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Recent Research and Developments in Biodiesel Production from Renewable

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184 Recent Patents on Chemical Engineering, 2013, 6, 184-193

Recent Research and Developments in Biodiesel Production from Renew-

able Bioresources

Mohamed Chaker Ncibi* and Mika Sillanpää

Laboratory of Green Chemistry, Faculty of Technology, Lappeenranta University of Technology, Sammonkatu 12,
50130, Mikkeli, Finland

Received: November 29, 2013 Revised: December 23, 2013 Accepted: December 24, 2013

Abstract: Research and development (R&D) in the field of biofuels in general and biodiesel in particular are not new en-
deavours. However, they gained momentum in the last couple of decades due to the increasing economic concerns and
environmental awareness about the use of petroleum-derived fossil fuels. In this review article, recent patents and research
and studies dealing with the production of biodiesel from bioresources will be investigated and discussed. The main objec-
tive is to present the latest research undertakings, findings and innovations in the scientific and industrial communities on
biodiesel production for various bioresources and wastes.
Keywords: Agricultural wastes, Biomass, Biodiesel, Extraction, Transesterification.

1. INTRODUCTION 2. BIODIESEL IN THE WORLD

Several inexpensive and accessible bioresources and
agro-industrial wastes are available for liquid and gaseous
biofuels production including biodiesel, bioethanol and
biogas [1]. This study will focus on the research works re-
lated to the subject of biodiesel production.
In the course of the last decades, R&D accomplishments
in this important energetic issue permitted the development
of several alternative and sustainable ways of producing
biodiesel away from the controversial food crops-derived
diesel [2, 3].
The production of biofuels in general and biodiesel in
particular is gradually becoming a vital issue due to the rare-
faction of the fossil fuels and the urgent need to decrease the
amounts of greenhouse gas emissions [4]. Thus, the energy
concerns, the growing environmental awareness and the
economic considerations are the major driving forces behind
the worldwide direction towards producing biofuel from
bioresources.
After reviewing the bioconversion of renewable biore-
sources and agricultural by-products into bioethanol in a
previous article in Recent Patents in Chemical Engineering
[5], the objective of the present review is to investigate,
based on recent research works, the possibilities of using
low-cost and highly available bioresources and/or wastes to
produce biodiesel. Environmental and economic considera-
tions are also discussed, along with some perspectives re-
garding this important energetic issue.
*Address correspondence to this author at the Laboratory of Green Chemistry,
Faculty of Technology, Lappeenranta University of Technology, Sammonkatu
12, 50130, Mikkeli, Finland; Tel: +358 294 462 111; Fax: +358 5411 7201;
E-mails: chaker.Necibi@lut.fi; and ncibi_mc@yahoo.com
Biodiesel was defined as a renewable fuel derived from
natural oil sources such as vegetable oil, recycled waste
cooking oil and animal fats.
Biomass is the most abundant
renewable resource on earth. Thus, transforming biomass
into biodiesel is a promising way to replace regular fossil
diesel without affecting the vital need for energy.
Chemically, biodiesel is a fatty acid methyl ester (FAME)
produced by a chemical transesterification process. The
properties of biodiesel depend very much on the nature of its
raw material as well as the technologies related to the bio-
conversion process. Yet, generally when compared to con-
ventional fossil diesel, biodiesel has a better combustion
quality due to the higher cetane number (45-65 compared to
40-55). However, the biodiesel has higher viscosity (3.5-5.5
centistokes at 40°C) compared to petroleum-derived diesel
(2-3.5 cSt at 40°C), which makes it difficult to use directly in
a conventional diesel engine [6]. To lower the oil viscosity,
the use of alcohol (mainly methanol) in the transesterifica-
tion phase was proven to be an efficient solution [7]. The
only issue is that the used alcohol has to be renewable in
order to produce a 100% renewable biodiesel.
Environmentally, biodiesel is better for the environment
because it is composed of renewable materials emitting less
greenhouse gas than petroleum diesel, reducing therefore
health risks associated with air pollution [8].
Worldwide, the production of biodiesel has become of
strategic importance in many countries for two main reasons:
(i) establishing oil independence and (ii) reducing CO2 emis-
sions. There is a wide range of bioresources that could be
used for biodiesel production which goes from rapeseed and
soybeans in the US to palm oil and Jatropha in Asian coun-
tries [9].

