Clean Techn Environ Policy (2010) 12:459–493

DOI 10.1007/s10098-009-0268-6

REVIEW

Advances in biodiesel fuel for application in compression

ignition engines
Jo-Han Ng • Hoon Kiat Ng • Suyin Gan

Received: 28 August 2009 / Accepted: 13 November 2009 / Published online: 19 December 2009
 Springer-Verlag 2009

Abstract The importance of biodiesel as a renewable and to the physical properties and chemical composition of the
economically viable alternative to fossil diesel for appli- fuels. Despite the purported benefits, widespread adoption
cations in compression ignition (CI) engines has led to of biodiesel usage in CI engines is hindered by outstanding
intense research in the field over the last two decades. This technical challenges, such as low temperature inoperability,
is predominantly due to the depletion of petroleum resour- storage instabilities, in-cylinder carbon deposition and fuel
ces, and increasing awareness of environmental and health line corrosion. It is imperative that these issues are
impacts from the combustion of fossil diesel. Biodiesel is addressed appropriately to ensure that long-term biodiesel
favoured over other biofuels because of its compatibility usage in CI engines does not negatively affect the overall
with present day CI engines, with no further adjustments engine durability. Possible solutions range from biodiesel
required to the core engine configurations when used in fuel reformulation through feedstock choice and production
either neat or blended forms. Studies conducted to date on technique, to the simple addition of fuel additives. This calls
various CI engines fuelled with varying biodiesel types and for a more strategic and comprehensive research effort
blends under numerous test cycles have shown that key internationally, with an overarching approach for co-ordi-
tailpipe pollutants, such as carbon monoxide, aromatics, nating sustainable exploitation and utilisation of biodiesel.
sulphur oxides, unburnt hydrocarbons and particulate mat- This review examines the combustion quality, exhaust
ters are potentially reduced. The effects of biodiesel on emissions and tribological impacts of biodiesel on CI
nitrogen oxides emission require further tests and valida- engines, with specific focus on the influence of biodiesel’s
tions. The improvement in most of the diesel emission physico-chemical properties. Ongoing efforts in mitigating
species comes with a trade-off in a reduction of brake power problems related to engine operations due to biodiesel usage
and an increase in fuel consumption. Biodiesel’s lubricating are addressed. Present day biodiesel production methods
properties are generally better than those of its fossil diesel and emerging trends are also identified, with specific focus
counterpart, which result in an increased engine life. These on the conventional transesterification process wherein
substantial differences in engine-out responses between factors affecting its yield are discussed.
biodiesel and fossil diesel combustion are mainly attributed
Keywords Biodiesel  Properties  Production 
Combustion  Emissions

J.-H. Ng  H. K. Ng (&)
Department of Mechanical, Materials and Manufacturing
Introduction
Engineering, The University of Nottingham Malaysia Campus,
Jalan Broga 43500, Semenyih, Selangor, Malaysia
e-mail: [email protected] The search for an alternative fuel for diesel engines has
intensified in recent years with the imminent depletion of
S. Gan
fossil fuel in the next four decades, based on present con-
Department of Chemical and Environmental Engineering,
The University of Nottingham Malaysia Campus, sumption rate of the proven reserves (BP 2008). Other key
Jalan Broga 43500, Semenyih, Selangor, Malaysia factors contributing to this include growing environmental

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460 J.-H. Ng et al.

concerns and volatile crude oil prices. Among alternative during shipment because its flash point at 423 K is sig-
fuels touted, biodiesel is currently favoured in the ground nificantly higher than that of fossil diesel at 337 K
transportation sector due to the availability of current (Demirbas 2009).
production technology, and compatibility with existing Despite the many apparent benefits from the usage of
infrastructure of conventional diesel fuel. Owing to a biodiesel in diesel engines, widespread adoption of the fuel
combination of these factors and encouraging measures within the automotive sector is hindered mainly by the high
adopted by policy makers in the form of fiscal policies, cost and associated operational problems. At present, bio-
mandatory blending, trading laws, biodiesel standards and diesel is still not as cost-competitive as fossil diesel due to
emission legislations, biodiesel has since seen a rapid the high price of the feedstock oil (Lapuerta et al. 2008).
annual increment in its worldwide production (Ng et al. Positive governmental policies and subsidies have proven
2009). The 2008 global biodiesel production stood at to encourage the initial uptake of biodiesel. Nevertheless,
14.282 million tonnes (Biofuels Platform 2009), which the eventual cost competitiveness of biodiesel in the long-
represented increases of 52.3 and 125% from the 2007 and term future is expected to be governed by maturing pro-
2006 production levels of 9.378 and 6.350 million tonnes, duction technology, utilisation of cheaper non-edible oil as
respectively (Biofuels Platform 2008; EBB 2006). Even in feedstock and the rising trend in global crude oil prices.
countries where other alternative fuels are commonplace, Outstanding technical challenges in areas involving low
biodiesel has now gained a foothold in the market share. temperature operation, storage, carbon deposition and
For example, in Brazil where bioethanol is traditionally corrosion have been addressed, with varying degrees of
favoured, the country has launched a National Program of success, through simple measures, such as fuel preheating,
Production and Use of Biodiesel in December 2004 to biocide application, proper filter maintenance and drainage
guarantee the economic viability of the fuel (Pousa etal. of retained water (Demirbas 2007; Murillo et al. 2007;
2007). A mandatory blending of 2 and 5% of biodiesel in Bozbas 2008). Quality and usability of biodiesel can be
diesel fuel by 2008 and 2013, respectively are introduced further improved upon through the use of fuel additives in
through the scheme. As such, biodiesel is expected to play the form of antioxidants, cetane enhancer, corrosion
a major role in the ever-expanding transportation sector in inhibitor and cold flow improver. However, production of
the near future, specifically the on-road diesel engines sub- effective biodiesel fuel additives proves to be more chal-
sector. For this reason, extensive research activities have lenging as fuel additives are effective for specific com-
been concentrated on the assessment of biodiesel impact on pounds in fuels. Hence, the larger variations in the
tailpipe emissions, power output, engine performance and physico-chemical properties of the biodiesel produced in
durability. The various studies conducted thus far have different batches make it harder to produce an effective
aggregately shown that the use of biodiesel could poten- additive, in contrast to fossil diesel which has more con-
tially reduce major pollutants typical of diesel engines, sistent properties. The differences in fuel composition and
such as particulate matters (PMs), carbon monoxide (CO), properties of the various biodiesel fuels have been shown
nitrogen oxides (NOx), sulphur oxides (SOx), polycyclic to also produce marked effects on in-cylinder combustion
aromatic hydrocarbons (PAHs) and monocyclic aromatic and emission characteristics of diesel engines. For exam-
hydrocarbons (MAHs). The reduction in emissions was ple, fuel-bound oxygenation effect of biodiesel helps
shown to be due to the desirable biodiesel properties such improve combustion efficiency, although the lower energy
as higher oxygen content, lower sulphur and aromatic density of the fuel means that lower mileage is achieved
levels, and greater biodegradability when compared with with biodiesel usage. From here, it can be deduced that
fossil diesel (Kalam et al. 2003; Kalligeros et al. 2003; the physico-chemical properties of biodiesel are all-
Labeckas and Slavinskas 2006). Biodiesel also has the important, since these properties are highly sensitive to the
highest energy content by volume among any available variety of feedstock used and the production method
alternative fuels (NAFA 2003), although it is still typically employed.
between 75.6 and 89.9% of the total energy content of To that end, this article reviews the nature of biodiesel
conventional No. 2 diesel values. The maximum achiev- fuel through an examination of its physico-chemical
able engine power output is therefore, inherently lower. properties. This is to establish links between biodiesel from
However, vehicle driveability from biodiesel and fossil various feedstocks and the associated impacts on diesel
diesel usage is indistinguishable during day-to-day opera- engine combustion and emission characteristics. Emphasis
tion as typical engine operation is usually within the part is placed on the technical challenges associated with bio-
load range, which is unaffected by the lower maximum diesel usage in diesel engines, and the range of measures
output power produced by biodiesel. The use of biodiesel adopted to alleviate these. Progress in the production
has been found to significantly improve lubricity, thereby methods for improved yields, and in fuel additives to
reducing engine wear. In addition, biodiesel fuel is safer enhance biodiesel properties are also addressed.

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Advances in biodiesel fuel 461

Fuel properties of biodiesel greater intermolecular association that results in even

higher density and viscosity values. Vegetable oils and
Chemical structure their methyl esters contain exceptionally low level of
aromatics, in contrast to the 29.3 wt% of aromatic content
Figure 1 shows the chemical structures of vegetable oil seen in typical commercial grade No. 2 diesel with
methyl ester, vegetable oil and hydrocarbon-based fossil monoaromatics, diaromatics and polyaromatics each con-
diesel. Vegetable oil and its methyl ester differ from that of tributing 13.0, 13.3 and 3.0 wt%, respectively (Benjumea
hydrocarbon in the additional ester functional group (Sastre et al. 2008). As summarised in Table 1, fatty acid com-
et al. 2003). Owing to the distinctive characteristics of the positions of naturally occurring vegetable oils varies with
methyl ester functional group, their density and viscosity feedstock. These fatty acids also vary in chain length and
are higher relative to hydrocarbon. Vegetable oil, with number of double bonds. Most vegetable oils and their
three hydrocarbon chains attached to a common group, has methyl ester derivatives contain a significant portion of
unsaturated fats, which possess at least one reactive double
bond. These features are contrary to fossil diesel which
contains mainly saturated hydrocarbons with only single
bonds. Hydrogen atoms can be added to an unsaturated fat
for each degree of unsaturation, as opposed to a saturated
fat due to the absence of double bonds. For this reason,
unsaturated fatty acids such as palmitoleic and oleic acids
are more reactive than saturated fatty acids such as palmitic
and stearic acids.
A list of the chemical structure, boiling point (B.P.) and
melting point (M.P.) of common fatty acids and their
methyl ester derivatives is provided in Table 2. The B.P.
and M.P. for both saturated fatty acids and their corre-
sponding methyl esters are shown to increase as the length
of carbon chain increases. The strength of inter-molecular
van der Waals forces is positively influenced by the num-
ber of electrons surrounding a molecule, and this is pro-
portional to the molecular weight (Pauling 1988). The
increase in carbon chain length produces a rise in the
Fig. 1 Generic molecular structures for vegetable oil, vegetable oil molecular weight, thus strengthening the van der Waals
methyl ester and hydrocarbon (Sastre et al. 2003) forces and subsequently raising the B.P. and M.P. The B.P

Table 1 Typical chemical composition of vegetable oils (summarised from Graboski and McCormick 1998; Ma and Hanna 1999; Graboski and
McCormick 1998)
Vegetable oil Fatty acid composition (wt%)
12:0 14:0 16:0 18:0 20:0 22:0 24:0 18:1 18:2 18:3

Corn 0 0–2 8–12 1–4 Tr 0 0 25–50 0–6 Tr

Cottonseed 0 0–3 17–28 1–3 0 0 0 13–41 34–58 0
Linseed 0 Tr 5–9 0–2 0 0 0 9–29 8–29 45–67
Peanut 0 Tr 6–11 2–6 1 2 1 39–66 17–38 1
Rapeseed 0 0 2–5 1–2 0 0 0 10–64 10–22 5–10
Safflower 0 0 5–9 2 0 0 0 12 78 0
H.O. Safflower 0 Tr 5 2 Tr 0 0 79 13 0
Sesame 0 0 13 4 0 0 0 53 30 0
Soybean 0 Tr 7–12 3–6 0 0 0 22–34 50–60 2–10
Sunflower* 0 0 6 3–4 0 0 0 17–19 69–74 Tr
Palm* Tr 1 42 5 0 0 0 41 10 Tr
Coconut* 47 19 10 3 0 0 0 7 2 0
*
The values of the specific feedstock are rounded to the nearest integer. Tr denotes trace amount

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462 J.-H. Ng et al.

