Renewable and Sustainable Energy Reviews 70 (2017) 399–412

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Renewable and Sustainable Energy Reviews

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

Tribology with biodiesel: A study on enhancing biodiesel stability and its

fuel properties
crossmark
⁎
F. Sundus , M.A. Fazal, H.H. Masjuki
Department of Mechanical Engineering, Faculty of Engineering, University of Malaya, 50603 Kuala Lumpur, Malaysia

A R T I C L E I N F O A BS T RAC T

Keywords: Biodiesel is a potential renewable and biodegradable fuel source comprising of fatty acid methyl esters (FAME).
Biodiesel It is produced from transesterification reaction of animal fats and vegetable oils. It has been selected as a
Degradation suitable alternative to conventional diesel fuel as it furnishes several advantages such as reduced environmental
Instability emissions, renewability and enhanced lubricity. However, biodiesel poses various tribological challenges. It has
Tribological properties
compatibility issues with certain materials, is inherent instable and highly corrosive in nature. Sporadic efforts
Additives
have been carried out to understand the aforementioned issues, however significant knowledge has not been
obtained until yet, especially on stability of biodiesel of biodiesel and its lubrication behaviour. In this review,
different tribological aspects of biodiesel have been highlighted by critically analysing the recent available
literature. Commencing from the basics of tribology, this review extends towards the properties of biodiesel and
various aspects of metal contamination, moisture absorption, temperature and storage time. Tribological issues
arising due to the usage of biodiesel and the use of additives in order to stabilize biodiesel and improve its
tribological compatibility have been examined. Various factors affecting the stability and usage of biodiesel (long
term/short term), properties have been discussed and improvements in refining technologies for biodiesel
production have been summarized. Major concerns ascribed have been reviewed and possible remedies to
improve the stability of biodiesel have also been included.

1. Introduction
The demand of energy in transportation sector has hiked with the
growth of population and it keeps increasing. This has led to a rapid
depletion in the world's reserve of fossil fuel. The high usage of fossil
fuel in engine contributes to the environmental pollution with emis-
sions of unburned hydrocarbons, carbon monoxide and nitrogen
oxides. These factors make significant impact on the environment as
global warming, smog, deforestation, ozone depletion, acidification etc.
[1]. These environment vulnerabilities have encouraged researchers to
investigate suitable alternatives to fossil fuel. Biodiesel is considered to
be the most promising fuel since it reduces major environmental
concerns and gives harmonious connection between rapidly growing
fuel demand and energy conservation [2,3]. Biodiesel can be produced
from edible and non-edible vegetables, animal fat and waste cooking
oils by the process of transesterification. It is non-toxic, biodegradable
and environmental friendly [4]. In addition, biodiesel is completely
miscible with conventional diesel and several blends of diesel-biodiesel
can be used in the currently employed compression ignition engines
without any modification. The usage of diesel and biodiesel blends can
improve fuel qualities and may have positive effects on emissions [5–
8]. The excess sulfur in diesel fuel poses great environmental problems
in terms of emissions. Hence, biodiesel containing lesser sulfur
contents has the ability to eliminate these problems by virtue of its
inherent lubricity and environmental friendliness. The oxygen content
in biodiesel is about 11% of the total molecule which aids in the
combustion process and reduces the harmful emissions such as CO,
CO2 etc. [9]. A study by Vedaraman et al. [10] showed that B20 blend
(20% Palm biodiesel and 80% diesel) resulted in less CO and HC
emissions whereas the NOx emissions were almost the same as diesel
fuel. They further added small quantities of different additives (metha-
nol, ethanol, distilled water, and diethyl ether) to reduce
NOxemissions. Among these 2% distilled water showed the lowest
NOxemissions.
However, like many other fuels, biodiesel comes with several
drawbacks and unfavourable characteristics such as auto-oxidation,
poor thermal stability, material corrosion and wear, higher fuel
consumption etc. [11]. Biodiesel has higher viscosity, depending on
the raw material used for its production such as palm oil or animal fat,
as compared to normal diesel which causes problems like clogging of

⁎
Corresponding author.
E-mail addresses: sundusfatimah@gmail.com (F. Sundus), fazal@um.edu.my (M.A. Fazal), masjuki@um.edu.my (H.H. Masjuki).