1874-4788/13 $100.00+.00 © 2013 Bentham Science Publishers

Biodiesel Production from Renewable Bioresources
Fig. (1). World production of major oilseeds [10].
Fig. (1) depicts the world production of the major oil-
seeds for the 2010/2011 campaign [10]. As shown, soybean
presents the highest amount with 265.2 million tonnes.
3. BIODIESEL CHARACTERICTICS
A wide variety of bioresources has been studied to pro-
duce biodiesel. The feedstocks were from different origin
such as oilseeds, used cooking oils, algae lipids and so forth.
The origin of the oil source itself has an important impact on
the properties of the produced biodiesel. These properties are
mainly related to the oil chemical structure (i.e. carbons
chain length and degree of unsaturation).
The composition of oils, from vegetable and algal source,
is made of triglycerides which are a combination of saturated
and unsaturated fatty acids of different molecular weights.
The chemical characteristics of the fatty acids will influence
key properties of the produced biodiesel including cetane
number, density and viscosity. Table 1 presents the most
known fatty acid contained in several feedstocks, based on
two main factors: the chain length (i.e. number of carbons)
and the degree of unsaturation (i.e. number of carbon-carbon
double bonds).
Generally, high viscosity, low volatility and the reactivity
of unsaturated hydrocarbon chains were disadvantageous for
a good biodiesel production [24]. The increase in saturation
and chain length of fatty acids increases the cetane number,
which tends to enhance the combustion quality. Besides,
high cetane number was proven to be obtained from oils rich
with high saturated and also monounsaturated fatty acids
[25]. Thus, high contents of saturated (C16:0) and mono-
unsaturated (C18:1) fatty acids are two reliable criteria to
assess to suitability of a determined oil to produce high qual-
ity biodiesel.
According to the results presented in table 1, and based
on those criteria, Palm, Mahua, Jatropha, Karanja, rapeseed,
Recent Patents on Chemical Engineering, 2013, Vol. 6, No. 3 185
as well as the microalga Chlorococcum humicola should
have the highest cetane numbers and therefore suitable for
biodiesel production.
For the case of used cooking oils from sunflower, soy-
bean and palm, the data from table 1 shows that the triglyc-
erides content is quite similar between the raw and used oils,
expect for the palm oil where the frying process seems to
affect the fatty acids composition by significantly decreasing
the content of both C16:0 and C18:1. In general, the waste
cooking oil undergoes several reactions during the frying
process which lead to the formation of undesirable com-
pounds such as polymers and free fatty acids. This poses
several challenges in the transesterification of used cooking
oil, requiring an additional pretreatment step to remove these
impurities.
4. BIODIESEL PRODUCTION PROCEDURES
One of the key endeavours regarding the biodiesel pro-
duction is the process optimisation. Indeed, R&D efforts
revealed that the main problems with vegetable oils are the
high viscosity, low volatility, reactivity of unsaturated hy-
drocarbon chains and the high contain of free fatty acids,
which cause poor combustion in conventional diesel engines.
To overcome such difficulties, different techniques and mul-
tiple chemical steps were proposed such as dilution, micro-
emulsification, pyrolysis, catalytic cracking and transesterifi-
cation [26].
Practically, two major steps are involved in biodiesel
production: (i) oil extraction from the feedstock and (ii) its
subsequent conversion into biodiesel (i.e. Transesterified
vegetable oil).
4.1. Procedures of Oil Extraction
Basically, the extraction process of vegetable oils aims to
separate the fat from protein in order to obtain high quality
186 Recent Patents on Chemical Engineering, 2013, Vol. 6, No. 3 Ncibi and Sillanpää

Table 1. Fatty acids composition in various feedstocks profile.

Saturated Fatty Acid Unsaturated Fatty Acid

C16:0 C18:0 C16:1 C18:1 C18:2 C18:3 Refs.

Rapeseed 3.5 0.9 0.1 54.1 22.3 - [11]

Sunflower 6.4 2.9 0.1 17.7 72.9 0.00 [12]

Soybean 11.2 3.7 - 22.0 55.0 6.80 [13]

Oil seeds Palm 47.9 4.23 0.04 37.0 9.07 0.26 [14]

Jatropha 14.2 7.0 0.7 44.7 32.8 0.20 [15]

Karanja 9.6 6.5 - 50.0 16.0 3.10 [16]

Mahua 17.8 14 - 46.3 17.9 - [17]

C. humicola 40.3 2.43 1.36 23.3 13.83 14.64 [18]

C sorokiniana 13.7 - 4.6 14.4 14.1 26.4 [19]

Algae
C. vulgaris 66 5 - 7 11 12 [20]

D. salina 19.4 1.5 1.7 5.3 6.2 38.7 [21]

Sunflower 6.8 3.7 0.4 22.8 65.2 0.1 [12]

Used cooking oil Soybean 11.5 4.0 - 24.5 53.0 7.0 [22]