Table 2 Structural formula, melting point and boiling point for common fatty acids and methyl esters in the diesel boiling range (Graboski and
McCormick 1998)
Acid chain No. of Structure Fatty acids Methyl esters
carbons
Melting point Boiling point Melting point Boiling point
(C) (C) (C) (C)

Saturated
Caprylic 8 CH3(CH2)6COOH 16.5 239 -40.0 193
Capric 10 CH3(CH2)8COOH 31.3 269 -18.0 224
Lauric 12 CH3(CH2)10COOH 43.6 304 5.2 262
Myristic 14 CH3(CH2)12COOH 58.0 332 19.0 295
Palmitic 16 CH3(CH2)14COOH 62.9 349 30.0 338
Stearic 18 CH3(CH2)16COOH 69.9 371 39.1 352
Arachidic 20 CH3(CH2)18COOH 75.2 – 50.0 –
Behenic 22 CH3(CH2)20COOH 80.0 – 54.0 –
Monounsaturated
Palmitoleic 16 CH3(CH2)5CH=CH(CH2)7COOH 33.0 – 0 –
Oleic 18 CH3(CH2)7CH=CH(CH2)7COOH 16.3 – -19.9 349
Eicosenoic 20 CH3(CH2)7CH=CH(CH2)9COOH 23.0 – -15.0 –
Erucic 22 CH3(CH2)7CH=CH(CH2)11COOH 34.0 – – –
Polyunsaturated
Linoleic 18 CH3(CH2)4CH=CHCH2CH=CH(CH2)7COOH -5.0 – -35.0 366
Linolenic 18 CH3CH2CH=CHCH2CH=CHCH2CH=CH(CH2)7COOH -11.0 – – –

and M.P. of methyl esters are also found to be lower than are summarised in Fig. 2. Important aspects of biodiesel
that of the corresponding fatty acids of the same carbon fuel properties, and the corresponding effects are high-
chain length. Contrary to fatty acids, esters are unable to lighted and discussed in the following sections.
form hydrogen bonds which are stronger than the typical
van der Waals associations. The presence of carbon–carbon Combustion properties
double bonds in the chain of an unsaturated fatty acid or
methyl ester prohibits close packing among neighbouring The ignition quality of a fuel can be deduced through its
molecules for the van der Waals dispersion forces to be cetane number. A fuel with good ignition quality has a high
strong (Pauling 1988). Thus, M.P. for fatty acids or methyl cetane number, where the ignition delay period between
esters of the same carbon chain length decreases with the start of fuel injection and the onset of autoignition is
increasing degree of unsaturation. For example, M.P. for short. A short ignition delay period lowers the peak com-
acid chains of stearic, oleic, linoleic and linolenic (all with bustion temperature which suppresses NOx formation.
carbon chain length of 18 in ascending order of unsatura- Cetane number of biodiesel varies with the feedstock used,
tion) are 69.9, 16.3, -5 and -11C, respectively. In brief, but is generally in the higher end of the typical No. 2 diesel
the length of carbon chain and presence of unsaturated sites fuel range. The value of cetane number is found to gen-
greatly affects the physical properties of the acid chains. erally increase with increasing carbon chain length. This is
due to the higher concentration of hydroperoxyalhyl radi-
Properties of biodiesel cals, which is the principal source of chain-carrying OH
radicals pertinent during the fuel ignition phase. Combus-
The differences in length and degree of unsaturation in the tion is thus initiated more rapidly (Heck et al. 1998).
fatty acid alkyl chains found in biodiesel produced from However, cetane number decreases with an increase in the
different feedstocks give each a unique set of fuel prop- number of double bonds, or when double bonds and car-
erties. The physical properties of biodiesel can be grouped bonyl group move towards the centre of the chain
and compared in terms of their impacts on combustion, (Graboski and McCormick 1998). In a study by Candeia
flow and storage behaviours. Table 3 provides an overview et al. (2009) on the properties of soybean biodiesel, it was
of these pertinent biodiesel properties. The independent also found that an ethyl ester possesses higher cetane value
effects of the biodiesel properties on various operational than a methyl ester. The cetane index of the soy methyl
aspects of diesel engine when compared with fossil diesel ester is 56 when compared with its ethyl ester counterpart

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Advances in biodiesel fuel 463

Table 3 Properties of biodiesel from various feedstocks

Methyl ester type Kinematic Cetane Lower Cloud Pour Flash Density
viscosity number heating point point point (kg/m3)
at 40C (-) value (C) (C) (C)
(mm2/s) (MJ/kg)

Peanut (Srivastava and Prasad 2000) 4.90a 54.0 38.1 5.0 – 176 883
Soybean (Srivastava and Prasad 2000; 4.10 45.0–51.0 37.3–37.9 1.0 (-7) 178 885
Rakopoulos et al. 2006)
Babassu (Srivastava and Prasad 2000) 3.60a 63.0 36.1 4.0 – 127 879
Palm (Srivastava and Prasad 2000; Choo et al. 4.40-5.70 50.0–62.4 37.2–38.1 13.0–14.5 15 164–174 855–880
2005; Rakopoulos et al. 2006; Yung et al. 2006)
Sunflower (Srivastava and Prasad 2000; Kalligeros 4.13–4.60 49.0–58.0 37.4–39.0 1.0–1.5 (-7)–(-3) 110–183 860–885
et al. 2003; Lapuerta et al. 2005;
Rakopoulos et al. 2006)
Tallow (Graboski and McCormick 1998; Srivastava 4.80 58.8 40.0–40.4b 12.0 9 96–148 877
and Prasad 2000; Schober and Mittellbach 2004)
Tall (Altiparmak et al. 2007) 7.10 54.0 40.0b 1.0 – 89 922
Rapeseed (Graboski and McCormick 1998; 4.45-4.70 48.0–61.8 37.1–37.3 (-11.0)–0 (-15)–(-7) 148 885
Schober and Mittellbach 2004;
Rakopoulos et al. 2006)
Cynara (Lapuerta et al. 2005) 4.88 59.0 37.2 – – – 887
b
Distilled Palm (Yung et al. 2006) 4.42 58.3 35.0 13.6 15 182 878
Cottonseed (Graboski and McCormick 1998; 4.00 51.2–52.0 37.5–38.9 – 3 110 880–885
Rakopoulos et al. 2006)
Olive (Kalligeros et al. 2003) 4.70 61.0 32.8 (-2.0) (-3) [110 880
Diesel #2c (Graboski and McCormick 1998; 2.73–3.16 47.0–50.0 42.7–43.4 (-15.0)–5.0 -35–(-15) 73 822–837
Lapuerta et al. 2005; Rakopoulos et al. 2006;
Altiparmak et al. 2007;
Keskin et al. 2008)
Values in parentheses denote negative values
a
The kinematic viscosity was measured at 37.8C instead of 40C
b
Gross heat of combustion values were quoted instead of lower heating value
c
The range of values for the fuel properties covers normal and low-sulphur commercial diesel fuel

Fig. 2 Biodiesel fuel properties

and their associated impact on
engine operation, storage and
transportation as compared to
fossil diesel

with a value of 60. The higher cetane index for the ethyl systems, which allows improved control over the timing
ester is due to the addition of CH2 moiety of the ethyl ester and rate of injection. With this improvement, combustion
biodiesel, and possible residual of methanol in the methyl phasing is controlled more precisely, thus reducing the
ester biodiesel. Cetane number is losing its significance in sensitivity of the combustion process on fuel’s cetane
recent years due to the advancement in fuel injection number (Knothe 2005).

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464 J.-H. Ng et al.

Biodiesel’s boiling curve is appreciably flatter than that 880 kg/m3 is about 7% higher relative to that of conven-
of fossil diesel. This is due to the fact that biodiesel is tional No. 2 diesel. As such, higher fuel mass is actually
composed mainly of relatively similar compounds such as injected since fuel metering is volumetric rather than mass
saturated and unsaturated fatty acid alkyl esters, contrary to based. This partially offsets the higher fuel energy require-
fossil diesel which possesses a wide variation of com- ment for each unit of developed power output from the lower
pounds such as paraffin, naphthene, aromatic, olefin and energy content of the biodiesel. Therefore, biodiesel should
sulphur. A study by Choo et al. (2005) on palm oil showed have 80.9–96.2% of the fuel energy delivered by fossil
that the B.P. for palm oil alkyl ester has a narrower range diesel per unit volume of the injected fuel.
of 296–365C when compared with fossil diesel where the The bulk modulus of biodiesel is deduced to be strongly
range is within 228–400C as illustrated in Fig. 3. This influenced by the permanent dipole moment created by its
narrower range is not expected to affect the start of the oxygen content (Hess et al. 2007). As oxygenated mole-
combustion for biodiesel since ignition in compression cules show stronger hydrogen bonding and greater affinity
ignition (CI) engines is not spark assisted. Distillation for one another when compared with hydrocarbon mole-
temperature influences the degree of air–fuel mixing and cules, the increase in inter-molecular attraction reduces the
evaporation rate, where high distillation temperature tends available free space for compression. This increases the
to result in lower amount of mixture during premixed bulk modulus of biodiesel, rendering it to be less com-
burning phase (Qi et al. 2009). pressible in comparison to fossil diesel. Pressure builds up
Apart from ignition quality, energy content is an impor- more rapidly inside the injector’s nozzle when biodiesel is
tant indication of the suitability of a fuel. The energy used. The injection nozzle opening pressure is reached
available in a fuel as measured by its heat of combustion earlier in this case, leading to advancement in injection
must be high, as this is inversely proportional to the brake timing where a stronger premixed combustion phase fol-
specific fuel consumption. Heat of combustion is found to lows. However, injection timing is now less dependent on
increase with carbon chain length (Knothe 2005). As CH2 the fuel’s bulk modulus as the latest generation of fuel
unit increases for every additional carbon, higher number of injection equipment for automotive diesel engines greatly
carbon–carbon and carbon–hydrogen bonds which can be enhances flexibility and precision control over the pattern of
broken to release the energy contained within them increases fuel delivery.
(Western Oregon University 2009). In general, the values of
combustion heat of biodiesel are within the range of 75.6– Flow properties
89.9% that of fossil diesel. Thus, the brake specific fuel
consumption of engines running on biodiesel is expected to Viscosity of fuel affects the dynamics of fuel spray atom-
be higher as compared to that when running on fossil diesel. isation process. A high viscosity value is undesirable as this
However, the density of biodiesel with a typical value of causes poor atomisation, with the possibility of plugged

Fig. 3 Comparison of boiling

curves of alkyl esters of palm oil
against that of fossil diesel
(adapted from Choo et al. 2005)

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Advances in biodiesel fuel 465

injection system and carbon deposition problems. The use Typically, the auto-oxidation process of biodiesel is ini-
of biodiesel with its viscosity values within the range as tiated with the formation of free radicals that can react
prescribed by the biodiesel standards is crucial for effective directly with oxygen to form peroxide or hydroperoxide
atomisation and to avoid excessive pumping pressure. (McCormick et al. 2007). The hydroperoxide produced is
Although the viscosity of biodiesel is 30–160% higher than highly unstable and a variety of secondary oxidation prod-
that of fossil diesel, most biodiesel fuels with a notable ucts can be easily formed from this (Knothe 2007). The
exception of tall oil meet the EN 14214 and ASTM D6751 greater tendency of biodiesel to undergo auto-oxidation as
specifications for usage in CI engines. Viscosity is found to compared to fossil diesel can be traced to the higher pro-
increase with an increase in chain length and degree of portion of the more reactive double bonds typical to the
saturation (Knothe 2005). For example, stearic methyl ester unsaturated fatty acid methyl esters component (Knothe
(18:0) has a kinematic viscosity value of 4.74 mPa.s, which 2005). This is especially true for polyunsaturated methyl
is greater than that of lauric methyl ester (12:0) at esters such as methyl linoleate (18:2) and methyl linolenate
1.95 mPa.s. This is attributed to the longer carbon chain in (18:3) (Xin et al. 2009), where the double bonds are more
the stearic methyl ester. Similarly, stearic methyl ester with susceptible to attack from oxygen in air to form mixture of
higher degree of saturation has greater kinematic viscosity products such as polymers and short-chain compounds
when compared with the 3.73 mPa.s of oleic methyl ester (Paligová et al. 2008). These products increase the viscosity
(18:1). of the fuel, leading to the formation of insoluble species that
The cold flow properties of biodiesel such as pour point in turn causes operational problems in the fuel delivery
and cloud point are measures of its operability at low system (Knothe 2007). The adverse effects of unsaturated
temperatures. Pour point is defined as the lowest temper- fatty acid methyl esters on oxidative stability are also high-
ature a fuel can be poured through gravity, whereas cloud lighted in a study by Sarin et al. (2009b). It was reported that
point is the temperature in which wax formation occurs. the jatropha biodiesel which was tested did not meet the
No. 2 diesel has better cold flow properties, with its cloud prescribed limit of a 6-h induction period according to the EN
point and pour point 10–30C lower than that of biodiesel. 14112 oxidative stability test. The high unsaturated fatty acid
Chemical structures of biodiesel influence its cold flow methyl ester content of 78.9% in this biodiesel was identified
properties, where improvement in cold flow properties is as the main cause. It was deduced from the study that bio-
achieved when chain length is decreased or chain branch- diesel fuels with high level of saturated fatty acid methyl
ing is increased (Graboski and McCormick 1998). Certain esters would have stronger oxidative stability than those with
biodiesel fuels such as palm methyl esters have cold flow high level of unsaturated fatty acid methyl ester. It must be
properties that are significantly above the normal ambient stressed here, however, that the presence of even a small
temperatures during winter due to its relatively high pro- amount of the unsaturated fatty compounds can have a dis-
portion (*50 wt% of the total) of saturated fatty acid in the proportionately strong adverse effect on oxidative stability
total fatty acid composition (Gui et al. 2008). This is a (Knothe 2007). In general, biodiesel has weaker oxidative
cause for concern when used in cold climate countries with stability than fossil diesel because biodiesel invariably
temperature below its operability limits, lending to poten- contains unsaturated fatty compound in its composition.
tial cold start problems such as plugged fuel filter. The use Apart from the degree of unsaturation, oxidation rates
of additives, preheating before injection and filtration of are also influenced by the position of double bonds. The
solid are examples of the common measures implemented allylic positions which are adjacent to the double bonds are
to improve low temperature operation of biodiesel. highly susceptible to oxidation (Knothe 2005). Polyunsat-
urated fatty acid such as linoleic acid has double bonds at
Storage and transport properties D9 and D12, the 9 and 12th carbon–carbon bond from the
carboxylic acid end, respectively. This configuration
One fundamental problem afflicting biodiesel usage is in results in one bis-allylic position at the 11th carbon posi-
the poorer oxidative stability during prolonged storage, tion from the carboxylic acid end. The bis-allylic positions
which causes fuel deterioration. The instability of biodiesel are found to be more vulnerable to auto-oxidation than the
remains a major barrier in the effort to increase the adop- allylic positions due to the formers’ greater tendency to
tion level among engine and fuel injection equipment undergo hydrogen radical abstraction during the initiation
manufacturers (Dinkov et al. 2009). In fact, a vote at the step of oxidation. This is mainly due to the low dissociation
Annual Biodiesel Technical Workshop held in January energy of its C–H bond (Xin and Saka 2009). In fact, the
2005 placed the research on biodiesel stability as the top relative oxidation rate for esters of linoleic acids are 41
priority (Sarin et al. 2009a). The concerns are justified as times greater than that of oleic acid esters. The oxidation
fuel deterioration reduces storage life and facilitates rate is found to correlate well with the total number of bis-
deposit formation. allylic sites (McCormick and Westbrook 2009).

