Demirbas 2016

Original Article
Energy Exploration & Exploitation

Biodiesel production from 2016, Vol. 34(2) 290–318
! The Author(s) 2016
non-edible plant oils Reprints and permissions:

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DOI: 10.1177/0144598716630166
eea.sagepub.com
Ayhan Demirbas, Abdullah Bafail, Waqar Ahmad
and Manzoor Sheikh
Abstract
Biodiesel is an alternative to petroleum-based fuels derived from a variety of feedstocks, including
vegetable oils, animal fats, and waste cooking oil. At present, biodiesel is mainly produced from
conventionally grown edible oils such as soybean, rapeseed, sunflower, and palm. The cost of
biodiesel is the main obstacle to commercialization of the product. Biodiesel produced from
edible oils is currently not economically feasible. On the other hand, extensive use of edible
oils for biodiesel production may lead to food crisis. These problems can be solved by using low-
cost feedstocks such as non-edible oils and waste cooking oils for biodiesel production. This
paper reviews numerous options of non-edible oils as the substantial feedstocks, biodiesel pro-
cessing, and effect of different parameters on production of biodiesel.
Keywords
Non-edible oil, viscocity, FFA, biodiesel, transesterification, fuel characteristics
Introduction
Interest in the use of biofuels worldwide has grown strongly in recent years due to the limited
oil reserves, concerns about climate change from greenhouse gas emissions and the desire to
promote domestic rural economies (Balat and Balat, 2009; Ozturk, 2014). The term biofuel is
as such referred to solid, liquid, or gaseous fuels that are produced from plant matter and
residues, agricultural crops, municipal wastes, and agricultural and forestry by-products
(Aburas and Demirbas, 2015a; Qin et al., 2009, 2010; Altun and Yasar, 2013). Liquid bio-
fuels can be used as an alternative to traditional fossil fuels in the transportation sector
(Aburas, 2015).
Department of Industrial Engineering, King Abdulaziz University, Jeddah, Saudi Arabia

Corresponding author:
Ayhan Demirbas, Department of Industrial Engineering, King Abdulaziz University, P.O. Box 80204,
Jeddah 21589, Saudi Arabia.
Email: ayhan.demirbas@hotmail.com
Demirbas et al. 291
Globally, the transportation sector is a major source of energy consumption and carbon
dioxide (CO2) emissions. This sector is responsible for 18% of primary energy consumption
(Wang et al., 2014) and 23% of all energy-related CO2 emissions globally (Du Ploy and Nel,
2012). The world energy demand continues to increase. This growth will affect the stability
of ecosystems and global climate as well as global oil reserves. The most feasible way to meet
this growing demand is by utilizing alternative fuels (Demirbas et al., 2015a, 2015b).
Production of biofuel from biomass is one way to reduce both the consumption of crude
oil and environmental pollution (Ayanoglu and Aksoy, 2015).
Global production of biofuels has been growing rapidly in recent years, rising from about
18 billion liters in 2000 (Kemausuor et al., 2013) to 110 billion liters in 2013 (IEA, 2014). It is
expected to reach to 140 billion liters by 2018 (IEA, 2014). Current consumption of biofuels
globally constitutes about 3.5% of transportation fuels by energy content, and this could
expand to about 4% by 2018 (IEA, 2014).
Majority of liquid biofuels is produced in the form of bioethanol (around 80%) and the
rest constitutes biodiesel (Figiel and Hamulczuk, 2014). The global biodiesel industry is one
of the fastest-growing markets. Since 2004, global biodiesel production increased 15-fold,
while bioethanol production grew nearly fourfold (REN21, 2014). This paper reviews dif-
ferent processing techniques for biodiesel production from common non-edible vegetable
oils and determines the most suitable one.
Raw materials for biodiesel production

Biodiesel production is a very modern and technological area for researchers due to the
relevance that it is winning every day because of the increase in the petroleum price and the
environmental advantages (Aburas and Demirbas, 2015b; Marchetti et al., 2007). Biodiesel
can be derived from a variety of sources including vegetable oils, animal fats, and waste
cooking oil.
Vegetable oils, also known as triglycerides, are chemically triglycerides molecules in which
three fatty acids groups are esters attached to one glycerol molecule. Vegetable oils from
renewable oil seeds can be used when mixed with diesel fuels (Demirbas, 2008a). The advan-
tages of vegetable oils as diesel fuel are their portability, ready availability, renewability,
higher heat content (about 88% of no. 2 Diesel fuel), lower sulfur content, lower aromatic
content, and biodegradability (Demirbas et al., 2015b). The main disadvantages of vegetable
oils as diesel fuel are higher viscosity, higher cost, lower volatility, and the reactivity of
unsaturated hydrocarbon chains (Demirbas, 2009a,b). The vegetable oils were all extremely
viscous, with viscosities ranging 10–20 times greater than no. 2 Diesel fuel (Aburas et al.,
2015; Demirbas, 2003). Fuel-related properties of various vegetable oils are shown in
Table 1. Blending of vegetable oils with diesel, however, reduces the viscosity drastically
and the fuel handling system of the engine can handle vegetable oil–diesel blends without any
problems (Agarwal et al., 2008; Rao et al., 2008). The conversion of vegetable oils into fatty
acid methyl esters (FAME) is an effective way to overcome all the problems associated with
the vegetable oils.
Most of the biodiesel is currently made from soybean, rapeseed, sunflower, and palm oils
(Demirbas, 2015b). New plant oils that are under consideration include mustard seed,
peanut, sunflower, and cotton seed. Soybean oil is commonly used in the United States
and rapeseed oil is used in many European countries for biodiesel production, whereas,
coconut oil and palm oils are used in Malaysia and Indonesia for biodiesel production
292 Energy Exploration & Exploitation 34(2)
Table 1. Fuel-related properties of selected vegetable oils.
Viscositye
a b c d
OilA Iodine value CN CP (K) PP (K) FP (K) (mm2/s) References
A. indica 82–98 – 286.0 280.0 – 35.83 Aransiola et al. (2014)

J. curcas 101 23 283.0f 267.0 459 35.4 Singh and Padhi (2009)
M. indica 65 – 287.0 288.0 499 25.0 Padhi and Singh (2010)
P. pinnata 87 42 276.5 279.0 498 40.2 Bobade and Khyade (2012)
R. communis 84.4 42.0 274.0 259.0 >533 240.1 Deligiannis et al. (2009)
Rapeseed 94–120 37.6 269.1 241.3 519 37.0 Knothe et al. (1997)
Soybean 117–143 37.9 269.1 260.8 527 32.6 Knothe et al. (1997)
Sunflower 110–143 37.1 280.2 258.0 547 37.1 Knothe et al. (1997)
a
CN: cetane number; bCP: cloud point; cPP: pour point; dFP: flash point; emeasured at 313 K; fcloud point combined from
Rashid et al. (2010).
(Ghadge and Raheman, 2005; Srivastava and Verma, 2008). About 80% of the European
Union’s total biofuel production is comprised of biodiesel produced from rapeseed and
sunflower seeds (Ahmad et al., 2010). Soybean oil accounts for approximately 90% of the
biodiesel produced in the United States (Balat and Balat, 2010). Rapeseed oil has 59% of
total global biodiesel raw material sources, followed by soybean (25%), palm oil (10%),
sunflower oil (5%), and other (1%) (Pahl, 2008).
Food versus fuel