Palm 9.45 - - 19.69 2.91 - [23]

oil and produce high extraction yields. In practice, extracting
vegetable oil depends on the physical and chemical charac-
teristics of the raw feedstock. Two major extraction tech-
niques are applied. The first is chemical based on the use of
solvents and the second is mechanical based on pressure
application. Generally, the chemical extraction method en-
sures more oil extracted yields while the mechanical one can
produce better oil quality [27].
4.1.1. Chemical Extraction
It is a process based on placing grounded oilseeds in
contact with a solvent that allows dissolution of the oil. The
efficiency of the process depends on the preparation of oil-
seed, temperature, operation mode and the nature of solvent
itself [28]. Practically, the choice of solvent relies on two major
considerations: oil solubility and the related utilisation cost.
On the other hand, the difficulty to extract the oil from
the cells, due to a slow diffusion process, requires a pre-
treatment phase of the raw feedstock to facilitate the diffu-
sion. Commonly, the used solvents for oil extraction include
n-hexane, white spirit, trichloroethylene, carbon sulfide and
some bio-solvents. Currently, hexane is widely used as sol-
vent for the extraction of vegetable oil [29]. In general, there
are three methods used for the chemical oil extraction proc-
ess: immersion, percolation or mixed immersion-percolation.
In practice, most of the extractors run in a continuous flow,
where solid particles (i.e. pretreated oleaginous biomass) are
placed on a perforated base forming a bed that moves
throughout the unit while the liquid (i.e. pure or mixed sol-
vent) flows through the bed in one of two different modes:
immersion or percolation. In the case of immersion, the
liquid is kept on the top of the bed and each extraction stage
is flooded with a slow-flowing bath of miscella (i.e.
oil/solvent mixture). As for percolation, the liquid is sprayed
onto the bed surface at a rate low enough to avoid bed flood-
ing. In some chemical extraction procedures, the two modes
could be combined [30].
For the case of algal biomass, an American research team
published a patent on integrated processes and systems for
production of biofuels using algae. The feedstock is formed
by autotrophically growing algal biomass. The algal biomass
is converted to algal oil by introducing a sugar feed to oil-
producing algae under growth conditions sufficient to en-
courage formation of algal oil within the oil-producing algae.
Then, the algal oil can be extracted from the oil-producing
algae and can further be converted to biodiesel. The chemi-
cal extraction is performed via a hexane or butane solvent
recovery step. Supercritical fluid extraction was also used in
extracting the oil from oil vesicles of the oil-producing algae
[31].
Another invention presented a process to produce biodie-
sel or fuel oil from microbial oilseed and algal biomass. The
oil-producing biomasses and algal yeast recovered after
spinning were sent to an extraction unit. Alternatively, the
researchers proposed that the wet or dry biomass may pass
through a cell disruption process to facilitate the subsequent
extraction of lipids in the extractor based on organic solvents
[32].
4.1.2. Mechanical Extraction
This widely used process is a pressure-based method that
preserves the characteristics of the oilseed and the residual
product [33]. The seeds are fed into an extruder that com-
presses it, warming them in the process. A preliminary
Biodiesel Production from Renewable Bioresources
crushing action is often used before reaching the extruder in
the case of oilseeds with high oil content. Generally, the use
of the screw press is preferred because of its low cost pro-
duction and energetic efficiency [34]. The mechanical screw
press consists of a vertical feeder and a horizontal screw with
increasing body diameter to exert pressure on the oilseeds as
it advances along the length of the press. The oil is collected
in a trough under the screw and the de-oiled cake is dis-
charged at the end of the barrel. The press type depends on
the raw material. Seeds containing lipids in quantities ex-
ceeding 20% wt are usually fully or partially treated by me-
chanical means [28].
Another invention developed a process and apparatus for
assisting the extraction and processing of biodiesel oil from
organic feedstock. The whole process includes extracting the
amount of biodiesel oil from the crushed oil-bearing organic
feedstock. The interesting feature in the present invention is
the use of anaerobic digestion to process the high oil meal
slurry from the biodiesel process, in order to eliminate the
solvent extraction portion of the process [35].
4.1.3. Combined Extraction
In practice, the two systems mechanical and chemical
procedures are often combined to enhance efficiency of oil
extraction.
The results, presented in a recent patent, showed that
soybean oil was extracted by a two-stage process in which
up to 85% of the soybean oil is extracted by mechanical or
solvent extraction to produce first extracted oil and oil-
containing meal. The first extracted oil is then refined by
caustic or physical refining. Substantially, all of the oil re-