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Besides fatty acid composition, other factors such as The advantages as shown in Table 4 include better
level of natural antioxidant, presence of metal ion con- lubricity and biodegradability, flexibility in usage whether
taminants and storage conditions can greatly affect the in neat or blended form, improved combustion quality and
oxidative stability of biodiesel (Xin and Saka 2009). In a excellent compatibility with hardware setup of standard
study by Sarin et al. (2009b), the presence of metal con- diesel engines. On the contrary, outstanding operational
taminant was reported to accelerate the free radical oxi- challenges hindering large-scale biodiesel adoption as
dation due to a metal-mediated initiation process. illustrated in Table 5 are the fuel filter blockage, microbial
However, it was found that metal contaminant had the contamination, corrosion, fuel degradation and cold start
same detrimental effect on the oxidative stability of bio- problems. A typical problem from the introduction of
diesel irrespective of the quantity of the contaminant in the biodiesel in engines which have been operating on hydro-
fuel. It was believed that the metal contaminant acted as a carbon-based fossil diesel is plugged fuel filter. This occurs
catalyst here to hasten oxidation. The study by Ferrari et al. due to the exceptional solvent properties of biodiesel,
(2005) highlighted that natural antioxidants in biodiesel is which dissolve layers of deposits in the fuel tank formed
important in improving the oxidative stability of the fuel. A from fossil diesel usage (Bozbas 2008), causing the dis-
comparison between biodiesel produced from neutralised solved deposit to clog fuel lines and filters. This can be
and refined soybean oils showed that the former had an simply addressed through proper maintenance of the filter.
induction period twice that of the latter due to the higher The use of biodiesel under low temperature conditions
level of natural antioxidant in the neutralised soybean oil. poses problems associated to the plugging of the fuel
Fuel with high flash point is highly coveted, as the risk injection system which causes cold start problems. ‘Win-
associated with fuel transportation is greatly minimised. terisation’ of biodiesel fuel has been successfully applied to
This is attributed to the inability of combustible air–fuel improve low temperature operability and cold start prob-
vapour mixture to ignite below the flash point. Therefore, it lems. This technique requires the temperature of the bio-
is safer to transport biodiesel with a higher flash point diesel to be lowered to a level where the formation of wax
range of 89–183C than No. 2 diesel fuel with a lower or solid fuel begins. The solidified portion is then filtered
typical flash point of 73C. Most biodiesel fuels are clas- out from the liquid biodiesel. The remaining filtered liquid
sified as non-hazardous, as the US Department of Trans- fraction is used under the cold conditions, and solid frac-
portation considers a material with a flash point of 90C tion of the filtered fuel is kept for summer usage when
and above as non-hazardous in terms of storage and fire ambient temperatures are higher. However, the remaining
hazard (Graboski and McCormick 1998). liquid fraction of the biodiesel comprises mainly unsatu-
rated fatty acids that possess poorer oxidative stability and
Technical challenges and the potential solutions lower cetane number, which are detrimental to the storage
for biodiesel usage and combustion qualities. Apart from winterisation, pre-
heating biodiesel fuels can improve fuel flow through the
The use of biodiesel as an alternative to fossil diesel brings injection system. Cold flow improvers such as anti-gelling
about various technical advantages as well as challenges. agents can also be added to depress the pour point of the

Table 4 Technical advantages

Advantages Description
of biodiesel over conventional
diesel fuel (Demirbas 2007; Prolongs engine life Better lubricating properties
Murillo et al. 2007; Bozbas
2008) Reduces maintenance required
Safer for transportation, storage and Higher flash point, less likely to be ignited during
handling transportation
Same storage conditions as those of fossil diesel
Less toxic and very biodegradable
Can be used in neat form or as blends Used directly or blend in any amount in diesel engines
Blending allows gradual change from fossil diesel to
biodiesel
Higher combustion efficiency Higher oxygen content improves the combustion
process
Works in any conventional diesel engine No modification on diesel engine is required
Compatible with catalyst for emissions Low sulphur content reduces catalyst poisoning
control

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Advances in biodiesel fuel 467

Table 5 Technical challenges

Problems Reasons Potential solutions
associated with the use of
biodiesel (Demirbas 2007; Low temperature Weaker cold flow properties such Cold flow improvers
Murillo et al. 2007; Bozbas inoperability as high cloud point, pour point and
2008) Preheating of biodiesel
cold filter plugging point before injection
Winterisation
Degradation under long Poor oxidation stability Anti-oxidant additives
period of storage Avoid storing biodiesel
for more than 3 months
Blocked fuel filter for engine Loosening of carbon deposit Proper filter maintenance
that used fossil diesel
Microbial contamination Water contamination in fuel, Draining fuel from bottom of
promoting growth of micro-organism fuel tank to remove water
Use of biocide
Fuel system corrosion Reduced water separation capability due Anti-corrosive additives
to addition of biodiesel

fuel for improved cold temperature operation. Water raises public confidence in accepting the fuel as an alter-
entrained in biodiesel during production is known to cor- native to fossil diesel. The standards adopted by policy
rode fuel tank and injection system over prolonged period makers worldwide such as the US ASTM D6751 and
of use. This is mitigated with the use of corrosion inhibi- European Union’s EN 14214 are discussed in detail by Ng
tors, through the formation of a protective layer to prevent et al. (2009).
contact between the fuel and metal surfaces. While long-
term usage and low temperature operation of biodiesel are Biodiesel additives
not completely problem-free, none of these is insur-
mountable with mitigation methods already in place. Additives such as antioxidants, cetane enhancer, corrosion
From here, biodiesel properties are evidently crucial in inhibitors and cold flow improvers can be blended with
ensuring the fuel’s suitability for use in diesel engines biodiesel in small quantity to improve the functionality of
which ultimately determine its successful penetration into the fuel and reduce certain emission species. The use of
the fuel market. As such, national standards are developed additive is especially useful when only specific properties
worldwide to prescribe the minimum requirements of the of the biodiesel fuel require enhancement to meet the
biodiesel properties for diesel engine operations. In addi- specification of a standard. The known effects of each
tion, the maximum allowable blending levels with fossil independent additive are summarised in Fig. 4.
diesel are also prescribed. For example, the US ASTM
D6751 covers the use of neat biodiesel as a blending Antioxidant
component of up to 20% by volume (DieselNet 2002). The
evaluation of fuel quality based on a standardised bench- Biodiesel oxidises much more rapidly when compared with
mark ensures the integrity of the biodiesel used, which fossil fuel. This observed reduction in oxidative stability

Fig. 4 Independent effects of

biodiesel additives on engine
operations compared with
untreated biodiesel

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468 J.-H. Ng et al.

can be traced to the unsaturated fatty acids content in

biodiesel, which are more susceptible to react with air to
form peroxide. Most neat biodiesel fuels do not conform to
the EN 14214:2003 standard, as dictated by the Rancimat
test under the EN 14112 where biodiesel must maintain its
oxidative stability at an elevated temperature of 110C for
a minimum 6-h induction period. This was shown in a
study by Schober and Mittelbach (2004), where low
Rancimat induction periods (RIPs) of 5.13 h for neat
rapeseed methyl ester and 4.74 h for neat tallow methyl
ester were recorded at 110C. As such, the addition of
antioxidants typically at a concentration of 0.1 wt% is Fig. 5 Oxidative stability of distilled palm oil methyl ester at 110C,
necessary to stabilise the fuel against oxidation during with air flow rate at 10 L/h using a-T, BHT and TBHQ antioxidants
storage. Antioxidants can be broadly classified by their (Yung et al. 2006)
mechanism of action, namely the chain-breaking and the
preventive type (Frankel 1980). Antioxidants of the chain-
breaking type prevent oxidation by interfering in the improving the fuel’s oxidative stability. Figure 5 illustrates
radical propagation reactions, whereas preventive type that at a concentration of 500 ppm, TBHQ is the best
antioxidants inhibit oxidation by deactivating metal ions antioxidant with a RIP value of 30.2 h, followed by
that promotes the initiation and decomposition of hydro- BHT and finally a-T with RIP values of 13.1 and 5 h,
peroxides (Hess et al. 2005). respectively.
In the same study by Schober and Mittelbach (2004), A study by Xin et al. (2009) also showed improvement
antioxidants were shown to significantly improve oxidative on the oxidative stability of safflower biodiesel when a
stability of biodiesel produced from different feedstocks. chain-breaking type antioxidant, propyl gallate is added. In
Dramatic increase in induction period signifying improved the same study, concentration of propyl gallate was varied
stability were reported with the addition of commercial from 0 to 5,000 ppm. By means of extrapolation, it was
antioxidants such as DTBHQ, IONOX 220, Vulkanox BKF found that an addition of 400 ppm of propyl gallate guar-
and Baynox, in concentrations ranging from 1,000 to anteed a storage duration of 6 months without noticeable
5,000 mg/kg. It was also noted that the impact of antioxi- degradation in the biodiesel, whereas a one-year storage
dant on biodiesel are highly dependent on the feedstock period at 25C required 1,000 ppm concentration of the
used—the most effective antioxidant for each of the bio- said additive. In order to ensure that the biodiesel does not
diesel produced from different feedstocks is shown in degrade within the widely regarded maximum commercial
Table 6. An evaluation of the oxidative stability of palm storage life of biodiesel under common market conditions
biodiesel by Yung et al. (2006) showed that synthetic (Bondioli et al. 2003), the optimum concentration to be
antioxidants such as tert-butyl hydroquinone (TBHQ) and used for this biodiesel–antioxidant combination is fixed at
butylated hydroxytoluene (BHT) are more effective than 400 ppm.
the tested natural antioxidant, a-tocopherol (a-T) in The formation of prompt NO involves hydrocarbon fuel
radicals and nitrogen molecules reacting within the flame
front to form compounds that will further react with oxy-
Table 6 List of biodiesel fuels with their most effective antioxidants gen to produce NO. Quenching of free radicals during
for improved oxidative stability (Schober and Mittellbach 2004) combustion through the use of antioxidants could poten-
Biodiesel Most suitable Stabilisation tially control NOx formation, where the antioxidants donate
antioxidant factor hydrogen atoms to interfere with radical propagation
reactions to force radical termination that inhibits oxida-
Rapeseed methyl ester Baynox 2.05
tion. This limits the available free radicals to participate in
Recycled cooking oil DTBHQ 4.55
the sequence of NOx formation reactions. An assessment
methyl ester
on the effects of antioxidants addition to B20 methyl soyate
Distilled recycled cooking Vulkanox 13.07
oil methyl ester BKF by Hess et al. (2005) showed that common antioxidants
Tallow methyl ester Vulkanox BKF 11.02 used to improve oxidative stability could in most cases
produce a drop in NOx emission. The use of butylated
* The most suitable antioxidant for each biodiesel was chosen from
hydroxyanisole reduced exhaust NOx by 4.4%, although
11 commercial antioxidants. Stabilisation factor is defined as the ratio
of the induction period of the fuel with antioxidants to the induction the addition of diphenylamine raised NOx level marginally
period of the same fuel without the addition of antioxidants by 0.7% as shown in Table 7. A separate study performed

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Advances in biodiesel fuel 469

Table 7 Effects of various

Fuel type with the Change in NOx emission
antioxidants on NOx emission
corresponding additives from the B20 levels (%)
(Hess et al. 2005)
Diesel fuel (B0) -6.6 ± 1.7
B20 ? 2,20 -methylenebis(6-tert-butyl-4-methylphenol) ?0.2 ± 1.0
B20 ? citric acid -0.7 ± 0.5
B20 ? a-tocopherol ?0.3 ± 0.2
B20 ? ascorbic acid 6-palmitate -1.3 ± 0.9
B20 ? tert-butyl hydroquinone -0.3 ± 1.6
B20 ? propyl gallate -0.4 ± 2.8
B20 ? diphenylamine ?0.7 ± 1.3
B20 ? butylated hydroxytoulene -2.9 ± 1.5
B20 ? butylated hydroxyanisole -4.4 ± 1.0

by McCormick et al. (2003) on the use of TBHQ to treat a CH3 CH2

soybean B20 fuel blend achieved similar results. Engine- EHN
out NOx level for the B20 blend with 0.2 wt% of TBHQ CH2 CH ONO2
CH3
was 0.67% lower when compared with an untreated B20
blend, although a further reduction of 0.89% was required
CH2 CH2 CH2
to match to the level produced from conventional diesel.
The observed NOx reduction also came with a trade-off in
CH3 CH3
the exhaust PM emission, where the PM level for the DTBP
treated B20 blend increased by 9.18% relative to the C C
untreated B20 blend. Despite the increase, tailpipe PM O O
CH3 CH3
concentration is still significantly below the level produced
CH3 CH3
from conventional diesel. The selection of a suitable anti-
oxidant would be highly dependent on the cost, availability Fig. 6 Structures of EHN and DTBP (Suppes et al. 2001)
and the possible negative effects on the various emission
species. It is evident from these evaluations that the use of
antioxidants to improve both the oxidative stability and turn lowers peak in-cylinder temperature, resulting in the
tailpipe NOx concentration should be exercised with care. reduction of NOx formation rate (Hess et al. 2005). The
Present research effort is limited to determining the impact market share of cetane improver is currently topped by
of antioxidant types and the associated quantity added, EHN, with DTBP as a strong alternative. This is attributed
which lacks the fundamental understanding to completely to the lower EHN price, which is 62.5% that of DTBP
elucidate the individual effect on biodiesel fuel and engine- volume-wise. It should be noted here that while EHN has
out responses. More comprehensive studies should instead the cost advantage, its nitrogen content is higher relative to
be concentrated on the investigation of the elementary that of DTBP. This could contribute to the NOx formation
chemical interactions between the antioxidants and bio- process. Study conducted on both these cetane improvers at
diesel fuels to fully utilise the potential of these antioxi- a concentration of 0.5–1.5 vol% illustrated their effective-
dants for improved oxidation stability and engine-out NOx ness in reducing NOx (McCormick et al. 2003). Both EHN
concentration. and DTBP showed a 4% NOx reduction for B20 blends. A
study by Szybist et al. (2005) on a Yanmar L70EE direct
Cetane enhancer injection (DI) engine equipped with an in-line pump-line–
nozzle type fuel injection system showed the potential of
Cetane improver is a prospective control strategy to address using cetane improver to reduce NOx. The use of EHN at a
the elevated tailpipe NOx level typically seen from diesel concentration of 1,000 ppm improved the derived cetane
engines fuelled with biodiesel. Addition of cetane enhancer number of a B20 soybean blend from 48.2 to 53.5. Fuel
such as di-tert-butyl peroxide (DTBP) and ethyl-hexyl injection timing was varied, where injection timing from -
nitrate (EHN) as depicted in Fig. 6 has been shown to 12.5 to -11.5 after top-dead-centre (ATDC), -10.2 to -
improve ignition quality by hastening radical formation and 9.0 ATDC and -7.7 to -6.8 ATDC were classified as
thus shortening the ignition delay, which reduces the early, mid and late injection, respectively. When untreated,
intensity of the premixed combustion (PMC) phase. This in engine-out NOx for the B20 blend increased by 3–5%

