking oil (base oil).
S. Bhimani et al. [89] produced emulsified canola oil as fuel
using methanol instead of water. The authors found that the
addition of methanol is inversely related to the stability of
emulsion. Kumar et al. [30] used animal fat emulsified with
ethanol. Ethanol has high miscibility with diesel, vegetable oils,
and animal fats, as well as cleaner burning characteristics and a
high cetane number compared with methanol [30,109,110].
4.1.3.4. Effect of water concentration on emulsion stability. Emulsion
stability increases with the addition of water, but the emulsion
starts to destabilize after exceeding a certain level of water because
of the admission of water in the continuous phase of the emulsion,
transforming W/O emulsion to O/W emulsion [61,67,90]. The
increase in the volume of dispersed droplets leads to an increased
rate of coalescence as the entropy for collision increases [50,91].
Therefore, an upper limit for water addition exists after which the
emulsified fuel becomes unstable. This upper limit depends on the
basefuel. Al-Yarri et al. [90] investigated the influence of water
fraction on emulsion stability. The W/O emulsion was prepared
using brine solution as aqueous phase and kerosene (SAFra D60) as
oil phase with HLB 6.8. Their results showed that the emulsion
1570 S.S. Reham et al. / Renewable and Sustainable Energy Reviews 52 (2015) 1566–1579

Table 2
Different types of emulsified biofuel and their stability time.

Fuel Type of Surfactant HLB Stability time

emulsion value

Soybean [79] O/W/O Tween 80þ Span 80 6 After 5 min O/W layer formed and
after 20 min water layer formed
10 After 20 min water layer formed
along with O/W layer
13 After 3 h O/W layer formed

Palm oil emulsion [50] W/O Laboratory prepared surfactant (reacting Polymeric 1 week
hydroxystearic acid (DHSA)/ DHSA-estolide with polyhydric
alcohol)

Palm oil methyle esterþ water 5% [13] W/O Span 80 4.3 After 180 min almost no deposition
Tween 80þ Span 80 5 is observed
Tween 80þ Span 80 6
Palm oil methyle esterþ water 10% [13] W/O Span 80 4.3
Tween 80þ Span 80 5
Tween 80þ Span 80 6

Waste cooking oil (WCO)þ 15% water [51] W/O Span 80þ Ethanol 4.3 2 weeks

Waste cooking palm oil (B70) þ 0.5% water Micro- Span 80þ Ethanol 4.3 4 weeks
(approx.) [24] emulsion

Soybean biodiesel þ 0.5/0.9% (approx.) water Micro- Span 80þ Ethanol 4.3 Stable
[26] emulsion

88.4% Canola oilþ 9.8% methanol þ 1.8% W/O Span 80þ Tween 80 7 7h
surfactant [89] (methanol
83.07% Canola oilþ 14.66% methanol þ2.27% in oil) 4h
surfactant [89]

93% Jatropha methyl estersþ 2% W/O Span 80þ Tween 80 10 5 Days

surfactant þ 5% water [97]
93% Jatropha methyl estersþ 2%
surfactant þ 5% waterþ 25/50/100 ppm
CNT [97]

Table 3
Physicochemical properties of biofuels and their emulsions.

Fuel composition (% v/v) Type of Density Heating value Cetane Kinetic viscosity Flash point Ref.
emulsion (kg/m3) (kJ/kg) number (mm2/s) (1C)

Diesel 840 42,490 45 4.59 52–96 [51]

Crude Jatropha oil 899 36,530 33.10 252 [27]
JME (Jatropha methyl ester) 895 38,880 53 5.05 85 [97]
93% JMEþ 2% surfactant þ5% water W/O 899.8 37,050 51 5.40 140
93% JMEþ 2% surfactant þ5% water þ25 ppm CNT (carbon 897.2 37280 54 5.43 130
nano tube) (JME25CNT)
93% JME þ2% surfactant þ 5% waterþ 50 ppm CNT (JME50CNT) 897.8 37,350 55 5.76 125
93% JMEþ 2% surfactant þ5% water þ100 ppm CNT 899.4 37,850 56 5.91 122
(JME100CNT)
JB10 (10% Jatropha biodiesel and 90% diesel) 837 40,850 2.91 62 [27]
JB10 þ 0.5% surfactant (HLB 5) þ10% water 858 38,720 3.93 68 [27]
POME (Palm oil methyl ester) 870 41,700 51 4.7 121 [47]
POME þ 5% surfactant þ5% water W/O 890 37,880