The major obstacle for commercialization of biodiesel is its cost approximately 70%–90% of
biodiesel cost is arises from the cost of raw materials (Shikha and Rita, 2012). Therefore,
biodiesel produced from edible vegetable oils is currently not economically feasible. Non-
edible oil plants are easily available in developing countries and are very economical com-
parable to edible plant oils. The production of biodiesel from different non-edible oilseed
crops has been extensively investigated over the last few years.
Extensive use of edible oils may cause other significant problems such as starvation in
developing countries. Using edible oils to produce biodiesel raises major nutritional and
ethical concerns. About 13% of global vegetable oil supplies were used for biodiesel pro-
duction in 2012. World annual petroleum consumption and vegetable oil production is
about 4.018 and 0.107 billion tons, respectively (Demirbas, 2010). Biodiesel production
accounted for 25.6% of the global demand for rapeseed oil, 16.1% of the global soybean
oil demand, and 5.9% of global palm oil demand in 2012.
On the other hand, extensive use of edible vegetable oils may cause other significant
problems such as starvation in developing countries. There are concerns that biodiesel feed-
stock may compete with food supply in the long term (Chhetri et al., 2008). Biodiesel
produced from non-edible vegetable oil has good potential as an alternative diesel fuel.
The use of non-edible plant oils when compared with edible plant oils is very significant
because of the tremendous demand for edible oils as food, and they are far too expensive to
be used as fuel at present (Mahanta et al., 2006). Non-edible oil plants can be grown in waste
lands that are not suitable for food crops and the cost of cultivation is much lower because
Demirbas et al. 293
Table 2. Comparison of fatty acid composition between various edible and non-edible vegetable oils.
Palmitic Palmitoleic Stearic Oleic Linoleic Linolenic

Oil (C16:0) (C16:1) (C18:0) (C18:1) (C18:2) (C18:3) References
A. indica 12.01 – 12.95 34.09 38.26 0.3 Muthu et al. (2010)

J. Curcas 14.2 0.7 7.0 44.7 32.8 0.2 Edem (2002)
M. indica 24.5 – 22.7 37.0 14.3 – Bhatt et al. (2004)
tabacum 7.9 – 3.1 17.1 70.6 – Zdremnan and Zdremnan (2006)
P. pinnata 10.2 – 7.0 51.8 17.7 3.6 Akoh et al. (2007)
communisa 1.3 – 1.2 5.5 0.5 7.3 Salimon et al. (2010)
Rapeseed 3.5 0 0.9 64.1 22.3 8.2 Demirbas (2003)
Soybean 13.9 0.3 2.1 23.2 56.2 4.3 Demirbas (2003)
Sunflower 6.4 0.1 2.9 17.7 72.9 0 Demirbas (2003)
a
R. communis oil contains 89.6% ricinoloic acid.
these plants can still sustain reasonably high yield without intensive care (Fatah et al., 2012).
Non-edible oil plants are well adapted to arid, semi-arid conditions and require low fertility
and moisture demand to grow (Atabani et al., 2013).
Non-edible vegetable oils as raw material

In order to overcome the above-mentioned problems, researches have been made to produce
biodiesel by using alternative resources like non-edible vegetable oils. Oils from non-edible
resources are unsuitable for human consumption because of the presence of some toxic
components (Bankovic-Ilic et al., 2012). Non-edible vegetable oils are therefore expected
to help the biodiesel to be competitive in price as compared to the use of food-grade vege-
table oils. The advantages of non-edible vegetable oils as a diesel fuel are their liquid nature
portability, ready availability, renewability, higher combustion efficiency, lower sulfur, and
aromatic content and higher biodegradability (Shikha and Rita, 2012). However, as a serious
drawback, most non-edible oils contain a high content of free fatty acids (FFAs), which
increases the biodiesel production cost (Bankovic-Ilic et al., 2012). The type and quantifica-
tion of fatty acids contained in vegetable oil depends on the plant species and on the growth
conditions of the plant (Thangaraj et al., 2014). Table 2 shows comparison of fatty acid
composition between various edible and non-edible vegetable oils.
There are many examples for non-edible oilseed crops such as jatropha tree (Jatropha
curcas), karanja (Pongamia pinnata), mahua (Madhuca indica), castor bean seed (Ricinus
communis), neem (Azadirachta indica), rubber seed tree (Hevea brasiliensis), tobacco seed
(Nicotiana tabacum), rice bran, etc. The production of biodiesel from different non-edible
oilseed crops has been extensively investigated over the last few years (Ghadge and
Raheman, 2005; Gimbun et al., 2013; Heroor and Bharadwaj, 2013; Ong et al., 2011;
Padhi and Singh, 2010; Thangaraj et al., 2014). Table 3 shows the oil contents of some
non-edible plants as suitable feedstock for biodiesel production.
Jatropha curcas
Jatropha curcas is a tall bush or small tree, up to 5–7 m tall, belonging to the Euphorbiaceae
family (Atabani et al., 2013). Originally from Central America, Jatropha curcas is found
Table 3. The oil content in seeds and kernels of some non-edible plants.
Oil content
Botanical name Plant type wt% Seed Kernel References
Azadirachta indica (neem) Tree 25–45 30–50 Anya et al. (2012); Djenontin et al. (2012)
Calophyllum inophyllum (polanga) Tree 60–75 50–70 Azam et al. (2005); Chavan et al. (2013)
Hevea brasiliensis (rubber) Tree 40–50 35–45 Fadeyibi and Osunde (2012);
Kant et al. (2011)
Jatropha curcas Tree 36 56 Karaj and Müller (2010)
Madhuca indica (mahua) Tree 30–45 20–50 Jha et al. (2013); Puhan et al. (2005)
Melia azedarach (syringa) Tree/shrub 10–45 – Atabani et al. (2013)
Moringa oleifera (drumstick) Tree 30–40 – Mohammed et al. (2003)
Nicotiana tabacum (tobacco) Herb 33–40 17 Bankovic-Ilic et al. (2012);
Khan et al. (2014)
Pongamia pinnata (karanja) Tree 27–39 30–40 Rahman et al. (2011);
Armah et al. (2011)
Ricinus communis (castor) Tree/shrub 48–60 –
Sapindus mukorossi (soapnut) Tree 51 – Chigozie et al. (2014)
Simmondsia chinensis (jojoba) Shrub 45–55 – Borugadda and Goud (2012)
throughout the tropics including much of Africa and Asia (Nahar and Sunny, 2014). It has
been planted in several arid regions, in these regions it only yields about 0.5 ton per hectare
(Balat and Balat, 2010). The plant is important for climate change issues as a mature plant or
tree absorbs CO2 at a rate of 18 lbs per year (Nahar and Sunny, 2014). A research study
(Becker et al., 2013) showed that one hectare of Jatropha curcas could capture up to 25 tons
of CO2 from the atmosphere every year (over a 20-year period). Jatropha curcas oil is a
leading candidate for the commercialization of non-edible vegetable oils (No, 2011).
Jatropha curcas seeds have an oil content ranging between 30% and 40% (Pandey et al.,
2012). Jatropha curcas oil contains approximately 24.60% of crude protein, 47.25% of crude
fat, and 5.54% of moisture content (Akintayo, 2004). Most of the non-edible oils including
Jatropha curcas carry a high level of FFAs. The oil fraction of Jatropha curcas consists of
both saturated (14.2% palmitic acid and 7.0% stearic acid) and unsaturated fatty acids
(44.7% oleic acid and 32.8% linoleic acid) (Table 2).
Pongamia pinnata (Karanja)

Pongamia pinnata, commonly known as karanja, is a medium-sized glabrous, perennial tree
grows in the littoral regions of South Eastern Asia and Australia (Satyavati et al., 1987). It is
a hardy tree of 12–15 m height, branches spread into hemispherical crown of dense green
leaves (Naik and Katpatal, 2013). The yield of oilseed per tree is between 8 and 24 kg (Doshi
and Srivastava, 2013). The seeds of Pongamia pinnata contain around 30%–40% of oil
(Scott et al., 2008). Pongamia pinnata oil is considered to be less toxic and cheaper than
Jatropha curcas oil, so it has become the subject of biodiesel research (Khayoon et al., 2012).
Most of the physical and chemical properties of the Pongamia pinnata oil are similar to those
of the diesel fuel, however this oil is more viscous and produce higher carbon residue
Demirbas et al. 295
(Meenakshi, 2014). Pongamia pinnata oil contains oleic acid (51.8%) as the major fatty acid
followed by linoleic (10.7%), palmitic (10.7%), and stearic (7%) acids (Table 2).
Madhuca indica (Mahua)