123
470 J.-H. Ng et al.

depending on injection timing relative to the baseline metal when the engine was fuelled with biodiesel fuels
petroleum diesel. Addition of 1,000 ppm of EHN was found produced from jatropha, karanja, mahua and pilu. Corro-
to be ineffective with early injection, where the NOx pro- sion rate was found to be the highest for pilu biodiesel due
duced was even greater than that from untreated biodiesel. to its extremely high level of sulphur content at 1,200 ppm.
However, EHN was effective in controlling NOx for mid It was also postulated that engine parts corrosion could be
and late injection timings at the same treat rate. Here, NOx linked to the heightened oxidation activities in biodiesel
emissions were reduced to near the baseline level. It was fuels due to the presence of linoleic acid, or double bonds
also concluded by Szybist et al. (2005) that NOx emission as in general. Maru et al. (2009) tested the compatibility of
a whole was insensitive to the derived cetane number for the soybean and sunflower biodiesel fuels with common
range investigated. Here, bulk modulus of the biodiesel fuel materials used for automotive tank and fuel storage, such
was believed to play a larger role in dictating NOx emission as carbon steel and high density polyethylene (HDPE).
although this was only relevant to earlier fuel injection Although analyses of the tested biodiesel showed evidence
systems. While cetane enhancer can potentially improve of ageing in this study, it did not significantly increase the
combustion efficiency and reduce NOx, the appropriate use corrosivity of the fuel on carbon steel and HDPE. This is in
of specific cetane improvers with certain types of fuel contrast with the findings by Kaul et al. (2007). In fact, the
injection systems must be established to be fully effective. compatibility issue of biodiesel with common materials
Further selection criteria for cetane improvers include cost, used for engine and storage tanks remains open for further
effectiveness in increasing cetane number, nitrogen content, evaluation.
storage and transport (Suppes et al. 2001). Nevertheless, the study by Kalam and Masjuki (2002)
In the commercial biodiesel market, the use of cetane demonstrated that the addition of a commercial corrosion
enhancers aided the successful resolution of the highly inhibitor, IRGANOR NPA at a low concentration of
publicised biodiesel sale ban under the Texas Low Emis- 50 ppm into palm oil-derived biodiesel could decrease the
sion Diesel (TxLED) programme. The ban was originally corrosive tendency of biodiesel as measured by the total
introduced as previously gathered data from stationary base number (TBN). TBN provides an indication of the
engine dynamometer tests showed an increase in tailpipe oil’s ability to counter corrosive effects due to oxidation,
NOx concentration with biodiesel usage (Irwin 2007). with higher values showing improved oxidative stability. It
Although the TxLED programme was drawn up in 2005 was found that reduction of TBN values for biodiesel
with a grace period until December 2007, it was only in blends treated with only 50 ppm of corrosion inhibitor was
March 2007 that a cetane enhancer, Oryxe LED gained much lower than untreated diesel. The corrosion inhibitor
certification of compliance. The cetane enhancer is able to was also found to improve lubricity, increase brake power
lower NOx emission levels to the TxLED limit for blending and reduce exhaust emissions within the set up and con-
levels of up to B20, allowing the sale of biodiesel blends dition of this experiment, although no specific explanations
within the TxLED regulated areas. This shows that cetane were provided as to how the corrosion inhibitor helped
enhancers and additives in general can be crucial in improve lubricity and brake power. Hancsók et al. (2007)
meeting the ever more stringent fuel regulations. synthesised succinic anhydride derivatives from vegetable
oil-based sources to serve as a multifunctional additive that
Corrosion inhibitor improves lubricity and inhibits corrosion. Based on the
copper strip corrosion test whereby higher values indicated
Corrosion of fuel injection system as a result of long-term greater corrosive tendency, untreated baseline diesel scored
biodiesel usage is a well-known problem. The occurrence a rating of 3 whereas addition of only 10 ppm additive to
is due to the tendency of high water entrainment level the fuel reduced the rating to 2. While the additive was not
during biodiesel production. Alleman and McCormick tested on biodiesel, it was designed for use with both diesel
(2008) tested for both the free and entrained water contents and biodiesel. Corrosion problems arising from the use of
of 32 B20 biodiesel samples collected from public pumps biodiesel need to be resolved for improved public percep-
and vehicle fleet, through the use of the Karl Fisher tion of biodiesel. The use of corrosion inhibitors could be a
method. The average moisture reading from the survey was potential solution, and more focussed research on the
found to be 130 ppm, but the maximum could be as high as treatment dosage and suitability for biodiesel from various
325 ppm. The use of corrosion inhibitor could greatly feedstocks are necessary.
alleviate this corrosion problem, through the formation of a
thin protective layer known as the passivation layer on the Cold flow improver
surface of the fuel to prevent direct contact between the
corrosive substances in fuel and the metal. Kaul et al. As discussed earlier, the relatively poorer cold flow prop-
(2007) conducted a corrosion test on piston liner and piston erties of biodiesel when compared with fossil diesel is a

123
Advances in biodiesel fuel 471

cause of concern when used under low-temperature envi- acid esters as compared to its saturated counterparts is due
ronments. The higher cold filter plugging point (CFPP), to the cis conformation, which results in a bent geometry
pour point and cloud point of biodiesel imply that the fuel (Smith et al. 2009, Soriano et al. 2005). With this geomet-
would potentially solidify as temperature drops below rical restriction, close packing in the molecular structure is
these values, posing serious problems for cold start-up limited. As crystals are not formed so readily with unsatu-
conditions. Flow improver additives are commonly used to rated fatty acid esters, their pour point is lower than that of
enhance low-temperature performance of biodiesel. Flow the saturated counterparts (Soriano et al. 2006). The addi-
improvers are typically anti-gelling in nature, and work by tion of cold flow improvers is especially crucial for bio-
reducing the size and shape of the wax crystals. They inhibit diesel with exceptionally poor cold flow properties such as
the crystals from growing to a size large enough to plug palm oil to allow usage during winter without requiring pre-
filters. A study conducted by Chiu et al. (2004) highlighted treatment such as ‘winterisation’ or blending with kerosene.
that cold flow improvers reduced the pour point of soybean It was claimed that the use of commercial cold flow
biodiesel. Figure 7 shows the pour points of B80–B100 improver, VISCOPLEX 10-330 at a treat rate of 0.75% (wt/
soybean biodiesel blended with No. 1 diesel that were wt) on palm methyl ester improved CFPP, pour point and
treated with cold flow improver, Bio Flow-875, at various cloud point by 5, 2 and 2C, respectively (RohMax 2008).
concentrations up to 0.2 wt%. Bio Flow-875 works by In general, CFPP values increase as biodiesel blend
distorting the plate-like shape of the crystals formed at low level is raised (Weyenberg 2007). Therefore, higher treat
temperature to irregular forms while reducing their sizes. rate is required to achieve the target performance for fuel
This improves bulk movement properties and results in blends with higher biodiesel content, as shown in Fig. 8.
lower pour points. Pour point for neat biodiesel was As in the case of fossil diesel, the use of cold flow improver
observed to decrease by 6C when 0.2 wt% of Bio Flow-875 on biodiesel is feedstock-specific (Quigley 2007). This is
was added, when compared with an 18C decrease for the expected as the distinct chemical makeup of biodiesel
B80 counterpart under the same concentration. This dem- produced from different feedstock contains varying amount
onstrated that the cold flow improver used in the test was of saturated fatty acid esters known to interfere with the
more effective on blended than on neat biodiesel. A plau- action of cold flow improver on wax crystal formation.
sible explanation for this is that the additive is more Owing to the greater tendency of saturated fatty acid esters
effective on the diesel portion of the biodiesel–diesel fuel to form crystals, it can also be inferred that it is more
blend, as wax and crystals formations in fossil diesel and difficult for a general cold flow additive to treat biodiesel
biodiesel are very different in nature. The wax formation in produced from feedstock with higher levels of saturated
fossil diesel originates from the paraffin component of the fatty acid content (Chandler 2008).
fuel, whereas the crystal formation from biodiesel comes An example of practical uses of cold flow improvers can
from the saturated fatty acid esters (Chandler 2008). The be seen in a project conducted by Decker Truck Line,
lower tendency of crystal formation for unsaturated fatty involving an on-road study of a truck fleet powered by B20
Fig. 7 Effects of cold flow
additive concentration on pour
point temperature for various
biodiesel blend levels (adapted
from Chiu et al. 2004)

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472 J.-H. Ng et al.

Fig. 8 Effects of cold flow

additive concentration on CFPP
temperature for various
biodiesel blend levels (adapted
from Weyenberg 2007)

soy biodiesel (ISA 2007). The two-year, all-season project biodiesel from edible and non-edible oils. Among these
was projected to accumulate an equivalent of two million methods, transesterification is the process of choice for
miles of road usage. The B20 blend used was treated with industrial applications due to its simplicity and cost
commercial cold flow improvers, allowing the fuel blend to effectiveness (Babu and Devaradjane 2003).
be used during winter. Interim results from this project
conclusively showed that biodiesel blends could be used on Transesterification
road all year round, and concerns over their usability
during winter should no longer be relevant. Whilst the Transesterification is simply described as the chemical
potential of using cold flow improvers to mitigate problems breaking of oil using alcohol to form alcohol esters and
associated with low temperature usage is immense, further glycerol (Tashtoush et al. 2003). Transesterification of a
research calls for the development of cold flow improvers triglyceride typically consists of a series of consecutive
capable of producing reliable results for a range of bio- reversible reactions. The triglyceride is converted stepwise
diesel blend levels. into a diglyceride, a monoglyceride and finally a glycerol,
with the removal of an alkyl in each step (Asakuma et al.
2009). Transesterification process is performed with the
Methods of biodiesel production purpose of lowering the viscosity of crude vegetable oil to
improve flow properties. The process also degums, dew-
The European Union views biodiesel as the methyl ester axes and removes triglyceride from the vegetable oil
produced from biomass or biodegradable fraction of waste (Shahid and Jamal 2008). The stoichiometry of transeste-
to be used as biofuel (European Union 2003). However, rification process requires three moles of alcohol such as
broader definition of biodiesel covers any processed veg- methanol and one mole of oil to produce three moles of
etable oil, waste vegetable oil or animal fat with similar desired fatty acid esters and one mole of glycerol as
properties to fossil diesel. Various processes are available byproduct (Ali and Hanna 1994). Although ethanol is the
to improve the relevant properties of potential feedstock preferred alcohol for transesterification due to its renew-
oils to the level similar to that of fossil diesel for use in able biomass origin and lower toxicity level (Demirbas
modern diesel engines (Yang et al. 2007). The three most 2008), methanol is most commonly used due to its price
extensively studied methods of biodiesel production are competitiveness compared with other common alcohols
transesterification, pyrolysis and microemulsion (Ranga- such as ethanol and isopropanol. This leads to the pre-
nathan et al. 2008). These are covered in this article, but are dominance of fatty acid methyl esters (FAME) among the
limited only to the present day production method of fatty acid alkyl esters in the market (Knothe 2005; Choo

123
Advances in biodiesel fuel 473

1 mole x Renewable 3 mole x Methyl transesterification at 65C with a 30:1 molar ratio of
fat or oil esters methanol to oil required 69 hours to achieve a 90% con-
(1000 kg) (1004.5 kg)
catalyst version rate. Enzyme-catalysed transesterification has the
+ +
advantage of low temperature operation, and the enzymes
3 mole x Methanol 1 mole x Glycerol can be reused without further separation. Contrary to acid-
(107.5 kg) (103 kg)
and base-catalysed transesterification processes, water
Fig. 9 Stoichiometric material balance of transesterification process content in feedstock does not cause adverse effects or
(adapted from Graboski and McCormick 1998) interference in an enzyme-catalysed transesterification
(Marchetti et al. 2007). However, enzymes are generally
expensive and enzyme’s action has been found to be
et al. 2005). Figure 9 shows the stoichiometric material deactivated when methanol concentration is high (Ranga-
balance of the transesterification process. nathan et al. 2008). The enzyme inhibitive effect by
In order to improve the yield and reaction rate, transe- methanol can be mitigated with a step-by-step addition of
sterification process is commonly catalysed by acids, bases methanol. Lu et al. (2007) examined the enzyme-catalysed
or enzymes (Demirbas 2005). The advantages and disad- transesterification of lard at 40C using a three-step addi-
vantages of the different catalysts are shown in Table 8. tion of methanol, which obtained a total yield of 87.4%
Only base catalyst is commonly used on an industrial scale after 30 h of reaction.
due to the high reaction rate obtainable at low temperature. As summarised in Table 9, important factors governing
A base-catalysed transesterification at approximately 60C the transesterification process and ultimately the yield of
with a molar ratio of 6:1 of alcohol to soybean oil achieved alcohol esters include molar ratio, catalyst, reaction time,
a 90–98% conversion to methyl esters within 90 min reaction temperature and contents of moisture and FFA.
(Zhang et al. 2003). Meanwhile, an acid-catalysed Yield was found to be reduced to only 6%, when 5% of