http://dx.doi.org/10.1016/j.rser.2016.11.217
Received 17 September 2015; Received in revised form 2 November 2016; Accepted 16 November 2016
1364-0321/ © 2016 Elsevier Ltd. All rights reserved.
F. Sundus et al.
injection pins leading to poor atomization, plugging of fuel filter and
the tribo-pairs sticking [11,12]. It is also prone to auto-oxidation owing
to its chemical composition and higher degree of unsaturation. Upon
oxidation, biodiesel causes corrosion of fuel system and decreases
compatibility with engine metals [13]. Other problems associated with
the use of biodiesel include higher sensitivity to light, temperature and
moisture [14]. Furthermore, it is more corrosive than diesel and its
higher blends are not yet suitable for commercial usage because of it
detrimental tribological properties [15]. Enzhu et al. [16] studied the
effect of biodiesel on corrosion properties of mild carbon steel, copper,
stainless steel and aluminium. They observed noticeable corrosion of
these metals when immersed in biodiesel at 43 °C for 60 days. Fazal
et al. [17] also found that corrosion rate of copper used as fuel
transport tubing, increases when immersed in biodiesel. These studies
carried out so far indicate instability of biodiesel and its related
tribological properties with regard to engine components. Therefore,
a comprehensive knowledge and understanding related to the factors
which are associated with biodiesel stability is very essential in order to
make it stable for higher blends [18]. Several studies have also
highlighted that properties of biodiesel change due to factors such as
auto-oxidation [19], moisture absorption [20], thermal instability [21],
storage time [22] and metal contamination [23,24].
Over the last decade, it has become a global quest to replace fossil
fuels with renewable fuels. Due to environment friendliness and less
harmful emissions more and more researches are emerging to com-
prehend compatibility and characteristics of biodiesel. Interestingly, an
increase of almost 90% is seen during the last decade for the papers
published on the stability and improvement of biodiesel as a fuel.
Combined works on tribology and stability of biodiesel has literature.
Although ample research has been done in the field of biodiesel
stability, there is a need for in-depth and combined understanding of
tribology and stability of biodiesel. In addition to this, factors which are
hindering commercialization of biodiesel as a sustainable fuel needs to
be further researched on. The scope of the present study is to collect
and summarize the literature produced in previous years about stability
and tribology in biodiesel and summarize them together.
2. Basics of tribology
Tribology is a science that deals with the interaction between two
moving bodies or surfaces in relative motion. It is mainly related to
friction, wear-lubricity, corrosion, surface degradation of metals, en-
gine life and energy losses. Since a great amount of energy is wasted
because of these phenomenon, it is greatly emphasized to minimize and
eliminate the losses caused by friction and wear [25]. A brief explana-
tion of some of the terminologies that affect tribology has been given in
the following section.
2.1. Friction
Friction is the force, which generates heat due to resistance between
two contacting surfaces which are moving in relative motion. Energy of
the system is wasted due to friction, causes the temperature to increase
and produces wear of the mating surfaces [26]. As shown in Fig. 1,
some of the major types of friction include a) static friction, b) sliding
friction, c) fluid friction and d) rolling friction, and their corresponding
phenomena are depicted [27]. Static friction exists between a station-
ary object and the surface upon which it is resting, whereas sliding
friction is between a moving (sliding) surface and a stationary surface.
When a round body rolls on a surface it generates rolling friction. Fluid
friction occurs between layers of fluids moving relative to each other, or
an object moving through fluid.
2.1.1. Friction coefficient
As mentioned earlier, friction is the resisting force exerted between
two surfaces in contact. Friction is measured with coefficient of friction,
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Renewable and Sustainable Energy Reviews 70 (2017) 399–412
which is a dimensionless quantity. Conceptually defined, friction
coefficient is the ratio of the two forces namely normal (perpendicular)
force and the parallel to the surface force to an interface between the
two bodies under relative motion [28]. Fig. 2 shows the detailed
concept of friction coefficient. Knowledge of friction coefficient makes it
convenient to depict the relative ease with which one surface can slide
over another.
2.2. Lubrication
In order to overcome and reduce friction between mating compo-
nents, lubrication is applied. A lubricant is interjected between the two
relatively moving bodies. Friction could be increased when appropriate
lubrication is not provided or the lubrication film formed is not
effective. The fuel used in a vehicle accounts for the compatibility with
the engine components and providing lubrication to the moving parts.
Although there is no restriction on the type of material required in
order to form a lubricating film but it impacts the effectiveness of the
lubricant film [29]. Fig. 3 shows graphical representation of boundary
lubrication, mixed lubrication and full film lubrication. Full film
lubrication can be broken down in hydrodynamic and Elasto-hydro-
dynamic lubrication [30]. Hydrodynamic lubrication occurs when two
relatively sliding surfaces are completely separated by a film of fluid.
Elasto-hydrodynamic lubrication is similar but in this the two relative
surfaces are in rolling motion. Lubrication film formed in Elasto-
hydrodynamic lubrication is much thinner than hydrodynamic lubrica-
tion and the pressure exerted it is also greater. Boundary lubrication
happens where there are repeated starts and stops. Shock-loading
condition also results in boundary lubrication. Boundary lubrication
may not be ideal as it causes high wear, friction and generates heat.
Mixed lubrication is a mix of boundary and hydrodynamic lubrication.
The asperities in this lubrication still manage to make contact with each
other even though they are separated by a lubricating film.
2.3. Degradation of metal surfaces
In a tribological contact, metals are prone to degradation because of
wear and corrosion. Surface fatigue also occurs when a surface is
subjected to repeated loading and unloading. Different forms of
corrosion could also aggravate surface degradation. Any fluid or
lubricating oil itself could be corrosive for the metal surface.
According to Nernst's theory [32], all metals have tendency to corrode
in solution. The presence of metal ions in the fuel can be the reason for
the occurrence of corrosion. However, the extent of corrosion is
dependent on metal ions oxidation potential and prevailing conditions
such as temperature, water content etc. in the fuel [33]. Wear is the
progressive loss of material or substance occurring due to the relative
motion of two surfaces. Any metal or metal contact results in wear of
some form. Major types of corrosion include uniform, galvanic, erosion
and pitting corrosion [34]. In addition, surface fatigue may occur due
to the building up of surface stresses in a material [35]. These types are
briefly described in Table 1(a–g).
2.4. Energy losses
Energy losses that occur daily in the form of heat due to friction are
extremely high. These need to be minimized to improve efficiency.
When two bodies are pressed together and move in a relative motion,
they always dissipate energy in the form of heat. Friction consumes
about one-third of the world energy resources [38]. Furthermore, the
heat generation, temperature rise and heat loss due to frictional
heating at the contact of two bodies is an important parameter in
engine parts and machinery where friction is a concern [39]. Energy
losses in engines are crucially important domain which occurs in form
of thermal, frictional and mechanical losses. In automobile engine, only
12% of energy from the fuel goes to the driving wheels and as much as
F. Sundus et al. Renewable and Sustainable Energy Reviews 70 (2017) 399–412

Static Kinetic
a)
Resisti ve
friction al
Force

Applied
d force

Sttatic d)
b) Static Kinetic

Resistive

Rolling
Sliding
frictional
Force Fricction

Applied force
Flluid
c)

Fig. 1. Some major types of friction.

21.5%. Energy consumption in an engine is shown in Fig. 4. These

losses due to friction can be reduced by investing in economical
technologies such as aerodynamics, tribology, braking and tyres
[42,43]. In addition to these technologies, usage of fuel which imparts
better lubrication plays an important role in overcoming these energy
losses. Numerous researchers have tested lubrication properties of
biodiesel [44–47]. Studies show biodiesel is an effective fuel with
favourable lubrication properties.

3. Biodiesel production and its properties

Globally, there are more than 350 oil-bearing crops identified as

Fig. 2. Basic definition of coefficient of friction.
potential sources for biodiesel production [48]. The most common oils
include soybean [49,50], corn, used fried oil, sunflower, olive [51],
rapeseed [52–54], castor, lesquerella [55], milkweed (Asclepias) seed
[56], Jatropha curcas [57], karanja, Madhuca indica (Mahua) and
Salvadora [58], palm oil [59–61], animal fat in Brazil etc. Biodiesel
derived from these sources can be defined as mono-alkyl esters of long
chain fatty acids [62]. Biodiesel is produced by transesterification
reaction with monohydric alcohol, usually methanol [63]. Triglycerides
react with methanol and reduce to methyl ester and glycerol in the
presence of catalyst as depicted in Fig. 5. Glycerol is removed as by-
product and the produced esters are known as biodiesel. According to
ASTM D6751 standard biodiesel should have minimum 96.4% esters.
The rest could be impurities such as water, sediment, free glycerol,
methanol, monoglycerides, diglycerides, triglyceride, alkaline metals,
alkaline earth metals etc. Presence and concentration of these compo-
nents can greatly influence the properties of fuel.

Fig. 3. Graphical illustration of various types of lubrication modes [31].