maining in the meal is extracted by solvent extraction to
produce second extracted oil and substantially oil-free meal.
The second extracted oil is to be transesterified for use in
biodiesel fuel [36].
An investigation on the feasibility of an aqueous process
to extract sunflower seed oil using a co-rotating twin-screw
extruder was carried out. The analysis showed that the aque-
ous extraction of the oil was more efficient in the twin-screw
extruder than the reference trial (batch reactor). The best oil
extraction yield obtained was about 55% and the residual oil
content of the cake meal was approximately 30% [37].
In another invention, a research work was performed in
order to optimise diesel extraction from algae. The process
starts from the stage of cultivation of algae, continues with
the extraction of algae lipids and transformation of lipids in
the final product extraction process. In the lipid extraction
section, there is an ultrasonic reactor where the external
walls of the alga are ruptured together with those of the oil
sac to permit the extraction of lipids. The authors revealed
that the exposure area of the algae to the ultrasound within
the reactor may be jacketed to reduce algae temperature
when being exposed to the treatment. In turn, extracted lipids
are sent to the secondary extraction equipment that is operat-
ing by compression. The mixture is subsequently sent to a
centrifuge that eliminates excess of water and further sent to
storage tanks for biodiesel production. In the transesterifica-
tion area there is also an ultrasonic reactor which ruptures
the molecules of the fluid which passes through to accelerate
the reaction and render it almost immediately [38].
Recent Patents on Chemical Engineering, 2013, Vol. 6, No. 3 187
Another research team studied different methods for the
oil extraction consisting of mechanical press with and with-
out solvent and cold percolation. The maximum oil content
(49%) was found by mechanical press with periodic addition
of solvent [39].
4.2. Transesterification
The transesterification procedure is one of the most
commonly used method for converting vegetable oils into
biodiesel and a reliable solution to the high viscosity prob-
lem. Generally, there are two ways to convert vegetable oils
into biodiesel by transesterification; the first method employs
a catalyst and the second one is a non-catalyst option includ-
ing supercritical processes and co-solvent systems. Various
catalysts are used, to increase the yield and reaction rate,
such as base catalysts like NaOH, KOH and NaMeO, along
with acid catalysts that include H2SO4, H3PO4, and CaCO 3
and lipase enzymes [11]. Nonetheless, some studies men-
tioned that the use of homogeneous catalysts such as KOH
and NaOH induces a serious risk for the environment due to
their hygroscopic nature. Heterogeneous catalysts, on the
other hand, seem to have more advantages. Indeed, hetero-
geneous catalytic reaction converts triglycerides into methyl
ester (and glycerol as a by-product) enabling therefore the
production of biodiesel in an eco-friendly and cost-effective
method due to the reusability of catalysts for both batch and
continuous process, along with the easy separation phase
[40]. In this context, an invention was developed for the
production of biodiesel through the heterogeneous trans-
esterification reaction of triglycerides present in vegetable
(soy, cotton seed, canola, castor and peanut) oils and animal
fat using apatite catalyst and mixture of solid oxides [41]. It
was revealed that a conversion of 100% was obtained using
the prepared heterogeneous catalysts. The purity of both
product (biodiesel) and by-product (glycerin), in the compo-
sition is greater than 96.5%.
Overall, the biodiesel production follows a multi-step
path. First, the catalyst is dissolved in the alcohol with a
standard mixing machine. The oil is added with the mix and
then put into a closed reaction vessel. The reaction takes
place when the temperature of the mix reaches 70 °C. After 1
to 8 h of reaction time, the conversion of oils into esters
should be completed. An excess alcohol is usually used to
ensure the complete conversion. At the end of the process
there will be two outputs, glycerin and biodiesel. The separa-
tion of the two outputs is based on the difference in density
of glycerol relative to biodiesel (glycerol denser). Therefore
the separation is made using the gravimetric method by
drawing off the bottom of the settling vessel. In some cases,
it is possible to use centrifuge to separate the two phases [9].
The crude biodiesel needs to be purified before use. This
purification is done in three steps: (i) neutralisation, (ii) a
passage through an alcohol stripper and (iii) finally the wash-
ing step. To neutralise the unreacted alkali catalyst and split
any soap, acid solution must be added to crude biodiesel.
The distillation process must take place to remove unreacted
alcohol. The last step was conducted by washing the rem-
nants of the catalyst, soaps, salts, residual alcohol and free
glycerol from the crude biodiesel [42].
188 Recent Patents on Chemical Engineering, 2013, Vol. 6, No. 3 Ncibi and Sillanpää