Table 8 The advantages and disadvantages of various catalyst types for catalyst-assisted transesterification
Type Common catalyst Advantages Disadvantages

Acid Sulphuric acid High yield Corrosive

Sulphonic acid Low reaction rate
Alkali Sodium hydroxide (NaOH) Most effective Risk of water or free acid contamination
Potassium hydroxide (KOH) Least corrosive Separation of catalyst difficult
High reaction rate at low temperature (60C) Recovery of byproduct (glycerol) difficult
Carried out in industrial scale
Enzyme Lipase Enzyme can be reused Enzymes are expensive
Good low temperature operations (50C) Inhibitive effects when methanol is used

Table 9 Variables affecting the yield of catalytic transesterification process (Ma and Hanna 1999; Agarwal 2007)
Variable Effects

Moisture and free fatty acid Either an increase in moisture or FFA reduces ester yield
Glyceride of an alkali-catalysed process has to have an acid value \1
Reactants must be reasonably anhydrous
Moisture content partially alters reaction to saponification, reduced catalyst efficiency and ester yield
Catalyst type and concentration Alkaline-catalyst: Faster conversion of ester
Acid-catalyst: Slower, suitable with high free fatty acid and water content of the glyceride
Conversion yield increases with catalyst concentration
Catalyst concentration [1% do not improve conversion rate further
Reaction temperature Increased temperature increase ester conversion and reaction rate
Molar ratio Higher molar ratio promotes greater and faster ester conversion due to excess alcohol driving the reaction
to the right
Reaction time Increased reaction time improves conversion yield
Conversion yield stagnant when maximum reaction time is exceeded

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474 J.-H. Ng et al.

Table 10 Biodiesel yield and

Feedstocks Acid value Biodiesel yield Biodiesel purity Acid value
purity from three feedstocks
in raw oil (wt%) (wt%) in biodiesel
(Guo et al. 2002)
Grease trap oils 4.1 77.3 97.7 0.21
Recycled oils 0.9 91.0 95.6 0.15
Edible canola oil \0.5 91.0 98.0 0.08

water was added in an acid-catalysed transesterification of carriers were tested here before MgO metal oxide was
(Kusdiana and Saka 2004). This could be attributed to the selected due to its additional base effect, which produced
fact that the catalyst was consumed by water, and thus the highest yield. With the optimised parameters of 0.7:1 of
reduced its efficiency. Research conducted by Guo et al. KF/MgO ratio and 1% of catalyst per unit vegetable oil, a
(2002) showed that yield and purity of biodiesel produced yield of 99.3% was obtained at 70C in just 2 h. In fact, it
from transesterification were reduced when acid value of has been reported that heterogeneous catalyst is already in
the feedstock used was raised. Among the feedstocks use at a FAME plant of Diester Industrie at Sète, France
analysed, canola oil with the lowest acid value in its raw oil (Chew and Bhatia 2008)
state had the greatest biodiesel yield and purity (refer to Supercritical methanol (SCM) transesterification is a
Table 10). A study by Ramadhas et al. (2005) on biodiesel form of non-catalytic transesterification method for bio-
production from rubber seed oil with high free fatty acids diesel production. This process is based on the idea of
(FFAs) content highlighted that the conversion efficiency supercritical treatment, which utilises the relationships
increased as the methanol to triglyceride molar ratio was between pressure and temperature upon thermophysical
raised. It was found that maximum ester yield was properties of a solvent such as dielectric constant, specific
achieved when molar ratio was raised to 9:1 (stoichio- weight, polarity and viscosity. Application of high tem-
metrically, the molar ratio is 3:1), although any additional perature and pressure in SCM approach forces simulta-
increase in molar ratio did not further improve conversion neous transesterification of triglycerides and methyl
efficiency. esterification of fatty acids (Demirbas 2005). SCM
The main factor determining the cost of present day transesterification requires the highest amount of excess
biodiesel production is the feedstock cost of its refined oil, alcohol among all the transesterification processes at a ratio
which can amount to 88% of the total production cost (Di of 40:1 of methanol to vegetable oil (Demirbas 2003).
Serio et al. 2007). Total production cost can be greatly However, this method is not only limited to methanol since
reduced by lowering the cost of feedstock with the use of ethanol, propanol and butanol have also been used suc-
more economical alternatives such as waste fats or oils. cessfully. Kusdiana and Saka (2001) demonstrated that the
The widely used homogeneous alkaline catalyst in the SCM approach is potentially suitable for large-scale
industry requires that the refined oils are in anhydrous industrial production of biodiesel, as 95% of rapeseed oil
condition, and no more than 0.5% of FFA is present in the was successfully converted into rapeseed methyl esters at
oils. As such, there is an emerging research trend currently 350C in just 4 min. This non-catalytic method also allows
on heterogeneous catalyst with the aim of reducing bio- simpler purification process, whereby the catalyst removal
diesel production cost through the use of cheaper feed- step can be omitted from the production stage. A study
stock. An extensive study by Di Serio et al. (2007) on eight done by Madras et al. (2004) on the synthesis of biodiesel
heterogeneous catalysts showed that satisfactory level of in various supercritical fluids found that the conversion rate
activities in the transesterification reaction was achieved. It in supercritical ethanol was higher than that for SCM. It
was found that hydrotalcite was effective in treating refined was deduced that the higher conversion rate of ethanol was
oil, whereas TiO2/SiO2 catalyst could be used for oils with due to the similar solubility limit between ethanol and the
high FFA concentration. Heterogeneous catalyst can feedstock oil. Nevertheless, the conversion rate using SCM
therefore be considered as a suitable replacement for remained high at 96%, with a molar ratio of 40:1 (alcohol
homogeneous alkaline catalyst, especially in treating oils to oil) at 400C and 200 bar. The presence of water in
with high level of FFA and/or water. Other added advan- SCM method affects the formation of methyl esters posi-
tages associated with this type of catalyst include the tively, contrary to the catalysed transesterification process.
exclusion of an extra neutralisation step that is otherwise In this case, water acts as a catalyst akin to an acid catalyst
necessary with the alkaline-catalysed process, the produc- which is stronger than methanol itself. A study by Kusdi-
tion of a higher value, cleaner glycerol as by-product and ana and Saka (2004) reported that waste palm oil with
the ability to be easily recycled. In another study involving water content of over 61 wt% achieved a methyl ester yield
heterogeneous catalysts, the KF/MgO catalyst–carrier of 95.8% using the SCM approach, where no reaction
combination was proposed by Liang et al. (2009). A variety occurs if acid or alkaline catalyst were used. This is

123
Advances in biodiesel fuel 475

invaluable as it permits waste oil that has significant cost and pressure required, as well as the high cost associated to
advantage over other crude vegetable oils to be used with the equipment. A comparison of the economic indicators of
minimal production problems as seen with the conven- all the four simulated cases from the two studies above is
tional transesterification method. provided in Table 11. Ultimately, the penetration of bio-
In addition to the technical aspects, the economical diesel into the fuel market will be influenced by a combi-
feasibility of biodiesel is also of great importance to assess nation of technical and economic factors. Nonetheless, the
its overall viability. As such, a techno-economic assess- practicality of a sustained biodiesel production plant will
ment of the major processes in biodiesel production is inherently be more dependent on its economical viability
necessary to enhance market penetration of the biodiesel rather than the technical capability of the plant. In line with
fuel. A techno-economic analysis by Marchetti et al. (2008) this, the outlook of biodiesel production points towards the
using a process simulator was conducted to analyse the usage of cheaper feedstock to lower the overall production
productivity, raw material consumption, environmental cost rather than focusing purely on the product yield.
impact and ultimately the economic competitiveness of
three conceptual production plants. The methods of oper- Pyrolysis
ation of these plants differed from one another in the type
of catalysts used, namely homogeneous alkaline catalyst, Pyrolysis is a process of utilising heat in the absence of air
homogeneous acid catalyst and heterogeneous solid cata- or oxygen with a catalyst to bring about chemical changes
lyst. The focus of this study was on feedstock with high in organic materials such as vegetable oils, animal fats,
FFA content due to its lower cost. Based on the analysis, all natural fatty acids, methyl ester of fatty acids or even solid
the three plants were technically suitable for biodiesel wastes (Agarwal 2007). Different types of feedstock such
production using feedstock with high FFA content. The as soybean, rapeseed, palm, castor, safflower, olive husk
plant using heterogeneous solid catalyst was the most and tung have been used with varying degrees of success to
optimum, as it required the lowest capital investment due produce oil through pyrolysis (Balat and Balat 2008).
to the fewer number of essential equipments. The glycerol Thermal decomposition of triglycerides through this
produced also had higher purity, allowing it to be sold at a approach produces alkanes, alkenes, alkadienes, carboxylic
higher price which improved the economic competitive- acids, aromatics and a small amount of gaseous product.
ness. A follow-up process simulation study was performed Alkanes and alkenes account for approximately 60% of the
by Marchetti and Errazu (2008) on a supercritical biodiesel total weight of pyrolysis yield (Demirbas 2003). The vis-
production plant. This production plant was found to be a cosity is reduced during pyrolysis through the breaking of
good technical alternative, but a poor economic option as chemical bonds at high temperatures of 300–400C,
compared to the previous three plants due to its high reducing long hydrocarbon chains to shorter chains. In
operating cost. This is attributed to the high temperature addition to the reduced viscosity, thermally decomposed

Table 11 Economical indicators of the process simulation for the various biodiesel production plant types
Homogeneous alkaline Homogeneous acid Heterogeneous solid Supercritical (Marchetti
catalyst (Marchetti catalyst (Marchetti catalyst (Marchetti and Errazu 2008)
et al. 2008) et al. 2008) et al. 2008)

Plant capacity (ton/year) 36,036 36,036 36,036 36,036

Biodiesel revenues (US$/year) 16,029,000 16,023,000 16,281,000 16,309,000
Credits for glycerine (US$/year) 2,660,000 2,548,000 3,573,000 2,432,000
Total incomes (US$/year) 18,689,000 18,571,000 19,854,000 18,741,000
Equipment cost (US$) 1,503,000 1,477,000 1,010,000 1,377,000
Total investment (US$) 7,415,000 7,327,000 5,151,000 8,438,000
Raw material cost (US$/year) 14,414,000 14,414,000 14,414,000 14,414,000
% of the total operating cost (US$/year) 79.60 78.51 76.28 40.58
Total operating costs (US$/year) 18,109,000 18,359,000 18,896,000 35,514,000
Biodiesel unitary cost (US$/kg) 0.5084 0.5156 0.5223 0.9800
Gross margin (%) 5.50 4.16 7.74 1.41
Return over investment (%) 19.68 16.69 33.23 11.00
Net present value (7%) $1,797,000 $(1,275,000) $7,789,243 $(2,575,271)
Internal return rate (%) 11.17 6.95 31.95 1.80

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476 J.-H. Ng et al.