[13]
Soybean oil 864 40,557
4.25
[69]
Soybean biodiesel þ10% water W/O 880 39,669
7.29
[79]
O/W/O 888 39,219
7.66
[69]
Soybean biodiesel þ10% waterþ5% aqueous ammonia O/W/O 885 39,624
6.97
[69]
Soybean oilþ 20% ethanol þ0.5% water Micro-emulsion 854.5 31,294 – – – [26]
Soybean oilþ 20% ethanol þ1% Water 855.2 31,283 – – –
Canola oil 960 40173 – 57.29
[89]
Canola oilþ 9.8% methanol þ 1.8% surfactant (Span 80 and W/O (methanol 900 38,396 – 43.11

Tween 80) HLB 7 in oil)
Biodiesel produced from seed oil of Thevetia Peruviana (TP) 860 41,032 – 6.0 160 [98]
TP þ 5% Water W/O 867 38,665 – – –
Waste cooking palm oil (B70)þ 0.5% water (approx.) Micro-emulsion 841.98 37,950 – 3.52 16.5 [24]

became more stable with the increase in water fraction. The droplet study showed that 2–5% of water content provides stable
size of the dispersed phase became smaller. According to their emulsions, but emulsified palm biodiesel become unstable when
findings, 0.7 volume fraction of water prepared the most stable the water content is higher than 7% [50]. Therefore, the effect of
emulsion, and their optimak ratio was 1:1 by volume. Another water concentration on preparing a stable emulsion has no fixed
 S.S. Reham et al. / Renewable and Sustainable Energy Reviews 52 (2015) 1566–1579 1571

amount, but rather depends on the base fuel. Moreover, the water
concentration strongly influences the fuel properties of emulsified
biofuel.
4.1.3.5. Effect of type of emulsion prepared. Water W/O emulsions
are common in fuel, pharmaceutical, cosmetic, and food
industries. Meanwhile, O/W emulsions are used in oil recovery
method [92]. Both emulsions are a function of salinity, water oil
ratio, and hydrophobicity of the surfactant–soap system [92,93].
However, the stabilization of these emulsions differs. O/W
emulsion is stabilized by steric and electrostatic repulsion,
whereas W/O emulsion is expected to stabilize by steric force
only because of low electric conductivity of the continuous phase
(i.e., oil) [67,94]. Generally W/O emulsions are less stable because
of highly mobile water droplets, which can easily sediment,
flocculate, or coalesce [39,67]. O/W is not suitable as a fuel
because its water content is high; moreover, during combustion,
it will come in contact with the engine parts and corrode them
easily, and less oil will result in poor combustion or failure to
combust [40,95]. W/O is widely used as an alternate fuel. Water in
diesel emulsion fuel is used instead of water in gasoline emulsion
fuel because the boiling point is much higher between water and
diesel, unlike that between water and gasoline [40,111]. Pyrolysis
oil can form both O/W and W/O emulsions depending on the ratio
of pyrolysis oil and diesel [96]. W/O emulsion is obtained when
45% w/w bio crude oil (BCO) is added to the diesel oil phase,
whereas O/W emulsion is obtained when 45% w/w of diesel is
added to BCO. A bicontinuous emulsion in which both oil and
water are in continuous phase is formed when diesel and BCO are
close to 50% by weight.
Table 2 shows the stability period of different emulsified biofuels
from different feedstock. Based on the table, micro emulsions show
better stability period than other types of emulsions. After producing
the most stable emulsion, the next prime concern is the physico-
chemical properties of biofuel emulsion. To gain acceptance for
commercial usage, biofuel should meet the standards of that of diesel
fuel and perform as well as diesel. The subsequent sections discus the
fuel properties, combustion, performance, and emission characteristics
of biofuel emulsion.
4.2. Comparative analysis physicochemical properties of tested
biofuels
Table 3 shows the physicochemical properties of different biofuel
emulsions. Among these 93% JMEþ2% surfactantþ 5% waterþ 100 ppm
CNT (JME100CNT) emulsion possesses better physicochemical proper-
ties. The flash point of JME biodiesel is higher than that of diesel fuel,
and the emulsified JME biodiesel with 5% water addition has an even

JB10
POME
Soybean oil
Thevetia Peruviana
Canola oil emulsion with methanol
920
910
900
Density, kg/m3

890
880
870
860
850
840
830
820
0 5 10 15 20 25
Percentage of dispersed phase in the biofuel emulsion

Fig. 2. Variation of density with water concentration of different fuels.

Soybean oil
Canola oil emulsion with methanol
POME
Thevetia Peruviana
50
45
Kinematic Viscosity, mm2/s

40
35
30
25
20
15
10
5
0
0 5 10 15 20 25
Percentage of dispersed phase in the biofuel emulsion

Fig. 3. Variation of kinematic viscosity with water concentration of different fuels.