5. BIORESOURCES FOR BIODIESEL PRODUCTION are mainly characterised by their high oil content. The most
studied oil-bearing feedstocks are sunflower, soybean, rape-
In order to minimise the world dependency on fossil
seed, palm seed, Jatropha, Karanja, along with algae.
diesel in the short term, and find a sustainable solution for
the future, several bioresources were investigated. The main
potential feedstocks for oil production are oilseeds, algae and 5.1. Sunflower (Helianthus annuus)
even animal fats. Sunflower is classified as the one of the principal oils
Due to the increasing economic concerns and obvious used by the biodiesel industry [44]. Several researchers have
environmental reasons, the transformation of non-edible oil investigated the potential and the quality of sunflower for oil
into biodiesel should be the foremost choice to substitute production. The oil content of sunflower seeds is often more
fossil diesel. However, considering the major importance of than 35% and the annual oil yield about 800 kg/ha (Cf.
such fuel substitution for the decades to come, the edible oils Table 2). Another interesting property of sunflower oil is that
could be used if the country’s natural resources are rich in it contains mostly unsaturated fatty acid (18:2) [21].
oily feedstocks, in one hand, and if the agricultural landscape Sunflower seed oil with high heat stability has a saturated
allows it, on the other hand. Indeed, the exploitation in the fatty acid content (palmitic acid and stearic acid) between
latter case (i.e. biodiesel from edible oils) should be carefully 15% and 45% of the total fatty acids. The oleic acid content
planned and based mainly on a gradual substitution of the is between 45% and 75% of the total fatty acids present in
regular diesel with the biodiesel produced from oil plants the oil, along with a gamma-tocopherol and delta-tocopherol
cultivated in marginal lands, using high-yielding varieties sum content greater than 85% of the total tocopherols present
and avoiding the use of chemicals in the cultivation cycle. in the oil. The high heat stability of the oil makes it suitable
Thus, the competition with the vital food crops remains for industrial processes requiring or causing high tempera-
minimal, and therefore, a reasonable balance could be man- tures, like the biodiesel and biolubricants production sector
aged between food and energy demands. [45].
In this section, various oil-bearing bioresources will be In order to monitor the effect of several key parameters in
presented based on the research works of multiple teams biodiesel production from sunflower, such as energy de-
worldwide. Indeed, many researchers have concentrated on mands, time consumption and catalyst use, many studies
producing vegetable oil fuels for diesel engines. The follow- were conducted with promising results [28, 46].
ing table 2 illustrates the oil content and the annual yield of
various oilseeds and algae. 5.2. Soybeans (Soja angustifolia)
Soybean is an edible species grown for the oil content of
Table 2. Oil content and annual yield of various oilseeds and its beans, 20% (Cf. Table 2). Therefore, it has been investi-
algae. gated as a potential feedstock for biodiesel production, espe-
cially that it could be grown in arid condition and mountain-
Annual oil yield per ous regions [47]. Similar to sunflower, soybean oil composi-
Oil content (%)
Bioresources cultivated hectare
[9, 15, 43]
(kg ha-1) [9, 11]
tion contain more than 80% unsaturated fatty acid [15].
In the US, a research team worked on the production of
Oilseeds: biodiesel from soybean based on the fact that over 80% of
Sunflower 25-35 655-800 vegetable oil production in the United States is soybean oil,
which is 61% polyunsaturated. In their patent, they indicated
Rapeseed 38-46 1000 that soybean oil may be the most preferred material for bio-
Palm 30-60 5000
fuel production. Their invention, as shown in Fig. 2, consists
of a triglyceride-to-fuel conversion process including the
Coconut 63-65 2260 steps of (i) preconditioning unsaturated triglycerides by
catalytic conjugation, cyclisation, and cross-link steps; (ii)
Jatropha 30-40 1595
contacting the modified triglycerides with hot-compressed
Soybean 15-20 520 water containing a catalyst and (iii) refining the crude hydro-
carbon oil to produce various grades of biofuels [48].
Peanut 45-55 3000
The ultrasonic effect on the transesterification by No-
Karanja 21- 32 - vozym 435 (immobilised lipase from Candida Antarctica) to
Mahua 35-42 - produce biodiesel from soybean oil was tested. The results
showed that, under the optimum conditions, 96% yield of
Algae: fatty acid methyl ester (FAME) could be achieved in 4 h.
Furthermore, repeated use of Novozym 435 after five cycles
Chlorella Sp 28-32 -
showed no obvious loss in enzyme activity [49].
Cylindrotheca Sp 16-37 -
5.3. Rapeseed (Brassica napus)
Botryococcus braunii 25-75 -
This biomass could be used for human consumption,
Edible and non-edible feedstocks are an important source animal feed and in the energetic field for biodiesel produc-
of oil selected for biodiesel production. These raw materials tion. Rapeseed is one of the most profitable crops available
Biodiesel Production from Renewable Bioresources
Fig. (2). Soybean oil to biofuel conversion process [48].
and has provided excellent sources of oil for biodiesel pro-
duction. Indeed, it can yield at about 36 % to over 46 % of
oil. The major fatty acids content found belonged to the
group of monounsaturated fats with 61.16% of oleic acid
[50].
Saka and Kusdiana [24] investigated transesterification
of rapeseed oil in supercritical methanol in a one-step proc-