conventional biodiesel and diesel fuels with low- and high-

sulphur content. It was reported that although the pyrolysed
fuel conformed to the kinematic viscosity criterion of the
ASTM D6751 and EN 14214:2003 standards, its kinematic
viscosity value of 4.5 mm2 s-1 at 40C is still 9.8, 66.7 and
104.5% higher than that of conventional biodiesel, low-
sulphur diesel and high-sulphur diesel, respectively. The
higher viscosity suggests that atomisation is expected to be
poorer for the pyrolysed oil. Pyrolysis of waste products
provides additional routes to minimising the utilisation of
natural resources, although reactor design and operating
conditions for optimum yield need to be carefully
Fig. 10 Schematic representation of the thermal decomposition determined.
mechanism of triglycerides (Ma and Hanna 1999)
Microemulsification
product also possesses desirable higher cetane number as
compared to crude vegetable oil (Ali and Hanna 1994). The Microemulsion refers to an optically isotropic fluid
mechanism of thermal decomposition is shown in Fig. 10. microstructure formed spontaneously from two normally
The product of pyrolysis is similar to fossil diesel in terms immiscible liquids, and one or more ionic or non-ionic
of chemical composition, due to the removal of oxygen amphiphile. The dimension of the said microstructure is
content during the process. As such, any potential reduc- within the 1–150 nm range (Ma and Hanna 1999). Con-
tion in PMs, CO and UHCs commonly associated with the version of vegetable oil to microemulsion fuels is able to
oxygenated nature of biodiesel is offset with the absence of reduce the high viscosity of the raw oil. Microemulsion
oxygen. High equipment cost and the occasional higher formation and stability are dependent upon interactions
gasoline yield than diesel produced make pyrolysis less among molecules in the constituents. These are greatly
economical compared to transesterification (Ma and Hanna influenced by the type and concentration of emulsifier and
1999). A pilot plant experiment by Wiggers et al. (2009) the amount of energy input (Ali and Hanna 1994). The
for a continuous fast pyrolysis process was used to perform explosive vaporisation of low boiling point constituents in
thermal cracking on waste fish oil. In this study, yield of the micelles enhanced the spray characteristics of the fuel.
light bio-oil which is the gasoline-equivalent was found to Formation of microemulsion requires the use of solvents
be higher than that of diesel-equivalent heavy bio-oil at such as methanol, ethanol, butanol, hexanol and octanol
35.86 and 34.83%, respectively. Nonetheless, the potential (Agarwal 2007). 2-octanol was found to be an effective
of pyrolysis as a feasible biodiesel production method is amphiphile in the micellar solubilisation of methanol in
good as the technologies involved are similar to that of the soybean oil and triolein (Ma and Hanna 1999). A study by
well-established conventional petroleum refining. This Ziejewski et al. (1984) on an emulsion ratio of 53:13.3:33.4
meant compatibility with existing infrastructure, engines by volume of winterised sunflower oil, 190-proof ethanol
hardware configurations and fuel standards, on top of the and 1-butanol, respectively showed no significant deterio-
flexibility in feedstock options (Maher and Bressler 2007). ration in engine performance after a 200-h endurance test.
Furthermore, crude glycerol was not produced from the However, problems related to heavy carbon deposits,
pyrolysis of vegetable oil (Doll et al. 2008), which can irregular injector needle sticking and increase in lubricating
either be an economic advantage or disadvantage depend- oil viscosity were reported. de Castro Dantas et al. (2001)
ing on the market value of this byproduct. Research study demonstrated that microemulsion system of diesel and
by Murugan et al. (2008) on diesel blends with distilled vegetable oil mixture possesses properties suitable for use
tyre pyrolysis oil demonstrated the potential of using in diesel engines. Parameters such as microemulsion area,
pyrolysis for the generation of alternative fuel for CI surfactant type, cosurfactant type, surfactant/cosurfactant
engines using solid waste. Engine fuelled by blends of up ratio and composition of oil phase were optimised to pro-
to 90% distilled tyre pyrolysis oil and 10% fossil diesel was duce the microemulsified fuel which can possibly be used
able to operate satisfactorily. However, engine-out UHC in diesel engines. Nonetheless, one key problem observed
level increased by 5.3% relative to that of fossil diesel at with the use of microemulsified fuels lies in their stabilities
high load. This was due to the failure of unsaturated at sub-zero temperature. A way to counter this low-tem-
hydrocarbon content in the pyrolysis oil to break during perature instability of the microemulsified fuels was dis-
combustion. Doll et al. (2008) compared the kinematic covered by Fernando and Hanna (2004), where soybean
viscosity values of pyrolysed soybean oil against methyl ester was used as an amphiphile to form a stable

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Advances in biodiesel fuel 477

ethanol–biodiesel–diesel microemulsion at the lowest cetane number, biodiesel is expected to combust earlier
temperature of –13C. Highest stabilities were recorded for from the shorter ignition delay. This was proven in a
ethanol:biodiesel:diesel ratios of 3.75:25:71.25 and 4:20:76 comparative study on combustion characteristic of rice
when low sulphur diesel and ultra-low sulphur diesel bran oil-derived biodiesel blend (B20) against fossil diesel
(12 ppm sulphur) were used as the base diesel fuel, in a naturally aspirated diesel engine (Agarwal 2007). In
respectively. It was concluded that the ratio of biodiesel to this study, the B20 blend had an earlier start of combustion
ethanol must be greater than unity for the formation of a under various load conditions at an engine speed of
stable microemulsion. Although the biodiesel was used as 1,400 rev/min. The start of combustion as indicated by the
an amphiphile, its significant content of 20–25% in the fuel burning of 10% fuel mass, were found to be 2.5 crank
blends indicated that it was effectively a B20–B25 blend. angle (CA), 1.5 and 1.0 CA earlier for the B20 blend when
The microemulsified blend produced showed a 2.3-fold compared with fossil diesel for engine loads of 0, 50 and
increase in lubricity for the fuel blend with low sulphur 100%, respectively. Comparison of the cumulative heat
diesel, and a 4-fold increase for its ultra-low sulphur diesel release curves produced from the combustion of the B20
counterpart. However, cetane number was reduced by 3.6% blend and fossil diesel is shown in Fig. 11. Despite a later
for the former and 1.2% for the latter. Although the start of combustion, fossil diesel showed a faster burn rate.
apparent simplicity associated with the microemulsification This was attributed to the higher rate of heat release during
process appears attractive, its viability as a biodiesel pro- the PMC phase caused by the longer ignition delay period.
duction method should only be promoted after long-term The lower total heat released of approximately 8% for the
impacts from the usage of the produced biodiesel on engine B20 blend was in agreement with the typically lower heat
durability, combustion and emission characteristics are of combustion found in biodiesel fuels. A combustion
ascertained. analysis performed by Sahoo and Das (2009) on a Kirlos-
kar DAF8 single-cylinder air-cooled, four-stroke diesel
engine fuelled with biodiesel from non-edible feedstocks
Effects of biodiesel on diesel engines showed a collective shortening of the ignition delay dura-
tion. The shortening in ignition delay periods for jatropha,
Combustion karanja and polanga neat biodiesel fuels were in the range
of 4.2–5.9, 4.5–6.3 and 4.2–5.7 CA, respectively. This
As discussed earlier, combustion characteristic is heavily was caused by the breakdown of high-molecular-weight
influenced by the properties of the fuel such as cetane liquid esters into gases of low-molecular weight through
number, heat of combustion, oxygen content and bulk chemical reactions encouraged by biodiesel injection high
modulus. A marked difference in the combustion charac- temperature. Rapid gasification of the fuel spread out the
teristic is expected due to the distinct variations in fuel spray jet, producing volatile combustion compounds that
properties between biodiesel and fossil diesel. With higher promote faster ignition. As ignition delay was shortened,

Fig. 11 Cumulative heat

release at 100% engine load for
a medium-duty direct injection
(DI) transportation engine
(adapted from Agarwal 2007)

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478 J.-H. Ng et al.

PMC phase also became less intense. This in turn lowered therefore possible for an increase in power output to be
the peak heat release rate (HRR), where the values at full achieved when neat biodiesel is introduced into conven-
load for neat jatropha, karanja and polanga biodiesel fuels tional diesel fuel. However, when the biodiesel proportion
were 69.97, 70.93 and 68.37 J/CA, respectively when exceeds a certain critical limit, output power has been
compared with the peak HRR of 90.96 J/CA for conven- observed to decrease. Here, it is deduced that the improve-
tional diesel fuel. Maximum HRR also occurred earlier for ment in combustion efficiency is unable to offset the loss of
biodiesel as a direct consequence of the shorter ignition power due to the lower calorific values of biodiesel. Similar
delay. trends were observed for the brake specific fuel consump-
Engines running on biodiesel normally have higher brake tion, whereby fuel economy improved with the addition of
specific fuel consumption relative to fossil diesel-fuelled biodiesel into the fuel blend up to an optimum blending
engines, since biodiesel has lower heat of combustion. Ke- proportion but deteriorated past that point. Figure 12 shows
skin et al. (2007) conducted a fuel economy study on a the variations in output power and brake specific fuel con-
single-cylinder Lombardini 6LD 400 DI engine over a speed sumption as a function of the proportion of methyl soyate.
range of 1,800–3,200 rev/min. Fuel consumption of a B60 The resulting engine output power when using biodiesel and
tall oil biodiesel blend, with a calorific value of 41.51 MJ/ its blends is dependent on either improved combustion
kg, was compared to fossil diesel with a calorific value of quality or lower calorific value is dominant.
43.76 MJ/kg. It was reported that the B60 blend resulted in a Murillo et al. (2007) conducted the ISO 3046 C3 per-
3.22–6.00% increase in specific fuel consumption across the formance test on an outboard diesel engine 8D Diesel. It
entire speed range tested. In contrast, experiments per- was observed that any increase in waste cooking oil bio-
formed by Ali et al. (1995) on a Detroit diesel 6 V-92 TA diesel content in the fuel blends reduced the achievable
Coach engine fuelled with methyl soyate–diesel fuel blends output power. At low biodiesel blends of B10 and B30, a
indicated that output power increased with only a small power loss of less than 5% was noticed in contrast to the
addition of methyl soyate in the blend, suggesting a potential 8% reduction in power when B50 or B100 fuel blends were
improvement in combustion efficiency. Despite the lower used. A study by Lin et al. (2008) on a diesel generator
calorific value, the high oxygen content in biodiesel pro- QC495 fuelled with palm biodiesel also showed similar
motes a more complete combustion due to improved trend, with the best energy efficiency achieved in the B10–
homogeneity in local fuel–air mixture (Demirbas 2007). B20 blend range (Lin et al. 2006). Keskin et al. (2008)
Furthermore, biodiesel fuel–air mixtures are able to achieve tested the cotton oil soapstock biodiesel blends in a single-
stoichiometric condition which supports complete com- cylinder DI Lister Peter TD111 engine. The fuels were
bustion almost 15% quicker than fossil diesel–air mixture tested at full-load conditions, with engine speeds between
(Rakopoulos et al. 2006). This is in spite of the longer 1,600 and 3,000 rev/min. An average power loss of 6.2%,
evaporation time for the larger mean fuel droplet size caused torque loss of 5.09% and specific fuel consumption
by the higher kinematic viscosity value of biodiesel. It is increase of 7.8% were recorded when B60 blend is used.

Fig. 12 Percentage difference

in output power and brake
specific fuel consumption as a
function of % methyl soyate in
fuel blend (adapted from Ali
et al. 1995)

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Advances in biodiesel fuel 479

However, an increase in torque was observed for B20 blend DI diesel engine. The average effective engine power at
at the high-speed range of 2,800–3,000 rev/min as shown five test speeds across the range of 1,000–3,000 rev/min for
in Fig. 13. Better engine thermal efficiency as implied by B5, B20, B50 and B100 were 2.65, 2.90, 2.40 and 4.00%,
the lower heat loss to exhaust from the combustion of the respectively, lesser than that produced from conventional
B20 blend was thought to be the cause for this observation. diesel. However, the effective engine power for the bio-
Specific fuel consumption remained high at all speeds diesel blends was higher despite the lower calorific values
relative to that from fossil diesel as shown in Fig. 14. at the lower speeds of 1,000 and 1,500 rev/min. A possible
Maximum torque and lowest specific fuel consumption explanation for this is the better biodiesel combustion at
were found to occur at 2,000 and 2,400 rev/min, respec- low engine speeds, as more time is available for the
tively. It was also observed that the characteristics of combustion process. This showed that although fuel prop-
power, torque and specific fuel consumption were main- erties such as the calorific value plays a key role in
tained irrespective of the blend proportion. Biodiesel at low determining the power output, it is equally important to
blending proportions of approximately 10–20 vol% can be account for the engine operating conditions. More con-
concluded as the optimum blending level for higher power centrated research efforts must be dedicated to this, in
and torque output with lower brake specific fuel con- order to utilise higher fractions of biodiesel blends or neat
sumption. This is predominantly due to improved com- biodiesel for optimum engine performance.
bustion quality from the presence of fuel-bound oxygen in Biodiesel is generally less compressible due to the
biodiesel. Above the B20 level, however, improvement in higher bulk modulus, causing nozzle opening pressure to
combustion quality is offset by the lower energy content. be exceeded prematurely (Hess et al. 2007). Fuel injection
In a separate study, Öner and Altun (2009) conducted an is thus advanced, leading to longer and more intense PMC
experiment to observe the use of inedible animal tallow phase that raises in-cylinder temperature, soot oxidation
biodiesel on a Rainbow LA186 single-cylinder, four-stroke and NOx formation rate. Boehman et al. (2004) conducted a

Fig. 13 Torques of various

cotton oil soapstock biodiesel–
diesel blends at full-load
condition (Keskin et al. 2008)

Fig. 14 Specific fuel

consumption of various cotton
oil soapstock biodiesel–diesel
blends at full-load condition
(Keskin et al. 2008)

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480 J.-H. Ng et al.

a Renault F8Q IDI diesel engine when fuelled with sun-

flower and cynara methyl esters.

Emissions

Conversion of biodiesel chemical energy under high pres-

sure and temperature in CI engines produces emissions
such as CO2, NOx, PM, CO, UHCs and aromatic com-
pounds. The average biodiesel emissions when compared
with conventional diesel fuel according to a technical
analysis on the effects of biodiesel on exhaust emissions
from diesel-powered vehicles by the United States Envi-
ronmental Protection Agency (US EPA) are demonstrated
in Fig. 16 (EPA 2002). The results here were average
values from 43 heavy-duty highway engines under tran-
sient or steady-state tests, namely the Federal Test Proce-
dure (FTP) composite, FTP hot-start and R49 13-mode.
Fig. 15 Measured fuel injection timing for biodiesel–diesel fuel The engines varied from pre-1983 up to 2001 models, with
blends shown as relative spray intensity as a function of crank angle
position relative to top dead centre (TDC). A relative spray intensity
60% of the total number of the tested engines being models
of 0.2 indicates the start of fuel injection (Boehman et al. 2004) from 1991 till 1997. These average values provided an
indication of the general effects of biodiesel on emissions,
but the quantities and types of emissions emitted were
comprehensive engine testing programme based on the highly dependent on engine operating parameters, condi-
steady-state G2 test modes using neat soybean biodiesel. tions and geometry of the combustion chamber, fuel
The Yanmar L40 AE D DI engine with in-line, pump-line– injection variables and fuel characteristics (Cipolat 2007).
nozzle injection system was used in the study. An injection There is a need to perform an in-depth impact assessment
timing shift of up to 1 CA was observed for neat soybean of the factors affecting emissions from biodiesel-fuelled
biodiesel, whereas a 0.2–0.3 CA of advancement in diesel engines. The individual influences of the biodiesel
injection timing was recorded for B20 soybean–biodiesel properties on emissions when compared with fossil diesel
blend as presented in Fig. 15. The trends were found to be are shown in Fig. 17. Detailed discussion of these effects
in agreement with a study done by Lapuerta et al. (2005) on on emissions is presented in the following sub-sections.