1572 S.S. Reham et al. / Renewable and Sustainable Energy Reviews 52 (2015) 1566–1579

JB10
Soybean oil
Canola oil emulsion with methanol
POME
45

Heating Value, MJ/kg

40

35

30

25
0 5 10 15 20 25
Percentage of dispersed phase in the biofuel emulsion

Fig. 4. Variation of heating value with water concentration of different fuels.

higher flash point, which is an advantage [97]. However, Kannan et al.
[24] found a much reduced flash point for emulsified waste cooking oil
with 0.5% water addition. The lower flash point is due to the addition of
19% (v/v) ethanol. As ethanol is highly flammable, its presence in fuel
strongly affects its flash point. Hence, the use of ethanol is restricted
when considering the fuel properties. The cetane number is higher in
the case of emulsified fuel. Though micro emulsions have better
stability than other types of emulsions, their calorific value is poor
compared with that of other emulsions. Two-phase emulsion of
soybean oil biodiesel possesses better properties compared with other
types [79]. Figs. 2–4 show the changes in properties of different fuels (JB
10 (Jathropa biodiesel) [27], POME [47], soybean oil [7], Thevetia
peruviana [98], and canola oil [89]) with the variation in water
concentration from different research studies. The observations of other
properties from each of the graphs are stated below in corresponding
sub-sections.
4.2.1. Density
Majority of emulsified fuel has a larger density than the base fuel
and diesel fuel itself because of the presence of water droplets in fuel
[13,27]. Water addition of 5% increases density by 0.54% [97], 2.3% [13],
and 0.8% for emulsified JME, POME, and emulsified TP, respectively.
However, if alcohol is used for emulsion, the density will decrease [89].
Another study showed that three-phase emulsions have higher density
than two-phase emulsions [79]. Therefore, the extent of variation in
density depends not only on the water but also on the base fuel, type of
emulsion, and presence of alcohol.
Density also changes with the change in water concentration. This
is illustrated in Fig. 2.
From Fig. 2 following observation can be made
 density is increased when water concentration is increased;
 density is increased when methane concentration is increased
for Canola oil. For emulsion of canola biodiesel methane was
used instead of water.
 In the case of POME, the rate of increase is much higher than
the rest between 10% and 15% water concentraion.
 JB 10, TP and Soybean oil give similar increasing trend and also
offers a linear relationship with the concentraion of water.
oil in three-phase emulsions, but the largest values are found in canola
oil. Even though the viscosity is slightly larger than that of diesel, the
engine encounters no problem during the operation for three-phase
emulsions [99]. Table 3 shows that the viscosity of emulsified fuel
increases because of the water content in the dispersed phase of
water
emulsified biofuel [99]. Emulsifying with 10% water increases
viscosity by 35%, 71%, 80%, and 64% for JB10, two-phase emulsion of
soybean biodiesel, three-phase emulsion of soybean biodiesel, and
three-phase emulsion, respectively, with the addition of aqueous
ammonia of soybean biodiesel. However, alcohol can be used to reduce
viscosity for emulsion purposes. According to the authors, the viscosity
of methanol-emulsified canola biodiesel decreases by 24% [89]. High
viscosity of animal fats is also reduced using methanol [29].
From Fig. 3
 The viscosity is almost constant with a minor variation with the
increase in water for all except Canola oil;
 Canola oil has higest viscosity and the increasing rate is also a
bit higher than the rest.
4.2.3. Heating value
The calorific value of emulsified fuel is less than that of the base fuel
[13,69,89,97] because of the increase in water content in the fuel. The
water content is vaporized during combustion, taking up the heat
generated in the combustion chamber and lowering the calorific value
of fuel. Kannan et al. [24] limited water addition between 0.5 and 2 ml
because of the reduction in lower heating value. Table 3 shows that the
addition of the same amount of water (10%) for emulsion results in a
two-phase emulsion with a higher calorific value than the three-phase
emulsion. With the same base oil (soybean biodiesel), Qi et al [26,83]
found very low heating value with 0.5% water addition compared with
that found by Lin et al. [79] with 10% water addition. The poorer heating
value can be explained by the addition of a large amount of ethanol
because ethanol has a lower energy content. Koc et al. [7] found the
heating value of biodiesel was around 10% less than the diesel fuel on
weight basis. However, the calorific value can be increased using some
additives, such as carbon nanotube (CNT) [97] or aqueous ammonia for
emulsion [69]. By adding CNT up to 100 ppm, the heating value may
increase by 2% [97].
From Fig. 4