ess without using any catalyst. Experiments were carried out
in a preheated batch-type reaction vessel at a pressure of
45-65 MPa, and with a molar ratio of methanol to rapeseed
oil of 42:1. The authors demonstrated that, in a preheating
temperature of 350°C (at a pressure of 45 MPa), 240 s of
supercritical treatment of methanol was sufficient to convert
the rapeseed oil to methyl esters (>95%) and that the pre-
pared methyl esters were basically the same as those ob-
tained by the conventional method with a basic catalyst. The
researchers revealed that, due to the non-catalytic nature of
the supercritical methanol process, the downstream process-
ing of products after the transesterification reaction was
found to be much simpler, as compared to the conventional
(base-catalysed) method, in which all the catalyst and
saponified products have to be removed to obtain biodiesel
and glycerol.
5.4. Palm Seeds
The lower need in water, fertilisers and pesticides, along
with the high production yield of palm trees, makes palm
seeds among the most prospective feedstock for biodiesel
production, compared to other oilseeds.
For countries in the temperate zone (between the Sub-
tropics and both the Arctic and Antarctic circles), fuel oils
are graded according to their cold flow properties. Indeed, a
summer grade fuel oil should exhibit pour point not higher
than 0°C, a spring or autumn grade fuel oil should exhibit
pour point not higher than -10°C and a winter grade fuel oil
should exhibit pour point not higher than -20°C.
In this regard, Malaysian inventors developed several
formulations in order to enhance cold flow properties of a
palm-based biodiesel in crude or refined form. Thus, the
authors proposed four methods for enhancing cold flow
properties of a palm-based biodiesel including (i) blending a
palm-based biodiesel with a petroleum-based fuel oil to form
a biodiesel blend; (ii) blending a palm-based biodiesel or
palm-based biodiesel blend with alkyl ester of C6 - C18
saturated or unsaturated fatty acid (or a mixture); (iii) blend-
ing a palm-based biodiesel blend with a polyalkyl methacry-
late (PAMA) additive; and (iv) enhancing the unsaturation
Recent Patents on Chemical Engineering, 2013, Vol. 6, No. 3 189
level of a palm-based biodiesel before blending it with a
polyalkyl methacrylate (PAMA) additive [51].
In Japan, a research team tried to optimise the transesteri-
fication of palm oil and has evaluated its solvent extraction
and fuel properties. The results showed that the optimised
process gave a maximum ester yield of 97% [14].
5.5. Jatropha (Jatropha curcas)
The oil content in Jatropha seeds is about 40% and the
yield production is about1600 kg/ha (Cf. Table 2). Jatropha
seeds are considered as one of the most promising potential
oil source to produce biodiesel. The plant could grow in
marginal lands with rapid growth and an easy propagation,
even in arid, semi-arid and tropical regions [52]. Many re-
searchers were interested in the Jatropha oil for biodiesel
production. A recent invention provided an energy efficient
process for the preparation of fatty acid methyl ester (biodie-
sel) from sun dried whole seed capsules of Jatropha curcas
integrated with value addition of seed shells, de-oiled cake
and crude glycerol co-product stream. The related results
showed that 90% of the 0.58 mole equivalent excess metha-
nol and almost all of the KOH catalyst used in the process of
transesterification are confined to the glycerol layer through
the process of glycerol washing [53].
In China, Jatropha curcas oil was selected as the best
biodiesel feedstock for their non-edible oil content [54] and a
Chinese research group worked on optimising the production
of biodiesel from Jatropha curcas oil by two-phase solvent
extraction [55].
5.6. Karanja (Pongamia Pinnata)
This plant is characterised by a rapid growth in various
types of soil, along with a high tolerance to drought and
salinity. The seeds are a good source of oil production and
can produce up to 21-32 % of oil (Cf. Table 2).
In a recent patent, an improved process for producing
biodiesel from free fatty acids (FFA) crude vegetable oils,
expelled and/or solvent extracted, from Karanja was pro-
posed [56]. The multi-step process consists of (i) a liquid-
liquid extraction (LLE) of the crude oil with methanol to
remove the bioactive constituents, polar materials and FFA
from non-polar glycerides, (ii) esterification of the FFA
present in the extract with an acid catalyst, (iii) transesterifi-
cation of resulting oil and separation of glycerol and crude
ester in basic medium, and (iv) purification of crude ester by
LLE to biodiesel [56].
190 Recent Patents on Chemical Engineering, 2013, Vol. 6, No. 3
Another study investigated the use of Karanja oil for the
production of biodiesel. The results revealed that this non-
edible raw material can be considered as a good alternative
to regular diesel fuel based on the fact that, in Karanja oil,
the oleic acid (C18:1) is the most abounded fatty acid with
about 50% [16]. A dual process mechanism for the produc-
tion of biodiesel from Karanja oil containing FFA up to 20%
was also developed. The related results revealed a biodiesel
yield from high Karanja oil’s FFA of about 97% [57].
5.7. Microlgae
Microalgae are marine organisms characterised with their
high biomass productivity, photosynthetic efficiency and
interesting oil content, which makes them a promising feed-
stock for biodiesel production without any competition with
food crops. Algae can reach high level of oil content like 75
% of dry basis for Botryococcus braunii. The major constitu-
ent of most algal oil are unsaturated fatty acids such as