Madhuca indica, commonly known as mahua or butternut tree, is a middle-sized large
deciduous tree, which grows to a height of 10–15 m (Chidrewar et al., 2010). It belongs to
the family Sapotaceae. The Madhuca indica tree starts producing seeds after 10 years and
continues for up to 60 years (Pandey, 2008). An average yield of 800 kg/ha can be expected in
a Mahua plantation after a decade (Kant et al., 2011). Each tree yields about 20–40 kg of
seed per year (Borugadda and Goud, 2012). Madhuca indica seed contains 35% oil and 16%
protein (Panigrahi et al., 2014). Fresh Madhuca indica oil from properly stored seeds is
yellow, while commercial oils are generally greenish yellow with an offensive odor and
disagreeable taste (Puhan et al., 2005). The Madhuca indica oil contains a high level of
FFAs (up to 20%) (Ghadge and Raheman, 2005) and a procedure for converting this oil
to biodiesel is very much required. FFA composition of Madhuca indica oil is shown in
Table 2.
Ricinus communis (Castor)

Ricinus communis, commonly known as castor oil plant, is a plant species of the
family Euphorbiaceae. It originates in Africa but it is found in both wild and cultivated
states in all the tropical and subtropical countries of the world (Forero, 2004). Ricinus
communis is a small wooden tree that can reach a height of about 6 m. The comparative
advantage of Ricinus communis is that its growing period is much shorter than that of
Jatropha curcas and Pongamia pinnata, and there is considerably greater experience and
awareness among farmers about its cultivation (Rajagopal, 2007). Ricinus communis is an
ideal candidate for production of high value, industrial oil feedstocks because of the very
high oil content (48%–60%) of the seed, and the extremely high levels of potential oil
production (500–1000 l of oil/acre). The main constituent of Ricinus communis oil is ricino-
leic acid (90%), which contains 18 carbon atoms with a hydroxyl group position 12.
Therefore, Ricinus communis oil contains more oxygen than other oils and, therefore,
Ricinus communis oil and its derivatives are more soluble in alcohols during the transester-
ification reactions. The main disadvantage of Ricinus communis oil is its high viscosity
(240.12 mm2/s at 313 K) (Deligiannis et al., 2009). The high viscosity of Ricinus communis
oil to its poor atomization of the fuel, incomplete combustion, choking of the fuel injectors,
and ring carbonization (Baroutian et al., 2010).
Azadirachta indica (Neem)

Azadirachta indica (commonly known as ‘‘neem tree’’), a member of the family Meliaceae, is
a majestic, evergreen, tropical forest tree, with a broad crown and a height of approximately
25 m. Most parts of the Azadirachta indica plant such as leaves, bark, flower, fruit, seed, and
root have applications in the field of medicine. Azadirachta indica is well established plant in
at least 30 countries worldwide, in Asia, Africa, and Central and South America. Some small
scale plantations are also reportedly successful in Europe and United States of America
(Kumar and Navaratnam, 2013). Azadirachta indica tree normally begins to bear fruit
between 3 and 5 years and becomes fully productive in 10 years. From the 10th year
onwards, it can produce up to 50 kg of fruits annually (Girish and Shankara, 2008). It

requires little water and plenty of sunlight and rainfall in the range of 450 to 1200 mm
with wide temperature range of 273 to 322 K (Heroor and Bharadwaj, 2013). Azadirachta
indica seeds contain about 45% of a brownish-yellow of fixed oil (Radha and Manikandan,
2011), mainly constituted by oleic acid (34.01%), palmitic acid (12.1%), stearic acid
(12.95%), linoleic acid (38.26%) (Muthu et al., 2010). Traditionally, Azadirachta indica oil
has been used as fuel in lamps for lighting purpose in rural areas and it is used on an
industrial scale for manufacturing of soaps, cosmetics, pharmaceuticals, and other non-
edible products (Gahadwal and Yadav, 2014).
Hevea brasiliensis (Rubber)

Hevea brasiliensis, commonly known as rubber tree, is a fast growing tree that belongs to the
family Euphorbiaceae. It is the major source of natural rubber and is native to the Amazon
forests and is now widely cultivated in tropics across the world (Kant et al., 2011). Growing
up to 34 m in height, the tree requires heavy rainfall and produces seeds weighing from 2 to
4 g that do not currently have any major industrial applications (Moser, 2011). Normal seed
production yields vary from 70 to 500 kg per hectare per year while the annual Hevea
brasiliensis seed production potential in India is about 150 kg per hectare (Reksowardojo
et al., 2011). The yields of various non-edible oil feedstocks are given in Table 4. Hevea
brasiliensis seed contain approximately about 40% of kernel with 20%–25% of moisture
(Gimbun et al., 2013). Apart from its use in latex production for foreign exchange, Hevea
brasiliensis tree produces oil-bearing seed whose oil content in dried kernel varies from 35%
to 45% (Fadeyibi and Osunde, 2012). Hevea brasiliensis oil does not contain any unusual
fatty acids, and its rich source of essential fatty acids C18:2 and C18:3 that make up 52% of
its total FFA composition (Salimon and Abdullah, 2009).
Nicotiana tabacum (Tobacca)

Nicotiana tabacum, commonly referred to tobacco, is an annually grown herbaceous plant
belonging to the Solanaceae family, widespread in North and South America, commonly
Table 4. The yields of various non-edible oil feedstocks.
Energy crop Kg per hectare References
Azadirachta indica (neem) 2670 Azam et al. (2005)

Calophyllum inophyllum (polanga) 4680 Atabani et al. (2013)
Cynara cardunculus (cardoon) 500–750 Razon (2009)
Hevea brasiliensis (rubber) 150 Reksowardojo et al. (2011)
Jatropha curcas 2500 Katwal and Soni (2003)
Moringa oleifera (drumstick) 3000 Mohammed et al. (2003)
Nicotiana tabacum (tobacco) 1171 Zdremnan and Zdremnan (2006)
Pongamia pinnata (karanja) 900–9000 Karmee and Chadha (2005)
Ricinus communis (castor) 450 Razon (2009)
Simmondsia chinensis (jojoba) 1125–2250 Razon (2009)
Vernicia fordii (tung) 450–600 Zhuang et al. (2011)
Demirbas et al. 297
grown for the collection of leaves. The highest seed production is found in the Nicotiana
tabacum varieties used to obtain the chewing Nicotiana tabacum, reaching 1171 kg seeds per
hectare, which corresponds to 432.9 kg oil per hectare (Zdremnan and Zdremnan, 2006). The
seed oil content ranges between 33 and 40 wt% (Khan et al., 2014). The major fatty acids in
seed triacylglycerols are linoleic acid (70.6%), oleic acid (17.1%), palmitic acid (7.9%), and
stearic acid (3.1%) (Table 2).
Rice bran
Rice is the main cultivation in subtropical Southern Asia, and it is a staple food for a large
part of the world’s human population especially in East, South, and South Eastern Asia,
making it the most consumed cereal grain (Subbaiah et al., 2010). Rice bran is a low value
co-product of rice milling, which contains approximately 15%–23% oil (Sinha et al., 2008).
The oil fraction of rice bran consists of both saturated (15.0% palmitic acid and 1.9% stearic
acid) and unsaturated fatty acids (42.5% oleic acid and 39.1% linoleic acid) (Mohanty,
2013). Rice bran oil is an underutilized non-edible vegetable oil, which is available in
large quantities in rice cultivating countries like China and India, and very little research
has been done to utilize this oil as a replacement for mineral diesel (Sinha et al., 2008).
Moringa oleifera (Drumstick tree)