4.2.2. Viscosity  The variation of heating value gives a decreasing trend with the
Viscosity is one of the significant properties of fuel because it increase in water content;
controls fuel injection characteristics, quality of atomization, and  The decreasing rate is slightly higher in the case of emulsified
combustion. Large kinematic viscosities are found in emulsified soybean POME;
 S.S. Reham et al. / Renewable and Sustainable Energy Reviews 52 (2015) 1566–1579
Table 4
Combustion analysis of emulsified biofuel.
Combustion Effect/phenomena
parameter
Peak During combustion, the peak pressure inside the cylinder is lower for
pressure in emulsified biofuel than that of bio-diesel and diesel at low load
cylinder applications [13,26,51]
The peak pressure for emulsified fuel can be same as bio-diesel or even
greater than diesel at high load application [26,27].
Heat release HRR for emulsified biofuel is higher than that of biodiesel and diesel
rate (HRR) [24,27,49]]
 JB 10 and Soybean oil give similar decreasing trend.
5. Combustion, performance and emission studies of
emulsified biofuels
5.1. Combustion analysis
During combustion of emulsified biofuel, three significant events
take place; (1) micro-explosion, (2) heat sink effect and (3) ignition
delay. Micro-explosion breaks-down large droplets into several smal-
ler droplets due to vaporization of water. This vaporization is instan-
taneous and intense which leads to turbulent mixing of fuel and air.
Heat sink effect occurs before the commencement of combustion,
when water droplets from fuel forms vapor and consumes substantial
amount of heat [13]. Ignition delay is due to the presence of water.
When water evaporates, it slows down the rate of the increase in
temperature of the droplets, and the water vapor reduces the
concentration of fuel [40,98,100]. Due to these phenomena, several
changes are observed during combustion analysis compared to that of
biodiesel and diesel. Table 4 illustrates that peak pressure in the
cylinder and the heat release rate change because of ignition delay,
heat sink effect, and water concentration in fuel for emulsified
1573
Cause
1. Ignition delay period
The peak cylinder pressure depends on the combustion rate. At low load, the
temperature of residual gas and wall is low, thus promoting lower mixing
temperature. As a result, the ID period is prolonged [24]. Due to prolonged
ignition delay (ID) the explosion also occurs in larger space and thus leading
to lower peak pressure [12,51].
2. Spray envelope of injected fuel
If the fuel viscosity if higher then it leads to poor atomization and mixture
preparation with air during the ignition delay period and resulted in reduced
cylinder peak pressure and maximum rate of pressure rise [51].
3. Heat sink effect
This phenomenon is again boosted by the water produced by the oxygen
present in the chemical structure of POME according to their study. As
compared to diesel, the average drop in peak pressures for emulsified bio-
diesel and bio-diesel are 15.1% and 1.5% [13].
4. Water concentration:
The peak pressure decreased with increasing water concentration [74].
Raheman and Kumari [27] found 4% decreased in peak pressure when the
proportion of water in emulsified fuel was increased from 10% to 15%.
Ignition delay:
In higher loads, the ignition delay decreases because the gas temperature
inside the cylinder is higher [26]. As, reduced engine load results in reduced
residual gas temperature and wall temperature, leading to lower charge
temperature at injection, and lengthens the ignition delay. Qi, Chen [26] found
that, when BMEP is lower than 0.266 MPa, the peak cylinder pressure of
micro-emulsions is lower than that of biodiesel, and when the BMEP is higher
than 0.266 MPa, the peak cylinder pressure of emulsified fuel is almost
identical to that of biodiesel.
1. Reduced cetane number due to addition of water and ethanol for the case of
micro-emulsion [24]
2. Ignition delay
At higher loads the peak HRR increased due to improved premixed
combustion, which is enhanced by the ignition delay. Ignition delay increases
amount of fuel available for combustion which increases the heat release rate
[24].
3. Water concentration
With the increase in water concentration the HRR also reduced due to reduced
volatility of emulsified fuels. About 6% HRR decreased in average when water
proportion is increased from 10% to 15% according to the findings of Raheman
et al. [27].
biodiesel compared with those in biodiesel and diesel. However,
ignition delay caused by emulsified fuel can be reduced by increasing
the oxygen concentration [101]. As a result, complete combustion is
promoted, and ignition time advances with higher cylinder pressure
with increasing heat release rate.
5.2. Performance analysis
Table 5 shows that the BTE is increased at higher loads and
decreased at lower loads for emulsified biodiesel compared with
diesel and biodiesel. This behavior is due to the heat sink phenomena
caused by the presence of water, and its effect is negligible at high
loads. The BSFC is increased because of the lower heating value of
emulsified biofuel. However, in several studies, the BSFC is reduced for
emulsified fuel compared with that for biodiesel and diesel fuel.
According to their Chen et al. [19], 10% increase in energy efficiency is
found after adding 16% bio-solution additives in the emulsion com-
pared with diesel fuel. Table 5 illustrates that the BP and torque are
reduced when emulsified biofuel is used. However, at a constant
speed, the BP for emulsified POME is not different from those for
POME and diesel [13]. Constant engine speed provides specific BP in
each load, and it is independent of compression ratio and ignition
1574 S.S. Reham et al. / Renewable and Sustainable Energy Reviews 52 (2015) 1566–1579