Fig. 16 Average biodiesel

emissions of heavy-duty
highway engines (adapted
from EPA 2002)

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Advances in biodiesel fuel 481

Higher peak Lower peak

NOx increase NOx decrease
temperature temperature

Shorter
Stronger premixed
ignition delay Lower adiabatic
combustion phase
period flame
temperature

Advancement
Higher peak Higher cetane
in injection
temperature number Lower PAHs and
timing
aromatics MAHs
content decrease

Higher bulk
Biodiesel
modulus

Higher Spray droplets

UHCs
kinematic with larger
decrease Lesser sulphate
Lower sulphur viscosity mean size
adsorbed on
content
soot

Flame
Higher oxygen Slower
propagation not
PM decrease content evaporation
sustainable

More complete Limited rich Air-fuel ratio UHCs Incomplete

CO decrease PM increase
combustion combustion too lean increase combustion

Fig. 17 Direct impact and corresponding interactions of biodiesel fuel properties on emissions as compared to fossil diesel

Oxides of nitrogen (NOx) which is associated to rapid pressure rise was also reduced
accordingly. This provided adequate time for cooling
Oxides of nitrogen, NOx consist of nitric oxide (NO) and through heat transfer and dilution, which arrested the high
nitrogen dioxide (NO2). Among the two, NO is predomi- peak combustion temperature necessary for NOx genera-
nantly formed within the combustion chamber (Monyem tion. As shown in Fig. 18, the B50 blend of olive methyl
and Van Gerpen 2001; Canakci et al. 2006). Thermal NO esters (cetane number of 61 in neat form) demonstrated
which is produced from the reaction between atomic greater NOx reduction of 12.6–22.3% at varying load
nitrogen and oxygen under high temperature is believed to conditions, in contrast to the 6.1–15.2% reduction achieved
be the main mechanism responsible for in-cylinder NOx by its sunflower counterpart (cetane number of 58 in neat
formation. Its production rate is highly dependent on gas form). It has been postulated that fuels with higher aro-
temperature and the residence time of the high temperature matic content generally aid the formation of locally rich
gas, as nitrogen is inert up to 1,100C (Nabi et al. 2009). regions, and high temperature zones due to their higher
Above all, high temperature is necessary to overcome the adiabatic flame temperature during combustion. These
high activation energy needed to break the nitrogen– regions of high flame gas temperature promote NOx for-
nitrogen triple bonds in the nitrogen molecules. This allows mation. Thus, the reduction of aromatic content in the fuel
the nitrogen radicals to participate in thermal NO reactions, helps moderate NOx production. Similar trend was found
typically when gas temperature rises to around 1,500C by Kalam and Masjuki (2002) in an investigation on an
during combustion. Isuzu 4FB1 IDI diesel engine powered by palm oil–bio-
Reports from the various studies conducted to determine diesel blend. In this study, it was observed that an increase
the effects of biodiesel on NOx emission have so far been of biodiesel fraction in the fuel blend from 7.5 to 15% at an
inconclusive. It is widely believed that biodiesel can engine speed of 1,200 rev/min decreased the concentration
potentially reduce NOx emission under certain engine of NOx emission from 147 to 135 ppm.
operating conditions. Kalligeros et al. (2003) carried out a In contrast, an 80,000-km durability test conducted by
study using sunflower- and olive-derived biodiesel blends Yang et al. (2007) on two identical Mitsubishi 4M40-2AT1
of up to B50 in a Petter AV1-LAB diesel engine. Experi- diesel engines using a B20 biodiesel blend derived from
mental measurements showed larger reduction in tailpipe waste cooking oil showed elevated NOx emission levels at
NOx as biodiesel fraction in fuel blend was raised under both the beginning and end of the test. NOx emission for
five different loads, ranging from 0.01 to 3.80 kW. The the B20 fuel was 11.3% higher than that of conventional
reduction is credited to the higher cetane number and lower diesel at the start of the test. Numerous engine studies also
aromatic content of biodiesel. The higher cetane number reported an increase in NOx with the use of biodiesel (Hess
shortened the ignition delay period, and the PMC period et al. 2007; Murillo et al. 2007; Nabi et al. 2009). The

123
482 J.-H. Ng et al.

Fig. 18 Percentage change in

total NOx emissions as a result
of the addition of sunflower oil
and olive oil biodiesel into
conventional fossil diesel
(Kalligeros et al. 2003)

presence of fuel-bound oxygen promotes better combus- Particulate matter (PM)

tion, resulting in higher in-cylinder bulk gas temperature
and consequently, NOx emissions. It is also postulated that Along with NOx, PM emission forms the two major tailpipe
NOx increase could be due to the additional contribution pollutants from CI engines. The conventional chemical
from prompt NO mechanism within the flame region composition of PM is depicted in Fig. 19. PM concentra-
(McCormick et al. 2001). The double bonds in biodiesel tion in the exhaust stream can be reduced by using fuel
may participate in combustion and pre-combustion chem- with lower level of components that constitute PM, for
istry of hydrocarbon free radicals. Formation of NO example sulphur. Usage of biodiesel with much lower
through the prompt pathway is encouraged if high level of concentration of sulphur can limit the fraction of this which
certain hydrocarbon radicals is present in the fuel-rich zone gets adsorbed onto soot particles, thereby decreasing the
of the diesel spray jet. Advancement in fuel injection emission of PM (Kalligeros et al. 2003). Schumacher et al.
timing due to higher bulk modulus of biodiesel is also (1996) conducted an engine testing programme on a 1991
thought to be responsible for the increased NOx level, Detroit 6 V-92TA DI diesel engine using blends of soy-
although this is not expected to be significant as typical bean biodiesel of up to B40 under the EPA heavy-duty test
injection advancement seen due to this is limited to only 1 cycle. Results showed decreasing level of PM with
CA. McCormick et al. (2005) conducted a heavy-duty increasing biodiesel fraction in fuel blend. The reduction in
transient test on two engines with different fuel injection PM levels obtained for B10, B20, B30 and B40 relative to
systems. The 2003 5.9L DDC Series 60 engine used an fossil diesel were 5.7, 11.0, 12.1 and 17.8%, respectively.
electronic unit injector (EUI), while the 2002 14.0L The lower PM levels are attributed to the high oxygen
Cummin ISB utilised a high pressure common rail fuel content in biodiesel, which suppresses the formation of
(HPCRF) injection system. Here, the results suggested that fuel-rich regions, and therefore, allowing a more complete
the average rate of NOx emission increase with B20 blends combustion to take place. It was observed that the exhaust
from soybean, canola, yellow grease and beef tallow was PM reduction associated with biodiesel usage applies to the
4.5 times greater for the EUI injection system compared to solid and carbon fractions of PM that usually require a
the HPCRF injection system. This could be attributed to particulate trap for removal from the exhaust stream. This
the way common rail fuel-injection system works, whereby permits the use of oxidation catalyst to oxidise the soluble
the system does not rely on the transfer of pressure wave to fractions. This is shown to be crucial from a study by
initiate injection contrary to older pump-line-nozzle and Durbin et al. (1999) on four light heavy-duty diesel vehi-
unit injection systems. Ultimately, NOx formation is cles, where neat biodiesel was reported to produce PM with
influenced by a number of interacting factors such as higher level of soluble organic fraction when compared
ignition period, combustion quality and injection timing, with reformulated diesel fuel. Here, soluble organic frac-
although the final NOx concentration emitted is dependent tion of 63.3–91.2% of total PM was distinctly higher than
on which of these are dominant. that of reformulated diesel fuel at 49.1–84.8%. Other

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Advances in biodiesel fuel 483

research studies conducted on biodiesel from various found, and the lower mean diameter observed was a direct
feedstocks such as sunflower, cynara and olive also showed result of the oxidation process of larger particles to form
distinct reduction in PM emission (Schumacher et al. 1996; smaller particles. Lin et al. (2007) studied the use of waste
Kalligeros et al. 2003; Lapuerta et al. 2005). cooking oil-derived biodiesel on a 2.2L Yueloong Diesel
Lapuerta et al. (2008) reported the results of an assess- SD22, tested at engine speeds ranging from 1,000 to
ment on particulate emission from waste cooking oil- 2,000 rev/min. Most of the results from the investigation
derived biodiesel in a four-cylinder, four-stroke DI engine. showed an increased exhaust PM levels with the use of B20,
Five steady-state operating modes were selected to simulate B50, B80 and neat biodiesel blend as seen in Fig. 21. This
typical road conditions. It was observed that both mean could be due to the deterioration of the test engine or its
diameter and concentration of PM for all biodiesel blends main components, which affected fuel distribution and air
were reduced. As discussed earlier, a reduction in mean utilisation. In addition, it was also suggested that the higher
diameter could signify that smaller PM particles which pose kinematic viscosity of the waste oil-derived biodiesel used,
greater health hazards were being emitted. From Fig. 20, no which was 64.5% higher than that of the fossil diesel, led to
increase in the amount of smallest particles PM10 was poorer atomisation. This meant larger fuel droplets were
formed thereby inhibiting complete evaporation and the
ensuing combustion process. The larger mean droplet size
40% 8% of biodiesel shown in Fig. 22 was confirmed in a separate
study by Lapuerta et al. (2005) involving cynara methyl

31%
7%

14%

Unburnt lubricating oil Elemental carbon

Sulfate and moisture Unburnt fuel Fig. 21 A comparison of PM10 emissions from various waste
Metal and other substances cooking oil-derived biodiesel blends against fossil diesel at various
engine speeds (Lin et al. 2007)
Fig. 19 Typical composition of particulate matter (adapted from
Agarwal 2007)

Fig. 20 Particle size distributions from the combustion of various

waste cooking oil-derived biodiesel blends against conventional Fig. 22 Sauter mean diameter (SMD) of fuel droplets is shown as a
diesel fuel in an engine operating at a speed of 1410 rev/min, brake varying function of brake mean effective pressure (bmep) for
mean effective pressure of 1.499 bar, effective torque of 26 Nm and different biodiesel fuel blends tested. The plot indicated that the
an exhaust gas recirculation (EGR) ratio of 0.365 (Lapuerta et al. atomisation of biodiesel fuels generally produces droplets with larger
2008) mean droplet size (Lapuerta et al. 2005)

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484 J.-H. Ng et al.

ester and sunflower methyl ester. Although biodiesel usage In another evaluation by Kalam and Masjuki (2002), the
resulted in mostly PM reduction, elevated PM level could use of palm biodiesel was found to have very little impact
still arise if the biodiesel viscosity is too high or engine on tailpipe CO concentration from naturally aspirated or
components such as fuel injector are not properly regulated. turbocharged diesel engines as these engines were already
Nonetheless, the use of biodiesel is still an effective mea- running lean with excessive air. The importance of fuel-
sure in the control of tailpipe PM emission. bound oxygen content is also dependent on engine oper-
ating conditions, as reported in the study carried out on an
Carbon monoxide (CO) 8D outboard diesel engine fuelled with waste cooking oil-
derived biodiesel (Murillo et al. 2007). The highest
Carbon monoxide (CO) is an intermediate product of reduction in CO emission was achieved at full load using
combustion, formed in the earlier stages of the oxidation B50, with a 29.6% reduction over conventional diesel fuel.
process before full conversion into CO2. It is emitted in the More oxygen was needed for complete combustion at high
exhaust stream when its progression to CO2 is not complete load as larger amount of fuel was injected, thus the avail-
due to cooling of fuel flame temperature, or when the ability of fuel-bound oxygen in biodiesel was crucial here
engine operation is too fuel rich (Kalam and Masjuki for complete combustion. However, CO emissions for
2004). The oxygenated nature of biodiesel means that various biodiesel blends as shown in Fig. 24 were com-
oxygen is readily available to limit fuel-rich regions, due to parable or even higher than conventional diesel at part
which combustion is improved, and CO is reduced. Alti- load, as sufficient oxygen for complete combustion was
parmak et al. (2007) examined the impact of tall oil methyl present from normal air intake. In this case, the oxygen
ester and conventional diesel fuel blends on a single-cyl- content in biodiesel was not necessary for the promotion of
inder 6LD 400 diesel engine tested over an engine speed complete combustion.
range of 1,800–3,200 rev/min. It was found that CO
reduction for the B50, B60 and B70 blends were attained at
all engine speeds tested. As illustrated in Fig. 23, the
greatest reduction of 38.9% was achieved with a B60 blend
at 3,200 rev/min under full-load condition. The findings
are in good agreement with the results from the study by
Monyem and van Gerpen (2001) on a John Deere 4276T DI
diesel engine fuelled with oxidised biodiesel. The oxidised
biodiesel was obtained by bubbling oxygen through the
fuel. The investigation indicated that 15% and 28%
reduction in CO values was achieved over typical unoxi-
dised biodiesel and fossil diesel, respectively. This implied
that CO emission decreases with increasing oxygen content
in the fuel. A study by Nabi et al. (2009) on cottonseed
biodiesel when used in a naturally aspirated, single-cylin- Fig. 24 CO emissions versus engine load during C-3 test cycle
der four-stroke DI diesel engine also reported similar trend according to ISO 8178 for different used cooking oil-derived
with a 24% CO reduction for a B30 blend. biodiesel blends in an outboard diesel engine (Murillo et al. 2007)

Fig. 23 CO emissions of
various blends of tall oil methyl
ester against baseline No. 2
diesel for operating speed range
of 1,800–3,200 rev/min at full-
load condition (Altiparmak
et al. 2007)

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Advances in biodiesel fuel 485