3.1. Transesterification and catalysts in producing biodiesel

15% is dissipated as frictional and energy losses [40]. Frictional losses
make up the major portion of the energy consumption, which is 48%.
Other portions include cruising and acceleration resistance. Friction
loss is a major occurrence in piston skirt, piston rings and bearings
[41]. In another study the breakdown of energy losses in an engine
amounted to 30–37% of heat loss. Frictional losses constitute 33% and
air drag 5%. After the losses, the energy used to move the car is only
Biodiesel differs chemically from conventional diesel as it is derived
from vegetable oils or animal fats. It mainly consists of triglyceride
molecules [65]. Presence of glyceride makes the oil viscous and sticky.
In order to make the oil useable in diesel engine, its viscosity is reduced
with the help of the process of transesterification [66]. The process of
biodiesel production and transesterification is explained in details in
several papers [5,6,67,68]. Transesterification process is boosted with

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F. Sundus et al. Renewable and Sustainable Energy Reviews 70 (2017) 399–412

Table 1 Table 1 (continued)

Characteristics of various modes of surface degradation.
Surface degradation modes Characteristics Ref
Surface degradation modes Characteristics Ref
• Occurs due to [36]
• Occurs
high
when [26] relative motion
of a corrosive
temperatures, and a metal
loads and surface.
pressures make
two relatively
• Erosion
corrosion in
Adhesive wear moving surfaces engine: Fluid
asperities to exposed engine
spot weld components
together then
tear apart
immediately.
Occurs in shaft
rotating in a
bushing
• Exists when two
surfaces are
[26]
the use of catalyst that also aids in achieving better yields. Three types
of catalysts used are namely acidic, alkaline and enzymes. Sodium
moving relative hydroxide, sodium meth-oxide and potassium hydroxide are some of
to each other the commonly used alkaline catalysts [69]. The process of catalysation
and one is
is faster for alkaline catalysts and the conditions are moderate and
harder than the
other. hence they are utilized more often. Although the reaction is faster and

(b) Abrasive wear • Material

due to hard
loss moderate, there is the drawback of formation of soap in the process of
transesterification of vegetable oils. The soap formation is undesirable
particles
• Takes place in
Piston ring/
because it decreases the yield of biodiesel, partially consumes the
catalyst and makes the separation and purification steps difficult [70].
cylinder bore Usage of sodium hydroxide and potassium hydroxide produces soap as
system side-reaction, since they have the necessary hydroxide group (–OH).
• Occurs when a
surface is
[36] However, as meth-oxide do have the (–OH) group, therefore it does not
produce soap through triglyceride saponification [12]. Using acid
subjective to
repeated loading catalysts also helps avoid the formation of soap. Although acid catalysts
and unloading are studied less, sulphuric acid, hydrochloric acid and sulfonic acid are
• Most common
failure mode of
frequently preferred as acid catalysts. In addition to this, acid catalysts
enhance the esterification of free fatty acids to produce fatty acid
rolling contact
and occurs in
methyl esters, which increases the yield of biodiesel. The drawback of
engine bearing acid catalysts is slower process as compared to the alkaline catalysts
and also the acid-catalysed transesterification needs more extreme
conditions [15,18,65,71]. The third type of catalyst is the enzyme type
which comes under the heterogeneous category. These include tita-
(c) Surface fatigue nium-silicates, anion exchange resins, alkaline earth-metals com-
pounds etc. In recent years, there has been more development in
• Caused by
chemical or
a [36] heterogeneous catalysts, since their usage in biodiesel production
greatly reduces the post-treatment costs and simplifies it.
electrochemical Furthermore, enzyme catalysts do not produce soap through triglycer-
reaction that
ide saponification free fatty acid neutralization as side reactions. The
proceeds
uniformly on the drawbacks met by these heterogeneous catalysts are the extreme
(d) Uniform corrosion entire exposed temperature and pressure conditions and the reaction time is slower
surface of a than the alkaline catalysts [69,72,73].
metal.
• An
electrochemical
[36]
3.2. Fuel properties
process due to
the contact Biodiesel can be characterized by several properties, including
between two viscosity, density, cetane number, flash point and cloud point. Due to
different metals its favourable properties and environmental friendliness, biodiesel is
(e) Galvanic corrosion in the presence
nearly an ideal alternative fuel for direct-ignition compression ignition
of an electrolyte,
in a corrosive (diesel) engines. Physical properties of biodiesel are influenced by
environment. structural features such as: degree of unsaturation, chain length and
• Localized form
of corrosion
[37] branching of chain. Chemical composition which makes up biodiesel
fuel characteristics include cloud point (CP), cetane number (CN),
which results in
cavities and density, viscosity cold filter plugging point (CFPP), oxidative stability,
holes in the iodine value (IV), peroxide value (PV), flash point and lubricity [74,75].
metal and is Physical and chemical properties of biodiesel are shown in Table 2.
difficult to be Density is the key property for any fuel. Engine characteristics such
detected.
as heating value and cetane number are related to density therefore it
directly influences the engine performance. The range of density limit
(continued on next page)
established by European norm is 860–900 kg/m3 [74]. Viscosity of

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F. Sundus et al. Renewable and Sustainable Energy Reviews 70 (2017) 399–412

Fig. 4. Energy losses in automobile engine (adapted from [43]).

and transportation is concerned [81]. Biodiesel fuel properties change

when it undergoes oxidation, temperature rise, stored for a long period
of time or exposed to metal. Analysis of fuel by Fazal et al. [82] showed
degradation after being exposed to metals. As-received biodiesel is
colourless, while after it was exposed to cast iron, brass and copper,
there was a slight change from its original colour. This change in
colorization indicates changes in composition of the fuel.

Fig. 5. Transesterification reaction (R1, R2, and R3 represent the hydrocarbon chains of
3.3. Biodiesel oxidation stability
the fatty acid triglyceride) [64].