timing. Therefore, the power showed a linear relation with the load
and no variation among fuels. Table 5 shows that exhaust gas
temperature is highest in biodiesel compared with that in emulsified
biodiesel and diesel because of the heat sink effect.
5.3. Emission analysis
Table 6 shows the emission characteristics of different types of
emulsified biofuels. The type of emission is similar for all emulsi-
fied fuels, irrespective of the emulsion type. Among the fuels, JME
(93%) þ2% surfactant (2%) þwater (5%) þ25/50/100 ppm CNT [97]
resulted in the best emission results. Unlike other emulsified fuels,
the CO emission is reduced significantly for this emulsion, result-
ing in more complete combustion. For micro emulsions, CO
emission is increased compared with that of biodiesel and diesel.
The following subsections provide more details about the emission
characteristics of emulsified fuel.
5.3.1. Hydro carbon (HC) emission
The As Table 6 shows, HC emission for emulsified biofuel is lower
at low loads and higher at high load applications compared with
biodiesel and diesel [13,26]. Low HC emission for emulsified fuel is due
to the higher oxygen in emulsified fuel, which helps burn more fuel
compared with biodiesel and diesel [25]. When the water concentra-
tion is increased in emulsified fuel, the HC content also decreases.
Prakash et al. [25] found 35% lower HC emission in emulsified JME
compared with that in JME alone. However, the HC emission is
increased at low loads. Debnath et al. [13] found a 22% increase in
HC emission in emulsified POME compared with that in POME alone
at low loads, and HC emission is 6.7% lower in the emulsified fuel at
high loads. Generally, HC emission is a function of engine speed [22].
HC concentration decreases when engine speed increases. According
to the authors, the high temperature in combustion chamber at high
loads increases the micro-explosion of emulsified fuel and enhances
the combustion process, which results in lower HC emission [13,104].
The use of ethanol in the emulsion forms a quench layer of unburned

Table 5
Performance analysis of emulsified biofuel.

Performance Effect/phenomena Cause

parameter

Brake thermal BTE of emulsified biofuel is higher than that of biodiesel and 1. Micro-explosion phenomena [27]:
efficiency (BTE) diesel at high engine loads [13,51]. Micro-explosion results in more complete combustion and higher release of energy
and therefore, BTE is improved [13,51].
2. Higher oxygen content:
Prakash et al. [25] found that emulsified biodiesel (JME) and the acid treated
emulsion have 11.3% and 8.2% higher thermal efficiency than that of diesel and
11.6% and 8.5% higher than that of JME respectively. This is due to the improvement
of the combustion process as oxygen content is higher in the fuels and faster
combustion [25,102].
BTE of emulsified biofuel is lower than that of biodiesel and 1. Low calorific value [24]
diesel at low engine loads [24,27] 2. Heat sink effect [103].
Brake specific fuel Brake specific fuel consumption is increased in the case of 1. Lower heating value:
consumption emulsified fuel due to the low calorific value [13,24,25,43– To produce same amount of power the fuel consumption should be higher for
(BSFC) 46]. emulsified fuel than that of biodiesel and diesel due to lower heating value [69].
Kannan et al. [24] found highest BSFC in emulsified biodiesel compared to that of
neat biodiesel and diesel fuel.
2. Higher viscosity:
Kerihuel et al. [29] experimented with animal fat as fuel and found higher BSFC due
to high viscosity of animal fat compared to diesel.
3. Water concentration:
Higher water content gives higher BSFC as the lower heating value of emulsified
fuel is reduced [7]. Koc et al. [7] found with 15% water concentration in emulsion
the BSFC is 7% higher than the 5% of water concentration.
BSFC is reduced for emulsified fuel compared to biodiesel and 1. Micro explosion and ignition delay:
diesel fuel Due to ignition delay the fuel is injected when piston is nearer to TDC (Top dead
centre), i.e., in reduced total volume in cylinder compared to the diesel setting.
These give a warmer environment due to higher compression inside the cylinder
prior to the injection of fuel. Therefore, it increases the rate of micro-explosion. As a
result combustion is improved. According to Debnath et al. [13], BSFC of emulsified
POME is reduced by 11% from POME and 2% from diesel at 1500 rpm.
2. Bio solution additive:
Chen et al. [19] found that emulsified palm-biodiesel with bio solution additives
reduces fuel consumption by 9–12% compared with Brassica carinata biodiesel,
rapeseed biodiesel, biodiesel
algal emulsion, and diesel emulsion.
Brake specific BSEC increased in emulsified biofuel [19,24] 1. Use of ethanol lowered the viscosity and promote higher atomization and
energy vaporization therefore, better mixing
consumption 2. Micro-explosion
(BSEC) 3. Use of bio-additives:
Around 10% increase in energy efficiency is found for adding 16% bio-solution
additives in the emulsion compared to diesel fuel [19].
Brake power and Break power and torque is reduced for emulsified fuel [7] 1. Lower heating value
torque Koc et al. [7] found biodiesel with 5% and 15% water emulsion produced around
0.75% and 3.85% respectively less engine break power than the diesel due to lower
calorific value.
2. Engine torque is reduced with increase in water concentration
Exhaust gas The exhaust temperature of the engine is reduced while Heat sink effect:
temperature using emulsified bioduel [25,28,30,69]. During combustion process the water absorbs heat energy while going through
vaporization process and decreases the flame temperature. This leads to lower
exhaust temperature at full load [13,25,46,49].
 S.S. Reham et al. / Renewable and Sustainable Energy Reviews 52 (2015) 1566–1579 1575