Unburned hydrocarbons (UHCs) ‘‘semi-volatile organic compound’’ due to their vapour

pressure distribution in the order of 107 (Correa and Arbilla
Similar to CO, UHCs are the outcome of incomplete com- 2006). The phases in which PAHs exist are dependent on
bustion. Possible causes of UHCs are fuel-rich combustion, the number of aromatic rings, and these are shown in
flame quenching, misfiring, crevice flows, valve overlap and Table 12. PAH emission for biodiesel can be expected to
desorption of hydrocarbon from oil film in and around the reduce as biodiesel has only trace amounts of aromatics in
cylinder (Kalam and Masjuki 2004). In a study involving its composition compared to fossil diesel. A study by Lin
soybean-derived biodiesel blends in a 1991 Detroit 6 V-92TA et al. (2006) on a diesel generator QC 495 using palm
DI diesel engine (Schumacher et al. 1996), UHC values were biodiesel blends reported that the average PAH concen-
found to vary almost linearly with the proportion of biodiesel trations from the 21 individual PAHs emitted were reduced
in the fuel blends. Here, B10, B20, B30 and B40 blends with the increase of biodiesel fraction in the fuel blends. It
showed reduction in UHC levels of 13.4, 22.7, 25.8 and was clearly evident that this was due to the lower aromatic
40.2%, respectively. This indicated that the increased oxygen content and the improved combustion quality of biodiesel.
content in the biodiesel blend promoted more complete As the majority of PAH mass is destroyed during the
combustion, which resulted in lower UHCs. This trend was combustion process (Mi et al. 2000), the improved com-
further substantiated in another investigation by Zheng et al. bustion quality of biodiesel reduces PAH emission. The
(2008) on a Yanmar NFD170 single-cylinder, horizontal-type average PAH value as a function of biodiesel content when
DI diesel engine. Reduction of 20–70% in engine-out UHC compared with baseline case of the mentioned study is
levels when compared with the ultra-low-sulphur diesel fuel shown in Fig. 25. Similar trend was observed by Correa
was reported when neat biodiesel from soy, canola and yellow and Arbilla (2006) in a separate investigation on the aro-
grease were used. These neat biodiesel fuels require lower matic hydrocarbon emission of 10 PAHs and eight MAHs
stoichiometric air–fuel ratio for complete combustion. The from a six-cylinder heavy-duty MWM DI diesel engine
ratios were 12.34, 12.44 and 12.54 for soy, canola and yellow under steady-state condition at 1,500 rev/min, using B2,
grease biodiesel, respectively when compared with that of the B5 and B20 blends of castor oil ethyl ester. The average
ultra-low sulphur diesel’s value of 14.57. Another study by Al- PAHs reductions for the B2, B5 and B20 blends were 2.7,
Widyan et al. (2002) on a TEQUIPMENT TD 43 test rig using 6.3 and 17.2%, respectively. MAHs reductions for the same
B25, B50, B75 and B100 blends of waste vegetable oil ethyl blends was in the order of 4.2% for B2, 8.2% for B5 and
esters showed lower UHC concentrations at the speed range of 21.1% for B20. Yang et al. (2007) reported that lower level
1,450–1,800 rev/min. The reduction in tailpipe UHCs with of PAHs was emitted in a study on 21 PAHs under engine
the use of biodiesel can also be attributed to its higher cetane durability testing on the Mitsubishi 4M40-2AT1 diesel
number, which promotes the formation of ignitable mixtures engine using a B20 biodiesel blend. Total PAH emission
more readily for better combustion. was found to decrease as mileage increased, albeit with
Although most of the reported studies showed reduction higher particulate PAH emission (refer to Fig. 26). The
of UHCs with increasing biodiesel fraction in fuel blend, results also indicated that the average PAH emission for a
research study by Ali et al. (1995) showed otherwise. The B20 biodiesel blend comprises mainly two-ring aromatics
study was conducted on a 2-stroke Detroit 6 V-92 diesel at 69.8 wt%, which implied that gas phase PAHs were
engine programmed to maintain an air–fuel ratio of 40:1. dominant here.
UHC emission was shown to increase as methyl soyate in Karavalakis et al. (2009) monitored the emissions of 11
blends exceeded the B20 level. The investigators argued PAHs and five nitro-PAHs from a Toyota Corolla 2.0 TD
that the stoichiometric air–fuel ratio became too lean to passenger vehicle equipped with a four-cylinder IDI diesel
sustain flame propagation as biodiesel fraction was raised, engine tested under two test cycles, namely the Athens
resulting in an increase in the UHC concentration. The rise Driving Cycle (ADC) and a modified hot-start version of
in UHCs could also be due to larger droplet size from higher the New European Driving Cycle (NEDC). The engine was
fuel viscosity of biodiesel, and the under-mixing of air and fuelled with low sulphur diesel and soy methyl ester at B5,
fuel. This generated locally fuel-rich regions, thus pro- B10 and B20 blends. The measurements suggested that the
moting UHC formation. Similar to CO emission, engine-out
UHC level is often reduced with the use of biodiesel due to
Table 12 Phases in which PAHs exist
its oxygenated nature which improves combustion quality.
Number of rings Phase
Aromatic hydrocarbons
2 Almost entirely in gas phase
3–4 In gas phase or adsorbed into PM
The presently unregulated PAHs are chemical compounds
5–7 Predominantly adsorbed into PM
that comprise the fused aromatic rings, and are classified as

123
486 J.-H. Ng et al.

Fig. 25 Average PAHs values

as a function of increasing
biodiesel proportion in fuel
blend (adapted from Lin et al.
2006)

emission. This was due to the relatively low positive

acceleration values, when compared with the more
aggressive ADC test with an acceleration duration of
36.21% of the entire cycle. This implies that PAH emission
would increase with more aggressive driving pattern.
Nonetheless, a majority of the PAHs were found to
decrease with increasing biodiesel content in the fuel blend
with low sulphur diesel despite the distinct variation in the
test cycles characteristics. Therefore, engine-out PAHs
values are lower with biodiesel usage regardless of the
engine operating conditions due to the negligible aromatic
content in biodiesel.

Sensitivity of engine parameters on emissions

Other governing factors that affect the relationship between

biodiesel and emissions include types of test cycles, feed-
stock types, blend fractions, engine technology and the
base diesel fuel used. US EPA evaluated the aforemen-
tioned factors utilising a statistical approach to gauge the
significance of those factors on emissions, as summarised
in Table 13 (EPA 2002). It was discovered that the test
cycles had no real impacts on biodiesel emissions, with the
Fig. 26 PAHs emission factors of waste cooking oil methyl ester B20 exception of PM and CO emissions under the R49 13-mode
blend against fossil diesel as determined by an 80,000-km engine steady-state test cycle. Hence, the possibility remains that
durability test (Yang et al. 2007) the use of a steady-state test cycle for the prediction of PM
and CO emissions may result in an overestimation of the
principal PAHs emitted from both diesel and biodiesel said species. A comparison of emission levels from dif-
were of lower molecular weights, containing only two or ferent biodiesel sources showed that NOx and CO con-
three rings such as phenanthrene, anthracene and pyrene. centrations are highly dependent on feedstock type.
PAH emission was also dependent on the driving cycle, Figure 27 highlighted the effects of different biodiesel
where the NEDC test with an acceleration time of 20.93% feedstock on CO emission, whereby biodiesel produced
of the entire test cycle, consistently showed lower PAH from animal-based feedstock showed the most promising

123
Advances in biodiesel fuel 487

Table 13 Factors influencing the relationship between biodiesel and emissions (summarised from EPA 2002)
Regulated emissions Quantity Sensitivity
Test cycle Feedstock Blend fraction Engine (model year) Base diesel fuel

NOx :a · 4 4 · 4
PM ; ?b · 4 ?c 4
CO ; ?b 4 4 · 4
UHCs ; · · 4 · 4
a
Despite the prevalence of studies reporting increase in NOx emissions with the use of biodiesel, the effects of biodiesel on NOx emissions
remained open for discussions
b
The steady-state test cycles were found to increase the emissions of PM and CO
c
Engine models from year 1991–1993 were found to decrease the PM emissions

Fig. 27 Variation in CO
emissions based on different
biodiesel feedstock for
production, and biodiesel
fraction (EPA 2002)

results. This could have been due to varying oxygen con- affected by the type of diesel fuel used for blending, blend
tent in various feedstock options that affects the oxygen levels and feedstock type used in biodiesel production. Test
availability for the promotion of complete combustion. As cycle and engine make did not play an important role in
the productions of NOx and CO are sensitive to oxygen dictating the characteristics of diesel engine emissions.
content in the fuel, the use of different feedstock for bio- Clearly, fuel properties are the most crucial elements in
diesel production will influence tailpipe emissions of both influencing engine-out emissions.
species. With improvements in engine technology, tech-
nology-specific effects on biodiesel emissions may also Tribological effects
arise. For this reason, engines were grouped by model
years according to the requirements of a single set of Engine wear
emission standards. It was found that there was no statis-
tically significant variation in biodiesel emissions as a The relative motion of metallic components in a mechan-
function of engine standards group for models from pre- ical system results in wear, where progressive loss of
1983 to 2001 apart from PM emission. This was found to substance at the surface of the components in contact
be significantly lower when engine models from 1991 to occurs. The degree of engine wear depends on the load,
1993 were studied as shown in Fig. 28. The base diesel fuel speed, soot formation, temperature, hardness, surface fin-
used in the biodiesel blends also affects all the regulated ish, presence of foreign materials, corrosion and environ-
emission species due to the differing properties of the mental conditions (Agarwal et al. 2003a). Diesel engine
various diesel fuel types. It can be concluded from here that components that are usually subjected to heavy wear are
the quantity of regulated diesel emissions are heavily piston, piston ring, cylinder liner, bearing, crankshaft,

123
488 J.-H. Ng et al.

Fig. 28 Effects of engine

grouped by model years and
biodiesel fraction on tailpipe
emissions (EPA 2002)

tappet and valves (Agarwal 2007). A wear assessment Carbon deposit

exercise for a biodiesel-fuelled CI engine under a 512-h
durability test by Agarwal et al. (2003a) using a B20 lin- The use of carbon-based fuels such as fossil diesel and
seed oil methyl ester blend reported lower wear and biodiesel in diesel engines generally leads to the forma-
improved service life of components commonly experi- tion of deposits on the cylinder head, piston top and
encing heavy wear. A quantitative analysis of wear debris injector head (Agarwal 2007). The amount of carbon
in terms of elements such as Fe, Cu, Zn, Mg, Co and Pb deposited is commonly quantified by first dismantling the
showed significant reduction in the amount of wear metal test engine, so that these deposits on the affected surfaces
when running on biodiesel at all stages of the durability test can be scrapped off before they are weighed. Agarwal
as indicated in Fig. 29. et al. (2003b) conducted a carbon deposition study on a
Lubrication oil can be diluted with a small amount of fuel single-cylinder Perry diesel engine fuelled with linseed oil
that passes through to the oil sump via blow-by losses methyl ester biodiesel under a 512-h endurance test. It can
during normal engine operation. This causes changes to the be clearly seen from Fig. 31 that more carbon by weight
viscosity of lubrication oil, leading to a higher wear rate for was deposited on the cylinder head when fossil diesel was
engine components. The relatively higher viscosity of bio- used. In fact, a qualitative examination on the carbon
diesel helps to ‘seal’ the clearance between piston rings and deposit at the injector tip showed more carbon deposition
cylinder liner, thereby reducing blow-by losses and fuel after only 200 h in the diesel-fuelled engine than that of
dilution of the lubricating oil. This prevents the change in the engine running on the B20 blend after 512 h. Carbon
the viscosity of the lubrication oil. As a result, biodiesel has deposited on the piston top for the B20 blend was found
better lubricity than fossil diesel, reducing engine wear to be 40% lower when compared with its fossil diesel
significantly. In the same study by Agarwal et al. (2003a), it counterparts. Reksowardojo et al. (2006) investigated the
was also found that the coefficient of friction was reduced as effects of biodiesel proportion on engine wear using B10
biodiesel concentration in fuel blends was raised. As shown and B100 of both palm oil and Jatropha curcas biodiesel
in Fig. 30, a decrease in the value of friction coefficient of in a DI diesel engine. The data confirmed the trends,
up to 33% relative to fossil diesel was achieved when bio- where biodiesel-fuelled engine produced lower carbon
diesel fraction was raised by up to 30%. In another study on deposition. Carbon deposition on the cylinder head
wear metal debris by Kalam and Masjuki (2002), the use of reduced as biodiesel in fuel blend increased for both the
corrosion inhibitor in B7.5 and B15 palm oil–biodiesel biodiesel tested. In fact, a relative reduction of 47% in the
blends was able to control corrosion and reduce wear. A thickness of the carbon deposit on the cylinder head was
reduction in most of the wear metal debris was reported as achieved when neat jatropha biodiesel was used. This
biodiesel fraction increased. In conclusion, the greater reduction is attributed to the improved combustion pro-
lubricity of biodiesel has the potential to reduce engine wear cess from the higher oxygen content, which resulted in
significantly in the long term, thus prolonging engine life. lower carbon deposition.

123
Advances in biodiesel fuel 489

Fig. 29 Wear concentration of

a iron, b magnesium, c copper,
d cobalt, e zinc and f lead as a
function of lubrication oil usage
(Agarwal et al. 2003a)

Conclusions

Extensive research and development work have shown that

the physico-chemical properties of biodiesel conform to the
requirements for use in diesel engines. Neat biodiesel and
its blends can be used in current configuration of diesel
engines with little to no hardware modifications, although
regular engine maintenance and servicing are recom-
Fig. 30 Coefficient of friction of biodiesel blend concentration
(Agarwal et al. 2003a) mended. However, the distinct properties specific to

Fig. 31 Carbon deposits after

512 h of engine operation on the
cylinder head of a a diesel-
fuelled and b B20 biodiesel
blend-fuelled engine (adapted
from Agarwal et al. 2003b)

123
490 J.-H. Ng et al.

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