Biodiesel has stability issues and several factors affect its composi-
Table 2
Chemical and physical properties of biodiesel (Adapted from [76]).
tion. Researchers are searching for the techniques to enhance stability
of biodiesel so that it can be used and stored for a longer period of time.
Properties Biodiesel EN standard Biodiesel cannot be stored for longer period of time as it gets oxidized
and degrades. Several studies have been conducted to understand the
Density/15 °C (kg/m3) 870–890 860–900
Kinematic viscosity/40 °C (mm2/s) 3.5–6.2 3.5–5.0
factors that make biodiesel less stable as a fuel [19,83,84]. In addition
Cetane number 46–65 51.0 to this, the ability of biodiesel to absorb moisture from its surrounding
Lower heating value (kJ/kg) 36,400–39,500 34,759 also accelerates its degradation process. Among other factors that affect
Oxygen content (% weight) 10–12 11 the stability of biodiesel, temperature and metal contamination are also
Sulfur content (ppm) < 10 10
significant. These factors are discussed in detail below.
Boiling point (°C) 345a 315–350
Flash point (°C) 140–180 > 101 Oxidation stability is the most important factor to evaluate biodiesel
fuel quality. Since biodiesel is more sensitive to the reaction of the fuel-
a
Average value. bound oxygen with hot air environment, therefore it is more prone to
auto-oxidation. As biodiesel has almost 10% higher content of oxygen
biodiesel is influenced by position, number and nature of double bonds, compared to conventional diesel fuel, consequently degradation of
chain length and the nature of oxygenated moieties. High value of oxidation stability occurs [85]. When biodiesel auto-oxidizes, it forms
viscosity causes incomplete combustion, carbon deposition on the products such as aldehydes, carboxylic acids, alcohols, sediments in the
injectors and poor fuel atomization [77]. On the other hand, fuels fuel and insoluble gum. These products are harmful for the automotive
having low viscosity may not provide sufficient lubrication. Phankosol engine as the insoluble gum can choke the injection pin and the acids
et al. [78] proposed a model which can be extended to find out corrode the metallic engine components. Biodiesel is also more prone
kinematic viscosity of biodiesel from its number of double bonds and to oxidation because of the presence of unsaturated free fatty acid
carbon number at different temperatures without knowing viscosity double bonds. Longer induction periods show more oxidation stability.
value of individual FAME. In previous studies, Knothe and Steidley A study carried out to measure different induction periods (IP) of
[79] also used an equation to estimate kinematic viscosity of biodiesel. different biodiesels showed that palm biodiesel has an IP of 13.37 h
They confirmed from their equation that viscosity of biodiesel is while that of sunflower biodiesel is only 1.73 h. This difference in
directly related to its methyl esters content. They predicted kinematic induction period is due to the difference of percentage of saturated fatty
viscosities of several feedstocks by their kinematic viscosities values of acid in biodiesels [11]. Induction period decreases with the increase in
individual biodiesel components. the percentages of unsaturated fatty acid in the fuels. Oxidation
Density increases with decreasing chain length and increasing instability of biodiesel is accelerated because of several factors such
degree of unsaturation. Study on effect of thermal decomposition on as temperature and hygroscopy [86,87].
biodiesel cold flow properties was conducted by Ronghong Lin et al.
[80]. Their research concluded that cis-trans isomerization reactions 3.3.1. Effect of storage time
had nominal effect on cold flow properties and viscosity of biodiesel but Storage stability is the ability of a fuel to retain its properties and
pyrolysis and polymerization reactions had substantial influence on resist any physical and chemical change. The resistance to composi-
these properties. Biodiesel's flash point temperature is higher than tional changes during storage is an important issue for biodiesel [88].
conventional diesel fuel, making it less volatile and safer when storage When biodiesel is stored for a long period of time, storage stability

403
F. Sundus et al.
Table 3
General characteristics values employed for measuring stability of biodiesel (adapted
from [93]).
Properties of biodiesel Indication criterion
Induction period (IP) Lower the IP lower the oxidation stability.
Acid value (AV) Higher the acid value, higher the formation of acidic
products by oxidation.
Peroxide value (PV) Higher PV values, higher the rate of peroxide
formation.
Iodine value (IV) Lower iodine number is resulted due to the lower
degree of unsaturation.
Density (D) & viscosity Oxidation products are higher in molecular weight
(V) and thus increase density, which also results in higher
viscosity.
FAME concentration FAME concentration determines the composition of
biodiesel, which indicates the degradation of fuel.
comes into concern. Long time storage leads to compositional changes
occur in biodiesel and it is probably among the primary concerns for
the storage stability. In 1985, Du Plessis et al. [89] studied the storage
stability of biodiesel for the first time. They stored biodiesel for 90 days
and reported production of acids, aldehydes, peroxides and also
increase in the viscosity. Robert O. Dun [90] checked the effect of
oxidation on the fuel properties of methyl Soyate under accelerated
conditions for oxidation. The obtained results support earlier works
conducted in the same domain by Thompson et al. [91], Plessis et al.
[89] and Bondioli et al. [92]. The works carried out by these
researchers consisted of 90 days to 2 years of storage period, where
Induction period (IP), Acid value (AV), Peroxide value (PV), viscosity
and density are some of the properties that are considered for
measuring stability of biodiesel. Table 3 lists the indication criterion
for these properties.
3.3.2. Effect of humidity and moisture absorption on biodiesel
lubricity
Biodiesel is hygroscopic in nature, which is a major source of fuel
contamination. Water typically enters into the fuel through fuel tanks,
vents and seals as humidity in the air. The maximum amount of water
content allowed in biodiesel specified by ASTM standard D9751 is
0.05% by volume. The increase in the water content of biodiesel is often
caused by improper handling after processing [6] or by absorbing
atmospheric moisture during storage. Water content in biodiesel
causes two major problems: it causes and accelerates the corrosion
process of the engine fuel system components and microbial growth
that further leads to slug formation and fuel filter plugging. Microbial
growth are species of bacteria, fungi and yeast that grows because of
the presence of water in the fuel [94].
He et al. [95] carried out experiments to determine the water
absorbance in biodiesel from different feedstock (three vegetable oils
and two primary alcohols) at three temperatures. They observed that
there was no significant difference in moisture absorption in biodiesel
from different origins. In the temperature range of 4–35 °C, biodiesel
moisture was 15–25% greater than that of diesel. They also observed
that petro-diesel blends have a lower capacity for moisture absorption
from the atmosphere. Their results were supported by Kaminski and
Kurzydlowski [96] who determined that microorganisms in the envir-
onment results in the increase in viscosity only at biofuel/water
interface. Experiments carried out by Haseeb et al. [97] also showed
that biodiesel absorbs moisture during storage and when exposed to
metals. Their as-received biodiesel does not have detectable water
content; however the fuel picks up water when exposed to copper and
bronze (Table 4).
3.3.3. Effect of metal contamination
Metals contamination is proven to be detrimental to biodiesel
oxidation stability. Various transition metals like iron, nickel, manga-
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Renewable and Sustainable Energy Reviews 70 (2017) 399–412
Table 4
Relative water content of as-received biodiesel and biodiesel immersed in bronze and
copper at room temperature [97].
Concentration of biodiesel in % of water
blend
As-received Exposed to Exposed to
bronze copper
B0 0 0 0
B50 0 0.1 0.14
B100 0 0.42 0.33
nese, cobalt and copper are found in metal containers. These metals are
exposed to biodiesel during storage. Experiments carried on by Sarin
et al. [98] showed the influence of metal contamination on palm methyl
ester. Rancimat method in accordance with EN 14112 was employed
and the results showed that smaller extent of metal contamination had
same detrimental effect on biodiesel oxidation stability as greater
amounts. Presence of metals in biodiesel accelerates the free radical
oxidation because of metal-mediated initiation reaction. Among cobalt,
manganese, iron, copper and nickel; copper showed the strongest
catalytic and damaging effect. Sarin et al. [99] also investigated the
effect of metal contamination in Jatropha biodiesel and found similar
results. Copper affected the oxidation stability most strongly.
Furthermore, it was noted that metal contaminants affected the
oxidation stability irrespective of the quantity. Results indicated that
as the concentration of metal contamination (in ppm) increases, the
induction period for the biodiesel decreases.
3.3.4. Effect of temperature
The oxidation stability of biodiesel also depends on temperature. A
change in temperature has detrimental effects on biodiesel stability.
This parameter, along with others such as exposure to air, moisture
absorption, lower volatility, are more inclined to influence the lubrica-
tion properties of biodiesel and speed up wear of various engine
components. According to the findings of Maleque et al. [100], addition
of 5% POME in lubricant increases the total acid number (TAN) at
higher temperature. They also observed excess wear due to oxidation of
lubricants at high temperature. Furthermore, Haseeb et al. [101]
conducted tests on palm biodiesel at temperatures 30, 45, 60 and
75 °C using four-ball tribotester to investigate the influence of different
temperatures on biodiesel stability. They compared petroleum diesel
(B0) with three diesel/biodiesel blends namely B10, B20 and B50 for
1 h and at 1200 rpm. Their finding also conforms to the results of
Maleque et al. by verifying that friction and wear increases with the
increase in temperature. Moreover, deformation of worn surface was
also reported with the increase in temperature. Storing biodiesel at
elevated temperatures also resulted in deterioration of its properties
[90,92]. Similar results were found by other researches as well which
are summarized in Table 5.
4. Major concerns regarding tribological compatibility in
biodiesel
Although biodiesel have lifted up several environmental and fossil
fuel depletion concerns but it imposes some serious problems for the
tribologists. Among them the most serious problem is the compatibility
of automotive materials with the biodiesel fuel [106]. Key components,
such as cylinder, piston, piston rings, bearings etc., are of much
concern when biodiesel is used. At present, biodiesel is used in some
percentage with the conventional diesel in the form of blends as B10
(with 10% being biodiesel and 90% conventional diesel), B20, B40 and
B50. Challenges imposed by biodiesel in terms of material compat-
ibility that will be discussed in this paper include wear and friction,
corrosion and tribo-corrosion.
F. Sundus et al. Renewable and Sustainable Energy Reviews 70 (2017) 399–412