palmitic acid (C16:0), along with significant amounts of
highly unsaturated species [15].
A method for producing biofuels is provided in a recent
patent that includes dewatering intact algal cells to make an
algal biomass, extracting neutral lipids from the algal bio-
mass, and esterifying the neutral lipids with a catalyst in the
presence of an alcohol. The method also includes separating
a water soluble fraction comprising glycerin from a water
insoluble fraction comprising fuel esters and distilling the
fuel esters under vacuum. The process permitted the produc-
tion of a jet fuel blend stock (from C16 or shorter fuel esters)
or a diesel blend stock (from C16 or longer fuel esters) [58].
In another invention, a process for biodiesel production
from algae was developed based on the cultivation of oil-
producing algae, extracting the algal oil, and converting the
algal oil to biodiesel. Extracting the algal oil from the oil-
producing algae included biologically rupturing cell wall and
oil vesicles of the algae using enzymes such as glycoprotein-
ase, a structured enzyme system such as a cellulosome, a
virus or combination of these biomaterials [59].
The direct transformation of some microorganisms into
biodiesel was also reported. For instance, a research group
developed a single-step, process for the direct conversion of
the algae Nannochloropsis Salina to crude biodiesel under
supercritical ethanol conditions. Ethanol was used for the
simultaneous extraction and transesterification of lipids in
algae to produce fatty acid ethyl esters at supercritical condi-
tions. The experimental results revealed that a maximum
yield of about 67% of fatty acid ethyl esters was obtained at
265 °C, 20 min of reaction time and 1:9 (wt./vol.) dry algae
to ethanol ratio [60].
5.8. Fungi
Several oleaginous fungal species were proven to be
promising feedstocks for biodiesel production, considering
that some of these microorganisms can accumulate triacyl-
glycerols, as cellular storage lipids, up to 70% of the biomass
[61].
In India, a research group invented a biodiesel production
process based on a new oleaginous yeast isolate of the genus
Pichia, Pichia kudriavzevii. The isolated yeast cells were
Ncibi and Sillanpää
able to accumulate about 50% of its weight as oil under
optimal operating conditions, i.e a culture medium including
1% w/v crude glycerol, 2% w/v corn steep liquor and 0.5%
w/v yeast autolysate at pH 5.5. The fermentation was per-
formed using a fed batch fermentor at about 28°C for 100
hours. The chemical analysis of the extracted oil revealed
that it is composed of 41% oleic acid, 15% linoleic, 10%
palmitic, 6% linolenic acid and about 1% stearic acid [62].
In another interesting invention, a process was developed
for lipid production by culturing oleaginous fungi with
lignocellulosic materials [63]. The idea is to perform a si-
multaneous saccharification and fermentation (SSF) of sev-
eral pre-treated lignocellulosic biomass including wheat
straw, barley straw, grass straw, corn stover and sugarcane
bagasse. The produced liquid and solid fractions were sepa-
rated. Then, sugars in the liquid fraction are cultured with
oleaginous microorganisms (yeasts and fungi) capable of
producing and accumulating lipids, namely, Aspergillus
niger, Aspergillus terreus, Chaetomium globosum, Cunning-
hamella elegans, Mortierella isabellina, Mortierella vinacea,
Mucor circinelloides, Neosartorya fischeri, Rhizopus oryzae,
Mucor plumbeus and Thermomyces lanuginosus. The related
results showed that the lipid contents varied among the dif-
ferent strains and ranged from 4.1 to 67.0% of the dry cell
weight, the highest content being reached by M. isabellina
with 67.0% on glucose and 50.9% on xylose.
6. ENVIRONMENTAL AND ECONOMIC BENEFITS
Compared to conventional fossil diesel, vegetable and
algae oil-derived biodiesels are becoming more attractive
because of their substantial environmental and economic
advantages including their availability and renewability
6.1. Environmental Advantages
Biodiesel is an eco-friendly fuel because of its biode-
gradable nature. It exhausts less emission in terms of carbon
monoxide, hydrocarbons, polycyclic aromatic hydrocarbon
(PAHs) compounds and nitrited polycyclic aromatic hydro-
carbon compounds (nPAHS) [12]. Indeed, the combustion of
biodiesel alone can reduce 90% of unburned hydrocarbons
and 75 to 90% of PAHs [64]. Some researchers tested the
blend of soybean biodiesel with conventional diesel. The
results showed that the higher the proportion of biodiesel in
the blend is, the lower the sulfur content and the emissions of
CO2 and SOx will be. Therefore, the use of biodiesel as an
alternative fuel should have important environmental bene-
fits by minimising global air pollution and reducing emission
levels of potential carcinogens [65].
6.2. Economic Considerations
The assessment of the cost and viability of biodiesel
production from oil-bearing bioresources is an important and
strategic subject of study, compared with the petroleum-
based fuel. Several factors must be considered in the calcula-
tion of biodiesel production costs such as the feedstock
source, which is about 80% of the total production cost,
labour, solvent and catalyst [26]. Currently, the high produc-
tion cost of biodiesel (approximately one and a half times
more than the petroleum-based diesel, depending on the
Biodiesel Production from Renewable Bioresources
nature of the feedstock [66]) is the major barrier to the large
scale commercialisation of biodiesel, despite its proven envi-
ronmental advantages.
From a pure economic point of view, several estimations