ethanol at low loads and increases this emission [26]. Therefore, the
presence of ethanol also increases HC emission. Moreover, the higher
water content in biodiesel shows higher HC emission even in high
load operations because of the higher heat sink effect [25].
5.3.2. CO and CO2 emission
During combustion, incomplete fuel burning leads to CO emis-
sions. If sufficient oxygen exists, CO will oxidize to CO2 [25,79].
Table 6 shows that CO emission is increased at high loads and
reduced at low loads for emulsified biodiesel. Given that higher
latent heat of vaporization leads to incomplete combustion, more
CO is produced at low and medium loads. A thickened quench layer
created by the cooling effect of vaporization of ethanol and water
can cause increased CO production [26]. However, at 100% load, the
CO emissions for the emulsified blends were found to be 50–70%
higher than those for diesel because of the lower air fuel ratio [27].
According to Prakash et al. [25], the CO emission in emulsified fuel
is higher than that in diesel at full load because of longer spray
penetration, larger fuel droplets, and insufficient swirl. However, a
significant reduction in CO emission is found when CNT is used in
emulsion because of intensive secondary atomization and good
distribution of fuel [97]. CO emission increases with water concen-
tration [7]. CO emission produced by 5% water
emulsified biodie-
sel was 6.5% and 8.5% lower than that of 10% and 15% water
concentrations, respectively. Higher amount of water means higher
amount of OH radicals from water, which promotes higher oxida-
tion of carbon. However, even fuel with high water content has
lower CO emission than diesel fuel [7]. For emulsified fuel, CO2
emission increases when CO decreases and vice versa. Raheman
et al. [27] found reduced CO2 emission at higher loads caused by
improved combustion.

Table 6
Emission analysis of emulsified biofuel.

Type of emulsion Fuel composition HC CO CO2 NOx Smoke opacity

W/O JME (93%) þ2% Surfactant (2%)þ Water High compared to High compared to JME Low compared Low compared
(5%)–(JME2S5W) [97] JME and CNT blended and CNT blended to JME to JME
emulsion emulsion
JME (93%) þ2% Surfactant (2%)þ Water Marginal reduction Significant reduction Low Compared Low
(5%) þ25/50/100 ppm CNT [97] compared to JME and to JME2S5W Compared to
emulsified JME and JME JME2S5W and
JME
W/O JB10þ 0.5% surfactant (HLB 5) þ 10/15% Increased at low load 7
8% lesser emission decreased
Water [27] and decreased at high compared to diesel at
loads high loads
W/O (methanol Biodiesel
canola oil (88.4/83.07%)þ Decreased Decreased Increased Decreased
in oil) Methanol (9.8/14.66%) þSurfactant
(1.8/2.27%) [89]
Micro-emulsion Waste cooking palm oil (B70)þ 0.5% Slight increase Slight increase compared Slight increase Decrease Decrease
water (approx.) compared biodiesel biodiesel compared biodiesel compared compared
biodiesel biodiesel
Soybean biodiesel þ0.5/0.9% (approx.) Increased at low and Increased at low and Slightly decreased
water [26] medium engine loads medium engine loads decreased
Decreased at higher Decreased at higher
engine loads engine loads
Nano-emulsion Surfactant (7.5%) þ Biodiesel
Soybean Decreased compared to Increased compared to Decreased Decreased
oil (17.5%)þ Water (5/10/15%) þDiesel diesel diesel compared to compared to
(70/65/60%) [7] diesel diesel
Relation with Proportional [25] Proportional [7,22] Proportional [7] Inversely Inversely
water proportional proportional
concentration [7,47] [7]
Relation with Inversely Inversely proportional Proportional Inversely
methanol proportional proportional
concentration
[89]

Table 7
Other types of biofuel emulsion.