Table 5
Effect of temperature on biodiesel properties.

Feedstock Method Temperature Finding Ref.

POME Modified universal wear and friction testing apparatus 40–140 °C [99]

Palm biodiesel Four ball 30–45–60–75 °C [19]

Used cooking oil Rancimat 743 equipment 110–130 °C [102]

Soybean biodiesel
Animal fats

Soybean Rancimat method 60 °C and 110 °C [85]

Methyl Soyate Storage 40 °C [103]

Soybean oil (SO) – 180 °C [104]

Soybean: Palm oil (6:4) (MO)

Palm High temperature storage 60 °C [105]

4.1. Wear and friction in biodiesel
Tribologists are determined to overcome the complexities asso-
ciated with engine components and fuel interaction. Fuel usually comes
in direct contact with filter, fuel tank, cylinder liner, piston, piston
rings, connecting rod, etc. Hence, in order to understand mechanism of
wear and friction in fuels diesel and biodiesel, several tests have been
conducted with different diesel-biodiesel blends. Four-ball test con-
ducted on different biodiesel-diesel blends for 1 h with the conditions
of 40 kg load, varying speed of 600–1500 rpm by Fazal et al. showed
less wear as the percentage of biodiesel was increased in the blend
[106]. Table 6 shows laboratory wear scar and coefficient of friction
data of different biodiesel sources and blends. Data shows that with the
increase in the percentage of biodiesel, wear scar diameter decreases.
The same trend was also observed in case of coefficient of friction.
Friction coefficient decreases with the increase in ratio of biodiesel in
the blend. Kumar et al. [107] observed a slight altered trend with the
wear scar value of B40 being 0.62 mm and value for B100 was
0.68 mm. For their experiment, addition of biodiesel from 40% to
100% increased the wear scar diameter. A similar phenomenon was
observed for the trend in coefficient of friction for B40 and B100 under
the load of 60 kg. Wear investigation of piston rings was executed by
Sorate et al. [108]. Long-term usage test was conducted by running an
engine fueled with diesel and biodiesel for the duration of 512 h. As the
top most piston ring faces the highest temperature, therefore it
encountered highest weight loss. After the first ring, compression ring
was observed to have greater weight loss. The least weight loss was
observed in oil ring. Overall, greater weight loss was observed in
biodiesel. Fig. 6 shows the weight loss of piston rings in diesel and
biodiesel.

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F. Sundus et al. Renewable and Sustainable Energy Reviews 70 (2017) 399–412

Table 6
Short term wear and friction data of different blends and sources of biodiesel.

Biodiesel Sources Test Temperature (°C) Load (kg) Frequency (rpm) Time (s) Wear CoF (µ) Ref

B20 B20 Soybean HFRR 25 – – – 166 µm 0.139 [116]

Animal fat 175 µm 0.124
B10 Used vegetable oil HFRR – – – – 283 µm – [117]
B10 POME – Ambient 51.2–64 1500 60 – 0.058 [118]
B10 0.85 mm 0.088 [106]
B20 Palm Four-ball 75 40 600–1500 3600 0.77 mm 0.0865
B50 0.75 mm 0.086
B100 0.7 mm 0.084
B10 0.61 mm 0.04 [101]
B20 Palm Four-Ball 30, 45, 60, 75 40 1200 3600 0.60 mm 0.039
B50 0.53 mm 0.035
B20 0.72 mm 0.076 [107]
B40 Jatropha Four-ball 45–60–75 40–50–60 1500 3600 0.62 mm 0.072
B100 0.68 mm 0.069

Diesel (D) Biodiesel (BD) corrosion [93,121].