Moringa oleifera, also called drumstick tree, is a softwood perennial tree. This plant belongs
to the monogeneric family Moringaceae and is an extremely fast growing tree that can get to
10 m. Moringa oleifera is most commonly cultivated in South India, Ethiopia, Philippines,
Sudan, and has been grown in West, East and South Africa, tropical Asia, Latin America,
the Caribbean, Florida, and the Pacific Islands (Fahey, 2005). The fast growing, drought-
tolerant Moringa oleifera can tolerate poor soil, a wide rainfall range (25 to 300 + cm per
year), and soil pH from 5.0 to 9.0 (Rashid et al., 2008). It has been reported that some
3000 kg of Moringa oleifera seeds could be obtained from one hectare, equivalent to 900 kg
oil per hectare, comparable to soybean which also yields an average of 3000 kg seeds per
hectare but with only 20% oil yield (Mohammed et al., 2003; Orhevba et al., 2013). Moringa
oleifera seed has an oil content of between 30% and 40%, depending on the plant variety and
climate (Mohammed et al., 2003). Moringa oleifera oil contains oleic acid (67.7%) as the
major fatty acid followed by stearic (8.3%), behenic (7.4%), arachidic (4.7%), palmitic
(6.9%), linoleic (10.7%), and eicosenoic (2.3%) acids (Sunga and Whitby, 1995).
Calophyllum inophyllum (Polanga)

Calophyllum inophyllum, commonly known as polanga or honne, is a large evergreen,
belongs to the Clusiaceae family, widespread in East Africa, India, South East Asia, and
Australia (Silitonga et al., 2013). Calophyllum inophyllum is a medium and large-sized ever-
green sub-maritime tree that averages 8–20 m in height with a broad spreading crown of
irregular branches (Ong et al., 2011). Each tree yields about 20–100 kg of whole fruits per
year (Venkanna and Reddy, 2009). Trees begin to bear significantly after 4–5 years (Chavan
et al., 2013). The nut kernel contains 50%–70% oil and the mature tree may produce 1–10 kg
of oil per year depending upon the productivity of the tree and the efficiency of extraction
process (Chavan et al., 2013). Traditionally, Calophyllum inophyllum oil has been used as a
medicine, soap, lamp oil, hair grease, and cosmetic in different parts of the world (Ong et al.,
2011).
Simmondsia chinensis (Jojoba)

Simmondsia chinensis, commonly known as jojoba, is a perennial shrub belonging to the
Simmondsiaceae family (Moser, 2011). This plant is native to the Mojave and Sonoran
deserts of Mexico, California, and Arizona. A 10-year old tree yields on an average 1 kg
of seeds per year (Kant et al., 2011). Simmondsia chinensis is unique among plants in the fact
that its seeds contain about 50% of oil by weight, which is more than amount in soybean and
somewhat more than in most oil seed crops (Sharma and Singh, 2011). Simmondsia chinensis
oil is practically colorless and odorless and it is composed mainly of straight chain monoe-
sters of C20 and C22 acids and alcohols with two double bonds (Zaher et al., 2004).
Sapindus mukorossi (Soap nut)

Sapindus mukorossi (soap nut) is a perennial tree belonging to the family Sapindaceae,
indigenous to northern India (Philomina and Rao, 2000). This plant grows very well in
deep loamy soils and leached soils so cultivation of Sapindus mukorossi in such soil avoids
potential soil erosion (Chhetri et al., 2008). Sapindus mukorossi tree can be used for rural
building construction, oil and sugar presses, and agricultural implements (Chhetri et al.,
2008). Sapindus mukorossi seeds contain 23% oil of which 92% is triglycerides (Atabani
et al., 2013).
Melia azedarach (Syringa)

Melia azedarach (syringa) is a deciduous tree that grows between 7 and 12 m in height in the
mahogany family of Meliaceae that is native to Pakistan, India, Bangladesh, Southeast Asia,
and Australia (Moser, 2011; Sarin, 2012). The oil content of dried syringe berries is around
10 wt% (Atabani et al., 2013). Melia azedarach oil is characterized by a high percentage of
unsaturated fatty acids such as oleic (21.8%) and linoleic (64.1%) acids (Moser, 2011). Other
constituents that are present in greater than 1% are saturated species such as palmitic
(10.1%) and stearic (3.5%) acids (Moser, 2011).
Vernicia fordii (Tung)

Vernicia fordii, commonly known as tung tree, is an oil-bearing woody plant belonging to the
Euphorbecaeae family that is native to China, Burma, and Vietnam. It is a small- to
medium-sized deciduous tree, which grows up to 20 m in height. The oil content of
Vernicia fordii seeds and whole nuts is approximately 21 and 41 wt%, respectively (Yu
et al., 2013), and the average yield of oil is about 450–600 kg per hectare (Zhuang et al.,
2011). Its seed oil had been conventionally used in lamps for lighting, as well as an ingredient
for wood paint and varnish (Wang et al., 2011). Tung oil principally contains the unusual
conjugated fatty acid, eleostearic acid (9,11,13-octadecatrienoic acid; 63.8%), with linoleic
(11.5%), oleic (8.6%), and behenic (8.4%) acids also present in significant quantities
(Moser, 2011).
Demirbas et al. 299
Schleichera oleosa (Kusum)

Schleichera oleosa, also called as kusum, is medium-sized (up to 40 m in height) deciduous or
nearly evergreen tree belonging to the Sapindaceae family that is native to South and South
East Asia. The fruits, seeds, and young leaves of this plant are edible and used for medicinal
and dye purposes (Kant et al., 2011). The oil content of kusum seeds is 51%–62% but the
yields are 25%–27% in village ghanis (oil mills) and about 36% oil in expellers (Acharya
et al., 2011). Iodine value of the oil is 215–220 and its total fatty acid content is 91.6%
(Acharya et al., 2011).
Derivatives of non-edible oils as diesel fuels

Non-edible vegetable oils can be used as fuels for diesel engines. The primary problems
associated with using straight these oils as alternative fuel in compression ignition (CI)
engines are caused by very high fuel viscosity and low volatility (Basavaraja et al., 2005).
The high viscosity of non-edible vegetable oils can be reduced by several techniques which
include dilution, microemulsion, pyrolysis, and transesterification.
Dilution of non-edible vegetable oils

The oil–diesel fuel blend is a simple way to reduce the viscosity of non-edible vegetable oil.
This method does not require any chemical process. A number of researchers have examined
the use of blends of conventional diesel fuel with non-edible vegetable oils, such as Jatropha
curcas oil (Pramanik, 2003), Pongamia pinnata oil (Agarwal and Rajamanoharan, 2009),
Azadirachta indica oil (Prasad and Agarwal, 2012), etc.
Pramanik (2003) studied the effect of temperature on viscosities of Jatropha curcas oil and
its various blends at a temperature range from 298 to 348 K. Results of this study showed
that viscosity values of 50:50 Jatropha curcas oil/diesel fuel and 40:60 Jatropha curcas oil/
diesel fuel are close to diesel in the range of 328–333 K and at about 318 K, respectively,
whereas the blend containing 30:70 Jatropha curcas oil/diesel fuel has viscosity close to diesel
at the range of 308–313 K. In another study, Agarwal and Rajamanoharan (2009) investi-
gated the performance and emission characteristics of a CI engine fueled with karanja
(Pongamia pinnata) oil and diesel fuel blends and the effect of preheated oil on engine
performances. They reported that karanja oil blends with diesel (up to 50% v/v) without
preheating as well as with preheating could be replaced diesel for operating the CI engine
with lower emissions and improved performance.
Using microemulsions for non-edible vegetable oils

