Biodiesel Production From Non Edible Plant Oils
Biodiesel Production From Non Edible Plant Oils
Biodiesel Production From Non Edible Plant Oils
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).
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.
Viscositye
a b c d
OilA Iodine value CN CP (K) PP (K) FP (K) (mm2/s) References
(Ghadge and Raheman, 2005; Srivastava and Verma, 2008). About 80% of the European
Unions total biofuel production is comprised of biodiesel produced from rapeseed and
sunower 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%),
sunower oil (5%), and other (1%) (Pahl, 2008).
Table 2. Comparison of fatty acid composition between various edible and non-edible vegetable oils.
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).
Jatropha curcas
Jatropha curcas is a tall bush or small tree, up to 57 m tall, belonging to the Euphorbiaceae
family (Atabani et al., 2013). Originally from Central America, Jatropha curcas is found
294 Energy Exploration & Exploitation 34(2)
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 2545 3050 Anya et al. (2012); Djenontin et al. (2012)
Calophyllum inophyllum (polanga) Tree 6075 5070 Azam et al. (2005); Chavan et al. (2013)
Hevea brasiliensis (rubber) Tree 4050 3545 Fadeyibi and Osunde (2012);
Kant et al. (2011)
Jatropha curcas Tree 36 56 Karaj and Muller (2010)
Madhuca indica (mahua) Tree 3045 2050 Jha et al. (2013); Puhan et al. (2005)
Melia azedarach (syringa) Tree/shrub 1045 Atabani et al. (2013)
Moringa oleifera (drumstick) Tree 3040 Mohammed et al. (2003)
Nicotiana tabacum (tobacco) Herb 3340 17 Bankovic-Ilic et al. (2012);
Khan et al. (2014)
Pongamia pinnata (karanja) Tree 2739 3040 Rahman et al. (2011);
Armah et al. (2011)
Ricinus communis (castor) Tree/shrub 4860
Sapindus mukorossi (soapnut) Tree 51 Chigozie et al. (2014)
Simmondsia chinensis (jojoba) Shrub 4555 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).
(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).
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 worlds 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).
medicine, soap, lamp oil, hair grease, and cosmetic in different parts of the world (Ong et al.,
2011).
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
300 Energy Exploration & Exploitation 34(2)
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 oildiesel blend is a good
option.
Catalytic transesterification methods. Vegetable oils can be transesteried by heating them with a
large excess of anhydrous methanol and a catalyst. Transesterication reactions can be
catalyzed by alkalis, acids, or enzymes.
Biodiesel produced by transesterication 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 triuoride (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 transesterication methods. Acid-catalyzed reactions require
Catalyst
Triglyceride + Alcohol Ester + Glycerol
Figure 1. Transesterification of triglycerides with alcohol.
Demirbas et al. 301
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 difcult, so that the ideal alcohol/oil ratio has to be established empirically, con-
sidering each individual process.
Transesterication 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
transesterication 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 nal mixture is stirred vigorously for 2 h at 340 K in
ambient pressure. A successful transesterication reaction produces two liquid phases: ester
and crude glycerol. However, due to the high FFA content of non-edible oils, these oils
cannot be transesteried 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 transesterication process is preferred. FFA content of oil could be reduced to less
than 1% using an acid catalyst at the rst stage. The second step is base catalyzed transes-
terication in which oil reacts with methanol in the presence of an alkaline catalyst to form
ester and glycerol (Fadhil et al., 2012).
The transesterication 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 transesterication 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
302 Energy Exploration & Exploitation 34(2)
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.
Table 7. Comparisons between catalytic methanol (MeOH) method and SCM method for biodiesel
from vegetable oils by transesterification.
have proposed that biodiesel fuels may be prepared from vegetable oils via non-catalytic
transesterication 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 transesterication of triglycerides and methyl esterication
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,
specic weight, and polarity (Aysu et al., 2014; Kusdiana and Saka, 2001). In the super-
critical alcohol transesterication method, the yield of conversion increases to 50%95%
in the rst 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 transesterication. Some researchers recently have successfully produced biodiesel fuel
from various non-edible vegetable oils under different conditions using supercritical alco-
hol transesterication 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.
studied the transesterication 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.
100
80
Methyl ester, %
60
40
20
0
0 1 2 3 4 5
Water content, %
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.
Table 8. ASTM standards of maximum allowed quantities in diesel and biodiesel (Lotero
et al., 2006).
iodine value, acid value, cloud and pour point, distillation range, ash 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 American
Society for Testing and Materials) and the European standard EN 14214. ASTM D6751
standard identies 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 signicantly 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 ner droplets (Islam and Beg, 2004). The viscosity
values of vegetable oil methyl esters decrease sharply after transesterication. 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 (1.96.0 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
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 ash point. Flash point of a fuel is the
lowest temperature at which it will spontaneously ignite without the presence of a ame or
spark. Non-edible oil methyl esters have quite high ash 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 rst becomes visible when the
fuel is cooled. The pour point is the temperature at which the amount of wax from a solution
is sufcient to gel the fuel; thus it is the lowest temperature at which the fuel can ow.
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 1525 K higher than those of diesel fuels (Table 8). The
cloud and pour points of non-edible methyl esters vary signicantly 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. Specic gravity is the ratio of the density of a
liquid to the density of water. Specic 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
310 Energy Exploration & Exploitation 34(2)
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.
Funding
The author(s) received no nancial support for the research, authorship, and/or publication of this
article.
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