100 BD
90 BD
80
Weight Loss (mg)

4.2. Metal corrosion in biodiesel

70 D
60 D
50
40
30
20
10
0 Materials such as copper, lead, tin, zinc, brass and bronze are not
Top ring Compression ring Scrap ring
Fig. 6. Piston rings weight loss in diesel and biodiesel fueled engine [108].
Kalam and Masjuki [109] conducted an experiment to see the
results of wear of materials in biodiesel and diesel. They operated an
engine for 300 h with a blend carrying 15% palm biodiesel and 85%
being diesel. It was observed that there were less wear particles in oil
analyses; hence engine exhibited less wear with B15 than diesel fuel.
Tests conducted for 500 h with a B20 blend by Agarwal et al. [110] also
showed lesser wear. Clark et al. [111] and Peterson et al. [112]
operated the engine for 200 h with B100 (Methyl and ethyl soyate)
and Rapeseed methyl and ethyl ester respectively and they both
observed a similar wear as that with diesel fuel. Another field test
run by Agarwal et al. [113] gave less wear when run on biodiesel. They
ran two similar engines, one with B20 and one with conventional diesel
fuel, for 512 h. Results showed the amount of carbon deposited on the
system tested with B20 was 40% less than that of diesel run engine.
Injector tip of diesel-fueled system after 200 h had more carbon
deposition as compared to injector tip of B20-fueled system after
512 h run. Several researchers conducted tests with biodiesel in engine
for 2–4 years [111,114,115]. Their obtained results showed almost
similar wear as that of diesel fuel being used in an engine.
Results show that the use of biodiesel reduces wear and friction for
the short-term use but biodiesel use for long term is still a challenge.
Based on these studies, it can be said that during short term tests,
biodiesel provides better lubricity, hence less wear as compared to
conventional diesel. On the other hand, long term tests results show
that biodiesel loses its lubricity over long time run and its wear also
becomes similar to that of diesel fuel. This is because biodiesel is
susceptible to auto-oxidation [119]. Auto-oxidation occurs when
biodiesel is exposed to oxygen and the process is accelerated with
elevated temperatures. Biodiesel gets oxidized when it is stored or even
when it is circulating in an engine [120]. This is due to the chemical
composition of biodiesel, which contains several unsaturated fatty acid
components and more carbon-to-carbon double bonds. Auto-oxidation
results in degradation of the fuel properties like viscosity, cloud point,
flash point, density etc., which can affect the performance of the engine
and reduce the engine life by enhancing wear, corrosion and tribo-
BD Since, in the engine, fuel comes in contact with various components
such as fuel pump, fuel injector, piston, piston rings filters, and
D
BD bearings. Studies indicate that cast iron, carbon steel, aluminium and
D stainless steel materials are relatively compatible with pure biodiesel.
Oil ring compatible with biodiesel. These materials decrease biodiesel stability
and increase its corrosiveness [122].
Several factors contribute to the corrosiveness of biodiesel.
Biodiesel is more hygroscopic in nature than conventional diesel fuel.
When biodiesel is stored for a long time, it absorbs moisture and water
content which in turn accelerates the hydrolysis of ester bonds. This
produces free fatty acids (FFA), which increases corrosiveness
[93,123]. Other factors, which contribute to the corrosiveness of
biodiesel, include auto-oxidation, microorganisms attack and some
remaining impurities after the process of trans-esterification, light and
temperature.
Sgroi et al. [124] experimented with bronze in biodiesel for 10 h by
using sintered bronze filters at 70°. They observed pitting corrosion on
the surface. Haseeb et al. [97] carried static immersion tests for copper
and leaded bronze in B0, B50 and B100. They immersed these
materials in the mentioned fuels for 2640 h at room temperature.
From the results, they concluded that copper is more susceptible to
corrosion in biodiesel as compared to leaded bronze. Several other
researchers have researched on the corrosion challenge of biodiesel and
to know its causes. Another static immersion test was carried out by S.
Kaul et al. [58] using non edible biodiesels: Jatropha curcas,
Salvadora oleoides, Madhuca Indica and Pongamia glabra. They
immersed cut engine parts namely piston metal and piston liner and
immersed them into fuels for 300 days at room temperature. They
observed a weight loss in piston liner case with all biodiesel samples
but no gum formation was seen in any of the test material. These
studies are further backed up by the corrosion tests performed by D.P.
Geller et al. [125]. Copper, aluminium, brass, bronze and zinc are put
forward as incompatible with biodiesel elsewhere as well [126].
Immersion tests were carried out on copper surfaces in palm biodiesel
by Fazal et al. [17]. Fig. 7 shows the SEM images of their biodiesel
immersed copper surfaces at different immersion times. They observed
small pits on the surface of 200 h immersed copper surface (Fig. 7b).
These pits seem to progress as the immersion time in biodiesel is
increased. These pits increased due to increase in oxygen concentration
with the increase in immersion time.
An increased corrosion rate for mild steel was also observed by
Fazal et al. [127], for both diesel and biodiesel fuel, as the temperature
was increased. In another study, Fazal et al. [128] observed that at

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F. Sundus et al. Renewable and Sustainable Energy Reviews 70 (2017) 399–412

Fig. 7. Copper surface before and after exposure in palm biodiesel at different immersion times [17].

room temperature the corrosion rate for diesel and biodiesel is 0.046 summarizes some of the tests and their results for corrosiveness of
and 0.052 mpy respectively. Increasing the temperature to 80 °C biodiesel. Corrosion rate of biodiesel increases as its concentration in
changes the corrosion rate to 0.05 mpy in diesel and 0.059 mpy in the blend is increased. Corrosion takes place even with a small
biodiesel. Hence, showing that biodiesel is more corrosive than percentage of 2–5% biodiesel in the blend [132]. There is still need
conventional diesel fuel. for research in order to make biodiesel more compatible with the
Degradation of biodiesel fuel changes the fuel properties. TAN engine material and to overcome its corrosion challenge.
number, viscosity, density, cetane number, flash point etc. are changed
which further increases the corrosion rate. In addition to this, biodiesel
4.3. Tribo-corrosion in biodiesel
feedstock also affects the corrosive nature of biodiesel [129]. Kaul et al.
[58] carried out experiments with non-edible Jatropha curcas,
Tribo-corrosion is the combined effect of corrosion and wear. It
Pongamia glabra (Karanja), Madhuca indica (Mahua) and
basically involves the science of surface transformation and degrada-
Salvadora oleoides (Pilu) oils and studied their effect on corrosion.
tion of material. It is because of mechanical loading and chemical/
They observed biodiesel from Salvadora showed clear corrosion on
electro-chemical reactions that occur between two interacting surfaces.
both metal parts of diesel engine whereas biodiesel from other oils
Corrosive environment leads to tribo-corrosion taking place between
showed little or/no corrosion as compared to conventional diesel fuel.
the elements of a tribo-system [136]. Fig. 8 shows the basic concept of
A number of experiments are in coherence with the finding that
tribo-corrosion. Since this phenomenon is widespread in many appli-
biodiesel is more corrosive because it is highly prone to oxidation as
cations and very noticeable in automotive engines therefore tribologists
opposed to conventional diesel [130,131]. Generally, static immersion
need to fully understand the effect of biodiesel on the parts moving in
tests are carried out to study the corrosive nature of biodiesel. Table 7
relative motion. Tribo-corrosion results in high material loss, affects

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F. Sundus et al. Renewable and Sustainable Energy Reviews 70 (2017) 399–412

Table 7
Corrosion rate of different biodiesel feedstock.