Microemulsions are transparent, thermodynamically stable colloidal dispersions in which
the diameter of the dispersed phase particles is less than one-fourth the wavelength of visible
light (Goering et al., 1983). To reduce of the high viscosity of vegetable oils, microemulsions
with immiscible liquids such as methanol and ethanol and ionic or non-ionic amphiphiles
have been studied (Billaud et al., 1995).
Liquid fuel and biodiesel from non-edible vegetable oils via pyrolysis
Conversion of vegetable oils using pyrolysis type reactions represents a promising option
for the production of biodiesel fuel. Pyrolysis is the conversion of one substance into
another by means of heat or by heat with the aid of a catalyst (Sonntag, 1979). Thermal
decomposition of triglycerides produces the compounds of classes including alkanes,
alkenes, alkadienes, aromatics, and carboxylic acids. Different types of vegetable oils
produce large differences in the composition of the thermally decomposed oil (Srivastava
and Prasad, 2000).
In recent years, many investigators have studied the pyrolysis of non-edible vegetable
oils and their cakes such as Jatropha curcas (Manurung et al., 2009), Madhuca indica
(Kalaiselvan et al., 2014), tung (Lima et al., 2004), and castor oil (Figueiredo et al., 2009)
to obtain the suitable alternative fuel for CI engine. For instance, Figueiredo et al. (2009)
described the production of pyrolysis oil from castor seeds via a low temperature con-
version process and showed that the use of this oil in a pyrolysis oil–diesel blend is a good
option.
Biodiesel via transesterification from non-edible vegetable oils

Transesterification is the chemical reaction between a triglyceride and an alcohol (mostly
methanol or ethanol) in the presence of a catalyst and consists of a sequence three consecu-
tive reversible reactions where triglycerides are converted to diglycerides and then diglycer-
ides are converted to monoglycerides followed by the conversion of monoglycerides to
glycerol. In each step, an ester is produced and thus three ester molecules are produced
from one molecule of triglycerides (Sharma and Singh, 2008). Ethanol is a preferred alcohol
in the transesterification process compared to methanol because it is derived from agricul-
tural products and is renewable and biologically less objectionable in the environment
(Demirbas, 2003). However, methanol is preferable because of its low cost and its physical
and chemical advantages (polar and shortest chain alcohol). Triacylglycerols are esters of
long-chain carboxylic acids combined with glycerol. Carboxylic acids {R– C( ¼ O)–O–H}
can be converted into methyl esters {R–C( ¼ O)–O– CH3} by the action of a transesterifica-
tion agent (Demirbas, 2009a). Figure 1 shows the transesterification reaction of triglycerides
with alcohol.
Transesterification of vegetable oils can be carried out by two ways: (a) catalytic transes-
terification and (b) non-catalytic transesterification methods.
Catalytic transesterification methods. Vegetable oils can be transesterified by heating them with a
large excess of anhydrous methanol and a catalyst. Transesterification reactions can be
catalyzed by alkalis, acids, or enzymes.
Biodiesel produced by transesterification reaction can be catalyzed by methanolic sulfuric
acid (Ghadge and Raheman, 2005; Ramadhas et al., 2004; Tiwari et al., 2007), ferric sulfate
(Wang et al., 2007), sulfonic acid (Veljkovic et al., 2006), methanolic hydrogen chloride
(Darnoko and Cheryan, 2000), and methanolic boron trifluoride (Rule, 1997). These cata-
lysts give very high yields in alkyl esters, but the reactions are slow. Table 5 shows com-
parison of various methanolic transesterification methods. Acid-catalyzed reactions require
Catalyst
Triglyceride + Alcohol Ester + Glycerol
Figure 1. Transesterification of triglycerides with alcohol.
Demirbas et al. 301
Table 5. Comparison of various methanolic transesterification methods.
Method Reaction temperature (K) Reaction time (min)
Acid or alkali catalytic process 303–338 60–360

Boron trifluoride–methanol 360–390 20–50
Sodium methoxide–catalyzed 293–298 4–6
Non-catalytic supercritical methanol 523–573 6–12
Catalytic supercritical methanol 523–573 0.5–1.5
the use of high alcohol-to-oil molar ratios in order to obtain good product yields in practical
reaction times. However, ester yields do not proportionally increase with molar ratio (Lotero
et al., 2006). On the other hand, an excessive amount of alcohol makes the recovery of the
glycerol difficult, so that the ideal alcohol/oil ratio has to be established empirically, con-
sidering each individual process.
Transesterification can be catalyzed by alkaline catalysts, preferably by sodium or potas-
sium methoxide (Muthu et al., 2010; Padhi and Singh, 2010; Prabaningrum, 2011;
Thangaraj et al., 2014). Sodium methoxide (CH3ONa) is the most widely used biodiesel
catalyst with over 60% of industrial plants using this catalyst (Huber et al., 2006).
Alkaline catalysts have the advantages, e.g. short reaction time and relatively low tempera-
ture can be used with only a small amount for catalyst and with little or no darkening of
color of the oil (Singh and Padhi, 2009). Alkaline metal alkoxides (as CH3ONa for the
methanolysis) are the most active catalysts, since they give very high yields (>98%) in
short reaction times (30 min) even if they are applied at low molar concentrations
(0.5 mol%). However, they require the absence of water, which makes them inappropriate
for typical industrial processes (Schuchardt et al., 1998). In the alkali catalytic methanol
transesterification method, the catalyst is dissolved into methanol by vigorous stirring in a
small reactor. The oil is transferred into a biodiesel reactor and then the catalyst/alcohol
mixture is pumped into the oil. The final mixture is stirred vigorously for 2 h at 340 K in
ambient pressure. A successful transesterification reaction produces two liquid phases: ester
and crude glycerol. However, due to the high FFA content of non-edible oils, these oils
cannot be transesterified in the presence of an alkaline base catalyst for it leads to catalyst
deactivation and soap formation (Fadhil et al., 2012). For high FFA oils, two step acid-base
catalyzed transesterification process is preferred. FFA content of oil could be reduced to less
than 1% using an acid catalyst at the first stage. The second step is base catalyzed transes-
terification in which oil reacts with methanol in the presence of an alkaline catalyst to form
ester and glycerol (Fadhil et al., 2012).
The transesterification process is catalyzed by lipases such as Candida antarctica, Candida
rugasa, Pseudomonas cepacia, immobilized lipase (Lipozyme RMIM), Pseudomonas sp., and
Rhizomucor miehei (Kumari et al., 2007; Wang et al., 2011; Zarei et al., 2014). In recent work
(Shah et al., 2004), three different lipases (Chromobacterium viscosum, Candida rugosa, and
Porcine pancreas) were screened for a transesterification reaction of jatropha oil in a solvent-
free system to produce biodiesel; only lipase from Chromobacterium viscosum was found to
give appreciable yield. In particular, it should be noted that the byproduct, glycerol, can be
easily recovered with simple separation processes. Nevertheless, enzymatic catalysts are often
Table 6. Summary of catalytic transesterification of some selected non-edible oils.
Non-edible Catalyst Temperature Reaction Yield

Catalyst oil (wt%) (K) time (h) (%) References
KOH Castor 1.5 333 10 min 80.1 Hincapié et al. (2014)