are predicting that global oil production rates will peak in a
couple of decades and then begin to decline, resulting in a
steady increase in crude oil prices, to which will be added
the rising global demand, especially from China and India,
and the excessive oil speculation. Thus, it was estimated that
a future large scale biodiesel production scenario would be
plausible if the cost of crude oil will exceed 100 $ per barrel
(which already happened in 2008) [67].
But, as far as R&D are concerned, the issue of biodiesel’s
high production cost was and is still being addressed, espe-
cially by targeting the factor responsible of the major load of
charge: the feedstock source. Thus, the use of edible feed-
stock for biodiesel production, in addition to the food -
related ethical issue, was tested and proven not to be eco-
nomically competitive with diesel fuel because of the high
cost involved in growing the crops (seeds for plantation,
fertilisation, pesticides, harvesting and labour…) and the
process of conversion into biodiesel (solvents, catalysts,
labour,…). The use of non-edible resources enhanced the
competitiveness of the derived biodiesel since it involves
growing non-food crops in marginal land without agricul-
tural treatments or even better using natural wastes or indus-
trial by-products. In this context, the use of waste cooking
oils seems to be a promising short term solution to lower the
biodiesel production cost. Indeed, a Brazilian team assessed
the economic benefits of using waste cooking oil for biodie-
sel production instead of virgin oils. The analysis revealed a
45% reduction of direct production costs for the case of used
oil, even when considering the additional costs of the pre-
treatment phase [66].
As well, in the US, a research team calculated the input
and output for the biodiesel production from soybean oil.
The related results showed that great benefits could be
gained if the soybean feedstock was produced with low agri-
culture input, on lands with marginal agricultural value, and
using low-input energy to convert it to biodiesel [68].
7. CURRENT AND FUTURE DEVELOPMENTS
Despite many years of research and development, no real
breakthroughs have been made with respect to large scale
use of biodiesel in the transportation sector.
The basic path forward will generally rely on consolida-
tion of the diverse processing steps, both in the engineering
and biological sense. For instance, microbial cells will be
expected to conduct multiple conversion reactions with high
efficiency and to remain robust to process conditions. Recent
research endeavours focused on the optimisation of biodiesel
production process through minimizing the input and maxi-
mising the output.
Yin et al. [46] studied several methods in order to opti-
mise biodiesel production from sunflower oil involving ul-
trasonic irradiation. The results showed that biodiesel pro-
duction with ultrasound irradiation assistance is better than
using only mechanical stir. Other researchers paid attention
to the use of enzymes as biocatalyst for biodiesel production
Recent Patents on Chemical Engineering, 2013, Vol. 6, No. 3 191
in order to substitute the conventional alkaline process. Thus,
a Romanian team used the lipase for the conversion and
purification of biodiesel and confirmed that the use of en-
zymes in biodiesel production ensures high productivity,
several possibilities of reuse and low reaction time [69]. As
well, a novel and robust recombinant Pichia pastoris yeast
whole cell catalyst (WCC) with functional intracellular ex-
pression of Thermomyces lanuginosus lipase (Tll) was con-
structed and characterized for biodiesel production from
waste cooking oils. The developed WCC was able to convert
the waste oils to biodiesel with a yield of 82% within 84 h at
6% dosage whole cells. The results also showed that the
WCC had a catalytic activity of 0.73 U/mg of dry cell weight
[70].
Therefore, the industrial improvements of enzymatic
production of biodiesel can be a viable option for the future.
A serious focus on the optimisation of biodiesel production
from microalgae should be conducted, starting with an effi-
cient culture process in order to grow and harvest algae with
high production yields and lipid content. A Malaysian re-
search group [71] investigated the use of organic fertiliser as
an alternative nutrient source to cultivate Chlorella vulgaris
in an industrial scale biodiesel production process. Numer-
ous advantages in terms of environmental perspective and
cost effectiveness have been obtained using this interesting
technique.
Regarding the extraction step, several studies were car-
ried out in order to optimise the lipid extraction process. In
Australia, for instance, scientists analysed different techno-
logical options currently available for laboratory-scale mi-
croalgal lipid extraction, with a primary focus on the pros-
pect of organic solvent and supercritical fluid extraction. The
study also provided an assessment of recent breakthroughs in
this rapidly developing field and reported on the suitability
of microalgal lipid compositions for biodiesel conversion
[72].
Ultimately, renewable bioresources conversion into bio-
diesel remains an attractive path for clean energy. And since
developing the technology for cost-effective motor fuel pro-
duction is not yet fully operational at large scale, scientific
R&D endeavours should be continued to reach this crucial
goal, both for economic and environmental reasons.
CONFLICT OF INTEREST
The authors confirm that this article content has no con-
flicts of interest.
ACKNOWLEDGEMENTS
Declared none.
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