Feedstock Material Static immersion Corrosion rate (mpy) Findings Ref.

parameters

Palm Cu, Mild Steel Room temperature, Cu: 0.91057 Enhanced corrosion rate of Cu as [133]
20, 40, 60 days Mild Steel: 0.06916 compared to mild steel
Sunflower Al, Cu, Mild Room temperature Cu: 0.323615 Corrosiveness of biodiesel is [134]
Carbon Steel and 60 C Mild Carbon Steel: 0.170124 greater than diesel. It increases
3000 h Al: 0.162201 with increasing temp.
Palm Cu, BS, Al, CI Room temperature, Cu: 0.39278 Biodiesel is more corrosive than [82]
2880 h BS: 0.209898 diesel fuel
Al: 0.173055
CI: 0.112232
Soybean, Sunflower CS 60 C Checked after 60 – Soybean biodiesel is more [129]
and 115 days compatible with CS than sunflower
biodiesel and diesel
Palm Cu, leaded Room temperature, Cu and leaded bronze show greater [97]
Bronze 2460 h corrosion rate in biodiesel

Jatropha curcas, Aluminium alloy Room temperature, Corrosion in Salvadora and Jatropha biodiesel is twice as Jatropha: 0.0117, Karanja: [58]
Karanja, mahua, 300 days compared to diesel 0.0058, Mahua: 0.0058,
Salvadora Salvadora: 0.01236, diesel: 0.0058
Poultry fat CS, Grey CI, 316 Room temperature, – Cu and BS are more prone to [125]
SS, BS, 7342 h (10 months) corrosion in biodiesel
Palm Al, Cu, SS 80 °C 600 and 1200 h Cu: 0.586, Al: 0.202, SS: 0.015 Cu shows higher corrosion rate [135]
at 250 rpm

Cu: Copper; Al: Aluminium; BS: Brass; CI: Cast Iron; CS: Carbon steel; SS: Stainless steel

with biodiesel were found to enhance the lubricity [19,137].

S urface degrad
dation Due to the aforementioned contradiction in biodiesel, there is still a
process need to take up further investigations and studies to understand the
combined effect of wear and corrosion both for long and short
duration. Over the time, the corrosiveness of biodiesel increases which
results in excessive wear of the engine components those are in relative
sliding motion and in contact with fuel. The lubricating oil in the
Mechanica l Chemical crankcase can also get contaminated which further enhances the wear
and corrosion of lubricated engine components.

ogy (friction +
Tribolo 5. Biodiesel stability improvement
Corrosion
wear + lubrication) Environment
Stability issues with biodiesel include thermal, oxidative and
storage stability. Due to the presence of saturated bonds, biodiesel
readily becomes oxidized and losses its stability. Das et al. [74] carried
out long-term storage stability test on Karanja biodiesel and reported
that its oxidative stability decreased with an increase in peroxide value
and viscosity. In order to overcome the problems linked with the
stability of biodiesel and its usage, refining biodiesel in early produc-
Tribo-corrossion tion stage and adding additives is very productive and cost-effective.
Production of biodiesel using alkaline catalysts such as sodium hydro-
xide (NaOH), potassium hydroxide (KOH) and sodium, potassium
Fig. 8. Basic definition of tribo-corrosion. methoxides (CH3ONa and CH3OK) gives a higher yield of biodiesel but
it also causes problem of soap formation. Therefore, refining of
the durability and life of a vehicle. biodiesel is important. The purification of biodiesel can be achieved
Biodiesel have proved to be contradictory in its nature to tribolo- via wet and dry washing. A new technology called membrane technol-
gists and researchers. At elevated temperatures, biodiesel gets oxidized ogy has opened easy and more promising doors for biodiesel refining
and its ability to corrode materials gets more aggressive with long time and purification. Purification and refining increases lubrication prop-
of usage. This is mainly due to the increase in the water content and erty of biodiesel and makes it more compatible with the engine
oxidation products in biodiesel, which leads to tribo-corrosion and components [90,138]. Additives are the chemicals which are mixed
tribological challenges. On the other hand, short tribological tests run with the fuels to improve efficiency and fuel economy [139]. Addition of

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F. Sundus et al. Renewable and Sustainable Energy Reviews 70 (2017) 399–412

additives has proven to be biodiesel lubrication enhancer. Moreover,

Waste cooking palm oil based

Soybean oil fatty acid methyl

Palm olien and diesel blends

they also help the fuel in meeting the standard environmental emis-

Three different biodiesels

sions and to improve its engine performance.

Five biodiesels blended

Rape seed methyl ester
Palm Oil Methyl Ester

FFA based biodiesel

Jatropha biodiesel
Soybean biodiesel
Soybean biodiesel
5.1. Improvement by adding additives

esters (SME)
Feed stock

biodiesel.
The use of additives is an effective and convenient way to improve
emission and performance of an engine run with biodiesel-diesel blend
[140]. Additives such as antioxidants significantly slow down biodiesel

–
degradation process [141]. A Study carried out by Dunn [90] focuses

a-tocopherol, BHA, BHT, DTBHQ, Ethanox 4740, ethanox 4760E,

on the effects of oxidation under controlled accelerated conditions on
methyl Soyate (SME) fuel properties. Tests were carried out for
temperatures up to 150 °C. Under these conditions, he found antiox-
idants TBHQ and α-tocopherol beneficial in retarding oxidative
degradation. Jain et al. [23] experimented with Jatropha biodiesel

Caffeic acid, Ferulic acid, and Terthydroquinone

and found antioxidant pyrogallol (PY) to be most effective on metal

α-tocopherol, BHT, TBP, OBPA, and TBHQ

contaminated biodiesel/diesel blend. Contrary to this, Sarin et al. [98]

MBMTBP, PDA, PG, PY, TBHQ synthetic).

TCP, DBPi, SO, ZDDP, PN agent, B agent
measured oxidation stability of highly stable Palm methyl ester (PME)
in the presence of metal contaminants with varying dosages of different
antioxidants, at temperature 110 °C. They found antioxidant TBHQ to
be most effective among all.

BHT, TBHQ, BHA PG, PA

TBHQ, PrG, α-Tocopherol
Karavalakis et al. [142] concluded after their experiment with

IRGALUBE 349 additive

Ferric chloride (FeCl3)
biodiesel blends and anti-oxidant additives that PG, PA and TBHQ

BHT, BHA, TBHQ

showed the most effective results in neat methyl esters, whereas BHA

Additives used

2-dihydroxybenz
IRGANOR NPA
and BHT were least effective. Another study shows the same results
[75]. Sarin et al. studied the effect of natural and synthetic antioxidants
on oxidation stability (OS) of non-edible biodiesel (Jatropha curcas).

BHT
They found both natural and synthetic antioxidants showing improve-
ment in biodiesel OS but, comparatively, synthetic antioxidants were
found to be more effective [143]. They concluded the efficiency of used

Single cylinder, four-stroke water cooled, naturally

antioxidants as TBHQ > BHT > TBP > OBPA > a-Tocopherol. Some of
the tests conducted with additives and their results are summarized in
P-DSC analyses were conducted with a TA
The Isuzu 4FBIfour-cylinder diesel engine

Table 8. Mostly synthetic additives such as BHT, TBHQ, PG, PY etc. are

4-cylinder and 4-stroke IDI diesel engine

aspirated, direct injection diesel engine
utilized. Addition of additives improves wear and friction. They enable
automotive engine to give better performance by safeguarding biodiesel
from the effects of auto-oxidation (Table 9).