KOH Karanja 1 338 3 97 Meher et al. (2004)
NaOH Jatropha 1 338 1 97.6 El Diwani et al. (2009)
Pretreatment Jatropha KOH 0.55% 333 1 93 Bojan and Durairaj (2012)
acid-catalyzed
(H2SO4, NaOH)
Pseudomonas cepacia Jatropha 5-April 323 8 98 Shao et al. (2008)
CH3ONa Mahua 8 338 1 95 Padhi and Singh (2010)
Pretreatment Neem NaOH1% 333 1 85 Thangaraj et al. (2014)
acid-catalyzed
(H2SO4, NaOH)
HCl Rice bran 10 343 6 >90 Rachmaniah et al. (2004)
NaOCH3 Rice bran 0.88 328 1 83.3 Rashid et al. (2009)
KOH Rubber 3.5 333 2 74.5 Abdulkadir et al. (2014)
Novozyme 435 lipase Tung 10 328 24 48 Wang et al. (2011)
immobilized
more expensive than chemical catalysts, so recycling and reusing them is often a must for
commercial viability. The reaction yields as well as the reaction times are still unfavorable
compared to the base-catalyzed reaction systems (Schuchardt et al., 1998). Due to their
ready availability and the ease with which they can be handled, hydrolytic enzymes have
been widely applied in organic synthesis. Reaction conditions reported in the literature using
different catalyst are summarized in Table 6.
Non-catalytic transesterification methods

There are two basic routes to produce biodiesel by non-catalyzed transesterification. These
are BIOX co-solvent process and supercritical alcohol process. BIOX co-solvent process uses
either tetrahydrofuran (THF) or methyl tert-butyl ether as a co-solvent to generate a one-
phase system. The result is a fast reaction, on the order of 5–0 min, and no catalyst residues
in either the ester or the glycerol phase (Demirbas, 2009a). The THF co-solvent is chosen, in
part, because it has a boiling point very close to that of methanol. This system requires a
rather low operating temperature, 303 K (Helwani et al., 2009).
In the conventional transesterification of fats and vegetable oils for biodiesel produc-
tion, FFAs and water always produce negative effects, since the presence of FFAs and
water causes soap formation, consumes catalyst, and reduces catalyst effectiveness, all of
which results in a low conversion (Komers et al., 2001). The transesterification reaction
may be carried out using either basic or acidic catalysts, but these processes require
relatively time-consuming and complicated separation of the product and the catalyst,
which results in high production costs and energy consumption (Demirbas, 2009a).
To minimize these problems, Kusdiana and Saka (2001) and Demirbas (2002a, 2003)
Demirbas et al. 303
Table 7. Comparisons between catalytic methanol (MeOH) method and SCM method for biodiesel
from vegetable oils by transesterification.
Catalytic MeOH process SCM method
Methylating agent Methanol Methanol

Catalyst Alkali (NaOH or KOH) None
Reaction temperature (K) 303–338 523–573
Reaction pressure (MPa) 0.1 10–25
Reaction time (min) 60–360 7–15
Methyl ester yield (wt%) 96 98
Removal for purification Methanol, catalyst, glycerol, soaps Methanol
Free fatty acids Methyl esters,
Saponified products water
Smelling from exhaust Soap smell Sweet smelling
SCM: supercritical methanol.
have proposed that biodiesel fuels may be prepared from vegetable oils via non-catalytic
transesterification with supercritical methanol. A non-catalytic biodiesel production route
with supercritical methanol has been developed that allows a simple process and high
yield because of simultaneous transesterification of triglycerides and methyl esterification
of fatty acids (Demirbas, 2002b). A reaction mechanism of vegetable oil in supercritical
methanol was proposed based on the mechanism developed by Krammer and Vogel
(2000) for the hydrolysis of esters in sub/supercritical water. The basic idea of supercrit-
ical treatment is based on the effect of the relationship between pressure and temperature
upon the thermophysical properties of the solvent, such as dielectric constant, viscosity,
specific weight, and polarity (Aysu et al., 2014; Kusdiana and Saka, 2001). In the super-
critical alcohol transesterification method, the yield of conversion increases to 50%–95%
in the first 10 min (Demirbas, 2005). Table 7 shows the comparisons between the catalytic
methanol method and the supercritical methanol method for biodiesel from vegetable oils
by transesterification. Some researchers recently have successfully produced biodiesel fuel
from various non-edible vegetable oils under different conditions using supercritical alco-
hol transesterification method. For instance, biodiesel production from Jatropha oil by
supercritical methanol method was studied by Hawash et al. (2009). They found at
593 K, oil to methanol molar ratio of 1:43 and 4 min of reaction time, 100% of
FAME yields at 8.4 MPa.
Effect of different reaction parameters on the biodiesel yield

The main factors affecting transesterification are alcohol/oil molar ratio, reaction time,
reaction temperature and pressure, catalyst, water content, and FFA content. It is evident
that at subcritical states of alcohol, the reaction rate is so low and gradually increased as
either pressure or temperature rises (Madras et al., 2004). The most important variables
affecting the methyl ester yield during transesterification reaction are alcohol/oil molar ratio
and reaction temperature.
Effect of molar ratio and alcohol type

One of the most important variables affecting the yield of alkyl ester is the molar ratio of
alcohol to oil. In the supercritical alcohol transesterification method, the yield of conversion
raises 50%–95% for the first 10 min.
The stoichiometric ratio for transesterification reaction requires 3 mol of alcohol and
1 mol of triglyceride to yield 3 mol of fatty acid ester and 1 mol of glycerol. Higher alco-
hol/oil molar ratios are used to enhance the solubility and to increase the contact between
the triglyceride and alcohol molecules (Noureddini et al., 1998). The alcohol/oil molar ratio
of 6:1 or higher generally gives the maximum yield (higher than 98 wt%).
The vegetable oils are transesterified 1:6–1:40 oil/alcohol molar ratios in catalytic and
supercritical alcohol conditions (Demirbas, 2002a). Transesterification of Jatropha curcas oil
in supercritical methanol conditions was carried out at different oil/methanol molar ratios
from 10 to 43 (Hawash et al., 2009). It was observed that increasing molar ratio had a
favorable influence on methyl ester conversion.
Acid-catalyzed reactions require the use of high alcohol/oil molar ratios in order to obtain
good product yields in practical reaction times. However, ester yields do not proportionally
increase with molar ratio. Ramadhas et al. (2004) and Sahoo et al. (2007) have reported 6:1
alcohol/oil molar ratio during acid esterification and 9:1 alcohol/oil molar ratio during
alkaline esterification to be the optimum amount for biodiesel production from high FFA
rubber seed oil and polanga seed oil, respectively.
Another important variable affecting the yield of ester is the type of alcohol to triglycer-
ide. In general, short chain alcohols such as methanol, ethanol, propanol, and butanol can
be used in the transesterification reaction to obtain high ester yields.
Effect of reaction temperature and time

Transesterification reaction can occur at different temperatures depending on the type of oil
employed. It was observed that increasing the reaction temperature, especially to supercrit-
ical conditions, had a favorable influence on the yield of ester conversion. In the alkali-
catalytic transesterification reaction, the temperature maintained by the researchers during
different steps range between 318 and 338 K. The boiling point of methanol is 337.9 K.
Temperature higher than this will burn the alcohol and will result in much lesser yield.
Leung and Guo (2006) showed that temperature higher than 323 K had a negative impact
on the product yield for neat oil, but had a positive effect for waste oil with higher viscosities.
Encinar et al. (2002) studied the transesterification reaction, with ethanol, of Cynara
cardunculus oils using NaOH and KOH as catalysts and reported 91.6% conversion at
room temperature. Alkali-catalytic transesterification of Pongamia pinnata oil was carried
out at five different temperatures with 1% KOH catalyst concentration, methanol/oil ratio
6:1, and 30 min of reaction time. The conversion was increased with increase in temperature
and the optimum temperature was found to be 333 K beyond that point no change was
observed with increase in temperature.
Effect of reaction temperature and the reaction time was investigated on the conversion of
Jatropha curcas oil to biodiesel (Vyas et al., 2011). Maximum FAME yields 93.5% was
observed at 323 K and 45 min of reaction time.
The methyl ester conversion rate increases with the reaction time. Different researchers
have reported different reaction times for the transesterification process. Kim et al. (2004)
Demirbas et al. 305
studied the transesterification reaction, with methanol/oil ratio (6:1), of vegetable oils using
NaOH and Na/NaOH/c-Al2O3 as catalysts at 333 K. They reached the maximum biodiesel
yield within 1 h both for the case of homogeneous and heterogeneous catalyst systems.
Effect of water and FFA