Type of emulsion Composition Stability Performance Emission

Emulsified Acetone
butanol
ethanol in the water emulsified Stable  Fuel consumption is highest  Emulsion lowered the PM and NOx
biodiesel biodiesel [107]  Thermal efficiency increased emission by 4.3
30.7% and
without a 10.9
63.1% respectively.
surfactant [107]  Poly-cyclic aromatic hydrocarbon
emission is reduced by
26.7
67.6%

Fuel containing 10% Chlorella vulgaris micro alga (5
10 micrometer in 14 days  Fuel consumption is highest.  CO is highest
microalgae size), 80% transesterified rapeseed oil, 20% water and 0.5% However, the fuel used per hour is  NOx is lowest
[108] surfactant (Triton X-100) similar to that of diesel
 The exhaust temperature is
reduced
1576 S.S. Reham et al. / Renewable and Sustainable Energy Reviews 52 (2015) 1566–1579
Emulsified Biofuel
Stability Fuel
Propertie
Base Fuel Performance
Type of
Combustion
Emulsion
Surfactan
Emission
HLB
Water
Alcohol
Fig. 5. Interrelation among constituents of emulsion, stability, properties, and
performance indicators.
5.3.3. NOx emission
High temperature High temperature and availability of oxygen
increase NOx emission [27]. Emulsified fuel reduces NOx emission
compared with biodiesel and diesel fuel [6,13,16,22,25,26,
47,50,69,97,99,103,105]. High latent heat of vaporization of water
and availability of oxygen in emulsified fuel help reduce NOx
emission [24,26]. Higher latent heat of vaporization of water
reduces the adiabatic flame temperature [24]. The finely dispersed
water droplets function as the heat sink. Thus, the peak ignition
temperature and NOx emission are both reduced. Micro-explosion
plays a key role in minimizing NOx emission. Emulsified fuel
possesses reduced oxygen concentration because of ignition delay,
which reduces NOx emission [47]. NOx emission increases with the
increase in load on engine as more heat energy is released.
However, after 80% load, NOx formation is reduced because of
the lesser availability of oxygen [27]. The large amount of water
present in emulsified fuel helps reduce higher amounts of NOx
emission [7]. Debnath et al. [13] found a 20% reduction in NOx with
emulsified POME. They justified their reasoning with exhaust gas
temperature, in which emulsified biodiesel gave lower tempera-
ture burnt gas compared with neat biodiesel and neat diesel.
5.3.4. Smoke opacity
Emulsified biodiesel has reduced smoke opacity compared with
diesel and biodiesel [7,25,105,106]. Both emulsified and neat biodiesel
are rich in oxygen and have high OH radical concentration, which
contributes to better combustion process and reduces smoke formation
[25]. Moreover, micro-explosion results in atomization of fuels and
contributes to better air-fuel mixing, thereby causing lower smoke
opacity in emulsified fuel [25]. Similar results were found in the
literature [7]. Prakash et al. [25] found that smoke opacity is reduced by
19.6% and 27.8% with JME and emulsified JME, respectively, compared
with diesel. The increase in biodiesel concentration decreases smoke
formation compared with diesel fuel. When water concentration is
increased in biodiesel nanoemulsion, the soot opacity is also reduced.
5.4. Other biofuel emulsions
Table 7 shows, emulsion without surfactant showed good stabiliza-
tion and also good emission characteristics. The emulsion containing
micro-algae increased energy efficiency but increased the CO emission.
6. Discussion
Fig. 5 shows the interrelation among constituents of emulsion,
stability, properties, and performance indicators. When choosing a
surfactant for preparing emulsions, HLB value and base fuel need to
be considered. The preparation of emulsion does not require much
time, but determination of the best composition of constituents is time
consuming. Even if the emulsion made has good stability, it also should
possess good physicochemical properties on which the performance of
the fuel largely depends. One of the main shortcomings of emulsified
biofuel is its lower calorific value, thereby reducing fuel consumption,
BTE, brake torque, and BP. To overcome these shortcomings bio
solutions, CNT, additives, algae can be used. Although fuel consumption
is higher in emulsified biofuel, the percentage of increment is not
significant compared with the use of fossil fuel. Kannan et al. [24] found
that emulsified biodiesel, biodiesel, and diesel require 0.33, 0.32, and
0.28 kg per kWh at 100% load condition. The percentage of diesel in
emulsified biodiesel is approximately 9.6%. Therefore, 0.032 kg of diesel
is used to produce 1 kWh, which is very low compared with that of
pure diesel fuel. The engine torque reduction (6.47% for 5% water
addition) was not statistically significant compared with diesel [7].
Although the BSFC is high, emulsified fuel possesses increased energy
efficiency compared with diesel because of the micro-explosion phe-
nomena. The prolong ID can be advanced by introducing more oxygen.
However, NOx emission will also increase if the oxygen supply is too
high. Alcohol has various roles in emulsified fuel. Alcohol is used as a
co-surfactant for better stability and to reduce the viscosity of fuel,
thereby increasing micro-explosion. However, a higher amount of
ethanol usage reduces its cetane number and increases the HC
emission. Therefore, the ethanol concentration in fuel should be
considered carefully. Although the micro-emulsion has better stabiliza-
tion, the two phase emulsion with CNT showed better physicochemical