5.2. Improvement by refining technologies

Optimol SRV tester

Rancimat Method
Rancimat method
Rancimat method

Rancimat method

Rancimat method

Rancimat method
After the process of transesterification, crude biodiesel has to be
separated from the by-product glycerol. Only after this separation
Instruments
Method

biodiesel can meet the international standard specification provided by

EN 14214 [149]. There are two types in the washing technique namely
–

wet washing technologies and dry washing technologies. The process of

wet washing of biodiesel involves addition of certain amount of water
Decreased brake specific fuel consumption (BSFC) of 8.6% while the

Better engine performance, reduces unnecessary exhaust emissions

Effect of various additives on different biodiesel oxidation stability and wear.

to crude biodiesel and then heating it up gently in order to avoid

Reduction in oxidation processes at the initial time of storage.

3000 ppm of BHA or TBHQ is recommended for safeguarding

Reduction in insoluble formation. Increases blends’ resistance

emulsion formation. The process is repeated until the wash water turns
Increase in the oxidation stability of Jatropha methyl ester
Increase in Brake power, SFC and emissions performance.

colourless which indicates that all the impurities have been removed.
Induction period increased linearly with the anti-oxidant

This process requires a great amount of water [150]. The major

biodiesel from effects of autoxidation during storage.

Noticeable increase in Induction period of biodiesel

disadvantage of using water to purify biodiesel is the increased cost

toward secondary oxidation products formation.

and wear debris concentration of engine parts.

and production time [151]. Dry washing technologies were introduced

brake thermal efficiency increased by 6.3%.

in order to substitute water washing but the understanding of these dry

Increased stability. BHT > TBHQ > BHA

Increase in biodiesel oxidation stability

washing technologies is little [152]. Silicates (Magnesol or Trisyl),

celluosics, activated clay, activated fiber, ion exchange resins
(Amberlite or purolite) and activated carbon are usually used to obtain
PG > PA > TBHQ > BHT > BHA

purified biodiesel in dry washing technique [153]. This process is

Improved wear protection

mostly carried on at a temperature of 65 °C and is completed in 20–

30 min. The advantage this process have over wet washing technology
is that it is waterless, purification time is less, no water-waste, it can be
concentration.

easily incorporated with the existing plant and it has strong affinity
Findings

with the polar compounds [154].

The difficulties of water content and skeletal understanding asso-
ciated with wet and dry washing technologies have given rise to involve
research in membrane technology to purify crude biodiesel. The
Table 8

[144]
[145]
[139]

[146]
[114]

[102]

[111]

[115]

[147]

[143]

[148]
[28]
Ref

membrane equipment produced for the separation and purification of

crude biodiesel shows many advantages over the conventional methods

409
F. Sundus et al.
Table 9
Advantages and disadvantages of different refining techniques [156].
Technique Advantages
Wet washing – Excellent methanol removal
– Can reduce methanol, soap and free glycerol levels below the amount
needed by EN14214, with biodiesel purity of 99%
Dry washing – Magnesol can remove free and bonded glycerol, soap and potassium.
– Magnesol is efficient and has the Ability to replace water washing
– Can effectively remove residual methanol, catalyst traces
– Can augments the stability of bio-diesel in the oxidation process,
besides it ability to remove sulfur
– Can save time, lower energy, save capital cost, and lead significant
disposal cost reduction
Membrane – Provided good yield, high purity and quality finished products that are
purification comparable to the conventional diesel fuels, simple, with less energy
consumption, provide enormous environmental benefits and energy
savings
– Reduction in separation and purification costs, improved fuel quality,
and high recovery of valuable products
– Zero waster washing with no waste discharges, and provide biodiesel
with less glycerol content
[155]. It minimizes high production cost, no usage of water hence no
wastewater and provides high surface area for mass transfer.
Membrane equipment for purification of biodiesel is usually made
from inorganic microporous ceramic membranes [156].
6. Summary and conclusion
Although biodiesel serves as a promising alternative to conventional
diesel fuel in terms of biodegradability, environmental friendliness,
renewability and better lubrication, it poses some major threats to the
engine components in terms of wear, friction and clogging of the
injection pin. Biodiesel properties could be affected by storage, high
temperature, moisture absorption and metal contamination. While
properties of as-received biodiesel comply with the given standard,
many properties can change with the continued usage upon its
degradation. As mentioned in the literature studies, it has been found
that biodiesel decreases wear and friction when utilized for short-term.
When long-term usage of biodiesel is in consideration, then its wear
and friction is about the same as that of diesel. It is more corrosive in
nature than conventional diesel fuel and due to its corrosive nature the
employment of biodiesel poses major challenges with the automotive
engine components.
Biodiesel is hygroscopic in nature and it absorbs moisture from the
atmosphere when stored for a longer period of time. Furthermore, at
higher temperatures it gets oxidized, which further increases the free
water content. This leads to degradation of biodiesel fuel properties.
Exposure to different metals and metal contamination has negative
effect on the oxidation stability of biodiesel. Even small concentration
of metal contaminants decrease biodiesel induction period (IP) while
increasing its water content, acid value (AV) and Peroxide value (PV).
The introduction of refining technologies for biodiesel ensures im-
provement in biodiesel by making it pure before the usage. Membrane
technology for separation and purification of biodiesel has minimized
the separation and purification difficulties to a great extent. However,
there still is need for more thorough exploration to determine its
potential for biodiesel mixture separation and purification.
Furthermore, additions of additives show effective performance by
increasing the oxidation stability of neat biodiesels.
Although some research has been carried out on the stability of
biodiesel and its improvement but there is major scope for more
research, development and commercialization to minimize the effect of
detrimental factors that cause biodiesel instability and fuel degrada-
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Renewable and Sustainable Energy Reviews 70 (2017) 399–412
Disadvantages
– Emulsion formation, wastewater treatment, no effects on glycerides, and
drying of final product
– Consumption of water and Na2SO4, high biodiesel products drying cost
long time for water washing and the process is less ecologically viable
– Considerable loss in product due to formation of soap and emulsion, and
treatment could incur high energy cost
– Information regarding the chemical composition of the resin is difficult
and little effects on methanol
– Involve highly consumable incurring expensive, require significant
resources, larger size of powder grains making them exceedingly
difficult to remove, and this caused an abrasive contaminated fuel
– Organic membranes are less stable and easily get swollen in organic
solvent
– No large-scale industrial applications
tion. Further research on best suitable anti-corrosion and anti-oxidant
additives is also required to decrease corrosiveness of biodiesel and
stabilize its oxidation process.
Acknowledgment
The authors would like to appreciate University of Malaya for
financial support through High Impact Research grant titled:
‘‘Development of Alternative and Renewable Energy Carrier
(DAREC)’’ having Grant number UM.C/625/1/HIR/MOHE/ENG/60.
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