The water and FFA content are key parameters for determining the viability of the vegetable
oil transesterification process. In the transesterification process, the vegetable oil should have
an acid value less than 1 and all materials should be substantially anhydrous. If acid value is
greater than 1, more alkali (NaOH or KOH) is injected to neutralize the FFAs.
Water content is an important factor in the conventional catalytic transesterification of
vegetable oil. Water can cause soap formation and frothing. The resulting soaps can induce
an increase in viscosity, formation of gels and foams, and made the separation of glycerol
difficult (Agra et al., 1992; Ghadge and Raheman, 2005). In the conventional transesterifica-
tion of fats and vegetable oils for biodiesel production, FFAs and water always produce
negative effects, since the presence of FFAs and water causes soap formation, consumes the
catalyst, reduces its catalytic effectiveness which results a low conversion in biodiesel pro-
duction. FFAs react with the alkaline catalyst to produce soaps that inhibit the separation of
the ester, glycerin, and wash water (Canakcı and Van Gerpen, 1999). Ma et al. (1998)
reported that water and FFA contents of beef tallow catalyzed by NaOH had to be main-
tained below 0.06 wt% and 0.5 wt%, respectively. Using NaOH catalyzed transesterification,
methyl esters can generally be prepared in high yields for low FFA oils.
In catalyzed methods, the presence of water has negative effects on the yields of methyl
esters. The presence of water had negligible effect on the conversion while using lipase as a
catalyst (Madras et al., 2004). At the same time, the presence of water had a positive effect in
the yield of methyl esters when methanol at room temperature was substituted by supercrit-
ical methanol (Demirbas, 2006). Kusdiana and Saka (2004) studied the effect of water and
FFA contents on the yield of methyl esters by the supercritical methanol treatment (623 K,
43 MPa, 4 min of treatment with a methanol to oil molar ratio of 42:1) compared with those
from alkaline- and acid-catalyzed method. Effects of water and FFA contents on the alka-
line- and acid-catalyzed and supercritical transesterification of triglycerides are shown in
Figures 2 and 3.
Effect of catalyst content and type

Catalysts used for the transesterification of triglycerides are classified as alkali, acid, enzyme.
Several studies have examined the effects of catalyst content and type in transesterification of
triglycerides (Ma et al., 1998; May, 2004; Meneghetti et al. (2006); Stavarache et al., 2005).
The effect of different catalyst concentrations on base-catalyzed transesterification during
biodiesel production from vegetable oil by means of ultrasonic energy were investigated by
Stavarache et al. (2005). The highest yields were obtained when the catalyst was used in small
concentration, i.e. 0.5% wt/ of oil.
Hossain and Mazen (2010) investigated the effects of different homogeneous catalysts
(NaOH, KOH) on the biodiesel yield. The experiments were carried out at room temperature
with 0.5% catalyst concentration, methanol/oil ratio 1:1, and 2 h of reaction time. The
results showed that NaOH (71.2%) gave the better yield, compared with KOH (68.9%).
In addition, different concentrations of NaOH like 0.5, 1.0, and 1.5% were used. The highest
Supercritical methanol Alkaline catalyst Acid catalyst
100
80
Methyl ester, %
60
40
20
0
0 1 2 3 4 5
Water content, %
Figure 2. Yields of methyl esters as a function of water content in transesterification of triglycerides.
Supercritical methanol Alkaline catalyst Acid catalyst
100
80
Methyl ester, %
60
40
20
0
0 1 2 3 4 5
Water content, %
Figure 3. Yields of methyl esters as a function of free fatty acid content in transesterification of
triglycerides.
yield was obtained with 1.0% of NaOH concentration. In another study, Meneghetti et al.
(2006) reported that HCl is much more effective than NaOH at higher reaction
temperatures.
Fuel properties of biodiesel from non-edible vegetable oils

Just like petroleum-based diesel fuel, biodiesel operates in the CI engines. The biodiesel is
characterized for its physical and fuel properties, including density, viscosity, cetane number,
Demirbas et al. 307
Table 8. ASTM standards of maximum allowed quantities in diesel and biodiesel (Lotero
et al., 2006).
Property Diesel Biodiesel
Standard ASTM D975 ASTM D6751

Composition HCa (C10–C21) FAMEb (C12–C22)
Kinematic viscosity (mm2/s) at 313 K 1.9–4.1 1.9–6.0
Specific gravity (g/mL) 0.85 0.88
Flash point (K) 333–353 373–443
Cloud point (K) 258–278 270–285
Pour point (K) 238–258 258–289
Water (vol.%) 0.05 0.05
Carbon (wt%) 87 77
Hydrogen (wt%) 13 12
Oxygen (wt%) 0 11
Sulfur (wt%) 0.05 0.05
Cetane number 40–55 48–60
HFRRc (lm) 685 314
BOCLEd scuff (g) 3600 >7000
ASTM: American Society for Testing and Materials.

a
Hydrocarbons; bFatty acid methyl esters; cHigh frequency reciprocating rig; dBall-on-cylinder lubricity
evaluator.
iodine value, acid value, cloud and pour point, distillation range, flash point, ash content,
sulfur content, carbon residue, copper corrosion, and higher heating value (HHV)
(Demirbas et al., 2015a). Some biodiesel standards are ASTM D6751 (ASTM ¼ American
Society for Testing and Materials) and the European standard EN 14214. ASTM D6751
standard identifies the parameters the pure biodiesel (B100) must meet before being used as a
pure fuel or being blended with petroleum-based diesel fuel. ASTM standards of maximum
allowed quantities in diesel and biodiesel are given in Table 8.
As per the literature survey, many researchers have investigated the fuel properties of
biodiesel from non-edible vegetable oils such as Jatropha curcas (Jatropha), Pongamia
pinnata (Karanja), Schleichera oleosa (Kusum), Ricinus communis (Castor), Hevea brasilien-
sis (Rubber), Rice bran, etc. Table 9 shows the properties of biodiesel fuels from various
non-edible vegetable oil.
The injection and atomization characteristics of the vegetable oils are significantly differ-
ent than those of petroleum-derived diesel fuels, mainly as the result of their high viscosities
(Cigizoglu et al., 1997). High viscosity leads to poorer atomization of the fuel spray and less
accurate operation of the fuel injectors. The lower the viscosity of the biodiesel, the easier it
is to pump and atomize and achieve finer droplets (Islam and Beg, 2004). The viscosity
values of vegetable oil methyl esters decrease sharply after transesterification. The viscosity
values of vegetable oils are between 27.2 and 53.6 mm2/s, whereas those of vegetable oil
methyl esters are between 3.6 and 4.6 mm2/s (Demirbas, 2006). The kinematic viscosity in
biodiesel is determined using ASTM D6751 (1.9–6.0 mm2/s) (Table 8). Compared to ASTM
D6751 standards for biodiesel fuel, some of non-edible vegetable oil methyl esters are highly
viscous, such as Ricinus communis and Schleichera oleosa methyl esters (Table 9).
308
Table 9. Fuel-related properties of biodiesel from non-edible oils.
Density CPc PPd FPe Viscosityf CVg SCh ACi WCj