properties and emission characteristics. For the case of performance, the
addition of bio-solution additives and algae in emulsions showed
improved performance by lowering fuel consumption and by increasing
energy efficiency. Therefore, the most suitable biofuel emulsion can be
get using proper additives. The inclusion of water in the fuel by
emulsion does not cause any corrosion because the water is on the
inverse phase of the emulsion and hence never comes in contact with
the engine parts [112].
7. Conclusion
Biodiesel has become a popular choice among researchers to
replace fossil fuels and minimize the effects of global warming.
However, the high NOx and carbon particulate emission associated
with biodiesel need to be reduced by emulsion. Emulsified biodiesel
is proven to exhibit excellent performance and emission character-
istics compared with diesel and biodiesel. This review paper
explored the primary factors starting from the preparation of stable
emulsion to its performance and emission. This paper also provides
shortcomings of emulsified fuel and possible solutions. Constructive
and parametric investigations, as well as cost calculations, on
emulsified biofuel are urgently needed to overcome the barriers
that hinder its commercial use. Emulsified biodiesel has potential to
replace fossil fuels and mitigate environmental and climate change
issues. Some major findings from the review are summarized below.
1. For a specific base fuel, an optimal composition of surfactant,
co-surfactant, and water can result in the best stability. Factors
that have effects on stability of biofuel emulsion are
base
fuel, surfactant, HLB value of surfactant, type of emulsion,
water and alcohol. Micro emulsion has better stability char-
acteristic than other types of emulsions.
 S.S. Reham et al. / Renewable and Sustainable Energy Reviews 52 (2015) 1566–1579
2. Lower heating value increases the BSFC, BP, and torque for
emulsified biofuel, but the increment is not significant com-
pared with diesel and biodiesel.
3. Increase in water concentration increases density, viscosity and cetane
number, but decreases heating value. Due to these changes in fuel
properties the engine showed poorer performance, but the emulsified
fuel improved combustion rate and emission characteristics.
4. Ignition delay occurs because of the presence of water in
emulsified fuel. This phenomenon reduces peak pressure at
low load and increases HRR. However, ignition delay can be
advanced by increasing oxygen concentration.
5. Heat sink effect caused by water vapor formation of emulsified
fuel also lowers the peak cylinder pressure but reduces the
exhaust gas temperature. Therefore, NOx is reduced.
6. Micro-explosion phenomena increase BTE and energy efficiency.
By increasing micro-explosion, BSFC can also be reduced.
7. Addition of bio-solution additives, CNTs, and algae in emulsions
proved to improve the fuel properties and performance by
lowering fuel consumption and increasing energy efficiency.
8. The emissions of HC, CO, CO2, and NOx, as well as smoke
opacity, improve for emulsified biofuel compared with those
for diesel and biodiesel fuel. However, with the increase in
water concentration of HC, CO, CO2 emission increased and NOx
and smoke opacity emission is reduced.
8. Recommendations
Significant studies need to be carried out in numerous potential
research areas to improve the characteristics of emulsified biofuel.
Extensive and focused research on emulsified biofuel may help
mitigate its shortcomings on usage. Emulsified biofuel will have a
potential future by replacing the conventional use of diesel, and it can
contribute to make a greener world. For future work on emulsified
biofuel, the following recommendations are suggested.
 A major research area for emulsified fuel is its preparation. The
prepared emulsified biofuel should be stable, non-reactive,
easy to handle, and cost effective.
 The process of acquiring the best composition is based on the
sampling method. The use of any fast and constructive method for
finding the optimal composition would save much time and work.
This method can be a potential area for researchers to study.
 The lowered calorific value of emulsified fuel is one of its major
drawbacks. A highly significant study is needed to overcome
this problem. This disadvantage may be addressed in the form
of additives or by increasing energy efficiency. Therefore, the
total fuel usage would be reduced.
 Ignition delay and heat sink effect have some drawbacks and
advantages. Thorough investigation of these areas is required to
overcome their shortcomings.
 BP and torque are reduced in the case of emulsified fuel. In-
depth studies in this area are desired.
 The use of water
emulsified biofuel in winter season when the
temperature is below 0 1C would be a problem. Therefore, an
alternative for water is required to prepare emulsified fuel.
 Although the emulsified fuel does not contribute to corrosion
of engine parts, it is not clear what happens when water vapor
forms in the combustion chamber. Therefore, the corrosion of
inside wall of the engine cylinder needs to be investigated.
Acknowledgement
The authors would like to thank University of Malaya for financial
support through High Impact Research grant titled: Development of
1577
alternative and renewable energy carrier (DAREC) having Grant no.
UM.C/HIR/MOHE/ENG/60.
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