a b
Biodiesel IV (kgm–3) CN (K) (K) (K) (mm2/s) (MJ/kg) (%) (%) (%) References
k
Castor 80 886 53 28 247 43 12 38 – – 0.17 Bello and Makanju (2011);
Rengasamy et al. (2014)
Jatropha – 880 l 51–52 0 279 3 4.8 39.23 0.011 0.016 0.025 Parawira, 2010; Rao et al. (2009);
Rashid et al. (2010)
Karanja 91 889 l 41.7 283 288.8 461 6.88 36.12 – 0.003 0.005 Bobade and Khyade (2012);
Meher et al. (2004);
Panigrahi et al. (2012)
Kusum – 850f 42–48 279 – 491 9.2 41.65 – – – Gandhi et al. (2011);
Jawre and Lawankar (2014)
Mahua – 916 51 – 279 423 3.98 39.40 – – 0.075 Atabani et al. (2013)
Neem – 890 – 278 276 402 5.53 39.21 – – – Aransiola et al. (2014);
Kr Vishnoi et al. (2013)
Rubber – 892 66.2 279 265 423 5.81 36.50 – – – Gimbun et al. (2013);
Krishnakumar et al. (2013);
Ramadhas et al. (2004);
Rice bran 102 872 51.6 277 269 403 4.81 38.72 – – – Mohanty (2013); Subbaiah et al. (2010)
a
IV: iodine value; bCN: cetane number; cCP: cloud point; dPP: pour point; eFP: flash point; fmeasured at 313 K; gCV: calorific value; hSC: sulfur content; iAC: ash content; jWC:
water content; kmeasured at 308 K; lmeasured at 288 K.
Energy Exploration & Exploitation 34(2)
Demirbas et al. 309
The cetane number is an important parameter for the determination of diesel fuel quality,
especially the ignition quality. It measures the readiness of the fuel to auto-ignite when
injected into the engine. Ignition quality is one of the properties of biodiesel that is deter-
mined by the structure of the FAME component (Bamgboye and Hansen, 2008). As shown
in Table 9, cetane number of non-edible oil methyl esters is higher than that of petroleum;
therefore they can replace diesel for the combustion engine.
Another important property of biodiesel fuel is its flash point. Flash point of a fuel is the
lowest temperature at which it will spontaneously ignite without the presence of a flame or
spark. Non-edible oil methyl esters have quite high flash points which make them less
volatile and safer to transport or handle than diesel fuel.
Two important parameters for low-temperature applications of a fuel are cloud point and
pour point. The cloud point is the temperature at which wax first becomes visible when the
fuel is cooled. The pour point is the temperature at which the amount of wax from a solution
is sufficient to gel the fuel; thus it is the lowest temperature at which the fuel can flow.
Compared to ASTM D6751 standards for biodiesel fuel, cloud and pour points of non-
edible oil methyl esters are similar biodiesel fuel. Biodiesel has a higher cloud and pour
points compared to conventional diesel (Prakash, 1998). The vegetable oil methyl esters have
cloud point and pour point that are 15–25 K higher than those of diesel fuels (Table 8). The
cloud and pour points of non-edible methyl esters vary significantly with feedstock depend-
ing on fatty acid compositions (Atabani et al., 2013; Silitonga et al., 2013).
The density is an another important property of biodiesel fuel. It is the mass per unit
volume of any liquid at a given temperature. Specific gravity is the ratio of the density of a
liquid to the density of water. Specific gravity of biodiesels ranges between 0.87 and 0.89
(Demirbas, 2006). An increase in density from 860 to 885 kg/m3 for vegetable oil methyl
esters increases the viscosity from 3.59 to 4.63 mm2/s and the increases are highly regular
(Demirbas, 2005, 2009a). There is high regression between the density and viscosity values of
vegetable oil methyl esters (Demirbas, 2009a). According to ASTM D6751 standards, dens-
ity should be tested at the temperature reference of 288 K. The density of non-edible methyl
esters is higher than that of common diesel fuel. This may be due to the presence of higher
molecular weight triglycerides (Hotti and Hebbal, 2015).
HHV is an important parameter in the selection of a fuel. The HHVs of biodiesels (39–
41 MJ/kg) are slightly lower than those of gasoline (46 MJ/kg), petrodiesel (43 MJ/kg), or
petroleum (42 MJ/kg) (Demirbas, 2008b) because of their higher oxygen content. Ash and
extractive content are two important parameters directly affecting the heating value. High
ash content of a plant part makes it less desirable as fuel, whereas high extractive content
adds to its desirability (Demirbas, 2002c).
Conclusion
Edible plant oil fuels presently do not compete economically with petroleum-based fuels
because they are more expensive but due to the recent increase in petroleum prices and
uncertainties concerning petroleum availability, there is renewed the interest in non-edible
plant oil fuels for diesel engines.
Non-edible plant oils are unsuitable for human food because of the presence of some toxic
components. These plants are easily available in developing countries and are very econom-
ical comparable to edible plant oils. Biodiesel produced from non-edible plant oils has good
potential as an alternative diesel fuel. However, as a serious drawback, most non-edible oils
contain a high content of FFAs, which increases the biodiesel production cost.
Declaration of conflicting interests

The author(s) declared no potential conflicts of interest with respect to the research, authorship, and/or
publication of this article.
Funding
The author(s) received no financial support for the research, authorship, and/or publication of this
article.
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Energy Exploration & Exploitation

non-edible plant oils Reprints and permissions:

Department of Industrial Engineering, King Abdulaziz University, Jeddah, Saudi Arabia

Raw materials for biodiesel production

Table 1. Fuel-related properties of selected vegetable oils.

A. indica 82–98 – 286.0 280.0 – 35.83 Aransiola et al. (2014)

Food versus fuel

Palmitic Palmitoleic Stearic Oleic Linoleic Linolenic

A. indica 12.01 – 12.95 34.09 38.26 0.3 Muthu et al. (2010)

Non-edible vegetable oils as raw material

Pongamia pinnata (Karanja)

Madhuca indica (Mahua)

Ricinus communis (Castor)

Azadirachta indica (Neem)

onwards, it can produce up to 50 kg of fruits annually (Girish and Shankara, 2008). It

Hevea brasiliensis (Rubber)

Nicotiana tabacum (Tobacca)

Table 4. The yields of various non-edible oil feedstocks.

Energy crop Kg per hectare References

Azadirachta indica (neem) 2670 Azam et al. (2005)

Moringa oleifera (Drumstick tree)

Calophyllum inophyllum (Polanga)

Simmondsia chinensis (Jojoba)

Sapindus mukorossi (Soap nut)

Melia azedarach (Syringa)

Vernicia fordii (Tung)

Schleichera oleosa (Kusum)

Derivatives of non-edible oils as diesel fuels

Dilution of non-edible vegetable oils

Using microemulsions for non-edible vegetable oils

Biodiesel via transesterification from non-edible vegetable oils

Table 5. Comparison of various methanolic transesterification methods.

Method Reaction temperature (K) Reaction time (min)

Acid or alkali catalytic process 303–338 60–360

Table 6. Summary of catalytic transesterification of some selected non-edible oils.

Non-edible Catalyst Temperature Reaction Yield

KOH Castor 1.5 333 10 min 80.1 Hincapié et al. (2014)

Non-catalytic transesterification methods

Catalytic MeOH process SCM method

Methylating agent Methanol Methanol

SCM: supercritical methanol.

Effect of different reaction parameters on the biodiesel yield

Effect of molar ratio and alcohol type

Effect of reaction temperature and time

Effect of water and FFA

Effect of catalyst content and type

Supercritical methanol Alkaline catalyst Acid catalyst

Figure 2. Yields of methyl esters as a function of water content in transesterification of triglycerides.

Supercritical methanol Alkaline catalyst Acid catalyst

Fuel properties of biodiesel from non-edible vegetable oils

Property Diesel Biodiesel

Standard ASTM D975 ASTM D6751

ASTM: American Society for Testing and Materials.

Table 9. Fuel-related properties of biodiesel from non-edible oils.

Density CPc PPd FPe Viscosityf CVg SCh ACi WCj

Declaration of conflicting interests

Energy Production Agriculture, and Technological Advancements. New York: Springer

Padhi SK and Singh RK (2010) Optimization of esteriﬁcation and transesteriﬁcation of Mahua

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